KR20130108650A - Black azo pigment and process for production thereof, colored composition, coloring method, and colored articles - Google Patents

Abstract

The present invention provides a black azo pigment that exhibits optical properties of both visible light blocking properties and infrared transmission properties, wherein at least one 2-hydroxy-11H-benzo [a] introduced from two or more azo bonds in a molecule and a coupling component is used. It is a black polyazo pigment which has a structure which has] -carbazole-3-carboxylic acid amide residue, and its average particle diameter is 10 nm-200 nm. According to the present invention, a black pigment that exhibits excellent physical properties and fastness as a pigment, as well as exhibits optical properties of both visible light-shielding properties and infrared permeability, which can be applied to various uses, a method for producing the pigment, and the pigment It can provide the coloring composition formed by containing, the coloring method using this, and colored articles.

Description

Black azo pigment, manufacturing method, coloring composition, coloring method and coloring article {BLACK AZO PIGMENT AND PROCESS FOR PRODUCTION THEREOF, COLORED COMPOSITION, COLORING METHOD, AND COLORED ARTICLES}

This invention relates to a black azo dye, its manufacturing method, a coloring composition, a coloring method, and coloring articles. More specifically, the present invention relates to a black polyazo pigment having a specific structure, which has a characteristic of using for absorbing in the visible light region and having an optical property that is transmissive in the infrared region and useful for use with infrared rays. And a manufacturing method thereof, a coloring composition, a coloring method using the same, and colored articles.

As a black pigment used for coloring agents, such as a coating material, printing ink, and a plastics, a carbon black pigment, an iron oxide type black pigment, etc. are common. These black pigments have shown black by absorbing the light ray of all the wavelength ranges of light. The sunlight is an electromagnetic wave, and light in an area of approximately 380 nm to 780 nm becomes visible light, and light in an area of 0.7 μm to 2.5 μm having a longer wavelength than the visible light is near infrared. Although black can be shown by absorbing the light of the wavelength range of this visible light, a carbon black pigment absorbs not only visible light but the light of a near-infrared region as a result.

Near-infrared rays have almost no adverse effects on the human body, unlike short-wavelength light such as ultraviolet rays, and are safe lights. Recently, many electronic devices using infrared irradiation and reception have been developed. For example, an infrared remote control transmitter and its main body receiver include electric appliances, lighting fixtures, hot water toilets, cameras, car door locks, engine stators, opening and closing of garages, infrared security cameras or infrared surveillance cameras around streets or buildings. It is widely used in everyday life.

In addition, Patent Document 1 proposes a vehicle darkening device equipped with a light emitter which simultaneously emits visible light of an automobile headlight and near-infrared light for identifying an obstacle ahead of a vehicle, and a filter that blocks visible light and transmits infrared rays. Doing.

As a pigment used in these infrared transmitters, infrared filters of receivers, infrared filters of infrared cameras, etc., it exhibits optical characteristics that transmit light in the infrared region and completely shield the light in the visible region, and exhibit heat resistance, light resistance, and solvent resistance. The pigment | dye which has the function which was excellent in durability, etc. is desired.

In recent years, photovoltaic power generation systems have received widespread attention as clean energy. The photovoltaic module constituting the photovoltaic power generation system is attached to a place directly irradiated with sunlight, in particular on the roof or roof of an outdoor vacant lot or outdoor building. However, irradiating with sunlight and absorbing light causes an increase in the temperature of the photovoltaic module, leading to a decrease in the output of the power generation cell. In addition, in order to make the appearance and the contamination of the power generation module inconspicuous, black, dark oil color, and deep oil color may be colored from an aesthetic view. In some cases, this causes a significant temperature increase. Therefore, as a photovoltaic power generation system, the coloring system which suppresses temperature rise as much as possible even if it coloring in black is anticipated. The solar cell backsheet which consists of a perylene pigment is proposed (patent document 2).

In addition, in view of recent improvements in the living environment, comfort, and energy saving, heat-shielding coating by reflection of sunlight is desired, and development of a heat ray reflecting material therefor has been desired in various applications. For example, roofs and walls of houses, offices, warehouses, buildings, buildings, etc. can be painted, road paving, exteriors and interiors of automobiles, ships, etc. Etc., and heat dissipation materials such as electronic parts are also desired.

Also, in the field of information technology, with the great development of information equipments these days, liquid crystal displays (hereinafter sometimes referred to as LCDs) are TVs, projectors, personal computers, and mobile information devices as information display members. Display devices such as monitors, car navigation systems, mobile phones, electronic calculators or electronic dictionary displays, information boards, information boards, function panels, signs, signs of digital cameras or video cameras, etc. I am used over. As a result, the display quality of the display is improved and the cost is reduced, and the quality of the color filter (hereinafter sometimes abbreviated as 'CF') is improved and the cost is reduced. Also for CF mounted on LCD, superior quality is required in terms of color characteristics and optical characteristics of image performance such as fineness, color density, light transmittance, contrast, and the like. The development of the material which has is desired.

In the CF of an LCD, R (red), G (green), and B (blue) pixels are arranged in a stripe shape, a mosaic shape, a triangle shape, and the like, and irradiated with a backlight from the back surface, and R, G, B The transmitted light of the pixels is colored by a color mixture to form an image. A black matrix (hereinafter sometimes abbreviated as 'BM') is formed in a lattice shape around each pixel to shield unnecessary light and to prevent color mixing. Although red pigment, green pigment, blue pigment, yellow pigment, purple pigment, etc. are used about a chromatic pixel, improvement is respectively performed. In addition, BM is a light-shielding material for completely shielding light in the visible light region of the backlight, and shifts from a metal chromium film to a resin BM using a black pigment from problems such as an increase in substrate size and environmental load of a chromium compound. It has been.

Backlight has also led to improvement of color purity and expansion of color reproduction area by replacing light emitting diodes (LEDs) from cold cathode fluorescent tubes. Light emission in the red region was sharp light of approximately 600 to 620 nm in the backlight of the cold cathode fluorescent tube, but light from the red light emitting portion in the backlight of the LED, and was approximately 540 as the emission wavelength range in the vicinity of the maximum emission wavelength of 640 nm. It is proposed to use wide light in the range of nm to 800 nm (Patent Document 3). Therefore, as BM, it is a requirement that the light on the long wavelength side of visible light can also be sufficiently shielded.

In addition, various improvements have been proposed also in the display system of CF pixels, and in addition to this, improvements in BM and improvement of light-shielding black pigments used in BM are also being performed. For example, in order to obtain a wide viewing angle, which is a weak point of conventional LCDs, an in-plane switching method (IPS method) is proposed in which an electric field is applied in parallel to a substrate and a liquid crystal layer is converted to display pixels. It is becoming. In addition, the black matrix on-array method (BOA method) and the color filter on-array method (COA method) for forming BM on the thin film transistor TFT have a large aperture area, so that the pixel area can be increased. In addition, in the work process, the pasting process work is improved and can be rationalized.

Moreover, in order to achieve these improvement methods more completely, especially in the IPS system, it is necessary to keep the space | interval (cell gap) of the board | substrate which pinches a liquid crystal layer at high precision uniformly. However, it is difficult to adjust the cell gap uniformly by the method of spreading the conventional bead-shaped spacer. Therefore, as a method of realizing a uniform cell gap by a fixed spacer, supporting the cell gap of the substrate such as increasing the thickness of the BM itself or superimposing a high gap support member resin such as a colored layer or a photoresist layer on the BM. A method is proposed. Moreover, the fall of the display quality by scattering of light and permeation | transmission also improves by not using a bead-shaped spacer (patent document 4, 5).

The above-described methods such as the IPS method, the BOA method, and the COA method are methods for forming BM on an active element such as a TFT, and if the BM is not electrically insulating, there is a possibility that the TFT may malfunction. Carbon black pigments generally used as light-shielding black pigments are inherently low pigments with low electrical resistance, and are not suitable as light-shielding black pigments used in these methods, and are preferably light-shielding materials having high electrical insulation.

On the other hand, the carbon black pigment prescribed | regulated by the amount of oxygen was coat | covered with the resin film with high insulation, and the proposal for the carbon black pigment which improved electrical insulation (patent document 6), or insulating carbon black which selected and measured the volume resistivity value. The carbon black pigment which coat | covered with a pigment or resin and improved the electrical insulation is used, and insulating BM is formed and there exists indication about the application to COA system (patent document 7).

However, carbon black pigments are inherently conductive materials, and it is difficult to make the insulation perfect even when the resin is coated as in the conventional art.

In addition, in displays using organic EL devices, which have been recently developed, the use of BM has been proposed to prevent color mixing of adjacent light from light emitting devices and to improve the clarity of light emitting screens (Patent Document 8). .

Japanese Patent Publication No. 4120513 Japanese Unexamined Patent Publication No. 2007-128943 Japanese Patent Application Publication No. 2006-148051 Japanese Unexamined Patent Publication No. 2000-66018 Japanese Unexamined Patent Publication No. 2002-341332 Japanese Patent Publication No. 3543501 Japanese Patent Publication No. 4338479 Japanese Patent Application Publication No. 2004-221081

From the above circumstances, it is desirable to develop a black pigment that exhibits excellent physical properties and fastness as a pigment and exhibits optical properties of both visible light-shielding properties and infrared-transmittance properties, which are useful for various applications. have. Specifically, for example, the use of an infrared filter for electronic equipment used to shield unnecessary visible light and transmit a signal by infrared rays, or a black or dark-colored back sheet constituting a solar power system, the solar light The multilayer coloring system which formed the infrared-transmissive black layer on the solar reflective base which can suppress the temperature rise by this, and completes the light of visible region even in the case of LED backlight with wide emission wavelength range as BM of CF. It can be effectively shielded, and also maintains high electrical insulation even when BM is formed on active elements such as TFTs, and is useful for various applications in which TFTs do not cause malfunctions. Furthermore, visible light is also used in BMs of organic EL displays. The black pigment which is suitable for the light-shielding use etc. and has the outstanding physical property and fastness also as a pigment is required. And there.

Accordingly, an object of the present invention is not only to exhibit excellent physical properties and fastness as a pigment, but also to show a black pigment exhibiting optical properties of both visible light-shielding properties and infrared permeability, which are applicable to various applications as described above, and pigments thereof. It is providing the manufacturing method of this, the coloring composition containing this pigment, the coloring method using this, and coloring articles.

MEANS TO SOLVE THE PROBLEM The present inventors earnestly researched and studied the chemical structure of black organic pigment so that the objective of this invention may be achieved, and, as for the black polyazo pigment which has a specific structure, the wavelength range of the light which absorbs is visible region. Absorbs light at a wavelength of approximately 400 to 750 nm, which is almost the entire region, at a high level, and exhibits high transmittance on the long wavelength side of the infrared region of approximately 900 to 1500 nm, and has an average particle diameter of 10 nm to The black pigment refine | miniaturized and pigmented so that it might become 200 nm discovered the thing suitable for the various uses listed previously, solved the said subject, and came to complete this invention.

That is, the present invention is a black azo pigment which exhibits optical properties of both visible light blocking property and infrared ray transmitting property, wherein at least one 2-hydroxy-11H-benzo introduced from two or more azo bonds and a coupling component in a molecule thereof. It is a black polyazo pigment which has a structure which has [a] -carbazole-3-carboxylic acid amide residue, and its average particle diameter is 10 nm-200 nm, The black azo pigment is provided. do.

As a preferable aspect of this invention, the following black azo pigment is mentioned.

The visible light-shielding property is that the black colored film containing the black azo pigment on the transparent substrate exhibits a spectral transmittance of about 5% or less in the wavelength range of approximately 400 to 750 nm, which is the visible light range, and the infrared transmittance is the black colored film. The black azo pigment which shows the transmittance | permeability about 30% or more in the wavelength range of 900-1500 nm which is an infrared region.

The black azo pigment in which the structure of the said polyazo pigment has at least any one of the structures of following (1)-(4).

(1) A diazonium salt obtained by diazotizing a compound (representative: H ₂ N-Ar-NH ₂ ) having two or more amino groups as a diazo component is used. Represented by [HBC-N = N-Ar-N = N-HBC] formed by azo-coupling of oxy-11H-benzo [a] -carbazole-3-carboxylic acid arylamide (abbreviated as 'HBC') rescue.

(2) A diazonium salt formed by diazotizing a compound (representative: H ₂ N-Ar-NH ₂ ) having two or more amino groups as a diazo component is used. Oxy-11H-benzo [a] -carbazole-3-carboxylic acid arylamide (abbreviated as 'HBC') and a coupling component other than the compound (denoted as 'Cp') formed by azo-coupling [ HBC-N = N-Ar-N = N-Cp].

(3) a coupling component having two or more 2-hydroxy-11H-benzo [a] -carbazole-3-carboxamide residues (abbreviated as 'HBC-') in its molecule ('HBC-HBC') [Ar-N = N-HBC- formed by diazotizing and azo-coupling a compound having one amino group (denoted as 'Ar-NH ₂ ') as a diazo component, HBC-N = N-Ar].

