CN103282443B - Black azo pigment and process for production thereof, colored composition, coloring method, and colored articles - Google Patents

Abstract

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

Description

Black azopigment, manufacture method, coloured composition, colorize method and dyed articles class

Technical field

The present invention relates to black azopigment, its manufacture method, coloured composition, colorize method and dyed articles class.More specifically, relate to being presented to utilize and carry out the purposes that absorbs with covering visible region and at region of ultra-red, there is transmissivity and make use of optical characteristics useful in ultrared purposes, there is the black polyazo pigment of ad hoc structure, and then relate to its manufacture method, coloured composition, the colorize method using this coloured composition and dyed articles class.

Background technology

As the black pigment used in the tinting material for coating, printing-ink or plastics etc., be generally carbon black series pigments or iron oxide black pigment etc.These black pigments show black by the light in light absorbing all wavelengths region.Sunlight is hertzian wave, and the light in the region of about 380nm ~ 780nm is as visible ray, and the light in the region of 0.7 μm ~ 2.5 μm that this visible ray of wavelength ratio is long is near infrared ray.Black shows by absorbing the light of the wavelength region of this visible ray, but charcoal blacks not only absorbs visible ray from the results of view, and absorbs the light of near infrared region.

In light, near infrared ray is different from the light of the short wavelengths such as ultraviolet, and almost not having detrimentally affect to human body, is safe light, therefore develops the electronics much utilizing ultrared irradiation, receiving infrared-ray in recent years.Such as, universal in the daily life such as the infrared rays security camera of infrared remote-controlled transmitting machine and main body receiving apparatus thereof the switch in the door lock of electrical equipment, lighting fixtures, warm water toilet, camera and then automobile, engine starter, garage, street corner or Around Buildings or infrared monitor control camera.

In addition, propose the visible ray being equipped with and sending car headlamp simultaneously in patent documentation 1 and make the night viewing device for vehicle of the wave filter of infrared transmission for the projection light of the near infrared light that confirms vehicle front obstacle and blocking visible light.

As the pigment used in the infrared filter of these infrared transmitters, receiving apparatus and the infrared filter of infrared camera etc., expect that display makes the Transmission light of infrared spectral range, the optical characteristics of being blocked completely by the light of visible region have the pigment of the function of the excellent in te pins of durability such as thermotolerance, photostabilization, solvent resistance.

In addition, in recent years, photovoltaic power generation system is attracted attention as green energy resource, popularizes.Form the solar power generation module of photovoltaic power generation system to be installed in by the roof of the place of direct irradiation of sunlight, the vacant lot being particularly arranged on field or outdoor architecture thing or roof etc.But, be sunlighted, absorb light can cause the intensification of solar power generation module, cause the power reduction of generating battery.And then in order to the outward appearance or dirt making electricity generation module becomes not obvious, from aesthetic, be also coloured to black, dark colour, dense colour, according to circumstances this becomes the reason that obvious temperature rises.Therefore, in photovoltaic power generation system, even if expectation is coloured to the coloring system that black also can suppress temperature to rise as far as possible.Propose the solar cell backboard (backsheet) (patent documentation 2) of Han You perylene pigments.

In addition, to improve, comfortableization and energy-conservation from the view point of living environment in recent years, expect to utilize the reflection of sunlight and the heat insulation application that obtains, the exploitation of invisible heat reflecting material is for this purpose expected in a variety of applications where.Such as, the application can enumerating the application use of the roof of the houses such as house, business quarters, warehouse, mansion or buildings or wall, road pavement, the extraneous adornment of automobile or interior finish, boats and ships with etc., and then, agricultural with in also expect lagging material etc., also expect the heat sink material of electronic unit etc. in addition.

In addition, in areas of information technology, along with the fast development of recent Informationization Equipment, liquid-crystal display (below sometimes referred to as " LCD ") is used in all information displaying associate device of the shooting picture etc. of indicating meter, digital camera or pick up camera of display frame, Information Bulletin Board, notice bulletin board, Fumction display plate, marking plate etc. of TV, projector, PC, portable information equipment, watch-dog, auto navigation, portable phone, robot calculator or e-dictionary in many aspects as information displaying component.Meanwhile, expect raising and the cost degradation of the display quality of indicating meter, carried out the quality-improving of colour filter (below sometimes referred to as " CF "), cost cutting.For the CF being equipped on LCD, the chromatic characteristic of the image properties such as tractability, depth of shade, light transmission, comparative, optical characteristics in, require more excellent quality, expect that exploitation has the material of characteristic that can be corresponding with these qualities.

In the CF of LCD, R(is red), G(is green), B(is blue) pixel is arranged in striated, mosaic shape, triangular shape etc., irradiate from back side backlight, make its color development by the mixture of colours that adds of the transmitted light of R, G, B pixel, form image.And then the surrounding along each pixel forms black matrix" (below sometimes referred to as " BM ") with reticulation, is blocked by unwanted light, prevents colour mixture.About colour element, use red pigment, veridian, blue pigments, yellow ultramarine, violet pigment etc., but improve respectively.In addition, as being used for the opacifying property material that blocked completely by the light of the visible region of backlight in BM, from problems such as the carrying capacities of environment of the maximization of substrate size and chromium cpd, changed into the resin B M using black pigment by chromium metal film.

Backlight also reason cold cathode fluorescent tube replaces to photodiode (LED), thus involves the raising of purity of color and the expansion in color rendering region.Following content is proposed: the luminescence of red area is the sharp-pointed light of about 600 ~ 620nm in the backlight of cold cathode fluorescent tube in patent documentation 3, but, as the light from emitting red light portion in the backlight of LED, utilize maximum emission wavelength near 640nm, as the light of emission wavelength range for the wide region of about 540nm ~ 800nm scope.Therefore, as BM, also can by the light of the long wavelength side of visible ray fully shading be considered as prerequisite.

In addition, in the display mode of the pixel of CF, it is also proposed various improvement, accompany therewith, also carry out the improvement of the opacifying property black pigment used in the improvement of BM and then BM.Such as, in order to bring the wide viewing angle of the weakness as LCD in the past, propose to substrate-parallel apply electric field, make liquid crystal layer convert thus the plane conversion mode of display pixel (IPS mode).In addition, increase due to aperture opening ratio in upper black matrix" array way (BOA mode), the color filter array mode (COA mode) forming BM of thin film transistor (TFT), therefore can increase elemental area, and operation sequence, bonding process can be made to operate raising, rationalize.

In addition, in order to particularly realize these modification methods more completely in IPS mode, need interval (cell gap) that the is constant and substrate of maintenance clamping liquid crystal layer accurately.But, in the mode of distribution pearl spacer in the past, be difficult to adjustment unit gap equably.As the method utilizing fixing spacer to realize uniform cell gap herein, propose the thickness that improves BM self or on BM, overlap chromatograph or photoresist oxidant layer bracing member resin and improve the method for supporting of the cell gap of the substrates such as thickness at equal intervals.And then by not using pearl spacer, the reduction of the display quality caused by scattering of light or transmission is also improved (patent documentation 4,5).

These IPS modes or the method such as BOA mode, COA mode of above-mentioned explanation are the methods forming BM on the active components such as TFT, certainly when BM is not electrical insulating property, have TFT to make a mistake the possibility of work.As opacifying property black pigment, normally used charcoal blacks is the pigment that resistance value is low originally, is not suitable for, expects the opacifying property material that electrical insulating property is high as the opacifying property black pigment used in these modes.

To this, propose in patent documentation 6 and carry out coating with the high resin coating of insulativity to the charcoal blacks that oxygen consuming amount specifies thus improve the charcoal blacks (patent documentation 6) of electrical insulating property; Or Patent Document 7 discloses and use by measuring volumetric resistivity value and selected insulativity charcoal blacks or carrying out coating with resin and charcoal blacks that is that improve electrical insulating property forms insulativity BM, be applicable to COA mode.

But charcoal blacks is the material with electroconductibility originally, even if carry out resin-coated as above-mentioned prior art, is also difficult to make insulativity become complete.

And then, propose in patent documentation 8 in the indicating meter of the organic EL employing exploitation recently, in order to prevent from the colour mixture of the adjacent light of self-emission device, improve the distinctiveness of luminescent picture, use BM.

Prior art document

Patent documentation

Patent documentation 1: Japanese Patent No. 4120513 publication

Patent documentation 2: Japanese Unexamined Patent Publication 2007-128943 publication

Patent documentation 3: Japanese Unexamined Patent Publication 2006-148051 publication

Patent documentation 4: Japanese Unexamined Patent Publication 2000-66018 publication

Patent documentation 5: Japanese Unexamined Patent Publication 2002-341332 publication

Patent documentation 6: Japanese Patent No. 3543501 publication

Patent documentation 7: Japanese Patent No. 4338479 publication

Patent documentation 8: Japanese Unexamined Patent Publication 2004-221081 publication

Summary of the invention

The problem that invention will solve

By the above-mentioned fact, expect to develop the black pigment of display as the excellent physical property of pigment, stability and display visible ray opacifying property useful in a variety of applications where and these two kinds of optical characteristics of infrared transmission.Specifically, such as, expect following black pigment, this black pigment is useful in following various uses: the signal transmission block unwanted visible rays, infrared rays being formed and carry out the purposes of the infrared filter of the electronics utilized; The temperature rising caused by sunlight, the multilayer coloring system being provided with infrared transmission black layer on sunlight reflective substrate can be suppressed in the black forming photovoltaic power generation system or dark colored backboard, or as the BM of CF, even if even if also the light of visible region fully can be blocked and form the purposes that BM also maintains high electrical insulating properties, TFT can not make a mistake work on the active component such as TFT in the situations such as the wide LED-backlit in emission wavelength region; And then this black pigment is suitable for for the purposes etc. that visible ray opacifying property in the BM of OLED display is also high, and this black pigment, as pigment, also can expect to have excellent physical property, stability.

Therefore, the object of the present invention is to provide display as the excellent physical property of pigment, stability and also can be suitable in above-mentioned various uses, the manufacture method of the black pigment that shows visible ray opacifying property and these two kinds of optical characteristics of infrared transmission, this pigment, the coloured composition containing this pigment, the colorize method using this coloured composition and dyed articles class.

For solving the means of problem

The present inventor etc. have carried out repeatedly furtheing investigate in order to the object realizing the invention described above, that studies the chemical structure of black pigment dyestuff found that, the wavelength region of the light of absorption is that the light of about 400 ~ 750nm wavelength in the almost whole region of visible region absorbs with high level by the polyazo pigment with the black of ad hoc structure, and then show high transmissivity at the long wavelength side of the infrared spectral range of about 900 ~ 1500nm, and then carry out miniaturization according to the mode that its median size reaches 10nm ~ 200nm, implement pigmenting and the black pigment that obtains is suitable in various uses enumerated supra, thus solve above-mentioned problem, complete the present invention.

Namely, the invention provides a kind of black azo-dye, it is characterized in that, it is for showing the black azo-dye of visible ray opacifying property and these two kinds of optical characteristics of infrared transmission, it is have the polyazo pigment of the black of the structure of at least one 2-hydroxyl-11H-benzo [a]-carbazole-3-carboxylic acid amide residue comprising more than 2 azo bond in the molecule, imported by coupling composition, and its median size is 10nm ~ 200nm.

Optimal way of the present invention can enumerate following black azo-dye.

Described visible ray opacifying property is the black colorant film containing black azo-dye in transparent substrate is the black azo-dye of above-mentioned black colorant film in the transmissivity of the wavelength region display about more than 30% of 900 ~ 1500nm of region of ultra-red in the spectral transmission of the wavelength region display about less than 5% of the about 400 ~ 750nm of visible-range, described infrared transmission property.

The structure of described polyazo pigment at least has the black azo-dye of any one in the structure of following (1) ~ (4).

(1) structure shown in [HBC-N=N-Ar-N=N-HBC], it uses the compound (representative formula: H with more than 2 amino using as diazo component ₂n-Ar-NH ₂) diazonium salt of diazotization, make this salt and 2-hydroxyl-11H-benzo [a]-carbazole-3-carboxylic acid aryl amide (being slightly designated as HBC) as coupling composition carry out azo coupling.

(2) structure shown in [HBC-N=N-Ar-N=N-Cp], it uses the compound (representative formula: H with more than 2 amino using as diazo component ₂n-Ar-NH ₂) diazonium salt of diazotization, make this salt and to carry out azo coupling as 2-hydroxyl-11H-benzo [a]-carbazole-3-carboxylic acid aryl amide (being slightly designated as HBC) of coupling composition and other coupling compositions (being expressed as Cp) except this compound.

(3) structure shown in [Ar-N=N-HBC-HBC-N=N-Ar], it uses to have 1 amino compound and (be expressed as Ar-NH ₂) carry out diazotization as diazo component after, carry out azo coupling with the coupling composition (being expressed as HBC-HBC) in the molecule with more than 2 2-hydroxyl-11H-benzo [a]-carbazole-3-carboxamide residues (being slightly designated as HBC-);

(4) structure shown in [Ar-N=N-HBC-Cp-N=N-Ar], it uses to have 1 amino compound and (be expressed as Ar-NH ₂) carry out diazotization as diazo component after, carry out azo coupling with the coupling composition (being expressed as HBC-Cp) in the molecule with 2-hydroxyl-11H-benzo [a]-carbazole-3-carboxamide residues (being slightly designated as HBC-) and other coupling component residue (being expressed as Cp-) except this compound.

