CN101928467B - Black material, black particle dispersion liquid, black shading film using same and base material with black shading film - Google Patents
Black material, black particle dispersion liquid, black shading film using same and base material with black shading film Download PDFInfo
- Publication number
- CN101928467B CN101928467B CN2010102637938A CN201010263793A CN101928467B CN 101928467 B CN101928467 B CN 101928467B CN 2010102637938 A CN2010102637938 A CN 2010102637938A CN 201010263793 A CN201010263793 A CN 201010263793A CN 101928467 B CN101928467 B CN 101928467B
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- China
- Prior art keywords
- black
- blocking film
- silver
- film
- black light
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C5/00—Alloys based on noble metals
- C22C5/06—Alloys based on silver
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/102—Metallic powder coated with organic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/16—Metallic particles coated with a non-metal
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
- C03C17/007—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character containing a dispersed phase, e.g. particles, fibres or flakes, in a continuous phase
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/06—Surface treatment of glass, not in the form of fibres or filaments, by coating with metals
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- C—CHEMISTRY; METALLURGY
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Abstract
The invention provides a black shading film Which at least contains black material and macromolecule dispersant, and is characterized in that the black material is composed of particles with silver-tin alloy as main component, and the average grain diameter of the particles is larger than 1nm and smaller than 300nm. In addition, base material with the black shading film is characterized in that the black shading film is arranged on one main surface of the base material.
Description
The application divides an application, the application number of its female case application: PCT/JP2005/017176 (200580031597.5), the applying date: 2005.9.16, denomination of invention: black material, black particle dispersion liquid and used its black light-blocking film and with the base material of 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 the various display unit such as recording materials, liquid-crystal display, degree of blackness is high, 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 with the base material of black light-blocking film, be particularly related in the black matrix that is applicable to recording materials, various display unit, the black decorating film etc., degree of blackness is high, the good membrane technique of opacifying property.
The application quotes its content here based on Patent 2005-040432 number opinion right of priority of the application on February 17th, Patent 2005-040431 number 1 of the application on February 17th, Patent 2004-273349 number 1 of application on September 21st, 2004.
Background technology
In the past, as black material, known had (for example with reference to patent documentations 1) such as carbon black, low order titanium oxide, ferric oxide, chromium, silver-colored particulates.
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, although can adopt the method that forms the mulch film that is consisted of by black oxide on the surface of the mother metal of these metal or alloy, but in the 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, namely, by to gold, platinum family element or their alloy or in described arbitrarily metal or alloy, added in the silver-colored alloy, add the metals such as copper, nickel, iron, with its oxidation, and at the good black oxide layer (with reference to patent documentation 2) of surface formation adhesion.
In addition, in the field of sensitive materials, as improving distinctiveness, will 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, proposing in the water-based gelatin, to have disperseed the black colloidal silver dispersion (with reference to patent documentation 3) of black colloidal silver.
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), in order to improve the contrast gradient of its display surface, be formed with the high black matrix of opacifying property.
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 the image quality as display unit.
Should the situation that be formed at the tft array substrate side and 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, because black matrix directly contacts with pixel capacitors and TFT, therefore black matrix is required high-insulativity.
On the other hand, for the situation that is formed at the colour filter side, particularly in 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.
Although should black matrix be the metallic membrane that utilizes the high Cr of vacuum vapour deposition or the sputtering method partial coverage 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 that opacifying property is high, manufacturing process is simple and can having realized low price forms use material, and among the practicality.
Material is used in black matrix formation as this kind, for example proposes: disperseed to utilize resin or silicon oxide to cover on the surface and carried out the carbon black of insulating or the dispersion liquid (for example with reference to patent documentation 4,5) that titanium is deceived in organic solvent; The dispersion liquid (for example with reference to patent documentation 6,7) that in organic solvent, has disperseed the metal particles such as silver-colored particulate.
Patent documentation 1: Unexamined Patent 5-127433 communique
Patent documentation 2: Unexamined Patent 10-8235 communique
Patent documentation 3: JP 2000-155387 communique
Patent documentation 4: JP 2002-201381 communique
Patent documentation 5: JP 2002-267832 communique
Patent documentation 6: JP 2004-317897 communique
Patent documentation 7: JP 2004-334180 communique
But although the 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, in order to use the film that contains these black materials light is covered, just need to contain by thickly coating the coating fluid of black material, maybe this coating fluid repeatedly is coated with overlappingly, and forms the film with thickness at base material.
In the situation that these black materials are used as the recording materials of describing the black line in 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 clearly problem of line thereby have.
In addition, in the situation that these black materials are used as the light masking material, in order to improve optical shielding property, need to 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 strength decreased of filming can't be kept the problem of filming and can't keep the reliability of photomask for a long time thereby have.
In addition, although chromium is good aspect degree of blackness and optical shielding property, owing to be heavy metal, environmental pressure is large, the various reasons of high in cost of production, and the problem that the product that can use to some extent is restricted.
In addition, although 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 a part of expensive product by way of exception, generally can not use as the black material of the universal product.
In addition, although 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, because gelatin is insoluble to organic solvent, therefore can not in organic solvent, disperse, thus can only be used for the coating of water class, thus the very narrow problem of scope of coating is arranged.
In addition, when using silver colloid to make black coating film, although this blackwash is good aspect opacifying property, owing to absorb the color that causes with metallic color or by phasmon (plasmon), therefore have or not method to show the problem of good degree of blackness.
Summary of the invention
One of the present invention finishes in order to solve described problem, and its purpose is, degree of blackness height, the good black material of opacifying property are provided.
The present invention's two finishes in order to solve described problem, its purpose is, the black that can obtain moderate and the black particle dispersion liquid that opacifying property is good and environmental pressure is little, cheap is provided and used its black light-blocking film and with 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 in the situation of black matrix, because opacifying property is not enough, therefore need to utilize the high density of dispersion liquid or overlapping coating etc. to increase thickness.But because when increasing thickness, black matrix namely becomes large 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 in the uneven situation, produce easily 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 large, the occupied area of black matrix namely 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, although 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 for particle is scattered in the gas phase, therefore will be under the state that contacts 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 for under reduced pressure alkoxide of surplus being removed, 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, although 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 equably surface treatment, be to obtain with the pulverulence of having condensed between the particle but for example carbon black or titanium are black, it is very difficult therefore they being scattered in water or the organic solvent.