(4) In the molecule thereof, 2-hydroxy-11H-benzo [a] -carbazole-3-carboxamide residue (abbreviated as' HBC- ') and a coupling component residue other than the compound (' Diazotizing a compound having one amino group (denoted as' Ar-NH ₂ ') as a diazo component to a coupling component having a Cp-') (denoted as' HBC-Cp '), A structure represented by [Ar-N = N-HBC-Cp-N = N-Ar] formed by azo coupling.

In addition, in the above, "Ar" represents the residue of an aromatic compound and a heterocyclic compound typically, and when there are two or more in a formula, it may be same or different. In addition, "Ar-N = N-" or "-N = N-Ar-N = N-" in the formula means an "arylazo moiety" to which the diazonium salt of the diazo component is coupled. The same applies to the following.

The present invention is, as another embodiment, a production method for obtaining the black azo pigment of the present invention, as a production method having a step of synthesizing a black polyazo pigment and a step of miniaturizing the pigment as necessary. I) The synthesis | combination method of a black polyazo pigment is any one classified into four types mentioned later, and when the polyazo pigment synthesize | combined by these methods is coarse and large, the average particle diameter of a pigment is known by any of the well-known methods mentioned later. It provides a process for producing a black azo pigment, characterized in that it has a step of making it fine into 10 nm to 200 nm.

As another embodiment, the present invention comprises a pigment component comprising the black azo pigment of the present invention described above or the black azo pigment obtained by the above production method in a liquid dispersion medium or a solid dispersion medium. It provides a coloring composition.

As another embodiment, the present invention provides a method for coloring an article, wherein the coloring composition is used when coloring the article to black or dark color by coloring the surface of the article or coloring the article itself.

In another embodiment, the present invention provides a colored article, wherein a method of coloring the article is performed.

In another embodiment, the present invention provides a back sheet of a photovoltaic module in which a black or dark infrared transparent layer is laminated on a light reflective sheet, comprising two or more azo bonds in a molecule in an infrared transparent layer, Has a structure having at least one 2-hydroxy-11H-benzo [a] -carbazole-3-carboxylic acid amide residue (abbreviated as 'HBC-') introduced from the coupling component, the average particle diameter of which is 10; The backsheet of the photovoltaic module which contains the black polyazo pigment which is nm-200nm is provided.

As another embodiment of the present invention, the substrate having light reflectivity in the substrate itself is used as the light reflective sheet, or the substrate on which the light reflective base formed in advance is formed is used as the light reflective sheet. At least two azo bonds in the molecule and at least one 2-hydroxy-11H-benzo [a] -carbazole-3-carboxylic acid amide residue ('HBC) introduced from the coupling component on the surface or on the light reflective basis of the Coating, coating, adhering, welding, intermediate, and coloring composition having a structure having an abbreviation of-'and containing a black polyazo pigment having an average particle diameter of 10 nm to 200 nm, By printing, inkjet printing, electrophotographic printing, or electrostatic printing, coloration showing reflectivity is performed in the infrared region, and a black or dark infrared transparent layer is laminated on the light reflective sheet. It provides a method of producing a backsheet for photovoltaic module of.

According to another embodiment of the present invention, at least one of a black matrix (BM) formed on a color filter (CF) substrate or an organic EL light emitting substrate is introduced from two or more azo bonds and a coupling component in a molecule thereof. A black polyazo pigment having a structure having a hydroxy-11H-benzo [a] -carbazole-3-carboxylic acid amide residue (abbreviated as 'HBC-') and having an average particle diameter of 10 nm to 200 nm The present invention provides a color display panel containing the same.

According to the present invention described above, the black colored film containing the black azo pigment exhibits almost complete absorption in the wavelength range of approximately 400 to 750 nm covering the visible light range on the transparent substrate. And in the infrared wavelength region of longer wavelength than that, it shows high transmittance | permeability on a transparent substrate, and shows the useful optical characteristic which combines visible light shading | shield and infrared transmittance | permeability. Since it has such a characteristic, the black azo pigment of this invention is used effectively as an infrared filter of an infrared remote controller and a main body receiver. Moreover, the black azo pigment of this invention can be used also as an infrared filter of the infrared sensing apparatus which detects and identifies road-blocking obstacles, such as a motor vehicle which is put into practical use.

In addition, since the black azo pigment of the present invention exhibits an optical property covering the visible light region and almost completely absorbing the long wavelength side, the LED backlight corresponding to a red pixel, for example, as a light-shielding black material of BM of CF. The wavelength range of the light from the red light emitting portion can be sufficiently absorbed and shielded, and the color of the LCD is not only black but also other colored colors are vividly colored. Moreover, since it has high electrical insulation, various CF improvement methods which form BM on active elements, such as TFT, for example, BM which maintains the thickness of a liquid crystal layer instead of a spacer, IPS system, COA system, etc. It is also suitable as a light-shielding black pigment forming BM of CF. In particular, it is the most preferable light-shielding black pigment in IPS system liquid crystal panel etc. which employ | adopted LED backlight, and also in organic electroluminescent display.

In addition, since it sufficiently transmits infrared rays, houses and buildings that are attracting attention from the viewpoint of improvement of the living environment, comfort, and energy saving from the functions reflected by white pigments or extender pigments added to foundations or coating materials, etc. It is used as a material for preventing the temperature rise by direct sunlight, such as the painting, the pavement of the road, and the painting of the deck, the exterior of the ship. Moreover, also in a photovoltaic power generation system, it is used for the back seat | sheet which formed the black or dark-colored infrared permeable layer in multiple layers on the reflective base layer which can suppress the temperature rise by sunlight. It is also used for camouflage coloring materials or anti-counterfeiting of military equipment.

Next, the present invention will be described in more detail with reference to the best mode for carrying out the invention.

The black azo pigment which characterizes this invention is an optical characteristic, and it absorbs across a visible light region, shows especially nearly complete absorption even in the wavelength range of the long wavelength side, and shows the high transmittance in a near-infrared region. Specifically, the spectral transmittance of the black colored thin film on the transparent substrate is approximately 5% or less in the wavelength range of 400 to 750 nm, which is approximately the visible light range, and approximately 30% in the wavelength range of the infrared region of approximately 900 nm to 1500 nm. The above is shown. Moreover, as electrical characteristics, very high electrical insulation is shown.

MEANS TO SOLVE THE PROBLEM As a black azo pigment which shows the said characteristic optical characteristic, the present inventors examined the pigment which has several chromophore in a molecule and resonated them mutually, and especially the ease of synthesis and stable manufacture As possible, black polyazo pigments have been developed that have two or more azo bonds in the molecule and have a specific chemical structure. In addition, since high transmittance in particular in the infrared region is 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 approximately 10 nm to 200 nm. In addition, when a high transmittance is desired, an ultrafine black polyazo pigment having an average particle diameter of approximately 10 nm to 50 nm, or a black azo pigment having a dispersive dye-like property of bringing molecular dispersion into the medium in a coloring process is preferable. Do.

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

As a chemical structure in which a polyazo pigment is black, the present inventors have at least one 2-hydroxy-11H-benzo [a] -carbazole having at least two azo bonds in a molecule and introduced from the coupling component. A chemical structure with 3-carboxamide residues (see formula below) was found.

2-hydroxy-11H-benzo [a] -carbazole-3-carboxamide residue

As the method for producing the polyazo pigment, since it is necessary to bring two or more azo bonds into the molecule, for example, an azo couple using a diazo component having two or more amino groups which are changed into diazonium groups as the diazo component. The method of ringing, the method of azo-coupling, etc. using the coupling component in which a coupling component has two or more coupling positions are mentioned. This point is explained in full detail.

It is preferable that the black polyazo pigment of this invention has either of the structures of following (1)-(4).

(1) A diazonium salt formed by diazotizing a compound (representative: H ₂ N-Ar-NH ₂ ) having two or more amino groups as a diazo component, and using the salt as a coupling component, 2- Represented by [HBC-N = N-Ar-N = N-HBC] formed by azo-coupling of hydroxy-11H-benzo [a] -carbazole-3-carboxylic acid arylamide (abbreviated as 'HBC') Black polyazo pigment of the structure made.

As an example of the black polyazo pigment which has a structure (1) represented by said [HBC-N = N-Ar-N = N-HBC], Benzidine or phenylene which has two or more amino groups in a diazo component is shown below. Examples of the structure in the case of using a diamine are listed.

(2) A diazonium salt formed by diazotizing a compound (representative: H ₂ N-Ar-NH ₂ ) having two or more amino groups as a diazo component is used. Oxy-11H-benzo [a] -carbazole-3-carboxylic acid arylamide (abbreviated as 'HBC') and a coupling component other than the compound (denoted as 'Cp') formed by azo-coupling [ A black polyazo pigment having a structure represented by HBC-N = N-Ar-N = N-Cp].

Examples of the black polyazo pigment having the structure (2) represented by the above [HBC-N = N-Ar-N = N-Cp] include benzidine or phenylene having two or more amino groups in the diazo component. Examples of the structure in the case of using 2-hydroxy-3-naphthoic acid arylamide as another coupling component using diamine are listed.

(3) a coupling component having two or more 2-hydroxy-11H-benzo [a] -carbazole-3-carboxamide residues (abbreviated as 'HBC-') in its molecule ('HBC-HBC') [Ar-N = N-HBC- formed by diazotizing and azo-coupling a compound having one amino group (denoted as 'Ar-NH ₂ ') as a diazo component, Black polyazo pigment of the structure represented by HBC-N = N-Ar].

Examples of the black polyazo pigment having the structure (3) represented by the above [Ar-N = N-HBC-HBC-N = N-Ar] include, for example, 2-, with phenylene or biphenylene interposed therebetween. Diazolation by using aniline having one amino group as a diazo component for HBC-HBC of a coupling component having two hydroxyl-11H-benzo [a] -carbazole-3-carboxamide residues bonded thereto. The example of the structure at the time of the case is listed.

(4) In the molecule thereof, 2-hydroxy-11H-benzo [a] -carbazole-3-carboxamide residue (abbreviated as' HBC- ') and a coupling component residue other than the compound (' Diazotizing a compound having one amino group (denoted as' Ar-NH ₂ ') as a diazo component to a coupling component having a Cp-') (denoted as' HBC-Cp '), A black polyazo pigment having a structure represented by [Ar-N = N-HBC-Cp-N = N-Ar] formed by azo coupling.

As an example of the black polyazo pigment having the structure (4) represented by [Ar-N = N-HBC-Cp-N = N-Ar], the following procedure is given to 2-hydride with phenylene or biphenylene interposed therebetween. Of a coupling component to which a hydroxy-11H-benzo [a] -carbazole-3-carboxamide residue and a residue of 2-hydroxy-3-naphthoic arylamide which is a coupling component other than the compound are bound. Examples of the structure in the case of diazotizing using aniline which has one amino group as a diazo component for HBC-Cp are listed.

The black azo pigment of the present invention is a black azo pigment of the present invention having a synthesis step of a polyazo pigment having a structure as listed above, and a step of adjusting the particle size of the pigment particles to refine the pigment, if necessary It can be obtained easily according to the manufacturing method. Hereinafter, the manufacturing method of the black azo pigment of this invention is demonstrated.

The synthesis | combining method of the black polyazo pigment which comprises the manufacturing method of the black azo pigment of this invention is selected from the method of following (1)-(4).

The method (1), an amino group having two or more compounds to the diazonium salt formed by (a representative formula _{H 2 N-Ar-NH 2} ) to diazotization, 2-hydroxy -11H- benzo [a] - carbazol Azo-coupling sol-3-carboxylic acid arylamide (abbreviated as "HBC"). The black polyazo pigment obtained by the synthesis method of (1) will have a structure represented by [HBC-N = N-Ar-N = N-HBC] demonstrated previously.

The method (2) is an amino group having two or more compounds to the diazonium salt formed by (a representative formula _{H 2 N-Ar-NH 2} ) to diazotization, 2-hydroxy -11H- benzo [a] - carbazol A method for synthesizing a polyazo pigment having azo-coupled structure of a sol-3-carboxylic acid arylamide (abbreviated as 'HBC') and a coupling component other than the compound (represented by 'Cp') with an amino group. Azo-coupling an equimolar or its coupling component (Cp) to a diazonium salt formed by diazotizing a compound having two or more (representative formula: H ₂ N-Ar-NH ₂ ) And, if necessary, a synthetic method of separating and removing a polyazo pigment to which two or more coupling components (Cp) are coupled, and then azo-coupling the coupling component (HBC) to an uncoupled diazonium group. to be. The black polyazo pigment obtained by the synthesis method of (2) will have a structure represented by [HBC-N = N-Ar-N = N-Cp] demonstrated previously.

The method of (3) is the following (3-1) or (3-2) method. The black polyazo pigment obtained by the synthesis method of these (3-1) and (3-2) has a structure represented by [Ar-N = N-HBC-HBC-N = N-Ar] demonstrated previously. It becomes.