Wherein, in above-mentioned, " Ar " represents the residue of aromatics and hetero ring type compound with representing, when having in formula more than 2 can identical also can be different.In addition, " Ar-N=N-" or "-N=N-Ar-N=N-" in formula represents that the diazonium salt of diazo component carries out " the arylazo residue " of coupling.Below too.

In the present invention, embodiment as other provides a kind of manufacture method of black azo-dye, it is characterized in that, it is the manufacture method of the black azo-dye for obtaining the invention described above, it has the synthesis procedure of the polyazo pigment of black and as required this pigment is carried out to the operation of miniaturization, (I) synthetic method of the polyazo pigment of black is categorized as any one method in aftermentioned 4 kinds of methods, when the polyazo pigment utilizing these methods to synthesize is thick, to have the median size miniaturization of pigment by aftermentioned any one method known to the operation of 10nm ~ 200nm.

In the present invention, embodiment as other provides coloured composition, it is characterized in that, formed containing the black azo-dye of the present invention recorded before comprising or the pigment composition of black azo-dye that obtained by above-mentioned manufacture method in liquid dispersion medium or in solid dispersion medium.

In the present invention, the embodiment as other provides the colorize method of article, it is characterized in that, when color goods to be become black or be dark-coloured by the painted of the surface by article or article self painted, uses above-mentioned coloured composition.

In the present invention, the embodiment as other provides dyed articles, it is characterized in that, it is the colorize method of implementing above-mentioned article.

In the present invention, embodiment as other provides the backboard of solar power generation module, it is characterized in that, it for being laminated with the backboard of the solar power generation module of black or dark colored infrared transmission layer on light reflective sheet material, polyazo pigment containing black in infrared transmission layer, the polyazo pigment of described black has the structure of at least a kind of 2-hydroxyl-11H-benzo [a]-carbazole-3-carboxylic acid amide residue (being slightly designated as HBC-) comprising more than 2 azo bond in the molecule and imported by coupling composition, and its median size is 10nm ~ 200nm.

In the present invention, embodiment as other provides the manufacture method of the backboard of solar power generation module, it is characterized in that, the base material using base material self to have light reflective is provided with the base material of preformed light reflective substrate as light reflective sheet material as light reflective sheet material or use, the surface of these base materials or light reflective substrate use the coloured composition of the polyazo pigment containing black pass through application, coating, paste, deposition, overlapping, printing, ink jet printing, electronic photo printing or xeroprinting, enforcement shows reflexive painted in region of ultra-red, stacked black or dark colored infrared transmission layer on light reflective sheet material, the polyazo pigment of described black has the structure of at least 1 2-hydroxyl-11H-benzo [a]-carbazole-3-carboxylic acid amide residue (being slightly designated as HBC-) comprising more than 2 azo bond in the molecule and imported by coupling composition, its median size is 10nm ~ 200nm.

In the present invention, color display panel is provided as other embodiments, it is characterized in that, be formed at the polyazo pigment of black matrix" (BM) containing black on colour filter (CF) substrate or organic EL light-emitting substrate, the polyazo pigment of described black has the structure of at least 1 2-hydroxyl-11H-benzo [a]-carbazole-3-carboxylic acid amide residue (being slightly designated as HBC-) comprising more than 2 azo bond in the molecule and imported by coupling composition, and its median size is 10nm ~ 200nm.

Invention effect

By above the present invention, the black colorant film containing black azo-dye shows and almost absorbs completely in transparent substrate, in the wavelength region of about 400 ~ 750nm covering visible-range.And in the region of ultra-red that wavelength is longer, transparent substrate shows high transmissivity, display has the useful optical characteristics of visible ray opacifying property and infrared transmission concurrently.Owing to having this characteristic, therefore black azo-dye of the present invention is effectively utilised as the infrared filter of infrared remote controller and main body receiving apparatus.And black azo-dye of the present invention also can be used as the infrared filter just hindering the infrared ray sensing equipment of thing on the roads such as practical detection, identification automobile and uses.

And then, black azo-dye of the present invention is owing to showing the optical characteristics also almost absorbed completely by long wavelength side with covering visible region, therefore as the opacifying property black material of the BM of CF, the wavelength region may of light in emitting red light portion such as from the LED-backlit corresponding to red pixel fully can be absorbed, shading, the colour generation of LCD yes black, other colour also can develop the color brightly.And then, owing to having high electrical insulating property, modification method, such as replacement spacer therefore as the various CF forming BM on the active components such as TFT keep the BM of thickness of liquid crystal layer or the opacifying property black pigment for the formation of the BM of the CF of IPS mode, COA mode etc. to be also applicable.Particularly, be also highly preferred opacifying property black pigment in IPS mode liquid crystal panel that have employed LED-backlit etc. and OLED display.

In addition, from because of infrared rays transmission the function of the reflection such as the white pigment be added in substrate or coating material etc. or pigment extender fully, can be used as the application on the house that receives much concern from improving living environment, comfortableization and energy-conservation viewpoint in recent years or fabrication etc., road mat formation so that the application etc. on deck, extraneous adornment etc. of boats and ships prevents the materials'use of the intensification caused because of direct sunlight.And then, in photovoltaic power generation system, also can be used for suppressing because of the photogenic temperature of the sun rise by the backboard forming black or dark colored infrared transmission layer stacked on reflective substrate layer.In addition, be also used in the camouflage coloured material or anti-counterfeiting etc. of military hardware.

Embodiment

Then, enumerating the best mode for carrying out an invention, illustrating in greater detail the present invention.

Visible region is absorbed as optical characteristics by the characteristic black azo-dye of tool of the present invention with covering, particularly also shows to the wavelength region of long wavelength side and almost absorb completely, and show high transmissivity near infrared region.Specifically, the spectral transmission of the black colorant film in transparent substrate shows about less than 5%, in the wavelength region of the region of ultra-red of about 900nm ~ 1500nm, shows about more than 30% in the wavelength region of about 400 ~ 750nm of visible-range.In addition, as electrical characteristic, show very high electrical insulating property.

The present inventor etc. have inquired into the black azo-dye of pigment as the above-mentioned distinctive optical characteristics of display having multiple chromophoric group in the molecule and then make their mutual resonance, result, owing to synthesizing easily and can stably manufacture, therefore develops in molecule the black polyazo pigment having more than 2 azo bond, have specific chemical structure.And then owing to particularly requiring the highly transmissive of region of ultra-red, therefore preferably black polyazo pigment is the pigment of fine particle size, the median size of pigment needs for about 10nm ~ 200nm.And then when expecting high-transmission rate, preferred median size is the ultra tiny black polyazo pigment of about 10nm ~ 50nm or has the black azo-dye of the dispersed dye character causing molecular dispersion in painted manufacturing procedure in media as well.

In the present invention, polyazo pigment refers to the disazo pigment or trisazo pigment etc. in the molecule with more than 2 azo bond as mentioned above.

As the chemical structure of polyazo pigment display black, the present inventor etc. find to have more than 2 azo bond in the molecule and have the chemical structure of 2-hydroxyl-11H-benzo [a] of at least one-carbazole-3-carboxamide residues (with reference to following formula) imported by its coupling composition.

2-hydroxyl-11H-benzo [a]-carbazole-3-carboxamide residues

As the manufacture method of above-mentioned polyazo pigment, because more than 2 azo bond introduced in the molecule by needs, therefore can enumerate such as to use as diazo component and there are more than 2 the variable diazo component changing into diazo amino to carry out the method for azo coupling; Coupling composition use there are more than 2 coupling sites be coupled to a point method etc. of carrying out azo coupling.This point is described in detail.

Black polyazo pigment optimization of the present invention has any one of following (1) ~ (4) structure.

(1) the black polyazo pigment of the structure shown in [HBC-N=N-Ar-N=N-HBC], it uses the compound (representative formula: H with more than 2 amino using as diazo component ₂n-Ar-NH ₂) diazonium salt of diazotization, make this salt and 2-hydroxyl-11H-benzo [a]-carbazole-3-carboxylic acid aryl amide (being slightly designated as HBC) as coupling composition carry out azo coupling.

As the example of black polyazo pigment with structure (1) shown in above-mentioned [HBC-N=N-Ar-N=N-HBC], as described belowly enumerate the example that diazo component uses structure when having more than 2 amino p-diaminodiphenyl or phenylenediamine.

(2) the black polyazo pigment of the structure shown in [HBC-N=N-Ar-N=N-Cp], it uses the compound (representative formula: H with more than 2 amino using as diazo component ₂n-Ar-NH ₂) diazonium salt of diazotization, make this salt and to carry out azo coupling as 2-hydroxyl-11H-benzo [a]-carbazole-3-carboxylic acid aryl amide (being slightly designated as HBC) of coupling composition and other coupling compositions (being expressed as Cp) except this compound.

As the example of black polyazo pigment with structure (2) shown in above-mentioned [HBC-N=N-Ar-N=N-Cp], as described below enumerate diazo component use there is more than 2 amino p-diaminodiphenyl or phenylenediamine, the example of structure when using 2-hydroxyl-3-naphthoic acid arylamide as other coupling composition.

(3) the black polyazo pigment of the structure shown in [Ar-N=N-HBC-HBC-N=N-Ar], it uses to have 1 amino compound and (be expressed as Ar-NH ₂) carry out diazotization as diazo component after, carry out azo coupling with the coupling composition (being expressed as HBC-HBC) in the molecule with more than 2 2-hydroxyl-11H-benzo [a]-carbazole-3-carboxamide residues (being slightly designated as HBC-).

As the example of black polyazo pigment with structure (3) shown in above-mentioned [Ar-N=N-HBC-HBC-N=N-Ar], as described belowly enumerate on the HBC-HBC of the coupling composition being combined with 2 2-hydroxyl-11H-benzo [a]-carbazole-3-carboxamide residues via phenylene or biphenylene, use as diazo component and there is the example that 1 amino aniline carries out structure when diazotization forms.

(4) the black polyazo pigment of the structure shown in [Ar-N=N-HBC-Cp-N=N-Ar], it uses to have 1 amino compound and (be expressed as Ar-NH ₂) carry out diazotization as diazo component after, carry out azo coupling with the coupling composition (being expressed as HBC-Cp) in the molecule with 2-hydroxyl-11H-benzo [a]-carbazole-3-carboxamide residues (being slightly designated as HBC-) and other coupling component residue (being expressed as Cp-) except this compound.

As the example of black polyazo pigment with the structure (4) shown in above-mentioned [Ar-N=N-HBC-Cp-N=N-Ar], as described belowly enumerate on the HBC-Cp of the coupling composition of the 2-hydroxyl-3-naphthoic acid arylamide residue being combined with 2-hydroxyl-11H-benzo [a]-carbazole-3-carboxamide residues and other coupling compositions except this compound via phenylene or biphenylene, use as diazo component and there is the example that 1 amino aniline carries out structure when diazotization forms.

Above-mentioned black azo-dye of the present invention easily obtains by the manufacture method of the black azo-dye of the present invention with following operation: have the synthesis procedure of the polyazo pigment of above-mentioned cited structure, as required by the adjustment operation of the particle diameter of the pigment particles of this pigment miniaturization.Below, the manufacture method of black azo-dye of the present invention is described.

The synthetic method forming the black polyazo pigment of the manufacture method of black azo-dye of the present invention is selected from the method for following (1) ~ (4).

(1) method is for making 2-hydroxyl-11H-benzo [a]-carbazole-3-carboxylic acid aryl amide (being slightly designated as HBC) and the compound (representative formula: H by having more than 2 amino ₂n-Ar-NH ₂) diazonium salt of diazotization carries out the synthetic method of azo coupling.The black polyazo pigment with the structure shown in [HBC-N=N-Ar-N=N-HBC] illustrated before the black polyazo pigment obtained by the synthetic method of this (1) is become.

(2) method makes 2-hydroxyl-11H-benzo [a]-carbazole-3-carboxylic acid aryl amide (being slightly designated as HBC) and other coupling compositions (being expressed as Cp) except this compound for having and will have the compound (representative formula: H of more than 2 amino ₂n-Ar-NH ₂) diazonium salt of diazotization carries out the synthetic method of the polyazo pigment of the structure of azo coupling, in this synthetic method, makes to have more than 2 amino compound (representative formula: H ₂n-Ar-NH ₂) diazotization diazonium salt with to wait mole or its following coupling composition (Cp) carries out azo coupling, coupling there is the polyazo pigment of more than 2 coupling compositions (Cp) to be separated, to remove as required, then make above-mentioned coupling composition (HBC) carry out azo coupling with the diazo of non-coupling.The black polyazo pigment with the structure shown in [HBC-N=N-Ar-N=N-Cp] illustrated before the black polyazo pigment obtained by the synthetic method of these (2) is become.

(3) method is the method for following (3-1) or (3-2).The black polyazo pigment with the structure shown in [Ar-N=N-HBC-HBC-N=N-Ar] illustrated before the black polyazo pigment obtained by the synthetic method of these (3-1) and (3-2) is become.

(3-1) the coupling composition (being expressed as HBC-HBC) making to have in the molecule more than 2 2-hydroxyl-11H-benzo [a]-carbazole-3-carboxamide residues (being slightly designated as HBC-) with will there is 1 amino compound (Ar-NH ₂) diazo component of diazotization carries out the synthetic method of azo coupling.

(3-2) make (to be expressed as Ar-NH by having 1 amino compound ₂) diazonium salt of diazotization and 2-hydroxyl-11H-benzo [a]-carbazole-3-carboxylic acid carry out azo coupling, then make the carboxylic acid of azopigment and aryl polyamines condensation and make the synthetic method of many methane amides.

