CN101914316A

CN101914316A - Black material, black particle dispersion liquid and the base material that has used its black light-blocking film and had black light-blocking film

Info

Publication number: CN101914316A
Application number: CN2010102670300A
Authority: CN
Inventors: 竹田洋介; 木下畅; 中野丰将; 温井秀树
Original assignee: Sumitomo Osaka Cement Co Ltd
Current assignee: Sumitomo Osaka Cement Co Ltd
Priority date: 2004-09-21
Filing date: 2005-09-16
Publication date: 2010-12-15
Anticipated expiration: 2025-09-16
Also published as: TW200619327A; WO2006033305A1; CN102702802A; TWI395795B; TW201302930A; KR101008747B1; KR20070053712A; CN101914316B

Abstract

The invention provides a kind of black material, it is characterized in that, constitute by following offspring, promptly, this offspring is assembled at the primary particle more than the 1nm and below 200nm by the particle diameter that constitutes with metal and is formed, the particle diameter of this offspring is more than the 5nm and below 300nm, and this offspring contains one or more the element that is selected from silver (Ag), tin (Sn), the nickel (Ni).In addition, the invention provides a kind of black particle dispersion liquid, it is characterized in that, contain described black material and macromolecule dispersing agent.In addition, the invention provides a kind of black particle, it is characterized in that, the surface of described black material is covered by the insulating film that is made of organic high molecular compound.

Description

Black material, black particle dispersion liquid and the base material that has used its black light-blocking film and had black light-blocking film

The application divides an application, the application number of its female case application: PCT/JP2005/017178 (200580031598.X), the applying date: 2005.9.16, denomination of invention: black material, black particle dispersion liquid and the base material that has used its black light-blocking film and had black light-blocking film

Technical field

The present invention relates to a kind of black material (black particle), particularly be applicable in the black matrix etc. of various display unit such as recording materials, liquid-crystal display degree of blackness height, the good black material of opacifying property.In addition, the invention still further relates to black particle dispersion liquid and used its black light-blocking film and had the base material of black light-blocking film, particularly be applicable in the black matrix, black decorating film etc. of various display unit degree of blackness height, the good membrane technique of opacifying property.

The application is willing to that based on the spy of application on September 21st, 2004 spy of application on February 17th, 2004-273348 number 1 is willing to that the spy of application on February 17th, 2005-040257 number 1 is willing to advocate right of priority 2005-040258 number, quotes its content here.

Background technology

In the past, as black material, known had metallic substance or inorganic materials (for example with reference to patent documentation 1) such as carbon black, low order titanium oxide, ferric oxide, chromium, silver-colored particulate.

These black materials are used as the material use of the black matrix material of black optical shielding property film, black optical shielding property glass, black paper, black cloth, black ink, plasma display (PDP) or liquid-crystal display (LCD), black sealing material, black mask material etc. being given black or optical shielding property.

On the other hand, with gold, platinum family element or their alloy black the time, though can adopt the method that forms the mulch film that constitutes by black oxide on the mother metal surface of these metal or alloy, but in this method, black oxide is peeled off from mother metal easily, can't obtain to have the black au-alloy of weather resistance.So, the scheme of following black alloy was proposed, promptly, by to gold, platinum family element or their alloy or in described metal or alloy arbitrarily, added in the silver-colored alloy, add metals such as copper, nickel, iron, with its oxidation, and form the good black oxide layer (with reference to patent documentation 2) that constitutes by metal oxide of connecting airtight property on the surface.

In addition, in the field of sensitive materials, as improving distinctiveness, will proposing in the water-based gelatin, to have disperseed the black colloidal silver dispersion thing (with reference to patent documentation 3) of black colloidal silver from the optical information of back-exposure with appropriate concentration records and the sensitive materials used of the photo of the infrared detection characteristic when having improved development treatment.

But, in the past as slim and large-scale flat display, the known liquid-crystal display (LCD) that can realize panchromatic demonstration.

In this colour liquid crystal display device, in rectangular each pixel that is arranged in R (red), G (green) on the transparency carrier, B (indigo plant),, be formed with the high black matrix of opacifying property in order to improve the contrast gradient of its display surface.

Particularly in the liquid-crystal display (TFT-LCD) of the active array type that has used thin film transistor (TFT), should deceive the caused leakage current of light that matrix can prevent TFT, and stop the seeing through of light beyond the display surface of each pixel and improve the contrast gradient of each pixel, thereby can improve image quality as display unit.

Should the situation that be formed at the tft array substrate side, the situation that is formed at the colour filter side be arranged black matrix.

For the situation that is formed at the tft array substrate side,, therefore black matrix is required high-insulativity because black matrix directly contacts with pixel capacitors and TFT.

On the other hand, for the situation that is formed at the colour filter side, particularly under the situation of the liquid-crystal display (LCD) of transverse electric field type of drive, the black matrix of colour filter side is also required high-insulativity.

Though should black matrix be the metallic membrane that utilizes the high Cr of vacuum vapour deposition or the sputtering method part mulched ground formation opacifying property beyond will transparent pixel capacitors etc. in the past, yet in recent years, as the material that replaces it, the black matrix of having developed the opacifying property height, manufacturing process is simple and can have realized low price forms uses material, and has been used among the practicality.

Form as the black matrix of this kind and use material, for example proposed: in organic solvent, disperseed to utilize resin or silicon oxide to cover the surface and insulating carbon black or the titanium dispersion liquid (for example with reference to patent documentation 4,5) of deceiving; The dispersion liquid (for example with reference to patent documentation 6,7) that in organic solvent, has disperseed metal particles such as silver-colored particulate.

Patent documentation 1: the spy opens flat 5-127433 communique

Patent documentation 2: the spy opens flat 10-8235 communique

Patent documentation 3: the spy opens the 2000-155387 communique

Patent documentation 4: the spy opens the 2002-201381 communique

Patent documentation 5: the spy opens the 2002-267832 communique

Patent documentation 6: the spy opens the 2004-317897 communique

Patent documentation 7: the spy opens the 2004-334180 communique

But though metallic substance such as carbon black in the past, low order titanium oxide, ferric oxide or inorganic materials are black, optical shielding property (opacifying property) is insufficient.So, if will use the film that contains these black materials that light is covered, just need contain the coating fluid of black material by coating thickly, maybe with the repeatedly coating overlappingly of this coating fluid, and on base material, form film with thickness.

Under the situation that these black materials are used as the recording materials of describing the black line on the white substrate, because a little less than the opacifying property, therefore will blur with the boundary part of the white substrate of substrate, can't describe the problem of line clearly thereby have.

In addition, under the situation that these black materials are used as the light masking material, in order to improve optical shielding property, need increase the volume ratio of the black material in the material, the content of tackiness agent will relatively reduce.So when using these black materials to make black coating film, the intensity of filming reduces, and can't keep the reliability problems of filming and can't keep photomask for a long time thereby have.

In addition, though chromium is good aspect degree of blackness and optical shielding property, owing to be heavy metal, environmental pressure is big, and various reasons such as cost height just have the problem that the product that can use is restricted.

In addition, though by silver particles that Silver monobromide reduction used in the photographic film etc. is generated good aspect degree of blackness and the opacifying property, but because silver self is precious metal, and high price, therefore except the product of the costliness of by way of exception a part, generally can not use as the black material of the universal product.

In addition, though by silver particles that Silver monobromide reduction used in the photographic film etc. is generated or black silver colloid good aspect degree of blackness and the opacifying property, but these black silver particles can only be synthesized in the presence of gelatin, and gelatin can't be separated fully with silver particles after synthetic.

In addition,, therefore can not in organic solvent, disperse,, the very narrow problem of scope of coating be arranged so can only be used for the coating of water class because gelatin is insoluble to organic solvent.

In addition, when using silver colloid to make black coating film,,, therefore have or not method to show the problem of good degree of blackness owing to have metallic color or absorb the color that causes by phasmon (plasmon) though this blackwash is good aspect opacifying property.

Summary of the invention

One of the present invention finishes in order to solve described problem, and its purpose is, the black pigment that degree of blackness height and optical shielding property are good and environmental pressure is little, cheap is provided.

The present invention's two finishes in order to solve described problem, its purpose is, black that can obtain moderate and the black particle dispersion liquid that opacifying property is good and environmental pressure is little, cheap are provided and have used its black light-blocking film and had the base material of black light-blocking film.

But, with having used in the past carbon black or the black dispersion liquid of titanium to make under the situation of black matrix, because the opacifying property deficiency, therefore need utilize the high densityization of dispersion liquid or overlapping coating to wait and increase thickness.But because when increasing thickness, black matrix promptly becomes big with the overlapping of each pixel, the flatness of colour filter reduces, and produces inequality in the cell gap of each pixel, so has the problem of the pixel that is difficult to form homogeneous.

Produced in cell gap under the uneven situation, be easy to generate irregular colour in display surface, consequently, the quality of display surface will reduce.

In addition, when the overlapping change of deceiving matrix and each pixel was big, the occupied area of black matrix promptly became greatly in each pixel, thereby the problem of the aperture opening ratio reduction of each pixel is arranged.When aperture opening ratio reduced, the brightness of each pixel reduced, and consequently, the brightness of the display surface integral body of display unit will reduce.

In addition, though carbon black or titanium are black to be to utilize vapor phase process or liquid phase method to carry out surface treatment, yet when utilizing vapor phase process to carry out surface treatment, owing to be difficult to particle is scattered in the gas phase, therefore will be under state of contact between the particle with carry out the surface-treated material and mix, so the surface-treated homogeneity is poor, the cohesion between the particle etc. also becomes problem.So, also had in the surperficial Gas Phase Adsorption of particle behind the alkoxide such as tetraethoxysilane, the method that too much alkoxide is removed under reduced pressure, however in the method, there is operation miscellaneous and spend the problem of more time and cost.