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, owing to synthesize silver-colored particulate with gelatin, therefore after synthetic, gelatin fully can't be removed, so be difficult to silver-colored particulate is scattered in the organic solvent equably.In 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 have the black particle of high-insulativity and black particle dispersion liquid and black light-blocking film and with the base material of black light-blocking film.
The material that the inventor etc. are good to degree of blackness and optical shielding property is good conducts in-depth research, found that, by tin particle is in the past replaced with silver-colored tin alloy particle, it is above and below the 300nm that median size that in addition should silver tin alloy particle is made as 1nm, just can obtain degree of blackness height, the good black material of opacifying property, find that in addition it is more good that this silver tin alloy particle and tin particle etc. are compared thermotolerance, thereby finished the present invention.
That is, one of the present invention's feature is that black material is made of the particle take silver-colored tin alloy as principal constituent, and the median size of this particle is more than the 1nm and below 300nm.
Described silver-colored tin alloy preferably contains the above and silver below 90 % by weight of 47.6 % by weight.
In addition, the material that the inventor etc. are good to degree of blackness, opacifying property is good conducts in-depth research, found that, if use and contain median size at the silver-colored tin alloy particle more than the 1nm and below 300nm and the black particle dispersion liquid of 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 finish the present invention.
That is, the present invention's two feature is, black particle dispersion liquid contains with silver-colored tin alloy as principal constituent and median size at the particulate more than the 1nm and below 300nm (black material) and macromolecule dispersing agent.
Described silver-colored tin alloy preferably contains the above and silver below 90 % by weight of 47.6 % by weight.
In described particulate, no matter be contain with silver alloys as principal constituent and median size more than the 1nm and the particulate below the 300nm, with tin alloy as principal constituent and the median size any one party at the particulate more than the 1nm and below 300nm, still making both sides mix existence can.
Described macromolecule dispersing agent preferably contains more than 1 % by weight with respect to the gross weight of described particulate and below 10 % by weight.
Described macromolecule dispersing agent preferably polyethylene base pyrrolidone.
The feature of black light-blocking film of the present invention is to be coated with described black particle dispersion liquid and to form.
The feature of the base material with black light-blocking film of the present invention is on an interarea of base material, to possess described black light-blocking film.
L* is below 10 for the preferred CIE luminance brightness of described black light-blocking film, and colourity a* is more than-1 and below 1, and colourity b* is more than-1 and below 1, as the OD value of optical concentration more than 3.
In addition, the inventor etc. to be scattered in easily in the solvent, degree of blackness is high and material with high-insulativity conducts in-depth research, found that, silver-colored particulate by will be in the past replaces with silver-colored tin alloy as principal constituent and median size at the particulate more than the 1nm and below 300nm, surface with this particulate covers with insulating film in addition, just can obtain to be scattered in easily in the solvent, degree of blackness is high and has the black particle of high-insulativity, thereby finish the present invention
That is, the present invention's three is a kind of black particles, it is characterized in that, is insulated the film covering with silver-colored tin alloy on the surface of the particulate more than the 1nm and below 300nm (black material) as principal constituent and median size.
Described insulating film preferable alloy oxide compound or organic high molecular compound.
Described silver-colored tin alloy preferably contains the above and silver below 90 % by weight of 47.6 % by weight.
The feature of the black particle dispersion liquid of the present invention here is to contain described black particle.
The feature of black light-blocking film of the present invention is to be coated with described black particle dispersion liquid and to form.
The feature of the base material with 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.
Black material one of according to the present invention, owing to adopt with the material of silver-colored tin alloy as the particle formation of principal constituent, and the median size of this particle is made as more than the 1nm and below 300nm, therefore just can improves the degree of blackness of black material self, can improve opacifying property.
In addition, owing to used silver-colored tin alloy particle, therefore compare with tin particle etc. and can improve thermotolerance.
Two black particle dispersion liquid according to the present invention, owing to contain with silver-colored tin alloy as principal constituent and median size at the particulate more than the 1nm and below 300nm (black material) and macromolecule dispersing agent, therefore just can improve the degree of blackness of particulate self, can improve this black particle dispersion liquid of use and the degree of blackness of filming self that forms.
So, can obtain black and high black light-blocking film and the black decorating film of opacifying property of moderate.
In addition, because the principal constituent of particulate is made as silver-colored tin alloy, therefore with tin compare as the particle of principal constituent etc., can improve thermotolerance.
Three black particle according to the present invention, owing to will cover with insulating film on the surface of the particulate more than the 1nm and below 300nm as principal constituent and median size with silver-colored tin alloy, therefore just can make it to be scattered in easily in the solvent, the degree of blackness of black particle self can be improved, insulativity can be improved.
The present invention's four black light-blocking film, at least contain the black material and the macromolecule dispersing agent that are consisted of by silver-colored tin alloy particle, it is characterized in that, be coated with silicon-dioxide on the described black material, and the median size of described silver-colored tin alloy particle is more than the 10nm and below 30nm.
The present invention's five black light-blocking film is the present invention's four described black light-blocking films, it is characterized in that, also contains benzyl methacrylate/methacrylic acid interpolymer and dipentaerythritol acrylate as resinous principle.
The present invention's six black light-blocking film is the present invention's four or five described black light-blocking films, it is characterized in that, described silver-colored tin alloy contains the above and silver below 90 % by weight of 47.6 % by weight.
The present invention's seven is a kind of base materials with black light-blocking film, it is characterized in that, on an interarea of base material, possess the present invention's four～six in the described black light-blocking film of any one.
The present invention's eight is seven described base materials with black light-blocking film of the present invention, it is characterized in that, the CIE luminance brightness L* of described black light-blocking film is below 10, and colourity a* is more than-1 and below 1, and colourity b* is more than-1 and below 1, and the OD value is more than 3.
The present invention's nine is eight described base materials with black light-blocking film of the present invention, it is characterized in that the volume resistance of described black light-blocking film is 10
10More than the Ω cm.
The present invention's ten is manufacture method of a kind of black light-blocking film, with the silica-coating median size after the black more than the 10nm and below 30nm silver tin alloy particle, with contain at least this silver-colored tin alloy particle that is coated with silicon-dioxide, as the Solspers 20000 of dispersion agent with as the black material dispersion liquid of the benzyl methacrylate of resinous principle/methacrylic acid interpolymer and dipentaerythritol acrylate, be coated on the substrate and form.
