WO2012091083A1

WO2012091083A1 - Black azo pigment and process for production thereof, colored composition, coloring method, and colored articles

Info

Publication number: WO2012091083A1
Application number: PCT/JP2011/080370
Authority: WO
Inventors: 中村　道衛; 士郎山宮; 坂本　茂; 岡本　久男; 悟松崎; 伊藤　秀樹
Original assignee: 大日精化工業株式会社
Priority date: 2010-12-28
Filing date: 2011-12-28
Publication date: 2012-07-05
Also published as: JPWO2012091083A1; CN103282443B; KR20130108650A; JP5866299B2; CN103282443A; TWI478983B; TW201241098A; KR101638669B1

Abstract

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

Description

Black azo dye, production method, coloring composition, coloring method and colored articles

The present invention relates to a black azo dye, a production method thereof, a coloring composition, a coloring method, and colored articles. More specifically, it has a specific structure that exhibits optical characteristics useful for applications that use absorption in the visible light region, and that is transparent in the infrared region and that uses infrared rays. The present invention relates to a black polyazo dye, and further relates to a production method, a colored composition, a coloring method using the same, and colored articles.

Carbon black pigments and iron oxide black pigments are common as black pigments used in colorants for paints, printing inks and plastics. These black pigments exhibit black color by absorbing light in all wavelength regions of light. Sunlight is an electromagnetic wave, and light in the region of about 380 nm to 780 nm is regarded as visible light, and light in the region of 0.7 μm to 2.5 μm having a longer wavelength than the visible light is near infrared. Black can be shown by absorbing light in the visible light wavelength range, but as a result, the carbon black pigment absorbs not only visible light but also light in the near infrared region.

Near-infrared rays, unlike short-wavelength light such as ultraviolet rays, have almost no adverse effects on the human body and are safe light. In recent years, many electronic devices that use infrared irradiation and reception have been developed. Yes. For example, an infrared remote control transmitter and its main receiver can be used for electric appliances, lighting fixtures, warm toilet seats, cameras, automobile door locks, engine starters, opening / closing garages, infrared security cameras and infrared surveillance around streets and buildings. Widely used in daily life, such as cameras.
Moreover, in patent document 1, the projector which light-emits simultaneously the visible light of a vehicle headlamp, and the near infrared light for confirmation of the front obstacle of a vehicle, and the filter which interrupt | blocks visible light and permeate | transmits infrared rays are equipped. A night vision device for vehicles is proposed.
As a pigment used in these infrared transmitters, infrared filters of receivers, infrared filters of infrared cameras, etc., it shows optical properties that transmit light in the infrared region and completely block light in the visible region, There is a demand for a dye having a function with excellent durability such as heat resistance, light resistance, and solvent resistance.

In recent years, photovoltaic power generation systems have been in the spotlight as clean energy and are becoming popular. A photovoltaic power generation module constituting a photovoltaic power generation system is attached to a place that is directly irradiated with sunlight, particularly an outdoor open space, a rooftop of an outdoor building, a roof, and the like. However, irradiation with sunlight and absorption of light brings about a rise in temperature of the photovoltaic power generation module and a reduction in the output of the power generation cell. Furthermore, in order to prevent the appearance and dirt of the power generation module from being noticeable, it is sometimes colored black, dark chromatic, or dark chromatic from the aesthetic point of view. In some cases, this causes a significant temperature increase. ing. Therefore, even if it is colored black in a solar power generation system, a coloring system that suppresses temperature rise as much as possible is expected. A solar cell backsheet comprising a perylene pigment has been proposed (Patent Document 2).

Also, in recent years, thermal barrier coating by reflection of sunlight has been demanded from the viewpoint of improvement of living environment, comfort, and energy saving, and development of heat ray reflective materials for this purpose has been demanded in various applications. For example, for roofs and walls of houses and buildings such as houses, offices, warehouses, buildings, road paving, automobile exteriors and interiors, ships, etc. Materials and the like are demanded, and heat dissipation materials such as electronic parts are also demanded.

In the information technology field, liquid crystal displays (hereinafter sometimes abbreviated as “LCD”) are used as information display members for televisions, projectors, personal computers, mobile phones, and the like due to the recent development of information-oriented devices. Information display devices such as information devices, monitors, car navigation systems, mobile phones, display screens for electronic computers and electronic dictionaries, information bulletin boards, information bulletin boards, function display boards, signboard displays, digital camera and video camera shooting screens, etc. It is used widely. Along with this, improvement of display quality and cost reduction of display are demanded, and quality of color filters (hereinafter sometimes abbreviated as “CF”) are improved and costs are reduced. CFs mounted on LCDs are also required to have superior quality in terms of color characteristics and optical characteristics of image performance such as definition, color density, light transmission, and contrast. There is a demand for development of materials having characteristics.

In the CF of the LCD, R (red), G (green), and B (blue) pixels are arranged in stripes, mosaics, triangles, etc., and illuminated from the back with a backlight. Colors are generated by additive color mixing of transmitted light to produce an image. A black matrix (hereinafter sometimes abbreviated as “BM”) is formed around each pixel in a lattice shape to shield unnecessary light and prevent color mixing. For chromatic pixels, red pigments, green pigments, blue pigments, yellow pigments, purple pigments, and the like are used, but each has been improved. In addition, BM uses a black pigment from a metallic chromium film as a light-shielding material for completely shielding the visible light region of the backlight due to problems such as an increase in substrate size and the environmental impact of chromium compounds. It has shifted to resin BM.

The backlight has been replaced with a light emitting diode (LED) instead of a cold cathode fluorescent tube, leading to an improvement in color purity and an expansion of the color reproduction range. The light emitted from the red region was sharp light of about 600 to 620 nm in the backlight of the cold cathode fluorescent tube, but in the LED backlight, the maximum emission wavelength is around 640 nm as the light from the red light emitting part. It has been proposed to use broad light having a range of approximately 540 nm to 800 nm (Patent Document 3). Therefore, it is a necessary condition for the BM to be able to sufficiently shield light on the long wavelength side of visible light.

Also, various improvements have been proposed in the display method of the CF pixel, and accompanying this, improvements have been made to the BM, and further to the light-shielding black pigment used in the BM. For example, in order to provide a wide viewing angle, which is a weak point of conventional LCDs, an in-plane switching method (IPS method) in which an electric field is applied in parallel to the substrate to convert the liquid crystal layer to display pixels has been proposed. ing. In addition, the black matrix on array method (BOA method) and the color filter on array method (COA method) in which a BM is formed on a thin film transistor (TFT) have a high aperture ratio. The bonding process work can be improved and rationalized in the work process.

In order to achieve these improved methods, particularly in the IPS system more completely, it is necessary to keep the distance between the substrates (cell gap) sandwiching the liquid crystal layer constant and with high accuracy. However, it is difficult to uniformly adjust the cell gap with the conventional method of spraying bead-shaped spacers. Therefore, as a method of realizing a uniform cell gap by a fixed spacer, the thickness of the BM itself is increased, or a substrate such as a layer support member resin such as a colored layer or a photoresist layer is stacked on the BM to increase the thickness. A cell gap support method has been proposed. Furthermore, the use of a bead-shaped spacer improves the deterioration of display quality due to light scattering and transmission (Patent Documents 4 and 5).

These IPS, BOA, and COA methods described above are methods for forming a BM on an active element such as a TFT. Of course, if the BM is not electrically insulating, the TFT malfunctions. There is a fear. Carbon black pigments generally used as light-shielding black pigments are inherently low in electrical resistance, are not suitable as light-shielding black pigments used in these systems, and are light-shielding materials with high electrical insulation. It is desirable.

In contrast to this, a proposal for a carbon black pigment in which a carbon black pigment defined by an oxygen amount is coated with a highly insulating resin film to improve electrical insulation (Patent Document 6), or a volume resistance value is measured. Insulating BM is formed using an insulating carbon black pigment or a carbon black pigment that has been coated with a resin and improved in electrical insulation, and applied to a COA system (Patent Document 7). ).
However, carbon black pigments are inherently conductive materials, and it is difficult to achieve complete insulation even with resin coating as in the prior art described above.
Furthermore, in the display using the organic EL element which is being developed recently, the use of BM is proposed to prevent color mixing of adjacent light from the light emitting element and to improve the sharpness of the light emitting screen. (Patent Document 8).

Japanese Patent No. 4120513 JP 2007-128943 A JP 2006-148051 A JP 2000-66018 A JP 2002-341332 A Japanese Patent No. 3543501 Japanese Patent No. 4338479 JP 2004-221081 A

In view of the circumstances described above, development of black pigments that exhibit both excellent physical properties and fastness as pigments, as well as optical properties of both visible light shielding properties and infrared transmission properties, which are useful for various applications, are desired. Has been. Specifically, for example, in the use of an infrared filter for an electronic device that shields unnecessary visible light and transmits an infrared signal, or in a black or dark back sheet constituting a solar power generation system, Even in the case of LED backlights with a wide emission wavelength range, such as a multi-layer coloring system in which an infrared transmissive black layer is provided on a sunlight-reflective substrate that can suppress temperature rise due to sunlight. It is useful for various applications that can completely block the light in the visible light region and maintain high electrical insulation even when a BM is formed on an active element such as a TFT so that the TFT does not malfunction. Furthermore, it is suitable for applications where the visible light shielding property is high in the BM of the organic EL display, and a black pigment having excellent physical properties and fastness as a pigment is desired. It has been.

Therefore, the object of the present invention is not only to exhibit excellent physical properties and fastness as a pigment, but also to optical properties of both visible light shielding properties and infrared transmittance properties applicable to various applications as described above. The present invention provides a black pigment, a method for producing the pigment, a coloring composition containing the pigment, a coloring method using the pigment, and colored articles.

As a result of studying the chemical structure of black organic pigments, the present inventors have conducted intensive research to achieve the object of the present invention. As a result, black polyazo pigments having a specific structure have a visible light wavelength range. Absorbs light with a wavelength of approximately 400 to 750 nm in almost the entire optical region at a high level, and further exhibits high transmittance on the long wavelength side of the infrared region of approximately 900 to 1500 nm, and further has an average particle diameter of 10 nm. It has been found that a black pigment that has been refined and pigmented to have a thickness of ˜200 nm is suitable for the various uses mentioned above, and has solved the above-mentioned problems and completed the present invention.

That is, the present invention is a black azo pigment exhibiting both optical properties of both visible light shielding properties and infrared ray transparency, and at least one 2 introduced from a coupling component and two or more azo bonds in the molecule. A black polyazo pigment having a structure having a hydroxy-11H-benzo [a] -carbazole-3-carboxylic acid amide residue and having an average particle diameter of 10 nm to 200 nm An azo pigment is provided.

As preferable forms of the present invention, the following black azo pigments can be mentioned.
The visible light shielding property is that a black colored film containing a black azo pigment on a transparent substrate exhibits a spectral transmittance of about 5% or less in a wavelength range of about 400 to 750 nm in the visible light range. The external transmittance is a black azo pigment in which the black colored film exhibits a transmittance of about 30% or more in the wavelength range of 900 to 1500 nm in the infrared region.