In addition, when utilizing liquid phase method to carry out surface treatment, though owing to can under particle is scattered in state in the liquid phase, carry out surface treatment, therefore compare with vapor phase process and can carry out surface treatment equably, but for example carbon black or titanium are black is to obtain with the pulverulence of having condensed between the particle, and therefore they being scattered in water or the organic solvent is unusual difficulty.

On the other hand, with in the past use the dispersion liquid of metal particle when making black matrix, if just disperseed the black matrix of metal particle, then have the problem that can't obtain high-insulativity.

Particularly, for the situation of the dispersion liquid that has used black silver particulate,, therefore after synthetic, gelatin fully can't be removed, so be difficult to silver-colored particulate is scattered in the organic solvent equably owing to use gelatin to synthesize silver-colored particulate.Under this situation, when not using gelatin, then can't synthesize silver-colored particulate.

Like this, the present invention's three finishes in order to solve described problem, its purpose is, provides to be scattered in easily in the solvent and degree of blackness is high and the base material that has the black particle of high-insulativity and black particle dispersion liquid and black light-blocking film and have black light-blocking film.

The inventor etc. to degree of blackness good and optical shielding property excellent material further investigate, found that, by particle diameter is being formed particle diameter at the offspring more than the 5nm and below 300nm more than the 1nm and in the primary particle convergence that is made of metal and/or metal oxide below the 200nm, outermost layer with this offspring is made as the Au that is selected from that contains more than the 50 weight % in addition, Pt, Pd, Ag, Ru, Cu, Si, Ti, Sn, the structure of the element of one or more among the Ni or their oxide compound, just can obtain the black material that degree of blackness is good and optical shielding property is good, thereby finish the present invention.

Promptly, feature as one of the present invention's black material is, it is assembled the offspring that forms by primary particle and constitutes, described primary particle is a particle diameter at the particle that is made of metal and/or metal oxide more than the 1nm and below 200nm, the particle diameter of described offspring is more than the 5nm and below 300nm, the outermost layer of this offspring contain 50 weight % above be selected among Au, Pt, Pd, Ag, Ru, Cu, Si, Ti, Sn, the Ni one or more element or their oxide compound.

Described offspring is preferably in inside and is formed with spatial portion.

Described offspring is preferably in described outermost layer or is formed with spatial portion by the inboard that comprises the outer shell that described outermost a plurality of layers constitute.

Described offspring is the core shelly preferably, and this core shelly is that the outside surface that will become the material of nuclear forms with described outermost layer or by comprising that described outermost a plurality of layers of outer shell that constitutes cover.

Described outer shell is preferably fine and close.

In addition, the inventor etc. are good to degree of blackness, the opacifying property excellent material is furtherd investigate, found that, contain the black particle dispersion liquid of median size if use at offspring more than the 5nm and below 300nm and macromolecule dispersing agent, then can obtain the good black light-blocking film of degree of blackness height, opacifying property or black decorating film etc., thereby finished the present invention, to be median size at the primary particle of the particulate that is made of metal and/or metal oxide more than the 1nm and below 200nm assemble described offspring forms.

Promptly, feature as the present invention's two black particle dispersion liquid is, contain median size at offspring more than the 5nm and below 300nm and macromolecule dispersing agent, to be median size at the primary particle of the particulate that is made of metal and/or metal oxide more than the 1nm and below 200nm assemble described offspring forms.

Described particulate preferably contains one or more in the group that is selected from silver, tin, nickel.

Described macromolecule dispersing agent preferably contains more than the 1 weight % with respect to the gross weight of described particulate and below 10 weight %.

Described macromolecule dispersing agent preferably polyethylene base pyrrolidone.

Described offspring is preferably in inside and is formed with spatial portion.

Described offspring is preferably in outermost layer or is formed with spatial portion by the inboard that comprises the outer shell that these outermost a plurality of layers constitute.

The preferred core shelly of described offspring, this core shelly are that the outside surface that will become the material of nuclear forms with described outermost layer or by comprising that described outermost a plurality of layers of outer shell that constitutes cover.

The feature of black light-blocking film of the present invention is to be coated with black particle dispersion liquid of the present invention and to form.

The feature that has the base material of black light-blocking film of the present invention is to possess black light-blocking film of the present invention on an interarea of base material.

The preferred CIE luminance brightness of described black light-blocking film L ^*Below 10, colourity a ^*More than-1 and below 1, colourity b ^*More than-1 and below 1, as the OD value of optical concentration more than 3.

In addition, the inventor etc. are to being scattered in easily in the solvent, high and the material that have a high-insulativity of degree of blackness is furtherd investigate, found that, by silver-colored particulate is in the past replaced with median size at the offspring more than the 5nm and below 300nm, surface with this offspring covers with insulating film in addition, just can obtain to be scattered in the solvent easily, degree of blackness is high and have a black particle of high-insulativity, thereby finished the present invention, to be median size at the primary particle of the particulate that is made of metal and/or metal oxide more than the 1nm and below 200nm assemble described this offspring forms.

Promptly, feature as the present invention's three black particle is, median size is insulated film and covers on the surface of the offspring more than the 5nm and below 300nm, to be median size at the primary particle of the particulate that is made of metal and/or metal oxide more than the 1nm and below 200nm assemble described offspring forms.

Described insulating film preferable alloy oxide compound or organic high molecular compound.

The feature of black particle dispersion liquid of the present invention is to contain black particle of the present invention.

The feature that has the base material of black light-blocking film of the present invention is on an interarea of base material, to possess black light-blocking film of the present invention.

One of the present invention's black material is to be made of following offspring, promptly, the particle diameter that is made of metal and/or metal oxide forms in the convergence of the primary particle more than the 1nm and below 200nm, the particle diameter of this offspring is more than the 5nm and below 300nm, make the outermost layer of this offspring contain 50 weight % above be selected among Au, Pt, Pd, Ag, Ru, Cu, Si, Ti, Sn, the Ni one or more element or their oxide compound, therefore just can improve the degree of blackness of black material self, also can improve optical shielding property.

In addition,, do not have the situation of the intensity reduction of filming yet, can keep for a long time and film even using this black material to make under the situation of black coating film.

In addition and since with the outermost layer of offspring be made as contain more than the 50 weight % be selected among Au, Pt, Pd, Ag, Ru, Cu, Si, Ti, Sn, the Ni one or more element or the formation of their oxide compound, so environmental pressure is little, cheap.

According to above explanation, can provide the black material that degree of blackness height and optical shielding property are good and environmental pressure is little, cheap.

Two black particle dispersion liquid according to the present invention, owing to contain median size at offspring more than the 5nm and below 300nm and macromolecule dispersing agent, therefore just can obtain the black and the high black light-blocking film or the black decorating film of opacifying property of moderate, described offspring is to be assembled at the primary particle of the particulate more than the 1nm and below 200nm by the median size that metal and/or metal oxide constitute to form.

In addition, under the situation of using this black particle dispersion liquid making to film, because the offspring that is scattered in the black particle dispersion liquid is good in degree of blackness or opacifying property aspect certainly, therefore can reduce in filming amount with respect to the black particle of tackiness agent, so just do not have the situation of the intensity reduction of filming, can keep for a long time and film.

Three black particle according to the present invention, because median size is insulated film and covers on the surface of the offspring more than the 5nm and below 300nm, therefore just can make it to be scattered in the solvent easily, can improve the degree of blackness of black particle self, can improve insulativity, to be median size at the primary particle of the particulate that is made of metal and/or metal oxide more than the 1nm and below 200nm assemble described offspring forms.

The present invention's four is a kind of black materials, it is characterized in that,

Be made of following offspring, that is, this offspring is assembled at the primary particle more than the 1nm and below 200nm by the particle diameter that constitutes with metal and is formed,

The particle diameter of this offspring is more than the 5nm and below 300nm,

This offspring contains one or more the element that is selected from silver (Ag), tin (Sn), the nickel (Ni).

The present invention's five is four described black materials of the present invention, it is characterized in that, described offspring contains the element more than a kind or 2 kinds that is selected from silver-colored tin alloy, silver, tin, the nickel.

The present invention's six is five described black materials of four or the present invention of the present invention, it is characterized in that described offspring is formed with spatial portion in inside.

The present invention's seven is five described black materials of four or the present invention of the present invention, it is characterized in that, described offspring is formed with spatial portion at described outermost layer or by the inboard that comprises the outer shell that described outermost a plurality of layers constitute.

The present invention's eight is five described black materials of four or the present invention of the present invention, it is characterized in that described offspring is to become the outside surface of material of nuclear with described outermost layer or by comprising that the outer shells that described outermost a plurality of layer constitutes cover the core shellies that form.

The present invention's nine is seven described black materials of the present invention, it is characterized in that described outer shell densification.

The present invention's ten is eight described black materials of the present invention, it is characterized in that described outer shell densification.

The present invention's 11 is a kind of black particle dispersion liquid, it is characterized in that, contain the present invention four～the present invention ten in any described black material and macromolecule dispersing agent.

The present invention's 12 is 11 described black particle dispersion liquids of the present invention, it is characterized in that, with respect to the gross weight of described particulate, the content of described macromolecule dispersing agent is more than the 1 weight % and below 10 weight %.

The present invention's 13 is 11 or 12 described black particle dispersion liquids of the present invention, it is characterized in that, described macromolecule dispersing agent is a Polyvinylpyrolidone (PVP).

The present invention's 14 is a kind of black light-blocking films, it is characterized in that, the coating the present invention 11 to the present invention 13 in any described black particle dispersion liquid form.

The present invention's 15 is a kind of base materials that have black light-blocking film, it is characterized in that, is that the 14 described black light-blocking films that possess the present invention on an interarea of base material form.

