CN1459348A - Indium series metal particle and mfg. method thereof, coating liquid containing same, base material with covering film and dispay device - Google Patents
Indium series metal particle and mfg. method thereof, coating liquid containing same, base material with covering film and dispay device Download PDFInfo
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- CN1459348A CN1459348A CN03136718A CN03136718A CN1459348A CN 1459348 A CN1459348 A CN 1459348A CN 03136718 A CN03136718 A CN 03136718A CN 03136718 A CN03136718 A CN 03136718A CN 1459348 A CN1459348 A CN 1459348A
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- indium
- metal particle
- overlay film
- metal
- transparent conductivity
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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
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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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
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/14—Conductive material dispersed in non-conductive inorganic material
- H01B1/16—Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
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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
- B22F2301/00—Metallic composition of the powder or its coating
- B22F2301/30—Low melting point metals, i.e. Zn, Pb, Sn, Cd, In, Ga
Abstract
To provide indium based metal fine particles and a dispersion sol appropriately usable for forming a transparent and conductive film having an excellent antistatic property and electromagnetic shielding property and also having an excellent manufacturing reliability and cost effectiveness. The indium based metal fine particles have a 2-200 nm average particle size. The indium based metal fine particles contain indium metal only or one or more kinds of metal components selected from among Sb, Sn, Ag, Au, Zn, Cu, Bi and Cd together with the indium metal. The indium based metal fine particles dispersion sol is obtained by dispersing the indium based metal fine particles in water and/or an organic solvent. In a method for manufacturing the indium based metal fine particles, a reducing agent is added to a mixed alcohol solution containing an indium compound and an organic stabilizing agent and having a >=40 wt.% alcohol content in the solvent.
Description
Technical field
The indium that the present invention relates to median size and the be 2～200nm indium that to be metal particle and this microparticulate form in water and/or organic solvent be metal particle disperse colloidal sol, this indium be metal particle manufacture method, contain the coating fluid that indium is a metal particle, the base material and the display unit of band overlay film.
Background technology
All the time, for the anti-charged and antireflection in the surface that makes these class transparent substrates of display panel such as cathode tube, fluorescent display tube, LCD panel, generally form a kind of transparent overlay film with anti-charged and anti-reflective function on its surface.
And well-known, can give off hertzian wave from cathode tube etc., therefore, except original anti-charged, antireflection, preferably also want shielding electromagnetic wave and follow the electromagnetic field of electromagenetic wave radiation formation.
Shielding one of these electromagnetic methods is to form a kind of conductive film covering that is used for shielding electromagnetic wave on the surface of display panels such as cathode tube.If the anti-charged conductive film covering of using, as long as its surface resistivity reaches 10
8Just enough about Ω/, the conductive film covering that the shielding electromagnetism is used then must have 10
2～10
4The surface resistivity that Ω/ is low like this.
If adopt the coating fluid of existing this class electroconductive oxide of Indium sesquioxide (ITO) that contains the stannic oxide (ATO) of mixing antimony or mix tin to form the lower conductive film covering of this surface resistivity, compare the overlay film of existing anti-charging property, just must increase the thickness of film.But, problem has also produced thereupon, if promptly the film thickness of conductive film covering is not in the scope of 10～200nm, the effect that does not then have antireflection, therefore, with the existing such electroconductive oxide of Indium sesquioxide (ITO) of mixing the stannic oxide (ATO) of antimony or mixing tin, it is low to be difficult to obtain surface resistivity, the electromagnetic wave shielding performance is good, and the also good conductive film covering of antireflection property.
In addition, also having a kind of method is to adopt the coating fluid of metal particle such as argentiferous to form the low conductive film covering of surface resistivity at substrate surface.In this kind method, the colloidal metal particle is scattered in material that polar solvent obtains as coating fluid.This coating fluid is handled the metal particle surface with organic system stablizers such as polyvinyl alcohol, polyvinylpyrrolidone or gelatin for improving the dispersiveness of colloidal metal particulate.
But also existing problems, promptly metal particle is different with aforementioned electroconductive oxide, and is originally just light tight, and therefore the conductive film covering that forms with metal particle is influenced by the density of the metal particle in the conductive film covering and film thickness etc., and is transparent low.
And, adopt metal particle, when particularly adopting the alloy particle of fine particle of noble metal such as Au, Ag, Pt, Pd or these precious metals, cost is higher, so seeking the method that reduces cost.
According to this situation, specialized in the electrically conductive microparticle that can solve above-mentioned all problems, found that to adopt and have specified particle diameter and be that the indium of single dispersion (not aggegation) is a metal particle, can form anti-charging property, electromagnetic wave shielding is good, and fabrication reliability and cost be unusual ideal transparent conductivity overlay film also, thereby has finished the present invention.
Also have, existing indium is a metal particle, and promptly enabling to obtain metal particle also is the aggegation particulate, is difficult to obtain reproducible monodispersed metal particle, and is if be used for transparent conductivity overlay film etc., not ideal enough with the binding property and the electroconductibility of the base material of film.But also have following problems, promptly in water dispersion medium, reach in the aqueous dispersion medium the same generation oxyhydroxide that can mix with other base metals.
The purpose of this invention is to provide can form anti-charging property and electromagnetic wave shielding good, and fabrication reliability and cost also very the indium of ideal transparent conductivity overlay film is a metal particle, it disperses colloidal sol and manufacture method thereof, contains the coating fluid that indium is a metal particle, the base material and the display unit of band overlay film.