(4) method is the method for following (4-1) or (4-2).The black polyazo pigment with the structure shown in [Ar-N=N-HBC-Cp-N=N-Ar] illustrated before the black polyazo pigment obtained by the synthetic method of these (4-1) and (4-2) is become.

(4-1) the coupling composition (being expressed as HBC-Cp) making to have in a part 2-hydroxyl-11H-benzo [a]-carbazole-3-carboxamide residues (being slightly designated as HBC-) and other coupling component residue (being expressed as Cp-) except this compound (is expressed as Ar-NH with by having 1 amino compound ₂) diazonium salt of diazotization carries out the synthetic method of azo coupling.

(4-2) make (to be expressed as Ar-NH by having 1 amino compound ₂) carboxylic acid to be coupled to 2-hydroxyl-11H-benzo [a]-carbazole-3-carboxylic acid and other respectively point of the diazonium salt of diazotization carries out azo coupling, then make the carboxylic acid of two of gained kinds of azopigments and aryl polyamines condensation and make the synthetic method of many methane amides.

The diazo component that can use in the above-mentioned each synthetic method enumerated and being coupled to point is described.

(A) dual composition divides and carries out concrete example.

A () as coupling composition (HBC), such as, is 2-hydroxyl-11H-benzo [a]-carbazole-3-anilide (anilide), 2-hydroxyl-11H-benzo [a]-carbazole-3-naphthoamide etc. and their derivative.1 ~ 10), alkoxyl group (carbonatoms: 1 ~ 10), trifluoromethyl, halogen, alkyloxycarbonyl, cyclic imide base dioxy base, alkyl sulphonyl, aminocarboxyl, benzoylamino, alkyl amino-carbonyl, anilinocarbonyl, ring-type urylene, carboxyl, alkyl imino etc. are imported into one or more coupling composition as the substituting group such as alkyl (carbonatoms: of derivative.

Specifically, 2-hydroxyl-11H-benzo [a]-carbazole-3-anilide, 2-hydroxyl-11H-benzo [a]-carbazole-3-carboxyl-p-anisidine, 2-hydroxyl-11H-benzo [a]-carbazole-3-carboxyl-(2-methyl)-p-anisidine, 2-hydroxyl-11H-benzo [a]-carbazole-3-carboxy-N-benzimidazolone-5-acid amides, 2-hydroxyl-11H-benzo [a]-carbazole-3-carboxyl-naphthoamide etc. can such as be enumerated.

B () as coupling composition (HBC-HBC), such as, is phenylene-bis-(2-hydroxyl-11H-benzo [a]-carbazole-3-methane amide), biphenylene-bis-(2-hydroxyl-11H-benzo [a]-carbazole-3-methane amide), naphthalene-bis-(2-hydroxyl-11H-benzo [a]-carbazole-3-methane amide) etc. and their derivative.1 ~ 10), alkoxyl group (carbonatoms: 1 ~ 10), the coupling composition of trifluoromethyl, halogen etc. as the substituting group of derivative, in its aryl, one or more known substituting group, such as alkyl (carbonatoms: is imported.

Specifically, it is such as phenylene-(1, 4-) two (2-hydroxyl-11H-benzo [a]-carbazole-3-methane amide), 2-chloro-phenylene-(1, 4-) two (2-hydroxyl-11H-benzo [a]-carbazole-3-methane amide), 2, 5-bis-chloro-phenylene-(1, 4-) two (2-hydroxyl-11H-benzo [a]-carbazole-3-methane amide) 2-methyl-phenylene-(1, 4-) two (2-hydroxyl-11H-benzo [a]-carbazole-3-methane amide), biphenylene-(4, 4 '-) two (2-hydroxyl-11H-benzo [a]-carbazole-3-methane amide), 3, 3 '-two chloro-biphenylene-(4, 4 '-) two (2-hydroxyl-11H-benzo [a]-carbazole-3-methane amide), naphthalene-(1, 5-) two (2-hydroxyl-11H-benzo [a]-carbazole-3-methane amides) etc.

C () as coupling composition (Cp), such as, can enumerate 2-hydroxyl-3-naphthoic acid arylamide, 2-hydroxyl-6-naphthoic acid arylamide, 2-hydroxyl-3-anthroic acid arylamide, 2-hydroxyl-3-diphenylene-oxide carboxylic acid aryl amides, 2-hydroxyl-1-carbazole carboxylic acid aryl amides etc. and their derivative.Be such as C.I. ice dyeing coupling component (azoic coupling component) 2,4,6,7,8,10,11,12,14,17,18,19,20,21,22,23,24,27,28,29,31,32,37,41,45,46,111,112,113,15,16,36,2-hydroxyl-3-naphthoic acid-N-benzimidazolone-5-acid amides, 2-hydroxyl-3-naphthoic acid-N phlhalimide base-4-acid amides etc.

D () is as coupling composition (HBC-Cp), carry out the carboxylic acid of the Cp residue of amide linkage as the amino with HBC residue, 2-hydroxyl-3-naphthoic acid, 2-hydroxyl-6-naphthoic acid, 2-hydroxyl-3-anthroic acid, 2-hydroxyl-3-diphenylene-oxide formic acid, 2-hydroxyl-1-carbazole formic acid etc. can be enumerated.Such as, for phenylene (-1)-(2-hydroxyl-11H-benzo [a]-carbazole-3-methane amide) (-4)-(2-hydroxyl-3-naphthoic acid acid amides), phenylene (-1)-(2-hydroxyl-11H-benzo [a]-carbazole-3-methane amide) (-4)-(2-hydroxyl-3-naphthoic acid acid amides), (2-methyl-) phenylene (-1)-(2-hydroxyl-11H-benzo [a]-carbazole-3-methane amide) (-4)-(2-hydroxyl-3-naphthoic acid acid amides), biphenylene (-4)-(2-hydroxyl-11H-benzo [a]-carbazole-3-methane amide) (-4 ')-(2-hydroxyl-3-naphthoic acid acid amides) etc.

(B) concrete example is carried out to diazo component.

A () is as the compound (representative formula: H with more than 2 amino of diazo component ₂n-Ar-NH ₂), be such as phenylenediamine, benzidine, diaminonaphthalene, diamino-anthraquinone, diamino-benzophenone, diamino-pyridine etc. and their derivative.1 ~ 10), alkoxyl group (carbonatoms: 1 ~ 10), the diazo component of trifluoromethyl, halogen etc. substituting group as derivative is imported with one or more known substituting group, such as alkyl (carbonatoms: on its aryl.

Specifically, Isosorbide-5-Nitrae-phenylenediamine, the chloro-Isosorbide-5-Nitrae-phenylenediamine of 2-, 2,5-bis-chloro-Isosorbide-5-Nitrae-phenylenediamines, the chloro-5-methyl isophthalic acid of 2-can such as be enumerated, 4-phenylenediamine, 2,5-dimethyl-Isosorbide-5-Nitrae-phenylenediamine, 2-nitro-Isosorbide-5-Nitrae-phenylenediamine; Chloro-1, the 3-phenylenediamine of 1,3-phenylenediamine, 4-, 4-methoxyl group-1,3-phenylenediamine, 4-nitro-1,3-phenylenediamine; Chloro-1, the 2-phenylenediamine of 4-, 4,5-dimethyl-1,2-phenylenediamines, 4-nitro-1,2-phenylenediamine; 3,3 '-two chloro-4,4 '-p-diaminodiphenyl, 2,2 ', 5,5 '-four chloro-4,4 '-p-diaminodiphenyl, 3,3 '-dimethyl-4,4 '-p-diaminodiphenyl, 3,3 '-dimethoxy-4 ', 4 '-p-diaminodiphenyl; 1,5-diaminonaphthalene 1,2-diaminonaphthalene; 1,2-diamino-anthraquinone, 1,5-diamino-anthraquinone; 3,4-diamino-benzophenone; DAP etc.

B () (is expressed as Ar-NH as 1 the amino compound that has of diazo component ₂), be such as aniline, naphthylamines, aminoanthraquinone, phenoxybenzamine, phenylimino aniline etc. and their derivative.1 ~ 10), alkoxyl group (carbonatoms: 1 ~ 10), the diazo component of halogen, nitro, phenyl ether, phenylimino, benzoylamino, anilinocarbonyl, ring-type urylene etc. substituting group as derivative is imported with one or more known substituting group, such as alkyl (carbonatoms: on its aryl.Specifically, C.I. azoic diazo component 5,8,9,10,32,33,34,35,36,37,41,42,43,47 etc. can such as be enumerated.

To form black azo-dye of the present invention manufacture method, the adjustment operation of the particle diameter of the pigment particles that as required this pigment carried out to miniaturization is described.The median size miniaturization of pigment, when the particle diameter of the polyazo pigment obtained by the above-mentioned synthetic method enumerated is thick, obtains to about 10nm ~ 200nm by utilizing any one method in following (1) or (2) by black azo-dye of the present invention.That is, in order to improve the infrared transmission rate of the film that employs the polyazo pigment obtained by the above-mentioned synthetic method enumerated etc., be necessary that the particle diameter of disperseed pigment is less than wavelength, the specifically median size of light for about 10nm ~ 200nm.Therefore, black azo-dye of the present invention, when the pigment synthesized by aforesaid method is thick, in order to the median size of pigment is adjusted to required particle diameter, needs to carry out following cited known pigment miniaturization operation, manufactures miniaturization pigment.

Specifically, carry out the pigment miniaturization operation being selected from following 2 methods, be adjusted to median size and reach about 10nm ~ 200nm:(1) use the miniaturization method of the colo r mill that is selected from the group be made up of ball mill, sand mill, masher, horizontal continuum dispersion machine, kneader, continous way singe screw mixing roll, continous way twin screw compounder, triple-roller mill, open roller continuous mixer etc. or colo(u)rant dispersion machine; (2) in mixing roll with water soluble salt, carry out the known methods such as salt mill method that is mixing, that grind together with the water-miscible organic solvent used as required.And then when needing ultrared high-transmission rate further, preferably preparation median size is about the ultra tiny pigment of 10nm ~ 50nm.

The particle diameter of pigment adjusts according to used purposes.The adjustment of particle diameter controls relative to the ratio of the amount of pigment or mixing time mainly through salt.Requiring in the purposes that the infrared rays colour filter of high-transmission rate is such, expect that pigment particles is less, the such as dispersion state of the ultra tiny pigment particles of micropigment particle, the more preferably 10nm ~ 30nm of preferred 10nm ~ 50nm, the dissolved state of final expectation molecular dispersion in the carrier, such as plastic medium of dispersion.

On the other hand, in the purposes that the BM of the CF requiring the opacifying property of visible ray is such, expect the about 50nm ~ 100nm slightly larger than transmission purposes.In addition, in the purposes requiring infrared reflectivity, preferred substrate is reflectivity, but, and then also can be that pigment particles is comparatively large, even if 100nm ~ 200nm also can use.

In the above-mentioned lyonium salt mill method enumerated, water-soluble inorganic salt is added as grinding auxiliary agent in pigment, the amount of this water-soluble inorganic salt be according to required pigment particle size carry out the pigment ground several times amount, be in particular 3 ~ 20 times amount, and then add the sticking water-miscible organic solvents of tool such as ethylene glycol, Diethylene Glycol, polyoxyethylene glycol, carry out mixing grinding.Grind the water-soluble inorganic salt used in auxiliary agent and use sodium-chlor or sodium sulfate etc.After grinding, be added in dilute sulphuric acid, water etc., dissolving grinds auxiliary agent and carries out filtering, washing, and obtains the filtration thickener (filter cake) of pigment.Filter cake directly carries out dispersion processing with wet type dispersion machine, or be processed into penetrating stain by backwashing manner, or carry out pulverizing with Dry-crusher after carrying out warm air drying and make powder pigment, or utilize above-mentioned various wet type dispersion machine or mixing roll etc. to disperse etc. further, become various tinting material according to purposes processing treatment.In addition, also preferred plastic resin treatment of carrying out in water makes easily disperse process pigment or processed pigment.

When using black azo-dye of the present invention as tinting material, particularly in aqueous dispersible pigment dispersion, also preferred pigment derivative of adding anionic property or cationic in black azo pigment.As the addition means of these pigment derivative, undertaken by following known method: when the synthesis of above-mentioned pigment, use diazo component or the coupling composition with ionic group, utilize auxiliary coupling (accessory coupling) method to carry out the method imported; Or when micronize manufacturing process or conditioned pigment dispersion liquid time add the method etc. with the pigment derivative of ionic group of in addition synthesis.As pigment derivative now, except black, the colored pigment derivative such as yellow, blue, red suitably used in the mode comprising hue adjustment etc.

Here, the spectral transmission of film is according to black pigment composition contained in film and coating thickness numerically visible some difference, but can confirm, with the relation of wavelength, carrying out the tendency all showing absorption under the wavelength absorbed, under the wavelength carrying out transmission, to show the tendency of transmission.Table 1 and table 2 represent the spectral transmission (%) of the black disazo pigment (" black pigment-1 ") using aftermentioned Production Example 1 of the present invention to obtain, the visibility region comprising the film of black pigment-1 prepared by aftermentioned embodiment 1 and region of ultra-red.

Result is as shown in table 1, confirms that containing in the film of black pigment-1, throughout the whole wavelength region may of 400 ~ 750nm of visible ray, transmissivity is 0%, does not show transmissivity in visibility region.On the other hand, as shown in table 2, there is the transmission of 34% under the 900nm of region of ultra-red, comparatively its more long wavelength side transmissivity rise reposefully, estimate also to show high-transmission rate at higher wavelength place.