(3-1) Coupling component having two or more 2-hydroxy-11H-benzo [a] -carbazole-3-carboxamide residues (abbreviated as' HBC- ') in a molecule (' HBC-HBC a plus mark "), a synthetic method of a diazo component formed by the diazotization of the compound (Ar-NH ₂₎ which has one amino group, an azo coupled.

(3-2) 2-hydroxy--11H- benzo [a] - carbazol-3-carboxylic acid, the compound having one amino group (as represented la 'Ar-NH _2'), the diazonium salt formed by diazotization To azo-coupling, and then carboxylic acid of an azo dye is condensed with an aryl polyamine, and it is a synthesis method which makes a polycarboxamide.

The method of (4) is the method of following (4-1) or (4-2). The black polyazo pigment obtained by the synthesis method of these (4-1) and (4-2) has a structure represented by [Ar-N = N-HBC-Cp-N = N-Ar] demonstrated previously. It becomes.

(4-1) 2-hydroxy-11H-benzo [a] -carbazole-3-carboxamide residue (abbreviated as 'HBC-') in one molecule, and a coupling component residue other than the compound ( Diazonium salt formed by diazotizing a compound having one amino group (denoted as 'Ar-NH ₂ ') to a coupling component having an amino group (denoted as 'Cp-') (denoted as 'HBC-Cp'). It is a synthesis method of azo-coupling.

(4-2) Compounds each having one amino group in 2-hydroxy-11H-benzo [a] -carbazole-3-carboxylic acid and carboxylic acid of another coupling component (denoted as 'Ar-NH ₂ ') It is a synthesis | combining method which azo-couples the diazonium salt formed by diazotizing, and condenses the carboxylic acid of the both azo dyes obtained by aryl polyamine to make polycarboxamide.

The diazo component and coupling component which can be used by each synthesis method enumerated above are demonstrated.

(A) It illustrates concretely about a coupling component.

As (a) coupling component (HBC), for example, 2-hydroxy-11H-benzo [a] -carbazole-3-anilide, 2-hydroxy-11H-benzo [a] -carbazole- 3-naphthylamide and the like and derivatives thereof. As a substituent of a derivative, an alkyl (carbon number; 1-10) group, an alkoxy (carbon number; 1-10) group, a trifluoromethyl group, a halogen group, an alkyloxycarbonyl group, a cyclic imino dioxy group, an alkyl sulfo, for example A coupling component in which one, more than one, such as a silyl group, an aminocarbonyl group, a benzamide group, an alkylaminocarbonyl group, an anilinocarbonyl group, a cyclic ureylene group, a carboxyl group and an alkylimino group is introduced.

Specifically, for example, 2-hydroxy-11H-benzo [a] -carbazole-3-anilide, 2-hydroxy-11H-benzo [a] -carbazole-3-carboxy - p-no Let Id, 2-hydroxy -11H- benzo [a] - carbazol-3-carboxy-2- (2-methyl) -p- not let Id, 2-hydroxy -11H- benzo [a] - carbazol -3 -Carboxy - N-benzimidazolone-5-amide, 2-hydroxy-11H-benzo [a] -carbazole-3-carboxy - naphthylamide, etc. are mentioned.

As the coupling component (HBC-HBC), for example, phenylene-bis (2-hydroxy-11H-benzo [a] -carbazole-3-carboxamide) and biphenylene-bis ( 2-hydroxy-11H-benzo [a] -carbazole-3-carboxamide), naphthalene-bis (2-hydroxy-11H-benzo [a] -carbazole-3-carboxamide) and the like and their Derivatives. Examples of the substituent of the derivative include one or more substituents known to the aryl group, for example, an alkyl (carbon number; 1 to 10) group, an alkoxy (carbon number; 1 to 10) group, a trifluoromethyl group, a halogen group, and the like. Introduced coupling component.

Specifically, for example, phenylene- (1,4-) bis (2-hydroxy-11H-benzo [a] -carbazole-3-carboxamide) and 2-chloro-phenylene- (1 , 4-) bis (2-hydroxy-11H-benzo [a] -carbazole-3-carboxamide), 2,5-dichloro-phenylene- (1,4-) bis (2-hydroxy- 11H-Benzo [a] -carbazole-3-carboxamide) 2-methyl-phenylene- (1,4-) bis (2-hydroxy-11H-benzo [a] -carbazole-3-carbox Mead), biphenylene- (4,4 '-) bis (2-hydroxy-11H-benzo [a] -carbazole-3-carboxamide), 3,3'-dichloro-biphenylene- ( 4,4 '-) bis (2-hydroxy-11H-benzo [a] -carbazole-3-carboxamide), naphthalene- (1,5-) bis (2-hydroxy-11H-benzo [a ] -Carbazole-3-carboxamide).

(c) As coupling component (Cp), 2-hydroxy-3- naphthoic acid arylamide, 2-hydroxy-6-naphthoic acid arylamide, 2-hydroxy-3- anthracene carboxylic acid arylamide, for example. , 2-hydroxy-3-dibenzofuran carboxylic acid arylamide, 2-hydroxy-1-carbazole carboxylic acid arylamide, and derivatives thereof. For example, C.I. AZOIC Coupling Components 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-amide, 2-hydroxy-3-naphthoic acid- N-phthalimide-4-amide, etc.

(d) As the coupling component (HBC-Cp), 2-hydroxy-3-naphthoic acid, 2-hydroxy-6-naphthoic acid, 2-hydride as a carboxylic acid of a Cp residue which amide bonds with an amino group of an HBC residue. Hydroxy-3- anthracene carboxylic acid, 2-hydroxy-3-dibenzofuran carboxylic acid, 2-hydroxy-1-carbazole carboxylic acid, etc. are mentioned. For example, phenylene (-1)-(2-hydroxy-11H-benzo [a] -carbazole-3-carboxamide) (-4)-(2-hydroxy-3-naphthoic acid amide) , Phenylene (-1)-(2-hydroxy-11H-benzo [a] -carbazole-3-carboxamide) (-4)-(2-hydroxy-3-naphthoic acid amide), (2 -Methyl-) phenylene (-1)-(2-hydroxy-11H-benzo [a] -carbazole-3-carboxamide) (-4)-(2-hydroxy-3-naphthoic acid amide) Biphenylene (-4)-(2-hydroxy-11H-benzo [a] -carbazole-3-carboxamide) (-4 ')-(2-hydroxy-3- naphthoic acid amide), etc. to be.

(B) It illustrates concretely about a diazo component.

(a) a compound having two or more amino groups of the diazo component dogs: As (represented formula _{H 2 N-Ar-NH 2} ), for example, phenylene diamine, diamino biphenyl, diamino naphthalene, diamino anthraquinones , Diamino-benzophenone, diaminopyridine and the like and derivatives thereof. Examples of the substituent of the derivative include one or more substituents known to the aryl group, for example, an alkyl (carbon number; 1 to 10) group, an alkoxy (carbon number; 1 to 10) group, a trifluoromethyl group, a halogen group, and the like. Introduced diazo component.

Specifically, for example, 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-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-diaminoanthraquinone, 1,5-diaminoanthraquinone; 3,4-diamino-benzophenone; 2, 6- diamino pyridine etc. are mentioned.

(b) Examples of the compound having one amino group of the diazo component (denoted as 'Ar-NH ₂ ') include, for example, aniline, naphthylamine, aminoanthraquinone, phenoxyaniline, phenyliminoaniline, and the like. Their derivatives. As the substituent of the derivative, a substituent known in the aryl group, for example, an alkyl (carbon number; 1 to 10) group, an alkoxy (carbon number; 1 to 10) group, a halogen group, a nitro group, a phenyl ether group, a phenylimino group, A benzoylamide group, an anilinocarbonyl group, a cyclic ureylene group, etc. are the diazo component in which one or more were introduce | transduced. Specifically, CI azoic diazo component 5, 8, 9, 10, 32, 33, 34, 35, 36, 37, 41, 42, 43, 47, etc. are mentioned, for example.

The adjustment process of the particle diameter of the pigment particle which refine | miniaturizes the pigment as needed and which comprises the manufacturing method of the black azo pigment of this invention is demonstrated. As for the black azo pigment of this invention, when the polyazo pigment obtained by the synthesis method as listed above is large, and the particle size is coarse, the average particle diameter of a pigment by either of the following (1) or (2) methods. It can be obtained by making it fine into approximately 10 nm-200 nm. That is, in order to improve the transmittance of infrared rays, such as a coating film using the polyazo pigment obtained by the synthesis method as listed above, the particle diameter of the dispersed pigment is small compared with the wavelength of light, specifically, It is necessary for the average particle diameter to be approximately 10 nm to 200 nm. Therefore, when the pigment synthesize | combined by the above-mentioned method is coarse and large, the black azo pigment of this invention carries out the well-known pigment refinement | miniaturization process enumerated below, in order to adjust the average particle diameter of a pigment to the required particle size, and it refine | miniaturizes It is necessary to prepare a pigment.

Specifically,

(1) Ball mill, sand mill, attritor, horizontal continuous media disperser, kneader, continuous single axis kneader, continuous biaxial kneader, 3 rolls, open roll continuous kneader, etc. Micronization method using a pigment grinding group or pigment dispersing group selected from the group,

(2) Pigment refinement process selected from well-known methods, such as a solvent salt milling method which knead | mixes and grinds together with a water-soluble organic solvent in a kneading machine, and a water-soluble organic solvent as needed, and average particle diameter is about 10 nm-200 It is prepared so that it may become nm. In addition, when high infrared transmittance is desired, it is preferable to prepare the ultrafine pigment whose average particle diameter is about 10 nm-50 nm.

The particle diameter of the pigment is adjusted according to the use used. The adjustment of the particle diameter is mainly controlled by the amount ratio of salts to the pigment and the kneading time. In applications such as infrared color filters requiring a high transmittance, the pigment particles are preferably smaller. For example, fine pigment particles of 10 nm to 50 nm are dispersed, and ultrafine pigment particles of 10 nm to 30 nm are further dispersed. The state is preferred, and ultimately the dissolved state, which is molecularly dispersed in a carrier of dispersion, for example a plastic medium.

On the other hand, in applications such as BM of CF that require light shielding properties of visible light, it is more preferable that it is about 50 nm to 100 nm which is slightly larger than the transmission use. Moreover, in the use which requires infrared reflectivity, it is preferable that a base is reflective, In addition, a pigment particle may be comparatively large and it is used also in 100 nm-200 nm.

In the above-described solvent salt milling method, water is added to the pigment several times, specifically 3 to 20 times the amount of the pigment to be crushed by the particle diameter of the pigment of water-soluble inorganic salts as the grinding aid, and further, ethylene Viscous water-soluble organic solvents, such as glycol, diethylene glycol, and polyethylene glycol, are added and kneaded and ground. As a water-soluble inorganic salt used for grinding grinding, sodium chloride, sodium sulfate, etc. are used. After grinding, it is added to dilute acid, water or the like, the grinding aid is dissolved, filtered and washed with water to obtain a filtration paste (flake) of pigment. The press cake is processed by dispersing with a wet disperser as it is, or processed with an oily colorant by a flushing method, or dried by hot air drying, then pulverized by a dry grinder into a powder pigment, or the above-mentioned various wet dispersers or kneaders, or the like. It is disperse | distributed by the process, and is processed with various coloring agents according to a use. Moreover, it is also preferable to set it as a dispersible process pigment or a process pigment by resin-processing in water.

In using the black azo pigment of this invention as a coloring agent, it is also preferable to add anionic or cationic pigment derivative to a black azo pigment especially in a liquid pigment dispersion liquid. As a method for adding these pigment derivatives, a method of introducing the accessory by a coupling method using a diazo component or a coupling component having an ionic group at the time of synthesis of the pigment, or a pigment derivative having an ionic group synthesized separately And a known method such as a method of adding at the time of granulation production process or preparing a pigment dispersion. As a pigment derivative at this time, pigment derivatives of chromatic colors, such as yellow, blue, and red, other than black, are used suitably including adjustment of a hue, etc.

Here, although the spectral transmittance of a coating film shows the slight difference in numerical value according to the black pigment content and coating film thickness contained in a coating film, in the relationship with wavelength, all show the tendency of absorption in the wavelength to absorb, and transmit It is confirmed that it shows the tendency of transmission in the wavelength to say. In Table 1 and Table 2, the visible region of the coating film containing the black pigment-1 prepared in Example 1 mentioned later using the black disazo pigment ('black pigment-1') obtained by the manufacture example of this invention mentioned later and The spectral transmittance (%) of the infrared region is shown.

As a result, as shown in Table 1, in the coating film containing black pigment-1, it was confirmed that the transmittance | permeability is 0% over the full-wavelength region of 400-750 nm of visible light, and it does not show transparency in the visible region. On the other hand, as shown in Table 2, there is 34% transmission at 900 nm, which is an infrared region, and the transmittance gradually increases on the longer wavelength side, and it is assumed that the display shows high transmittance even at a high wavelength. .