Summary of the invention
Indium of the present invention is that metal particle disperses the feature of colloidal sol to be, is that the indium of 2～200nm is that metal particle is scattered in water and/or organic solvent forms by median size.
Above-mentioned indium is that metal particle can an indium-containing metal, also can indium-containing metal and be selected from the metal ingredient more than a kind of Sb, Sn, Ag, Au, Zn, Cu, Bi, Cd.
Indium of the present invention is that the feature of the manufacture method of metal particle is, adds reductive agent in the alcohol mixture solution of the pure content in containing indium compound and organic stabilizer and solvent more than 40 weight %.And, be preferably the compound that also contains the metal more than a kind that is selected from Sb, Sn, Ag, Au, Zn, Cu, Bi, Cd in the above-mentioned alcoholic solution.
The feature that transparent conductivity overlay film of the present invention forms with coating fluid is that containing above-mentioned indium is metal particle and polar solvent.Can also contain the electroconductive oxide particulate in this coating fluid.
The feature of the base material of band transparent conductivity overlay film of the present invention is, by on base material, the base material contain the transparent conductivity particulate layer that above-mentioned indium is a metal particle, the low transparent overlay film of refractive index ratio particulate layer on this particulate layer that is laid in constitutes.
The feature of display unit of the present invention is, possesses the front panel that the base material by above-mentioned band transparent conductivity overlay film constitutes, and the transparent conductivity overlay film is formed at the outside surface of this front panel.
Embodiment
Below, describe the present invention in detail.
Indium is a metal particle
Indium is that metal particle can be the particle that is made of separately indium metal, also can be the particle that contains indium and be selected from the metal ingredient in addition of the indium more than a kind of Sb, Sn, Ag, Au, Zn, Cu, Bi, Cd.If contain the metal ingredient beyond the indium, then indium is that the ratio of the metal ingredient beyond the indium contained in the metal particle will be preferably in below the 30 weight % below 50 weight %.
If being the ratio of the metal ingredient beyond the indium in the metal particle, indium surpasses 50 weight %, though according to the kind of the metal ingredient beyond indium difference to some extent, the welding effect that all to can not get low melting point indium described later be metal particle.
In addition, indium is a metal particle when containing metal ingredient beyond the indium, and the metal more than 2 kinds that constitutes indium and be metal particle can be the alloy that is in solid solution condition, also can be the eutectic that is not in solid solution condition, also can alloy and eutectic coexistence.
This indium is a metal particle, because the oxidation and the ionization of metal be suppressed, therefore can suppress indium and be the particle growth of metal particle etc., and this indium is the erosion resistance height of metal particle, and the decline of electroconductibility and transmittance is less, and reliability is good.
This indium is that the median size of metal particle is 2～200nm, especially with scope the best of 5～100nm.
If using median size is metal particle less than the indium of above-mentioned scope lower limit, when then forming conductive film covering, because being the resistance of the grain boundary between metal particle, the indium in the overlay film increases, so the surface resistivity of electrically conductive microparticle layer sharply increases, can not obtain having the overlay film of the low-resistance value that can reach purpose of the present invention.
If the indium that adopts median size to surpass above-mentioned range limit is a metal particle, when then forming overlay film, the indium in the overlay film is that the photoabsorption of metal particle increases, and the transmittance of electrically conductive microparticle layer reduces, and turbidity increases.If therefore will be used as the front panel of cathode tube with the base material of this overlay film, then the sharpness of display frame can be very poor.
Indium of the present invention is that the form that metal particle can powder is directly used, but adopts it to be scattered in water and/or organic solvent usually and the colloidal sol that forms.
Organic solvent used in the present invention comprises alcohols such as methyl alcohol, ethanol, propyl alcohol, butanols, Pyranton, furfuryl alcohol, tetrahydrofurfuryl alcohol, ethylene glycol, hexylene glycol; Ester such as methyl acetate, ethyl acetate class; Ethers such as ether, methyl glycol, glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, ethyl carbitol; Ketones such as acetone, butanone, methyl ethyl diketone, methyl aceto acetate etc.These organic solvents both can use separately, can mix use more than 2 kinds again.
Can be used in transparent conductivity overlay film described later and form with coating fluid and can access the transparent conductivity overlay film that possesses necessary performance as long as the indium in the colloidal sol is the concentration of metal particle, there is no particular limitation to it, be generally 0.5～20 weight %, more preferably 1～5 weight %.If indium be the concentration of metal particle in this scope, then can obtain indium is the stable, monodispersed colloidal sol of metal particle.
Can contain organic stabilizer as required in the colloidal sol.What can be used as this organic stabilizer has carboxylic acid and salt thereof such as gelatin, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid, hydroxypropylcellulose, formic acid, oxalic acid, propanedioic acid, succsinic acid, pentanedioic acid, hexanodioic acid, sebacic acid, toxilic acid, fumaric acid, phthalic acid, citric acid, xitix, saccharosonic acid, or ketones such as their mixture and methyl ethyl diketone etc.
The content of this organic stabilizer is that the indium corresponding to 1 weight part is a metal particle, is 0.005～20 weight part, more preferably 0.01～15 weight part.If quantity not sufficient 0.005 weight part of organic system stablizer then can not obtain dispersed and stable fully.If surpass 20 weight parts, not only then stability does not improve, and also can harm the electroconductibility of transparent conductivity overlay film sometimes.
