CN103282443A - 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 cover purposes that ground, visible region absorbs and have transmissivity and utilized optical characteristics useful in the ultrared purposes, have the black polyazo pigment of ad hoc structure at region of ultra-red, and then relate to its manufacture method, coloured composition, the colorize method that uses this coloured composition and dyed articles class.

Background technology

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

In the light, short wavelengths' such as near infrared ray and ultraviolet ray light is different, and human body is not almost had detrimentally affect, is safe light, has therefore developed the electronics that much utilizes ultrared irradiation, receiving infrared-ray in recent years.For example, infra-red remote control emitter and main body receiving apparatus thereof are popularized in daily lifes such as the infrared rays security camera around switch, street corner or the buildings in the door lock of electrical equipment, lighting fixtures, warm water toilet, camera and then automobile, engine starter, garage or infrared monitor control camera.

In addition, proposed in the patent documentation 1 to be equipped with the visible light that sends car headlamp simultaneously and being used for confirm the vehicle front obstacle near infrared light projection light and blocking visible light and make the night viewing device for vehicle of the wave filter of infrared transmission.

As the pigment that uses in the infrared filter of these infrared transmitters, receiving apparatus and the infrared filter of infrared camera etc., expectation shows the light transmission that makes infrared spectral range, the optical characteristics that the light of visible region is blocked fully and the pigment with function of 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.The solar power generation module that constitutes photovoltaic power generation system is installed in by the place of direct irradiation of sunlight, particularly be installed in the roof of open-air vacant lot or outdoor architecture thing or roof etc.But, the intensification that be sunlighted, absorb light can cause the solar power generation module, cause that the power of generating battery reduces.And then, for outward appearance or the dirt that makes electricity generation module becomes not obvious, from aesthetic, also be coloured to black, dark colour, dense colour, according to circumstances this becomes the reason that tangible temperature rises.Therefore, in photovoltaic power generation system, even if being coloured to black, expectation also can suppress the coloring system that temperature rises as far as possible.The solar cell backboard (backsheet) (patent documentation 2) of Han You perylene pigments has been proposed.

In addition, from recent years living environment improve, comfortableization and energy-conservation viewpoint, expectation utilizes sun reflection of light and the heat insulation application that obtains, the exploitation of invisible heat reflecting material is for this purpose expected in various uses.For example, can enumerate the extraneous adornment of application usefulness, road pavement, automobile of the roof of house such as dwelling house, business quarters, warehouse, mansion or buildings or wall or interior finish uses with the application of, boats and ships 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 information-based equipment, liquid-crystal display (following abbreviate as sometimes " LCD ") uses all information such as shooting picture of indicating meter, digital camera or the pick up camera of display frame at TV, projector, PC, portable information equipment, watch-dog, auto navigation, portable phone, robot calculator or e-dictionary, Information Bulletin Board, notice bulletin board, function display panel, marking plate etc. to show associate device many-sidedly as the information display member.Meanwhile, raising and the cost degradation of the display quality of expectation indicating meter have carried out quality-improving, the cost cutting of colour filter (the following abbreviation sometimes made " CF ").For the CF that is equipped on LCD, aspect the chromatic characteristic of image properties such as tractability, depth of shade, light transmission, comparative, optical characteristics, require more excellent quality, the expectation exploitation have can with the material of these quality corresponding characteristic.

Among the CF of LCD, with the R(redness), the G(green), the B(blueness) pixel arranges slivering line shape, mosaic shape, triangular shape etc., shines from the back side with backlight, the mixture of colours that adds of the transmitted light by R, G, B pixel makes its color development, the formation image.And then, around each pixel, form black matrix" (following abbreviate as sometimes " BM ") with reticulation, unwanted light is blocked, prevent colour mixture.About colour element, use red pigment, veridian, blue pigments, yellow ultramarine, violet pigment etc., but improve respectively.In addition, as the opacifying property material that blocks fully for the light with visible region backlight, from the maximization of substrate size and the problems such as carrying capacity of environment of chromium cpd, changed into the resin B M that uses black pigment by the chromium metal film among the BM.

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

In addition, also having proposed various improvement aspect the display mode of the pixel of CF, accompany therewith, also carried out the improvement of the opacifying property black pigment that uses among the improvement of BM and then the BM.For example, in order to bring the wide visual angle as the weakness of LCD in the past, thereby proposed substrate is applied electric field abreast, makes the plane conversion mode (IPS mode) of liquid crystal layer conversion display pixel.In addition, the black matrix" array way (BOA mode), the color filter array mode (COA mode) that form BM at thin film transistor (TFT) increase owing to aperture opening ratio, therefore can increase elemental area, and can make operation sequence, bonding process operation improve, rationalize.

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

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

To this, thereby the charcoal blacks (patent documentation 6) that the charcoal blacks of oxygen consuming amount regulation is covered and improved electrical insulating property with the high resin coating of insulativity has been proposed in the patent documentation 6; Perhaps disclose the charcoal blacks formation insulativity BM that uses the insulativity charcoal blacks selected by measuring the volume resistance value or be covered and improved electrical insulating property with resin in the patent documentation 7, be applicable to the COA mode.

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

And then, proposed in the patent documentation 8 in the indicating meter of the organic EL that has used nearest exploitation, for the colour mixture of the adjacent light that prevents from self-emission device, improve the distinctiveness of luminescent picture, use BM.

The prior art document

Patent documentation

Patent documentation 1: No. 4120513 communique of Japanese Patent

Patent documentation 2: TOHKEMY 2007-128943 communique

Patent documentation 3: TOHKEMY 2006-148051 communique

Patent documentation 4: TOHKEMY 2000-66018 communique

Patent documentation 5: TOHKEMY 2002-341332 communique

Patent documentation 6: No. 3543501 communique of Japanese Patent

Patent documentation 7: No. 4338479 communique of Japanese Patent

Patent documentation 8: TOHKEMY 2004-221081 communique

Summary of the invention

The problem that invention will solve

By the above-mentioned fact, expectation develop demonstration as the excellent rerum natura of pigment, stability and also in various uses useful demonstration visible light opacifying property and the black pigment of these two kinds of optical characteristics of infrared transmission.Specifically, for example expect following black pigment, this black pigment is useful in following various uses: block unwanted visible rays, make the formed signal transmission of infrared rays and the purposes of the infrared filter that the electronics that utilizes is used; The temperature that can suppress to be caused by sunlight in the backboard of the black that constitutes photovoltaic power generation system or dark colour rises, is provided with in the substrate of sunlight reflectivity the multilayer coloring system of infrared transmission black layer, perhaps as the BM of CF, even if also keep can the not make a mistake purposes of work of high electric insulation, TFT even if under the wide situations such as LED-backlit in emission wavelength zone, also the light of visible region fully can be blocked and form BM at active components such as TFT; And then this black pigment is suitable for for visible light opacifying property in the BM of OLED display also high purposes etc., and this black pigment also can expect to have excellent rerum natura, stability as pigment.

Therefore, the object of the present invention is to provide demonstration as excellent rerum natura, the stability of pigment and also can in above-mentioned various uses, be suitable for, show visible light opacifying property and the black pigment of these two kinds of optical characteristics of infrared transmission, the manufacture method of this pigment, the coloured composition that contains this pigment, the colorize method that uses this coloured composition and dyed articles class.

Be used for solving the means of problem

The inventor etc. have carried out further investigation repeatedly for the purpose that realizes the invention described above, to found that the chemical structure of black pigment dyestuff is studied, polyazo pigment with black of ad hoc structure is that the light of about 400～750nm wavelength in the almost whole zone of visible region absorbs with high level with the light wavelength scope that absorbs, 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, the black pigment of having implemented pigmenting and having obtained is suitable in the cited various uses in front, thereby solved above-mentioned problem, finished 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 light opacifying property and these two kinds of optical characteristics of infrared transmission, it is the polyazo pigment of black with structure of at least one 2-hydroxyl-11H-benzo [a]-carbazole-3-carboxylic acid amide residue that comprises 2 above azo bond in molecule, imported by the coupling composition, and its median size is 10nm～200nm.

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

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

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

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

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

(3) structure shown in [Ar-N=N-HBC-HBC-N=N-Ar], it is to use the compound with 1 amino (to be expressed as Ar-NH ₂) carry out diazotization as the diazonium composition after, carry out with the coupling composition (being expressed as HBC-HBC) that in molecule, has 2 above 2-hydroxyl-11H-benzo [a]-carbazoles-3-methane amide residue (slightly being designated as HBC-) that azo coupling forms;

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

Wherein, above-mentioned in " Ar " represent the residue of aromatics and hetero ring type compound with representing, have in the formula 2 can be identical when above also can be different.In addition, the diazonium salt of " Ar-N=N-" in the formula or " N=N-Ar-N=N-" expression diazonium composition carries out " the arylazo residue " that coupling forms.Below too.

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

Among the present invention, embodiment as other provides coloured composition, it is characterized in that, contain before comprising the black azo-dye of the present invention of record in liquid dispersion medium or in the solid dispersion medium or the pigment composition of the black azo-dye that obtains by above-mentioned manufacture method forms.

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

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

Among the present invention, the backboard of solar power generation module is provided as other embodiment, it is characterized in that, it is the backboard of the solar power generation module that is laminated with black or dark colored infrared transmission layer at the light reflective sheet material, the polyazo pigment that in the infrared transmission layer, contains black, 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 (slightly being designated as HBC-) that comprises 2 above azo bond and imported by the coupling composition in molecule, and its median size is 10nm～200nm.

Among the present invention, the manufacture method of the backboard of solar power generation module is provided as other embodiment, it is characterized in that, the base material that uses base material self to have light reflective is provided with the base material of preformed light reflective substrate as the light reflective sheet material as light reflective sheet material or use, surface or light reflective substrate at these base materials use the coloured composition of the polyazo pigment that contains black by application, coating, paste, deposited, overlapping, printing, ink jet printing, electronic photo printing or xeroprinting, be implemented in the region of ultra-red show reflexive painted, stacked black or dark colored infrared transmission layer on the 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 (slightly being designated as HBC-) that comprises 2 above azo bond and imported by the coupling composition in molecule, and its median size is 10nm～200nm.