The present invention's 16 is 15 described base materials that have black light-blocking film of the present invention, it is characterized in that the CIE luminance brightness L of described black light-blocking film ^*Below 10, colourity a ^*More than-1 and below 1, colourity b ^*More than-1 and below 1, the OD value is more than 3.

The present invention's 17 is a kind of black particles, it is characterized in that, the present invention's four～ten in the surface of any described black material be insulated film and cover and form.

The present invention's 18 is 17 described black particles of the present invention, it is characterized in that, described insulating film is metal oxide or organic high molecular compound.

The present invention's 19 is a kind of black particle dispersion liquids, it is characterized in that, contain the present invention 17 or 18 described black particle and dispersion agents.

The present invention's 20 is a kind of black light-blocking films, it is characterized in that, coating the present invention's 19 described black particle dispersion liquids form.

The present invention's 21 is a kind of base material that has black light-blocking film, it is characterized in that, is that the 20 described black light-blocking films that possess the present invention on an interarea of base material form.

The present invention's 22 is 21 described base materials that have black light-blocking film of the present invention, it is characterized in that the CIE luminance brightness L of described black light-blocking film ^*Below 10, colourity a ^*More than-1 and below 1, colourity b ^*More than-1 and below 1, the OD value is more than 3.

According to black particle dispersion liquid of the present invention, owing to contain black particle of the present invention, therefore can improve the dispersiveness of black particle, can improve coating.

Therefore according to black light-blocking film of the present invention,,, also can improve opacifying property and insulativity even when thickness approaches owing to coating black particle dispersion liquid of the present invention obtains.

If this black light-blocking film is applied in the black matrix of flat display such as liquid-crystal display, then can reduce the overlapping of black matrix and each pixel by the attenuate thickness, can reduce the inequality of the cell gap of each pixel, can realize the homogenization of pixel.So, in display surface, just be difficult to produce irregular colour, can improve the quality of display surface.In addition, the aperture opening ratio of each pixel can be improved, the brightness of the display surface integral body of display unit can be improved.

Description of drawings

Fig. 1 be the expression embodiments of the present invention (one of) the synoptic diagram of cross-section structure of black particle of black material, embodiment (two).

Fig. 2 be the expression embodiments of the present invention (one of) the synoptic diagram of other examples of cross-section structure of black particle of black material, embodiment (two).

Fig. 3 be the expression embodiments of the present invention (one of) the synoptic diagram of other examples of cross-section structure of black particle of black material, embodiment (two).

Fig. 4 be the expression embodiments of the present invention (one of) the synoptic diagram of other examples of cross-section structure of black particle of black material, embodiment (two).

Fig. 5 is the synoptic diagram of cross-section structure of the black particle of expression embodiments of the present invention (three).

Fig. 6 is the synoptic diagram of other examples of cross-section structure of the black particle of expression embodiments of the present invention (three).

Fig. 7 is the synoptic diagram of other examples of cross-section structure of the black particle of expression embodiments of the present invention (three).

Fig. 8 is the synoptic diagram of other examples of cross-section structure of the black particle of expression embodiments of the present invention (three).

Fig. 9 is the figure of x-ray diffractogram of powder shape of the powdered sample of expression embodiments of the invention 1,7.

Figure 10 is the figure of x-ray diffractogram of powder shape of the powdered sample of expression embodiments of the invention 2,8.

Figure 11 is the figure of x-ray diffractogram of powder shape of the powdered sample of expression embodiments of the invention 3,9.

Figure 12 is the figure of x-ray diffractogram of powder shape of the powdered sample of expression embodiments of the invention 4.

Figure 13 is the figure of x-ray diffractogram of powder shape of the powdered sample of expression embodiments of the invention 5.

Wherein, 1,11,21,31 black materials, 2 primary particles, 3 offsprings, 4 particulates, 5 insulating films, 12,23 spatial portions, the outer shell of 22 densifications, 32 emboliform nuclears

Embodiment

One of embodiment ():

At first, describe for mode as the best of one of the present invention's black material.

And this mode specifically describes for the purport of understanding invention better, and short of particularly pointing out just is not that qualification is of the present invention.

The black material of present embodiment is following black material, promptly, constitute at the offspring that the primary particle convergence that is made of metal and/or metal oxide more than the 1nm and below 200nm forms by median size, the particle diameter of this offspring is more than the 5nm and below 300nm, the outermost layer of this offspring contain 50 weight % above be selected among Au, Pt, Pd, Ag, Ru, Cu, Si, Ti, Sn, the Ni one or more element or their oxide compound.

This offspring if its outermost layer contain 50 weight % above be selected among Au, Pt, Pd, Ag, Ru, Cu, Si, Ti, Sn, the Ni one or more element or their oxide compound, material for the part except that this outermost layer is formed, and is unqualified.

This offspring most preferably is formed with the mode of spatial portion in inside, secondly, preferably be formed with the mode of spatial portion in the inboard of the outer shell that is made of a plurality of layers; The outside surface that perhaps will become the material of nuclear utilizes described outermost layer or by comprising that the outer shells that described outermost a plurality of layers constitute cover the modes as the core shelly that form.

Below, the section form of this black material is described.

This black material can adopt following various structures.

(1) close structure

Fig. 1 is the sectional drawing of cross-section structure that schematically shows the black material of present embodiment, among the figure, 1 is black material, particle diameter is assembled at the primary particle that is made of metal and/or metal oxide more than the 1nm and below 200nm 2, form particle diameter at the offspring more than the 5nm and below 300nm 3, the outermost layer of this offspring 3 by contain more than the 50 weight % be selected among Au, Pt, Pd, Ag, Ru, Cu, Si, Ti, Sn, the Ni one or more element or the particulate 4 as primary particle of their oxide compound constitute.This black material 1 is closely assembled because of primary particle 2, and is formed on the close structure that inside does not have spatial portion.

(2) hollow structure (one of)

Fig. 2 is other the sectional drawing of example of cross-section structure that schematically shows the black material of present embodiment, and the black material 1 different aspect of this black material 11 and Fig. 1 is, has formed spatial portion 12 in the inside of offspring 3.

(3) hollow structure (two)

Fig. 3 is other the sectional drawing of example of cross-section structure that schematically shows the black material of present embodiment, the black material 11 different aspects of this black material 21 and Fig. 2 are, only constitute fine and close outer shell 22, the inboard of this outer shell 22 is made as spatial portion 23 by particulate 4.

Though this outer shell 22 only is made as one deck of particulate 4 here, also can be made as by constituting that two-layer above multilayer forms.

(4) core shell structure

Fig. 4 is other the sectional drawing of example of cross-section structure that schematically shows the black material of present embodiment, the black material 1 different aspect of this black material 31 and Fig. 1 is, is constituting of covering of the outer shell 22 of densification that the outside surface utilization of emboliform nuclear 32 only is made of particulate 4.

Material as formation nuclear 32 is not particularly limited, but the good material of particulate 4 connecting airtight property preferred and formation outer shell 22 for example can preferably use silicon oxide (SiO ₂), titanium oxide (TiO ₂), zirconium white (ZrO ₂) etc.

These black materials 1～31 can use common particulate synthesis method to make.As the particulate synthesis method, no matter use gas-phase reaction method, spray heating decomposition, send method forth, which kind of method of liquid phase reaction method, freeze-drying, hydrothermal synthesis method etc. can.

Black material according to present embodiment, constitute at the following offspring more than the 5nm and below 300nm by particle diameter by it, and the outermost layer that makes this offspring contain 50 weight % above be selected among Au, Pt, Pd, Ag, Ru, Cu, Si, Ti, Sn, the Ni one or more element or their oxide compound, just can improve degree of blackness, also can improve optical shielding property, described offspring is that particle diameter forms in the primary particle convergence that is made of metal and/or metal oxide more than the 1nm and below 200nm.

Embodiment (two):

Below, for describing as the present invention's two the black particle dispersion liquid and the mode of the best having used its black light-blocking film and had a base material of black light-blocking film.

The black particle dispersion liquid of present embodiment contains median size at offspring more than the 5nm and below 300nm and high molecular dispersion liquid, and to be median size at the primary particle of the particulate that is made of metal and/or metal oxide more than the 1nm and below 200nm assemble described offspring forms.

In this black particle dispersion liquid, the organic binder bond that contain solvent, contains as required etc.

Though the element of this particulate is not particularly limited, preferably contain in the group that is selected from silver, tin, nickel one or more.

This offspring most preferably is formed with the mode of spatial portion in inside, secondly, and preferably at outermost layer or be formed with the mode of spatial portion by the inboard that comprises the outer shells that these outermost a plurality of layers constitute; The outside surface that perhaps will become the material of nuclear utilizes described outermost layer or by comprising that outer shells that described outermost a plurality of layers constitute cover the mode of the core shelly that forms.In addition, though the mode that this offspring also can only be a primary particle folder to be assembled every dispersion agent etc., more preferably primary particle does not press from both sides every dispersion agent etc. and the direct mode of contact mutually; Or between primary particle, has a mode that network ground engages.

Below, for the section form of the black particle that forms this offspring, will use described embodiment (one of) in Fig. 1～Fig. 4 of use describe.

This black particle can adopt following various structures.

(1) close structure

Fig. 1 is the sectional drawing of cross-section structure that schematically shows the black particle of present embodiment, among the figure, symbol 1 is black particle (black material), median size is assembled at the primary particle that is made of metal and/or metal oxide more than the 1nm and below 200nm 2, form median size at the offspring more than the 5nm and below 300nm 3, this black particle 1 is closely assembled because of primary particle 2, and is formed on the inner close structure that does not have big spatial portion except the gap of particle.In addition, no matter primary particle 2 is to be made of a kind of metal or metal oxide, and still being made of two or more metals and/or metal oxide can.In addition, the shape of this offspring is not particularly limited, and can use the particle of different shape such as spherical, unsetting, tabular.