Table 1: the spectral transmission of the visibility region of black pigment-1

Table 2: the spectral transmission of the region of ultra-red of black pigment-1

In addition, for the electrical insulating property of the film containing black azo-dye of the present invention, equally as shown in aftermentioned embodiment 1, confirm that the volume intrinsic resistance value of the film containing black pigment-1 is 10 ¹⁴Ω cm, show good electrical insulating property.

Find as the black pigment-1 of black azo-dye of the present invention it is that there is the pigment of optical function making the Transmission light of infrared spectral range, blocked completely by the light of visible region as mentioned above, therefore as the above-mentioned purposes of the infrared filter of ultrared electronics or the BM of CF of utilizing with being useful.Such as, black azo-dye of the present invention is applicable to the BM used time of CF, fully the light of the visible region of backlight can be blocked and show excellent electrical insulating property.

Black azo-dye of the present invention is carry out painted, the dead color of Achromatic color of dark-coloured colour or the coloured composition of the painted of black in use, according to differences such as painted object, purposes, using method, as the coloured composition containing the aqueous coloured composition of pigment composition or the solid containing the pigment composition containing black azo-dye in solid dispersion medium that contain black azo-dye in liquid dispersion medium, can use with variform.

Black azo-dye of the present invention can be used as pigment composition and is used alone black azo-dye, or as one of multiple pigment composition, the one kind or two or more coloured pigment of corresponding object Colour selection, white pigment, other black pigment and pigment extender etc., also use with them.In order to the color of correction black azo-dye, carry out with black azo-dye of the present invention and the compounding ratio of coloured pigment, white pigment, other black pigments or pigment extender be not particularly limited, use computer for colouring system to carry out optimized method and decide also to be preferred mode.

As with black azo-dye of the present invention and pigment, known pigment can be used, be not particularly limited.Such as can use and be selected from anthraquione pigmentss, quinacridone pigment, diketopyrrolo-pyrrole series pigments, indigo thioindigo series pigments, purple cyclic ketones series pigments, perylene pigments, phthualocyanine pigment, indoline series pigments, isoindoline series pigments, isoindolinone pigment, dioxazine series pigments, quinophthalone pigments, nickel azo pigment, metal complex pigment, insoluble azo pigment, soluble azo series pigments, high molecular azo pigment, azomethine azo system black pigment, the pigment dyestuffs such as nigrosine series pigments and charcoal blacks and composite oxides series pigments, iron oxide pigment, at least a kind of pigment in the mineral dyes such as titanium oxide base pigment or the mixture of two or more pigment, mixed crystal pigments.

As pigment dyestuff, such as, can enumerate C.I. Pigment Yellow 73 (being slightly designated as PY)-74 in yellow ultramarine, 83, 93, 94, 95, 97, 109, 110, 120, 128, 138, 139, 147, 150, 151, 154, 155, 166, 175, 180, 181, 185, 191 etc., C.I. pigment orange (being slightly designated as PO)-61 can be enumerated in orange pigments, 64, 71, 73 etc., C.I. Pigment red (being slightly designated as PR)-4 can be enumerated in red pigment, 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 etc.

In addition, be C.I. Pigment blue (being slightly designated as PB)-15:1 in blue pigments, 15:2, 15:3, 15:4, 15:5, 15:6, 16, 17:1, 60, 80, aluminium phthalocyanine blue etc., it is C.I. Pigment green (being slightly designated as PG)-7 in veridian, 36, 58, poly-(13-16) bromine phthalocyanine etc., it is C.I. pigment violet (slightly remembering PV)-19 in violet pigment, PV-23, PV-37 etc., be Aniline black pigment as black pigment, charcoal blacks, titanium oxide mineral black etc., as being matched with the pigment carrying out in black azo-dye of the present invention using during the special BM at CF uses, preferably carry out surface treatment and improve the charcoal blacks or titanium oxide mineral black etc. of insulativity.

Black azo-dye of the present invention, carrying out and the used time with the infrared reflectivity pigment such as white pigment, also can use the method proposed in Japanese Patent No. 4097926 publications or Japanese Unexamined Patent Publication 2005-330466 publication.That is, being suitable for the method that the surrounding parenchyma of the infrared reflectivity pigment such as white pigment is coated to, improve ultrared reflection efficiency with infrared transmission black azo-dye of the present invention is also preferred mode.

Aqueous coloured composition containing black azo-dye of the present invention mainly as being coated with article surface, impregnation, description, lettering etc. tinting material use, coating, coating agent, coloring plastic, fiber staining, printing-ink, stationery, image recording with, image display with etc. use in various uses.In the dispersion medium that black azo-dye of the present invention disperses, as by film formation material (or be coated with film formation material), can containing at least a kind of being selected from the reactive polymer or non-reacted polymer, the oligopolymer with reactive group or non-reacted oligopolymer with reactive group and the monomer with reactive group or the non-reacted monomer without reactive group etc., and himself can be liquid, or it can be the material further containing solvent and/or water.

And then, when preparing above-mentioned aqueous coloured composition, as long as get out the high density pigment processed goods be dispersed in high density differential by pigment used in advance in dispersion medium in advance, then it can be used easily to manufacture tinting material.Aqueous high density dispersible pigment dispersion is called " primary colours " or " basic ink " uses.

In addition, the coloured composition of the solid of the black azo-dye containing the invention described above mainly refers to the tinting material of the painted middle use in inside at plastics or synthon, such as, to use as the masterbatch powder, master batch (master batch) etc. of high density colo(u)rant dispersion thing and entirety through known article shape such as painted colored particles.As solid dispersion medium, at least a kind that is selected from thermoplastic resin, heat-curing resin, wax, fatty acid amide and fatty acid metal soap etc. can be used.

When using above-mentioned tinting material to carry out painted to article, carry out suitable painted according to the optics object of visible region and region of ultra-red.

Absorb carrying out making visible region, when making region of ultra-red transmission painted, the base material of article is set to transparent base material, use coloured composition by application, smear, dye, print, take down notes, describe, ink jet printing, electronic photo printing, xeroprinting or photolithography etc. carry out surface colour to this transparent base material, or in transparent base material mixing or impregnation coloured composition to carry out inside painted.Now, the black azo-dye of the application of the invention, the article of gained show the optical characteristics of following excellence.Namely, when using black azo-dye of the present invention, can carry out particularly in the wavelength region of the about 400 ~ 750nm of visible region, showing high-absorbable thus display visible ray opacifying property, in the region of ultra-red of about 900nm ~ 1500nm and then longer high wavelength, show the painted of highly transmissive.

In addition, absorb carrying out making visible region, region of ultra-red is reflected painted time, by forming the material of article self person that has light reflective or using preformed light reflective substrate, coloured composition of the present invention is used to carry out being coated with to realize thereon.The details of this aspect is described later.Colorize method now utilizes known method, such as application, smears, original liquid coloring, printing and dyeing, dip-dye, printing, notes, description, ink jet printing, electronic photo printing or xeroprinting etc., can carry out thus at visible region display high-absorbable, painted near infrared region display highly reflective.

Measure the spectral reflectance of above-mentioned black pigment-1, show the result in table 3.The sample measured is the White Board (hereinafter referred to as black color development paper) using applicator to carry out being coated with on white color development paper.

Table 3: the spectral reflectance of the black color development paper of black pigment-1

As shown in table 3, film containing above-mentioned black pigment-1 carries out to about 750nm the reflectivity absorbing, only show about 5% in visibility region, but to 900nm from about 800nm, reflectivity sharply rises, and then at the near infrared region place of the longer side of wavelength, almost maintain the reflectivity of 80%, can estimate also to show high-reflectivity in the region of ultra-red of longer high wavelength.This expression is reflected from the light of black coating film transmission by the blank sheet of paper of substrate, the substrate high by also use reflectivity or the reflecting material of white pigment or pigment extender etc., not only the light on the surface from black pigment is reflected again, the light of transmission is also reflected again, the high-reflectivity that display efficiency is good.

Play the resin glue (being called " vehicle " or " varnish " according to purposes) of function as the painting film formation material (by film formation material) used in the present invention, preferably can use resin glue and the photoresist tackiness agent of the baking-type not having the non-reacted dried at normal temperature of reactive group or there is reactive group.As the resin glue of dried at normal temperature or baking-type, such as can enumerate the image recording materials such as printing and dyeing agent, coating, coating agent or printing-ink, stationery, ink jet printing, electronic photo printing, xeroprinting with in the resin glue etc. that uses.In addition, as photoresist tackiness agent, such as, can enumerate the middle photoresist tackiness agent used of various coating, coating agent, printing-ink, jetted ink, photolithography etc. that are ultra-violet solidified or electron(beam)curing.

As the object lesson of the resin glue of the dried at normal temperature that can use in the present invention or baking-type, such as, synthetic rubber resin can be enumerated, acrylic resin, polystyrene (being total to) polymer, the Vinylites such as polyvinyl butyral system resin, polyester based resin, aminoresin modified poly ester system resin, polyurethane series resin, acrylic polyol carbamate system resin, soluble polyamide system resin, soluble polyimide system resin, soluble polyamide imide series resin, solubility polyester imide series resin, Synolac, alkyd amino system resin, epoxy base system resin, chlorinated rubber resin, silicone resin, fluoro-resin, cellulose acetate prime system resin, nitrocellulose prime system resin, hydroxy ethyl cellulose, the water-soluble salt of styrene-maleic acid ester based copolymer, (methyl) acrylic ester (being total to) polymeric water-soluble salt, water soluble amino alkyd system resin, water soluble amino polyester based resin and water-soluble polyamide based resin etc., these materials can be used alone or combinationally use two or more.

As reactive the reactive group that has by film formation material, such as can enumerate methylol, alkyl methylol, isocyanate group, the isocyanate group of sheltering, epoxy group(ing) etc.In addition, oligopolymer or monomer can be used according to purposes, and then also can also with linking agent, such as methylol melamine system or isocyanate-based, epoxy base system linking agent.

As the uv curing resin system that can use in the present invention, electron(beam)curing resin system homenergic ray-curable is coated with the object lesson of film formation material, such as can enumerate photosensitivity thermoprene system resin, photosensitivity phenolic aldehyde system resin, photosensitivity polyacrylic ester system resin, photosensitivity polyamide series resin, photosensitive polyimide system resin etc. and unsaturated polyester system resin, polyester acrylate system resin, poly-epoxy group(ing) acrylic ester resin, urethane acrylate system resin, polyether acrylate system resin, the tackiness agents such as polyalcohol acrylate system resin or the tackiness agent that further interpolation monomer obtains as reactive diluent in these materials.

As the plastics become by carrying out painted object as the plastics tinting material of coloured composition of the present invention, polyethylene can be enumerated as known thermoplastics, ethylene copolymer, the polyolefinss such as polypropylene, polystyrene, ABS, AS, styrol copolymer, vinyl chloride resin, methacrylic resin, polycarbonate, polymeric amide, polyacetal, thermoplastic polyester, cellulosic plastic, polyphenylene oxide resin, fluoro-resin, thermoplastic elastomer class etc., in addition as Thermocurable plastics, unsaturated polyester resin can be enumerated, epoxy resin, silicone resin, urethane resin, melamine resin, resol etc.

The amount of the black azo-dye of the present invention contained in the black colorant as coloured composition of the present invention changes according to purposes or application target, cannot treat different things as the same.Such as, carry out in painted purposes at coating, coating agent, printing and dyeing agent, printing-ink, printing press toning agent, jetted ink etc. on surface, because thickness is thin, the amount therefore as the black pigment contained in this tinting material is about 3% ~ 80%, is preferably about 5% ~ 60%.Particularly, when opacifying property black material as the BM of CF uses, particularly thickness thin, require opacifying property completely, therefore attempted pigment stably disperseed, remain on be suitable for being coated with viscosity, form the critical pigment concentration of uniform painted tunicle, be preferably about 30% ~ 60%.

In addition, when the original liquid coloring as the painted of plastics or spinning to painted material monolithic carry out inner painted time, also depend on articles colored thickness, be about 0.05% ~ 20%, be preferably about about 0.1% ~ 10%.

When the image recording coloured composition containing black azo-dye of the present invention is used as the BM formation coloured composition of CF, use this coloured composition, on CF substrate directly or via transfer printing or the plastic film pasted, utilize the formation method of one or two or more kinds be selected from photolithography, laser ablation method, ink jet printing method, print process, transfer printing, mounting method etc. to be formed.

As the thickness of BM, be 0.5 μm ~ 3 μm, be generally 1 μm ~ 2 μm.As optical density(OD) (OD) value, be more than 2.0, be preferably more than 3.0.When making it have the function of spacer, have thicken BM self situation, on BM the situation of overlaid pixel or the situation etc. of overlapping colourless resin molding, be preferably 5 μm ~ 10 μm.

In addition, on the CF substrate being formed with described BM, known colour element formation tinting material also can be used to utilize known pixel formation method to form colour element.

As the article preferably in the present invention with the speciality relevant to CF substrate or organic EL light-emitting substrate, following article can be enumerated.That is, the CF substrate being formed with the BM absorbing visibility region wavelength region can be enumerated or organic EL light-emitting substrate, particularly BM are essentially electrical insulating property, this BM is overlapping with electrode and the CF substrate that formed or organic EL light-emitting substrate and comprise their color display panel.Equally, the CF substrate defining colour element on the CF substrate being formed with above-mentioned BM, the liquid color display equipment being provided with the CF substrate defining BM and colour element can be enumerated or be equipped with the organic EL color display equipment of above-mentioned organic EL light-emitting substrate.