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

The invention effect

By above the present invention, the black colorant film that contains black azo-dye on the transparent substrate, covering the absorption that shows in the wavelength region of about 400～750nm of visible-range almost completely.And, in the longer region of ultra-red of wavelength, show high transmissivity at transparent substrate, show the useful optical characteristics that has visible light opacifying property and infrared transmission concurrently.Owing to have this specific character, therefore black azo-dye of the present invention is effectively utilized as the infrared filter of infrared remote controller and main body receiving apparatus.And black azo-dye of the present invention just also can be used as roads such as detection in practicability, identification automobile and hinders the infrared filter of the infrared ray sensing equipment of thing and use.

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

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

Embodiment

Then, enumerate be used to the best mode that carries out an invention, illustrate in greater detail the present invention.

The black azo-dye that makes the present invention have feature absorbs the visible region as optical characteristics with covering, particularly also shows almost completely absorption to the wavelength region of long wavelength side, and shows high transmissivity near infrared region.Specifically, the spectral transmission of the black colorant film on the transparent substrate in the wavelength region of 400～750nm of about visible-range, show about below 5%, in the wavelength region of the region of ultra-red of about 900nm～1500nm, show about more than 30%.In addition, as electrical characteristic, show very high electrical insulating property.

The inventor etc. have inquired into to have a plurality of chromophoric grouies and then makes the pigment of their mutual resonance as the black azo-dye of the above-mentioned distinctive optical characteristics of demonstration in molecule, therefore the result has developed the black polyazo pigment that has 2 above azo bond in the molecule, has specific chemical structure owing to synthesizing easily and can stably making.And then owing to particularly require the high transmissivity of region of ultra-red, therefore preferred black polyazo pigment is the pigment of fine particle size, and the median size of pigment need be about 10nm～200nm.And then when the expectation high-transmission rate, preferred median size is the ultra tiny black polyazo pigment of about 10nm～50nm or the black azo-dye with the dispersed dye character that causes molecular dispersion in painted manufacturing procedure in medium.

Among the present invention, polyazo pigment refers to have the disazo pigment of 2 above azo bond or trisazo pigment etc. as mentioned above in molecule.

Show that as polyazo pigment the chemical structure of black, the inventor's discoverys of etc.ing have 2 above azo bond and have chemical structure by 2-hydroxyl-11H-benzo [a]-carbazole-3-methane amide residue (the following formula of reference) of at least one of its coupling composition importing in molecule.

2-hydroxyl-11H-benzo [a]-carbazole-3-methane amide residue

As the manufacture method of above-mentioned polyazo pigment, owing to need in molecule, introduce 2 above azo bond, therefore can enumerate for example to use as the diazonium composition and have the method that the diazonium one-tenth that can be varied to diazo amino more than 2 assigns to carry out azo coupling; The coupling composition uses the coupling composition with 2 above coupling sites to carry out the method etc. of azo coupling.This point is described in detail.

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

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

The example of the black polyazo pigment of structure (1) shown in above-mentioned as having [HBC-N=N-Ar-N=N-HBC], the diazonium composition of enumerating as described below uses example of structure when having p-diaminodiphenyl amino more than 2 or phenylenediamine.

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

The example of the black polyazo pigment of structure (2) shown in above-mentioned as having [HBC-N=N-Ar-N=N-Cp], as described below enumerate the diazonium composition use have p-diaminodiphenyl amino more than 2 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 is to use the compound with 1 amino (to be expressed as Ar-NH ₂) carry out diazotization as the diazonium composition after, carry out with the coupling composition (being expressed as HBC-HBC) that in molecule, has 2 above 2-hydroxyl-11H-benzo [a]-carbazoles-3-methane amide residue (slightly being designated as HBC-) that azo coupling forms.

The example of the black polyazo pigment of structure (3) shown in above-mentioned as having [Ar-N=N-HBC-HBC-N=N-Ar], as described below enumerating on the HBC-HBC of the coupling composition that is combined with 2 2-hydroxyls-11H-benzo [a]-carbazole-3-methane amide residue by phenylene or biphenylene that is situated between uses the aniline with 1 amino to carry out the example of structure of diazotization when forming as the diazonium composition.

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

The example of the black polyazo pigment of the structure (4) shown in above-mentioned as having [Ar-N=N-HBC-Cp-N=N-Ar], as described below enumerating on the HBC-Cp of the coupling composition of the 2-hydroxyl-3-naphthoic acid arylamide residue that is combined with 2-hydroxyl-11H-benzo [a]-carbazole-3-methane amide residue and other coupling compositions except this compound by phenylene or biphenylene of being situated between, the aniline that use has 1 amino as the diazonium composition are carried out the example of structure of diazotization when forming.

Above-mentioned black azo-dye of the present invention can be by having following operation the manufacture method of black azo-dye of the present invention easily obtain: have the synthesis procedure of the polyazo pigment of above-mentioned cited structure, as required with 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 of black polyazo pigment that constitutes 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 (slightly being designated as HBC) and will having compound (representative formula: H amino more than 2 ₂N-Ar-NH ₂) diazonium salt that forms 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] of explanation before the black polyazo pigment that synthetic method by this (1) obtains becomes.

(2) method makes 2-hydroxyl-11H-benzo [a]-carbazole-3-carboxylic acid aryl amide (slightly being designated as HBC) and other coupling compositions (being expressed as Cp) except this compound and compound (the representative formula: H that will have amino more than 2 for having ₂N-Ar-NH ₂) diazonium salt that forms of diazotization carries out the synthetic method of the polyazo pigment of the structure that azo coupling forms, in this synthetic method, make to have compound (representative formula: H amino more than 2 ₂N-Ar-NH ₂) diazonium salt that forms of diazotization carries out azo coupling with waiting mole or the coupling composition (Cp) below it, as required coupling there is the polyazo pigment of 2 above coupling compositions (Cp) to separate, removes, then make above-mentioned coupling composition (HBC) and the diazo of coupling not carry out azo coupling.The black polyazo pigment with the structure shown in [HBC-N=N-Ar-N=N-Cp] of explanation before the black polyazo pigment that synthetic method by these (2) obtains becomes.

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

(3-1) make the coupling composition (being expressed as HBC-HBC) that in molecule, has 2 above 2-hydroxyl-11H-benzo [a]-carbazoles-3-methane amide residue (slightly being designated as HBC-) and the compound (Ar-NH that will have 1 amino ₂) the diazonium composition that forms of diazotization carries out the synthetic method of azo coupling.

(3-2) make the compound that to have 1 amino (be expressed as Ar-NH ₂) the diazotization diazonium salt and 2-hydroxyl-11H-benzo [a]-carbazole-3-carboxylic acid that form 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 following (4-1) or method (4-2).The black polyazo pigment that obtains by these (4-1) and synthetic method (4-2) becomes the black polyazo pigment with the structure shown in [Ar-N=N-HBC-Cp-N=N-Ar] of explanation before.

(4-1) make in a part, have the 2-hydroxyl-coupling composition (being expressed as HBC-Cp) and the compound that will have 1 amino of 11H-benzo [a]-carbazole-3-methane amide residue (slightly being designated as HBC-) and other coupling composition residues (being expressed as Cp-) except this compound (be expressed as Ar-NH ₂) diazonium salt that forms of diazotization carries out the synthetic method of azo coupling.

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

Diazonium composition and the coupling composition that can use in above-mentioned each synthetic method of enumerating described.

(A) carry out concrete example to being coupled to branch.

(a) as coupling composition (HBC), for example be 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, alkyl oxy carbonyl, cyclic imide base dioxy base, alkyl sulphonyl, aminocarboxyl, benzoylamino, alkyl amino-carbonyl, anilino carbonyl, ring-type urylene, carboxyl, alkyl imino etc. be imported into the coupling composition that one or more form as the substituting group of derivative alkyl (carbonatoms: for example.

Specifically, for example can enumerate 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.

(b) as coupling composition (HBC-HBC), for example be phenylene-two (2-hydroxyls-11H-benzo [a]-carbazole-3-methane amide), biphenylene-two (2-hydroxyl-11H-benzo [a]-carbazole-3-methane amide), naphthalene-two (2-hydroxyl-11H-benzo [a]-carbazole-3-methane amide) etc. and their derivative.1～10), alkoxyl group (carbonatoms: 1～10), the coupling composition that forms such as trifluoromethyl, halogen as the substituting group of derivative, in its aryl, imports one or more known substituting groups, for example alkyl (carbonatoms:.

Specifically, it for example is phenylene-(1,4-) two (2-hydroxyls-11H-benzo [a]-carbazole-3-methane amide), 2-chloro-phenylene-(1,4-) two (2-hydroxyls-11H-benzo [a]-carbazole-3-methane amide), 2,5-two chloro-phenylenes-(1,4-) two (2-hydroxyl-11H-benzo [a]-carbazole-3-methane amide) 2-methyl-phenylene-(1,4-) two (2-hydroxyls-11H-benzo [a]-carbazole-3-methane amide), biphenylene-(4,4 '-) two (2-hydroxyls-11H-benzo [a]-carbazole-3-methane amide), 3,3 '-two chloro-biphenylenes-(4,4 '-) two (2-hydroxyls-11H-benzo [a]-carbazole-3-methane amide), naphthalene-(1,5-) two (2-hydroxyls-11H-benzo [a]-carbazole-3-methane amide) etc.