(2) hollow structure (one of)

Fig. 2 is other the sectional drawing of example of cross-section structure that schematically shows the black particle of present embodiment, and the black particle 1 different aspect of this black particle (black material) 11 and Fig. 1 is, has formed spatial portion 12 in the inside of offspring 3.The shape of this offspring is not particularly limited, and can use the particle of different shape such as spherical, unsetting, tabular.In addition, this hollow structure also can not be complete state, both can link to each other with spatial portion 12 usefulness holes outside, also can become the shape that for example the globular offspring of Fig. 2 is divided into several.

(3) hollow structure (two)

Fig. 3 is other the sectional drawing of example of cross-section structure that schematically shows the black particle of present embodiment, the black particle 11 different aspects of this black particle (black material) 21 and Fig. 2 are, only constitute outer shell 22, the inboard of this outer shell 22 is made as spatial portion 23 by particulate 4.

Though this outer shell 22 is made as one deck of particulate 4 here, also can be made as by constituting that two-layer above multilayer forms.In addition, the shape of this black particle is not particularly limited, and can use the particle of different shape such as spherical, unsetting, tabular.In addition, this hollow structure also can not be complete state, both can link to each other with spatial portion 23 usefulness holes outside, also can become the shape that for example the globular black particle of Fig. 3 is divided into several.

(4) core shell structure

Fig. 4 is other the sectional drawing of example of cross-section structure that schematically shows the black particle of present embodiment, the black material 1 different aspect of this black particle (black material) 31 and Fig. 1 is, is constituting of covering of outer shell 22 that the outside surface utilization with emboliform nuclear 32 only is made of particulate 4.In addition, this outer shell 22 also can not be complete state, also the outside can be linked to each other with nuclear 32 usefulness holes.The shape of this black particle is not particularly limited, and can use the particle of different shape such as spherical, unsetting, tabular.

Material as formation nuclear 32 is not particularly limited, but the good material of particulate 4 connecting airtight property preferred and formation outer shell 22 for example can preferably use silver, tin, nickel, silicon oxide (SiO ₂), titanium oxide (TiO ₂), zirconium white (ZrO ₂) etc.

Macromolecule dispersing agent improves the dispersiveness of this particulate by improving the wettability of microparticle surfaces, consequently, has improved the homogeneity of dispersion liquid, for example can preferably use Polyvinylpyrolidone (PVP) (PVP), polyoxyethylene glycol, polyacrylic acid amide etc.

This macromolecule dispersing agent is with respect to the gross weight of particulate contained in the black particle dispersion liquid, preferably contain more than the 1 weight % and below 10 weight %, more preferably more than the 2 weight % and below the 8 weight %, further more than the preferred 3 weight % and below the 6 weight %.

As solvent,, for example can enumerate unary alcohols such as water, methyl alcohol, ethanol, n-propyl alcohol, 2-propyl alcohol, butanols though be not particularly limited; Di-alcoholss such as ethylene glycol; β-oxygen base ethyl-methyl ether (methylcyclohexane), β-oxygen benzyl ethyl ether (ethyl cellosolve), β-oxygen base ethyl propyl ether (propyl cellosolve), butyl-β-oxygen benzyl ethyl ether glycol ether (cellosolve) classes such as (ethylene glycol butyl ethers); Glycols such as ethylene glycol, propylene glycol; Ketones such as acetone, methyl ethyl ketone, dimethyl ketone; Ester classes such as ethyl acetate, butylacetate, jasmal; Ether alcohol such as methyl cellosolve, ethoxy ethanol class; Propylene glycol methyl ether acetate etc.

Black particle in the black particle dispersion liquid of present embodiment can use common particulate synthesis method to make.As the particulate synthesis method, no matter use gas-phase reaction method, spray heating decomposition, send method forth, which kind of method of liquid phase reaction method, freeze-drying, hydrothermal synthesis method etc. can.

Black particle dispersion liquid according to present embodiment, owing to contain median size at the offspring more than the 5nm and below 300nm, therefore can improve degree of blackness, can also improve opacifying property, to be median size at the primary particle of the particulate that is made of metal and/or metal oxide more than the 1nm and below 200nm assemble described offspring forms.

In addition, contain more than the 1 weight % and the macromolecule dispersing agent below 10 weight %, just can obtain good dispersion stabilization, can obtain good black opacifying property by gross weight with respect to particulate contained in the black particle dispersion liquid.

In addition, by using Polyvinylpyrolidone (PVP), just can obtain more good dispersion stabilization as macromolecule dispersing agent.Because this Polyvinylpyrolidone (PVP) also dissolves in the organic solvent, therefore by Polyvinylpyrolidone (PVP) is used as macromolecule dispersing agent, just can with microparticulate in various solvents, consequently, can be applied in the various coating.

According to above explanation, may be provided in black particle dispersion liquid into the raw material of degree of blackness height, opacifying property is good and environmental pressure is little, cheap black light-blocking film.

The black light-blocking film of present embodiment is by the black particle dispersion liquid of present embodiment being coated on the base material, being carried out drying thereafter and obtain.

If this black light-blocking film is formed on the interarea of base material, then becomes the base material that has black light-blocking film.

As base material,, can enumerate glass baseplate, plastic basis material (organic polymer base material) though be not particularly limited.In addition, as its shape, can enumerate flat board, film like, laminar etc.In addition, as described plastic basis material, preferred plastic tab, plastics film etc.

As the material of glass baseplate,, for example can from soda-lime glass, potassic glass, non-alkali glass etc., suitably select though be not particularly limited.

Material as plastic basis material; though be not particularly limited, for example can from cellulose ethanoate, polystyrene (PS), polyethylene terephthalate (PET), polyethers, polyimide, Resins, epoxy, phenoxy resin, polycarbonate (PC), polyvinylidene difluoride (PVDF), tri acetyl cellulose, polyethersulfone (PES), polyacrylic ester etc., suitably select.

As coating process, can use used method usually rightly, for example excellent cladding process, spin coating method, spray application method, ink jet method, pickling process, rolling method, stencil printing etc.

Coat the dispersion liquid on the base material owing to contain solvent, therefore utilize drying process thereafter that solvent is removed.

For example, by the base material that will be coated with dispersion liquid be positioned in the atmosphere, under the room temperature (25 ℃), perhaps with the temperature of regulation, for example in atmosphere, with 50 ℃～80 ℃ temperature heating, make solvent evaporates contained in the dispersion liquid, form black light-blocking film.

Described black light-blocking film is preferably by the normalized CIE luminance brightness of CIE (International Commission on Illumination) L ^*Below 10, colourity a ^*More than-1 and below 1, colourity b ^*More than-1 and below 1, as the OD value of optical concentration more than 3.

CIE luminance brightness L ^*Low more, then the degree of blackness of black light-blocking film just improves more, when using as black matrix, shows that contrast gradient improves.For colourity a ^*, colourity b ^*, no matter be positive value, still negative value owing to when numerical value becomes big, all can have form and aspect, is therefore considered from the viewpoint of display quality, preferably near 0 value, that is, best black light-blocking film does not have color.Because when OD value was low, then in order to obtain enough opacifying propertys, the thickness of black light-blocking film will become greatly, therefore particularly with black light-blocking film as the situation of deceiving the matrix use under, when the thickness of black light-blocking film becomes big, then can produce the unequal problem of demonstration.

Embodiment (three):

Below, to describing as the present invention's three black particle and black particle dispersion liquid and black light-blocking film and the mode of the best that has a base material of black light-blocking film.

For the black particle of present embodiment, median size is insulated film and covers on the surface of the offspring more than the 5nm and below 300nm, to be median size at the primary particle of the particulate that is made of metal and/or metal oxide more than the 1nm and below 200nm assemble described offspring forms.

Particulate as the integrant of this black particle can use common particulate synthesis method to make.As the particulate synthesis method, no matter use gas-phase reaction method, spray heating decomposition, send method forth, which kind of method of liquid phase reaction method, freeze-drying, hydrothermal synthesis method etc. can.

Insulating film is by median size is formed the high-insulativity particulate in the surface insulationization of the offspring more than the 5nm and below 300nm, to be median size at the primary particle of the particulate that is made of metal and/or metal oxide more than the 1nm and below 200nm assemble forms for preferable alloy oxide compound or organic high molecular compound, wherein said offspring.

As metal oxide, can preferably use metal oxide, for example silicon oxide (silica), aluminum oxide (aluminium sesquioxide), zirconium white (zirconium dioxide), yttrium oxide (yttrium oxide), titanium oxide (titanium dioxide) etc. with insulativity.

In addition, as organic high molecular compound, can preferably use resin, for example polyimide, polyethers, polyacrylic ester, polyamino compound etc. with insulativity.

For the insulativity on the surface that keeps described particulate fully, the thickness of the preferred 1～100nm of thickness of insulating film, more preferably 5～50nm.

This insulating film can utilize the paint-on technique on process for modifying surface or surface easily to form.Particularly, if use alkoxide such as tetraethoxysilane, aluminum ethylate,, therefore preferred then owing to the insulating film that can under lower temperature, form the thickness homogeneous.

Below, the section form of the black particle of present embodiment is described.

This black particle can adopt following various structures.

(1) close structure

Fig. 5 is the sectional drawing of cross-section structure that schematically shows the black particle of present embodiment, among the figure, symbol 1 is a black particle, median size is assembled at the primary particle that is made of metal and/or metal oxide more than the 1nm and below 200nm 2, form median size at the offspring more than the 5nm and below 300nm 3, this black particle 1 is closely assembled because of primary particle 2, and be formed on the inner close structure that except the gap of particle, does not have big spatial portion, in addition, the surface of offspring 3 is insulated film 5 coverings.In addition, no matter primary particle 2 is to be made of a kind of metal or metal oxide, and still being made of two or more metals and/or metal oxide can.In addition, the shape of this offspring is not particularly limited, and can use the particle of different shape such as spherical, unsetting, tabular.