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

TABLE 2 Spectral transmittance of infrared region of black pigment-1

In addition, about the electrical insulation of the coating film containing the black azo pigment of this invention, as shown in Example 1 mentioned later similarly, the volume specific resistance of the coating film containing black pigment-1 is 10 ¹⁴ ohm * cm, and it is favorable electrical insulation property It confirmed that it represents.

Since black pigment-1, which is a black azo pigment of the present invention, is a pigment having an optical function of transmitting light in the infrared region and shielding light in the visible region completely, as described above, The use of an infrared filter and the use of CF for BM have been found. For example, when the black azo pigment of this invention is applied for BM of CF, it can completely shield the light of the visible light region of a backlight, and will show the outstanding electrical insulation.

The black azo pigment of this invention is a coloring composition which carries out the coloration of a dark chromatic color, the achromatic color, or black color at the time of use, and the pigment component containing a black azo pigment according to a coloring purpose, a use, a usage method, etc., is a liquid dispersion medium. Use in various forms is possible as a liquid coloring composition contained in the inside, or a solid coloring composition contained in a solid dispersion medium.

The black azo pigment of the present invention is a pigment component, either a black azo pigment alone, or as one of a plurality of pigment components, one type of colored pigments, white pigments, other black pigments and extender pigments according to the desired color. Or two or more types can be selected and used together with these. In order to correct the color of the black azo pigment, the mixing ratio of the chromatic 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, but is optimized using a computer color matching system. Determining in such a manner is also a preferred form.

As a pigment used together with the black azo pigment of this invention, a well-known pigment can be used and it is not specifically limited. For example, anthraquinone pigments, quinacridone pigments, diketopyrrolopyrrole pigments, indigo thio indigo pigments, perinone pigments, perylene pigments, phthalocyanine pigments, indolin pigments, isoindolin pigments, Isoindolinone pigments, dioxadine pigments, quinophthalone pigments, nickel azo pigments, metal complex pigments, insoluble azo pigments, soluble azo pigments, high molecular weight azo pigments, azomethine azo black pigments, aniline blacks Organic pigments such as pigments and at least one pigment selected from inorganic pigments such as carbon black pigments and composite oxide pigments, iron oxide pigments and titanium oxide pigments, or mixtures of two or more pigments, or mixed pigments Can be used.

As an organic pigment, for example, as a yellow pigment, C.I. Pigment Yellow (abbreviated as 'PY')-74, 83, 93, 94, 95, 97, 109, 110, 120, 128, 138, 139, 147, 150, 151, 154, 155, 166, 175, 180 , 181, 185, 191 and the like are CI pigments, CI Pigment Orange (abbreviated as 'PO')-61, 64, 71, 73 and the like are red pigments, and C.I. 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.

In addition, as a blue pigment, C.I. Pigment Blue (abbreviated as 'PB')-15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, 16, 17: 1, 60, 80, aluminum phthalocyanine blue, etc. With green pigment, CI Pigment Green (abbreviated as 'PG')-7, 36, 58, poly (13-16) bromphthalocyanine and the like are C.I. Pigment violet (abbreviated as 'PV')-19, PV-23, PV-37 and the like are black pigments such as aniline black pigments, carbon black pigments, titanium oxide black pigments, and the like, and particularly for BM of CF, As a compound used for the black azo pigment of this invention, the carbon black pigment, titanium oxide black pigment, etc. which surface-treated and improved insulation are preferable.

When using the black azo pigment of this invention together with infrared reflecting pigments, such as a white pigment, the method proposed by Unexamined-Japanese-Patent No. 4097926 and Unexamined-Japanese-Patent No. 2005-330466 can also be used. That is, it is also a preferable aspect to apply the method of substantially covering the infrared reflecting pigments, such as a white pigment, with the infrared permeable black azo pigment of this invention, and improving the reflection efficiency of infrared rays.

The liquid coloring composition containing the black azo pigment of this invention is mainly used as a coloring agent which coats, impregnates, draws, prints, etc. the surface of an article, and is a coating material, coating agent, plastic coloring, fiber It is used for various purposes such as coloring, printing ink, stationery, image recording, and image display. The dispersion medium in which the black azo pigment of the present invention is dispersed does not have a reactive polymer or non-reactive polymer having a reactive group, an oligomer or non-reactive oligomer having a reactive group, and a monomer or reactive group having a reactive group as a film forming material (or a coating film forming material). At least one selected from non-reactive monomers, and the like, and may be a liquid itself or may contain a solvent and / or water.

Moreover, in preparing the said liquid coloring composition, if the pigment to be used is previously prepared as a highly concentrated pigment processed product undispersed in a high concentration dispersion medium, it can use for it and can manufacture a coloring agent easily. A liquid high concentration pigment dispersion liquid is called "base color" or "base ink" and is used.

Moreover, the solid coloring composition containing the black azo pigment of the said invention mainly consists of the coloring agent used for internal coloring of a plastic or synthetic fiber, For example, master powder which is a high concentration pigment dispersion, master batch, etc., And a known product shape such as colored pellets colored throughout. As a solid dispersion medium, at least 1 sort (s) chosen from a thermoplastic resin, a thermosetting resin, wax, fatty acid amide, fatty acid metal soap, etc. can be used.

In coloring the article using the colorant, appropriate coloring is achieved by the optical purpose of the visible and infrared regions.

In the case of performing the coloring which absorbs the visible light region and transmits the infrared region, the substrate of the article is made transparent and the transparent substrate is coated, coated, dyed, printed, handwritten or drawn using the coloring composition. , Inkjet printing, electrophotographic printing, electrostatic printing or photolithography The surface is colored by printing or the like, or the colored substrate is kneaded or impregnated into the transparent substrate to be internally colored. In this case, the article obtained by using the black azo pigment of this invention becomes what shows the following outstanding optical characteristic. That is, when the black azo pigment of the present invention is used, in particular, in the wavelength range of approximately 400 to 750 nm, which is the visible light region, it exhibits high absorptivity and exhibits visible light shielding properties, and is approximately 900 nm to 1500 nm and the higher wavelength infrared region. The coloring which shows high permeability can be performed in.

In addition, when performing the coloring which absorbs a visible light region and reflects an infrared region, the coloring composition of this invention uses the light reflecting base which the material which comprises the article itself has a light reflectivity, or formed previously. It can achieve by apply | coating using. Details on this point will be described later. The coloring method in this case is known in the visible region by using known methods, for example, painting, coating, undiluted coloring, printing, dyeing, printing, writing, drawing, inkjet printing, electrophotographic printing, or electrostatic printing. Coloration which shows water absorptivity and shows high reflectivity in the near-infrared region can be performed.

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

Table 3 Spectral transmittance of black color paper of black pigment-1

As shown in Table 3, the coating film containing the black pigment-1 absorbs from the visible region to about 750 nm and exhibits only a reflectance of about 5%, but the reflectance rapidly increases from about 800 nm to 900 nm. It is assumed that near 80% reflectance is maintained in the near-infrared region on the longer wavelength side, and high reflectance is also exhibited in the infrared region of higher wavelength. This indicates that the light transmitted through the black coating film is reflected by the base white paper, and the light transmitted through not only from the surface of the black pigment but also from the surface of the black pigment is used by using a reflective material such as a highly reflective base or a white pigment or a extender pigment. It reflects again and shows high reflectance with good efficiency.

As a resin binder (referred to as a "vehicle" or "varnish" by use) which functions as a coating film forming material (film forming material) used by this invention, it is a non-reactive normal temperature dry type or a reactive group which does not have a reactor. Glued resin binder and photosensitive resin binder can be used suitably. As a resin binder of normal temperature drying type or adhesive type, resin binder used for image recording materials, such as printing agent, paint, coating agent, or printing ink, stationery, inkjet printing, electrophotographic printing, electrostatic printing, etc. Can be mentioned. Moreover, as a photosensitive resin binder, the photosensitive resin binder used for various coatings, coating agents, printing inks, inkjet inks, photolithography, etc. of ultraviolet curable or electron beam hardening is mentioned, for example.

As a specific example of the normal temperature dry type or adhesive type resin binder which can be used by this invention, For example, vinyl resin, polyester, such as a synthetic rubber resin, an acrylic resin, a styrene-type (co) polymer, a polyvinyl butyral-type resin, etc. Resin, amino resin modified polyester resin, polyurethane resin, acrylic polyol urethane resin, soluble polyamide resin, soluble polyimide resin, soluble polyamideimide resin, soluble polyesterimide resin, alkyd resin, amino Alkyd resin, epoxy resin, rubber chloride resin, silicone resin, fluorine resin, cellulose acetate resin, nitrocellulose resin, hydroxyethyl cellulose, water soluble salt of styrene-maleic ester copolymer, (meth) acrylic acid ester Water-soluble salts of water-based (co) polymers, water-soluble aminoalkyd water , There may be mentioned a water-soluble amino-polyester resin and a water-soluble polyamide-based resin and the like, which are used alone or in combination of two or more thereof.

As a reactive group which a reactive film forming material has, a methylol group, an alkyl methylol group, an isocyanate group, a mascuic isocyanate group, an epoxy group, etc. are mentioned, for example. Moreover, an oligomer and a monomer are used according to a use, and a crosslinking agent, for example, methylol melamine type, an isocyanate type, and an epoxy type crosslinking agent is also used together.

As a specific example of energy-beam curable coating-film-forming materials, such as ultraviolet curable resin system and electron beam curable resin system which can be used by this invention, For example, photosensitive cyclization rubber type resin, photosensitive phenol type resin, photosensitive polyacrylate resin, Photosensitive polyamide resins, photosensitive polyimide resins, and the like, and unsaturated polyester resins, polyester acrylate resins, polyepoxy acrylate resins, polyurethane acrylate resins, polyether acrylate resins, and polyol acrylics. Binders, such as a rate-type resin, or the binder in which the monomer was added to these as a reactive diluent are mentioned further.

Examples of the plastics to be colored by the colorant for plastics as the coloring composition of the present invention include conventionally known thermoplastics, polyolefins such as polyethylene, ethylene copolymers and polypropylene, polystyrene, ABS, AS, styrene copolymers and chlorides. Unsaturated polyester resins, epoxy resins such as vinyl resins, methacryl resins, polycarbonates, polyamides, polyacetals, thermoplastic polyesters, cellulose plastics, phenylene oxide resins, fluorine resins, thermoplastic elastomers, and the like. And silicone resins, polyurethane resins, melamine resins, and phenol resins.

Content of the black azo pigment of this invention contained in the black coloring agent which is the coloring composition of this invention changes with a use and the objective to use, and cannot be determined collectively. For example, in the application of coloring on the surface of paints, coating agents, printing agents, printing inks, printer toners, inkjet inks, and the like, since the film thickness is thin, the content of the black pigment contained in the coloring agent is approximately 3% to 80%. %, Preferably about 5% to 60%. In particular, when used as a light-shielding black material of CF BM, since the film thickness is particularly thin and perfect light-shielding property is required, the pigment is stably dispersed, a viscosity suitable for coating is maintained, and a uniform colored film is obtained. The pigment concentration of the limit to form is attempted, Preferably it is about 30%-60%.

In addition, when internally coloring the whole material to be colored, such as coloring of plastic or spinning stock solution, depending on the thickness of the colored product, it is about 0.05% to 20%, preferably about 0.1% to 10%.

When using the coloring composition for image recording containing the black azo pigment of this invention as a coloring composition for BM formation of CF, using the coloring composition, a plastic film for direct transfer or transfer or attachment is used on the CF board | substrate. It interposes and is formed by the 1 type, or 2 or more types of formation method chosen from the photolithographic method, the laser ablation method, the inkjet printing method, the printing method, the transfer method, the adhesion method, etc.

As film thickness of BM, it is 0.5 micrometer-3 micrometers, and they are 1 micrometer-2 micrometers normally. As optical density (OD) value, it is 2.0 or more, Preferably it is 3.0 or more. In the case of providing the function of the spacer, in the case of thickening the BM itself, in the case of dropping a pixel on the BM or in the case of dropping a colorless resin film, 5 µm to 10 µm is preferable.

Further, on the formed CF substrate of the BM, a colored pixel can be further formed by a known pixel forming method using a known coloring pixel forming colorant.

The following are mentioned as a characteristic article regarding a CF board | substrate or an organic electroluminescent board | substrate suitable in this invention. That is, the formed CF substrate or organic EL light emitting substrate of BM absorbing the wavelength range of the visible region, in particular, the BM is substantially electrically insulating, and the CF substrate or organic EL light emitting substrate on which the BM and the electrode are overlapped, and including them And a color display panel. Similarly, a mounted CF liquid crystal display device of a CF substrate on which a colored pixel is formed on the formed CF substrate of the BM, and also a CF substrate on which a BM and chroma color pixels are formed, or an organic EL color display device equipped with the organic EL light emitting substrate. Can be mentioned.