(c) as coupling composition (Cp), for example 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 formic acid arylamide, 2-hydroxyl-1-carbazole formic acid arylamide etc. and their derivative.For example be C.I. azoic 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) as coupling composition (HBC-Cp), carry out the carboxylic acid of the Cp residue of amide linkage as the amino with the HBC residue, can enumerate 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.For example, phenylene (-1) - (2 - hydroxy-11H-benzo [a] - carbazole-3 - carboxamide) (-4) - (2 - hydroxy - 3 - naphthoic acid amide), sodium phenyl (-1) - (2 - hydroxy-11H-benzo [a] - carbazole-3 - carboxamide) (-4) - (2 - hydroxy - 3 - naphthoic acid amide), (2 - methyl--) phenylene (-1) - (2 - hydroxy-11H-benzo [a] - carbazole-3 - carboxamide) (-4) - (2 - hydroxy - 3 - naphthoic acid amide), biphenylene phenyl (-4) - (2 - hydroxy-11H-benzo [a] - carbazole-3 - carboxamide) (4 ') - (2 - hydroxy - 3 - naphthoic acid amide), etc.

(B) the counterweight nitrogen component carries out concrete example.

(a) as amino compound (the representative formula: H that has more than 2 of diazonium composition ₂N-Ar-NH ₂), for example be phenylenediamine, benzidine, diaminonaphthalene, diamino-anthraquinone, diamino-benzophenone, diamino-pyridine etc. and their derivative.As the substituting group of derivative import at its aryl one or more known substituting groups are arranged, 1～10), alkoxyl group (carbonatoms: 1～10), the diazonium composition of trifluoromethyl, halogen etc. for example alkyl (carbonatoms:.

Specifically, for example can enumerate 1,4-phenylenediamine, 2-chloro-1,4-phenylenediamine, 2,5-two chloro-1,4-phenylenediamine, 2-chloro-5-methyl isophthalic acid, 4-phenylenediamine, 2,5-dimethyl-1,4-phenylenediamine, 2-nitro-1,4-phenylenediamine; 1,3-phenylenediamine, 4-chloro-1,3-phenylenediamine, 4-methoxyl group-1,3-phenylenediamine, 4-nitro-1,3-phenylenediamine; 4-chloro-1,2-phenylenediamine, 4,5-dimethyl-1,2-phenylenediamine, 4-nitro-1,2-phenylenediamine; 3,3 '-two chloro-4,4 '-p-diaminodiphenyl, 2,2 ', 5,5 '-tetrachloro-4,4 '-p-diaminodiphenyl, 3,3 '-dimethyl-4,4 '-p-diaminodiphenyl, 3,3 '-dimethoxy-4 ', 4 '-p-diaminodiphenyl; 1,5-diaminonaphthalene 1, the 2-diaminonaphthalene; 1,2-diamino-anthraquinone, 1, the 5-diamino-anthraquinone; 3,4-diamino-benzophenone; 2,6-diamino-pyridine etc.

(b) compound with 1 amino as the diazonium composition (is expressed as Ar-NH ₂), for example be aniline, naphthylamines, aminoanthraquinone, phenoxybenzamine, phenylimino aniline etc. and their derivative.As the substituting group of derivative import at its aryl one or more known substituting groups are arranged, 1～10), alkoxyl group (carbonatoms: 1～10), the diazonium composition that forms such as halogen, nitro, phenyl ether, phenylimino, benzoylamino, anilino carbonyl, ring-type urylene for example alkyl (carbonatoms:.Specifically, for example can enumerate C.I. azoic coupling component 5,8,9,10,32,33,34,35,36,37,41,42,43,47 etc.

The adjustment operation of the particle diameter manufacture method that constitutes black azo-dye of the present invention, that as required this pigment is carried out the pigment particles of miniaturization is described.Black azo-dye of the present invention is when the particle diameter of the polyazo pigment that obtains by the above-mentioned synthetic method enumerated is thick, and any method in can following by utilizing (1) or (2) obtains the median size miniaturization of pigment to about 10nm～200nm.That is, in order to improve the infrared transmission rate of having used filming of the polyazo pigment that obtains by the above-mentioned synthetic method of enumerating etc., the particle diameter of the pigment that necessary is disperses is less than light wavelength, specifically median size is about 10nm～200nm.Therefore, black azo-dye of the present invention for the median size with pigment is adjusted to desired particle diameter, need carry out following cited known pigment miniaturization operation when thick by the synthetic pigment of aforesaid method, make miniaturization pigment.

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

The particle diameter of pigment is adjusted according to employed purposes.The adjustment of particle diameter is mainly controlled with respect to ratio or the mixing time of the amount of pigment by salt.In the such purposes of the infrared rays colour filter that requires high-transmission rate, the expectation pigment particles is littler, for example the micropigment particle of preferred 10nm～50nm, the more preferably dispersion state of the ultra tiny pigment particles of 10nm～30nm expect that finally molecular dispersion is in the carrier that disperses, the dissolved state in for example plastic medium.

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

In the above-mentioned lyonium salt mill method of enumerating, in pigment, add the water-soluble inorganic salt as grinding auxiliary agent, the amount of this water-soluble inorganic salt be the pigment that grinds according to needed pigment particle size the several times amount, be in particular 3～20 times of amounts, and then add the water-miscible organic solvent that ethylene glycol, Diethylene Glycol, polyoxyethylene glycol etc. have viscosity, carry out mixing grinding.Grind the water-soluble inorganic salt that uses in the auxiliary agent and use sodium-chlor or sodium sulfate etc.After grinding, be added in dilute sulphuric acid, the water etc., dissolving grinds auxiliary agent and filters, washes, and obtains the filtration thickener (filter cake) of pigment.Filter cake directly carries out dispersion processing with the wet type dispersion machine, or be processed into penetrating stain by backwashing manner, or carry out after the warm air drying pulverizing with Dry-crusher and make powder pigment, perhaps further utilize above-mentioned various wet type dispersion machine or mixing roll etc. to disperse etc., become various tinting materials according to the purposes processing treatment.In addition, also preferably in water, carry out plastic resin treatment and make easily disperse processing pigment or processed pigment.

When using black azo-dye of the present invention as tinting material, particularly in aqueous dispersible pigment dispersion, also preferably in the black azo pigment, add the pigment derivative of anionic property or cationic.Addition means as these pigment derivative, undertaken by following known method: when above-mentioned pigment synthetic, use has diazonium composition or the coupling composition of ionic group, the method for utilizing auxiliary coupling (accessory coupling) method to import; Perhaps add the method for the synthetic in addition pigment derivative with ionic group etc. when micronize manufacturing process or during the conditioned pigment dispersion liquid.As the pigment derivative of this moment, except black, the pigment derivative of colours such as yellow, blueness, redness suitably used in the mode that comprises tone adjustment etc.

Here, the black pigment composition that the spectral transmission basis of filming contains in filming and coating thickness be visible some difference numerically, but can confirm with the relation of wavelength in, under the wavelength that absorbs, all show the tendency that absorbs, under the wavelength that carries out transmission, show the tendency of transmission.The expression of table 1 and table 2 uses black disazo pigment (" black pigment-1 ") that aftermentioned Production Example 1 of the present invention obtains, by the visibility region of filming that comprises black pigment-1 of aftermentioned embodiment 1 preparation and the spectral transmission (%) of region of ultra-red.

The result is as shown in table 1, confirms in containing the filming of black pigment-1, and the whole wavelength region may that spreads all over 400～750nm of visible light, transmissivity is 0%, does not show transmissivity in visibility region.On the other hand, as shown in table 2, under the 900nm of region of ultra-red, have 34% transmission, than its more the 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 filming that contains black azo-dye of the present invention, shown in the embodiment 1, the volume intrinsic resistance value of filming that affirmation contains black pigment-1 is 10 equally as described later ¹⁴Ω cm, demonstration excellent electric insulating.

Discovery is the pigment of the optical function that has the light transmission that makes infrared spectral range, the light of visible region is blocked fully as mentioned above as the black pigment-1 of black azo-dye of the present invention, therefore as the BM of the above-mentioned purposes of utilizing the infrared filter that ultrared electronics uses or CF with being useful.For example, black azo-dye of the present invention is applicable to BM time spent of CF, can be fully the light of visible region backlight blocked and shows excellent electrical insulating property.

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

Black azo-dye of the present invention can be used as pigment composition and uses black azo-dye separately, perhaps as one of a plurality of pigment compositions, corresponding purpose color is selected the coloured pigment, white pigment more than a kind or 2 kinds, other black pigment and pigment extender etc., with them and use.Color for the revisal black azo-dye, carry out with black azo-dye of the present invention and the ratio that cooperates of coloured pigment, white pigment, other black pigments or the pigment extender of usefulness is not particularly limited, using the computer for colouring system to carry out that optimized method decides also is preferred mode.

As with the pigment of black azo-dye of the present invention and usefulness, can use known pigment, be not particularly limited.For example can use and be selected from anthraquione pigmentss, quinacridone pigment, the diketopyrrolo-pyrrole series pigments, indigo thioindigo series pigments, purple cyclic ketones series pigments perylene pigments, phthualocyanine pigment, the indoline series pigments, the isoindoline series pigments, isoindolinone pigment dioxazine series pigments, quinophthalone pigment, the nickel azo pigment, metal complex pigment, insoluble azo pigment, the dissolubility azo pigment, the high molecular azo pigment, the azomethine azo is black pigment, pigment dyestuff and charcoal blacks and composite oxides series pigments such as nigrosine series pigments, iron oxide pigment, at least a kind of pigment or 2 kinds of mixtures with paint in the mineral dyes such as titanium oxide base pigment, mixed crystal pigments.

As pigment dyestuff, for example can enumerate C.I. Pigment Yellow 73 (slightly being designated as PY)-74 in the 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., can enumerate C.I. pigment orange (slightly being designated as PO)-61 in the orange pigments, 64,71,73 etc., can enumerate C.I. Pigment red (slightly being designated as PR)-4 in the 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 (slightly being designated as PB)-15:1 in the blue pigments, 15:2,15:3,15:4,15:5,15:6,16,17:1,60,80, aluminium phthalocyanine blue etc., be C.I. Pigment green (slightly being designated as PG)-7 in the veridian, 36,58, poly-(13-16) bromine phthalocyanine etc., be C.I. pigment violet (slightly remembering PV)-19 in the violet pigment, PV-23, PV-37 etc., be nigrosine pigment as black pigment, charcoal blacks, titanium oxide mineral black etc., especially the BM of CF with in as being matched with the pigment that uses in the black azo-dye of the present invention, preferably carry out surface treatment and improved the charcoal blacks of insulativity or titanium oxide mineral black etc.