(2) hollow structure (one of)

Fig. 6 is other the sectional drawing of example of cross-section structure that schematically shows the black particle of present embodiment, and the black particle 1 different aspect of this black particle 11 and Fig. 1 is, has formed spatial portion 12 in the inside of offspring 3.In this black particle 11, the surface of offspring 3 also is to be insulated film 5 to cover.The shape of this offspring is not particularly limited, and can use the particle of different shape such as spherical, unsetting, tabular.In addition, this hollow structure also can not be complete state, both can link to each other with spatial portion 12 usefulness holes outside, also can become the shape that for example the globular offspring of Fig. 2 is divided into several.

(3) hollow structure (two)

Fig. 7 is other the sectional drawing of example of cross-section structure that schematically shows the black particle of present embodiment, the black particle 11 different aspects of this black particle 21 and Fig. 2 are, only constitute outer shell 22, the inboard of this outer shell 22 is made as spatial portion 23 by particulate 4.In this black particle 21, the surface of offspring 3 also is to be insulated film 5 to cover.

(4) core shell structure

Fig. 8 is other the sectional drawing of example of cross-section structure that schematically shows the black particle of present embodiment, the black material 1 different aspect of this black particle 31 and Fig. 1 is, is constituting of covering of outer shell 22 that the outside surface utilization with emboliform nuclear 32 only is made of particulate 4.In this black particle 31, the surface of offspring 3 is insulated film 5 and covers.In addition, this outer shell 22 also can not be complete state, also the outside can be linked to each other with nuclear 32 usefulness holes.The shape of this black particle is not particularly limited, and can use the particle of different shape such as spherical, unsetting, tabular.

As the material that constitutes nuclear 32,, preferably, for example can preferably use silver, tin, nickel, silicon oxide (SiO with the good material of particulate 4 connecting airtight property that constitutes outer shell 22 though be not particularly limited ₂), titanium oxide (TiO ₂), zirconium white (ZrO ₂) etc.

In the black particle of present embodiment, by median size is utilized insulating film cover on the surface of the offspring more than the 5nm and below 300nm, compare degree of blackness improves with Ag particle or Sn particle, opacifying property improves, insulativity also improves, and to be median size at the primary particle of the particulate that is made of metal and/or metal oxide more than the 1nm and below 200nm assemble described offspring forms.

In addition, by utilizing the insulating film that constitutes by metal oxide to cover on the surface of the offspring more than the 5nm and below 300nm median size, will form with metal particles such as Ag particle or Sn particles and compare more excellent material of thermotolerance, and physical strength is higher, more be difficult to wearing and tearing, and to be median size at the primary particle of the particulate that is made of metal and/or metal oxide more than the 1nm and below 200nm assemble described offspring forms.

The black particle dispersion liquid of present embodiment is the dispersion liquid that contains the black particle of present embodiment, in this black particle dispersion liquid, and the organic binder bond that contain solvent, contains as required etc.

As solvent,, for example can similarly use illustrated solvent in the described embodiment (two) though be not particularly limited.

In the black particle dispersion liquid of present embodiment, by containing the black particle that utilizes insulating film to cover on the surface of the offspring more than the 5nm and below 300nm median size, just may be provided in the black particle dispersion liquid into the raw material of the good and cheap black light-blocking film of degree of blackness height, opacifying property and insulativity, to be median size at the primary particle of the particulate that is made of metal and/or metal oxide more than the 1nm and below 200nm assemble described offspring forms.

As the material of glass baseplate and plastic basis material,, for example can similarly use the material of illustrated glass baseplate and plastic basis material in the described embodiment (two) though be not particularly limited.

When this black light-blocking film uses at the black matrix as liquid-crystal display display unit such as (LCD), preferably have high-insulativity, for example as volume resistance (Ω cm), 10 ⁷Ω cm is above to be preferred range.

In addition, preferably by the normalized CIE luminance brightness of CIE (International Commission on Illumination) L ^*Below 10, colourity a ^*More than-1 and below 1, colourity b ^*More than-1 and below 1, as the OD value of optical concentration more than 3.

CIE luminance brightness L ^*Low more, then degree of blackness just improves more, and particularly under the situation that the black matrix as liquid-crystal display display unit such as (LCD) uses, the low more contrast gradient that then shows just improves more.So, will be made as preferred range below 10 as what show scope that contrast gradient is good.

Consider colourity a from the viewpoint of display quality ^*, colourity b ^*Preferably do not have colour owing to when absolute value surpasses 1, will have tone, so with preferred range be made as do not have color absolute value below 1, that is, and more than-1 and below 1.

When the OD value is low, then can't obtain enough opacifying propertys, in addition, for the film of low OD value, in order to obtain enough opacifying propertys, the thickness of just having to increase, particularly under the situation that the black matrix as liquid-crystal display (LCD) etc. uses, because of thickness becomes big, just be easy to generate show uneven.So even with under the thin situation of thickness, the scope that also can obtain enough opacifying propertys is made as more than 3.

Embodiment

Below, for embodiments of the present invention (one of), utilize embodiment 1～6 and comparative example 1～3, more specifically illustrate, but the present invention is not limited by these embodiment.

(embodiment 1)

Get 10g tin colloid (median size: 90nm divides Gu form: 30 weight %, Osaka, Sumitomo cement company system), to wherein adding pure water, having obtained cubic capacity is the A liquid of 300ml.In addition, weighing and mixed nitrate silver 1.5g and Sulfothiorine 33g form the aqueous solution to wherein adding pure water, add strong aqua (NH in this aqueous solution ₃: 5ml 28%), add pure water again, having obtained cubic capacity is the B liquid of 100ml.

Then, use the magnetic stirrer, then, utilize centrifugation to clean, obtained solid formation and be divided into 15% C liquid these A liquid and B liquid mixing 10 minutes.

Utilize infiltration type electron microscope (TEM) to observe the shape of the particle in this C liquid, its result is, particle diameter is that the particle of 10～30nm has covered the shape on surface that particle diameter is the particle of 50～90nm.

In addition, utilize filtration method from this C liquid with separate particles, be dried thereafter, made the powdered sample of embodiment 1, the generation phase in this powdered sample of having used the X-ray diffraction device identification.

Fig. 9 is the figure of x-ray diffractogram of powder shape of the powdered sample of expression embodiment 1, and among the figure, zero is labeled as the diffracted ray of tin (Sn), and △ is labeled as Ag ₄Sn alloy phase or Ag ₃The diffracted ray of Sn alloy phase.

According to this x-ray diffractogram of powder shape and described synthesis procedure as can be known, the particle in the C liquid is will become the surface of Sn particle of nuclear with the covered core shell structure of AgSn alloy particle.

Then, in this C liquid, add the PVA aqueous solution, make it to reach the solid formation branch in the C liquid: PVA=50: 50 volume ratio, utilizing ultrasonic dispersing machine (ソニ Off アイヤ-450:BRANSON ULTRASONICS corporate system) to carry out after the dispersion treatment, left standstill 1 hour, and formed coating fluid.

Then, utilize spin coating method to coat on the glass substrate of thickness 1.1mm this coating fluid, formed filming of black.Here, by adjusting the amount of moisture in the coating fluid, the thickness of filming is made as 0.5 μ m.

Then, down after the drying, utilizing elcometer テ Application コ-Le (テ Application コ-Le company) to measure thickness in room temperature (25 ℃) this black film, utilizing sub-ray spectrometer to measure transmittance for the black film self of the light of the wavelength of 550nm.

In addition, in order to estimate the degree of blackness of this black film, based on by the normalized L of CIE (International Commission on Illumination) ^*a ^*b ^*Chromaticity diagram has been measured the CIE lightness L of this black film ^*Their measurement result is shown in the table 1.

(embodiment 2)

Adding pure water and dilute in the C liquid that obtains in embodiment 1 is 10 times, adds 100g aqueous tartaric acid solution (tartrate: 5%), stirred 10 minutes, utilize centrifugation to clean then, obtained solid formation and be divided into 15% D liquid in this diluent.

After utilizing infiltration type electron microscope (TEM) to observe the shape of the particle in this D liquid, finding to exist a plurality of particle diameters is 50～90nm and formed the particle of the hollow shape of spatial portion in inside.This hollow granule is the shape that the particle of particle diameter 10～30nm has been assembled.

In addition, utilize filtration method separating particle from this D liquid, be dried thereafter, made the powdered sample of embodiment 2, the generation phase in this powdered sample of having used the X-ray diffraction device identification.

Figure 10 is the figure of x-ray diffractogram of powder shape of the powdered sample of expression embodiment 2, and among the figure, zero is labeled as the diffracted ray of Sn, and △ is labeled as Ag ₄Sn alloy phase or Ag ₃The diffracted ray of Sn alloy phase.

According to above result as can be known, the particle in the D liquid is the hollow granule that is made of the AgSn alloy.

Then, in this D liquid, add the PVA aqueous solution, make it to reach the solid formation branch in the D liquid: PVA=50: 50 volume ratio, utilizing ultrasonic dispersing machine (ソニ Off アイヤ-450:BRANSON ULTRASONICS corporate system) to carry out after the dispersion treatment, left standstill 1 hour, and formed coating fluid.

Then, down after the drying, utilizing elcometer テ Application コ-Le (テ Application コ-Le company) to measure thickness in room temperature (25 ℃) this black film, utilizing sub-ray spectrometer to measure transmittance for the black film self of the wavelength light of 550nm.

In addition, based on by the normalized L of CIE ^*a ^*b ^*Chromaticity diagram has been measured the CIE lightness L of this black film ^*Their measurement result is shown in the table 1.

(embodiment 3)

Adding pure water and dilute in the D liquid that obtains in embodiment 2 is 10 times, uses sand mill that this diluent is carried out 5 minutes dispersion treatment, has obtained solid formation and has been divided into 15% E liquid.