This indium is that metal particle is compared with existing metal particle, and its monodispersity height is that particulate is compared with Indium sesquioxide, and then electroconductibility is higher.
Indium is the manufacture method of metal particle
Next, illustrate that indium of the present invention is the manufacture method of metal particle.
Indium of the present invention is that the feature of the manufacture method of metal particle is, adds reductive agent in the alcoholic solution that contains indium compound and organic stabilizer, reduction indium compound (and other contained as required compounds).
The compound that also can contain the metal more than a kind that is selected from Sb, Sn, Ag, Au, Zn, Cu, Bi, Cd in the above-mentioned alcoholic solution.
As long as the used indium compound of the present invention can be dissolved in or be scattered in the employed alcoholic solution, there is no particular limitation to it, specifically comprises indium nitrate, indium chloride, indium acetate, indium formate etc.
In addition, the compound that contains Sb, Sn, Ag, Au, Zn, Cu, Bi, Cd specifically comprises antimony chloride, tin protochloride, Silver Nitrate, hydrochloro-auric acid, zinc chloride, zinc bromide, cupric chloride, Bismuth trinitrate, Cadmium chloride fine powder etc.
The concentration of the indium compound in the alcoholic solution is that the calculating benchmark is 0.05～5.0 weight % with the indium metal, more preferably 0.1～2.0 weight %.
The concentration of indium compound is when calculating benchmark less than 0.05 weight % with the indium metal, not only yield descends and production efficiency is low, if the concentration of indium compound is to calculate benchmark to surpass 5.0 weight % with the indium metal, then oversize particle and agglutination particle can be generated, the particle of desired median size can not be obtained to have.
When containing the compound beyond the indium compound, be 0.05～5.0 weight % when adding up to concentration conversion for metal, 0.1～2.0 weight % more preferably.
The consumption of the compound beyond the indium compound to make the indium that finally obtains be the ratio of the metal ingredient beyond the indium in the metal particle below 50 weight %, be more preferably below 30 weight %.
The used alcohol of the present invention comprises alcohols and their mixtures such as methyl alcohol, ethanol, propyl alcohol, butanols, Pyranton, furfuryl alcohol, tetrahydrofurfuryl alcohol, ethylene glycol, hexylene glycol.Wherein, methyl alcohol, ethanol are easy to dissolving, disperse aforementioned indium compound and reductive agent described later, therefore are best selections.And as required, can also use N-N-methyl-2-2-pyrrolidone N-, propylene carbonate, diox organic solvents such as (diethylene dioxides) to dissolve indium compound and reductive agent.
At indium of the present invention is in the manufacture method of metal particle, uses the alcohol mixture solvent of pure content more than 40 weight % in the solvent.Except that alcohol, can also contain water in this solvent.At this moment, the content of water is more preferably below 30 weight % below 40 weight %.If the water-content in the alcohol surpasses 40 weight %, then can generate the oxyhydroxide of indium and the oxyhydroxide of the metal beyond the indium, be metal particle with regard to being difficult to obtain the high indium of electroconductibility like this.And along with the reduction of the ratio of alcohol, indium is that the formation speed (reduction rate) of metal particle can descend.
The used organic stabilizer of the present invention as hereinbefore.Wherein, therefore ketones such as methyl ethyl diketone can not harm the generation that indium is a metal particle because do not have carboxylic acid strong like that in particle surface coordinate ability, and can make the indium that obtains is that metal particle stably disperses.
Indium corresponding to 1 weight part gained is a metal particle, and the consumption of organic stabilizer is 0.005～20 weight part, more preferably 0.01～15 weight part.During quantity not sufficient 0.005 weight part of organic system stablizer, indium is that the dispersiveness and the stability of metal particle is abundant inadequately, when surpassing 20 weight parts, can harm the electroconductibility of transparent conductivity overlay film.
The used reductive agent of the present invention comprises ferrous salt, tin protochloride, zinc chloride, trisodium citrate, tartrate, L (+)-xitix, saccharosonic acid, sodium borohydride, sodium hypophosphites etc. such as ferrous sulfate.Wherein, sodium borohydride can not generate oversize particle and agglutination particle, and can obtain indium efficiently is metal particle.
Corresponding to other compounds beyond 1 mole indium compound and the indium, the consumption of reductive agent is 0.1～5.0 mole, more preferably 1.0～3.0 moles.In this amount ranges, indium is the yield height of metal particle.
Corresponding to 1 mole total compound, during 0.1 mole of the usefulness quantity not sufficient of reductive agent, reducing power is insufficient, causing indium is that the yield of metal particle is low, and when containing compound beyond the indium, because the reductibility of compound, be metal particle so can not obtain containing the indium of the metal beyond the indium.
Corresponding to 1 mole total compound, when the consumption of reductive agent surpasses 5.0 moles, not only yield can not improve, cost also can improve.
Use the reductive condition of this class reductive agent to be, as long as can reduce the compound of above-mentioned metal, there is no particular limitation to it, adds reductive agent in the alcoholic solution of above-mentioned concentration, if needed, can heat and stir compound.And, as required by slaking can access particle diameter more the indium of homogeneous be that metal particle is scattered in the colloidal sol that alcoholic solvent forms.Can also be as required, deionizing such as spent ion exchange resin, ultra-filtration membrane, by deionizing, can obtain more stable indium is the dispersion colloidal sol of metal particle.Remove alcoholic solvent with methods such as dryings from colloidal sol, just can obtain indium of the present invention is metal particle.