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, owing to coating black particle dispersion liquid of the present invention obtains, even in the thinner situation of thickness, also can improve opacifying property and insulativity.
If this black light-blocking film is applied in the black matrix of the 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 is the figure of x-ray diffractogram of powder shape of the powdered sample of expression embodiments of the invention 1.
Fig. 2 is the figure of x-ray diffractogram of powder shape of the powdered sample of expression embodiments of the invention 3.
Embodiment
One of embodiment ():
At first, describe for the mode as the best of one of the present invention's black material.
And this mode specifically describes for the purport of understanding better invention, as long as no particularly pointing out, just is not that restriction is of the present invention.
The black material of present embodiment is by consisting of as the particle of principal constituent with silver-colored tin (AgSn) alloy, and the median size of this particle is more than the 1nm and below 300nm.
At this AgSn alloy with chemical formula Ag
xIn the situation that Sn represents, the scope of the x that can obtain at chemically stable AgSn alloy is 1≤x≤10, and the scope that can obtain simultaneously the x of chemical stability and degree of blackness is 3≤x≤4.
Here, when obtaining the weight ratio of the Ag in the AgSn alloy in the scope at described x, then
In the situation of x=1, Ag/AgSn=0.4762
In the situation of x=3,3Ag/Ag
3Sn=0.7317
In the situation of x=4,4Ag/Ag
4Sn=0.7843
In the situation of x=10,10Ag/Ag
10Sn=0.9008.So, this AgSn alloy is containing more than 47.6 % by weight and just becoming chemically stable alloy in the situation of the Ag below 90 % by weight, is containing more than 73.17 % by weight and can effectively obtain chemical stability and degree of blackness with respect to the Ag amount in the situation of the Ag below 78.43 % by weight.
The black material of present embodiment consists of with the particle of AgSn alloy as principal constituent by utilizing, and the median size of this particle is made as more than the 1nm and below 300nm, compares degree of blackness with Ag particle or Sn particle and improves, and opacifying property improves.
In addition, it is more good to compare thermotolerance as the particle of principal constituent and Sn particle with the AgSn alloy.
In addition, it is higher to compare physical strength as the particle of principal constituent and Ag particle or Sn particle with the AgSn alloy, more is difficult to wearing and tearing.
The black material of present embodiment can be made of common particulate synthesis method.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, consist of with the particle of AgSn alloy as principal constituent owing to utilize, be made as the median size of this particle more than the 1nm and below 300nm, therefore just can improve degree of blackness, optical shielding property can also be improved, thermotolerance, physical strength can also be improved in addition.
According to above explanation, can easily provide degree of blackness height, opacifying property and excellent heat resistance and little, the cheap black material of environmental pressure.
Embodiment (two):
Below, for as the present invention's two black particle dispersion liquid with used its black light-blocking film and describe with the mode of the best of the base material of black light-blocking film.
The black particle dispersion liquid of present embodiment contains with silver-colored tin (AgSn) alloy as principal constituent and median size at the particulate more than the 1nm and below 300nm and macromolecule dispersing agent.
In this black particle dispersion liquid, the organic binder bond that contain solvent, contains as required etc.
At this AgSn alloy with chemical formula Ag
xIn the situation that Sn represents, the scope of the x that can obtain at chemically stable AgSn alloy is 1≤x≤10, and the scope that can obtain simultaneously the x of chemical stability and degree of blackness is 3≤x≤4.
This particulate is as long as the AgSn alloy is principal constituent, as other metal ingredient, such as also containing Ni, Pd, Au etc.
In addition, this particulate also can be except the AgSn alloy particle, also mixes the material that has Ag particulate or Sn particulate.
Here, the weight ratio of the Ag in the AgSn alloy and described embodiment in the scope of described x (one of) identical.So, contain more than 47.6 % by weight and in the situation of the Ag below 90 % by weight, just become chemically stable alloy at this AgSn alloy, containing more than 73.17 % by weight and in the situation of the Ag below 78.43 % by weight, chemical stability further improves.
Macromolecule dispersing agent improves the dispersiveness of this particulate by improving the wettability of microparticle surfaces, consequently, has improved the homogeneity of dispersion liquid, such as can preferably using 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 1 % by weight and below 10 % by weight, more preferably more than 2 % by weight and below 8 % by weight, further more than preferred 3 % by weight and below 6 % by weight.
As solvent, although be not particularly limited, such as enumerating the unary alcohols such as water, methyl alcohol, ethanol, n-propyl alcohol, 2-propyl alcohol, butanols; The 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-glycol ether (cellosolve) classes such as oxygen benzyl ethyl ether (ethylene glycol butyl ether); The glycols such as ethylene glycol, propylene glycol; The ketones such as acetone, methyl ethyl ketone, metacetone; The ester classes such as ethyl acetate, butylacetate, jasmal; The ether alcohol such as methyl cellosolve, ethoxy ethanol class; Propylene glycol methyl ether acetate etc.
In the black particle dispersion liquid of present embodiment, by containing with the AgSn alloy as principal constituent and median size at the particulate more than the 1nm and below 300nm, compare with Ag particulate or the Sn particulate of monomer, degree of blackness improves, and opacifying property improves.
In addition, it is more good to compare thermotolerance as the particulate of principal constituent and Sn particulate with the AgSn alloy.
Particulate in the black particle dispersion liquid of present embodiment can be made of common particulate synthesis method.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.
According to the black particle dispersion liquid of present embodiment, owing to contain with the AgSn alloy as principal constituent and median size at the particulate more than the 1nm and below 300nm, therefore can improve degree of blackness, can also improve opacifying property.
In addition, contain more than 1 % by weight and the macromolecule dispersing agent below 10 % by weight by the gross weight with respect to particulate contained in the black particle dispersion liquid, just can obtain good dispersion stabilization, can obtain good black opacifying property.
In addition, by using Polyvinylpyrolidone (PVP) as macromolecule dispersing agent, just can obtain more good dispersion stabilization.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, can provide the black particle dispersion liquid of degree of blackness height, opacifying property and the raw material that becomes black light-blocking film that thermotolerance is good and environmental pressure is little, cheap.
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 thereafter drying and obtain.
If this black light-blocking film is formed on the interarea of base material, then becomes the base material with black light-blocking film.
As base material, although be not particularly limited, can enumerate glass baseplate, plastic basis material (organic polymer base material).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, although be not particularly limited, such as can from soda-lime glass, potassic glass, non-alkali glass etc., suitably selecting.