Black azo-dye of the present invention also can use the method that proposes in No. 4097926 communiques of Japanese Patent or the TOHKEMY 2005-330466 communique carrying out and the time spent with infrared reflectivity pigment such as white pigment.That is, being suitable for infrared transmission black azo-dye of the present invention also is preferred mode with the method that is covered, improves ultrared reflection efficiency substantive around the infrared reflectivity pigment such as white pigment.

The aqueous coloured composition that contains black azo-dye of the present invention mainly as article surface is coated with, impregnation, describe, the tinting material of lettering etc. uses, at coating, apply agent, coloring plastic, fiber staining, printing-ink, stationery, image recording and use with, image demonstration etc. in the various uses and use.In the dispersion medium that black azo-dye of the present invention disperses, form material (or the formation material of filming) as tunicle, can contain and be selected from reactive polymer or the non-reacted polymer with reactive group, the oligopolymer with reactive group or non-reacted oligopolymer and have the monomer of reactive group or do not have in the non-reacted monomer etc. of reactive group at least a kind, and himself can be liquid, perhaps can be the material that further contains solvent and/or water.

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

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

Use above-mentioned tinting material that article are carried out carrying out appropriate colouring according to the optics purpose of visible region and region of ultra-red when painted.

When making the visible region absorb, make region of ultra-red transmission painted, the base material of article is made as 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 transparency base material, perhaps in transparent base material mixing or impregnation coloured composition to carry out inside painted.At this moment, the black azo-dye of the application of the invention, the article of gained show following excellent optical.Namely, when using black azo-dye of the present invention, thereby show in the wavelength region of about 400～750nm that can carry out particularly in the visible region that high-absorbable shows the visible light opacifying property, shows that height is radioparent painted in the region of ultra-red of about 900nm～1500nm and then longer high wavelength.

In addition, when making the visible region absorb, make region of ultra-red reflection painted, the person that can have the light reflective by the material that constitutes article self or use preformed light reflective substrate uses coloured composition of the present invention to be coated with to realize thereon.The details of this aspect is in the back narration.The colorize method of this moment utilizes known method, for example application, smears, original liquid coloring, printing and dyeing, dip-dye, printing, take down notes, describe, ink jet printing, electronic photo printing or xeroprinting etc., can carry out showing in the visible region high-absorbable thus, show the painted of highly reflective near infrared region.

Measure the spectral reflectance of above-mentioned black pigment-1, show the result in table 3.The sample of measuring is the White Board that uses applicator to be coated with at white color development paper (below be called black color development paper).

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

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

Form the resin glue (being called " vehicle " or " varnish " according to purposes) of material (tunicle formation material) performance function as filming of using among the present invention, can preferably use the non-reacted Air drying type that does not have reactive group or have resin glue and the photoresist tackiness agent of the baking-type of reactive group.As the resin glue of Air drying type or baking-type, for example can enumerate the resin glue of use in the image recording materials usefulness such as printing and dyeing agent, coating, coating agent or printing-ink, stationery, ink jet printing, electronic photo printing, xeroprinting etc.In addition, as the photoresist tackiness agent, for example can enumerate ultra-violet solidified or electron(beam)curing various coating, apply the photoresist tackiness agent that uses in agent, printing-ink, jetted ink, the photolithography etc.

Object lesson as the resin glue of the Air drying type that can use among the present invention or baking-type, for example can enumerate synthetic rubber resin, acrylic resin, polystyrene (being total to) polymer, polyvinyl butyral is Vinylites such as resin, polyester based resin, the aminoresin modified poly ester is resin, polyurethane series resin, the acrylic polyol carbamate is resin, soluble polyamide is resin, soluble polyimide is resin, soluble polyamide imide series resin, solubility polyester imide series resin, Synolac, alkyd amino is 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, the polymeric water-soluble salt of (methyl) acrylic ester (being total to), water soluble amino alkyd is resin, water soluble amino polyester based resin and water-soluble polyamide based resin etc., these materials can be used singly or in combination more than 2 kinds.

Form the reactive group that material has as reactive tunicle, for example 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 linking agent, for example methylol melamine system or isocyanate-based, epoxy base system linking agent can be and used.

As the uv curing resin system that can use among the present invention, electron(beam)curing resin system homenergic ray-curable is filmed and is formed the object lesson of material, and for example can enumerate the photosensitivity thermoprene is resin, the photosensitivity phenolic aldehyde is resin, the photosensitivity polyacrylic ester is resin, the polyamide-based resin of photosensitivity, photosensitive polyimide is that resin etc. and unsaturated polyester are resin, polyester acrylate is resin, poly-epoxy acrylate is resin, urethane acrylate is resin, polyether acrylate is resin, polyalcohol acrylate is tackiness agent such as resin or further adds the tackiness agent that monomer obtains as reactive diluent in these material.

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

The amount of the black azo-dye of the present invention that contains 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.For example, carry out in the painted purposes on the surface with toning agent, jetted ink etc. at coating, coating agent, printing and dyeing agent, printing-ink, printing press, because thickness is thin, therefore the amount as the black pigment that contains in this tinting material is about 3%～80%, preferably is about 5%～60%.Particularly, when using as the opacifying property black material of the BM of CF, particularly thickness thin, require opacifying property completely, therefore attempted pigment and stably disperseed, remain on the viscosity that is suitable for being coated with, the critical pigment concentration that forms uniform painted tunicle, preferably be about 30%～60%.

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

When the image recording that will contain black azo-dye of the present invention uses with coloured composition as the BM formation of CF with coloured composition, use this coloured composition, on the CF substrate directly or be situated between by transfer printing or paste usefulness plastic film, utilize one or two or more kinds the method that forms that is selected from photolithography, laser ablation method, ink jet printing method, print process, transfer printing, the mounting method etc. to form.

As the thickness of BM, be 0.5 μ m～3 μ m, be generally 1 μ m～2 μ m.As optical density(OD) (OD) value, be more than 2.0, be preferably more than 3.0.Under the situation that makes its function with spacer, the situation that thickens BM self is arranged, on BM the situation of overlaid pixel or situation of overlapping colourless resin molding etc., be preferably 5 μ m～10 μ m.

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

As the article that preferably have the speciality relevant with CF substrate or organic EL light-emitting substrate among the present invention, can enumerate following article.That is, can enumerate the color display panel that the CF substrate that is formed with the BM that absorbs the visibility region wavelength region or organic EL light-emitting substrate, particularly BM are essentially the CF substrate of the overlapping and formation of electrical insulating property, this BM and electrode or organic EL light-emitting substrate and comprise them.Equally, can enumerate the CF substrate that is formed with above-mentioned BM formed colour element the CF substrate, the liquid color display equipment of the CF substrate that has formed BM and colour element is installed or has equipped organic EL color monitor equipment of above-mentioned organic EL light-emitting substrate.

In addition, as the article relevant with photovoltaic power generation system, can enumerate and to suppress the backboard that on light reflective sheet materials such as reflectivity stratum basale, forms by the stacked black of the coloured composition that contains black azo-dye of the present invention or dark colored infrared transmission layer that the temperature that causes because of sunlight rises and the solar power generation module of having used this backboard.

Embodiment

Then, enumerate embodiment and comparative example is described more specifically the present invention.In addition, " g " or " % " then is quality criteria as long as there is not special instruction in the literary composition.

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

(1) the black disazo pigment is synthetic

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

(2) utilize miniaturization to handle and carry out the preparation of black particle pigment

100 parts of the coarse particle pigment of the black azo-dye that the building-up reactions by above-mentioned (1) is obtained join for 50 parts with 500 parts in sodium-chlor powder and Diethylene Glycol and are equipped with in the kneader that adds gland, and carrying out coarse particle pigment and the sodium-chlor powder of ready-mixed to the kneader becomes by even moistening agglomerate.Then, close autoclave, at pressure 6kg/cm ²Carry out mixing and grind while being pressed into content down.Specifically, make content reach 92～98 ℃ Yi Bian manage temperature, handled 2 hours Yi Bian carry out mixing grinding.The triturate of gained carried out filter after 1 hour the stir process in being heated to 3000 parts of warm water of 80 ℃, the filtrate of gained is washed, thereby remove sodium-chlor and Diethylene Glycol, obtain the filter cake through the black azo-dye of miniaturization.

Utilize following method to measure the particle diameter of the pigment of above-mentioned acquisition.Take the transmission electron microscope photo (60,000 times) of the black pigment of gained, use " image analysis formula size-grade distribution software Mac-View " (マ ウ Application テ ッ Network corporate system) to measure size-grade distribution.Consequently, median size is 50nm.In addition, in other Production Example, also measure the median size of pigment by method same as described above.

And then, pulverize behind the filtration cakes torrefaction with above-mentioned acquisition, acquisition has 3, the miniaturization powder pigment of the black pigment of the structure of 3 '-dimethoxy-biphenylene (4,4 '-) two (azos (1)-2-hydroxyl-11H-benzo [a]-carbazole-3-carboxyl-p-anisidine).Below be called " black pigment-1 ".

[Production Example 2] (manufacturing 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, with 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 of carrying out the thick pigment of gained is handled.The usage quantity of its method used sodium-chlor in (2) that Production Example 1 is put down in writing is used 8 times of amounts, according to Production Example 1(2 with respect to pigment) carry out miniaturization and handle.And then, utilize sour water to carry out the dissolving after-filtration of salt etc., with the filtrate washing of gained, obtain the filter cake of black azo-dye.The median size of the pigment of gained is 25nm.In addition, pulverize behind the filtration cakes torrefaction with above-mentioned acquisition, obtain the miniaturization powder pigment of black pigment.Below it is called " black pigment-2 ".