A black azo pigment in which the structure of the polyazo pigment has at least one of the following structures (1) to (4).
(1) A diazonium salt obtained by diazotizing a compound having two or more amino groups (representative formula: H ₂ N—Ar—NH ₂ ) is used as a diazo component, and 2-hydroxy- 11H-benzo [a] -carbazole-3-carboxylic acid arylamide (abbreviated as HBC) is a structure represented by [HBC-N = N-Ar-N = N-HBC] obtained by azo coupling.
(2) A diazonium salt obtained by diazotizing a compound having two or more amino groups (representative formula: H ₂ N—Ar—NH ₂ ) is used as a diazo component, and 2-hydroxy as a coupling component is used as the coupling component. -11H-benzo [a] -carbazole-3-carboxylic acid arylamide (abbreviated as HBC) and other coupling components (denoted as Cp) other than the compound are azo-coupled [HBC-N = N —Ar—N═N—Cp].
(3) A diazo-containing coupling component (denoted as HBC-HBC) having two or more 2-hydroxy-11H-benzo [a] -carbazole-3-carboxamide residues (abbreviated as HBC-) in the molecule. [Ar-N = N-HBC-HBC-N = N-Ar] formed by diazotization and azo coupling using a compound having one amino group as a component (indicated as Ar-NH ₂ ) Structure.
(4) In the molecule, 2-hydroxy-11H-benzo [a] -carbazole-3-carboxamide residue (abbreviated as HBC-) and other coupling component residues (Cp-) other than the compound A compound having one amino group as a diazo component (indicated as Ar—NH ₂ ) is diazotized with an azo coupling [Ar—N]. = N-HBC-Cp-N = N-Ar].
In the above, “Ar” typically represents a residue of an aromatic compound or a heterocyclic compound, and when there are two or more in the formula, they may be the same or different. Further, “Ar—N═N—” and “—N═N—Ar—N═N—” in the formula mean an “arylazo residue” coupled with a diazonium salt of a diazo component. The same applies to the following.

As another embodiment, the present invention is a production method for obtaining the above-described black azo pigment of the present invention, comprising a step of synthesizing a black polyazo pigment and a step of refining the pigment as necessary. A method for producing (I) a method for synthesizing a black polyazo pigment is any one of the following four types, and the polyazo pigment synthesized by these methods is coarse, which will be described later. Provided is a method for producing a black azo pigment, which comprises a step of refining the average particle size of the pigment to 10 nm to 200 nm by any known method.

As another embodiment, the present invention includes a pigment component containing 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. A coloring composition is provided.

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

The present invention provides, as another embodiment, a colored article characterized by being subjected to the above-described method for coloring an article.

The present invention, as another embodiment, is a back sheet of a photovoltaic module in which a black or dark infrared transmissive layer is laminated on a light reflective sheet, and the infrared transmissive layer includes: The molecule has two or more azo bonds and at least one 2-hydroxy-11H-benzo [a] -carbazole-3-carboxylic acid amide residue (abbreviated as HBC-) introduced from a coupling component. There is provided a back sheet for a photovoltaic power generation module characterized by containing a black polyazo pigment having a structure and an average particle diameter of 10 nm to 200 nm.

As another embodiment, the present invention uses a light-reflective sheet that is light-reflective on the substrate itself, or a substrate provided with a pre-formed light-reflective substrate as a light-reflective sheet. And at least one 2-hydroxy-11H-benzo [a]-introduced from the coupling component and two or more azo bonds in the molecule on the surface of the substrate or the light-reflective substrate. A coloring composition containing a black polyazo pigment having a structure having a carbazole-3-carboxylic acid amide residue (abbreviated as HBC-) and an average particle diameter of 10 nm to 200 nm; By sticking, welding, stacking, printing, ink jet printing, electrophotographic printing or electrostatic printing, the reflective region is colored in the infrared region and black on the light reflective sheet. Others provide a back sheet manufacturing method of the photovoltaic module, characterized in that the multilayer infrared permeable layer of dark color.

In another embodiment of the present invention, 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 the molecule. Black polyazo pigment having a structure having at least one 2-hydroxy-11H-benzo [a] -carbazole-3-carboxylic acid amide residue (abbreviated as HBC-) and an average particle diameter of 10 nm to 200 nm The present invention provides a color display panel characterized by containing.

According to the present invention described above, the black colored film containing the black azo pigment shows almost complete absorption in the wavelength range of about 400 to 750 nm covering the visible light range on the transparent substrate. In the infrared region having a longer wavelength, a high transmittance is exhibited on the transparent substrate, and useful optical characteristics having both visible light shielding properties and infrared transmittance properties are exhibited. Since it has such characteristics, the black azo pigment of the present invention is effectively used as an infrared filter for an infrared remote controller and a main body receiver. Furthermore, the black azo pigment of the present invention can be used as an infrared filter of an infrared sensing device that detects and identifies roadside obstacles such as automobiles that are being put into practical use.

Furthermore, since the black azo pigment of the present invention covers the visible light region and exhibits optical characteristics that absorb almost completely even on the long wavelength side, as a light-shielding black material for CF BM, for example, it supports red pixels. The wavelength range of the light from the red light emitting part of the LED backlight is sufficiently absorbed and can be blocked, and the color of the LCD is not only black but also other chromatic colors are vividly developed. Furthermore, since it has high electrical insulation, various CF improvement methods for forming a BM on an active element such as a TFT, for example, a BM that maintains the thickness of a liquid crystal layer in place of a spacer, a CF for an IPS method, a COA method, etc. It is also suitable as a light-shielding black pigment for forming the BM. In particular, it is the most preferable light-shielding black pigment for an IPS liquid crystal panel or the like employing an LED backlight and also in an organic EL display.

In addition, it is attracting attention from the viewpoint of improving the living environment, comfort and energy saving in recent years because it is sufficiently transparent to infrared rays and is reflected by white pigments and extender pigments added to the base and coating materials. It is used as a material for preventing temperature rise due to direct sunlight, such as painting on houses and buildings, road paving, and ship decks and exteriors. Furthermore, also in a solar power generation system, it is used for the back sheet | seat which formed the infrared rays transparent layer of the black or the dark color on the reflective base layer in multiple layers which can suppress the temperature rise by sunlight. In addition, it is also used for anti-counterfeiting coloring materials for 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 the present invention, absorbs the entire visible light region as an optical property, exhibits almost complete absorption even in the wavelength range on the long wavelength side, and has a high transmittance in the near infrared region. Indicates. Specifically, the spectral transmittance of the black colored thin film on the transparent substrate is about 5% or less in the wavelength range of 400 to 750 nm in the visible light range, and in the infrared wavelength range of about 900 nm to 1500 nm. About 30% or more. Moreover, as an electrical property, very high electrical insulation is shown.

As a result of studying a pigment having a plurality of chromophores in a molecule and resonating with each other as a black azo pigment exhibiting the above-mentioned characteristic optical properties, the present inventors have found that particularly easy synthesis. Therefore, a black polyazo pigment having a specific chemical structure having two or more azo bonds in the molecule was developed. Furthermore, since high transmittance in the infrared region is particularly required, the black polyazo pigment is preferably a pigment having a fine particle size, and the average particle size of the pigment needs to be about 10 nm to 200 nm. . When a higher transmittance is desired, an ultrafine black polyazo pigment having an average particle diameter of about 10 nm to 50 nm, or a black azo pigment having a disperse dye-like property that causes molecular dispersion in a medium in a coloring process. Is preferred.
In the present invention, the polyazo pigment means a disazo pigment or a trisazo pigment having two or more azo bonds in the molecule as described above.

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

Since the method for producing the polyazo pigment needs to provide two or more azo bonds in the molecule, for example, an azo cup using a diazo component having two or more amino groups that change to a diazonium group as a diazo component is used. Examples thereof include a ring method and a azo coupling method using a coupling component having a coupling component having two or more coupling positions. This point will be described in detail.

The black polyazo pigment of the present invention preferably has any of the following structures (1) to (4).
(1) A diazonium salt obtained by diazotizing a compound having two or more amino groups (representative formula: H ₂ N—Ar—NH ₂ ) is used as the diazo component, and 2-hydroxy- 11H-benzo [a] -carbazole-3-carboxylic acid arylamide (abbreviated as HBC) is an azo-coupled black polyazo having a structure represented by [HBC-N = N-Ar-N = N-HBC] Pigments.

Examples of black polyazo pigments having the structure (1) represented by the above [HBC-N═N—Ar—N═N—HBC] include benzidine or phenylenediamine having two or more amino groups in the diazo component as follows. An example of the structure when used is given.

(2) A diazonium salt obtained by diazotizing a compound having two or more amino groups as a diazo component (representative formula: H ₂ N—Ar—NH ₂ ) is used. Hydroxy-11H-benzo [a] -carbazole-3-carboxylic acid arylamide (abbreviated as HBC) and other coupling components (denoted as Cp) other than the compound are azo-coupled [HBC-N = A black polyazo pigment having a structure represented by 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 phenylenediamine having two or more amino groups in the diazo component as follows. An example of the structure when 2-hydroxy-3-naphthoic acid arylamide is used as another coupling component will be given.

(3) A diazo-containing coupling component (denoted as HBC-HBC) having two or more 2-hydroxy-11H-benzo [a] -carbazole-3-carboxamide residues (abbreviated as HBC-) in the molecule. [Ar-N = N-HBC-HBC-N = N-Ar] formed by diazotization and azo coupling using a compound having one amino group as a component (indicated as Ar-NH ₂ ) A black polyazo pigment with a structure.

Examples of the black polyazo pigment having the structure (3) represented by the above [Ar—N═N—HBC—HBC—N═N—Ar] are as follows: 2-hydroxy-11H-benzoate via phenylene or biphenylene Example of structure obtained by diazotization using aniline having one amino group as diazo component in HBC-HBC as a coupling component in which two [a] -carbazole-3-carboxamide residues are bonded Give up.

(4) In the molecule, 2-hydroxy-11H-benzo [a] -carbazole-3-carboxamide residue (abbreviated as HBC-) and other coupling component residues (Cp-) other than the compound A compound having one amino group as a diazo component (indicated as Ar—NH ₂ ) is diazotized with an azo coupling [Ar—N]. = N-HBC-Cp-N = N-Ar].

As an example of a black polyazo pigment having the structure (4) represented by [Ar—N═N—HBC—Cp—N═N—Ar], 2-hydroxy-11H-benzo [ a] -carbazole-3-carboxamide residue and HBC-Cp of the coupling component to which the residue of 2-hydroxy-3-naphthoic acid arylamide, which is another coupling component other than the compound, is bonded, Examples of structures obtained by diazotization using aniline having one amino group as the diazo component will be given.

The black azo pigment of the present invention is a black color of the present invention having a synthesis step of a polyazo pigment having the structure as described above, and a step of adjusting the particle size of pigment particles for refining the pigment as necessary. It can be easily obtained by a method for producing an azo pigment. Hereinafter, the manufacturing method of the black azo pigment of this invention is demonstrated.

The method for synthesizing the black polyazo pigment constituting the method for producing the black azo pigment of the present invention is selected from the following methods (1) to (4).
In the method (1), a diazonium salt formed by diazotizing a compound having two or more amino groups (representative formula: H ₂ N—Ar—NH ₂ ) is converted into 2-hydroxy-11H-benzo [a] -carbazole- In this synthesis method, 3-carboxylic acid arylamide (abbreviated as HBC) is azo-coupled. The black polyazo pigment obtained by the synthesis method (1) has a structure represented by [HBC-N = N-Ar-N = N-HBC] described above.

In the method (2), a diazonium salt obtained by diazotizing a compound having two or more amino groups (representative formula: H ₂ N—Ar—NH ₂ ) is converted to 2-hydroxy-11H-benzo [a] -carbazole- A method for synthesizing a polyazo pigment having a structure obtained by azo coupling 3-carboxylic acid arylamide (abbreviated as HBC) and other coupling component (denoted as Cp) other than the compound, having two or more amino groups A diazonium salt obtained by diazotizing a compound (representative formula: H ₂ N—Ar—NH ₂ ) is azo-coupled with an equimolar or less coupling component (Cp), and if necessary, two or more The coupling component (Cp) of the polyazo pigment was separated and removed, and then the coupling component (HB) was added to the uncoupled diazonium group. ) Which is a synthetic method for azo coupling. The black polyazo pigment obtained by the synthesis method (2) has a structure represented by [HBC—N═N—Ar—N═N—Cp] described above.