In addition, can be as required, water replaces solvent and obtains the water-sol or change solvent into alcohol other organic solvents in addition obtaining organosol.
With indium being metal particle when being used for hereinafter described coating fluid, can dryly disperse use behind the colloidal sol, also can not add to handle directly and use.
The transparent conductivity overlay film forms uses coating fluid
Next, illustrate that transparent conductivity overlay film of the present invention forms with coating fluid (hereinafter to be referred as coating fluid).
The feature of coating fluid of the present invention is that containing above-mentioned indium is metal particle and polar solvent.
The used polar solvent of the present invention comprises water; Alcohols such as methyl alcohol, ethanol, propyl alcohol, butanols, Pyranton, furfuryl alcohol, tetrahydrofurfuryl alcohol, ethylene glycol, hexylene glycol; Ester such as methyl acetate, ethyl acetate class; Ethers such as ether, methyl glycol, glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, ethyl carbitol; Ketones such as acetone, butanone, methyl ethyl diketone, methyl aceto acetate; Amines such as dimethyl formamide.These solvents both can use separately, can mix use more than 2 kinds again.
Except that above-mentioned indium is metal particle, can also contain the electroconductive oxide particulate in this coating fluid.
The electroconductive oxide particulate comprises stannic oxide, mixes the stannic oxide of Sn, F or P, Indium sesquioxide, mixes the Indium sesquioxide of Sn or F, weisspiessglanz, low order titanium oxide etc.
The median size of these electroconductive oxide particulates is 2～200nm, more preferably 5～150nm.
Containing this electroconductive oxide particulate, and is that metal particle forms transparent conductivity particulate layer and compares with indium only, can form better transparent conductivity particulate layer of the transparency.And, owing to contain the electroconductive oxide particulate, can make the base material of band transparent conductivity overlay film with cheap cost.
Above-mentioned indium corresponding to 1 weight part is a metal particle, and the content of this electroconductive oxide particulate is below 9 weight parts.If the content of electroconductive oxide particulate surpasses 9 weight parts, the electroconductive oxide particulate that then electroconductibility is low is too much, and the electroconductibility of the transparent conductivity overlay film that obtains reduces, and effectiveness also descends.And, when the electroconductive oxide particulate surpasses 9 weight parts (indium be metal particle more after a little while), the indium of the groove part that forms at the contact place of electroconductive oxide particulate is that the welding and the joint of metal particle is insufficient, thereby does not have the effect of the resistance that reduces electroconductive oxide particulate grain boundary to each other.
At electroconductive oxide particulate and indium is metal particle and time spent, the median size (D of electroconductive oxide particulate
0) and indium be the median size (D of metal particle
M) ratio (D
M)/(D
0) less than 1, be more preferably below 0.5.Aforementioned proportion is as long as within above-mentioned scope, and then welding and joint that indium is a metal particle can take place the groove part that forms at the contact place of electroconductive oxide particulate effectively.
When forming conductive film covering, utilizing with nearly indium is the temperature of metal particle fusing point, can also be the temperature that is higher than fusing point, and the best is to carry out this welding and joint at 160 ℃～250 ℃ temperature range internal heating.
The matrix composition that can contain the tackiness agent of the electrically conductive microparticle after forming as overlay film in the coating fluid of the present invention.This matrix composition preferably is made of silicon-dioxide.Comprise the hydrolytie polycondensation thing of silicoorganic compound such as organoalkoxysilane or the silicic acid polycondensate that obtains by the alkali metal silicate aqueous solution dealkalize or coating resin etc. specifically.The content of this matrix is the above-mentioned composition metal particulate corresponding to 1 weight part, is 0.01～0.5 weight part, more preferably 0.03～0.3 weight part.
And, in order to improve the dispersiveness that indium of the present invention is a metal particle, can contain organic stablizer in the coating fluid, the material that can be used as this organic stabilizer is as hereinbefore.
The content of this organic stabilizer is that the indium corresponding to 1 weight part is a metal particle, is 0.005～20 weight part, more preferably 0.01～15 weight part.If quantity not sufficient 0.005 weight part of organic system stablizer then can not obtain dispersiveness and stable fully,, then can harm conductivity if surpass 20 weight parts.
Form with in the coating fluid at transparent conductivity overlay film of the present invention, it is black in tinting material to contain carbon black fine particle and/or titanium, can also contain dyestuff and pigment.Contain this based colorant, can obtain the display unit of excellent contrast.
After mixing above-mentioned indium and be metal particle or disperseing colloidal sol, solvent and stablizer, stir with mixing tank and just can modulate coating fluid of the present invention.Above-mentioned indium is that metal particle disperses and the colloidal sol that forms can directly be used as coating fluid, can also be as required, by changing solvent, adjusting the method for compositions such as concentration and interpolation matrix, modulate coating fluid.
The base material of band transparent conductivity overlay film
Below, describe the base material of band transparent conductivity overlay film of the present invention in detail.
The feature of the base material of band transparent conductivity overlay film of the present invention is, possess film, thin plate and other base materials such as molding that glass, plastics, pottery etc. constitute, contain transparent conductivity particulate layer that above-mentioned indium is a metal particle and the low transparent overlay film of refractive index ratio transparent conductivity particulate layer on this transparent conductivity particulate layer that is laid on the base material.