[Production Example 3] (manufacturing 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, with 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 of carrying out the thick pigment of gained is handled.The usage quantity of used sodium-chlor is carried out miniaturization according to (2) of Production Example 1 record and is handled with respect to 10 times of amounts of pigment use in (2) that Production Example 1 is put down in writing.And then, utilize sour water to carry out the dissolving after-filtration of salt etc., with the filtrate washing of gained, obtain the filter cake of black azo-dye.The median size of the pigment of gained is 20nm.In addition, pulverize behind the filtration cakes torrefaction with above-mentioned acquisition, obtain the miniaturization powder pigment of black pigment.Below it is called " black pigment-3 ".

[Production Example 4] (manufacturing 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, with 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 of carrying out the thick pigment of gained is handled.Carrying out miniaturization according to (2) of Production Example 1 record handles.And then, utilize sour water with dissolving after-filtration such as salt, then with the filtrate washing of gained, obtain the filter cake of black azo-dye.The median size of the pigment of gained is 50nm.In addition, pulverize behind the filtration cakes torrefaction with above-mentioned acquisition, obtain the miniaturization powder pigment of black pigment.Below it is called " black pigment-4 ".

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

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, with itself and 2-hydroxyl-11H-benzo [a] carbazole-3-carboxyl-p-anisidine 7.65g(0.02 mole) coupling, thus obtain the thick pigment of black azo-dye.The receipts amount of the black azo-dye of gained is 9.86g.

Then, the miniaturization of carrying out the thick pigment of gained is handled.The usage quantity of used sodium-chlor is used 4 times of amounts with respect to pigment in (2) that Production Example 1 is put down in writing, with Production Example 1(2) similarly carry out miniaturization and handle.And then, utilize sour water to carry out the dissolving after-filtration of salt etc., with the filtrate washing of gained, obtain the filter cake of black azo-dye.The median size of the pigment of gained is 85nm.In addition, pulverize behind the filtration cakes torrefaction with above-mentioned acquisition, obtain the miniaturization powder pigment of black pigment.Below it is called " black pigment-5 ".

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

With Production Example 1(1) same, to 3,3 '-dimethoxy-4 ', 4 '-p-diaminodiphenyl 2.44g(0.01 mole) carry out diazotization.And then, with 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-naphthoamide 3.58g(0.01 mole) coupling, thereby the thick pigment of acquisition black azo-dye.The receipts amount of the black azo-dye of gained is 9.59g.Then, utilize Dry-crusher that the thick pigment of the black azo-dye of above-mentioned acquisition is pulverized, thereby carry out pigmenting, obtain the miniaturization powder pigment of black pigment.The median size of the pigment of gained is 110nm.Below it is called " black pigment-6 ".

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

(1) manufacturing of black pigment derivative-1

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

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

The filter cake of the black pigment derivative-1 that obtains in the filter cake of the black pigment-1 of gained and above-mentioned (1) in (1) that Production Example 1 is put down in writing cooperates than the mode that reaches 10:1 according to the pigment solids composition, is mixed to even fully.Then, with the said mixture drying, thereby acquisition contains the thick pigment of the black pigment of pigment derivative.Then, after the miniaturization that pigment is carried out in (2) put down in writing according to Production Example 1 is handled, utilize sour water to carry out the dissolving of salt etc., it is filtered, with the filtrate washing of gained, thereby obtain the filter cake of black azo-dye.The median size of the pigment of gained is 50nm.In addition, with above-mentioned filtration cakes torrefaction, pulverizing, acquisition contains the miniaturization powder pigment of the black pigment of anionic property pigment derivative.Below it is called " black pigment-7 ".

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

The method synthesizing cationic pigment derivative of utilizing Japanese Patent to put down in writing for No. 3268748.Specifically, at first be that the ratio of 2:1:1 makes 1-aminoanthraquinone, two (N, N-dimethylaminopropyl) amine and cyanuric chloride reaction with the mol ratio, as the cationic pigment derivative, two (N, the N-dimethylaminopropyl) amino-s-triazine of two (anthraquinonyl the amino)-6-of synthetic 2,4-.Filter cake and Production Example 1(1 with gained cationic pigment derivative) in the filter cake of the black pigment-1 that obtains reach 85:15 according to the solids component ratio and cooperate.And then it is dry that they are mixed to even back fully, and acquisition contains the thick pigment of the black pigment of cationic pigment derivative.Then, the method for (2) put down in writing according to Production Example 1 utilizes water with dissolving after-filtration such as salt after the thick pigment of gained is carried out miniaturization and handles, and with the filtrate washing, thereby obtains the filter cake of black azo-dye.The median size of the pigment of gained is 50nm.In addition, will pulverize behind the gained filtration cakes torrefaction, acquisition contains the miniaturization powder pigment of the black pigment of cationic yellow ultramarine derivative.Below it is called " black pigment-8 ".

[Production Example 9] (manufacturing 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, preparation tetrazolium boron fluoride double salt (diazonium salt).Therewith dividually, to thionamic acid 0.69g(0.004 mole) carry out diazotization.With with these 2 kinds of diazonium liquid and 2-hydroxyl-11H-benzo [a] carbazole-3-carboxyl-p-anisidine 7.65g(0.02 mole) mode of coupling simultaneously, the mode that almost finish simultaneously according to the dropping of above-mentioned 2 kinds of diazonium liquid on the limit is regulated the limit and is carried out coupling.Afterwards, filter, wash, obtain the filter cake of black azo-dye.To the gained filtration cakes torrefaction, obtain to contain the black pigment (thick pigment) with sulfonic black pigment derivative.The receipts amount of gained black pigment is 9.97g.Then, the miniaturization of carrying out the thick pigment of gained is handled.Specifically, after carrying out miniaturization and handle according to the method for (2) of Production Example 1 record, filter after utilizing sour water with dissolvings such as salt, with the filtrate washing of gained, the filter cake of acquisition black azo-dye.The median size of the pigment of gained is 50nm.To pulverize behind this filtration cakes torrefaction, obtain the miniaturization powder pigment of black pigment.Below it is called " black pigment-9 ".

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

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

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

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

For the optical characteristics of the black pigment-1 of observing Production Example 1 gained, preparation black coating fluid.As employed varnish, ratio with 80:20 cooperates the 50% dimethylbenzene-butanols mixed solvent solution (acid number 10mgKOH/g) of the acrylic resin with carboxyl and the 50% dimethylbenzene-butanols mixed solvent solution of butylation methylol melamine resin, preparation varnish (following it is called " varnish ").Diluting solvent uses the mixed solvent (4:1) (following it is called " diluting solvent ") of dimethylbenzene-butanols.

In 3 parts of black pigments-1,24 parts in varnish, 6 parts of diluting solvents and the 48 parts of dispersion usefulness containers of packing into of granulated glass sphere as dispersion medium, utilize paint mixer to disperse 3 hours.Afterwards, further append 36 parts in varnish, continue to disperse to take out after 10 minutes, as coating fluid.The ratio of the pigment composition in the coating fluid and resin solid composition is 1:10.Use rod be coated with black coating fluid that machine will as above obtain be coated on carry out drying on polyethylene terephthalate (PET) film after, under 130 ℃, make its curing, obtain black coating PET film.The average dry film thickness of formed black coating film is 34nm.

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

Use Hitachi's spectrophotometer (U-4100 type, Hitachi's system) the black coating PET film that obtains in above-mentioned (1) to be measured the transmissivity of visible portions and near infrared portion.Table 4 and table 5 have shown the measurement result that each is regional.

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

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

Shown in the measurement result of the spectral transmission of table 4 and table 5, confirmed to contain filming in the whole wavelength region may of the 400～750nm that spreads all over the visible region of black pigment-1, spectral transmission is 0%, almost not transmission (with reference to table 4).On the other hand, in the region of ultra-red, the transmissivity of 900nm is approximately 34%, and then confirms that in the longer side of wavelength transmissivity rises (with reference to table 5) reposefully.

(3) and then, use the high resistivity meter Hiresta-UP[ア of Mitsubishi Chemical of Co., Ltd. Na リ テ ッ Network system] black coating film on the PET film that above-mentioned (1) is obtained measures the volume intrinsic resistance.Measurement result is shown as 10 ¹⁴More than the Ω cm, confirm that insulativity is very high.

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

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

In order to observe the reflection characteristic of black pigment-1, the applicator that uses 6 mils carries out drying after being coated on the black coating fluid of preparation in (1) of embodiment 1 record on the white color development paper, it is solidified to form films, obtain black coating color development paper (below be called black color development paper).The measured value that is formed at the dry film thickness of the black coating film on this black color development paper is about 35～40nm at color development paper.

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

Table 6: the spectral reflectance that has used the black color development paper of black pigment-1

By the results verification shown in the table 6 in the black color development paper that uses black pigment-1 to make, to 750nm, only show 5～6% reflectivity, at 800nm～900nm, reflectivity rises sharp, and then is roughly 70%～80% or keep higher reflectivity at the near infrared region of the longer side of wavelength.Thought by these facts because from the reflection of surface of pigments the time, transmitted light is by the reflection of the blank sheet of paper of substrate, the light that causes is thus added and and become reflected light, so the reflection of light rate of black color development paper increases.Thereby, the transmitance by increasing black pigment, utilize the high substrate of reflectivity, can reflect near infrared ray efficiently.In addition, in above-mentioned table 6, the reflectivity to the 750nm is not to be 0% but to become 5% value, and this is relevant with determinator.

[embodiment 3]

(1) similarly to Example 1, use the black pigment-2～6 that obtains in the 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 display result.

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

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

(2) similarly to Example 2, use the black pigment-2～6 that obtains in the 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 at black color development paper.Measure spectral reflectance similarly to Example 2.Its result is that spectral reflectance is as shown in table 9, shows same tendency with the black coating color development paper that uses black pigment-1 to obtain.