The method (3) is the following method (3-1) or (3-2). The black polyazo pigments obtained by the synthesis methods (3-1) and (3-2) have the structure represented by [Ar—N═N—HBC—HBC—N═N—Ar] described above. It will have.

(3-1) A coupling component (denoted as HBC-HBC) having two or more 2-hydroxy-11H-benzo [a] -carbazole-3-carboxamide residues (abbreviated as HBC-) in the molecule In this synthesis method, a diazo component obtained by diazotizing a compound having one group (Ar—NH ₂ ) is azo-coupled.

(3-2) A diazonium salt obtained by diazotizing a 2-hydroxy-11H-benzo [a] -carbazole-3-carboxylic acid with a compound having one amino group (indicated as Ar—NH ₂ ) is an azo cup. In this synthesis method, the carboxylic acid of the azo dye is condensed with an aryl polyamine to form a polycarboxamide.

The method (4) is the following method (4-1) or (4-2). The black polyazo pigments obtained by the synthesis methods (4-1) and (4-2) have the structure represented by [Ar—N═N—HBC—Cp—N═N—Ar] described above. It will have.

(4-1) 2-hydroxy-11H-benzo [a] -carbazole-3-carboxamide residue (abbreviated as HBC-) in one molecule and other coupling component residues (Cp- And a diazonium salt obtained by diazotizing a compound having one amino group (indicated as Ar—NH ₂ ) to a coupling component (indicated as HBC-Cp).

(4-2) 2-hydroxy-11H-benzo [a] -carbazole-3-carboxylic acid and a compound (indicated as Ar—NH ₂ ) each having one amino group in the carboxylic acid of the other coupling component This is a synthesis method in which a diazonium salt obtained by diazotization is azo-coupled, and then the carboxylic acids of both azo dyes obtained are condensed with an aryl polyamine to form a polycarboxamide.

The diazo component and the coupling component that can be used in each of the synthesis methods listed above will be described.
(A) The coupling component is specifically exemplified.
(A) Examples of the coupling component (HBC) include 2-hydroxy-11H-benzo [a] -carbazole-3-anilide, 2-hydroxy-11H-benzo [a] -carbazole-3-naphthylamide, and the like. Their derivatives. Examples of the substituent of the derivative include an alkyl (carbon number: 1 to 10) group, an alkoxy (carbon number: 1 to 10) group, a trifluoromethyl group, a halogen group, an alkyloxycarbonyl group, a cyclic iminodioxy group, and an alkylsulfonyl. A coupling component in which one or more groups, aminocarbonyl group, benzamide group, alkylaminocarbonyl group, anilinocarbonyl group, cyclic ureylene group, carboxyl group, alkylimino group and the like are introduced.

Specifically, for example, 2-hydroxy-11H-benzo [a] -carbazole-3-anilide, 2-hydroxy-11H-benzo [a] -carbazole-3-carboxy-p-anisidide, 2-hydroxy-11H -Benzo [a] -carbazole-3-carboxy- (2-methyl) -p-anisidide, 2-hydroxy-11H-benzo [a] -carbazole-3-carboxy-N-benzimidazolone-5-amide, 2 -Hydroxy-11H-benzo [a] -carbazole-3-carboxy-naphthylamide and the like.

(B) Examples of the coupling component (HBC-HBC) include phenylene-bis (2-hydroxy-11H-benzo [a] -carbazole-3-carboxamide), 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. As a substituent of the derivative, a known substituent such as an alkyl (carbon number: 1 to 10) group, an alkoxy (carbon number: 1 to 10) group, a trifluoromethyl group, a halogen group, etc. One or more coupling components introduced.

Specifically, for example, phenylene- (1,4-) bis (2-hydroxy-11H-benzo [a] -carbazole-3-carboxamide), 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-carboxamide), 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] - carbazol-3-carboxamide), and the like.

(C) Examples of the coupling component (Cp) include 2-hydroxy-3-naphthoic acid arylamide, 2-hydroxy-6-naphthoic acid arylamide, 2-hydroxy-3-anthracenecarboxylic acid arylamide, 2 -Hydroxy-3-dibenzofurancarboxylic acid arylamide, 2-hydroxy-1-carbazolecarboxylic acid arylamide and the like and their derivatives. For example, C.I. 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 and the like.

(D) As the coupling component (HBC-Cp), 2-hydroxy-3-naphthoic acid, 2-hydroxy-6-naphthoic acid, carboxylic acid of Cp residue that is amide-bonded to the amino group of HBC residue, Examples include 2-hydroxy-3-anthracene carboxylic acid, 2-hydroxy-3-dibenzofuran carboxylic acid, 2-hydroxy-1-carbazole carboxylic acid and the like. 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-carboamido) (-4 ')-(2-hydroxy-3-naphthoic acid amide).

(B) The diazo component is specifically exemplified.
(A) Examples of the compound having two or more amino groups of the diazo component (representative formula: H ₂ N—Ar—NH ₂ ) include, for example, phenylenediamine, diaminobiphenyl, diaminonaphthalene, diaminoanthraquinone, diamino-benzophenone, diamino Pyridine and the like and derivatives thereof. As a substituent of the derivative, a known substituent such as an alkyl (carbon number: 1 to 10) group, an alkoxy (carbon number: 1 to 10) group, a trifluoromethyl group, a halogen group, etc. One or more diazo components introduced.

Specifically, for example, 1,4-phenylenediamine, 2-chloro-1,4-phenylenediamine, 2,5-dichloro-1,4-phenylenediamine, 2-chloro-5-methyl-1,4-phenylene Diamine, 2,5-dimethyl-1,4-phenylenediamine, 2-nitro-1,4-phenylenediamine; 1,3-phenylenediamine, 4-chloro-1,3-phenylenediamine, 4-methoxy-1, 3-phenylenediamine, 4-nitro-1,3-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'-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-diaminopyridine and the like.

(B) Examples of the compound having one amino group of the diazo component (indicated as Ar—NH ₂ ) include aniline, naphthylamine, aminoanthraquinone, phenoxyaniline, phenyliminoaniline, and derivatives thereof. As a substituent of the derivative, a known substituent for 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 diazo component having one or more phenylimino group, benzoylamide group, anilinocarbonyl group, cyclic ureylene group, etc. introduced therein. Specifically, for example, C.I. I. Azoic diazo components 5, 8, 9, 10, 32, 33, 34, 35, 36, 37, 41, 42, 43, 47 and the like.

The process for adjusting the particle size of the pigment particles that constitute the black azo pigment production method of the present invention, and which refines the pigment as necessary, will be described. The black azo pigment of the present invention is obtained by the following method (1) or (2) when the particle size of the polyazo pigment obtained by the synthesis method as described above is coarse. It can be obtained by reducing the average particle diameter of the pigment to about 10 nm to 200 nm. That is, in order to improve the infrared transmittance of the coating film using the polyazo pigment obtained by the synthesis method listed above, the particle diameter of the dispersed pigment is smaller than the wavelength of light, Specifically, the average particle size needs to be about 10 nm to 200 nm. Therefore, the black azo pigment of the present invention is a known pigment as described below in order to adjust the average particle size of the pigment to the required particle size when the pigment synthesized by the above method is coarse. It is necessary to carry out a refinement process and produce a refined pigment.

In particular,
(1) Pigment polishing selected from the group consisting of a ball mill, sand mill, attritor, horizontal continuous media disperser, kneader, continuous uniaxial kneader, continuous biaxial kneader, triple roll, open roll continuous kneader Miniaturization method using a crusher or pigment disperser,
(2) A pigment refining step selected from known methods such as a solvent salt milling method of kneading and grinding with a water-soluble salt and, if necessary, a water-soluble organic solvent in a kneader, and an average particle size of about 10 nm. Prepare to ˜200 nm. Furthermore, when higher infrared transmittance is desired, it is preferable to prepare an ultrafine pigment having an average particle diameter of about 10 nm to 50 nm.

The particle diameter of the pigment is adjusted according to the intended use. The adjustment of the particle size is controlled mainly by the ratio of the salt to the pigment and the kneading time. In applications such as infrared color filters that require high transmittance, it is desirable that the pigment particles be smaller. For example, the dispersion state of fine pigment particles of 10 nm to 50 nm, and further ultra fine pigment particles of 10 nm to 30 nm is preferable. Preferably, a dissolved state in which molecules are finally dispersed in a carrier for dispersion, for example, a plastic medium is desirable.

On the other hand, in applications such as CF BM, which requires a light-shielding property for visible light, a slightly larger value of about 50 nm to 100 nm is preferable than that for transmission. In applications that require infrared reflectivity, the base is preferably reflective, but the pigment particles may be relatively large and may be used at 100 nm to 200 nm.

In the solvent salt milling method described above, water-soluble inorganic salts are added to the pigment as a grinding aid, several times the amount of the pigment to be ground depending on the desired pigment particle size, specifically 3 to 20 times the amount. Further, a viscous water-soluble organic solvent such as ethylene glycol, diethylene glycol, polyethylene glycol or the like is added and kneaded and ground. As the water-soluble inorganic salt used for the grinding aid, sodium chloride, sodium sulfate and the like are used. After grinding, it is added to dilute sulfuric acid, water, etc. to dissolve the grinding aid, filtered and washed with water to obtain a pigment filtration paste (press cake). The press cake is directly processed by a wet disperser, processed into an oily colorant by a flushing method, dried with hot air, and then pulverized into a powder pigment by a dry pulverizer. Depending on the application, various colorants are processed, such as being dispersed by a wet disperser or a kneader. It is also preferable to treat the resin in water to make an easily dispersible processed pigment or processed pigment.

When using the black azo pigment of the present invention as a colorant, it is also preferable to add an anionic or cationic pigment derivative to the black azo pigment, particularly in a liquid pigment dispersion. As a method for adding these pigment derivatives, a method of introducing an accessory coupling method using a diazo component or a coupling component having an ionic group at the time of synthesis of the above-mentioned pigment, or a separately synthesized ionic group is used. It is carried out by a known method such as a method in which the pigment derivative is added at the time of the fine particle production process or when preparing the pigment dispersion. As the pigment derivative at this time, chromatic pigment derivatives such as yellow, blue, and red, as well as black, are appropriately used including adjustment of color tone.

Here, the spectral transmittance of the coating film is slightly different in numerical values depending on the black pigment content and coating film thickness contained in the coating film, but in relation to the wavelength, it is Has also been shown to exhibit a tendency to absorb, and to exhibit a tendency to transmit at the transmitted wavelength. In Tables 1 and 2, the black disazo pigment ("Black Pigment-1") obtained in Production Example 1 of the present invention described later is used, and the coating film containing Black Pigment-1 prepared in Example 1 described later is used. The spectral transmittance (%) in the visible region and the infrared region is shown.
As a result, as shown in Table 1, the coating film containing Black Pigment-1 has a transmittance of 0% over the entire wavelength region of visible light of 400 to 750 nm, and does not exhibit transparency in the visible region. confirmed. On the other hand, as shown in Table 2, there is a 34% transmission at 900 nm in the infrared region, and the transmittance gradually increases on the longer wavelength side, and the transmittance is increased even at higher wavelengths. It is assumed that

Further, regarding the electrical insulation of the coating film containing the black azo pigment of the present invention, the volume resistivity value of the coating film containing the black pigment-1 is 10 ¹⁴ as shown in Example 1 described later. It was Ω · cm, and it was confirmed that good electrical insulation was exhibited.