[transparent conductivity particulate layer]
The film thickness of transparent conductivity particulate layer is about 5～200nm, more preferably 10～150nm.Film thickness can obtain the base material of the good band transparent conductivity overlay film of effectiveness in this scope.
Can be as required, make that to contain above-mentioned indium in this particulate layer be electroconductive oxide particulate, matrix composition, organic system stablizer beyond the metal particle, particular content is as previously mentioned.
This particulate layer can form by the above-mentioned coating fluid after drying of coating on base material.
The method that forms the particulate layer specifically comprises methods such as pickling process, spinning method, spraying method, roller painting, flexible printing method, by aforesaid method coating fluid is coated on the base material, and is dry under the temperature of normal temperature～about 90 ℃ then.
Contain above-mentioned matrix in the coating fluid and be formed into timesharing, can carry out the hardening treatment that matrix forms composition.
When drying or after the drying, the overlay film that adds thermosetting with the temperature more than 150 ℃, with unhardened overlay films of electromagnetic wave irradiation such as the short ultraviolet ray of wavelength ratio visible rays, electron beam, X ray, gamma-rays, perhaps be exposed in the ammonia isoreactivity atmosphere gas, can promote overlay film to form the sclerosis of composition like this, obtain higher overlay film hardness.
[transparent overlay film]
In the base material of band transparent conductivity overlay film of the present invention, on above-mentioned transparent conductivity particulate layer, form the low transparent overlay film of the above-mentioned particulate layer of refractive index ratio.
The film thickness of the transparent overlay film that forms is 50～300nm, more preferably 80～200nm.
This transparent overlay film can be made of inorganic oxides such as silicon-dioxide, titanium dioxide, zirconium white and their composite oxides.Transparent overlay film among the present invention better is the silica-based coating that is formed by the silicic acid polycondensate that the hydrolytie polycondensation thing of water-disintegrable organic silicide or alkali metal silicate aqueous solution dealkalize obtain.The base material antireflection property of the band transparent conductivity overlay film that is formed by this overlay film is good.
In above-mentioned transparent overlay film, preferably also contain median size and be 5～300nm, 10～200nm more preferably, specific refractory power is 1.28～1.42, more preferably 1.28～1.40 low-refraction particulate.
The median size of the low-refraction particulate that is adopted can be made appropriate selection according to the thickness of formed transparent overlay film.
If the specific refractory power of low-refraction particulate is below 1.42, the bottom reflection rate and the visual sense reflectivity of the base material of the band transparent conductivity overlay film that then obtains are low, can bring into play good antireflection property.
It is 10～90 weight % that the content of the low-refraction particulate in the transparent overlay film is converted into oxide compound, more preferably 20～80 weight %.
The low-refraction particulate that the present invention is used needs only median size and specific refractory power in above-mentioned scope, and there is no particular limitation to it, can use existing known particulate.For example, the composite oxide sol that discloses in the flat 7-133105 communique of applicant application De Te Open, that discloses in the WO00/37359 communique has a tectal porous matter composite oxide particle.
And can be as required, make additives such as particulate that low-index materials such as containing useful magnesium fluoride in the above-mentioned transparent overlay film constitutes, dyestuff, pigment.
There is no particular limitation to the method that forms transparent overlay film, material according to this transparent overlay film, can adopt dry type film formation methods such as vacuum vapor deposition method, sputtering method, ion plating method, wet type film formation methods such as perhaps above-mentioned pickling process, spinning method, spraying method, roller painting, flexible printing method.
When adopting wet type film formation method to form above-mentioned transparent overlay film, can adopt to have known transparent overlay film formation coating fluid now.This transparent overlay film forms and use coating fluid, can adopt the coating fluid of inorganic oxide such as the silicon-dioxide that contains as transparent overlay film formation composition, titanium dioxide, zirconium white or their composite oxides specifically.
Transparent overlay film among the present invention forms and uses coating fluid, can use the hydrolytie polycondensation thing that contains hydrolysis organic silicon thing or the silica-based transparent overlay film of the silicate solution that obtained by the alkali metal silicate aqueous solution dealkalize forms and uses coating fluid.By the silica-based coating that this coating fluid forms, its specific refractory power is less than containing the electrically conductive microparticle layer that indium is a metal particle, and the antireflection property of the base material of gained band transparent conductivity overlay film is good.
Display unit
The base material of band transparent conductivity overlay film of the present invention has anti-charged and the shielding electromagnetism is required about 10
2～10
4The surface resistivity of Ω/, the transparency are also good, and have sufficient antireflection property in visible-range and near infra red region, suitable front panel as display unit.
Display unit of the present invention is the electrical means of cathode-ray picture tube (CRT), fluorescent display tube (FIP), plasm display device (PDP), liquid crystal indicator display images such as (LCD), and has been equipped with the front panel that the base material by above-mentioned band transparent conductivity overlay film forms.
When being equipped with the display unit work of existing front panel, front panel is also charged in display image, and radiated electromagnetic wave, and display unit of the present invention, because front panel is to have about 10 by above-mentioned
2～10
4The base material of the band transparent conductivity overlay film of the surface resistivity of Ω/ constitutes, therefore can prevent charged, shielding electromagnetic wave and follow electromagenetic wave radiation and the electromagnetic field that produces effectively.