Moreover, as an article concerning a solar power generation system, it is a coloring composition containing the black azo pigment of this invention on black reflective sheets, such as a reflective base layer which can suppress the temperature rise by sunlight, and black or dark The backsheet formed by laminating | stacking the colored infrared permeable layer, and the photovoltaic module using the same are mentioned.

Example

Next, an Example and a comparative example are given and this invention is demonstrated further more concretely. In addition, it is a mass reference | standard unless there is particular notice that "g" or "%" is used in a sentence.

[Production Example 1]

(Production of 'Black Pigment-1')

(1) Synthesis of Black Disazo Pigment

By conventional method, concentrated hydrochloric acid was added to 2.44 g (0.01 mol) of 3,3'-dimethoxy-4,4'-benzidine to make hydrochloric acid, and an excess of aqueous sodium acetate solution was added to diazotize. Next, hydrofluoric acid was added to this to prepare 3,3'-dimethoxydiphenylene (4,4'-) tetrazonium borohydride double salt (diazonium salt). Apart from this, 7.65 g (0.02 mol) of 2-hydroxy-11H-benzo [a] carbazole-3-carboxy - p-anisidide was added as a coupling component in 250 g of methanol dissolved in 0.8 g of sodium hydroxide. It dissolved and prepared. The tetrazonium boron fluoride double salt solution prepared first was kept at 15 degrees C or less, and the solution of the coupling component prepared above was gradually added to it. And after adjusting pH to 6.5-7.0 with sodium acetate and stirring for 1 hour, it stirred at 25 degreeC for 2 hours, it heated up at 40 degreeC, stirred for 3 hours, and completed the coupling reaction. After filtering the produced pigment, the filtrate was washed with methanol, and then washed with water and then dried to obtain a coarse pigment of a black azo pigment. The yield of the obtained black azo pigment was 9.78g.

(2) Preparation of Black Fine Particle Pigment by Refinement Treatment

100 parts of the defect particle pigments 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 kneader equipped with a pressurized lid, and the defect particle pigments and sodium chloride in the kneader Premix until the powder became a homogeneously wet mass. Subsequently, the pressure cooker was closed and kneading and grinding were carried out while pressing the contents at a pressure of 6 kg / cm 2. Specifically, the temperature was controlled to kneading and grinding for 2 hours so that the contents became 92 to 98 ° C. The obtained ground product was subjected to agitation for 1 hour in 3,000 parts of warm water heated to 80 ° C, and then filtered, followed by washing the obtained filtrate with water to remove sodium chloride and diethylene glycol, thereby making a fine black azo pigment press. Got a cake.

The particle diameter of the pigment obtained above was measured by the following method. The transmission electron microscope photograph (60,000 times) of the obtained black pigment was taken, and particle size distribution was measured using "image analysis type particle size distribution software Mac-View" (made by Mountain Tech). As a result, the average particle diameter was 50 nm. In addition, also in the other manufacturing example, the average particle diameter of the pigment was measured by the method similar to the above.

Furthermore, after drying the press cake obtained above, it grind | pulverized and 3,3'- dimethoxy- biphenylene (4,4 '-) bis (azo (-1) -2-hydroxy-11H-benzo [a] ] -Carbazole-3-carboxy-p-anisidide) to obtain a micronized powder pigment of a black pigment. Hereinafter, it is called "black pigment-1."

Preparation Example 2 (Preparation 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, by coupling this with 8.17 g (0.02 mol) of 2-hydroxy-11H-benzo [a] carbazole-3-carboxy-N-benzimidazolone-5-amide, the roughness of the black azo pigment was reduced. A pigment was obtained. The yield of the obtained black azo pigment was 10.07g.

Then, the refinement | miniaturization process of the obtained coarse pigment was performed. The method performed the refinement | miniaturization process according to manufacture example 1 (2) except having used the amount of sodium chloride used by (2) described in manufacture example 1 with respect to pigment eight times. And after melt | dissolving salt etc. with acidic water, it filtered and the obtained filtrate was washed with water and the press cake of the black azo pigment was obtained. The average particle diameter of the obtained pigment was 25 nm. Further, the press cake obtained above was dried and then ground to obtain a fine powder powder pigment of a black pigment. Hereinafter, this is called "black pigment-2."

[Production Example 3]

(Production 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. And, this, 2-hydroxy -11H- benzo [a] carbazole-3-carboxy - (2'-methyl) -p- not let Id 7.93g (0.02 mol) of coupling by having, black azo pigments A rough pigment of was obtained. The yield of the obtained black azo pigment was 10.26g.

Then, the refinement | miniaturization process of the obtained coarse pigment was performed. The refinement | miniaturization process was performed according to (2) of manufacture example 1 except having used the 10-fold amount of the sodium chloride used in (2) of manufacture example 1 with respect to a pigment. And after melt | dissolving salt etc. with acidic water, it filtered and the obtained filtrate was washed with water and the press cake of the black azo pigment was obtained. The average particle diameter of the obtained pigment was 20 nm. After drying the press cake obtained above, it grind | pulverized and obtained the fine powder powder pigment of a black pigment. Hereinafter, this is called "black pigment-3".

Preparation Example 4 (Preparation 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. And, this, 2-hydroxy -11H- benzo [a] carbazole-3-carboxy - (2'-methyl) -p- not let Id 7.93g (0.02 mol) of coupling by having, black azo pigments A rough pigment of was obtained. The yield of the obtained black azo pigment was 9.94g.

Then, the refinement | miniaturization process of the obtained coarse pigment was performed. According to (2) of manufacture example 1, the refinement | miniaturization process was performed, the salt etc. were dissolved and filtered with acidic water, and the obtained filtrate was washed with water, and the press cake of the black azo pigment was obtained. The average particle diameter of the obtained pigment was 50 nm. After drying the press cake obtained above, it grind | pulverized and obtained the fine powder powder pigment of a black pigment. Hereinafter, this is called "black pigment-4".

Production Example 5 (Production 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. And, this, 2-hydroxy -11H- benzo [a] carbazole-3-carboxy - p- not let Id 7.65g (0.02 mole) and by having the coupling to obtain a coarse pigment of black azo pigment. The yield of the obtained black azo pigment was 9.86g.

Then, the refinement | miniaturization process of the obtained coarse pigment was performed. Micronization treatment was carried out in the same manner as in Production Example 1 (2) except that the amount of sodium chloride used in (2) described in Production Example 1 was used four times as amount with respect to the pigment. And after melt | dissolving salt etc. with acidic water, it filtered and the obtained filtrate was washed with water and the press cake of the black azo pigment was obtained. The average particle diameter of the obtained pigment was 85 nm. After drying the press cake obtained above, it grind | pulverized and obtained the fine powder powder pigment of a black pigment. Hereinafter, this is called "black pigment-5".

Preparation Example 6 (Preparation 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, 3.96 g (0.01 mol) of 2-hydroxy-11H-benzo [a] carbazole-3-carboxy- (2'-methyl) -p-anisidide and 5'-chloro-3-hydroxy Coupling with 3.58 g (0.01 mol) of -2 ', 3'-dimethoxy-naphthanilide anilide gave a coarse pigment of a black azo pigment. The yield of the obtained black azo pigment was 9.59g. Subsequently, the coarse pigment of the black azo pigment obtained above was pigmented by grind | pulverizing with a dry mill, and the fine powder powder pigment of the black pigment was obtained. The average particle diameter of the obtained pigment was 110 nm. Hereinafter, this is called "black pigment-6".

Preparation Example 7 (Preparation of 'Black Pigment-7')

(1) Preparation of Black Pigment Derivative-1

1.73 g (0.01 mol) of sulfanic acid was diazotized. And, this, 2-hydroxy -11H- benzo [a] carbazole-3-carboxy - p- not let Id was coupled with 3.82 g (0.01 mol). And after filtering the obtained product, it washed with water and obtained the press cake of the black pigment derivative which has a sulfone group. Hereafter, this is called "the press cake of black pigment derivative-1." The yield of the obtained press cake was 5.49 g in terms of solid content. Furthermore, the said press cake was dried and pulverized and the fine powder pigment of the pigment derivative which has a sulfone group was obtained. Hereinafter, this is called "black pigment derivative-1."

(2) (Production of 'Black Pigment-7')

The press cake of the black pigment-1 obtained in (1) of manufacture example 1, and the press cake of the black pigment derivative-1 obtained in said (1) are mix | blended so that it may become 10: 1 by pigment solid ratio, and it may be made to be uniform. Mixed. And the rough pigment of the black pigment containing a pigment derivative was obtained by drying the said mixture. Subsequently, after performing the refinement | miniaturization process of a pigment according to (2) of manufacture example 1, salt etc. were dissolved with acidic water, this was filtered, and the obtained filtrate was washed with water, and the press cake of a black azo pigment was obtained. The average particle diameter of the obtained pigment was 50 nm. The press cake was dried and pulverized to obtain a fine powder powder pigment of a black pigment containing an anionic pigment derivative. Hereinafter, this is called "black pigment-7".

Preparation Example 8 (Preparation of 'Black Pigment-8')

Cationic pigment derivatives were synthesized using the method described in Japanese Patent No. 3268748. Specifically, first, 1-aminoanthraquinone, bis (N, N-dimethylaminopropyl) amine and cyanuric chloride are reacted in a molar ratio of 2: 1: 1 to give 2, as a cationic pigment derivative. 4-bis (anthraquinonylamino) -6-bis (N, N-dimethylaminopropyl) amino-s-triazine was synthesized. The press cake of the obtained cationic pigment derivative and the press cake of the black pigment-1 obtained by the manufacture example 1 (1) were mix | blended so that it might be set to 85:15 by solid ratio. And these were mixed enough so that it might become uniform, and it dried and obtained the rough pigment of the black pigment containing a cationic pigment derivative. Subsequently, after performing the refinement | miniaturization process according to the method of (2) described in manufacture example 1, the obtained rough pigment was filtered by dissolving salt etc. with water and washing the filtrate, and the press cake of a black azo pigment was obtained. The average particle diameter of the obtained pigment was 50 nm. After drying the obtained press cake, it grind | pulverized and obtained the fine powder powder pigment of the black pigment containing a cationic yellow pigment derivative. Hereinafter, this is called "black pigment-8".

Preparation Example 9 (Preparation of 'Black Pigment-9')

In the same manner as in Production Example 1 (1), after diazotizing 1.95 g (0.008 mol) of 3,3'-dimethoxy-4,4'-benzidine, hydrofluoric acid was added to the tetrazonium boron fluoride double salt (diazo (Nium salt) was prepared. Apart from this, 0.69 g (0.004 mol) of sulfamic acid was diazotized. These two types of diazo liquids are co-coupled with 2-hydroxy-11H-benzo [a] carbazole-3-carboxy - p-anisidide 7.65 g (0.02 mol), and the two types of diazo liquids described above. The dropping of was coupled while adjusting to terminate almost simultaneously. Then, it filtered and washed with water and the press cake of the black azo pigment was obtained. The obtained press cake was dried to obtain a black pigment (rough pigment) including a black pigment derivative having a sulfone group. The yield of the obtained black pigment was 9.97g. Then, the refinement | miniaturization process of the obtained coarse pigment was performed. Specifically, after performing the refinement | miniaturization process according to the method of (2) described in manufacture example 1, salt etc. were dissolved and filtered with acidic water, and the obtained filtrate was washed with water, and the press cake of the black azo pigment was obtained. The average particle diameter of the obtained pigment was 50 nm. After drying this press cake, it grind | pulverized and obtained the fine powder powder pigment of a black pigment. Hereinafter, this is called "black pigment-9".

Production Example 10 (Production 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-phenylcarbamoylaniline was diazotized and 1,4-phenylene-bis (2-hydroxy-11H -Coupling with 6.27 g (0.01 mol) of -benzo [a] carbazole-3-carboxamide), the coarse pigment of the black azo pigment was obtained. The quantity is 10.35g. Then, it grind | pulverized with the dry mill and the fine powder powder pigment of black pigment was obtained. Hereinafter, it is called "black pigment-10." The average particle diameter of the obtained pigment was 80 nm.

Example 1 Evaluation of Optical Properties of Coating Film Containing Black Pigment-1 of Production Example 1

(1) Preparation of Black Coated PET Film Using Black Pigment-1

In order to see the optical characteristic of the black pigment-1 obtained by the manufacture example 1, the black coating liquid was prepared. As a varnish to be used, a 50% xylene-butanol mixed solvent solution of an acrylic resin having a carboxyl group (acid value is 10 mgKOH / g) and a 50% xylene-butanol mixed solvent solution of a butylated methylol melamine resin were used at a ratio of 80:20. It mix | blended and prepared the varnish. (Hereinafter, this is called "varnish.") The mixed solvent (4: 1) of xylene-butanol was used for the diluting solvent. (Hereinafter, this is called a "dilution solvent.")