Since the black pigment-1 which is the black azo pigment of the present invention is a dye having an optical function of transmitting light in the infrared region and completely shielding light in the visible light region as described above, It has been found that it is useful for applications of infrared filters for electronic devices that use BF and for CF BM. For example, when the black azo pigment of the present invention is applied to CF BM, light in the visible light region of the backlight can be completely shielded, and excellent electrical insulation is exhibited.

The black azo pigment of the present invention is a coloring composition that, when used, has a dark chromatic color, an achromatic dark color, or a black color, and includes a black azo pigment depending on the purpose, application, usage, etc. It can be used in various forms as a liquid coloring composition containing the components in a liquid dispersion medium or a solid coloring composition containing the components in a solid dispersion medium.

The black azo pigment of the present invention has a chromatic color pigment, a white pigment, another black pigment, and an extender pigment as a pigment component, as a pigment component, alone or as one of a plurality of pigment components. In combination, one type or two or more types can be selected and used in combination. The mixing ratio of the chromatic color pigment, white pigment, other black pigment or extender pigment used in combination with the black azo pigment of the present invention to correct the color of the black azo pigment is not particularly limited, but a computer color matching system is used. It is also a preferred form to be determined by the method to be used and optimized.

As the pigment used in combination with the black azo pigment of the present invention, a known pigment can be used and is not particularly limited. For example, anthraquinone pigment, quinacridone pigment, diketopyrrolopyrrole pigment, indigo / thioindigo pigment, perinone pigment, perylene pigment, phthalocyanine pigment, indoline pigment, isoindoline pigment, isoindolinone pigment Organic pigments such as dioxazine 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 black pigments, and carbon black pigments At least one pigment selected from inorganic pigments such as composite oxide pigments, iron oxide pigments, titanium oxide pigments, a mixture of two or more pigments, and mixed crystal pigments can be used.

Organic pigments include, for example, yellow pigments and C.I. 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 C.I. I. Pigment Orange (abbreviated as PO) -61, 64, 71, 73, etc. are red pigments such as C.I. 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.

For blue pigments, C.I. 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. are green For pigments, C.I. I. Pigment Green (abbreviated as PG) -7, 36, 58, poly (13-16) bromophthalocyanine, etc. I. Pigment Violet (abbreviated as PV) -19, PV-23, PV-37, etc. are black pigments such as aniline black pigments, carbon black pigments, titanium oxide black pigments, and particularly for CF BM. As the compound used in the black azo pigment of the present invention, a carbon black pigment, a titanium oxide black pigment or the like whose surface is treated to improve insulation is preferable.

When the black azo pigment of the present invention is used in combination with an infrared reflective pigment such as a white pigment, the methods proposed in Japanese Patent No. 4097926 and Japanese Patent Application Laid-Open No. 2005-330466 can also be used. That is, it is also preferable to apply a method of substantially improving the infrared reflection efficiency by substantially covering the infrared reflective pigment such as a white pigment with the infrared transmissive black azo pigment of the present invention.

The liquid coloring composition comprising the black azo pigment of the present invention is mainly used as a coloring agent for coating, impregnating, drawing, printing, etc. on the surface of an article, and it is used as a paint, coating agent, plastic coloring, fiber coloring. , Printing ink, stationery, image recording, and image display. In the dispersion medium in which the black azo pigment of the present invention is dispersed, a reactive polymer having a reactive group or a non-reactive polymer, an oligomer having a reactive group, or a non-reactive polymer is used as a film-forming material (or film-forming material). It may contain at least one selected from a reactive oligomer, a monomer having a reactive group, a non-reactive monomer having no reactive group, and the like, and may itself be a liquid, or further It may contain a solvent and / or water.

Furthermore, when preparing the above-mentioned liquid coloring composition, if the pigment to be used is prepared in advance as a high-concentration pigment processed product in which the pigment to be used is finely dispersed in a dispersion medium, it is used for coloring. The preparation of the agent can be facilitated. The liquid high-concentration pigment dispersion is called “base color” or “base ink” and is used.

Further, the above-described solid coloring composition containing the black azo pigment of the present invention is a colorant mainly used for internal coloring of plastics and synthetic fibers, and is, for example, a high-concentration pigment dispersion. It is used in known product shapes such as master powder, master batch, etc., and colored pellets colored throughout. As the solid dispersion medium, at least one selected from thermoplastic resins, thermosetting resins, waxes, fatty acid amides, fatty acid metal soaps, and the like can be used.

When an article is colored using the above-described colorant, appropriate coloring is performed depending on optical purposes in the visible light region and the infrared region.
When coloring to absorb the visible light region and transmit the infrared region, make the base material of the article transparent, and use the coloring composition to paint, apply, dye, The surface is colored by printing, writing, drawing, ink jet printing, electrophotographic printing, electrostatic printing, photolithographic printing, or the like, or the transparent composition is kneaded or impregnated with the coloring composition to internally color. In this case, by using the black azo pigment of the present invention, the resulting article exhibits the following excellent optical properties. That is, when the black azo pigment of the present invention is used, particularly in the wavelength range of about 400 to 750 nm in the visible light region, high absorptivity and visible light shielding properties are exhibited, and a high wavelength of about 900 nm to 1500 nm and further higher. In the infrared region, it can be colored highly transmissive.

In addition, when coloring in which the visible light region is absorbed and the infrared region is reflected, the material constituting the article itself is light-reflective or a pre-formed light-reflective substrate is used. Furthermore, it can achieve by apply | coating using the coloring composition of this invention. Details of this point will be described later. The coloring method in this case is a known method, for example, painting, painting, undiluted solution printing, textile printing, dip dyeing, printing, writing, drawing, ink jet printing, electrophotographic printing, electrostatic printing, etc. Can exhibit high absorbency, and in the near-infrared region can be colored highly reflective.

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

As shown in Table 3, the coating film containing the above black pigment-1 absorbs from the visible region to about 750 nm and exhibits a reflectance of about 5%, but the reflectance rapidly increases from about 800 nm to 900 nm. It is assumed that the reflectance of about 80% is maintained in the near-infrared region on the longer wavelength side, and that the reflectance is also high in the infrared region of higher wavelength. . This indicates that the light that has passed through the black coating is reflected by the white paper of the base, and the surface of the black pigment can be obtained by using a highly reflective base or a reflective material such as a white pigment or extender. In addition to the above, the transmitted light is re-reflected to show an efficient high reflectance.

Resin binder that functions as a film-forming material (film-forming material) used in the present invention (referred to as “vehicle” or “varnish” depending on the application) is a non-reactive, room-temperature drying type or reaction that does not have a reactive group. A baking-type resin binder having a functional group and a photosensitive resin binder can be preferably used. Examples of the room temperature drying type or baking type resin binder include printing agents, paints, coating agents, or resin binders used for printing inks, stationery, inkjet printing, electrophotographic printing, electrostatic printing, and other image recording materials. Is mentioned. Examples of the photosensitive resin binder include photosensitive resin binders used in various ultraviolet curable or electron beam curable paints, coating agents, printing inks, inkjet inks, photolithography, and the like.

Specific examples of room temperature drying type or baking type resin binders that can be used in the present invention include, for example, synthetic rubber resins, acrylic resins, styrene (co) polymers, vinyl resins such as polyvinyl butyral resins, and polyester resins. , Amino resin-modified polyester resins, polyurethane resins, acrylic polyol urethane resins, soluble polyamide resins, soluble polyimide resins, soluble polyamideimide resins, soluble polyesterimide resins, alkyd resins, aminoalkyd resins, epoxy resins Resin, chlorinated rubber resin, silicone resin, fluororesin, cellulose acetate resin, nitrocellulose resin, hydroxyethyl cellulose, water-soluble salt of styrene-maleic acid ester copolymer, (meth) acrylic acid ester (co) heavy Body water-soluble salts of water-soluble amino alkyd resin, and water-soluble amino polyester resin and a water-soluble polyamide resin and the like, which are used in combination or alone or in combination.

Examples of the reactive group possessed by the reactive film forming material include a methylol group, an alkylmethylol group, an isocyanate group, a masked isocyanate group, and an epoxy group. In addition, oligomers and monomers are used depending on applications, and a cross-linking agent such as methylol melamine type, isocyanate type, and epoxy type cross-linking agent is also used in combination.

Specific examples of energy ray curable coating film forming materials such as ultraviolet curable resin systems and electron beam curable resin systems that can be used in the present invention include, for example, photosensitive cyclized rubber resins, photosensitive phenol resins, Photosensitive polyacrylate resins, photosensitive polyamide resins, photosensitive polyimide resins, etc., and unsaturated polyester resins, polyester acrylate resins, polyepoxy acrylate resins, polyurethane acrylate resins, polyether acrylate resins, polyols Examples thereof include binders such as acrylate resins, and binders in which monomers are further added as reactive diluents.

Examples of the plastic to be colored with the colorant for plastics which is the coloring composition of the present invention include conventionally known thermoplastics such as polyolefins such as polyethylene, ethylene copolymer, and polypropylene, polystyrene, ABS, AS, and styrene. Copolymers, vinyl chloride resins, methacrylic resins, polycarbonates, polyamides, polyacetals, thermoplastic polyesters, cellulosic plastics, phenylene oxide resins, fluororesins, thermoplastic elastomers, etc. Also, as thermosetting plastics, unsaturated polyester resins, Examples thereof include an epoxy resin, a silicone resin, a polyurethane resin, a melamine resin, and a phenol resin.

The content of the black azo pigment of the present invention contained in the black colorant which is the coloring composition of the present invention varies depending on the use and purpose of use, and is not generally determined. For example, in applications such as paints, coating agents, textile printing agents, printing inks, printer toners, inkjet inks, etc., where the film thickness is thin, the content of black pigment contained in the colorant is as follows: It is about 3% to 80%, preferably about 5% to 60%. In particular, when used as a light-shielding black material for CF BM, since the film thickness is particularly thin and complete light-shielding properties are required, the pigment is stably dispersed, the viscosity suitable for coating is maintained, and uniform The limit pigment concentration to form a simple colored film is tried, and is preferably about 30% to 60%.
Also, when the entire material to be colored is internally colored, such as plastic coloring or spinning stock solution coloring, it depends on the thickness of the colored product, but it is approximately 0.05% to 20%, preferably approximately 0%. About 1% to 10%.

In the case where the coloring composition for image recording containing the black azo pigment of the present invention is used as a coloring composition for BM formation of CF, the coloring composition is used to transfer directly or onto the CF substrate. It is formed by one or two or more forming methods selected from a photolithography method, a laser ablation method, an ink jet printing method, a printing method, a transfer method, a pasting method, etc. with a plastic film for pasting interposed.

The film thickness of BM is 0.5 μm to 3 μm, and usually 1 μm to 2 μm. The optical density (OD) value is 2.0 or more, preferably 3.0 or more. In order to provide the spacer function, there are cases where the BM itself is thickened, pixels are stacked on the BM, or a colorless resin film is stacked, and 5 μm to 10 μm is preferable.
Further, chromatic color pixels can be formed on the CF substrate on which the BM is formed by a known pixel forming method using a known chromatic color pixel forming colorant.