Also have, if the front panel in display unit has reflected light, then be difficult to see clearly shown image, display unit of the present invention, because front panel is made of the base material of the band transparent conductivity overlay film that has sufficient antireflection property in visible-range and near infra red region, therefore can prevent catoptrical generation effectively.
The invention provides can form anti-charging property and capability of electromagnetic shielding is good and fabrication reliability and cost all very the indium of ideal transparent conductivity overlay film be metal particle, this indium is that metal particle can make by low-down cost.
The present invention is described by the following examples, but the present invention is not limited to these embodiment.
The indium that adopts in present embodiment and comparative example is that metal particle, indium are that the composition of the electrically conductive microparticle beyond the metal particle etc. is summarized in table 1.
[embodiment 1]
Indium is the modulation that metal particle (P-1) disperses colloidal sol
Make indium nitrate trihydrate (In (NO
3)
33H
2O) 1.6 weight parts are dissolved in methyl alcohol 97.2 weight parts and the mixed solution as methyl ethyl diketone 1.2 weight parts of organic stabilizer.Then, in nitrogen atmosphere gas, adding concentration is sodium borohydride aqueous solution 22 weight parts of 1.5 weight %, stirs 30 minutes at 20 ℃, and modulating indium is the metal particle dispersion liquid.
The gained dispersion liquid passes through centrifuge separator decant repeatedly with ethanol, makes ion and salts out.
Then, with the indium that settles down at last is that metal particle is distributed in the ethanolic soln of methyl ethyl diketone that concentration is 20 weight %, making indium corresponding to 1 weight part is that the ethanolic soln of metal particle reaches 66.7 weight parts, and modulating indium is the dispersion colloidal sol of metal particle (P-1).
The gained indium is that the proterties of metal particle (P-1) sees Table 1.
[embodiment 2]
Indium is the modulation that metal particle (p-2) disperses colloidal sol
Except that replace methyl alcohol with ethanol, other are all identical with embodiment 1, and modulating indium is the metal particle dispersion liquid.
Then, the same with embodiment 1, carry out decant and dispersion etc., modulating indium is the dispersion colloidal sol of metal particle (P-2).
The gained indium is that metal particle (P-2) disperses the proterties of colloidal sol to see Table 1.
[embodiment 3]
Indium is the modulation that metal particle (P-3) disperses colloidal sol
Make indium nitrate trihydrate (In (NO
3)
33H
2O) 1.6 weight parts and concentration are that ethanolic soln 5.7 weight parts of the tin protochloride of 5 weight % are dissolved in methyl alcohol 91.5 weight parts and the mixed solution as methyl ethyl diketone 1.2 weight parts of organic stabilizer.Then, under nitrogen atmosphere gas, adding concentration is sodium borohydride aqueous solution 23 weight parts of 1.5 weight %, stirs 30 minutes at 20 ℃, and modulating indium is the metal particle dispersion liquid.
Then, the same with embodiment 1, carry out decant, dispersion etc., modulating indium is the dispersion colloidal sol of metal particle (P-3).
The gained indium is that metal particle (P-3) disperses the proterties of colloidal sol to see Table 1.
[embodiment 4]
Indium is the modulation that metal particle (P-4) disperses colloidal sol
Make indium nitrate trihydrate (In (NO
3)
33H
2O) 1.6 weight parts and concentration are that ethanolic soln 15 weight parts of the zinc chloride of 2.5 weight % are dissolved in methyl alcohol 91.5 weight parts and the mixed solution as methyl ethyl diketone 1.2 weight parts of organic stabilizer.Then, under nitrogen atmosphere gas, adding concentration is sodium borohydride aqueous solution 23 weight parts of 1.5 weight %, stirs 30 minutes at 20 ℃, and modulating indium is the metal particle dispersion liquid.
Then, the same with embodiment 1, carry out decant, dispersion etc., modulating indium is the dispersion colloidal sol of metal particle (P-4).
The gained indium is that metal particle (P-4) disperses the proterties of colloidal sol to see Table 1.
[reference example 1]
Electroconductive oxide particulate (P-5) disperses the modulation of colloidal sol
Modulation indium nitrate 79.9g is dissolved in the 686g water and the solution that obtains, and potassium stannate 12.7g to be dissolved in concentration be the solution that the potassium hydroxide solution of 10 weight % obtains, with 2 hours times these solution are added temperature and remain in 50 ℃ the 1000g pure water.PH value with reactive system during this remains 1.Leach the indium oxide hydrate and the washing that contain tin from the dispersion liquid of the indium oxide hydrate that contains tin that obtains, it is distributed in the water again, the concentration that modulates solids component is the metal oxide precursor oxyhydroxide dispersion liquid of 10 weight %.Under 100 ℃, this dispersion liquid is carried out spraying drying, modulate the metal oxide precursor hydroxide powder.Under nitrogen atmosphere gas, with this powder of 550 ℃ temperature heat treated 2 hours.
It is scattered in make concentration reach 30 weight % in the ethanol, with aqueous nitric acid pH is transferred to 3.5 again after, this mixed solution is remained on 30 ℃, and pulverized 0.5 hour with skin grinder, modulate colloidal sol.Then, add the electroconductive oxide particulate (P-5) that ethanol modulates concentration shown in the table 1 and (mix the Indium sesquioxide particulate of Sn: the ITO particulate) disperse colloidal sol.