3 parts of black pigment-1, 24 parts of varnish, 6 parts of diluting solvents, and 48 parts of glass beads as a dispersion medium were mix | blended in the dispersion container, and it disperse | distributed for 3 hours with the paint shaker. Then, 36 parts of varnishes were added, dispersion was further continued for 10 minutes, and it was taken out and it was set as the coating liquid. The ratio of pigment content and resin solid content in a coating liquid is 1:10. The black coating liquid obtained as mentioned above was apply | coated using the bar coater on the polyethylene terephthalate (PET) film, and it hardened | cured at 130 degreeC after drying, and obtained the black coating PET film. The average dry film thickness of the formed black coating film was 34 nm.

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

The transmittance | permeability of the visible part and near-infrared part of the black coating PET film obtained by said (1) was measured with the Hitachi spectrophotometer (U-4100 type, the Hitachi Corporation). In Table 4 and 5, the measurement result in each area | region was shown.

[Table 4] Spectral transmittance of visible light region of black coating film using black pigment-1

[Table 5] Spectral transmittance of infrared region of black coating film using black pigment-1

As shown in the measurement results of the spectral transmittances in Tables 4 and 5, the coating film containing black pigment-1 had a spectral transmittance of 0% over the full-wavelength region of 400 to 750 nm in the visible region, and confirmed that most of them were not transmitted. (See Table 4). On the other hand, in the infrared region, the transmittance at 900 nm was almost 34%, and it was confirmed that the wavelength was gradually increased on the longer wavelength side (see Table 5).

(3) In addition, the volume resistivity of the black coating film on the PET film obtained in the above (1) was measured using a high resistivity meter Hiresta UP (manufactured by Mitsubishi Chemical Co., Ltd.). . The measurement results are shown for more than 10 ¹⁴ Ω · ㎝, it was confirmed that the insulation is very high.

[Example 2] (Evaluation of Light Reflective Properties of Coating Film Containing Black Pigment-1 of Production Example 1)

(1) Preparation of black color paper using black pigment-1

In order to see the reflection characteristic of black pigment-1, the black coating liquid prepared in (1) of Example 1 was apply | coated on white color paper using a 6 millimeter applicator, and then dried and hardened to form a coating film. Black coated color paper (hereinafter referred to as black color paper) was obtained. The measured value of the dry film thickness of the black coating film formed on this black color paper was about 35-40 nm on the color paper.

(2) The reflectance of the visible part and near-infrared part in the black color paper obtained by said (1) was measured, and the measurement result was shown in Table 6.

[Table 6] Spectral light transmittance of black color paper using black pigment-1

From the results shown in Table 6, in the black color paper produced using the black pigment-1, the reflectance of only 5 to 6% is shown up to about 750 nm, but the reflectance rapidly increases over 800 nm to 900 nm. In the near-infrared region on the longer wavelength side, it was confirmed that the reflectance was maintained almost 70% to 80% or more. From these things, it is considered that the reflectance of the light of black color paper is increasing because the transmitted light is reflected by the basic white paper together with the reflection from the pigment surface, and the light resulting therefrom is added to the reflected light. Therefore, it is shown that the near-infrared ray can be efficiently reflected by making the light transmittance of a black pigment high and using the base with high reflectivity. On the other hand, in Table 6, the reflectance is not 0% but the value of 5% up to about 750 nm is a relationship with the measuring device.

[Example 3]

(1) A black coating film was prepared in the same manner as in Example 1 using the black pigments 2 to 6 obtained in Production Examples 2 to 6, respectively, and the spectral transmittances in the visible region and the infrared region were measured in the same manner as in Example 1. It was. Table 7 and Table 8 show the results.

[Table 7] Spectral transmittance of visible light region of black color paper using black pigment -2 to 6

Table 8 Spectral transmittance of infrared region of black color paper using black pigment -2 to 6

(2) In the same manner as in Example 2, a black coating film was formed using the black pigments 2 to 6 obtained in Production Examples 2 to 6, respectively, to prepare black color paper. The dry film thickness of the black coating film was about 35-40 nm on black color paper. In the same manner as in Example 2, the spectral reflectance was measured. As a result, as shown in Table 9, the spectral reflectance showed the same tendency as the black coated color paper obtained using black pigment-1.

TABLE 9 Spectral transmittances of visible and infrared regions of black pigments 2 to 6

Example 4 Polycarbonate Resin Molded Plate

20 parts of black pigment-2 prepared in Production Example 2 and 80 parts of polycarbonate resin powder were sufficiently mixed with a Henschel mixer (powder high speed mixer), and further mixed and kneaded with a twin screw extruder to give black color. A polycarbonate resin black master batch containing 20% of pigment-2 was prepared. Two parts of the obtained black masterbatch were mix | blended with 100 parts of polycarbonate resin pellets which consist of the above-mentioned resin powder, were mixed with the Henschel mixer, and further mixed and kneaded with the twin screw extruder, and it was set as black resin pellets. The obtained black resin pellet was shape | molded by the in-line screw injection molding machine, and the black polycarbonate resin plate excellent in pigment dispersibility was obtained. Since the black resin plate absorbs light in the visible light region and can sufficiently transmit near infrared rays, the black resin plate can be used for applications such as infrared transmission 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 with a Henschel mixer, and then mixed with a twin screw extruder. It knead | mixed and the acrylic resin black masterbatch containing 20% of black pigment-3 was prepared.

2 parts of the obtained black masterbatch were mix | blended with 100 parts of acrylic resin pellets which consist of above-mentioned resin, and further mixed by the Henschel mixer, and further mixed and kneaded with the twin screw extrusion kneader, and it was set as black resin pellets. The obtained black resin pellet was shape | molded by the in-line screw injection molding machine, and the black acrylic resin plate excellent in pigment dispersibility was obtained. This black resin plate absorbs light in the visible light region and can sufficiently transmit near infrared rays, and thus can be used as an infrared transmission filter.

Example 6 (Polyurethane Coating Agent)

The black pigment and the polycarbonate sulfur-free modified polyurethane were prepared such that the black pigment-4 prepared in Production Example 4 was 15 parts, 10 parts of the polycarbonate sulfur-free modified polyurethane resin, and 75 parts of dimethylformamide (hereinafter referred to as 'DMF'). A resin solution and DMF are prepared. This preparation liquid was fully disperse | distributed with the horizontal continuous medium disperser, and the black pigment high concentration dispersion liquid was obtained. Next, 10 parts of propyl acetate, 10 parts of isopropanol and 20 parts of the black pigment high concentration dispersion liquid prepared first were added as a diluent to 100 parts of a polycarbonate-free sulfur-modified polyurethane resin solution (solid content 30%, DMF solvent) for formation of a skin layer. It mixed and prepared the black polyurethane coating liquid.

Subsequently, the black coating solution prepared above was coated on a release paper DNTP-155T-FLAT (trade name, manufactured by Dainippon-Insatsu Co., Ltd.) in a sheet form so as to have a thickness of 50 μm, and then 100 ° C./10 minutes. It dried on condition of and formed the epidermal layer. Subsequently, 10 parts of toluene as a dilution solvent, MEK20 as a diluent solvent in 100 parts of polycarbonate type yellowing-type polyurethane resin solution (70% of solid content, toluene: methyl ethyl ketone (hereinafter, it is called "MEK") = 1: 1 solvent) as an adhesive agent. To the mixture was prepared a mixture of 20 parts of DMF, 10 parts of a modified polyisocyanate crosslinking agent (75% solid content, ethyl acetate solvent), and 0.15 part of an amine crosslinking catalyst (solid content 0.5% MEK solvent). And the adhesive agent was apply | coated in the sheet form so that it might become a film thickness of 75 micrometers on the skin layer surface (surface on the opposite side to the surface which contact | connects a release paper), and it dried on the conditions of 80 degreeC / 5 minutes. The obtained sheet having the adhesive layer and the skin layer was laminated on the substrate (fabric) with the adhesive layer side, and a laminate having a total thickness of 1,100 µm, and the resulting laminate was pressed and pressed in a laminate roll heated at 100 ° C with a gap of 500 µm. I was. Subsequently, after aging at 60 ° C./48 hours, the resultant was peeled from the release paper to obtain synthetic artificial leather. The obtained synthetic artificial leather is excellent in durability, such as heat reduction, reduction in heat storage deterioration, hydrolysis deterioration resistance, light deterioration resistance, and oleic acid resistance, and the like. It was suitable.

In addition, the adhesive used above is made of a skin layer containing a black azo pigment which contains a white pigment and colorizes white to give the adhesive layer light reflectivity and exhibits optical properties of both visible light shielding and infrared transmission. When the dual structure was formed, a polyurethane synthetic leather capable of reflecting heat rays was obtained. This synthetic leather is particularly suitable for applications such as interiors of automobiles.

Example 7 (Stock Color Spinning)

50 parts of black pigment-5 prepared in Production Example 5 and 50 parts of ethylene bis stearic acid amide powder as a pigment dispersant were mixed with a Henschel mixer to obtain a powder coloring agent (dry color) having a pigment content of 50%. Subsequently, 1.0 part of the obtained dry color was mix | blended with 99.0 parts of polypropylene resin pellets, and it mixed with the Henschel mixer, and knead | mixed with the vent type 40m / m extruder, and the pigment | dye content black resin pellet of 0.5% was prepared. . The obtained black resin pellets were spun by a melt spinning machine to obtain a clear black polypropylene stock solution colored yarn having excellent pigment dispersibility of 10 deniers. Since the woven fabric created using this colored yarn can reflect the heat ray of direct sunlight, the effect of avoiding temperature rising is expected. Therefore, it is especially suitable for uses, such as mass production and curtain.

Example 8 (Resin Molding)

5 parts of black pigment-6 prepared in Production Example 6, 20 parts of titanium oxide white pigment, 75 parts of polyethylene resin powders were mixed with the Henschel mixer as a pigment dispersant, and the powder coloring agent (dry color) was obtained. Subsequently, 1.0 part of the powder coloring agent obtained was mix | blended with 100 parts of polybutylene terephthalate (PBT) resin pellets, it mixed with the Henschel mixer, and knead | mixed with an extruder, and it was set as black resin pellets. The obtained black pellet was shape | molded by the in-line screw injection molding machine, and the black PBT resin molded board excellent in pigment dispersibility was obtained. The obtained resin molded plate was able to reflect the heat ray of direct sunlight. Therefore, use of this resin as a resin molded article which wants to avoid temperature rising is suitable.

Example 9 (heat shielding back sheet for photovoltaic module)

(1) 15 parts of the black pigment-4 prepared in Production Example 5, 25 parts of an acryl polyol (hydroxyl value: 100) butyl acetate solution (50% of solid content) and 50 parts of butyl acetate were sufficiently premixed, followed by glass beads as a dispersion medium. The black pigment high concentration dispersion liquid was prepared by disperse | distributing a pigment using the horizontal type continuous medium disperser which used.

To the black pigment high concentration dispersion liquid obtained above, 22 parts of the above-mentioned acryl polyol butyl acetate solution, 50 parts of the acryl polyol (hydroxyl value: 100) butyl acetate solution copolymerized with the benzotriazole monomer and the HALS monomer were added to the black ink. It was made. 24 parts of isocyanurate-type hexamethylene diisocyanate trimers (solid content: 100%, isocyanate% 21.7%) were added to this black ink-ized thing, after fully mixing, about 20 parts of butyl acetates were added, and a viscosity Was adjusted to prepare a black coating solution.

(2) 80 parts of titanium oxide white pigment was premixed with 40 parts of an acryl polyol butyl acetate solution and 20 parts of butyl acetate used in the above (1), followed by a horizontal continuous medium disperser as used in (1) above. By dispersing a pigment, the white pigment high concentration dispersion liquid was prepared.

44 parts of acryl polyol butyl acetate solutions were added to 140 parts of white pigment high concentration dispersion liquids obtained above, and white ink was carried out. And 18 parts of hexamethylene diisocyanate trimers same as what was used previously as a hardening | curing agent were added to this white ink-ized thing, after fully mixing, about 40 parts of butyl acetates were added, the viscosity was adjusted, and the white coating liquid was prepared.

(3) The black coating liquid prepared in said (1) was apply | coated to the surface of the polyethylene terephthalate (PET) base sheet (film thickness: 100 micrometers), and it dried and formed the black coating film (dry film thickness: 5 micrometers). . Moreover, the white coating liquid obtained by said (2) is apply | coated to the back surface of a base material, it is made to dry, and a white coating film (dry film thickness: 5 micrometers) is formed, and a black coating film is apply | coated on the surface and a white coating film is applied to the back surface. A white multilayer PET sheet was obtained.

(4) In order to further impart water vapor barrier properties and gas barrier properties to the black-white multilayer PET sheet obtained in the above (3), a silica-alumina-deposited polyester film (film thickness: 12) (Micrometer), and further laminated | stacked the PET base sheet (film thickness: 100 micrometers), and produced the PET backsheet for photovoltaic modules. The adhesive was used for the laminate. As the adhesive, an adhesive consisting of 70 parts of an acryl polyol solution as used in the above (1), 15 parts of hexamethylene diisocyanate trimer and 15 parts of butyl acetate was used.