The following items can be listed as examples of characteristic articles relating to the CF substrate or the organic EL light emitting substrate that are suitable in the present invention. That is, a CF substrate or an organic EL light emitting substrate on which a BM that absorbs a wavelength range in the visible region is formed, in particular, a BM is further substantially electrically insulating, and a CF substrate that is formed by overlapping the BM and an electrode. An organic EL light emitting substrate and a color display panel including them are exemplified. Similarly, a CF substrate in which chromatic pixels are formed on the CF substrate on which the BM is formed, a liquid crystal color display device on which the CF substrate on which BM and chromatic pixels are formed, or the above organic EL An organic EL color display device equipped with a light emitting substrate may be mentioned.
In addition, as an article related to the photovoltaic power generation system, a colored composition containing the black azo pigment of the present invention on a light-reflective sheet such as a reflective underlayer capable of suppressing a temperature rise due to sunlight, black Or the back sheet | seat formed by multilayering the dark-colored infrared rays transparent layer and a solar power generation module using the same are mentioned.

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

[Production Example 1] (Production of “Black Pigment-1”)
(1) Synthesis of black disazo pigment According to a conventional method, concentrated hydrochloric acid was added to 2.44 g (0.01 mol) of 3,3′-dimethoxy-4,4′-benzidine to form a hydrochloride, followed by excess nitrous acid. Diazotization was performed by adding an aqueous sodium solution. Next, borohydrofluoric acid was added thereto to prepare 3,3′-dimethoxy-diphenylene (4,4 ′-) tetrazonium / boron fluoride double salt (diazonium salt). Separately, 7.65 g (0.02 mol) of 2-hydroxy-11H-benzo [a] carbazole-3-carboxy-p-anisidide as a coupling component and methanol in which 0.8 g of sodium hydroxide was dissolved Prepared by dissolving in 250 g. The previously prepared tetrazonium / boron fluoride double salt solution was kept at 15 ° C. or lower, and the solution of the coupling component prepared above was gradually added thereto. After adjusting the pH to 6.5-7.0 with sodium acetate and stirring for 1 hour, the mixture was stirred at 25 ° C. for 2 hours, further heated to 40 ° C. and stirred for 3 hours to complete the coupling reaction. I let you. After the produced pigment was filtered, the filtrate was washed with methanol, then washed with water, and dried to obtain a crude black azo pigment. The yield of the obtained black azo pigment was 9.78 g.

(2) Preparation of black fine particle pigment by refining treatment 100 parts of coarse particle pigment of black azo pigment obtained by the synthesis reaction of (1) above, together with 500 parts of sodium chloride powder and 50 parts of diethylene glycol, a pressure lid The kneader equipped was charged and premixed until the coarse particle pigment and sodium chloride powder in the kneader were uniformly moistened. Next, the pressure kettle was closed, and kneading and grinding were performed while pressing the contents at a pressure of 6 kg / cm ² . Specifically, kneading and grinding were performed for 2 hours while controlling the temperature so that the contents were 92 to 98 ° C. The obtained ground product was stirred for 1 hour in 3,000 parts of warm water heated to 80 ° C. and then filtered, and the resulting filtrate was washed with water to remove sodium chloride and diethylene glycol. As a result, a miniaturized black azo pigment press cake was obtained.

The particle diameter of the pigment obtained above was measured by the following method. A transmission electron micrograph (60,000 times) of the obtained black pigment was taken, and the particle size distribution was measured using “image analysis type particle size distribution software Mac-View” (manufactured by Mountec). As a result, the average particle size was 50 nm. Also in other production examples, the average particle diameter of the pigment was measured by the same method as described above.

Further, the press cake obtained above was dried and then pulverized to obtain 3,3′-dimethoxy-biphenylene (4,4 ′-) bis (azo (-1) -2-hydroxy-11H-benzo [a]. A finely divided powder pigment of black pigment having the structure of (carbazole-3-carboxy-p-anisidide) was obtained. Hereinafter, it is referred to as “black pigment-1”.

[Production Example 2] (Production 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, this was coupled with 2-hydroxy-11H-benzo [a] carbazole-3-carboxy-N-benzimidazolone-5-amide (8.17 g, 0.02 mol) to obtain a black azo pigment. A crude pigment was obtained. The yield of the obtained black azo pigment was 10.07 g.

Subsequently, the obtained crude pigment was refined. The method was refined according to Production Example 1 (2) except that the amount of sodium chloride used in (2) described in Production Example 1 was 8 times the amount of 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 25 nm. Moreover, after drying the press cake obtained above, it grind | pulverized and the fine powder powder pigment of the black pigment was obtained. Hereinafter, this is referred to as “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. Then, this was coupled with 7.93 g (0.02 mol) of 2-hydroxy-11H-benzo [a] carbazole-3-carboxy- (2′-methyl) -p-anisidide to obtain a black azo pigment. Of crude pigment was obtained. The yield of the obtained black azo pigment was 10.26 g.

Subsequently, the obtained crude pigment was refined. The refinement | miniaturization process was performed according to (2) described in manufacture example 1 except having used the usage-amount of sodium chloride used in (2) described in manufacture example 1 10 times 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. The press cake obtained above was dried and then pulverized to obtain a finely divided powder pigment of black pigment. Hereinafter, this is referred to as “black pigment-3”.

[Production Example 4] (Production of “Black Pigment-4”)
In the same manner as in Production Example 1 (1), 2.44 g (0.01 mol) of 3,3′-dimethoxy-4,4′-benzidine was diazotized. Then, this was coupled with 7.93 g (0.02 mol) of 2-hydroxy-11H-benzo [a] carbazole-3-carboxy- (2′-methyl) -p-anisidide to obtain a black azo pigment. Of crude pigment was obtained. The yield of the obtained black azo pigment was 9.94 g.

Subsequently, the obtained crude pigment was refined. Refinement treatment was carried out according to (2) described in Production Example 1, and after salt and the like were dissolved in acidic water and filtered, the obtained filtrate was washed with water to obtain a black azo pigment press cake. The average particle diameter of the obtained pigment was 50 nm. The press cake obtained above was dried and then pulverized to obtain a finely divided powder pigment of black pigment. Hereinafter, this is referred to as “black pigment-4”.

[Production Example 5] (Production of “Black Pigment-5”)
In the same manner as in Production Example 1 (1), 2.53 g (0.01 mol) of 3,3′-dichloro-4,4′-benzidine was diazotized. Then, this was coupled with 7.65 g (0.02 mol) of 2-hydroxy-11H-benzo [a] carbazole-3-carboxy-p-anisidide to obtain a crude black azo pigment. The yield of the obtained black azo pigment was 9.86 g.

Subsequently, the obtained crude pigment was refined. A refinement treatment was performed 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 in an amount four times that of 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. The press cake obtained above was dried and then pulverized to obtain a finely divided powder pigment of black pigment. Hereinafter, this is referred to as “black pigment-5”.

[Production Example 6] (Production of “Black Pigment-6”)
In the same manner as in Production Example 1 (1), 2.44 g (0.01 mol) of 3,3′-dimethoxy-4,4′-benzidine was diazotized. Then, this was treated with 3.96 g (0.01 mol) of 2-hydroxy-11H-benzo [a] carbazole-3-carboxy- (2′-methyl) -p-anisidide and 5′-chloro-3-hydroxy- By coupling with 3.58 g (0.01 mol) of 2 ′, 3′-dimethoxy-naphthanylide anilide, a crude black azo pigment was obtained. The yield of the obtained black azo pigment was 9.59 g. Subsequently, the black azo pigment crude pigment obtained above was pulverized with a dry pulverizer to obtain a finely divided powder pigment of black pigment. The average particle diameter of the obtained pigment was 110 nm. Hereinafter, this is referred to as “black pigment-6”.

[Production Example 7] (Production of “Black Pigment-7”)
(1) Production of Black Pigment Derivative-1 1.73 g (0.01 mol) of sulfanilic acid was diazotized. This was then coupled with 3.82 g (0.01 mol) of 2-hydroxy-11H-benzo [a] carbazole-3-carboxy-p-anisidide. And after filtering the obtained product, it washed with water and the press cake of the black pigment derivative which has a sulfone group was obtained. Hereinafter, this is referred to as “press cake of black pigment derivative-1”. The yield of the obtained press cake was 5.49 g in terms of solid content. The press cake was dried and pulverized to obtain a fine powder pigment of a pigment derivative having a sulfone group. Hereinafter, this is referred to as “black pigment derivative-1”.

(2) (Production of “Black Pigment-7”)
The black pigment-1 press cake obtained in (1) described in Production Example 1 and the black pigment derivative-1 press cake obtained in (1) above have a pigment solid content ratio of 10: 1. And mixed well so as to be uniform. And the crude pigment of the black pigment containing a pigment derivative was obtained by drying the said mixture. Next, the pigment was refined in accordance with (2) described in Production Example 1, and then the salt and the like were dissolved with acidic water, and this was filtered. A pigment presscake 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 pigment of a black pigment containing an anionic pigment derivative. Hereinafter, this is referred to as “black pigment-7”.

[Production Example 8] (Production 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 at 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 black pigment-1 obtained in Production Example 1 (1) were blended so that the solid content ratio was 85:15. These were mixed sufficiently to be uniform and then dried to obtain a black pigment crude pigment containing a cationic pigment derivative. Next, the obtained crude pigment is subjected to a fine treatment according to the method of (2) described in Production Example 1, and then filtered by dissolving a salt and the like with water and washing the filtrate with water. An azo pigment presscake was obtained. The average particle diameter of the obtained pigment was 50 nm. The obtained press cake was dried and then pulverized to obtain a finely divided powder pigment of a black pigment containing a cationic yellow pigment derivative. Hereinafter, this is referred to as “black pigment-8”.

[Production Example 9] (Production of “Black Pigment-9”)
In the same manner as in Production Example 1 (1), 1.95 g (0.008 mol) of 3,3′-dimethoxy-4,4′-benzidine was diazotized, and then borohydrofluoric acid was added to tetrazonium-fluoride. Boron double salt (diazonium salt) was prepared. Separately from this, 0.69 g (0.004 mol) of sulfamic acid was diazotized. These two kinds of diazo liquids were combined with 7.65 g (0.02 mol) of 2-hydroxy-11H-benzo [a] carbazole-3-carboxy-p-anisidide, and the above two kinds of diazo liquids were combined. Coupling was performed while adjusting so that the dripping was completed almost simultaneously. Then, it filtered and washed with water and obtained the press cake of the black azo pigment. The obtained press cake was dried to obtain a black pigment (crude pigment) containing a black pigment derivative having a sulfone group. The yield of the obtained black pigment was 9.97 g. Then, the refinement | purification process of the obtained crude pigment was performed. Specifically, after performing the refinement treatment according to the method (2) described in Production Example 1, the salt and the like are dissolved in acid water and filtered, and the obtained filtrate is washed with water and washed with black azo A pigment presscake was obtained. The average particle diameter of the obtained pigment was 50 nm. The press cake was dried and then pulverized to obtain a finely divided powder pigment of black pigment. Hereinafter, this is referred to as “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 to give 1,4-phenylene-bis (2-hydroxy-11H-benzo [A] Carbazole-3-carboxamide) was coupled with 6.27 g (0.01 mol) to obtain a black azo pigment crude pigment. Yield is 10.35 g. Subsequently, it was pulverized by a dry pulverizer to obtain a finely divided powder pigment of black pigment. Hereinafter, it is referred to as “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 observe the optical characteristics of the black pigment-1 obtained in Production Example 1, a black coating solution 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 mg KOH / g) and a 50% xylene-butanol mixed solvent solution of a butylated methylol melamine resin are in a ratio of 80:20. To prepare a varnish. (Hereinafter, this is referred to as “varnish”.) As a diluting solvent, a mixed solvent of xylene-butanol (4: 1) was used. (Hereinafter, this is referred to as “diluting solvent”.)