Material as plastic basis material; although be not particularly limited, such as 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 selecting.
As coating process, can use rightly usually used method, such as spin coating method, spray application method, ink jet method, pickling process, rolling method, stencil printing, excellent cladding process 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 preferably by the normalized CIE luminance brightness of CIE (International Commission on Illumination) L* below 10, colourity a* is more than-1 and below 1, colourity b* is more than-1 and below 1, as the OD value of optical concentration more than 3.
L* is lower for the CIE luminance brightness, and then degree of blackness just improves, and particularly when the black matrix as liquid-crystal display (LCD) etc. used, its lower then display comparison degree just improved.So, will be as the good scope of display comparison degree be made as preferred scope below 10.
For colourity a*, colourity b*, consider preferably there is not color from the viewpoint of display quality, because when absolute value surpasses 1, then can be with tone, so preferred scope is made as do not have the colorful one absolute value below 1, namely 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 in the situation that the black matrix as liquid-crystal display (LCD) etc. uses, because thickness becomes large, just produce easily show uneven.So even with in the thin situation of thickness, the scope that also can obtain enough opacifying propertys is made as more than 3.
Embodiment (three):
Below, to describing as the present invention's three black particle and black particle dispersion liquid and black light-blocking film and with the mode of the best of the base material of black light-blocking film.
In the black particle of present embodiment, be insulated the film covering with silver-colored tin (AgSn) alloy on the surface of the particulate more than the 1nm and below 300nm as principal constituent and median size.
This particulate is as long as the AgSn alloy is principal constituent, as other metal ingredient, such as also containing Ni, Pd, Au etc.
In addition, this particulate also can be except the AgSn alloy particle, also mixes the material that has Ag particulate or Sn particulate.
At this AgSn alloy with chemical formula Ag
xIn the situation that Sn represents, the scope of the x that can obtain at chemically stable AgSn alloy is 1≤x≤10, and the scope that can obtain simultaneously the x of chemical stability and degree of blackness is 3≤x≤4.
Here, the weight ratio of the Ag in the AgSn alloy and described embodiment in the scope of described x (one of) identical.So, contain more than 47.6 % by weight and in the situation of the Ag below 90 % by weight, just become chemically stable alloy at this AgSn alloy, containing more than 73.17 % by weight and in the situation of the Ag below 78.43 % by weight, can effectively obtain chemical stability and degree of blackness with respect to the Ag amount.
Particulate as the integrant of this black particle can be made of common particulate synthesis method.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 forming the high-insulativity particulate at the surface insulation of the particulate more than the 1nm and below 300nm, preferable alloy oxide compound or organic high molecular compound as principal constituent and median size with the AgSn alloy.
As metal oxide, can preferably use the metal oxide with insulativity, such as silicon oxide (silicon-dioxide), aluminum oxide, zirconium white, yttrium oxide (yttrium oxide), titanium oxide (titanium dioxide) etc.
In addition, as organic high molecular compound, can preferably use the resin with insulativity, for example polyimide, polyethers, polyacrylic ester, polyamino compound.
In order to keep fully the insulativity of described microparticle surfaces, 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 the alkoxide such as tetraethoxysilane, aluminum ethylate, then owing to the insulating film that can under lower temperature, form the thickness homogeneous, therefore preferred.
In the black particle of present embodiment, by utilizing insulating film to cover as principal constituent and median size on the surface of the particulate more than the 1nm and below 300nm with the AgSn alloy, compare degree of blackness with metal particles such as Ag particle or Sn particles and improve, opacifying property improves, and insulativity also improves.
In addition, by utilizing the insulating film that is consisted of by metal oxide to cover as principal constituent and median size on the surface of the particulate more than the 1nm and below 300nm with the AgSn alloy, to compare thermotolerance more good with metal particles such as Ag particle or Sn particles, and physical strength is higher, more is difficult to wearing and tearing.
The black particle dispersion liquid of present embodiment is the dispersion liquid that contains the black particle of present embodiment, contains solvent and the organic binder bond that contains as required etc. in this black particle dispersion liquid.
As solvent, although be not particularly limited, such as enumerating the unary alcohols such as water, methyl alcohol, ethanol, n-propyl alcohol, 2-propyl alcohol, butanols; The 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-glycol ether (cellosolve) classes such as oxygen benzyl ethyl ether (ethylene glycol butyl ether); The glycols such as ethylene glycol, propylene glycol; The ketones such as acetone, methyl ethyl ketone, metacetone; The ester classes such as ethyl acetate, butylacetate, jasmal; The ether alcohol such as methyl cellosolve, ethoxy ethanol class; Propylene glycol methyl ether acetate etc.
In the black particle dispersion liquid of present embodiment, to utilize the covered black particle of insulating film on the surface of the particulate more than the 1nm and below 300nm as principal constituent and median size with the AgSn alloy by containing, the black particle dispersion liquid of the good and cheap raw material that becomes black light-blocking film of degree of blackness height, opacifying property and insulativity just can be provided.
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 thereafter drying and obtain.
If this black light-blocking film is formed on the interarea of base material, then becomes the base material with black light-blocking film.
As base material, although be not particularly limited, can enumerate glass baseplate, plastic basis material (organic polymer base material).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, although be not particularly limited, such as can from soda-lime glass, potassic glass, non-alkali glass etc., suitably selecting.
Material as plastic basis material; although be not particularly limited, such as can from cellulose ethanoate, polystyrene (PS), polyethylene terephthalate (PET), polyethers, polyimide, epoxy, benzene oxygen, polycarbonate (PC), polyvinylidene difluoride (PVDF), tri acetyl cellulose, polyethersulfone (PES), polyacrylic ester etc., suitably selecting.
As coating process, can use rightly usually used method, such as spin coating method, spray application method, ink jet method, pickling process, rolling method, stencil printing, excellent cladding process 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.
When this black light-blocking film uses as the black matrix of the display unit such as liquid-crystal display (LCD), preferably have high-insulativity, for example as volume resistance (Ω cm), 10
7Ω cm is above to be preferred scope.
In addition, preferably by the normalized CIE luminance brightness of CIE (International Commission on Illumination) L* below 10, colourity a* is more than-1 and below 1, colourity b* is more than-1 and below 1, as the OD value of optical concentration more than 3.