In addition, as the article relevant to photovoltaic power generation system, the backboard formed by the stacked black of coloured composition containing black azo-dye of the present invention or dark colored infrared transmission layer on the light reflective sheet materials such as reflective substrate layer and the solar power generation module employing this backboard that the temperature caused because of sunlight can be suppressed to rise can be enumerated.

Embodiment

Then, embodiment is enumerated and comparative example further illustrates the present invention.In addition, in literary composition, " g " or " % " as long as no special instructions, is then quality criteria.

[Production Example 1] (manufacture of " black pigment-1 ")

(1) synthesis of black disazo pigment

By ordinary method, at 3,3 '-dimethoxy-4 ', 4 '-p-diaminodiphenyl 2.44g(0.01 mole) in add after concentrated hydrochloric acid makes hydrochloride, add excessive sodium nitrite in aqueous solution and carry out diazotization.Then, fluoroboric acid is added wherein, preparation 3,3 '-dimethoxy-diphenylene (4,4 '-) tetrazolium boron fluoride double salt (diazonium salt).Therewith dividually, in the methyl alcohol 250g being dissolved with sodium hydroxide 0.8g, 2-hydroxyl-11H-benzo [a] carbazole-3-carboxyl-p-anisidine 7.65g(0.02 mole is dissolved as coupling composition) be prepared.The tetrazolium boron fluoride complex salt solution prepared before is remained on less than 15 DEG C, slowly adds the solution of the coupling composition of above-mentioned preparation wherein.And then, utilize sodium-acetate that pH is adjusted to 6.5 ~ 7.0, stir after 1 hour, stir 2 hours at 25 DEG C, and then be warming up to 40 DEG C, stir 3 hours, terminate coupled reaction.After the pigment filtering of generation, use methanol wash filtrate, after then carrying out washing, carry out drying, thus obtain the thick pigment of black azo-dye.The receipts amount of the black azo-dye of gained is 9.78g.

(2) miniaturization process is utilized to carry out the preparation of black particle pigment

The coarse particle pigment 100 parts of the black azo-dye building-up reactions by above-mentioned (1) obtained joins to be provided with and adds in the kneader of gland together with sodium chloride powder 500 parts and Diethylene Glycol 50 parts, and carrying out ready-mixed becomes by evenly moistening agglomerate to the coarse particle pigment in kneader and sodium chloride powder.Then, autoclave is closed, at pressure 6kg/cm ²be pressed into content while carry out mixing and grind down.Specifically, management temperature makes content reach 92 ~ 98 DEG C, while carry out mixingly grinding process 2 hours.Filter after the triturate of gained is carried out the stir process of 1 hour in the 3000 parts of warm water being heated to 80 DEG C, the filtrate of gained is washed, thus removing sodium-chlor and Diethylene Glycol, obtain the filter cake of the black azo-dye through miniaturization.

Following method is utilized to measure the particle diameter of the pigment of above-mentioned acquisition.The transmission electron microscope photo (60,000 times) of the black pigment of shooting gained, uses " image analysis formula size-grade distribution software Mac-View " (マ ウ ンテック Inc.) to measure size-grade distribution.Consequently, median size is 50nm.In addition, in other Production Example, also measured the median size of pigment by method same as described above.

And then, pulverize after the filtration cakes torrefaction of above-mentioned acquisition, acquisition has 3, the miniaturization powder pigments of the black pigment of the structure of 3 '-dimethoxy-biphenylene (4,4 '-) two (azo (-1)-2-hydroxyl-11H-benzo [a]-carbazole-3-carboxyl-p-anisidine).Hereinafter referred to as " black pigment-1 ".

[Production Example 2] (manufacture of " black pigment-2 ")

With Production Example 1(1) same, to 3,3 '-dimethoxy-4 ', 4 '-p-diaminodiphenyl 2.44g(0.01 mole) carry out diazotization.And then, by itself and 2-hydroxyl-11H-benzo [a] carbazole-3-carboxy-N-benzimidazolone-5-acid amides 8.17g(0.02 mole) coupling, thus obtain the thick pigment of black azo-dye.The receipts amount of the black azo-dye of gained is 10.07g.

Then, the miniaturization process of the thick pigment of gained is carried out.Its method is except using except 8 times amount, according to Production Example 1(2 by the usage quantity of sodium-chlor used in (2) described in Production Example 1 relative to pigment) carry out miniaturization process.And then, filter after utilizing sour water to carry out the dissolving of salt etc., the filtrate of gained is washed, obtain the filter cake of black azo-dye.The median size of the pigment of gained is 25nm.In addition, pulverize after the filtration cakes torrefaction of above-mentioned acquisition, obtain the miniaturization powder pigments of black pigment.Below call it as " black pigment-2 ".

[Production Example 3] (manufacture of " black pigment-3 ")

With Production Example 1(1) same, to 3,3 '-two chloro-4,4 '-p-diaminodiphenyl 2.53g(0.01 mole) carry out diazotization.And then, by itself and 2-hydroxyl-11H-benzo [a] carbazole-3-carboxyl-(2 '-methyl)-p-anisidine 7.93g(0.02 mole) coupling, thus obtain the thick pigment of black azo-dye.The receipts amount of the black azo-dye of gained is 10.26g.

Then, the miniaturization process of the thick pigment of gained is carried out.Except using except 10 times amount by the usage quantity of sodium-chlor used in (2) described in Production Example 1 relative to pigment, carry out miniaturization process according to (2) that Production Example 1 is recorded.And then, filter after utilizing sour water to carry out the dissolving of salt etc., the filtrate of gained is washed, obtain the filter cake of black azo-dye.The median size of the pigment of gained is 20nm.In addition, pulverize after the filtration cakes torrefaction of above-mentioned acquisition, obtain the miniaturization powder pigments of black pigment.Below call it as " black pigment-3 ".

[Production Example 4] (manufacture of " black pigment-4 ")

With Production Example 1(1) same, to 3,3 '-dimethoxy-4 ', 4 '-p-diaminodiphenyl 2.44g(0.01 mole) carry out diazotization.And then, by itself and 2-hydroxyl-11H-benzo [a] carbazole-3-carboxyl-(2 '-methyl)-p-anisidine 7.93g(0.02 mole) coupling, thus obtain the thick pigment of black azo-dye.The receipts amount of the black azo-dye of gained is 9.94g.

Then, the miniaturization process of the thick pigment of gained is carried out.Miniaturization process is carried out according to (2) that Production Example 1 is recorded.And then, filter after utilizing sour water to be dissolved by salt etc., then the filtrate of gained is washed, obtain the filter cake of black azo-dye.The median size of the pigment of gained is 50nm.In addition, pulverize after the filtration cakes torrefaction of above-mentioned acquisition, obtain the miniaturization powder pigments of black pigment.Below call it as " black pigment-4 ".

[Production Example 5] (manufacture of " black pigment-5 ")

Same with Production Example 1 (1), diazotization is carried out to 3,3 '-two chloro-4,4 '-p-diaminodiphenyl 2.53g (0.01 moles).And then, by itself and 7.65g (0.02 mole) coupling of 2-hydroxyl-11H-benzo [a] carbazole-3-carboxyl-p-anisidine, thus obtain the thick pigment of black azo-dye.The receipts amount of the black azo-dye of gained is 9.86g.

Then, the miniaturization process of the thick pigment of gained is carried out.Except using except 4 times amount by the usage quantity of sodium-chlor used in (2) described in Production Example 1 relative to pigment, carry out miniaturization process in the same manner as Production Example 1 (2).And then, filter after utilizing sour water to carry out the dissolving of salt etc., the filtrate of gained is washed, obtain the filter cake of black azo-dye.The median size of the pigment of gained is 85nm.In addition, pulverize after the filtration cakes torrefaction of above-mentioned acquisition, obtain the miniaturization powder pigments of black pigment.Below call it as " black pigment-5 ".

[Production Example 6] (manufacture of " black pigment-6 ")

Same with Production Example 1 (1), to 3,3 '-dimethoxy-4 ', 4 '-p-diaminodiphenyl 2.44g (0.01 mole) carries out diazotization.And then, by itself and 2-hydroxyl-11H-benzo [a] carbazole-3-carboxyl-(2 '-methyl)-p-anisidine 3.96g (0.01 mole) and 5 '-chloro-3-hydroxyl-2 ', 3 '-dimethoxy-naphthanilide 3.58g (0.01 mole) coupling, thus the thick pigment obtaining black azo-dye.The receipts amount of the black azo-dye of gained is 9.59g.Then, utilize Dry-crusher to be pulverized by the thick pigment of the black azo-dye of above-mentioned acquisition, thus carry out pigmenting, obtain the miniaturization powder pigments of black pigment.The median size of the pigment of gained is 110nm.Below call it as " black pigment-6 ".

[Production Example 7] (manufacture of " black pigment-7 ")

(1) manufacture of black pigment derivative-1

Diazotization is carried out to sulfanilic acid 1.73g (0.01 mole).Then, by itself and 3.82g (0.01 mole) coupling of 2-hydroxyl-11H-benzo [a] carbazole-3-carboxyl-p-anisidine.And then, wash after products therefrom is filtered, obtain the filter cake with sulfonic black pigment derivative.Below call it as " filter cake of black pigment derivative-1 ".The receipts amount of gained filter cake converts with solids component and counts 5.49g.In addition, drying, pulverizing are carried out to above-mentioned filter cake, obtain the fines pigment with sulfonic pigment derivative.Below call it as " black pigment derivative-1 ".

(2) (manufacture of " black pigment-7 ")

The filter cake of the filter cake of the black pigment-1 of gained in (1) described in Production Example 1 with the black pigment derivative-1 obtained in above-mentioned (1) is coordinated than the mode reaching 10:1 according to pigment solids composition, is mixed to fully evenly.Then, said mixture is dry, thus obtain the thick pigment of the black pigment containing pigment derivative.Then, after (2) described in Production Example 1 carry out the miniaturization process of pigment, utilize sour water to carry out the dissolving of salt etc., it is filtered, the filtrate of gained is washed, thus obtain the filter cake of black azo-dye.The median size of the pigment of gained is 50nm.In addition, by above-mentioned filtration cakes torrefaction, pulverizing, obtain the miniaturization powder pigments of the black pigment containing anionic property pigment derivative.Below call it as " black pigment-7 ".

[Production Example 8] (manufacture of " black pigment-8 ")

Utilize the method synthesizing cationic pigment derivative described in No. 3268748, Japanese Patent.Specifically, be first that the ratio of 2:1:1 makes 1-aminoanthraquinone, two (N, N-dimethylaminopropyl) amine and cyanuric chloride react with mol ratio, as cationic pigment derivative, two (N, the N-dimethylaminopropyl) amino-s-triazine of synthesis 2,4-two (anthraquinonyl is amino)-6-.By the filter cake of gained cationic pigment derivative and Production Example 1(1) in the filter cake of black pigment-1 that obtains reach 85:15 according to solids component ratio and coordinate.And then, they are mixed to fully evenly dry, obtain the thick pigment of the black pigment containing cationic pigment derivative.Then, after the thick pigment of method to gained of (2) described in Production Example 1 carries out miniaturization process, filter after utilizing water to be dissolved by salt etc., filtrate is washed, thus obtains the filter cake of black azo-dye.The median size of the pigment of gained is 50nm.In addition, pulverize after gained filtration cakes torrefaction, obtain the miniaturization powder pigments of the black pigment containing cationic yellow ultramarine derivative.Below call it as " black pigment-8 ".

[Production Example 9] (manufacture of " black pigment-9 ")

With Production Example 1(1) same, to 3,3 '-dimethoxy-4 ', 4 '-p-diaminodiphenyl 1.95g(0.008 mole) carry out diazotization after, add fluoroboric acid, prepare tetrazolium boron fluoride double salt (diazonium salt).Therewith dividually, to thionamic acid 0.69g(0.004 mole) carry out diazotization.With by these 2 kinds of diazo liquids and 2-hydroxyl-11H-benzo [a] carbazole-3-carboxyl-p-anisidine 7.65g(0.02 mole) mode of coupling simultaneously, while the mode almost terminated according to the dropping of above-mentioned 2 kinds of diazo liquids carries out adjusting edge carry out coupling simultaneously.Afterwards, carry out filtering, washing, obtain the filter cake of black azo-dye.To gained filtration cakes torrefaction, obtain containing the black pigment with sulfonic black pigment derivative (thick pigment).The receipts amount of gained black pigment is 9.97g.Then, the miniaturization process of the thick pigment of gained is carried out.Specifically, after carrying out miniaturization process according to the method for (2) of Production Example 1 record, filter after utilizing sour water to be dissolved by salt etc., the filtrate of gained is washed, obtains the filter cake of black azo-dye.The median size of the pigment of gained is 50nm.Pulverize after this filtration cakes torrefaction, obtain the miniaturization powder pigments of black pigment.Below call it as " black pigment-9 ".

[Production Example 10] (manufacture of " black pigment-10 ")

With Production Example 1(1) same; to 2-methoxyl group-5-N-phenylcarbamoyl aniline 4.85g(0.02 mole) carry out diazotization; make itself and 1; 4-phenylene-bis-(2-hydroxyl-11H-benzo [a] carbazole-3-methane amide) 6.27g(0.01 mole) coupling, obtain the thick pigment of black azo-dye.Receipts amount is 10.35g.Then, utilize Dry-crusher to pulverize, obtain the miniaturization powder pigments of black pigment.Hereinafter referred to as " black pigment-10 ".The median size of the pigment of gained is 80nm.