3 parts of black pigment-1, 24 parts of varnish, 6 parts of diluting solvent and 48 parts of glass beads as a dispersion medium were charged in a dispersion container and dispersed with a paint shaker for 3 hours. Thereafter, 36 parts of varnish was further added and dispersion was continued for 10 minutes. The ratio of pigment content to resin solid content in the coating solution is 1:10. The black coating solution obtained as described above was coated on a polyethylene terephthalate (PET) film using a bar coater, dried and then cured at 130 ° C. to obtain a black coated PET film. The average dry film thickness of the formed black coating film was 34 nm.

(2) Measurement of transmittance in visible region and near-infrared region The black coated PET film obtained in (1) above was measured with a Hitachi spectrophotometer (U-4100, manufactured by Hitachi, Ltd.) in the visible region and near red region. External transmittance was measured. Tables 4 and 5 show the measurement results in the respective regions.

As shown in the measurement results of spectral transmittance in Tables 4 and 5, the coating film containing Black Pigment-1 has a spectral transmittance of 0% over the entire wavelength region of 400 to 750 nm in the visible light region. It was confirmed that almost no transmission occurred (see Table 4). On the other hand, in the infrared region, the transmittance at 900 nm was approximately 34%, and it was confirmed that the transmittance gradually increased on the longer wavelength side (see Table 5).

(3) Further, the black coating on the PET film obtained in the above (1) was subjected to volume-specification using a high resistivity meter Hiresta UP (Hiresta-UP) [manufactured by Mitsubishi Chemical Analytech Co., Ltd.]. Resistance was measured. The measurement result showed 10 ¹⁴ Ω · cm or more, and it was confirmed that the insulation was very high.

[Example 2] (Evaluation of light reflection characteristics of coating film containing black pigment-1 of Production Example 1)
(1) Preparation of black colored paper using black pigment-1 In order to see the reflection characteristics of black pigment-1, the black coating solution prepared in (1) described in Example 1 was used with a 6 mil applicator. After coating on white color paper, it was dried and cured to obtain a black color paper (hereinafter referred to as black color paper) formed by forming a coating film. The measured value of the dry film thickness of the black coating film formed on the black color developed paper was approximately 35 to 40 nm on the color developed paper.

(2) The reflectance of the visible part and the near-infrared part in the black color paper obtained in (1) above was measured, and Table 6 shows the measurement results.

From the results shown in Table 6, the black color paper produced using the black pigment-1 shows only a reflectance of 5 to 6% up to about 750 nm, but the reflectance increases rapidly from 800 nm to 900 nm. Further, it was confirmed that the reflectance of approximately 70% to 80% or more was maintained in the near infrared region on the longer wavelength side. For these reasons, the light reflectance of the black color developed paper is high because the reflected light is reflected by the base white paper together with the reflection from the pigment surface, and the resulting light is added to become reflected light. It is considered a thing. Therefore, it is shown that near infrared rays can be efficiently reflected by increasing the light transmittance of the black pigment and using a highly reflective base. In Table 6 above, the reflectance is not 0% up to about 750 nm but a value of 5% because of the relationship with the measuring apparatus.

[Example 3]
(1) In the same manner as in Example 1, black pigments 2 to 6 obtained in Production Examples 2 to 6 were respectively used to prepare black coating films. The spectral transmittance of the outer region was measured. Tables 7 and 8 show the results.

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

[Example 4] (Polycarbonate resin molded plate)
After 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), they were further mixed and kneaded with a twin screw extruder, A polycarbonate resin black masterbatch containing 20% of black pigment-2 was prepared. 2 parts of the obtained black masterbatch was mixed with 100 parts of polycarbonate resin pellets made of the same resin powder as described above, mixed with a Henschel mixer, then mixed and kneaded with a twin screw extruder to obtain black resin pellets. . The obtained black resin pellet was molded by an in-line screw injection molding machine to obtain a black polycarbonate resin plate excellent in pigment dispersibility. Since this black resin plate absorbs light in the visible light region and can sufficiently transmit near infrared rays, it can be used for applications such as an infrared transmission filter.

[Example 5] (Acrylic resin molding 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 acrylic resin (polymethyl methacrylate) powder were sufficiently mixed with a Henschel mixer, and then further biaxial extrusion kneading. Mixing and kneading with a machine, an acrylic resin black masterbatch containing 20% of black pigment-3 was prepared.
After blending 2 parts of the obtained black masterbatch into 100 parts of acrylic resin pellets made of the same resin as described above, the mixture was further mixed with a Henschel mixer, and further mixed and kneaded with a twin-screw extrusion kneader. It was. The obtained black resin pellet was molded by an in-line screw injection molding machine to obtain a black acrylic resin plate excellent in pigment dispersibility. Since this black resin plate absorbs light in the visible light region and can sufficiently transmit near infrared rays, it can be used as an infrared transmission filter.

[Example 6] (Polyurethane coating agent)
15 parts of black pigment-4 prepared in Production Example 4, 10 parts of polycarbonate non-yellowing polyurethane resin, and 75 parts of dimethylformamide (hereinafter referred to as “DMF”) are mixed with black pigment and non-yellowing polycarbonate. A modified polyurethane resin solution, DMF, is prepared. This prepared liquid was sufficiently dispersed with a horizontal continuous medium disperser to obtain a black pigment high-concentration dispersion. Next, for the formation of the skin layer, 100 parts of a polycarbonate non-yellowing polyurethane resin solution (solid content 30%, DMF solvent), 10 parts of propyl acetate and 10 parts of isopropanol as dilution solvents, 20 parts of the concentration dispersion was added and mixed to prepare a black polyurethane coating solution.

Next, the black coating solution prepared above was applied to a release paper DNTP-155T-FLAT (trade name, manufactured by Dai Nippon Printing Co., Ltd.) so as to have a film thickness of 50 μm, and then 100 ° C./10 minutes. It was dried under conditions to form a skin layer. Next, as an adhesive, 100 parts of a polycarbonate-based yellowing polyurethane resin solution (solid content 70%, toluene: methyl ethyl ketone (hereinafter referred to as “MEK”) = 1: 1 solvent), 10 parts of toluene as a diluting solvent, 20 parts of MEK A mixture of 20 parts of DMF, 10 parts of a modified polyisocyanate crosslinking agent (solid content 75%, ethyl acetate solvent) and 0.15 part of an amine crosslinking catalyst (solid content 0.5% MEK solvent) was prepared. . And after apply | coating this adhesive agent in the sheet form so that it might become a film thickness of 75 micrometers on the surface of a skin layer (surface on the opposite side to the surface which is in contact with release paper), it was dried on condition of 80 degreeC / 5 minutes. The obtained sheet having the adhesive layer and the skin layer is laminated on the base material (woven fabric) on the adhesive layer side to obtain a laminate having a total thickness of 1,100 μm, and the obtained laminate is heated to 100 ° C. The laminate roll was pressed and adhered with a gap of 500 μm. Next, after aging at 60 ° C./48 hours, the product was peeled from the release paper to obtain a synthetic artificial leather. The obtained synthetic artificial leather is excellent in durability such as heat deterioration resistance, hydrolysis deterioration resistance, light deterioration resistance, oleic acid resistance, etc. in addition to reduction (reduction) of heat storage, and is suitable for vehicle use etc. It was a thing.

Further, the adhesive used above is colored white by containing a white pigment, thereby giving the adhesive layer light reflectivity and exhibiting both visible light shielding properties and infrared transmittance optical properties. When a double structure consisting of a skin layer containing a pigment was formed, a polyurethane synthetic leather capable of reflecting heat rays was obtained. This synthetic leather is particularly suitable for applications such as automobile interiors.

[Example 7] (Stock solution colored spinning)
50 parts of black pigment-5 prepared in Production Example 5 and 50 parts of ethylenebisstearic acid amide powder as a pigment dispersant were mixed with a Henschel mixer to obtain a powder colorant (dry color) having a pigment content of 50%. Obtained. Next, 1.0 part of the obtained dry color was blended in 99.0 parts of polypropylene resin pellets, mixed with a Henschel mixer, and further kneaded with a vent type 40 m / m extruder, so that the pigment content was 0. A 5% black resin pellet 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 a fineness of 10 denier and excellent pigment dispersibility. Since the woven fabric made using this colored yarn can reflect the heat rays of direct sunlight, the effect of avoiding the temperature rise is expected. Therefore, it is particularly suitable for uses such as parasols and curtains.

[Example 8] (Resin molding)
5 parts of black pigment-6 prepared in Production Example 6, 20 parts of titanium oxide white pigment, and 75 parts of polyethylene resin powder as a pigment dispersant were mixed with a Henschel mixer to obtain a powder colorant (dry color). It was. Next, 1.0 part of the obtained powder colorant was blended in 100 parts of polybutylene terephthalate (PBT) resin pellets, mixed with a Henschel mixer, and then kneaded with an extruder to obtain black resin pellets. The obtained black pellet was molded with an in-line screw injection molding machine to obtain a black PBT resin molded plate excellent in pigment dispersibility. The obtained resin molded board was able to reflect the heat rays of direct sunlight. For this reason, this resin is suitable for use as a molded resin product in which it is desirable to avoid an increase in temperature.

[Example 9] (Heat-shielding back sheet for photovoltaic module)
(1) 15 parts of black pigment-4 prepared in Production Example 5, 15 parts of an acrylic polyol (hydroxyl value: 100) butyl acetate solution (solid content 50%), and 50 parts of butyl acetate were sufficiently premixed and dispersed. A black pigment high-concentration dispersion was prepared by dispersing the pigment using a horizontal continuous medium disperser using glass beads as a medium.
Acrylic polyol (hydroxyl value: 100) butyl acetate obtained by copolymerizing 22 parts of an acrylic polyol butyl acetate solution similar to the above, benzotriazole monomer and HALS monomer in 90 parts of the black pigment high-concentration dispersion obtained above. 50 parts of the solution was added to make a black ink. Then, 24 parts of isocyanurate type hexamethylene diisocyanate trimer (solid content: 100%, isocyanate%: 21.7%) as a curing agent was added to this black ink and mixed well, and then butyl acetate was added. Approximately 20 parts were added to adjust the viscosity to prepare a black coating solution.

(2) 40 parts of acrylic polyol butyl acetate solution used in (1) above and 20 parts of butyl acetate used in (1) above are premixed in 80 parts of titanium oxide white pigment, and then the same horizontal continuous as used in (1) above. A white pigment high-concentration dispersion was prepared by dispersing the pigment with a medium disperser.
To 140 parts of the white pigment high-concentration dispersion obtained above, 44 parts of an acrylic polyol butyl acetate solution was added to obtain a white ink. Then, 18 parts of the same hexamethylene diisocyanate trimer used previously as a curing agent was added to this white ink, and after mixing well, approximately 40 parts of butyl acetate was added to adjust the viscosity. A white coating solution was prepared.

(3) The black coating solution prepared in (1) above is applied to the surface of a polyethylene terephthalate (PET) substrate sheet (film thickness: 100 μm), dried, and a black coating film (dry film thickness: 5 μm) Formed. Furthermore, the white coating liquid obtained in the above (2) is applied to the back surface of the base material and dried to form a white coating film (dry film thickness: 5 μm). A black-white multilayer PET sheet obtained by applying a white coating film to the film was obtained.

(4) In order to further impart water vapor barrier property and gas barrier property to the black-white multilayer PET sheet obtained in the above (3), a silica / alumina-deposited polyester film (film) (Thickness: 12 μm) was laminated, and a PET substrate sheet (film thickness: 100 μm) was further laminated thereon to produce a PET back sheet for a photovoltaic power generation module. The following adhesives were used for the above lamination. As the adhesive, an adhesive composed of 70 parts of the same acrylic 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 coated with the black coating film and the white coating film obtained as described above is excellent in aesthetics because of its black appearance, and the optical characteristics of the black pigment-4 used. To have the following optical properties. That is, the infrared light of sunlight passes through the black coating layer on the surface, and the transmitted infrared light is reflected by the white layer of the base and passes through the black layer again to the outside. Radiated. Therefore, the back sheet hardly absorbs sunlight and exhibits excellent heat shielding properties. Therefore, the back sheet is particularly suitable as a back sheet for a photovoltaic power generation module that is desired to avoid a temperature rise.