After utilizing infiltration type electron microscope (TEM) to observe the shape of the particle in this E liquid, find that particle diameter is the particle of particle convergence formation particle diameter 50～150nm of 10～30nm.

In addition, utilize filtration method separating particle from this E liquid, be dried thereafter, made the powdered sample of embodiment 3, the generation phase in this powdered sample of having used the X-ray diffraction device identification.

Figure 11 is the figure of x-ray diffractogram of powder shape of the powdered sample of expression embodiment 3, and among the figure, △ is labeled as Ag ₄Sn alloy phase or Ag ₃The diffracted ray of Sn alloy phase.

According to above result as can be known, particle in the E liquid is the particle that the AgSn alloy particle has been assembled.

Then, in this E liquid, add the PVA aqueous solution, make it to reach the solid formation branch in the D liquid: PVA=50: 50 volume ratio, utilizing ultrasonic dispersing machine (ソニ Off アイヤ-450:BRANSON ULTRASONICS corporate system) to carry out after the dispersion treatment, left standstill 1 hour, and formed coating fluid.

(embodiment 4)

Add water in glucose 2.3g, tartrate 0.2g and ethanol 4g, having obtained gross weight is the F liquid of 50g.In addition, in Silver Nitrate 1.5g, add strong aqua (NH ₃: 5ml 28%), add pure water again, having obtained gross weight is the G liquid of 50g.

Then,, this mixed solution is added in the A liquid used among the embodiment 1, when stirring this solution, in this solution, drip the aqueous sodium hydroxide solution 10g of 0.05N at leisure these F liquid and G liquid mixing.Then, use the magnetic stirrer, thereafter, utilize centrifugation to clean, obtained solid formation and be divided into 15% H liquid this solution stirring 10 minutes.

Utilize infiltration type electron microscope (TEM) to observe the shape of the particle in this H liquid, its result is, is the ganoid particle of particle diameter 80～100nm.

In addition, utilize filtration method separating particle from this H liquid, be dried thereafter, made the powdered sample of embodiment 4, the generation phase in this powdered sample of having used the X-ray diffraction device identification.

Figure 12 is the figure of x-ray diffractogram of powder shape of the powdered sample of expression embodiment 4, and among the figure, zero is labeled as the diffracted ray of Sn, * being labeled as the diffracted ray of silver (Ag), △ is labeled as Ag ₄Sn alloy phase or Ag ₃The diffracted ray of Sn alloy phase.

According to above result as can be known, the surface of the particle in the H liquid is made of the layer of the densification of Ag and AgSn alloy.

Then, in this H liquid, add the PVA aqueous solution, make it to reach the solid formation branch in the H liquid: PVA=50: 50 volume ratio, utilizing ultrasonic dispersing machine (ソニ Off アイヤ-450:BRANSON ULTRASONICS corporate system) to carry out after the dispersion treatment, left standstill 1 hour, and formed coating fluid.

(embodiment 5)

Add pure water in the H liquid that obtains in embodiment 4, dilution is 10 times, in this diluent, add aqueous tartaric acid solution (tartrate: 100g 5%), stirred 10 minutes, then, utilize centrifugation to clean, obtained solid formation and be divided into 15% I liquid.

After utilizing infiltration type electron microscope (TEM) to observe the shape of the particle in this I liquid, find that having a plurality of particle diameters is the particle of the hollow shape of 80～100nm, the particle of this hollow shape is formed by the outer shell of densification.

In addition, utilize filtration method separating particle from this I liquid, be dried thereafter, made the powdered sample of embodiment 5, the generation phase in this powdered sample of having used the X-ray diffraction device identification.

Figure 13 is the figure of x-ray diffractogram of powder shape of the powdered sample of expression embodiment 5, and among the figure, zero is labeled as the diffracted ray of Sn, and △ is labeled as Ag ₄Sn alloy phase or Ag ₃The diffracted ray of Sn alloy phase.

According to above result as can be known, the particle of the hollow shape that forms of the outer shell by densification in the I liquid is to be made of the AgSn alloy.

Then, in this I liquid, add the PVA aqueous solution, make it to reach the solid formation branch in the I liquid: PVA=50: 50 volume ratio, utilizing ultrasonic dispersing machine (ソニ Off アイヤ-450:BRANSON ULTRASONICS corporate system) to carry out after the dispersion treatment, left standstill 1 hour, and formed coating fluid.

(embodiment 6)

In pure water 100ml, be dissolved in and dissolved nickelous chloride powder (NiCl in the pure water ₂6H ₂O) 1.19g, tin chloride (SnCl ₂2H ₂O) 100g and to make total amount be the tin chloride aqueous solution 33.8ml of 1 liter (L) adds potassium pyrophosphate powder 9.9g, tartrate 7.5g, glycine 0.82g again in this solution, stirred 10 minutes.

Thereafter, add 1% polypyrrole alkane ketone aqueous solution 5.0g in this solution, the NaOH aqueous solution of Dropwise 5 N then is adjusted into 8.5 with the pH of this solution.

Then, this solution is being remained under 55 ℃ the state, the disposable solution that is dropped in dissolving sodium borohydride 1.1g among the pure water 50g and obtains stirred 1 hour., utilize centrifugation clean, obtained solid formation and be divided into 10% J liquid thereafter.

After utilizing infiltration type electron microscope (TEM) to observe the shape of the particle in this J liquid, find that particle diameter is that the particle of 1～10nm is that the surface coverage ground of the particle of 20～30nm adheres to particle diameter, forming particle diameter is the offspring of 30～50nm.

In addition, utilize filtration method separating particle from this J liquid, be dried thereafter, made the powdered sample of embodiment 6, after use electro-probe micro analyzer (EPMA) has carried out the ultimate analysis of this powdered sample, detected the B of Ni, Sn and trace.

Having used the X-ray diffraction device identification after the generation mutually in this powdered sample, detected the diffracted ray of Ni and Sn.

According to this x-ray diffractogram of powder shape and described synthesis procedure as can be known, the particle in the J liquid is will become the surface of Ni particle of nuclear with the covered core shell structure of Sn particulate.

Then, in this J liquid, add the PVA aqueous solution, make it to reach the solid formation branch in the J liquid: PVA=50: 50 volume ratio, utilizing ultrasonic dispersing machine (ソニ Off アイヤ-450:BRANSON ULTRASONICS corporate system) to carry out after the dispersion treatment, left standstill 1 hour, and formed coating fluid.

(comparative example 1)

To carbon black (HA3, East Sea carbon corporate system) adds the PVA aqueous solution in, and make it to reach similarly to Example 1 carbon black: PVA=50: 50 volume ratio, carry out the adjustment of the amount of moisture in dispersion treatment, the coating fluid, the coating on glass substrate similarly to Example 1, made thickness and be the filming of black of 0.5 μ m.

Then, identical with embodiment 1, carried out the drying of this black film, the mensuration of thickness, the mensuration of transmittance, CIE lightness L ^*Mensuration.Their measurement result is shown in the table 1.

(comparative example 2)

To the black (13M of titanium, ジエ system コ corporate system) adds the PVA aqueous solution in, and it is black to make it to reach similarly to Example 1 titanium: PVA=50: 50 volume ratio, carry out the adjustment of the amount of moisture in dispersion treatment, the coating fluid, the coating on glass substrate similarly to Example 1, made thickness and be the filming of black of 0.5 μ m.

(comparative example 3)

In Nano silver grain (Osaka, Sumitomo cement company system), add the PVA aqueous solution, reach Nano silver grain: PVA=50 similarly to Example 1: 50 volume ratio, carry out the adjustment of the amount of moisture in dispersion treatment, the coating fluid, the coating on glass substrate similarly to Example 1, made thickness and be the filming of black of 0.5 μ m.

[table 1]

?	The structure of particle	Thickness (μ m)	Transmittance (%)	CIE lightness L ^*
					Embodiment 1	The SnAg particulate	0.51?	0.00?	4.3?
Embodiment 2	SnAg alloy hollow granule	0.50?	0.00?	3.5?
					Embodiment 3	The SnAg alloy is assembled particle	0.52?	0.00?	3.9?
Embodiment 4	The fine and close shell particles of SnAg	0.51?	0.00?	4.4?
					Embodiment 5	The fine and close shell hollow granule of SnAg	0.53?	0.00?	4.0?
Embodiment 6	The NiSn particulate	0.55?	0.00?	4.7?
					Comparative example 1	Carbon black	0.55?	0.32?	5.1?
Comparative example 2	Titanium is black	0.53?	1.05?	8.6?

Comparative example 3

The Ag nanoparticle

0.52?

0.01?

24?

Can confirm that according to this table 1 black film of embodiment 1～6 is with respect to comparative example 1～3, transmittance is lower, CIE lightness L ^*Also better, more good aspect opacifying property and degree of blackness.

On the other hand, the transmittance of the black film of comparative example 1,2 is very high, illustrates that opacifying property is very poor with respect to the black film of embodiment 1～5.

In addition, though the black film of comparative example 3 can obtain the opacifying property roughly the same with embodiment 1～6, the color of film is a grey, aspect tone problem is arranged.

Below, to embodiments of the present invention (two), will utilize embodiment 7～10 and comparative example 4～6 to carry out specific description, yet the present invention is not limited by these embodiment.

(embodiment 7)

Get 20g tin colloid (particle diameter 20～80nm, median size: 30nm, divide Gu form: 15 weight %, Osaka, Sumitomo cement company system), it is joined in the pure water that has dissolved 0.15g Polyvinylpyrolidone (PVP) (PVP) (k15: Tokyo changes into industrial's system), and having obtained cubic capacity is the A liquid of 300ml.