[embodiment 1] (evaluation of the optical characteristics of the film of the black pigment-1 containing Production Example 1)

(1) preparation of the black coating PET film of black pigment-1 is used

In order to observe the optical characteristics of the black pigment-1 of Production Example 1 gained, prepare black coating fluid.As used varnish, coordinate with the ratio of 80:20 and there is the 50% dimethylbenzene-butanols mixed solvent solution (acid number 10mgKOH/g) of the acrylic resin of carboxyl and the 50% dimethylbenzene-butanols mixed solvent solution of butylation methylol melamine resin, prepare varnish (calling it as below " varnish ").Diluting solvent uses the mixed solvent (4:1) (calling it as below " diluting solvent ") of dimethylbenzene-butanols.

3 parts of black pigments-1,24 parts, varnish, diluting solvent 6 parts and the granulated glass sphere 48 parts as dispersion medium are loaded in dispersion container, utilizes paint mixer to disperse 3 hours.Afterwards, add 36 parts, varnish further, continue dispersion and take out after 10 minutes, as coating fluid.Pigment composition in coating fluid and the ratio of resin solid content are 1:10.After using bar coater that the black coating solution as above obtained is carried out drying on polyethylene terephthalate (PET) film, at 130 DEG C, make it solidify, obtain black coating PET film.The average dry film thickness of the black coating film formed is 34nm.

(2) mensuration of the transmissivity of visibility region and near infrared region

Hitachi's spectrophotometer (U-4100 type, Hitachi's system) is used to measure the transmissivity in visible portions and near infrared portion to the black coating PET film obtained in above-mentioned (1).Table 4 and table 5 show the measurement result of regional.

Table 4: the spectral transmission employing the visibility region of the black coated film of black pigment-1

Table 5: the spectral transmission employing the region of ultra-red of the black coated film of black pigment-1

As shown in the measurement result of the spectral transmission of table 4 and table 5, confirm the film containing black pigment-1 in the whole wavelength region may of 400 ~ 750nm throughout visible region, spectral transmission is 0%, almost non-transmission (with reference to table 4).On the other hand, in region of ultra-red, the transmissivity of 900nm is approximately 34%, and then confirms that transmissivity rises (with reference to table 5) reposefully in the side that wavelength is longer.

(3) and then, the black coating film in the PET film using high resistivity meter Hiresta-UP [Mitsubishi of Co., Ltd. chemistry ア Na リ テ ッ Network system] to obtain above-mentioned (1) measures volume intrinsic resistance.Measurement result is shown as 10 ¹⁴more than Ω cm, confirms that insulativity is very high.

[embodiment 2] (evaluation of the reflective character of the film of the black pigment-1 containing Production Example 1)

(1) preparation of the black color development paper of black pigment-1 is used

In order to observe the reflection characteristic of black pigment-1, in (1) that uses the applicator of 6 mils embodiment 1 to be recorded black coating solution of preparation on white color development paper after carry out drying, make it be solidified to form film, obtain black coating color development paper (hereinafter referred to as black color development paper).The measured value being formed at the dry film thickness of the black coating film on this black color development paper is about 35 ~ 40nm on color development paper.

(2) measure the visible portions of black color development paper and the reflectivity near infrared portion that above-mentioned (1) obtain, table 6 shows measurement result.

Table 6: the spectral reflectance employing the black color development paper of black pigment-1

Results verification is as shown in Table 6 in the black color development paper using black pigment-1 to make, the reflectivity of 5 ~ 6% is only shown to about 750nm, at 800nm ~ 900nm, reflectivity rises sharp, and then is roughly 70% ~ 80% or maintain higher reflectivity at the near infrared region of the longer side of wavelength.Thought by these facts, due to while the reflection from surface of pigments, transmitted light reflected by the blank sheet of paper of substrate, the light caused thus is added and and become reflected light, therefore the light reflectance of black color development paper increases.Thus, by the transmitance that increases black pigment, the substrate that utilizes reflectivity high, can reflect near IR line efficiently.In addition, in above-mentioned table 6, the reflectivity to about 750nm is not 0% but becomes the value of 5%, and this is relevant with determinator.

[embodiment 3]

(1) similarly to Example 1, use the black pigment-2 ~ 6 obtained in Production Example 2 ~ 6 respectively, make black coating film, measure the spectral transmission of visibility region and region of ultra-red similarly to Example 1.Table 7 and table 8 show result.

Table 7: the spectral transmission (%) using the visibility region of the black color development paper of black pigment-2 ~ 6

Table 8: the spectral transmission (%) using the region of ultra-red of the black color development paper of black pigment-2 ~ 6

(2) similarly to Example 2, use the black pigment-2 ~ 6 obtained in Production Example 2 ~ 6 respectively, form black coating film, make black color development paper respectively.The dry film thickness of black coating film is about 35 ~ 40nm on black color development paper.Measure spectral reflectance similarly to Example 2.Its result is that spectral reflectance is as shown in table 9, is coated with color development paper shows same tendency with the black using black pigment-1 to obtain.

Table 9: the spectral reflectance (%) using visible, the region of ultra-red of black pigment-2 ~ 6

[embodiment 4] (polycarbonate resin profiled sheeting)

After utilizing Henschel mixer (high-speed powder mixer) to mix black pigment-2 prepared by 20 parts of Production Examples 2, polycarbonate resin powder 80 parts fully, and then utilize twin screw extruder to carry out mixing, mixing, the polycarbonate resin black master batch of preparation containing 20% black pigment-2.The black master batch 2 parts of gained is engaged in the polycarbonate resin pellets 100 parts be made up of toner similar to the above, after utilizing Henschel mixer to mix, and then utilize twin screw extruder to carry out mixing, mixing, make black resin particle.Use screw rod injection moulding machine in upright arrangement to carry out shaping to gained black resin particle, obtain the black polycarbonate resin board of pigment-dispersing excellence.The resin board of this black absorbs the light of visible region, on the other hand due to can transmission near infrared ray fully, therefore can use in the purposes such as infrared transmission wave filter.

[embodiment 5] (acrylic resin profiled sheeting)

Similarly to Example 4, after utilizing Henschel mixer to mix black pigment-3 prepared by 20 parts of Production Examples 3,80 parts, acrylic resin (polymethylmethacrylate) powder fully, and then utilize twin screw extruder to carry out mixing, mixing, the acrylic resin black master batch of preparation containing 20% black pigment-3.

The black master batch 2 parts of gained is engaged in after in the acrylic resin particle 100 parts be made up of resin similar to the above, after utilizing Henschel mixer to mix further, and then utilize twin-screw extrusion mixing roll to carry out mixing, mixing, make black resin particle.Use the black resin particle of screw rod injection moulding machine in upright arrangement to gained to carry out shaping, obtain the black acrylic resin board of pigment-dispersing excellence.The resin board of this black absorbs the light of visible region, on the other hand due to can transmission near infrared ray fully, therefore can use as infrared transmission wave filter.

[embodiment 6] (polyurethane-coated agent)

According to the black pigment-4 of preparation in Production Example 4 be 15 parts, polycarbonate-based without xanthochromia type polyurethane resin be 10 parts, dimethyl formamide (hereinafter referred to as " DMF ") is 75 parts, concocts black pigment and polycarbonate-based without xanthochromia type polyurethane resin solution, DMF.Use horizontal continuum dispersion machine to disperse this blending liquid fully, obtain black pigment high concentration dispersion.Then, formation as epidermal area is used, polycarbonate-based without xanthochromia type polyurethane resin solution (solids component 30%, DMF solvent) 100 parts in add propyl acetate 10 parts as diluting solvent, Virahol 10 parts, the black pigment high concentration dispersion 20 parts prepared before mix, the polyurethane coated liquid of modulation black.

Then, the coating fluid of the black of above-mentioned modulation is coated on release paper DNTP-155T-FLAT(trade(brand)name, Janpanese Printing Co., Ltd's system with flake) on, make thickness reach 50 μm, under the condition of 100 DEG C/10 minutes, make it dry afterwards, form epidermal area.Then, as tackiness agent, prepare to mix in polycarbonate-based xanthochromia type polyurethane resin solution (solids component 70%, toluene: methylethylketone (hereinafter referred to as " MEK ")=1:1 solvent) 100 parts the tackiness agent obtained as the toluene 10 parts of diluting solvent, MEK20 part, DMF20 part and modified polyisocyanate system linking agent (solids component 75%, ethyl acetate solvent) 10 parts and amine system crosslinking catalyst (solids component 0.5%MEK solvent) 0.15 part.Then, this tackiness agent is coated on epidermal area surface (being contacted with the face of the opposition side in the face of release paper) with flake, makes thickness reach 75 μm, under the condition of 80 DEG C/5 minutes, then make it dry.Bonding coat side is layered on base material (fabric) sheet material with bonding coat and epidermal area of gained, makes the sandwich that total thickness is 1100 μm, utilize the laminating roll being heated to 100 DEG C closely sealed with the space of 500 μm pressurization to the sandwich of gained.Then, after carrying out slaking in 60 DEG C/48 hours, peel off from release paper, obtain synthesis of artificial leather.The synthesis of artificial of gained has been got rid of accumulation of heat and has been reduced outside (alleviating) to some extent, and the excellent durability such as resistance to thermal deterioration, hydrolysis deterioration, fast light deterioration, resistance to acidity of oil, are suitable for vehicular applications etc.

In addition, contain white pigment by making the tackiness agent of above-mentioned middle use, be coloured to white, when giving light reflective to binder layer, when forming the dual structure be made up of the epidermal area of black azo-dye containing display visible ray opacifying property and these two kinds of optical characteristics of infrared transmission, obtaining can the synthetic polyurethane leather of reverberation ray.This synthetic leather is particularly suitable for the purposes such as the interior finish of automobile.

[embodiment 7] (original liquid coloring spinning)

Utilize Henschel mixer to mix the black pigment-5 of preparation in the Production Example 5 of 50 parts, two 50 parts, the stearic amide powder of ethene as pigment dispersing agent, obtain the powder colorant (dry color) that pigment composition is 50%.Then, the dry color 1.0 parts of gained is engaged in after in acrylic resin particle 99.0 parts, utilizes Henschel mixer to mix, and then utilize exhaust 40m/m forcing machine to carry out mixing, thus prepare the black resin particle that pigment composition is 0.5%.Use the black resin particle of melt spinning machine to gained to carry out spinning, obtain the black polypropylene original liquid coloring silk that fiber number is the distinctness of your pigment-dispersing excellence of 10 Brittanies.The invisible heat of weaving cotton cloth owing to can reflect direct sunlight using this painted silk to make, therefore can expect the effect of avoiding heating up.Thus the purposes of parasol or curtain etc. is particularly suitable for.

[embodiment 8] (resin forming)

Utilize Henschel mixer to mix in 5 parts of Production Examples 6 black pigment-6 of preparation, titanium oxide white pigment 20 parts, polyethylene resin powder 75 parts as pigment dispersing agent, obtain powder colorant (dry color).Then, the powder colorant 1.0 parts of gained is engaged in polybutylene terephthalate (PBT) resin particle 100 parts, after utilizing Henschel mixer to mix, carries out mixing with forcing machine, thus obtain black resin particle.Use screw rod injection moulding machine in upright arrangement to carry out shaping to the black particle of gained, obtain the black PBT resin profiled sheeting of pigment-dispersing excellence.The resin forming plate of gained reflects the invisible heat of direct sunlight.Therefore, this resin is suitable for as avoiding the synthetic resin heated up to use.

[embodiment 9] (solar power generation module thermal insulation backboard)

(1) black pigment-4, the acrylic polyol (hydroxyl value: 100) after butylacetate solution (solids component 50%) 25 parts, butylacetate 50 parts of preparation in ready-mixed 15 parts of Production Examples 5 fully, utilize and use the horizontal continuum dispersion machine of granulated glass sphere by colo(u)rant dispersion as dispersion medium, thus prepare black pigment high concentration dispersion.

Add in the black pigment high concentration dispersion 90 parts of above-mentioned acquisition acrylic polyol butylacetate solution 22 parts similar to the above, by benzotriazole system monomer and HALS system monomer copolymerization acrylic polyol (hydroxyl value: 100) butylacetate solution 50 parts, carries out black ink.And then, in the product of black ink, add isocyanuric acid ester type hexamethylene diisocyanate 3 aggressiveness (solids component: 100%, isocyanic ester %:21.7%) 24 part as solidifying agent at this, fully after mixing, add the butylacetate of about 20 parts, adjustment viscosity, prepares black coating fluid.

(2) the acrylic polyol butylacetate solution 40 parts used in ready-mixed above-mentioned (1) in titanium oxide white pigment 80 parts and butylacetate 20 parts, then, use with identical horizontal continuum dispersion machine used in above-mentioned (1) by colo(u)rant dispersion, thus prepare white pigment high concentration dispersion.

In the white pigment high concentration dispersion 140 parts of above-mentioned acquisition, add acrylic polyol butylacetate solution 44 parts carry out white ink.Then, this add as solidifying agent in the product of white ink 18 parts with before identical hexamethylene diisocyanate 3 aggressiveness that uses after mix fully, add the butylacetate of about 40 parts, adjust viscosity, prepare white coating fluid.