L* is lower for the CIE luminance brightness, and then degree of blackness just improves, and particularly in the situation that the black matrix as display unit such as liquid-crystal displays (LCD) uses, lower then display comparison degree just more improves.So, will be as the good scope of display comparison degree be made as preferred scope below 10.
Consider that from the viewpoint of display quality colourity a*, colourity b* preferably do not have color, because when absolute value surpasses 1, will be with tone, so preferred scope is made as do not have the colorful one 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, film for low OD value, in order to obtain enough opacifying propertys, the thickness of just having to increase is particularly in the situation that the black matrix as liquid-crystal display (LCD) etc. uses, because thickness becomes large, just generation shows unequal easily.So even with in 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 1～2 and comparative example 1～4, more specifically illustrate, but the present invention is not limited by these embodiment.
(embodiment 1)
To being incubated in 60 ℃ pure water 300ml, add tin (Sn) colloid (median size: 50nm, solid composition: 20 % by weight, Osaka, Sumitomo cement company system) 15g, silver (Ag) colloid (median size: 10nm, solid composition: 20 % by weight, Osaka, Sumitomo cement company system) 60g stirred 60 minutes this colloidal solution being remained under 60 ℃ the state, shone 5 minute ultrasonic wave thereafter.Then, utilize centrifugation concentrated in this colloidal solution, obtained the solid composition and be 15% A liquid.
Then, in this A liquid, add the PVA aqueous solution, make it to reach the solid composition in the A liquid: PVA=50: 50 volume ratio, utilizing ultrasonic dispersing machine (ソ ニ Off ア イ ヤ-450:BRANSON ULTRASONICS company 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 thick 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, use heating unit 200 ℃ of lower heating 1 hour with the glass substrate of filming this, obtained the glass substrate with black film.
Then, measured this transmittance with the glass substrate of black film.Here, utilize sub-ray spectrometer to measure transmittance for the black film self of the light of 550nm wavelength.
In addition, in order to estimate the degree of blackness of this black film, based on the CIE luminance brightness L* that has been measured this black film by the normalized L*a*b* chromaticity diagram of CIE (International Commission on Illumination).Their measurement result is shown in the table 1.
In addition, utilize freeze-drying with described A liquid dried, made the powdered sample of embodiment 1, the generation phase in this powdered sample of having used the X-ray diffraction device identification.
Fig. 1 is the figure of x-ray diffractogram of powder shape of the powdered sample of expression embodiment 1, 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 A liquid is the particle that is made of the AgSn alloy.
(embodiment 2)
In embodiment 1, except the Sn colloid is made as 15g, the Ag colloid is made as beyond the 45g, made in the same manner the glass substrate with black film of embodiment 2 with embodiment 1.
Then, the mensuration of transmittance, the mensuration of CIE luminance brightness L* have been carried out in the same manner with embodiment 1.Their measurement result is shown in the table 1.
(comparative example 1)
To carbon black (HA3, East Sea carbon company system) adds the PVA aqueous solution in, reach similarly to Example 1 carbon black: PVA=50: 50 volume ratio, carry out similarly to Example 1 the amount of moisture in dispersion treatment, the coating fluid adjustment, utilize the coating on the glass substrate of spin coating method, made thickness and be the filming of black of 0.5 μ m.
Then, this is lower dry in room temperature (25 ℃) with the glass substrate of filming, obtained the glass substrate with black film.
Then, identical with embodiment 1, carried out the mensuration of the mensuration of transmittance, CIE luminance brightness L*.Their measurement result is shown in the table 1.
(comparative example 2)
To the black (13M of titanium, ジ エ system コ company system) adds the PVA aqueous solution in, it is black to reach similarly to Example 1 titanium: PVA=50: 50 volume ratio, carry out similarly to Example 1 the amount of moisture in dispersion treatment, the coating fluid adjustment, utilize the coating on the glass substrate of spin coating method, made thickness and be the filming of black of 0.5 μ m.
Then, this is lower dry in room temperature (25 ℃) with the glass substrate of filming, obtained the glass substrate with black film.
Then, identical with embodiment 1, carried out the mensuration of the mensuration of transmittance, CIE luminance brightness L*.Their measurement result is shown in the table 1.
(comparative example 3)
In Nano silver grain (Osaka, Sumitomo cement company system), add the PVA aqueous solution, reach similarly to Example 1 Nano silver grain: PVA=50: 50 volume ratio, carry out similarly to Example 1 the amount of moisture in dispersion treatment, the coating fluid adjustment, utilize the coating on the glass substrate of spin coating method, made thickness and be the filming of black of 0.5 μ m.
Then, this is lower dry in room temperature (25 ℃) with the glass substrate of filming, obtained the glass substrate with black film.
Then, identical with embodiment 1, carried out the mensuration of the mensuration of transmittance, CIE luminance brightness L*.Their measurement result is shown in the table 1.
(comparative example 4)
Use nigrosine black dyes (chemical institute system in the hole), utilize the coating on the glass substrate of spin coating method, made thickness and be the filming of black of 0.5 μ m.
Then, this is lower dry in room temperature (25 ℃) with the glass substrate of filming, obtained the glass substrate with black coating film.
Then, identical with embodiment 1, carried out the mensuration of the mensuration of transmittance, CIE luminance brightness L*.Their measurement result is shown in the table 1.
[table 1]
| The kind of particle | Thickness (μ m) | Light transmission (%) | CIE luminance brightness L* | |
| Embodiment 1 | The SnAg particulate | 0.48 | 0.00 | 4.3 |
| Embodiment 2 | The SnAg particulate | 0.49 | 0.00 | 4.4 |
| Comparative example 1 | Carbon black | 0.53 | 0.32 | 4.6 |
| Comparative example 2 | Titanium is black | 0.51 | 1.05 | 7.8 |
| Comparative example 3 | The Ag nanoparticle | 0.52 | 0.01 | 26 |
| Comparative example 4 | Nigrosine | 0.48 | 65.2 | 11 |
Can confirm that according to this table 1 embodiment 1,2 black film are compared with comparative example 1～4, transmittance is lower, and CIE luminance brightness L* is also better, and is more good aspect opacifying property and degree of blackness.
On the other hand, although the black film degree of blackness of comparative example 1 and embodiment 1,2 approach, transmittance is high, illustrates that opacifying property is poor with respect to embodiment 1,2 black film.
Find that in addition degree of blackness, the transmittance of comparative example 2,4 black film are all poor.
In addition, although the black film of comparative example 3 can obtain and embodiment 1,2 roughly the same opacifying propertys, the color of film is grey, and black does not have problem aspect tone.