In addition, weighing and mixed nitrate silver 1.5g and Sulfothiorine 33g form the aqueous solution to wherein adding pure water, add strong aqua (NH in this aqueous solution ₃: 5ml 28%), add pure water again, having obtained cubic capacity is the B liquid of 100ml.

Then, in this C liquid, add the PVA aqueous solution, make it to reach the solid formation branch in the C liquid: PVA=50: 50 volume ratio, utilizing ultrasonic dispersing machine (ソニ Off アイヤ-450:BRANSON ULTRASONICS corporate system) to carry out after the dispersion treatment, left standstill 1 hour, and formed black particle dispersion liquid.

Then, utilize spin coating method to coat on the glass substrate of thickness 1.1mm this black particle dispersion liquid, formed filming of black.Here, by adjusting the amount of moisture in the dispersion liquid, the thickness of filming is made as 0.5 μ m.

Then, down after the drying, obtained having the glass substrate of black light-blocking film in room temperature (25 ℃) this being had the glass substrate of filming.

Then, utilize elcometer テ Application コ-Le (テ Application コ-Le company) to measure the thickness of this black light-blocking film.

Then, measure this and had the transmittance of the glass substrate of black light-blocking film.Here, utilize sub-ray spectrometer to measure transmittance for the black light-blocking film self of the light of the wavelength of 550nm.

In addition, in order to estimate the degree of blackness of this black film, based on by the normalized L of CIE (International Commission on Illumination) ^*a ^*b ^*Chromaticity diagram has been measured the CIE lightness L of this black film ^*, colourity a ^*, colourity b ^*

In addition, use penetrating concentration instrumentation has been decided the OD value as the optical concentration of this black light-blocking film.Their measurement result is shown in the table 2.

In addition, utilize infiltration type electron microscope (TEM) to observe the shape of the particle in the described C liquid, its result is, is that median size is that the particle of 5～30nm is the shape of surface coverage of the particle of 20～80nm with median size.

In addition, utilize filtration method separating particle from described C liquid, be dried thereafter, made the powdered sample of embodiment 1, the generation phase in this powdered sample of having used the X-ray diffraction device identification.

Fig. 9 is the figure of x-ray diffractogram of powder shape of the powdered sample of expression embodiment 7, and among the figure, zero is labeled as the diffracted ray of tin (Sn), and △ is labeled as Ag ₄Sn alloy phase or Ag ₃The diffracted ray of Sn alloy phase.

According to above result as can be known, the particle in the C liquid is that the surface that becomes the Sn particle of nuclear is used by the covered core shell structure of AgSn alloy particle.

(embodiment 8)

Adding pure water and dilute in the C liquid that obtains in embodiment 7 is 10 times, adds 100g aqueous hydrochloric acid (hydrochloric acid: 4.5%), stirred 10 minutes, utilize centrifugation to clean then, obtained solid formation and be divided into 15% D liquid in this diluent.

Then, in this D liquid, add the PVA aqueous solution, make it to reach the solid formation branch in the D liquid: PVA=50: 50 volume ratio, utilizing ultrasonic dispersing machine (ソニ Off アイヤ-450:BRANSON ULTRASONICS corporate system) to carry out after the dispersion treatment, left standstill 1 hour, and formed black particle dispersion liquid.

Then, identical with embodiment 7, carried out the thickness of black light-blocking film, the mensuration of transmittance, CIE lightness L ^*, colourity a ^*, b ^*Mensuration, the mensuration of OD value.Their measurement result is shown in the table 1.

In addition, after utilizing infiltration type electron microscope (TEM) to observe the shape of the particle in the described D liquid, finding to exist a plurality of particle diameters is 20～80nm and formed the particle of the complete hollow shape of spatial portion in inside.In addition, also exist the part of the particle of hollow shape to be short of or to be divided into several particles simultaneously.This hollow granule is that median size is that the primary particle of 5～30nm is assembled the offspring form.

In addition, utilize filtration method separating particle from described D liquid, be dried thereafter, made the powdered sample of embodiment 8, the generation phase in this powdered sample of having used the X-ray diffraction device identification.

Figure 10 is the figure of x-ray diffractogram of powder shape of the powdered sample of expression embodiment 8, and among the figure, zero is labeled as the diffracted ray of tin (Sn), and △ is labeled as Ag ₄Sn alloy phase or Ag ₃The diffracted ray of Sn alloy phase.

Hence one can see that, the particle in the D liquid be the hollow granule that constitutes by the AgSn alloy and hollow shape particle part shortcoming or be divided into several particles.

(embodiment 9)

Adding pure water and dilute in the D liquid that obtains in embodiment 8 is 10 times, and this diluent was used the sand mill dispersion treatment 5 minutes, has obtained solid formation and has been divided into 15% E liquid.

Then, in this E liquid, add the PVA aqueous solution, make it to reach the solid formation branch in the E liquid: PVA=50: 50 volume ratio, utilizing ultrasonic dispersing machine (ソニ Off アイヤ-450:BRANSON ULTRASONICS corporate system) to carry out after the dispersion treatment, left standstill 1 hour, and formed black particle dispersion liquid.

Then, identical with embodiment 7, carried out the thickness of black light-blocking film, the mensuration of transmittance, CIE lightness L ^*, colourity a ^*, b ^*Mensuration, the mensuration of OD value.Their measurement result is shown in the table 2.

In addition, after utilizing infiltration type electron microscope (TEM) to observe the shape of the particle in the described E liquid, find that median size is the particle convergence formation offspring that median size is 30～150nm of 5～30nm.

In addition, utilize filtration method separating particle from this E liquid, be dried thereafter, made the powdered sample of embodiment 9, the generation phase in this powdered sample of having used the X-ray diffraction device identification.

Figure 11 is the figure of x-ray diffractogram of powder shape of the powdered sample of expression embodiment 9, and among the figure, △ is labeled as Ag ₄Sn alloy phase or Ag ₃The diffracted ray of Sn alloy phase.

Hence one can see that, and the particle in the E liquid is that the AgSn alloy particle is assembled the particle that forms.

(embodiment 10)

In pure water 100ml, be dissolved in and dissolved nickelous chloride powder (NiCl in the pure water ₂6H ₂O) 1.19g, tin chloride (SnCl ₂2H ₂O) 100g and to make total amount be the tin chloride aqueous solution 33.8ml of 1 liter (L) adds potassium pyrophosphate powder 9.9g, tartrate 7.5g and glycine 0.82g again in this solution, stirred 10 minutes.

Thereafter, add 1% polypyrrole alkane ketone (PVP) aqueous solution 5.0g in this solution, the NaOH aqueous solution of Dropwise 5 N then is adjusted into 8.5 with the pH of this solution.

Then, this solution is being remained under 55 ℃ the state, and disposablely be dropped in the solution that dissolving sodium borohydride 1.1g obtains among the pure water 50g, stirring 1 hour, then, utilizing centrifugation to clean, obtaining solid formation and be divided into 10% F liquid.

Then, in this F liquid, add the PVA aqueous solution, make it to reach the solid formation branch in the F liquid: PVA=50: 50 volume ratio, utilizing ultrasonic dispersing machine (ソニ Off アイヤ-450:BRANSON ULTRASONICS corporate system) to carry out after the dispersion treatment, left standstill 1 hour, and formed black particle dispersion liquid.

In addition, after utilizing infiltration type electron microscope (TEM) to observe the shape of the particle in the described F liquid, find that median size is that the particle of 1～10nm is that the surface coverage ground of the particle of 20～30nm adheres to median size, forming median size is the offspring of 30～50nm.

In addition, utilize filtration method separating particle from this F liquid, be dried thereafter, made the powdered sample of embodiment 10, after use electro-probe micro analyzer (EPMA) has carried out the ultimate analysis of this powdered sample, detected the B of Ni, Sn and trace.

Hence one can see that, and the particle in the F liquid is to become the surface of Ni particle of nuclear by the covered core shell structure of Sn particulate.

(comparative example 4)

To carbon black (HA3, East Sea carbon corporate system) adds the PVA aqueous solution in, reach carbon black: PVA=50 similarly to Example 7: 50 volume ratio, carry out similarly to Example 7 the amount of moisture in dispersion treatment, the coating fluid adjustment, utilize the coating on glass substrate of spin coating method, made thickness and be the filming of black of 0.5 μ m.

Then, it is dry down in room temperature (25 ℃) that this is had the glass substrate of filming, and obtained having the glass substrate of black light-blocking film.

(comparative example 5)

To the black (13M of titanium, ジエ system コ corporate system) adds the PVA aqueous solution in, it is black to reach titanium similarly to Example 7: PVA=50: 50 volume ratio, carry out similarly to Example 7 the amount of moisture in dispersion treatment, the coating fluid adjustment, utilize the coating on glass substrate of spin coating method, made thickness and be the filming of black of 0.5 μ m.

Then, identical with embodiment 7, carried out the thickness of this black light-blocking film, the mensuration of transmittance, CIE lightness L ^*, colourity a ^*, b ^*Mensuration, the mensuration of OD value.Their measurement result is shown in the table 2.

(comparative example 6)

In Nano silver grain (Osaka, Sumitomo cement company system), add the PVA aqueous solution, reach Nano silver grain: PVA=50 similarly to Example 7: 50 volume ratio, carry out similarly to Example 7 the amount of moisture in dispersion treatment, the coating fluid adjustment, utilize the coating on glass substrate of spin coating method, made thickness and be the filming of black of 0.5 μ m.

Then, identical with embodiment 7, carried out the thickness of this black light-blocking film, the mensuration of transmittance, aCIE lightness L ^*, colourity a ^*, b ^*Mensuration, the mensuration of OD value.Their measurement result is shown in the table 2.

[table 2]

Can confirm that according to this table 2 black light-blocking film of embodiment 7～10 is because with respect to comparative example 4～6, transmittance is lower, CIE lightness L ^*Also lower, colourity a ^*, b ^*Absolute value also littler, therefore good aspect opacifying property and degree of blackness.