(3) the black coating fluid applying preparation in above-mentioned (1) on the surface of polyethylene terephthalate (PET) substrate sheet (thickness: 100 μm) carries out drying, forms black coating film (dry film thickness: 5 μm).And then the white coating fluid obtained in the backside coating of base material above-mentioned (2) carries out drying, form white film (dry film thickness: 5 μm), obtain the black-white multilayer PET sheet material that surface scribbles black coating film, the back side scribbles white film.

(4) on the black-white multilayer PET sheet material obtained in above-mentioned (3), in order to give water vapor barrier and barrier properties for gases, with mode stacked silica alumina evaporation polyester film (thickness: 12 μm) overlapping on white film face overleaf, and then stacked PET base material sheet material (thickness: 100 μm) thereon, make the PET backboard of solar power generation module.Above-mentioned stacked time, use following tackiness agent.Tackiness agent use by with identical acrylic acid multielement alcoholic solution 70 parts used in above-mentioned (1) and hexamethylene diisocyanate 3 aggressiveness 15 parts and butylacetate 15 parts of tackiness agents formed.

As above obtain by have black coating film and the multi-layer coated and PET backboard that obtains of white film due to outward appearance be black, therefore aesthetic property is excellent, and due to the optical characteristics of black pigment-4 used, therefore has following optical property.That is, the light of the region of ultra-red in sunlight is from the light of the region of ultra-red of the black coating film layer transmission on surface, transmission by the white layer reflects of substrate, again emitted to outside from black layer transmission.Therefore, this backboard, owing to seldom absorbing the thermal insulation of sunlight, display excellence, is thus particularly suitable for the backboard being used as to wish to avoid the solar power generation module heated up.

When using the backboard of above-mentioned acquisition as solar power generation module, can use as follows according to conventional methods.Namely; the sealing material clamping solar power generation pond be made up of ethane-acetic acid ethyenyl ester system resin is utilized to seal; adhesive surface seal stock on the surface of sensitive surface side; as the protection sheet material of the non-sensitive surface side at the back side; after the black side of above-mentioned opacifying property backboard is pasted towards sensitive side; sensitive surface equips transparent glass substrate, thus solar power generation module can be made.

[embodiment 10] (solar power generation module thermal insulation backboard)

(1) utilize Henschel mixer to mix the black pigment-6, the polyester resin powder 60 parts that obtain in 40 parts of Production Examples 6, obtain powdered colorant.Then, the powdered colorant 12.5 parts of gained be engaged in PET resin particle 87.5 parts, after utilizing Henschel mixer to mix, and then it is mixing to utilize twin screw extruder to carry out, and utilizes tablets press to make black resin particle.Then, utilize T-die extrusion machine to carry out shaping, make the black PET film of thickness 50 μm.

(2) in addition, prepared to have carried out mixing painted white PET sheet (thickness: 180 μm) with titanium oxide pigments.Then, use in its surface and the identical acrylic polyol hexamethylene diisocyanate system tackiness agent described in (4) of embodiment 9, paste the black PET film of gained in above-mentioned (1), thus make the white PET sheet being laminated with black PET film.

(3) be laminated with in the white PET sheet of black PET film in above-mentioned acquisition, in order to give moisture resistance and barrier properties for gases, first on the back side of this sheet material, acrylic acid multielement alcohol ester (acrylic polyol) the hexamethylene diisocyanate system tackiness agent used in above-mentioned (2) is used, lamination silica alumina evaporation polyester film.And then, use tackiness agent same as described above to carry out lamination PET base material sheet material (thickness: 100 μm) thereon, thus make solar power generation module backboard.

The outward appearance employing the solar power generation module backboard of the sheet material black film of above-mentioned gained and white PET sheet are laminated is that black, aesthetic property are excellent, and due to the optical characteristics of used black pigment-6, therefore has following optical property.That is, the light of the region of ultra-red in sunlight, after the black rete transmission on surface, is reflected by white PET sheet below, again after black film transmission, is released to outside.Therefore, black-white multilayer PET sheet material seldom absorbs sunlight as solar power generation module backboard, the thermal insulation that display is excellent, is therefore particularly suitable for the solar power generation module backboard being used as to wish to avoid heating up.

When using the backboard of above-mentioned acquisition as solar power generation module, can use as follows according to conventional methods.Namely; the sealing material clamping solar power generation unit be made up of ethylene vinyl acetate system resin is utilized to seal; adhesive surface seal stock on the surface of sensitive surface side; as the protection sheet material of the non-sensitive surface side at the back side; after the black side of above-mentioned opacifying property backboard is pasted towards sensitive side; sensitive surface equips transparent glass substrate, thus solar power generation module can be made.

[embodiment 11] (weaving cotton cloth with printing and dyeing paste)

By contain 25 parts with solid component meter Production Example 1 in the filter cake 71 parts of black pigment-1 of gained, nonionic series pigments dispersion agent 10 parts, defoamer 1 part, 18 parts, water is fully after ready-mixed, utilize and use the horizontal continuum dispersion machine of granulated glass sphere by colo(u)rant dispersion as dispersion medium, prepare black pigment high concentration dispersion (black pigment substrate).Use refiner (powerful emulsion dispersion machine) that the black pigment substrate 20 parts of gained, 25 parts, reactive acroleic acid acid alkyl ester latex (solids component 40%), defoamer 0.5 part, dispersion agent 1 part, oil-in-water type emulsion dispersion stabilizer 3 parts, mineral turpentine 38 parts, 12.5 parts, water are carried out emulsion dispersion, preparation oil-in-water-type black emulsion mashed prod.Then, in prepared black emulsion mashed prod, add the linking agent (solids component 40%) 2 parts of carbodiimide system, mix fully, prepare black printing and dyeing and stick with paste.Whole printing on polyester-cotton blended fabric is stuck with paste in the printing and dyeing of the black of gained, at 120 DEG C, carries out the solidification of 15 minutes, obtain the plain color dyeing cloth that can block the black of invisible heat.

[embodiment 12] (gravure printing ink)

The black pigment-10 obtained in 11 parts of Production Examples 10 is added into and utilizes diamines to carry out chain length prolongation to isocyanic ester end polyester and in 40% methylethylketone-toluene (1:3) mixed solvent solution 30 parts of urethane resin that obtains.Then, add 40% toluene solution, methylethylketone-toluene-Virahol (50:30:20) mixed solvent 54.5 parts of cation property copolymer dispersion agent 2 parts, the 2.5 parts polycarbodiimide compounds obtained by tolylene diisocyanate, utilize homogenizer fully to mix.And then, utilized by said mixture the horizontal continuum dispersion machine as dispersion medium use granulated glass sphere to carry out differential to pigment and fall apart, prepare black gravure printing ink.Use gravure printing machine to be printed on polyamide membrane, polyester film, polypropylene screen respectively by the black gravure printing ink of gained, obtain the black polypropylene film that visible ray, the ultrared optical characteristics of transmission are blocked in display.

[embodiment 13] (formation of the BM of CF)

(1) (preparation of BM dispersible pigment dispersion)

(preparation of black pigment dispersion liquid)

By gained black pigment-9, benzyl methacrylate-methacrylic acid-2-hydroxyethyl methacrylate multipolymer (mol ratio: 60:20:20, weight-average molecular weight 30000) 40% solution 20 parts, cationic polymerization system dispersion agent 2 parts and propylene glycol monomethyl ether (PGMA) 53 parts ready-mixed fully in 25 parts of Production Examples 9.Then, use continous way horizontal media dispersion machine to be fallen apart by pigment differential, obtain black pigment dispersion liquid (calling it as below " black pigment dispersion liquid-1 ").

(2) (preparation of light sensitive black resist ink)

Using the black pigment dispersion liquid-1, the 50%PGMA solution 6 parts of acrylated acrylic acid multielement alcohol ester photoresist, Viscoat 295 1 part, dipentaerythritol acrylate 1 part, the ethyl ketone as Photoepolymerizationinitiater initiater that obtain in 40 parts above-mentioned (1); 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base]-, 1-(O-ethanoyl oxime) (" イ Le ガ キ ュ ア OXE02 ", BASF AG's system) 1 part and PGMA51 part coordinates.Afterwards, utilize homogenizer to be stirred to fully evenly, utilize aperture to be that the strainer of 3 μm filters, the black anti-corrosion agent ink (hereinafter referred to as " light sensitive black resist ink-1 ") of preparation containing black pigment-9.

(3) (evaluation of black anti-corrosion agent film)

Use the light sensitive black resist ink-1 of above-mentioned acquisition, utilize spin coater to be coated with on the glass substrate.And then carry out prebake conditions prepare drying at 60 DEG C after, after using ultrahigh pressure mercury lamp to expose with the light quantity of 400mJ/cm2, toast 30 minutes after carrying out at 230 DEG C, obtain the black coating film (black anti-corrosion agent ink film) that thickness is 3 μm.

The optical characteristics of this film is as shown in table 10, shows high-absorbable, in the region of ultra-red of 900 ~ 1500nm, show highly transmissive in the wavelength region of the about 400 ~ 750nm of visible region.In addition, the volume intrinsic resistance display 10 of this film ¹⁴more than Ω cm, therefore confirms as high-insulativity.

Table 10: the spectral transmission of black anti-corrosion agent film

(4) (preparation of BM pattern)

Use the light sensitive black resist ink-1 of above-mentioned acquisition, utilize spin coater to be coated with on the glass substrate according to conventional methods, prebake conditions 10 minutes at 80 DEG C, obtain the black coating film that thickness is 3 μm.Via the minus optical mask pattern of BM pattern on this film, use ultrahigh pressure mercury lamp, with 100mJ/cm ²light quantity expose after, utilize alkaline-based developer to develop, washing, after drying, form BM pattern.

To be formed by the BM film of the BM pattern of above-mentioned gained due to the high electrical insulating property of display as described in above-mentioned (3), therefore can be used in the modification method of the various CF forming BM on the active components such as TFT, such as replace spacer to keep the structure of BM, IPS mode, COA mode etc. of thickness of liquid crystal layer.In addition, this BM film is owing to can absorb visibility region fully to long wavelength region, and the BM that therefore also can be used as the LCD that have employed LED-backlit uses.

(5) (preparation of each dispersible pigment dispersion of redness, green, blueness, yellow, purple)

Same with described before (1), use PR254(diketopyrrolo-pyrrole red pigment), PR177(anthraquinone system red pigment), PG36(copper phthalocyanine veridian), PB15:6(ε type copper phthalocyanine blue pigments), PY138(yellow ultramarine) and PV23(dioxazine violet pigment) each pigment, add in this pigment 19 parts and corresponding with each pigment known there is sulfonic pigment derivative 1 part, obtain the color compositions of colors.Use the color compositions of gained, prepare the various pigments dispersion liquid of each pigment composition is 20%, pitch dispersant is 6% redness, green, blueness, yellow, purple respectively.

Then, gather the mixed solution 33 parts coordinated by the dispersible pigment dispersion respectively containing PR254 and PR177 of above-mentioned preparation with the ratio of 8:2, same with described before (2), add photoresist 50% solution 9.2 parts, photopolymerization monomer 3 parts, Photoepolymerizationinitiater initiater 0.3 part, solvent 54.5 parts, prepare red resist ink.As described above, coordinate the dispersible pigment dispersion respectively containing PG36 and PY138 with the ratio of 5:5, modulate green resist ink, coordinate the dispersible pigment dispersion respectively containing PB15:6 and PV23 with the ratio of 8:2, modulate blue resist ink.

(6) (formation of the rgb pixel of CF)

The glass substrate of the BM be formed made by above-mentioned (4) is arranged on spin coater, after the spin coating of the photosensitivity of above-mentioned preparation red resist ink, prebake conditions 10 minutes at 80 DEG C.And then, utilize the photomask with mosaic shape pattern, use proximity to aim at exposure machine, with ultrahigh pressure mercury lamp with 100mJ/cm ²the coated face of light quantity to this glass substrate expose.Then, after utilizing special developing solution and special leacheate to develop, carry out washing and drying, form red mosaic shape pattern on the glass substrate.And then as described above, the green resist ink of use sense photosensitiveness forms the pattern of green mosaic shape, and the blue resist ink of use sense photosensitiveness forms the pattern of blue mosaic shape, obtains the CF being formed with BM and rgb pixel.

In addition, replace the black pigment-9 of above-mentioned use, use the black pigment-7 obtained in Production Example 7, in addition as described above, carry out the preparation of light sensitive black resist ink, and then form above-mentioned BM pattern and rgb pixel pattern, obtain the CF being formed with BM and rgb pixel.

[embodiment 14] (formation of the BM of CF)

(1) (preparation of BM dispersible pigment dispersion)

(preparation of black pigment dispersion liquid)

With embodiment 13(1) in carry out same, 25 parts are replaced the black pigment-8 of black pigments-9, with after identical benzyl methacrylate-methacrylic acid-2-hydroxyethyl methacrylate multipolymer 40% solution 25 parts used before and propylene glycol monomethyl ether (PGMA) 53 parts fully ready-mixed, utilize continous way horizontal media dispersion machine by colo(u)rant dispersion, thus obtain black pigment dispersion liquid.Below call it as " black pigment dispersion liquid-2 ".

(2) (preparation of light sensitive black resist ink)

Replace the black pigment dispersion liquid-1 of (2) illustrated in embodiment 13, use the black pigment dispersion liquid-2 obtained in above-mentioned (1), in addition with embodiment 13(2) same, prepare black anti-corrosion agent ink.Below call it as " light sensitive black resist ink-2 ".