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

[embodiment 4] (polycarbonate resin profiled sheeting)

After utilizing Henschel mixer (powder high-speed mixer) to mix 80 parts in 20 parts of Production Examples 2 prepared black pigment-2, polycarbonate resin powder fully, and then utilize twin screw extruder mix, mixing, preparation contains the polycarbonate resin black master batch of 20% black pigment-2.2 parts of the black master batchs of gained are engaged in by in 100 parts of the polycarbonate resin particles that constitutes with above-mentioned same toner, utilize Henschel mixer to mix after, and then utilize twin screw extruder mix, mixing, make the black resin particle.Use screw rod injection moulding machine in upright arrangement that gained black resin particle is carried out moulding, 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 since transmission near infrared ray fully therefore can in purposes such as infrared transmission wave filter, use.

[embodiment 5] (acrylic resin profiled sheeting)

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

2 parts of the black master batchs of gained are engaged in by after in 100 parts of the acrylic resin particles that constitutes with above-mentioned same resin, after further utilizing Henschel mixer to mix, and then utilize twin screw extrude mixing roll mix, mixing, make the black resin particle.Use screw rod injection moulding machine in upright arrangement that the black resin particle of gained is carried out moulding, 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 since transmission near infrared ray fully therefore can be used as the infrared transmission wave filter and use.

[embodiment 6] (polyurethane-coated agent)

Be that 15 parts, polycarbonate-based no xanthochromia type polyurethane resin are that 10 parts, dimethyl formamide (below be called " DMF ") they are 75 parts according to the black pigment-4 of preparation in the Production Example 4, blending black pigment and polycarbonate-based no xanthochromia type polyurethane resin solution, DMF.Use horizontal continuum dispersion machine to disperse this blending liquid fully, obtain black pigment high density dispersion liquid.Then, formation as epidermal area is used, the black pigment high density dispersion liquid that adds 10 parts of propyl acetates, 10 parts of Virahols, preparation before as diluting solvent in 100 parts of polycarbonate-based no xanthochromia type polyurethane resin solutions (solids component 30%, DMF solvent) mixes the polyurethane coated liquid of modulation black for 20 parts.

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

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

[embodiment 7] (original liquid coloring spinning)

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

[embodiment 8] (resin forming)

Utilize Henschel mixer mix 20 parts of black pigment-6, the titanium oxide white pigments of preparation in 5 parts of Production Examples 6, as 75 parts of the polyethylene resin powder of pigment dispersing agent, obtain powder colorant (dry color).Then, 1.0 parts of the powder colorants of gained are engaged in 100 parts of polybutylene terephthalate (PBT) resin particles, utilize Henschel mixer to mix after, carry out with forcing machine mixing, thereby obtain the black resin particle.Use screw rod injection moulding machine in upright arrangement that the black particle of gained is carried out moulding, obtain the black PBT resin forming plate of pigment-dispersing excellence.The resin forming plate of gained has reflected the invisible heat of direct sunlight.Therefore, this resin is suitable for using as the synthetic resin of avoiding heating up.

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

(1) black pigment-4 of preparation in 15 parts of Production Examples 5 of ready-mixed, acrylic polyol (hydroxyl value: 100) behind 50 parts of 25 parts of the butylacetate solution (solids component 50%), butylacetate fully, the horizontal continuum dispersion machine that utilization is used granulated glass sphere as dispersion medium is with colo(u)rant dispersion, thus preparation black pigment high density dispersion liquid.

In 90 parts of the black pigment high density dispersion liquids of above-mentioned acquisition, add with above-mentioned same 22 parts of acrylic polyol butylacetate solution, with benzotriazole be monomer and HALS be monomer copolymerization form acrylic polyol (hydroxyl value: 100) butylacetate solution is 50 parts, carry out black inkization.And then, in the product of black inkization, add isocyanuric acid ester type hexamethylene diisocyanate 3 aggressiveness (solids component: 100%, isocyanic ester %:21.7%) 24 part, fully mix after, add about 20 part butylacetate as solidifying agent at this, adjust viscosity, preparation black coating fluid.

(2) 40 parts of the acrylic polyol butylacetate solution that uses in the ready-mixed above-mentioned (1) in 80 parts of titanium oxide white pigments and butylacetate are 20 parts, then, use with above-mentioned (1) in used identical horizontal continuum dispersion machine with colo(u)rant dispersion, thereby prepare white pigment high density dispersion liquid.

In 140 parts of the white pigment high density dispersion liquids of above-mentioned acquisition, add acrylic polyol butylacetate solution and carry out white inkization for 44 parts.Then, this in the product of white inkization, add as solidifying agent 18 parts with before identical hexamethylene diisocyanate 3 aggressiveness that use and mix fully after, add about 40 parts butylacetate, adjustment viscosity prepares white coating fluid.

(3) (thickness: the black coating fluid that surface 100 μ m) applies preparation in above-mentioned (1) carries out drying, forms black coating film (dry film thickness: 5 μ m) in polyethylene terephthalate (PET) substrate sheet.And then, applying the white coating fluid that obtains in above-mentioned (2) at the back side of base material and carry out drying, formation white is filmed, and (dry film thickness: 5 μ m), the acquisition surface scribbles black coating film, the back side is coated with black-white multilayer PET sheet material that adularescent is filmed and formed.

(4) on the black-white multilayer PET sheet material that in above-mentioned (3), obtains, in order to give water vapor barrier and barrier properties for gases, with the stacked silica alumina evaporation of mode polyester film (thickness: 12 μ m) overlapping on the white coated surface overleaf, and then stacked PET substrate sheet (thickness: 100 μ m), make the PET backboard processed that the solar power generation module is used thereon.When stacked, use following tackiness agent above-mentioned.Tackiness agent use by with above-mentioned (1) in used 70 parts of identical acrylic acid multielement alcoholic solutions and the tackiness agent of 15 parts of hexamethylene diisocyanate 3 aggressiveness and 15 parts of formations of butylacetate.

As above obtain will have black coating film and white film multi-layer coated and PET that obtain backboard processed because outward appearance is black, so aesthetic property excellence, and because the optical characteristics of used black pigment-4, so have following optical property.That is, the light of the region of ultra-red in the sunlight from the light of the region of ultra-red of the black coating film layer transmission on surface, transmission by the reflection of the white layer of substrate, emitted to the outside from the black layer transmission again.Therefore, this backboard is owing to seldom absorb sunlight, show excellent thermal insulation, thereby is particularly suitable for the backboard used as the solar power generation module of wishing to avoid to heat up.

When the backboard that uses above-mentioned acquisition is used module as solar power generation, the following use according to conventional methods.Namely; utilization is that the sealing material clamping solar power generation pond that resin constitutes seals by ethane-acetic acid ethyenyl ester; adhesive surface seal stock on the surface of sensitive surface side; protection sheet material as the non-sensitive surface side at the back side; with the black side of above-mentioned opacifying property backboard after sensitive side is pasted; equip transparent glass substrate at sensitive surface, thereby can make the solar power generation module.

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

(1) black pigment-6, the polyester resin powder that utilizes Henschel mixer to mix to obtain in 40 parts of Production Examples 6 is 60 parts, obtains powdered colorant.Then, 12.5 parts of the powdered colorant of gained are engaged in 87.5 parts of the PET resin particles, utilize Henschel mixer to mix after, and then it is mixing to utilize twin screw extruder to carry out, and utilizes tablets press to make the black resin particle.Then, utilize T-mouth mould forcing machine to carry out moulding, make the black PET film of thickness 50 μ m.

(2) in addition, prepared to have carried out mixing painted white PET sheet material (thickness: 180 μ m) with titanium oxide pigments.Then, using the identical acrylic polyol hexamethylene diisocyanate of putting down in writing with embodiment 9 (4) in its surface is tackiness agent, pastes the black PET film of gained in above-mentioned (1), thereby makes the white PET sheet material that is laminated with black PET film.

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

The solar power generation module of having used the sheet material that black film and white PET sheet material with above-mentioned gained be laminated is black, aesthetic property excellence with the outward appearance of backboard, and because therefore the optical characteristics of employed black pigment-6 has following optical property.That is, the light of the region of ultra-red in the sunlight is after the black rete transmission on surface, and the white PET sheet material reflection by following after the black film transmission, is released to the outside again.Therefore, black-white multilayer PET sheet material seldom absorbs sunlight as the solar power generation module with backboard, shows excellent thermal insulation, therefore is particularly suitable for as the solar power generation module backboard of wishing to avoid to heat up.

When using the backboard of above-mentioned acquisition to use module as solar power generation, can following according to conventional methods use.Namely; utilization is that the sealing material clamping solar power generation unit that resin constitutes seals by ethylene vinyl acetate; adhesive surface seal stock on the surface of sensitive surface side; protection sheet material as the non-sensitive surface side at the back side; with the black side of above-mentioned opacifying property backboard after sensitive side is pasted; equip transparent glass substrate at sensitive surface, thereby can make the solar power generation module.

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

18 parts in 71 parts of filter cakes, 10 parts of nonionic series pigments dispersion agents, 1 part of defoamer, the water that will contain the black pigment-1 of gained in 25 parts the Production Example 1 with solid component meter is fully after the ready-mixed, the horizontal continuum dispersion machine that utilization is used granulated glass sphere as dispersion medium is colo(u)rant dispersion, preparation black pigment high density dispersion liquid (black pigment substrate).Use refiner (powerful emulsification dispersion machine) 20 parts of black pigment substrates, 25 parts in reactive acroleic acid acid alkyl ester latex (solids component 40%), 0.5 part of defoamer, 1 part of dispersion agent, the oil-in-water type emulsion of gained to be carried out the emulsification dispersion for 12.5 parts with 3 parts of dispersion stabilizers, 38 parts of mineral turpentines, water, preparation oil-in-water-type black emulsion mashed prod.Then, 2 parts of the linking agents (solids component 40%) that the interpolation carbodiimide is in prepared black emulsion mashed prod mix fully, preparation black printing and dyeing paste.Whole printing on polyester-cotton blended fabric stuck with paste in the black printing and dyeing of gained, carry out 15 minutes curing under 120 ℃, acquisition can be blocked the plain color dyeing cloth of the black of invisible heat.