On the other hand, the transmittance height of the black light-blocking film of comparative example 4,5 illustrates that opacifying property is very poor with respect to the black light-blocking film of embodiment 7～10.

In addition, though the black light-blocking film of comparative example 6 can obtain the opacifying property roughly the same with embodiment 7～10, the color of film is a grey, aspect tone problem is arranged.

Below, for embodiments of the present invention (three), will utilize embodiment 11～12 and comparative example 7～9 more specifically to illustrate, yet the present invention is not limited by these embodiment.

" modulation of black particle "

Utilize following operation to modulate black particle.

(1) the silver-colored tin alloy of coated silica is assembled particle A

It is that the black silver tin alloy of the offspring of 20～150nm is assembled the aqueous dispersions of particle (the solid concentration that forms branch is 15 weight % that the primary particle that will be formed with median size and be 5～20nm is assembled the median size that forms, Osaka, Sumitomo cement company system) dilution of 100g use pure water is 10 times, in this solution, add 3-TSL 8330 (APS) 0.1 weight % aqueous solution 750g and stir, formed A liquid.

On the other hand, the solution that water has been diluted water glass is (with SiO ₂Be scaled 3%) 100g, use Zeo-karb that pH is adjusted into 10.5, formed B liquid.

Then, utilize the NaOH aqueous solution (0.1N) that pH is adjusted into 9.5 described A liquid, in this A liquid, drip described B liquid at leisure, stirred 1 hour.Then, use ultrafiltration from this solution, unreacted water glass, APS, ion etc. to be removed, concentrate thereafter, obtained dispersion liquid.

Then, utilize centrifugation, lyophilize etc. from this dispersion liquid with solution and separation of particles, carry out drying, the silver-colored tin alloy that has obtained coated silica is assembled particle A.

(2) the silver-colored tin alloy of coated silica is assembled particle B

It is that the black silver tin alloy of the offspring of 20～150nm is assembled the aqueous dispersions of particle (the solid concentration that forms branch is 15 weight % that the primary particle that will be formed with median size and be 5～20nm is assembled the median size that forms, Osaka, Sumitomo cement company system) dilution of 100g use pure water is 10 times, in this solution, add acetate, pH is adjusted into 4.8.

Then, after dropping contains the aqueous solution 200g of 1 weight % tetraethoxysilane in this solution, stirred 2 hours down at 60 ℃.Then, use ultrafiltration from this solution, to remove unreacted tetraethoxysilane, acetate etc., concentrate thereafter, obtained dispersion liquid.

Then, utilize centrifugation, lyophilize etc. from this dispersion liquid with solution and separation of particles, carry out drying, the silver-colored tin alloy that has obtained coated silica is assembled particle B.

" making of black particle dispersion liquid and black light-blocking film " (embodiment 11)

In the silver-colored tin alloy convergence particle A100g of coated silica, add dispersion agent (ソ Le スパ-ス 24000: ア PVC シア (strain) system) 2g, propylene glycol methyl ether acetate 100g, use ball mill (beads mill) to disperse, the silver-colored tin alloy that has obtained coated silica is assembled particle dispersion.In this dispersion liquid, add by benzyl methacrylate/Sipacril 2739OF: 64 weight parts, six vinylformic acid dipentaerythritol ester: the tackiness agent 50g that 26 weight parts, IRGACURE907:9 weight part constitute, mix, obtained coating fluid.Utilize spin coating method that this coating fluid is coated on the glass substrate, in room temperature (25 ℃) down after the drying, irradiation ultraviolet radiation (UV) has formed the black film of thick 0.6 μ m.

(embodiment 12)

Except in embodiment 11, the silver-colored tin alloy that replaces coated silica is assembled particle A, has used the silver-colored tin alloy of coated silica to assemble beyond the particle B, has been identically formed the black film of embodiment 12 with embodiment 11.

(comparative example 7)

Except the silver-colored tin alloy that has used uncoated silica is assembled particle, be identically formed black film with embodiment 11.

(comparative example 8)

Except the carbon black that has used coated silica, be identically formed black film with embodiment 11.

(comparative example 9)

Except the titanium that has used coated silica is deceived, be identically formed black film with embodiment 11.

" evaluation of black film "

Measured the volume resistance of embodiment 11～12 and comparative example 7～9 black film separately.Mensuration is according to the JIS C2103-1991 of Japanese Industrial Standards " volume specific resistance test ", utilizes four-terminal method to measure.

In addition, use penetrating concentration instrumentation has been decided the OD value as the optical concentration of this black film.

In addition, in order to estimate the degree of blackness of this black film, based on by the normalized L of CIE (International Commission on Illumination) ^*a ^*b ^*Chromaticity diagram has been measured the CIE lightness L of this black film ^*, colourity a ^*, b ^*

Their measurement result is shown in the table 3.

[table 3]

Can confirm according to this table 3, because the volume resistance of the black film of

embodiment

11,12 is greater than 10 ¹⁰Ω cm, the OD value is more than 4, CIE lightness L ^*Low, colourity a ^*, b ^*Absolute value little, therefore good aspect insulativity, opacifying property and degree of blackness.

Find on the other hand, though the OD value of the black film of comparative example 7 more than 4, CIE lightness L ^*Low, colourity a ^*, b ^*Absolute value little, but volume resistance is low to moderate 1.2 * 10 ⁶Ω cm, insulativity reduces.

Find in addition, though the volume resistance of the black film of comparative example 8,9 is greater than 10 ¹⁰Ω cm, but CIE lightness L ^*Height, the OD value is little to about 2, colourity a ^*, b ^*Absolute value also surpass 1, with respect to the black film of

embodiment

11,12, all very poor aspect degree of blackness, opacifying property.

The industrial possibility of utilizing

One of the present invention's black material is because good aspect degree of blackness, light-proofness, and cheap, therefore go for requiring degree of blackness or light-proofness or require degree of blackness and all objects of light-proofness in. For example, also can be used as the utilizations such as the black matrix material of the display unit such as black optical shielding property film, black optical shielding property glass, black paper, black cloth, black ink, flux of plasma display (PDP) or liquid crystal display (LCD), black encapsulant, black mask material.

The present invention's two black particle dispersion liquid is owing to can be used as aspect degree of blackness, light-proofness good, in addition good aspect heat resistance, and the material use of cheap black light-blocking film, therefore go for requiring in the material of degree of blackness, light-proofness, stable on heating all objects. For example, also can be used as the utilizations such as the black matrix material of the display unit such as black light-proofness film, black light-proofness glass, black paper, black cloth, black ink, flux of plasma display (PDP) or liquid crystal display (LCD), black encapsulant, black mask material.

The present invention's three black particle is owing to can be used as aspect degree of blackness, light-proofness, insulating properties goodly, and therefore the and material use of cheap black light-blocking film goes for requiring in the material of all objects of degree of blackness, light-proofness, insulating properties. For example, except as towards the black matrix material of the display unit such as liquid crystal display (LCD), plasma scope (PDP), electroluminescent display (ELD), electrochromism display (ECD), black encapsulant, black mask material etc., can also be as utilizations such as black light-proofness film, black light-proofness glass, black paper, black cloth, black inks.

Claims

1. a black material is characterized in that,

The particle diameter of this offspring is more than the 5nm and below 300nm,

2. black material according to claim 1 is characterized in that, described offspring contains the element more than a kind or 2 kinds that is selected from silver-colored tin alloy, silver, tin, the nickel.

3. black material according to claim 1 and 2 is characterized in that described offspring is formed with spatial portion in inside.

4. black material according to claim 1 and 2 is characterized in that, described offspring is formed with spatial portion at outermost layer or by the inboard that comprises the outer shell that described outermost a plurality of layers constitute.

5. black material according to claim 1 and 2 is characterized in that, described offspring is to become the outside surface of material of nuclear with outermost layer or by comprising that the outer shells that described outermost a plurality of layer constitutes cover the core shellies that form.

6. black material according to claim 4 is characterized in that, described outer shell densification.

7. black material according to claim 5 is characterized in that, described outer shell densification.

8. a black particle dispersion liquid is characterized in that, contains any described black material and macromolecule dispersing agent in the claim 1～7.

9. black particle dispersion liquid according to claim 8 is characterized in that, with respect to the gross weight of described particulate, the content of described macromolecule dispersing agent is more than the 1 weight % and below 10 weight %.

10. according to Claim 8 or 9 described black particle dispersion liquids, it is characterized in that described macromolecule dispersing agent is a Polyvinylpyrolidone (PVP).

11. a black light-blocking film is characterized in that, any described black particle dispersion liquid forms in the coating claim 8 to 10.

12. a base material that has black light-blocking film is characterized in that, is to possess the described black light-blocking film of claim 11 to form on an interarea of base material.

13. the base material that has black light-blocking film according to claim 12 is characterized in that, the CIE luminance brightness L of described black light-blocking film ^*Below 10, colourity a ^*More than-1 and below 1, colourity b ^*More than-1 and below 1, the OD value is more than 3.

14. a black particle is characterized in that, the surface of any described black material in the claim 1～7 is insulated the film covering and forms.

15. black particle according to claim 14 is characterized in that, described insulating film is metal oxide or organic high molecular compound.

16. a black particle dispersion liquid is characterized in that, contains claim 14 or 15 described black particle and macromolecule dispersing agents.

17. a black light-blocking film is characterized in that, the described black particle dispersion liquid of coating claim 16 forms.

18. a base material that has black light-blocking film is characterized in that, is to possess the described black light-blocking film of claim 17 to form on an interarea of base material.

19. the base material that has black light-blocking film according to claim 18 is characterized in that, the CIE luminance brightness L of described black light-blocking film ^*Below 10, colourity a ^*More than-1 and below 1, colourity b ^*More than-1 and below 1, the OD value is more than 3.