Below, for embodiments of the present invention (two), will utilize embodiment 3～4 and comparative example 5～8 more specifically to illustrate, but the present invention is not limited by these embodiment.
(embodiment 3)
To being incubated in 60 ℃ pure water 200ml, be added on and dissolved tin (Sn) colloid (median size: 20nm in the 100ml water, solid composition: 20 % by weight, Osaka, Sumitomo cement company system) 15g, silver (Ag) colloid (median size: 7nm, solid composition: 20 % by weight, Osaka, Sumitomo cement company system) solution of 60g, Polyvinylpyrolidone (PVP) (PVP) (k15: Tokyo changes into industrial's system) 0.75g has formed colloidal solution.
Then, stirred 60 minutes this colloidal solution being remained under 60 ℃ the state, thereafter, shone 5 minutes ultrasonic wave.Then, utilize centrifugation concentrated in this colloidal solution, obtained the solid composition and be 15% A liquid.
Then, in this A liquid, add the PVA aqueous solution, make it to reach the solid composition in the A liquid: PVA=50: 50 volume ratio, utilizing ultrasonic dispersing machine (ソ ニ Off ア イ ヤ-450:BRANSON ULTRASONICS company 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 thick 1.1mm this 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, use heating unit 200 ℃ of lower heating 1 hour with the glass substrate of filming this, obtained the glass substrate with black light-blocking film.
Then, measured this transmittance with 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 550nm wavelength.
In addition, in order to estimate the degree of blackness of this black light-blocking film, based on the CIE luminance brightness L*, colourity a*, the b* that have been measured this black light-blocking film by the normalized L*a*b* chromaticity diagram of CIE (International Commission on Illumination).
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 freeze-drying with described A liquid dried, made the powdered sample of embodiment 1, the generation phase in this powdered sample of having used the X-ray diffraction device identification.
Fig. 2 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.
Hence one can see that, and the particle in the A liquid is the particle that is made of the AgSn alloy.
(embodiment 4)
In embodiment 3, except the Sn colloid is made as 15g, the Ag colloid is made as beyond the 45g, made in the same manner the glass substrate with black light-blocking film of embodiment 4 with embodiment 3.
Then, the mensuration, CIE luminance brightness L*, the mensuration of colourity a*, b*, the mensuration of OD value of transmittance have been carried out in the same manner with embodiment 3.Their measurement result is shown in the table 2.
(comparative example 5)
To carbon black (HA3, East Sea carbon company system) adds the PVA aqueous solution in, reach similarly to Example 3 carbon black: PVA=50: 50 volume ratio, carry out similarly to Example 1 the amount of moisture in dispersion treatment, the dispersion liquid adjustment, utilize the coating on the glass substrate of spin coating method, made thickness and be the filming of black of 0.5 μ m.
Then, this is lower dry in room temperature (25 ℃) with the glass substrate of filming, obtained the glass substrate with black light-blocking film.
Then, the mensuration, CIE luminance brightness L*, the mensuration of colourity a*, b*, the mensuration of OD value of transmittance have been carried out in the same manner with embodiment 3.Their measurement result is shown in the table 1.
(comparative example 6)
To the black (13M of titanium, ジ エ system コ company system) adds the PVA aqueous solution in, it is black to reach similarly to Example 3 titanium: PVA=50: 50 volume ratio, carry out similarly to Example 3 the amount of moisture in dispersion treatment, the dispersion liquid adjustment, utilize the coating on the glass substrate of spin coating method, made thickness and be the filming of black of 0.5 μ m.
Then, this is lower dry in room temperature (25 ℃) with the glass substrate of filming, obtained the glass substrate with black light-blocking film.
Then, the mensuration, CIE luminance brightness L*, the mensuration of colourity a*, b*, the mensuration of OD value of transmittance have been carried out in the same manner with embodiment 3.Their measurement result is shown in the table 2.
(comparative example 7)
In Nano silver grain (Osaka, Sumitomo cement company system), add the PVA aqueous solution, reach similarly to Example 3 Nano silver grain: PVA=50: 50 volume ratio, carry out similarly to Example 3 the amount of moisture in dispersion treatment, the dispersion liquid adjustment, utilize the coating on the glass substrate of spin coating method, made thickness and be the filming of black of 0.5 μ m.
Then, this is lower dry in room temperature (25 ℃) with the glass substrate of filming, obtained the glass substrate with black light-blocking film.
Then, the mensuration, CIE luminance brightness L*, the mensuration of colourity a*, b*, the mensuration of OD value of transmittance have been carried out in the same manner with embodiment 3.Their measurement result is shown in the table 2.
(comparative example 8)
Use nigrosine black dyes (chemical institute system in the hole), utilize the coating on the glass substrate of spin coating method, made thickness and be the filming of black of 0.5 μ m.
Then, this is lower dry in room temperature (25 ℃) with the glass substrate of filming, obtained the glass substrate with black light-blocking film.
Then, the mensuration, CIE luminance brightness L*, the mensuration of colourity a*, b*, the mensuration of OD value of transmittance have been carried out in the same manner with embodiment 1.Their measurement result is shown in the table 2.
[table 2]
Can confirm that according to this table 2 because embodiment 3,4 black film compare with comparative example 5～8, transmittance is lower, CIE luminance brightness L* is also lower, and the absolute value of colourity a*, b* is also less, and is therefore more good aspect opacifying property and degree of blackness.
On the other hand, although the black film degree of blackness of comparative example 5 and embodiment 3,4 approach, transmittance is high, illustrates that opacifying property is poor with respect to embodiment 3,4 black film.
Find that in addition degree of blackness, the transmittance of comparative example 6,8 black film are all very poor.
In addition, although the black film of comparative example 7 can obtain and embodiment 3,4 roughly the same opacifying propertys, the color of film is grey, and black does not have problem aspect tone.
Below, for embodiments of the present invention (three), will utilize embodiment 5～6 and comparative example 9～11 more specifically to illustrate, but the present invention is not limited by these embodiment.
" modulation of black particle "
Utilize following operation to modulate black particle.
(1) the spherical particles A of AgSn alloy of coating silicon dioxide
Be the aqueous dispersions (concentration of solid composition: 15 % by weight of AgSn alloy spherical particle of the black of 10～30nm with median size, Osaka, Sumitomo cement company system) dilution of 100g use pure water is 10 times, add the aqueous solution 1200g that contains 3-sulfydryl propyl trimethoxy silicane (MPS) 0.1 % by weight in this solution and stir, formed A liquid.