[embodiment 12] (gravure printing ink)

The black pigment-10 that obtains in 11 parts of Production Examples 10 is added into utilizes diamines that the terminal polyester of isocyanic ester is carried out that chain length prolongs and in 30 parts of 40% methylethylketone-toluene (1:3) mixed solvent solutions of the urethane resin that obtains.Then, add 54.5 parts of 40% toluene solution, methylethylketone-toluene-Virahol (50:30:20) mixed solvents of the polycarbodiimide compound that 2 parts, 2.5 parts of cation property copolymer dispersion agents obtain by tolylene diisocyanate, utilize homogenizer fully to mix.And then, the said mixture utilization is used the horizontal continuum dispersion machine of granulated glass sphere pigment is carried out differential as dispersion medium and loose preparation black gravure printing ink.Use gravure printing machine that the black gravure printing ink of gained is printed on respectively on polyamide membrane, polyester film, the polypropylene screen, obtain to show the black polypropylene film of the optical characteristics of blocking visible light, transmits infrared.

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

(1) (the BM preparation of dispersible pigment dispersion)

(preparation of black pigment dispersion liquid)

With 53 parts of gained black pigment-9 in 25 parts of Production Examples 9,20 parts of 40% solution of benzyl methacrylate-methacrylic acid-2-hydroxyethyl methacrylate multipolymer (mol ratio: 60:20:20, weight-average molecular weight 30000), 2 parts of cationic polymerization system dispersion agents and propylene glycol monomethyl ether (PGMA) ready-mixed fully.Then, use the horizontal medium dispersion machine of continous way that the pigment differential is loose, obtain black pigment dispersion liquid (following it is called " black pigment dispersion liquid-1 ").

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

With 1 part of 1 part of 6 parts of 50%PGMA solution, Viscoat 295, the dipentaerythritol acrylate of black pigment dispersion liquid-1 of obtaining in 40 parts above-mentioned (1), acrylated acrylic acid multielement alcohol ester photoresist, as the ethyl ketone of Photoepolymerizationinitiater initiater; 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl]-, 1-(O-ethanoyl oxime) (" イ Le ガ キ ュ ア OXE02 ", BASF AG's system) 1 part and the cooperation of PGMA51 part.Afterwards, utilize homogenizer to be stirred to evenly fully after, utilizing the aperture is that the strainer of 3 μ m filters, preparation contains the black resist printing ink (below be called " light sensitive black resist printing ink-1 ") of black pigment-9.

(3) (evaluation of black resist film)

Use the light sensitive black resist printing ink-1 of above-mentioned acquisition, utilize spin coater to be coated on the glass substrate.And then carrying out prebake conditions after the preparation drying under 60 ℃, and after the use ultrahigh pressure mercury lamp exposes with the light quantity of 400mJ/cm2, under 230 ℃, carry out back baking 30 minutes, obtaining thickness is the black coating film (black resist ink film) of 3 μ m.

This optical characteristics of filming is as shown in table 10, shows in high-absorbable, the region of ultra-red at 900～1500nm to show high transmissivity in the wavelength region of about 400～750nm of visible region.In addition, this volume intrinsic resistance of filming shows 10 ¹⁴More than the Ω cm, therefore confirm as high-insulativity.

Table 10: the spectral transmission of black resist film

(4) (preparation of BM pattern)

Use the light sensitive black resist printing ink-1 of above-mentioned acquisition, utilize spin coater to be coated on the glass substrate according to conventional methods after, 80 ℃ of following prebake conditions 10 minutes, obtaining thickness was the black coating film of 3 μ m.At this minus optical mask pattern by the BM pattern of being situated between of filming, use ultrahigh pressure mercury lamp, with 100mJ/cm ²Light quantity expose after, utilize alkaline-based developer to develop, washing, after the drying, form the BM pattern.

Formation by the BM film of the BM pattern of above-mentioned gained because as the high electrical insulating property of demonstration as described in above-mentioned (3), therefore can be used at active components such as TFT and form the modification method of the various CF of BM, for example replace the structure of the BM, IPS mode, COA mode etc. of spacer maintenance thickness of liquid crystal layer.In addition, this BM film is owing to can absorb visibility region fully to the long wavelength zone, and the BM that therefore also can be used as the LCD panel that has adopted LED-backlit uses.

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

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

Then, collection cooperates the dispersible pigment dispersion that PR254 and PR177 form of containing respectively of above-mentioned preparation with 33 parts of the mixed solutions that form with the ratio of 8:2, same with described (2) before, add 9.2 parts of photoresist 50% solution, 3 parts of photopolymerization monomers, 0.3 part of Photoepolymerizationinitiater initiater, 54.5 parts of solvents, prepare red resist printing ink.With above-mentioned same, cooperate with the ratio of 5:5 and to contain dispersible pigment dispersion, the green resist printing ink of modulation that PG36 and PY138 form respectively, cooperate with the ratio of 8:2 and contain dispersible pigment dispersion, the blue resist printing ink of modulation that PB15:6 and PV23 form respectively.

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

The glass substrate that will be formed with the BM of above-mentioned (4) made is installed on the spin coater, after the spin coating of the red resist printing ink of the photosensitivity of above-mentioned preparation, 80 ℃ of following prebake conditions 10 minutes.And then, utilize the photomask with mosaic shape pattern, use proximity to aim at exposure machine, use ultrahigh pressure mercury lamp with 100mJ/cm ²Light quantity the coated face of this glass substrate is exposed.Then, utilize special-purpose developing solution and special-purpose leacheate to develop after, wash and dry, form red mosaic shape pattern at glass substrate.And then, with above-mentioned same, use the green resist printing ink of photosensitivity to form the pattern of green mosaic shape, the blue resist printing ink of use photosensitivity forms the pattern of blue mosaic shape, obtains to be formed with the CF of BM and rgb pixel.

In addition, replace above-mentioned use black pigment-9, use the black pigment-7 that obtains in the Production Example 7, in addition with above-mentioned same, carry out the preparation of light sensitive black resist printing ink, and then form above-mentioned BM pattern and rgb pixel pattern, obtain to be formed with the CF of BM and rgb pixel.

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

(1) (the BM preparation of dispersible pigment dispersion)

(preparation of black pigment dispersion liquid)

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

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

The black pigment dispersion liquid-1 that replaces (2) of explanation among the embodiment 13 uses the black pigment dispersion liquid-2 that obtains in above-mentioned (1), in addition with embodiment 13(2) same, preparation black resist printing ink.Below it is called " light sensitive black resist printing ink-2 ".

(3) (preparation of BM pattern)

Same with (4) that embodiment 13 is illustrated, utilize spin coater that light sensitive black resist printing ink-2 is coated on the glass substrate, carry out prebake conditions, be the black coating film of 3 μ m thereby obtain thickness.At this minus optical mask pattern by the BM pattern of being situated between of filming, use ultrahigh pressure mercury lamp to expose, utilize alkaline-based developer develop after washing, drying, form the BM pattern.

Form the BM film of this BM pattern owing to have high electrical insulating property, therefore similarly to Example 13, can be used at active component form the modification method of the various CF of BM, for example 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 the long wavelength zone, and the BM that therefore also can be used as the LCD panel that has adopted LED-backlit uses.

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

Same with (6) that embodiment 13 is illustrated, the glass substrate that is formed with BM that above-mentioned (3) are obtained is installed on the spin coater, use the red resist printing ink of the photosensitivity that obtains in (5) of explanation among the embodiment 13, the green resist printing ink of photosensitivity, the blue resist printing ink of photosensitivity to form mosaic shape pattern of pixels of all kinds, obtain to be formed with the CF of BM and rgb pixel.

[evaluation result]

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

Claims (20)

1. black azo-dye, it is characterized in that, it is for showing the black azo-dye of visible light opacifying property and these two kinds of optical characteristics of infrared transmission, described black azo-dye is the polyazo pigment of black with structure of at least 1 2-hydroxyl-11H-benzo [a]-carbazole-3-carboxylic acid amide residue that comprises 2 above azo bond and imported by the coupling composition in molecule, and the median size of described black azo-dye is 10nm～200nm.

2. black azo-dye according to claim 1, wherein, described visible light opacifying property is that the black colorant film that contains black azo-dye on the transparent substrate shows about spectral transmission below 5% in the wavelength region of about 400～750nm of visible-range, and described infrared transmission property is that above-mentioned black colorant film shows about transmissivity more than 30% in the wavelength region of 900～1500nm of region of ultra-red.

3. black azo-dye according to claim 1 and 2, wherein, the structure of described polyazo pigment has any in the structure of following (1)～(4) at least,

(1) structure shown in [HBC-N=N-Ar-N=N-HBC], it is to use the diazonium salt that compound diazotization amino more than 2 forms that has as the diazonium composition, make this salt and carry out as 2-hydroxyl-11H-benzo [a]-carbazole-3-carboxylic acid aryl amide HBC of coupling composition that azo coupling forms, wherein, described representative formula with compound amino more than 2 is H ₂N-Ar-NH ₂

(2) structure shown in [HBC-N=N-Ar-N=N-Cp], it is to use the diazonium salt that compound diazotization amino more than 2 forms that has as the diazonium composition, make this salt and carry out as 2-hydroxyl-11H-benzo [a]-carbazole-3-carboxylic acid aryl amide HBC of coupling composition and other coupling compositions Cp except this compound that azo coupling forms, wherein, described representative formula with compound amino more than 2 is H ₂N-Ar-NH ₂

(3) structure shown in [Ar-N=N-HBC-HBC-N=N-Ar], after it is to use the compound with 1 amino to carry out diazotization as the diazonium composition, carry out with the coupling composition HBC-HBC that in molecule, has 2 above 2-hydroxyl-11H-benzo [a]-carbazoles-3-methane amide residue HBC-that azo coupling forms, wherein, described compound with 1 amino is expressed as Ar-NH ₂

(4) structure shown in [Ar-N=N-HBC-Cp-N=N-Ar], after it is to use the compound with 1 amino to carry out diazotization as the diazonium composition, carry out with the coupling composition HBC-Cp that in molecule, has 2-hydroxyl-11H-benzo [a]-carbazole-3-methane amide residue HBC-and other coupling composition residues Cp-except this compound that azo coupling forms, wherein, described compound with 1 amino is expressed as Ar-NH ₂