The PET backsheet obtained by the multilayer coating of the black coating film and the white coating film obtained as described above has excellent aesthetics because the appearance is black, and has the following optical properties from the optical properties of the used black pigment-4. . That is, light in the infrared region of the sunlight passes through the black coating layer on the surface, and the light in the transmitted infrared region is reflected by the base white layer, and again passes through the black layer and is radiated to the outside. Therefore, the backsheet is less suitable for absorbing sunlight and exhibits excellent heat shielding properties, and therefore, the backsheet is particularly suitable as a backsheet for photovoltaic modules for which temperature increase is avoided.

When using the backsheet obtained above as a module for photovoltaic power generation, it may be used as follows in accordance with a conventional method. That is, the photovoltaic cell is sandwiched and sealed with a sealing material made of ethylene vinyl acetate-based resin, a surface sealing sheet is attached to the surface on the light receiving surface side, and the light shielding bag is used as a protective sheet on the non-light receiving surface side on the back surface. After pasting the black surface of a sheet toward a light receiving side, a photovoltaic module can be produced by equipping a light receiving surface with a transparent glass substrate.

Example 10 (heat shielding back sheet for photovoltaic module)

(1) 40 parts of black pigment-6 obtained by the manufacture example 6 and 60 parts of polyester resin powders were mixed with the Henschel mixer, and the powdery coloring agent was obtained. Subsequently, 12.5 parts of the obtained powder colorant were mix | blended with 87.5 parts of PET resin pellets, and it mixed with the Henschel mixer, and further knead | mixed with the twin screw extruder, and it was set as black resin pellets by the pelletizer. Next, it formed by the T-die extruder and produced the black PET film of 50 micrometers in film thickness.

(2) Separately, a white PET sheet (film thickness: 180 µm) kneaded and colored with a titanium oxide pigment was prepared. And a black PET film was laminated | stacked on the surface by sticking the black PET film obtained by said (1) using the acryl polyol hexamethylene diisocyanate type adhesive agent as described in (4) of Example 9. A white PET sheet was created.

(3) In order to give moisture-proof and gas barrier property to the white PET sheet which laminated | stacked the black PET film obtained above, first, the acryl polyol hexamethylene diisocyanate type | system | group used as said (2) on the back surface of this sheet. The silica alumina vapor-deposited polyester film was laminated using the adhesive agent. And the PET base sheet (film thickness: 100 micrometers) was laminated thereon using the adhesive agent mentioned above, and the solar cell module backsheet was created.

The backsheet for photovoltaic module which uses the sheet | seat which laminated | stacked the black film obtained above and the white PET sheet | seat was excellent in aesthetics with the appearance black, and from the optical characteristic of the used black pigment-6, It has a property. That is, the light in the infrared region of the sunlight passes through the black film layer on the surface, is reflected by the white PET sheet below, and again passes through the black film and is emitted to the outside. Therefore, the black-white multilayer PET sheet is particularly suitable as a solar power module backsheet which wants to avoid the temperature increase in order to reduce the absorption of sunlight as the solar power module backsheet and to exhibit excellent heat shielding properties. .

When using the backsheet obtained above as a module for photovoltaic power generation, it may be used as follows in accordance with a conventional method. That is, the photovoltaic cell is sandwiched and sealed with a sealing material made of ethylene vinyl acetate resin, a surface sealing sheet is attached to the surface on the light receiving surface side, and the black surface of the light-shielding back sheet is used as a protective sheet on the non-light receiving surface side on the back side. After bonding to the light-receiving side, a photovoltaic module can be produced by equipping a light-receiving surface with a transparent glass substrate.

Example 11 (woven fabric for woven fabric)

After preliminarily mixing the black pigment-1 obtained in Production Example 1 in a solid content of 71 parts of a press cake containing 25 parts, 10 parts of a nonionic pigment dispersant, 1 part of an antifoaming agent, and 18 parts of water, the glass was used as a dispersion medium. The pigment was dispersed with a horizontal continuous medium disperser using beads to prepare a black pigment high concentration dispersion (black color base). 20 parts of the obtained black color base, 25 parts of reactive acrylic acid alkyl ester latex (40% solids), 0.5 part of antifoaming agent, 1 part of dispersant, 3 parts of dispersion stabilizer for oil-in-water emulsion, 38 parts of mineral terpene, water 12.5 parts were emulsified-dispersed with the homogenizer (strong emulsifying disperser), and the oil-in-water type black emulsion paste was prepared. Then, two parts of a carbodiimide-based crosslinking agent (40% solids) was added to the prepared black emulsion paste, and the mixture was sufficiently mixed to prepare a black printing paste. The obtained black printing paste was printed on the polyester-cotton blended cloth whole surface, and cured for 15 minutes at 120 degreeC, and the black plain printing dyeing cloth which a heating wire is shielded was obtained.

Example 12 (gravure printing ink)

11 parts of black pigment-10 obtained in the preparation example 10, and 30 parts of 40% methyl ethyl ketone-toluene (1: 3) mixed solvent solutions of the outstanding polyurethane resin which extended the isocyanate terminal polyester with the diamine were added. Next, 2 parts of cationic polymer dispersant, 2.5 parts of 40% toluene solution of polycarbodiimide compound from tolylene diisocyanate, and 54.5 parts of methyl ethyl ketone-toluene-isopropyl alcohol (50:30:20) mixed solvent It was added and thoroughly mixed with a high speed stirrer. Then, the pigment was finely dispersed in a horizontal continuous medium disperser using glass beads as the dispersion medium to prepare a black gravure printing ink. The obtained black gravure printing ink is printed on a polyamide film, a polyester film, and a polypropylene film using a gravure printing machine, respectively, and shields visible light, and shows the black polypropylene film which shows the optical characteristic which permeate | transmits an infrared ray. Got it.

Example 13 (Formation of BM in CF)

(1) (Preparation of pigment dispersion for BM)

(Preparation of Black Pigment Dispersion)

25 parts of black pigment-9 obtained by the manufacture example 9, and 40% of benzyl methacrylate-methacrylic-acid 2-hydroxyethyl methacrylate copolymer (molar ratio: 60: 20: 20, weight average molecular weight 30,000) 20 parts and 2 parts of cationic polymeric dispersants and 53 parts of propylene glycol mono methyl ether acetate (PGMA) were sufficiently premixed. Subsequently, the pigment was undispersed using a continuous horizontal media disperser to obtain a black pigment dispersion (hereinafter, referred to as 'black pigment dispersion-1').

(2) (Preparation of Photosensitive Black Register Ink)

40 parts of black pigment dispersion liquid-1 obtained in said (1), 6 parts of 50% PGMA solution of acrylated acryl polyol photosensitive resin, 1 part of trimethylolpropane triacrylate, 1 part of dipentaerythritol hexaacrylate, and photopolymerization Ethanol, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyl oxime ('IRGACURE OXE02', manufactured by BASF) as an initiator Parts and 51 parts of PGMA were then mixed with a high-speed stirrer to be uniform, and then filtered through a filter having a pore diameter of 3 µm to prepare a black resist ink containing black pigment-9 (hereinafter, , "Photosensitive black register ink-1").

(3) (evaluation of black register film)

Using the photosensitive black resist ink-1 obtained above, it was applied onto a glass substrate with a spin coater. Then, after preliminary drying at 60 ° C, prebaking was performed and exposure was carried out at a light amount of 400 mJ / cm 2 using an ultra-high pressure mercury lamp. (Black Resist Ink Film) was obtained.

As shown in Table 10, the optical characteristic of this coating film showed high absorbency in the wavelength range of about 400-750 nm which is visible light region, and showed high transmittance in the infrared region of 900-1500 nm. Moreover, since the volume specific resistance of the coating film showed 10 ¹⁴ ohm * cm or more, it was confirmed that it is high insulation.

[Table 10] Spectral transmittance of black resist film

(4) (Preparation of BM Pattern)

After apply | coating on the glass substrate with the spin coater using the photosensitive black resist ink-1 obtained above according to a conventional method, it prebaked for 10 minutes at 80 degreeC, and the black coating film of thickness 3micrometer was obtained. After exposing to this coating film with the light quantity of 100mJ / cm <2> using the ultrahigh pressure mercury lamp through the negative photomask pattern of BM pattern, it developed with alkaline developing solution, washed with water, and dried, and formed the BM pattern.

Since the BM film forming the BM pattern obtained above exhibits high electrical insulation as described in the above (3), various CF improvement methods for forming BM on active elements such as TFTs, for example, It can be used for construction of BM, IPS method, COA method, etc. which hold | maintain the thickness of a liquid crystal layer instead of a spacer. In addition, since the BM film can sufficiently absorb the visible region up to the long wavelength region, it can also be used as the BM of an LCD panel employing an LED backlight.

(5) (Preparation of each pigment dispersion liquid of red, green, blue, yellow, purple)

In the same manner as in (1) described above, PR254 (diketopyrrolopyrrole red pigment), PR177 (anthraquinone-based red pigment), PG36 (copper phthalocyanine green pigment), PB15: 6 (ε copper phthalocyanine blue pigment), PY138 Using each pigment of (yellow pigment) and PV23 (dioxamine biored pigment), 1 part of pigment derivative which has a well-known sulfone group corresponding to each pigment is added to the pigment 19 part, and each color pigment composition is added Got it. Using the obtained pigment composition, each pigment pigment dispersion liquid of red, green, blue, yellow, and purple which is 20% and 6% of a resin dispersant was prepared, respectively.

Subsequently, 33 parts of the pigment dispersions containing the above-prepared PR254 and PR177, respectively, were added at a ratio of 8: 2, and in the same manner as in (2) described above, 9.2 parts of a photosensitive resin 50% solution and photopolymerizability 3 parts of monomers, 0.3 parts of photopolymerization initiators, and 54.5 parts of solvent were added to prepare a red register ink. As mentioned above, the pigment dispersion liquid containing PG36 and PY138, respectively, is mix | blended in the ratio of 5: 5, and the pigment dispersion liquid containing green resist ink and PB15: 6 and PV23, respectively is mix | blended in the ratio of 8: 2. The blue resist ink was prepared, respectively.

(6) (formation of CF RGB pixels)

The glass substrate on which BM prepared in (4) was formed was set in a spin coater, spin-coated the photosensitive red resist ink prepared above, and then prebaked at 80 占 폚 for 10 minutes. Then, the photomask having the mosaic pattern was exposed to a light amount of 100 mJ / cm 2 using an ultra-high pressure mercury lamp on a coated surface of the glass substrate using a proximity exposure machine. Next, after developing with a dedicated developer and a dedicated rinse, washing and drying were performed to form a red mosaic pattern on the glass substrate. In addition, in the same manner as described above, a green mosaic pattern was formed using photosensitive green resist ink and a blue mosaic pattern was formed using photosensitive blue resist ink, thereby obtaining CF having BM and RGB pixels.

A photosensitive black register ink was prepared in the same manner as above except that the black pigment-7 obtained in Production Example 7 was used instead of the black pigment-9 used above, and the above-described BM pattern and RGB pixel pattern were prepared. To form CF with BM and RGB pixels.

Example 14 (Formation of CF BM)

(1) (Preparation of pigment dispersion for BM)

(Preparation of Black Pigment Dispersion)

Benzyl methacrylate-methacrylic acid-2-hydroxyethyl methacrylate copolymer 40 as in the same manner as in Example 13 (1), using 25 parts of black pigment-8 instead of black pigment-9, previously The black pigment dispersion liquid was obtained by pre-mixing 25 parts of% solutions and 53 parts of propylene glycol mono methyl ether acetate (PGMA) sufficiently, and disperse | distributing a pigment with a continuous horizontal medium disperser. Hereinafter, this is called "black pigment dispersion liquid-2".

(2) (Preparation of photosensitive black register ink)

A black register ink was prepared in the same manner as in Example 13 (2) except that the black pigment dispersion-2 obtained in the above (1) was used instead of the black pigment dispersion-1 of (2) described in Example 13. . This is hereinafter referred to as "photosensitive black register ink-2".

(3) (Preparation of BM Pattern)

In the same manner as in (4) described in Example 13, a black coating film having a thickness of 3 µm was obtained by applying photosensitive black register ink-2 onto the glass substrate with a spin coater and prebaking. The coating film was exposed using an ultra-high pressure mercury lamp through a negative photomask pattern of the BM pattern, developed with an alkaline developer, washed with water and dried to form a BM pattern.

Since the BM film which forms this BM pattern has high electrical insulation property, like Example 13, the various methods of improving CF which form BM on an active element, for example, construction of BM as a fixed spacer, It can be used for constructing an IPS method or a COA method. In addition, since the visible light region can be sufficiently absorbed up to the long wavelength region, the visible light region can be used as a BM of an LCD panel employing an LED backlight.

(4) (formation of CF RGB pixels)

In the same manner as in (6) described in Example 13, the glass substrate having BM formed in (3) was set in a spin coater, and the photosensitive red register ink and photosensitive green resist ink obtained in (5) described in Example 13 were used. Using photosensitive blue resist ink, a mosaic pixel pattern of each color was formed to obtain CF in which BM and RGB pixels were formed.