When the backsheet obtained above is used as a photovoltaic power generation module, it may be used as follows according to 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 pasted on the surface on the light receiving surface side, and the above-described light shielding is used as a protective sheet on the non-light receiving surface side on the back surface. A solar power generation module can be produced by attaching a transparent glass substrate to the light receiving surface after bonding the black surface of the conductive back sheet toward the light receiving side.

[Example 10] (Heat-shielding back sheet for photovoltaic module)
(1) 40 parts of the black pigment-6 obtained in Production Example 6 and 60 parts of polyester resin powder were mixed with a Henschel mixer to obtain a powdery colorant. Next, 12.5 parts of the obtained powdery colorant was blended in 87.5 parts of PET resin pellets, mixed with a Henschel mixer, then kneaded with a twin screw extruder, and made into black resin pellets with a pelletizer. Subsequently, it was molded by a T-die extruder to prepare a black PET film having a film thickness of 50 μm.

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

(3) In order to impart moisture resistance and gas barrier properties to the white PET sheet obtained by laminating the black PET film obtained above, first, the acrylic polyol-hexamethylene used in (2) above on the back surface of the sheet A silica / alumina-deposited polyester film was laminated using a diisocyanate adhesive. And the back sheet | seat for photovoltaic power generation modules was created by laminating | stacking a PET base material sheet (film thickness: 100 micrometers) on it using the adhesive agent same as having mentioned above.

The back sheet for a photovoltaic power generation module using the sheet obtained by laminating the black film and the white PET sheet obtained above is black in appearance and excellent in aesthetics, and from the optical characteristics of the used black pigment-6, It has the following optical properties. That is, infrared light of sunlight passes through the black film layer on the surface, is reflected by the lower white PET sheet, passes through the black film again, and is emitted to the outside. Therefore, the black-white multi-layer PET sheet is a back sheet for a photovoltaic power generation module that absorbs less sunlight and exhibits excellent heat shielding properties. Particularly preferred.

When the backsheet obtained above is used as a photovoltaic power generation module, it may be used as follows according to 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 pasted on the surface on the light receiving surface side, and the above-mentioned light shielding as a protective sheet on the non-light receiving surface side on the back surface. A solar power generation module can be produced by attaching a transparent glass substrate to the light receiving surface after bonding the black surface of the conductive back sheet toward the light receiving side.

[Example 11] (Printing paste for woven fabric)
After fully premixing 71 parts of a press cake containing 25 parts of the solid content of the black pigment-1 obtained in Production Example 1, 10 parts of a nonionic pigment dispersant, 1 part of an antifoaming agent, and 18 parts of water, as a dispersion medium The pigment was dispersed with a horizontal continuous medium disperser using glass beads to prepare a black pigment high-concentration dispersion (black color base). 20 parts of the obtained black color base, 25 parts of reactive alkyl acrylate ester latex (solid content 40%), 0.5 part of antifoaming agent, 1 part of dispersing agent, 3 parts of dispersion stabilizer for oil-in-water emulsion type, mineral 38 parts of terpenes and 12.5 parts of water were emulsified and dispersed with a homogenizer (strong emulsifying disperser) to prepare an oil-in-water black emulsion paste. Then, 2 parts of a carbodiimide-based crosslinking agent (solid content: 40%) was added to the prepared black emulsion paste and mixed well to prepare a black printing paste. The obtained black printing paste was printed on the entire surface of a polyester-cotton blended fabric and cured at 120 ° C. for 15 minutes to obtain a black plain printed fabric in which heat rays were shielded.

[Example 12] (gravure printing ink)
11 parts of the black pigment-10 obtained in Production Example 10 and 30 parts of a 40% methyl ethyl ketone-toluene (1: 3) mixed solvent solution of a polyurethane resin in which the isocyanate-terminated polyester was chain-extended with diamine were added. Next, 2 parts of a cationic polymer dispersant, 2.5 parts of a 40% toluene solution of a polycarbodiimide compound from tolylene diisocyanate, and 54.5 parts of a mixed solvent of methyl ethyl ketone-toluene-isopropyl alcohol (50:30:20) And thoroughly mixed with a high-speed stirrer. Then, the above mixture was finely dispersed with a horizontal continuous medium disperser using glass beads as a dispersion medium to prepare a black gravure printing ink. The resulting black gravure printing ink is printed on a polyamide film, a polyester film, and a polypropylene film by using a gravure printing machine, respectively, and a black polypropylene film that exhibits optical characteristics of shielding visible light and transmitting infrared light. Got.

Example 13 (Formation of CF BM)
(1) (Preparation of pigment dispersion for BM)
(Preparation of black pigment dispersion)
25 parts of the black pigment-9 obtained in Production Example 9 and a 40% solution of benzyl methacrylate-methacrylic acid-2-hydroxyethyl methacrylate copolymer (molar ratio: 60:20:20, weight average molecular weight 30,000). 20 parts, 2 parts of a cationic polymer dispersant and 53 parts of propylene glycol monomethyl ether acetate (PGMA) were sufficiently premixed. Next, the pigment was finely dispersed using a continuous horizontal medium disperser to obtain a black pigment dispersion (hereinafter referred to as “black pigment dispersion-1”).

(2) (Preparation of photosensitive black resist ink)
40 parts of black pigment dispersion-1 obtained in (1) above, 6 parts of 50% PGMA solution of acrylated acrylic polyol photosensitive resin, 1 part of trimethylolpropane triacrylate, and 1 part of dipentaerythritol hexaacrylate Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (“Irgacure OXE02”, BASF) as a photopolymerization initiator 1 part) and 51 parts of PGMA were blended. Thereafter, the mixture was sufficiently stirred with a high-speed stirrer and filtered through a filter having a pore size of 3 μm to prepare a black resist ink containing black pigment-9 (hereinafter referred to as “photosensitive black resist ink-1”). Called).

(3) (Evaluation of black resist film)
The photosensitive black resist ink-1 obtained above was applied onto a glass substrate with a spin coater. Then, after preliminary drying at 60 ° C., pre-baking is performed, and exposure is performed with a light amount of 400 mJ / cm ² using an ultrahigh pressure mercury lamp, followed by post-baking at 230 ° C. for 30 minutes, and a black having a thickness of 3 μm. A coating film (black resist ink film) was obtained.
As shown in Table 10, the optical properties of this coating film showed high absorbency in the wavelength range of approximately 400 to 750 nm in the visible light region and high transmittance in the infrared region of 900 to 1500 nm. In addition, the volume resistivity of the coating film was 10 ¹⁴ Ω · cm or more, so that it was confirmed to be highly insulating.

(4) (Preparation of BM pattern)
The photosensitive black resist ink-1 obtained above was applied onto a glass substrate by a spin coater according to a conventional method, and prebaked at 80 ° C. for 10 minutes to obtain a black coating film having a thickness of 3 μm. This coating film was exposed to light of 100 mJ / cm ² through a BM pattern negative photomask pattern using an ultrahigh pressure mercury lamp, then developed with an alkaline developer, washed with water and dried to form a BM pattern. Formed.
Since the BM film forming the BM pattern obtained above exhibits high electrical insulation as described in (3) above, various CF improvement methods for forming a BM on an active element such as a TFT For example, it can be used for the construction of a BM, IPS system, COA system, etc. that retains the thickness of the liquid crystal layer instead of the spacer. Further, since the BM film can sufficiently absorb the visible region up to the long wavelength region, it can also be used as a BM of an LCD panel employing an LED backlight.

(5) (Preparation of red, green, blue, yellow and purple pigment dispersions)
Similar to (1) described above, PR254 (diketopyrrolopyrrole red pigment), PR177 (anthraquinone red pigment), PG36 (copper phthalocyanine green pigment), PB15: 6 (ε-type copper phthalocyanine blue pigment) , PY138 (yellow pigment) and PV23 (dioxazine violet pigment), and 1 part of a pigment derivative having a known sulfone group corresponding to each pigment is added to 19 parts of the pigment, and the pigment of each color A composition was obtained. Using the obtained pigment composition, pigment dispersions of red, green, blue, yellow, and purple colors each having a pigment content of 20% and a resin dispersant of 6% were prepared.

Next, 33 parts of the pigment dispersion containing PR254 and PR177 prepared above were blended at a ratio of 8: 2, and the photosensitive resin 50 was prepared in the same manner as in (2) described above. A red resist ink was prepared by adding 9.2 parts% solution, 3 parts photopolymerizable monomer, 0.3 part photopolymerization initiator, and 54.5 parts solvent. In the same manner as above, a pigment dispersion containing PG36 and PY138 is blended at a ratio of 5: 5 to give a green resist ink, and 8 pigment dispersions containing PB15: 6 and PV23, respectively. : Blue resist inks were prepared by blending at a ratio of 2.

(6) (Formation of CF RGB pixels)
The glass substrate on which the BM formed in the above (4) was formed was set on a spin coater, the photosensitive red resist ink prepared above was spin coated, and then prebaked at 80 ° C. for 10 minutes. And the photomask which has a mosaic pattern was exposed by the light quantity of 100 mJ / cm < ² > with the ultrahigh pressure mercury lamp on the application surface of this glass substrate using the 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. Further, in the same manner as described above, a green mosaic pattern is formed using the photosensitive green resist ink, and a blue mosaic pattern is formed using the photosensitive blue resist ink. A formed CF was obtained.

Further, a photosensitive black resist ink was prepared in the same manner as described above except that the black pigment-7 obtained in Production Example 7 was used instead of the black pigment-9 used above, and the BM pattern described above was prepared. And RGB pixel pattern was formed, and CF with BM and RGB pixels was obtained.

Example 14 (Formation of CF BM)
(1) (Preparation of pigment dispersion for BM)
(Preparation of black pigment dispersion)
As in Example 13 (1), 25 parts of black pigment-8 instead of black pigment-9, 40% of the same benzyl methacrylate-methacrylic acid-2-hydroxyethyl methacrylate copolymer as used previously After sufficiently premixing 25 parts of the solution and 53 parts of propylene glycol monomethyl ether acetate (PGMA), the pigment was dispersed with a continuous horizontal medium disperser to obtain a black pigment dispersion. Hereinafter, this is referred to as “black pigment dispersion-2”.

(2) (Preparation of photosensitive black resist ink)
The same procedure as in Example 13 (2) was conducted except that the black pigment dispersion liquid-2 obtained in (1) above was used instead of the black pigment dispersion liquid-1 in (2) described in Example 13. A black resist ink was prepared. Hereinafter, this is referred to as “photosensitive black resist ink-2”.

(3) (Preparation of BM pattern)
In the same manner as (4) described in Example 13, photosensitive black resist ink-2 was applied onto a glass substrate with a spin coater and prebaked to obtain a black coating film having a thickness of 3 μm. . This coating film was exposed using a super 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 forming this BM pattern has high electrical insulation, as in Example 13, various CF improvement methods for forming BM on the active element, for example, BM as a fixed spacer It can be used for construction, construction of IPS system, COA system and the like. Further, since the visible region can be sufficiently absorbed up to the long wavelength region, it can also be used as a BM of an LCD panel employing an LED backlight.

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

[Evaluation results]
The CFs obtained in Examples 13 and 14 had excellent quality in terms of color characteristics and optical characteristics of image performance such as definition, color density, light transmittance, and contrast.