4. black azo-dye according to claim 3, wherein, any one in described coupling composition and the described diazonium composition is selected from following any,

(A-a) described coupling composition HBC is 2-hydroxyl-11H-benzo [a]-carbazole-3-anilide, 2-hydroxyl-11H-benzo [a]-carbazole-3-naphthoamide and their derivative;

(A-b) described coupling composition HBC-HBC is phenylene-two (2-hydroxyls-11H-benzo [a]-carbazole-3-methane amide), biphenylene-two (2-hydroxyl-11H-benzo [a]-carbazole-3-methane amide), naphthalene-two (2-hydroxyl-11H-benzo [a]-carbazole-3-methane amide) and their derivative;

(A-c) described coupling composition Cp is 2-hydroxyl-3-naphthoic acid arylamide, 2-hydroxyl-6-naphthoic acid arylamide, 2-hydroxyl-3-anthroic acid arylamide, 2-hydroxyl-3-diphenylene-oxide formic acid arylamide, 2-hydroxyl-1-carbazole formic acid arylamide and their derivative;

(A-d) described coupling composition HBC-Cp is 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), (2-methyl-) phenylene (1)-(2-hydroxyl-11H-benzo [a]-carbazole-3-methane amide) (4)-(2-hydroxyl-3-naphthoic acid acid amides) and their derivative;

(B-a) compound H with amino more than 2 that uses as described diazonium composition ₂N-Ar-NH ₂Be phenylenediamine, benzidine, diaminonaphthalene, diamino-anthraquinone, diamino-benzophenone, diamino-pyridine and their derivative;

(B-b) the compd A r-NH with 1 amino that uses as described diazonium composition ₂Be aniline, naphthylamines, aminoanthraquinone, phenoxybenzamine, phenylimino aniline and their derivative.

5. be used for to obtain the manufacture method of each described black azo-dye of claim 1～4, it has the synthesis procedure of polyazo pigment of black and the operation of as required this pigment being carried out miniaturization,

(I) synthetic method of the polyazo pigment of described black is any method in following (1)～(4):

(1) diazonium salt that 2-hydroxyl-11H-benzo [a]-carbazole-3-carboxylic acid aryl amide HBC and the compound diazotization that will have amino more than 2 are formed carries out the synthetic method of azo coupling, and wherein, described representative formula with compound amino more than 2 is H ₂N-Ar-NH ₂

(2) has the synthetic method that diazonium salt that the compound diazotization that makes 2-hydroxyl-11H-benzo [a]-carbazole-3-carboxylic acid aryl amide HBC and other coupling compositions Cp except this compound and will have amino more than 2 forms carries out the polyazo pigment of the structure that azo coupling forms, in this synthetic method, make and to have more than 2 the diazonium salt that amino compound diazotization forms and carry out azo coupling with waiting mole or the coupling composition Cp below it, as required coupling there is the polyazo pigment of 2 above coupling composition Cp to separate, remove, then make above-mentioned coupling composition HBC and the diazo of coupling not carry out azo coupling, wherein, described representative formula with compound amino more than 2 is H ₂N-Ar-NH ₂

(3-1) make the coupling composition HBC-HBC that in molecule, has 2 above 2-hydroxyl-11H-benzo [a]-carbazoles-3-methane amide residue HBC-and the compd A r-NH that will have 1 amino ₂The diazonium composition that diazotization forms carries out the synthetic method of azo coupling;

(3-2) make and to have the compd A r-NH of 1 amino ₂The diazonium salt that diazotization forms and 2-hydroxyl-11H-benzo [a]-carbazole-3-carboxylic acid carries out azo coupling, then makes the carboxylic acid of azopigment and aryl polyamines condensation and makes the synthetic method of many methane amides;

(4-1) make and in a part, have the 2-hydroxyl-coupling composition HBC-Cp and the compd A r-NH that will have 1 amino of 11H-benzo [a]-carbazole-3-methane amide residue HBC-and other coupling composition residues Cp-except this compound ₂The diazonium salt that diazotization forms carries out the synthetic method of azo coupling;

(4-2) make and to have the compd A r-NH of 1 amino ₂The diazonium salt that diazotization forms carries out azo coupling with 2-hydroxyl-11H-benzo [a]-carbazole-3-carboxylic acid and other carboxylic acids that is coupled to branch respectively, then makes the carboxylic acid of two kinds of azopigments of gained and aryl polyamines condensation and makes the synthetic method of many methane amides;

And, (II) under the thick situation of the polyazo pigment synthetic by aforesaid method, have by any method in following (1) or (2) the median size miniaturization of the pigment operation to 10nm～200nm:

(1) uses any pigment masher be selected from the group of being formed by ball mill, sand mill, masher, horizontal continuum dispersion machine, kneader, the single screw mixing machine of continous way, continous way twin-screw mixer machine, triple-roller mill and open roll continuous mixer or the miniaturization method of colo(u)rant dispersion machine;

(2) in mixing roll, carry out salt mill method mixing, that grind with water-soluble salt, the water-miscible organic solvent that uses as required.

6. coloured composition, it is characterized in that the pigment composition that contains the black azo-dye that comprises the black azo-dye described in the claim 1～4 or obtain by the described manufacture method of claim 5 in liquid dispersion medium or in the solid dispersion medium forms.

7. coloured composition according to claim 6, wherein, the pigment composition that comprises described black azo-dye is formed separately by described black azo-dye or forms with paint in this black azo-dye and with a kind that is used for group that being selected from of this black azo-dye of revisal be made up of coloured pigment, white pigment, other black pigments and pigment extender, and this coloured composition is used for carrying out the painted of the dead color of painted or Achromatic color of colour of dead color or black.

8. coloured composition according to claim 7, wherein, described black azo-dye decides by using the computer for colouring system to carry out optimized method with the ratio that cooperates of the coloured pigment, white pigment, other black pigments or the pigment extender that are used for this black azo-dye of revisal.

9. coloured composition according to claim 6, wherein, described liquid dispersion medium contains at least a kind of tunicle that is selected from polymer, the oligopolymer that can have reactive group that can have reactive group and the monomer that can have reactive group and forms material, and described liquid dispersion medium is from as liquid or further contain solvent and/or water.

10. coloured composition according to claim 6, wherein, described solid dispersion medium contains at least a kind of solid dispersion medium that is selected from thermoplastic resin, heat-curing resin, wax, fatty acid amide and the fatty acid metal soap.

11. according to each described coloured composition in the claim 6～10, wherein, described coloured composition be used to coating with, apply agent with, plastics with, fiber with, printing-ink with, stationery with, image recording with and image show with in arbitrary at least purposes in.

12. the colorize method of article is characterized in that, color goods is become black or when dark-coloured, right to use requires 7 described coloured compositions at the painted or article self by article surface painted.

13. the colorize method of article according to claim 12, wherein, described article are formed by transparent base material, with this transparency base material by be selected from application, smear, dye, print, take down notes, describe, any method in ink jet printing, electronic photo printing, xeroprinting or the photolithography is carried out surface colour or by compounding process or contain leaching method to make above-mentioned base material self carry out inside painted.

14. the colorize method of article according to claim 13, wherein, described surface colour or inner painted according to the part that is colored in the wavelength region of about 400～750nm of visible region, shows about 5% below spectral transmission, the mode of the about transmissivity more than 30% of demonstration is carried out in the region of ultra-red of 900～1500nm, the feasible article that formed by transparent base material have visible light opacifying property and these two kinds of optical characteristics of infrared transmission concurrently.

15. the colorize method of article according to claim 12, wherein, use article self have the article of light reflective or are provided with the article of preformed light reflective substrate, on the surface of these article or the light reflective substrate uses that described coloured composition carries out application, coating, stickup, deposited, overlapping, original liquid coloring, printing and dyeing, dip-dye, printing, takes down notes, describes, ink jet printing, electronic photo printing or xeroprinting, thus be implemented in show in the region of ultra-red reflexive painted.

16. a dyed articles is characterized in that, it is that the colorize method of implementing each described article in the claim 12～15 forms.

17. the backboard of a solar power generation module, it is characterized in that, it is the backboard of the solar power generation module that is laminated with black or dark colored infrared transmission layer at the light reflective sheet material, the polyazo pigment that in the infrared transmission layer, contains black, the polyazo pigment of described black has the structure of at least 1 2-hydroxyl-11H-benzo [a]-carbazole-3-carboxylic acid amide residue HBC-that comprises 2 above azo bond and imported by the coupling composition in molecule, and the median size of the polyazo pigment of described black is 10nm～200nm.

18. the manufacture method of the backboard of a solar power generation module, it is characterized in that, use base material self to have the base material of light reflective as the light reflective sheet material, perhaps use and be provided with the base material of preformed light reflective substrate as the light reflective sheet material, surface or light reflective substrate at these base materials use the coloured composition of the polyazo pigment that contains black by application, coating, paste, deposited, overlapping, printing, ink jet printing, electronic photo printing or xeroprinting, be implemented in the region of ultra-red show reflexive painted, stacked black or dark colored infrared transmission layer on the 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 HBC-that comprises 2 above azo bond and imported by the coupling composition in molecule, and the median size of the polyazo pigment of described black is 10nm～200nm.

19. color display panel, it is characterized in that, be formed at the polyazo pigment that black matrix" BM on colour filter CF substrate or the organic EL light-emitting substrate contains structure with at least 1 2-hydroxyl-11H-benzo [a]-carbazole-3-carboxylic acid amide residue HBC-that comprises 2 above azo bond and imported by the coupling composition in molecule, black that its median size is 10nm～200nm.

20. color display panel according to claim 19, it has CF substrate or organic EL light-emitting substrate, is formed with black matrix" and the electrode that is essentially electrical insulating property with overlapping or state of contact on described CF substrate or the organic EL light-emitting substrate.