[Evaluation results]

CFs obtained in Examples 13 and 14 had excellent quality in terms of color characteristics and optical properties of image performance such as fineness, color density, light transmittance, and contrast.

Claims (20)

A black azo pigment that exhibits optical properties of both visible light blocking and infrared transmission, wherein at least one 2-hydroxy-11H-benzo [a] -carbazole is introduced from at least two azo bonds and a coupling component in the molecule It is a black polyazo pigment which has a structure which has a 3-carboxylic acid amide residue, and the black azo pigment whose average particle diameter is 10 nm-200 nm. The method of claim 1,
The visible light-shielding property is that the black colored film containing the black azo pigment on the transparent substrate exhibits a spectral transmittance of about 5% or less in the wavelength range of approximately 400 to 750 nm, which is the visible light range, and the infrared transmittance is the black colored film. The black azo pigment which shows the transmittance | permeability about 30% or more in the wavelength range of 900-1500 nm which is an infrared region. 3. The method according to claim 1 or 2,
The black azo pigment in which the structure of the said polyazo pigment has at least any one of the structures of following (1)-(4).
(1) A diazonium salt formed by diazotizing a compound (representative: H ₂ N-Ar-NH ₂ ) having two or more amino groups as a diazo component is used. Represented by [HBC-N = N-Ar-N = N-HBC] formed by azo-coupling of oxy-11H-benzo [a] -carbazole-3-carboxylic acid arylamide (abbreviated as 'HBC') rescue
(2) A diazonium salt formed by diazotizing a compound (representative: H ₂ N-Ar-NH ₂ ) having two or more amino groups as a diazo component is used. Oxy-11H-benzo [a] -carbazole-3-carboxylic acid arylamide (abbreviated as 'HBC') and a coupling component other than the compound (denoted as 'Cp') formed by azo-coupling [ HBC-N = N-Ar-N = N-Cp]
(3) a coupling component having two or more 2-hydroxy-11H-benzo [a] -carbazole-3-carboxamide residues (abbreviated as 'HBC-') in its molecule ('HBC-HBC') [Ar-N = N-HBC- formed by diazotizing and azo-coupling a compound having one amino group (denoted as 'Ar-NH ₂ ') as a diazo component, Structure represented by HBC-N = N-Ar]
(4) In the molecule thereof, 2-hydroxy-11H-benzo [a] -carbazole-3-carboxamide residue (abbreviated as' HBC- ') and a coupling component residue other than the compound (' Diazotizing a compound having one amino group (denoted as' Ar-NH ₂ ') as a diazo component to a coupling component having a Cp-') (denoted as' HBC-Cp '), Structure represented by [Ar-N = N-HBC-Cp-N = N-Ar] formed by azo coupling The method of claim 3, wherein
The black azo pigment which any one of the said coupling component and the said diazo component is chosen from any of the following.
(Aa) The coupling component (HBC) is 2-hydroxy-11H-benzo [a] -carbazole-3-anilide, 2-hydroxy-11H-benzo [a] -carbazole-3-naph Tilamide and their derivatives
(Ab) The coupling component (HBC-HBC) is phenylene-bis (2-hydroxy-11H-benzo [a] -carbazole-3-carboxamide), biphenylene-bis (2-hydroxy Hydroxy-11H-benzo [a] -carbazole-3-carboxamide), naphthalene-bis (2-hydroxy-11H-benzo [a] -carbazole-3-carboxamide) and derivatives thereof
(Ac) The coupling component (Cp) is 2-hydroxy-3-naphthoic arylamide, 2-hydroxy-6-naphthoic arylamide, 2-hydroxy-3-anthracenecarboxylic acid arylamide, 2- Hydroxy-3-dibenzofurancarboxylic acid arylamide, 2-hydroxy-1-carbazolecarboxylic acid arylamide and derivatives thereof
(Ad) The coupling component (HBC-Cp) is phenylene (-1)-(2-hydroxy-11H-benzo [a] -carbazole-3-carboxamide) (-4)-(2 -Hydroxy-3-naphthoic acid amide), biphenylene (-4)-(2-hydroxy-11H-benzo [a] -carbazole-3-carboxamide) (-4 ')-(2- Hydroxy-3-naphthoic acid amide), (2-methyl-) phenylene (-1)-(2-hydroxy-11H-benzo [a] -carbazole-3-carboxamide) (-4)- (2-hydroxy-3-naphthoic acid amide) and derivatives thereof
(Ba) a group of two having compound _{(H 2 N-Ar-NH} 2) is used as the diazo component, phenylene diamine, diamino biphenyl, diamino naphthalene, diamino anthraquinone, diamino-benzo Phenone, diaminopyridine and derivatives thereof
(Bb) Compound (Ar-NH ₂ ) having one amino group used as the diazo component is aniline, naphthylamine, aminoanthraquinone, phenoxyaniline, phenyliminoaniline and derivatives thereof As a manufacturing method which has a synthesis | combining process of the black polyazo pigment, and the process of refine | miniaturizing the pigment as needed, for obtaining the black azo pigment of any one of Claims 1-4,
(I) the synthesis method of the black polyazo pigment,
Any one of the following (1)-(4),
(1) 2-hydroxy-11H-benzo [a] -carbazole-3- to a diazonium salt formed by diazotizing a compound having two or more amino groups (representative: H ₂ N-Ar-NH ₂ ) A synthetic method of azo-coupling carboxylic acid arylamide (abbreviated as 'HBC');
(2) 2-hydroxy-11H-benzo [a] -carbazole-3- in a diazonium salt formed by diazotizing a compound having two or more amino groups (representative: H ₂ N-Ar-NH ₂ ) A method of synthesizing a polyazo pigment having a structure in which a carboxylic acid arylamide (abbreviated as 'HBC') and a coupling component other than the compound (represented by 'Cp') is azo-coupled, and has two or more amino groups. Azo-coupling an equimolar or less coupling component (Cp) to a diazonium salt formed by diazoazing a compound (representative formula: H ₂ N-Ar-NH ₂ ) having two or more A synthesis method of separating and removing a polyazo pigment coupled with a coupling component (Cp), and then azo-coupling the coupling component (HBC) with an uncoupled diazonium group;
(3-1) Coupling component having two or more 2-hydroxy-11H-benzo [a] -carbazole-3-carboxamide residues (abbreviated as' HBC- ') in a molecule (' HBC-HBC Synthetic method of azo-coupling a diazo component formed by diazotizing a compound (Ar-NH ₂ ) having one amino group in the formula (');
(3-2) 2-hydroxy--11H- benzo [a] - carbazol-3-carboxylic acid, the compound having one amino group (as represented la 'Ar-NH _2'), the diazonium salt formed by diazotization Azo-coupling, Next, the synthetic method of condensing the carboxylic acid of an azo pigment with an aryl polyamine to make polycarboxamide;
(4-1) 2-hydroxy-11H-benzo [a] -carbazole-3-carboxamide residue (abbreviated as 'HBC-') in one molecule, and a coupling component residue other than the compound ( Diazonium salt formed by diazotizing a compound having one amino group (denoted as 'Ar-NH ₂ ') to a coupling component having an amino group (denoted as 'Cp-') (denoted as 'HBC-Cp'). A synthesis method for azo-coupling; And
(4-2) Compounds each having one amino group in 2-hydroxy-11H-benzo [a] -carbazole-3-carboxylic acid and carboxylic acid of another coupling component (denoted as 'Ar-NH ₂ ') Synthesis method in which the diazonium salt formed by diazotizing is azo-coupled, and then the carboxylic acids of both azo dyes obtained are condensed with arylpolyamine to obtain a polycarboxamide.
Synthesized by a synthesis method selected from the group consisting of
Also,
(II) When the polyazo pigment synthesized by the above method is coarse and large, the step of miniaturizing the average particle diameter of the pigment to 10 nm to 200 nm by any of the following methods (1) or (2).
Method for producing a black azo pigment, characterized in that it has a.
(1) Any one of the pigment grinding machines selected from the group consisting of ball mills, sand mills, attritors, horizontal continuous media dispersers, kneaders, continuous single-axis kneaders, continuous biaxial kneaders, three rolls and open roll continuous kneaders Or micronization method using a pigment disperser
(2) Salt milling, kneading and grinding with a water-soluble salt and, if necessary, a water-soluble organic solvent in a kneader. The pigment component containing the black azo pigment as described in any one of Claims 1-4, or the black azo pigment obtained by the manufacturing method of Claim 5 is contained in liquid dispersion medium or a solid dispersion medium, It is characterized by the above-mentioned. Coloring composition. The method according to claim 6,
The pigment component containing the said black azo pigment is selected from the group consisting of a chromatic pigment, a white pigment, another black pigment, and a constitution pigment for correcting the black azo pigment to the black azo pigment alone or to the black azo pigment. The coloring composition for coloring of the dark colored chromatic color, to achromatic black or black color which consists of using at least 1 type of pigment together. The method of claim 7, wherein
The coloring composition in which the compounding ratio of the said black azo pigment and a chromatic pigment, a white pigment, another black pigment, or a sieving pigment for correcting the black azo pigment is determined by the method which is optimized using a computer color matching system. The method according to claim 6,
The liquid dispersion medium comprises at least one coating-forming material selected from a polymer which may have a reactive group, an oligomer which may have a reactive group, and a monomer which may have a reactive group, and is itself a liquid or a solvent and And / or a coloring composition further containing water. The method according to claim 6,
The coloring composition in which the said solid dispersion medium contains at least 1 sort (s) of solid dispersion medium chosen from a thermoplastic resin, a thermosetting resin, wax, fatty acid amide, and fatty acid metal soap. The method according to any one of claims 6 to 10,
The coloring composition used for at least any one of the said coloring composition for coatings, coatings, plastics, textiles, printing ink, stationery, image recording, and image display. The coloring composition of Claim 7 is used when coloring an article from black to dark by coloring of the surface of an article, or coloring of the article itself. 13. The method of claim 12,
The article is made of a transparent substrate, and the transparent substrate is coated, coated, dyed, printed, written, drawn, inkjet printed, electrophotographic printed, electrostatic The coloring method of the article which surface-colors by any method chosen from (vin- den) printing or photolithographic printing, or internally colors the said base material itself by the kneading method or the impregnation method. The method of claim 13,
The surface-colored or internal-colored portion exhibits a spectral transmittance of about 5% or less in the wavelength range of approximately 400 to 750 nm, which is a visible light region, and a transmittance of about 30% or more in the infrared region of 900 to 1500 nm. A method of coloring an article, which is carried out so that the article made of a transparent substrate has optical properties of both visible light shielding and infrared transmission. 13. The method of claim 12,
The article itself may be coated, coated, or coated with an optical reflective material or by using an article having a pre-formed optical reflective base formed thereon and using the coloring composition on the surface of the article or the optical reflective base. Articles which perform coloration that reflects in the infrared region by adhesion, welding, dropping, undiluted solution coloring, printing, printing, printing, writing, drawing, inkjet printing, electrophotographic printing, or electrostatic printing. Method of coloring. The coloring article of the article of any one of Claims 12-15 is implemented. The coloring article characterized by the above-mentioned. A backsheet of a photovoltaic module, in which a black or dark infrared transparent layer is laminated on the light reflective sheet, wherein the infrared transparent layer includes at least one azo bond in a molecule and at least one introduced from a coupling component. Black polyazo having a structure having a 2-hydroxy-11H-benzo [a] -carbazole-3-carboxylic acid amide residue (abbreviated as 'HBC-') and having an average particle diameter of 10 nm to 200 nm. A backsheet of a photovoltaic module comprising a pigment. The substrate having the light reflectivity on the substrate itself is used as the light reflecting sheet, or the substrate on which the light reflecting base formed in advance is formed is used as the light reflecting sheet. And a structure having the azo bonds described above and at least one 2-hydroxy-11H-benzo [a] -carbazole-3-carboxylic acid amide residue (abbreviated as 'HBC-') introduced from the coupling component, Reflective in the infrared region by coating, coating, welding, intermediate, printing, inkjet printing, electrophotographic printing or electrostatic printing of a coloring composition containing a black polyazo pigment having an average particle diameter of 10 nm to 200 nm. The manufacturing method of the backsheet of the photovoltaic module which performed the coloring which shows the above, and laminated | stacked the black or dark-colored infrared permeable layer on the light reflective sheet | seat. The black matrix (BM) formed on the color filter (CF) substrate or the organic EL light emitting substrate includes two or more azo bonds in the molecule and at least one introduced from the coupling component is 2-hydroxy-11H-benzo [a]. A color display having a structure having a carbazole-3-carboxylic acid amide residue (abbreviated as 'HBC-') and containing a black polyazo pigment having an average particle diameter of 10 nm to 200 nm. panel. The method of claim 19,
A color display panel having a CF substrate or an organic EL light emitting substrate which is formed with a substantially electrically insulating black matrix and a state in which the electrodes are placed in heavy or contact state.