(3) (preparation of BM pattern)

Same with (4) illustrated by embodiment 13, utilize spin coater by the coating of light sensitive black resist ink-2 on the glass substrate, carry out prebake conditions, thus obtain the black coating film that thickness is 3 μm.Via the minus optical mask pattern of BM pattern on this film, use ultrahigh pressure mercury lamp to expose, utilize alkaline-based developer to carry out development after washing, drying, form BM pattern.

Form the BM film of this BM pattern owing to having high electrical insulating property, therefore similarly to Example 13, the modification method of the various CF forming BM on active component can be used in, such as the structure of the BM of fixed spacers or the structure of IPS mode, COA mode etc.In addition, this BM film is owing to can absorb visibility region fully to long wavelength region, and the BM that therefore also can be used as the LCD that have employed LED-backlit uses.

(4) (formation of the rgb pixel of CF)

Same with (6) illustrated by embodiment 13, the glass substrate being formed with BM that above-mentioned (3) obtain is arranged on spin coater, use the red resist ink of the photosensitivity obtained in (5) illustrated in embodiment 13, the green resist ink of photosensitivity, the blue resist ink of photosensitivity to form assorted mosaic shape pattern of pixels, obtain the CF being formed with BM and rgb pixel.

[evaluation result]

The CF obtained in embodiment 13, embodiment 14 has excellent quality in the chromatic characteristic, optical characteristics of the image properties such as tractability, depth of shade, transmitance, comparative.

Claims (21)

1. a black azo-dye, it is characterized in that, it is for showing the black azo-dye of visible ray opacifying property and these two kinds of optical characteristics of infrared transmission, described optical characteristics is: the black colorant film containing this black azo-dye in transparent substrate shows the spectral transmission of less than 5% in the wavelength region of 400 ~ 750nm of visible-range, and then described black colorant film shows the transmissivity of more than 30% in the wavelength region of 900 ~ 1500nm of region of ultra-red;

Described black azo-dye is the polyazo pigment of the black of any one structure had at least following (1) ~ (3) of at least 1 2-hydroxyl-11H-benzo [a]-carbazole-3-carboxylic acid amide residue comprising more than 2 azo bond in the molecule and imported by coupling composition, and the median size of described black azo-dye is 10nm ~ 200nm

(1) structure shown in [HBC-N=N-Ar-N=N-HBC], it uses the diazonium salt with the compound diazotization of more than 2 amino using as diazo component, make this salt and to carry out azo coupling as 2-hydroxyl-11H-benzo [a]-carbazole-3-carboxylic acid aryl amide of coupling composition and HBC, wherein, the representative formula described in the compound of more than 2 amino is H ₂n-Ar-NH ₂, and be selected from 3,3 '-two chloro-4,4 '-p-diaminodiphenyl, 3,3 '-dimethoxy-4 ', any one in the group of 4 '-p-diaminodiphenyl; Described 2-hydroxyl-11H-benzo [a]-carbazole-3-carboxylic acid aryl amide is for being selected from any one in the group of 2-hydroxyl-11H-benzo [a]-carbazole-3-carboxyl-p-anisidine, 2-hydroxyl-11H-benzo [a]-carbazole-3-carboxyl-(2 '-methyl)-p-anisidine, 2-hydroxyl-11H-benzo [a]-carbazole-3-carboxy-N-benzimidazolone-5-acid amides;

(2) structure shown in [HBC-N=N-Ar-N=N-Cp], it uses the diazonium salt with the compound diazotization of more than 2 amino using as diazo component, make this salt and to carry out azo coupling as 2-hydroxyl-11H-benzo [a]-carbazole-3-carboxylic acid aryl amide of coupling composition and HBC and other coupling compositions Cp except this compound, wherein, the representative formula described in the compound of more than 2 amino is H ₂n-Ar-NH ₂, be 3,3 '-dimethoxy-4 ', 4 '-p-diaminodiphenyl; Described 2-hydroxyl-11H-benzo [a]-carbazole-3-carboxylic acid aryl amide is 2-hydroxyl-11H-benzo [a]-carbazole-3-carboxyl-(2 '-methyl)-p-anisidine; Described other coupling compositions Cp is 5 '-chloro-3-hydroxyl-2 ', 3 '-dimethoxy-naphthanilide;

(3) structure shown in [Ar-N=N-HBC-HBC-N=N-Ar], it uses to have after 1 amino compound carries out diazotization as diazo component, azo coupling is carried out with the coupling composition HBC-HBC in the molecule with more than 2 2-hydroxyl-11H-benzo [a]-carbazole-3-carboxamide residues and HBC-, wherein, there is described in 1 amino compound and be expressed as Ar-NH ₂, be 2-methoxyl group-5-N-phenylcarbamoyl aniline; Described coupling composition HBC-HBC is phenylene-(Isosorbide-5-Nitrae-) two (2-hydroxyl-11H-benzo [a]-carbazole-3-methane amide).

2., for obtaining the manufacture method of black azo-dye according to claim 1, it has the synthesis procedure of the polyazo pigment of black and as required this pigment is carried out to the operation of miniaturization,

(I) synthetic method of the polyazo pigment of described black is any one method in following (1) ~ (3):

(1) make 2-hydroxyl-11H-benzo [a]-carbazole-3-carboxylic acid aryl amide and HBC and the diazonium salt with more than 2 amino compound diazotization is carried out the synthetic method of azo coupling, wherein, the representative formula described in the compound of more than 2 amino is H ₂n-Ar-NH ₂, for being selected from 3,3 '-two chloro-4,4 '-p-diaminodiphenyl, 3,3 '-dimethoxy-4 ', any one in the group of 4 '-p-diaminodiphenyl; Described 2-hydroxyl-11H-benzo [a]-carbazole-3-carboxylic acid aryl amide is for being selected from any one in the group of 2-hydroxyl-11H-benzo [a]-carbazole-3-carboxyl-p-anisidine, 2-hydroxyl-11H-benzo [a]-carbazole-3-carboxyl-(2 '-methyl)-p-anisidine, 2-hydroxyl-11H-benzo [a]-carbazole-3-carboxy-N-benzimidazolone-5-acid amides;

(2) have and make 2-hydroxyl-11H-benzo [a]-carbazole-3-carboxylic acid aryl amide and HBC and other coupling compositions Cp except this compound and the synthetic method of the diazonium salt with more than 2 amino compound diazotization being carried out the polyazo pigment of the structure of azo coupling, in this synthetic method, make by the diazonium salt with more than 2 amino compound diazotization with to wait mole or its following other coupling compositions Cp carries out azo coupling, the polyazo pigment of more than 2 other coupling compositions Cp coupling is had to be separated as required, removing, then above-mentioned coupling composition HBC is made to carry out azo coupling with the diazo of non-coupling, wherein, the described representative formula with the compound of more than 2 amino is H ₂n-Ar-NH ₂, be 3,3 '-dimethoxy-4 ', 4 '-p-diaminodiphenyl, described 2-hydroxyl-11H-benzo [a]-carbazole-3-carboxylic acid aryl amide is 2-hydroxyl-11H-benzo [a]-carbazole-3-carboxyl-(2 '-methyl)-p-anisidine, described other coupling compositions Cp is 5 '-chloro-3-hydroxyl-2 ', 3 '-dimethoxy-naphthanilide,

(3) the coupling composition HBC-HBC making to have in the molecule more than 2 2-hydroxyl-11H-benzo [a]-carbazole-3-carboxamide residues and HBC-with will there is 1 amino compd A r-NH ₂the diazo component of diazotization carries out the synthetic method of azo coupling, and described coupling composition HBC-HBC is phenylene-(Isosorbide-5-Nitrae-) two (2-hydroxyl-11H-benzo [a]-carbazole-3-methane amide); It is described that to have 1 amino compound be 2-methoxyl group-5-N-phenylcarbamoyl aniline;

Further, (II), when the polyazo pigment synthesized by aforesaid method is thick, to have the median size miniaturization of pigment by any one method in following (1) or (2) to the operation of 10nm ~ 200nm:

(1) the miniaturization method of any one colo r mill or the colo(u)rant dispersion machine be selected from the group be made up of ball mill, sand mill, masher, horizontal continuum dispersion machine, kneader, continous way singe screw mixing roll, continous way twin screw compounder, triple-roller mill and open roller continuous mixer is used;

(2) in mixing roll with water-soluble salt, carrying out salt that is mixing, that grind together with the water-miscible organic solvent used grinds method as required.

3. a coloured composition, it is characterized in that, the pigment composition containing the black azo-dye comprising black azo-dye according to claim 1 or obtained by manufacture method according to claim 2 in liquid dispersion medium or in solid dispersion medium and being formed.

4. coloured composition according to claim 3, wherein, the pigment composition that comprises described black azo-dye is formed separately by described black azo-dye or is formed with paint with a kind of being selected from the group be made up of coloured pigment, other black pigments and pigment extender for this black azo-dye of correction in this black azo-dye, and this coloured composition is for carrying out the dead color of painted or Achromatic color or the painted of black of dark-coloured colour.

5. coloured composition according to claim 4, wherein, described black azo-dye decides by using computer for colouring system to carry out optimized method with the compounding ratio for the coloured pigment of this black azo-dye of correction, other black pigments or pigment extender.

6. coloured composition according to claim 3, wherein, described liquid dispersion medium contains and is selected from the polymkeric substance can with reactive group, the oligopolymer can with reactive group and can have in the monomer of reactive group at least a kind by film formation material, further containing solvent and/or water.

7. coloured composition according to claim 3, wherein, described solid dispersion medium contains at least a kind of solid dispersion medium be selected from thermoplastic resin, heat-curing resin, wax, fatty acid amide and fatty acid metal soap.

8. the coloured composition according to any one of claim 3 ~ 7, wherein, described coloured composition is used at least arbitrary purposes in coating use, plastics use and image recording use.

9. the coloured composition according to any one of claim 3 ~ 7, wherein, described coloured composition be used to coating agent, fiber, printing-ink, stationery with and Image texture with at least arbitrary purposes in.

10. a colorize method for article, is characterized in that, by the painted of article surface or article self painted color goods become black or dark-coloured time, use the coloured composition described in claim 4.

The colorize method of 11. article according to claim 10, wherein, described article are formed by transparent base material, this transparent base material are carried out surface colour by any one method be selected from application, dyeing, printing, notes or makes above-mentioned base material self carry out inside by compounding process or impregnation method painted.

The colorize method of 12. article according to claim 10, wherein, described article are formed by transparent base material, smeared by this transparent base material, describe, ink jet printing, electronic photo printing, any one method in xeroprinting or photolithography carry out surface colour or it is painted to make above-mentioned base material self carry out inside by compounding process or impregnation method by being selected from.

The colorize method of 13. article according to claim 11 or 12, wherein, described surface colour or the inner painted part according to being colored show in the wavelength region of 400 ~ 750nm of visible region less than 5% spectral transmission, in the region of ultra-red of 900 ~ 1500nm, the mode of the transmissivity of display more than 30% is implemented, and makes the article formed by transparent base material have visible ray opacifying property and these two kinds of optical characteristics of infrared transmission concurrently.

The colorize method of 14. article according to claim 10, wherein, article self are used to have the article of light reflective or be provided with the article of preformed light reflective substrate, the surface of these article or light reflective substrate use described coloured composition carry out application, stickup, deposition, original liquid coloring, printing and dyeing, dip-dye, notes, ink jet printing, electronic photo printing or xeroprinting, thus enforcement show reflexive painted in region of ultra-red.

The colorize method of 15. article according to claim 10, wherein, article self are used to have the article of light reflective or be provided with the article of preformed light reflective substrate, the surface of these article or light reflective substrate use described coloured composition carry out being coated with, overlapping, printing or describe, thus implement to show in region of ultra-red reflexive painted.

16. 1 kinds of dyed articles, is characterized in that, it is the colorize method of the article implemented the claims according to any one of 10 ~ 15.

The backboard of 17. 1 kinds of solar power generation modules, it is characterized in that, it for being laminated with the backboard of the solar power generation module of black or dark colored infrared transmission layer on light reflective sheet material, containing black azo-dye according to claim 1 in infrared transmission layer.

The manufacture method of the backboard of 18. 1 kinds of solar power generation modules, it is characterized in that, base material self is used to have the base material of light reflective as light reflective sheet material, or use the base material being provided with preformed light reflective substrate as light reflective sheet material, the surface of these base materials or light reflective substrate use the coloured composition containing black azo-dye according to claim 1 pass through application, paste, deposition, ink jet printing, electronic photo printing or xeroprinting, enforcement shows reflexive painted in region of ultra-red, stacked black or dark colored infrared transmission layer on light reflective sheet material.

The manufacture method of the backboard of 19. 1 kinds of solar power generation modules, it is characterized in that, the base material using base material self to have light reflective is provided with the base material of preformed light reflective substrate as light reflective sheet material as light reflective sheet material or use, the surface of these base materials or light reflective substrate use the coloured composition containing black azo-dye according to claim 1 by coating, overlapping or printing, enforcement shows reflexive painted in region of ultra-red, stacked black or dark colored infrared transmission layer on light reflective sheet material.

20. 1 kinds of color display panels, is characterized in that, the black matrix" BM be formed on colour filter CF substrate or organic EL light-emitting substrate contains black azo-dye according to claim 1.

21. color display panels according to claim 20, it has CF substrate or organic EL light-emitting substrate, and described CF substrate or organic EL light-emitting substrate are formed with state that is overlapping or contact the black matrix" and electrode that are essentially electrical insulating property.