On the other hand, the solution that water has been diluted water glass is (with SiO
2Be scaled 3%) 150g, 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, the described B liquid that drips at leisure in this A liquid stirred 1 hour.Then, use ultrafiltration from this solution, unreacted water glass, MPS, 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, by carrying out drying, obtained the spherical particles A of AgSn alloy of coating silicon dioxide.
(2) the spherical particles B of AgSn alloy of coating silicon dioxide
In described A liquid, add acetic acid (0.1N), pH is adjusted into 4.8.Then, in this solution, drip contain the aqueous solution 300g of 1 % by weight tetraethoxysilane after, heating and be made as 60 ℃ was stirred under this temperature 2 hours.Then, use ultrafiltration from this solution, to remove unreacted MPS, tetraethoxysilane, acetic acid etc., concentrate thereafter, obtained dispersion liquid.
Then, utilize centrifugation, lyophilize etc. from this dispersion liquid with solution and separation of particles, by carrying out drying, obtained the spherical particles B of AgSn alloy of coating silicon dioxide.
" making of black particle dispersion liquid and black light-blocking film " (embodiment 5)
In the spherical particles A 100g of AgSn alloy of coating silicon dioxide, add dispersion agent (ソ Le ス パ-ス 20000: ア PVC シ ア (strain) system) 2g, propylene glycol methyl ether acetate 100g, use ball mill (beads mill) to disperse, the AgSn alloy that has obtained coating silicon dioxide is assembled particle dispersion.In this dispersion liquid, add by benzyl methacrylate/methacrylic acid interpolymer: 64 weight parts, dipentaerythritol acrylate: the tackiness agent 50g that 26 weight parts, IRGACURE907:9 weight part consist of, mix, obtained coating fluid.Utilize spin coating method that this coating fluid is coated on the glass substrate, after the lower drying of room temperature (25 ℃), irradiation ultraviolet radiation (UV) has formed the black film of thick 0.6 μ m.
(embodiment 6)
Except in embodiment 5, replace the spherical particles A of AgSn alloy of coating silicon dioxide, used beyond the spherical particles B of AgSn alloy of coating silicon dioxide, be identically formed the black film of embodiment 6 with embodiment 5.
(comparative example 9)
Except the AgSn alloy spherical particle that has used uncoated silicon-dioxide, be identically formed black film with embodiment 5.
(comparative example 10)
Except the carbon black that has used coating silicon dioxide, be identically formed black film with embodiment 5.
(comparative example 11)
Except the titanium that has used coating silicon dioxide is deceived, be identically formed black film with embodiment 5.
" evaluation of black film "
Measured the volume resistance of embodiment 5～6 and comparative example 9～11 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 the CIE luminance brightness L*, colourity a*, the b* that have been measured this black film by the normalized L*a*b* chromaticity diagram of CIE (International Commission on Illumination).Their measurement result is shown in the table 3.
[table 3]
Can confirm according to this table 3, because the volume resistance of embodiment 5,6 black film is greater than 10
10Ω cm, the OD value is more than 4, and CIE luminance brightness L* is also low, and the absolute value of colourity a*, b* is little, and is therefore good aspect insulativity, opacifying property and degree of blackness.
Find on the other hand, although the OD value of the black film of comparative example 9 more than 4, L* is low for the CIE luminance brightness, the absolute value of colourity a*, b* is little, volume resistance is low to moderate 4.1 * 10
6Ω cm, insulativity reduces.
Find in addition, although the volume resistance of comparative example 10,11 black film is greater than 10
10Ω cm, but CIE luminance brightness L* is also low, the OD value is little to about 2, and the absolute value of colourity a*, b* also surpasses 1, and is with respect to embodiment 5,6 black film, all very poor aspect degree of blackness, opacifying property.
The industrial possibility of utilizing
One of the present invention's black material is owing to good aspect degree of blackness, opacifying property, good aspect thermotolerance in addition, and cheapness, therefore goes for requiring in degree of blackness, opacifying property, the 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 optical shielding property film, black optical shielding property glass, black paper, black cloth, black ink, flux of plasma indicating meter (PDP) or liquid-crystal display (LCD), black sealing material, black mask material.
The present invention's two black particle dispersion liquid is owing to can be used as aspect degree of blackness, opacifying property good, good aspect thermotolerance in addition, and the material use of cheap black light-blocking film, therefore go for requiring in the material of degree of blackness, opacifying property, stable on heating all objects.For example, also can be used as the utilizations such as black opacifying property film, black opacifying property glass, black paper, black cloth, black ink, the black matrix material towards display unit such as liquid-crystal display (LCD), plasma display (PDP), electroluminescent display (ELD), electrochromism indicating meters (ECD), black sealing material, black mask material.
The present invention's three black particle is owing to can be used as aspect degree of blackness, opacifying property, insulativity 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, opacifying property, insulativity.For example, except as towards the black matrix material of the display unit such as liquid-crystal display (LCD), plasma display (PDP), electroluminescent display (ELD), electrochromic display device (ECD), black sealing material, black mask material etc., can also be as utilizations such as black opacifying property film, black opacifying property glass, black paper, black cloth, black inks.
Claims (7)
1. black light-blocking film, at least contain the black material and the macromolecule dispersing agent that are consisted of by silver-colored tin alloy particle, it is characterized in that, be coated with silicon-dioxide on the described black material, and the median size of described silver-colored tin alloy particle is more than the 10nm and below 30nm.
2. black light-blocking film according to claim 1 is characterized in that, described black light-blocking film also contains benzyl methacrylate/methacrylic acid interpolymer and dipentaerythritol acrylate as resinous principle.
3. black light-blocking film according to claim 1 and 2 is characterized in that, described silver-colored tin alloy contains the above and silver below 90 % by weight of 47.6 % by weight.
4. the base material with black light-blocking film is characterized in that, on an interarea of base material, possesses the described black light-blocking film of any one in the claim 1～3.
5. the base material with black light-blocking film according to claim 4 is characterized in that, the CIE luminance brightness L* of described black light-blocking film is below 10, and colourity a* is more than-1 and below 1, and colourity b* is more than-1 and below 1, and the OD value is more than 3.
6. the base material with black light-blocking film according to claim 5 is characterized in that, the volume resistance of described black light-blocking film is 10
10More than the Ω cm.