Gained electroconductive oxide particulate (P-5) disperses the proterties of colloidal sol to see Table 1.
[reference example 2]
Electroconductive oxide particulate (P-6) disperses the modulation of colloidal sol
Tin chloride 57.7g and antimony chloride 7.0g are dissolved in 100g water modulate solution.Be hydrolyzed with synthetic solution being added in 4 hours among 90 ℃ the stirring pure water 1000g down, the precipitation of generation is filtered and washed.Then, in dry air,, obtained admixing the electroconductive tin oxide powder of antimony in 500 ℃ of burnings 2 hours.This powder 30g is added among potassium hydroxide aqueous solution (KOH that the contains 3.0g) 70g, mixed solution is remained on 30 ℃, and pulverized 3 hours, modulate colloidal sol with skin grinder.Then spent ion exchange resin is handled this colloidal sol, and dealkalize adds pure water, and the electroconductive oxide particulate (P-6) that modulates concentration shown in the table 1 (is mixed the stannic oxide particulate of Sb: the ATO particulate) disperse colloidal sol.
Gained electroconductive oxide particulate (P-6) disperses the proterties of colloidal sol to see Table 1.
[comparative example 1]
Indium is the modulation that metal particle (P-7) disperses colloidal sol
Make indium nitrate trihydrate (In (NO
3)
33H
2O) 1.6 weight parts are dissolved in methyl alcohol 36.2 weight parts, water 61 weight parts and the mixed solution as methyl ethyl diketone 1.2 weight parts of organic stabilizer.Then, under nitrogen atmosphere gas, adding concentration is sodium borohydride aqueous solution 22 weight parts of 1.5 weight %, stirs 30 minutes at 20 ℃, and modulating indium is the metal particle dispersion liquid.
The gained dispersion liquid passes through centrifuge separator decant repeatedly with ethanol, makes ion and salts out.
Then, with the indium that settles down at last is that metal particle is distributed in the ethanolic soln of methyl ethyl diketone that concentration is 20 weight %, making indium corresponding to 1 weight part is that the ethanolic soln of metal particle reaches 66.7 weight parts, and modulating indium is the dispersion colloidal sol of metal particle (P-1).Part in the gained metal particle is an oxyhydroxide, has produced aggegation.
The gained indium is that the proterties of metal particle (P-7) sees Table 1.
[comparative example 2]
Indium is the modulation that metal particle (P-8) disperses colloidal sol
Make indium nitrate three water salt (In (NO
3)
33H
2O) 1.6 weight parts are dissolved in water 98.4 weight parts.Then, under nitrogen atmosphere gas, adding concentration is sodium borohydride aqueous solution 22 weight parts of 1.5 weight %, stirs 30 minutes at 20 ℃.Clearly have the hydrogel of indium oxyhydroxide to generate, can not get indium is metal particle.
[embodiment 5～10, comparative example 3～5]
The transparent conductivity overlay film forms the modulation with coating fluid (C-1)～(C-9)
For to make above synthetic indium be metal particle (P-1)～(P-4) and (P-7) disperse colloidal sol and electrically conductive microparticle (P-5) and dispersion colloidal sol (P-6) to reach the composition shown in the table 2, its mixing solutions with ethanol/Isopropanediol/Pyranton (81/16/3) is mixed, modulate the transparent conductivity overlay film and form with coating fluid (C-1)～(C-9).
For making electrically conductive microparticle (P-6) disperse colloidal sol to reach the composition shown in the table 1, the mixing solutions of Qi Heshui/ethylene glycol butyl ether/N-N-methyl-2-2-pyrrolidone N-(82/16/2) is mixed, modulate the transparent conductivity overlay film and form with coating fluid (C-8).
The manufacturing of the face glass of band electrically conducting transparent spare overlay film
With cathode-ray picture tube with face glass (surface temperature of 14 ") remains on 45 ℃; with spraying method under 150rpm, 90 seconds condition more than the separate application synthetic transparent conductivity overlay film form with coating fluid (C-1)～(C-8); make the thickness of electrically conductive microparticle layer reach the film thickness shown in the table 1, and dry.
Then, the same spraying method that adopts is on each transparent conductivity particulate layer of above formation, under 150rpm, 90 seconds condition, be coated with synthetic separately as follows transparent overlay film formation coating fluid, and it is dry, make the thickness of transparent overlay film reach 100nm,, obtain face glass with the transparent conductivity overlay film 180 ℃ sintering temperatures 30 minutes.
Transparent overlay film forms the modulation with coating fluid
In addition, be concentrated hydrochloric acid 0.2g and the pure water 35.5g mixing of 35 weight % with ethanol 42.9g, concentration, add methyl orthosilicate (SiO therein
2Concentration is 51 weight %) behind the 21.4g, stirred 2 hours at 60 ℃, carry out the hydrolysis and the slaking of methyl orthosilicate.Then add Virahol 118.3g and methanol/ethanol/Isopropanediol/Pyranton (17/67/12/4) 873.1g, modulate SiO
2Concentration is the transparent overlay film formation coating fluid of 1 weight %.