Claims

A black azo pigment having optical properties of both visible light shielding properties and infrared ray transmissive properties, comprising at least one azo bond in the molecule and at least one 2-hydroxy-11H-benzo introduced from a coupling component [A] A black polyazo pigment having a structure having a carbazole-3-carboxylic acid amide residue, and having an average particle diameter of 10 nm to 200 nm.
The visible light shielding property is that a black colored film containing a black azo pigment on a transparent substrate exhibits a spectral transmittance of about 5% or less in a wavelength range of about 400 to 750 nm in the visible light range. The black azo pigment according to claim 1, wherein the external transparency is that the black colored film has a transmittance of about 30% or more in a wavelength range of 900 to 1500 nm in the infrared region.
The black azo pigment according to claim 1 or 2, wherein the structure of the polyazo pigment has at least one of the following structures (1) to (4).
(1) A diazonium salt obtained by diazotizing a compound having two or more amino groups as a diazo component (representative formula: H 2 N—Ar—NH 2 ) is used, and 2-hydroxy as a coupling component is used as the coupling component. A structure represented by [HBC-N═N—Ar—N═N—HBC] formed by azo coupling of -11H-benzo [a] -carbazole-3-carboxylic acid arylamide (abbreviated as HBC) (2 ) A diazonium salt obtained by diazotizing a compound having 2 or more amino groups as a diazo component (representative formula: H 2 N—Ar—NH 2 ) is used, and 2-hydroxy- 11H-benzo [a] -carbazole-3-carboxylic acid arylamide (abbreviated as HBC) and other coupling components (denoted as Cp) other than the compound were azo-coupled. [HBC-N═N—Ar—N═N—Cp] (3) In the molecule, 2-hydroxy-11H-benzo [a] -carbazole-3-carboxamide residue (HBC- and A compound having one amino group as a diazo component (indicated as Ar-NH 2 ) is used as a diazo component for a coupling component having two or more (abbreviated)) (indicated as Ar-NH 2 ) and azo-coupled. [Ar-N = N-HBC-HBC-N = N-Ar] (4) In the molecule, 2-hydroxy-11H-benzo [a] -carbazole-3-carboxamide residue (HBC A compound having a single amino group as a diazo component in a coupling component (denoted as HBC-Cp) having a coupling component residue other than the compound (denoted as Cp-) a structure represented by [Ar—N═N—HBC—Cp—N═N—Ar] obtained by diazotizing and azo coupling the compound (denoted r—NH 2 ).
The black azo pigment according to claim 3, wherein any one of the coupling component and the diazo component is selected from the following.
(Aa) the coupling component (HBC) is 2-hydroxy-11H-benzo [a] -carbazole-3-anilide, 2-hydroxy-11H-benzo [a] -carbazole-3-naphthylamide and the like (Ab) The coupling component (HBC-HBC) is phenylene-bis (2-hydroxy-11H-benzo [a] -carbazole-3-carboxamide), biphenylene-bis (2-hydroxy-11H- Benzo [a] -carbazole-3-carboxamide), naphthalene-bis (2-hydroxy-11H-benzo [a] -carbazole-3-carboxamide) and their derivatives (Ac) and the coupling component (Cp) 2-hydroxy-3-naphthoic acid arylamide, 2-hydroxy-6-naphthoic acid arylamide Amide, 2-hydroxy-3-anthracenecarboxylic acid arylamide, 2-hydroxy-3-dibenzofurancarboxylic acid arylamide, 2-hydroxy-1-carbazolecarboxylic acid arylamide and their derivatives (Ad) said 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-H Proxy-3-naphthoic acid amide) and derivatives thereof (B-a) a compound having two amino groups used as the diazo component (H 2 N-Ar-NH 2) is phenylene diamine, diamino biphenyl, diamino Naphthalene, diaminoanthraquinone, diamino-benzophenone, diaminopyridine and derivatives thereof (BB) The compound having one amino group used as the diazo component (Ar—NH 2 ) is aniline, naphthylamine, aminoanthraquinone , Phenoxyaniline, phenyliminoaniline and their derivatives
A method for producing a black azo pigment according to any one of claims 1 to 4, comprising a step of synthesizing a black polyazo pigment and a step of refining the pigment as necessary,
(I) The method for synthesizing the black polyazo pigment is any one of the following (1) to (4):
(1) A diazonium salt obtained by diazotizing a compound having two or more amino groups (representative formula: H 2 N—Ar—NH 2 ) into 2-hydroxy-11H-benzo [a] -carbazole-3-carboxylic acid Synthesis method of azo coupling arylamide (abbreviated as HBC) (2) A diazonium salt obtained by diazotizing a compound having two or more amino groups (representative formula: H 2 N—Ar—NH 2 ) Synthesis of polyazo pigments having a structure in which hydroxy-11H-benzo [a] -carbazole-3-carboxylic acid arylamide (abbreviated as HBC) and other coupling components (denoted as Cp) other than the compound are azo-coupled a method, a compound having two or more amino groups (the representative formula: H 2 N-Ar-NH 2) to the diazonium salt obtained by diazotizing an equimolar or its The following coupling component (Cp) is azo-coupled, and if necessary, the polyazo pigment coupled with two or more coupling components (Cp) is separated and removed, and then an uncoupled diazonium group Synthetic method for azo coupling the above coupling component (HBC) (3-1) 2-hydroxy-11H-benzo [a] -carbazole-3-carboxamide residue (abbreviated as HBC-) in the molecule 2 A synthesis method (3-2) in which a diazo component obtained by diazotizing a compound having one amino group (Ar—NH 2 ) is azo-coupled to a coupling component having two or more (indicated as HBC-HBC) 2- Hydroxy-11H-benzo [a] -carbazole-3-carboxylic acid having a single amino group (indicated as Ar—NH 2 ) Method of synthesizing diazonium salt formed by azotization, then condensing carboxylic acid of azo dye with aryl polyamine to form polycarboxamide (4-1) 2-hydroxy-11H-benzo in one molecule A coupling component (denoted as HBC-Cp) having a [a] -carbazole-3-carboxamide residue (abbreviated as HBC-) and another coupling component residue (denoted as Cp-) other than the compound; Synthesis method of azo coupling a diazonium salt obtained by diazotizing a compound having one amino group (indicated as Ar—NH 2 ) (4-2) 2-hydroxy-11H-benzo [a] -carbazole-3 A diazotized compound obtained by diazotizing a carboxylic acid and a carboxylic acid of another coupling component each with a compound having one amino group (indicated as Ar—NH 2 ) Azonium salt is azo-coupled, and then synthesized by a synthesis method selected from the group consisting of synthesis methods in which the carboxylic acids of both azo dyes obtained are condensed with an aryl polyamine to form a polycarboxamide,
and,
(II) When the polyazo pigment synthesized by the above method is coarse, the step of refining the average particle diameter of the pigment to 10 nm to 200 nm by any of the following methods (1) or (2) A method for producing a black azo pigment, comprising:
(1) Any one selected from the group consisting of a ball mill, a sand mill, an attritor, a horizontal continuous medium disperser, a kneader, a continuous uniaxial kneader, a continuous biaxial kneader, a triple roll and an open roll continuous kneader. Method of miniaturization using pigment grinder or pigment disperser (2) Salt milling method in which kneading and grinding with water-soluble salt and water-soluble organic solvent as required in kneader
A pigment component containing the black azo pigment according to any one of claims 1 to 4 or the black azo pigment obtained by the production method according to claim 5 is contained in a liquid dispersion medium or a solid dispersion medium. Coloring composition.
The pigment component containing the black azo pigment is composed of the black azo pigment alone, or a chromatic pigment, a white pigment, another black pigment, and an extender pigment for correcting the black azo pigment to the black azo pigment. The coloring composition according to claim 6, which is used in combination with one or more pigments selected from the group for dark chromatic coloring, achromatic dark coloring or black coloring.
A method in which the blending ratio of the black azo pigment and the chromatic pigment, white pigment, other black pigment or extender pigment for correcting the black azo pigment is optimized using a computer color matching system. The colored composition according to claim 7, which has been determined.
The liquid dispersion medium is at least one film formed selected from a polymer that may have a reactive group, an oligomer that may have a reactive group, and a monomer that may have a reactive group. 7. A coloring composition according to claim 6, which comprises a material and is itself liquid or further contains a solvent and / or water.
The colored composition according to claim 6, wherein the solid dispersion medium contains at least one solid dispersion medium selected from a thermoplastic resin, a thermosetting resin, a wax, a fatty acid amide, and a fatty acid metal soap.
11. The color composition according to claim 6, wherein the coloring composition is used for at least one of paint, coating agent, plastic, fiber, printing ink, stationery, image recording, and image display. The coloring composition according to item.
A method for coloring an article, wherein the coloring composition according to claim 7 is used when the article is colored black or dark by coloring the surface of the article or by coloring the article itself.
The article comprises a transparent substrate, and the transparent substrate is selected from painting, painting, dyeing, printing, writing, drawing, inkjet printing, electrophotographic printing, electrostatic printing, or photolithographic printing. 13. The method for coloring an article according to claim 12, wherein the surface is colored by the above method, or the substrate itself is internally colored by a kneading method or an impregnation method.
The surface coloring or internal coloring shows that the colored portion has a spectral transmittance of about 5% or less in the wavelength range of about 400 to 750 nm in the visible light region, and about 30% or more in the infrared region of 900 to 1500 nm. The method for coloring an article according to claim 13, wherein the article made of a transparent base material is formed so as to exhibit transmittance, and has both visible light shielding properties and infrared transmittance properties.
Using an article having light reflectivity for the article itself, or using an article provided with a preformed light-reflective substrate, the colored composition is placed on the surface of the article or the light-reflective substrate. Used for painting, coating, sticking, welding, stacking, undiluted solution coloring, textile printing, dyeing, printing, writing, drawing, ink jet printing, electrophotographic printing, or electrostatic printing, and coloring that shows reflectivity in the infrared region The method for coloring an article according to claim 12.
A colored article, wherein the method for coloring an article according to any one of claims 12 to 15 is applied.
A back sheet for a photovoltaic power generation module in which a black or dark infrared transmissive layer is laminated on a light reflective sheet, wherein the infrared transmissive layer has two or more azo bonds in the molecule. And 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, and having an average particle diameter of 10 nm A backsheet for a solar power generation module comprising a black polyazo pigment having a thickness of ˜200 nm.
The substrate itself having light reflectivity is used as a light reflective sheet, or a substrate provided with a previously formed light reflective base is used as a light reflective sheet, and the surface of these substrates or On the light-reflective substrate, two or more azo bonds in the molecule and at least one 2-hydroxy-11H-benzo [a] -carbazole-3-carboxylic acid amide residue introduced from the coupling component ( A coloring composition containing a black polyazo pigment having a structure having an average particle diameter of 10 nm to 200 nm, and coating, coating, sticking, welding, stacking, printing, inkjet By printing, electrophotographic printing or electrostatic printing, the infrared region is colored to reflect, and a black or dark infrared transmissive layer is formed on the light reflective sheet. Method for producing a backsheet for photovoltaic module, characterized in that the layers.
A black matrix (BM) formed on a color filter (CF) substrate or an organic EL light-emitting substrate has at least one azo bond and at least one introduced from a coupling component in the molecule being 2-hydroxy-11H-benzo It has a structure having [a] -carbazole-3-carboxylic acid amide residue (abbreviated as HBC-), and contains a black polyazo pigment having an average particle diameter of 10 nm to 200 nm. Color display panel.
The color display panel according to claim 19, further comprising a CF substrate or an organic EL light-emitting substrate formed in a state in which a substantially black matrix that is electrically insulating and an electrode are stacked or in contact with each other.