7. the manufacture method of a black light-blocking film, it is characterized in that, with the silica-coating median size after the black more than the 10nm and below 30nm silver tin alloy particle, with contain at least this silver-colored tin alloy particle that is coated with silicon-dioxide, as the Solsperse 20000 of dispersion agent with as the black material dispersion liquid of the benzyl methacrylate of resinous principle/methacrylic acid interpolymer and dipentaerythritol acrylate, be coated on the substrate and form.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004273349A JP4437063B2 (en) | 2004-09-21 | 2004-09-21 | Black material |
| JP2004-273349 | 2004-09-21 | ||
| JP2005-040431 | 2005-02-17 | ||
| JP2005-040432 | 2005-02-17 | ||
| JP2005040431A JP4237148B2 (en) | 2005-02-17 | 2005-02-17 | Black fine particle dispersion, black light shielding film using the same, and substrate with black light shielding film |
| JP2005040432A JP4223487B2 (en) | 2005-02-17 | 2005-02-17 | Black fine particles, black fine particle dispersion, black light shielding film, and substrate with black light shielding film |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200580031597 Division CN101027368A (en) | 2004-09-21 | 2005-09-16 | Black material, black particle dispersion liquid, black light-blocking film using same, and base with black light-blocking film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101928467A CN101928467A (en) | 2010-12-29 |
| CN101928467B true CN101928467B (en) | 2013-03-13 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010102637938A Expired - Fee Related CN101928467B (en) | 2004-09-21 | 2005-09-16 | Black material, black particle dispersion liquid, black shading film using same and base material with black shading film |
| CN2010102637868A Pending CN101899230A (en) | 2004-09-21 | 2005-09-16 | Black material, black particle dispersion liquid, black light-blocking film using same, and base with black light-blocking film |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010102637868A Pending CN101899230A (en) | 2004-09-21 | 2005-09-16 | Black material, black particle dispersion liquid, black light-blocking film using same, and base with black light-blocking film |
Country Status (4)
| Country | Link |
|---|---|
| KR (1) | KR101067206B1 (en) |
| CN (2) | CN101928467B (en) |
| TW (1) | TWI389850B (en) |
| WO (1) | WO2006033304A1 (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009503123A (en) * | 2005-08-02 | 2009-01-29 | 富士フイルム株式会社 | Black ink composition, inkjet recording method, recorded matter, and black dispersion |
| CN101268151B (en) * | 2005-09-16 | 2012-03-28 | 富士胶片株式会社 | Colored composition and photosensitive transfer material |
| CN102436142B (en) | 2010-09-29 | 2013-11-06 | 第一毛织株式会社 | Black photosensitive resin composition and light blocking layer using the same |
| KR101983691B1 (en) * | 2012-08-17 | 2019-05-30 | 삼성디스플레이 주식회사 | Light blocking member and display panel including the same |
| CN104031459B (en) * | 2014-06-09 | 2016-05-11 | 京东方科技集团股份有限公司 | A kind of Cu2Zn0.14Sn0.25Te2.34The preparation method of nanocrystal solution and preparation method, photosensitive resin solution, black matrix, color membrane substrates |
| US9618841B2 (en) | 2014-06-09 | 2017-04-11 | Boe Technology Group Co., Ltd. | Cu2Zn0.14Sn0.25Te2.34 nanocrystalline solution, its preparation method, photosensitive resin solution, method for forming black matrix, and color filter substrate |
| JP6607682B2 (en) * | 2015-03-05 | 2019-11-20 | 日鉄ケミカル＆マテリアル株式会社 | Black resin composition for light-shielding film, substrate with light-shielding film having light-shielding film obtained by curing said composition, and color filter and touch panel having said substrate with light-shielding film |
| JP6971834B2 (en) | 2017-12-26 | 2021-11-24 | 三菱マテリアル電子化成株式会社 | Powder for forming a black light-shielding film and its manufacturing method |
| CN109254445B (en) * | 2018-10-15 | 2020-12-25 | 深圳市华星光电技术有限公司 | Black matrix dispersion liquid, preparation method thereof and display panel |
| CN113249959A (en) * | 2021-06-18 | 2021-08-13 | 上海贝域实业有限公司 | Nano black silk physical shading curtain and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1482854A (en) * | 2002-07-18 | 2004-03-17 | ��ý���ɹ�ҵ��ʽ���� | Coating liquid for forming transparent conductive film, substrate with transparent conductive film, and display device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH1090511A (en) * | 1996-09-13 | 1998-04-10 | Dainippon Printing Co Ltd | Composition for nonconductive light shielding layer, nonconductive light shielding layer and color filter |
| JP3704615B2 (en) * | 1996-10-11 | 2005-10-12 | パイロットインキ株式会社 | Metal gloss color marking pen ink composition for writing board |
| JP2002266002A (en) * | 2001-03-12 | 2002-09-18 | Harima Chem Inc | Metallic fine particle-containing composition and producing method therefor |
| JP3687745B2 (en) * | 2002-03-18 | 2005-08-24 | 信越化学工業株式会社 | Highly dispersible metal powder, method for producing the same, and conductive paste containing the metal powder |
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2005
- 2005-09-16 KR KR1020077003790A patent/KR101067206B1/en active IP Right Grant
- 2005-09-16 TW TW094131973A patent/TWI389850B/en not_active IP Right Cessation
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- 2005-09-16 CN CN2010102637938A patent/CN101928467B/en not_active Expired - Fee Related
- 2005-09-16 CN CN2010102637868A patent/CN101899230A/en active Pending
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|---|---|---|---|---|
| CN1482854A (en) * | 2002-07-18 | 2004-03-17 | ��ý���ɹ�ҵ��ʽ���� | Coating liquid for forming transparent conductive film, substrate with transparent conductive film, and display device |
Non-Patent Citations (3)
| Title |
|---|
| JP特开2002-266002A 2002.09.18 |
| JP特开2003-268402A 2003.09.25 |
| JP特开平10-114881A 1998.05.06 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101899230A (en) | 2010-12-01 |
| TWI389850B (en) | 2013-03-21 |
| KR101067206B1 (en) | 2011-09-22 |
| KR20070052759A (en) | 2007-05-22 |
| WO2006033304A1 (en) | 2006-03-30 |
| CN101928467A (en) | 2010-12-29 |
| TW200616897A (en) | 2006-06-01 |
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