Adopt surface resistivity meter (Mitsubishi's oiling (strain) System: LORESTA) measure the surface resistivity that this is with the face glass of transparent conductivity overlay film, with turbidimetric apparatus (Japanese Electricity look (strain) System: 3000A) measure turbidity.Reflectivity albedometer (Da mound Electricity (strain) System: MCPD-2000) measure, the bottom reflection rate represents that with the reflectivity under the minimum wavelength of the scope internal reflection rate of wavelength 400～800nm the visual sense reflectivity is to represent at the average reflectance of wavelength 400～800nm scope.Transmitance is so that ((strain) System: UBest55) the mensuration wavelength is represented in the transmitance of 560nm in Japanese beam split by spectrophotometer.The particle diameter of particulate is measured the particle diameter of 20 particles by taking the infiltration type electron micrograph (TEM) of particulate, gets its mean value and gets, and The above results sees Table 2.
Table 1
| Electrically conductive microparticle | Disperse the solid component concentration (weight %) in the colloidal sol | |||||
| Particle No. | Kind | Median size nm | In ratio (weight %) | Other component proportionss (weight %) | ||
| Embodiment 1 | ?P-1 | ?In | ???20 | ??100 | ???0 | 1.5 |
| Embodiment 2 | ?P-2 | ?In | ???30 | ??100 | ???0 | 1.5 |
| Embodiment 3 | ?P-3 | ?In+Sn | ???20 | ??77 | ???23 | 1.5 |
| Embodiment 4 | ?P-4 | ?In+Zn | ???30 | ??91 | ???9 | 1.5 |
| Reference example 1 | ?P-5 | ?ITO | ???40 | ??- | ???- | 20 |
| Reference example 2 | ?P-6 | ?ATO | ???25 | ??- | ???- | 20 |
| Comparative example 1 | ?P-7 | In+ oxyhydroxide | 60 aggegations | ??100 | ???0 | 0.7 |
| Comparative example 2 | ?P-8 | In oxyhydroxide | ???- | ??- | ???- | - |
Table 2
| The transparent conductivity overlay film forms uses coating fluid | Electrically conductive microparticle layer thickness nm | The base material of band overlay film | ||||||||||
| Coating fluid No. | Electrically conductive microparticle | Solid component concentration weight % | Surface resistivity Ω/ * 10 3 | Bottom reflection rate % | Visual sense reflectivity % | Turbidity % | Transmitance % | |||||
| Metal particle | Oxide fine particle | |||||||||||
| Kind | Ratio weight % | Kind | Ratio weight % | |||||||||
| Embodiment 5 | ?C-1 | ?P-1 | ???100 | ??- | ??- | 0.6 | 40 | 0.8 | 0.2 | 0.5 | 0.2 | 70 |
| Embodiment 6 | ?C-2 | ?P-2 | ???100 | ??- | ??- | 0.6 | 60 | 1.0 | 0.3 | 0.7 | 0.4 | 65 |
| Embodiment 7 | ?C-3 | ?P-1 | ???10 | ??P-5 | ??90 | 3.5 | 200 | 1.5 | 1.2 | 1.5 | 0.5 | 80 |
| Embodiment 8 | ?C-4 | ?P-1 | ???20 | ??P-6 | ??80 | 3.5 | 200 | 5.0 | 1.4 | 1.7 | 0.7 | 80 |
| Embodiment 9 | ?C-5 | ?P-3 | ???100 | ??- | ??- | 0.6 | 40 | 0.6 | 0.2 | 0.5 | 0.2 | 70 |
| Embodiment 10 | ?C-6 | ?P-4 | ???100 | ??- | ??- | 0.6 | 60 | 2.0 | 0.4 | 0.9 | 0.6 | 65 |
| Comparative example 3 | ?C-7 | ?- | ???- | ??P-5 | ??100 | 3.5 | 200 | 4.0 | 1.0 | 1.4 | 0.4 | 100 |
| Comparative example 4 | ?C-8 | ?- | ???- | ??P-6 | ??100 | 3.5 | 200 | 100 | 1.0 | 1.7 | 0.5 | 100 |
| Comparative example 5 | ?C-9 | ?P-7 | ???100 | ??- | ??- | 0.6 | 130 | 20.0 | 1.4 | 1.7 | 0.9 | 65 |
Claims (9)
1. indium is a metal particle, it is characterized in that, median size is in the scope of 2～200nm.
2. indium as claimed in claim 1 is a metal particle, and its feature is that also above-mentioned indium is that metal particle only contains indium metal or contains indium metal and the metal ingredient more than a kind that is selected from Sb, Sn, Ag, Au, Zn, Cu, Bi, Cd.
3. indium is that metal particle disperses colloidal sol, it is characterized in that, and be that metal particle is scattered in water and/or organic solvent and forms by claim 1 or 2 described indiums.
4. claim 1 or 2 described indiums are the manufacture method of metal particle, it is characterized in that, add reductive agent in the alcohol mixture solution of the pure content in containing indium compound and organic stabilizer and solvent more than 40 weight %.
5. indium as claimed in claim 4 is the manufacture method of metal particle, and its feature also is, contains the compound of the metal more than a kind that is selected from Sb, Sn, Ag, Au, Zn, Cu, Bi, Cd in the above-mentioned alcoholic solution.
6. the transparent conductivity overlay film forms and to use coating fluid, it is characterized in that, contains claim 1 or 2 described indiums are metal particle and polar solvent.
7. transparent conductivity overlay film as claimed in claim 6 forms uses coating fluid, its feature also to be, also contains the electroconductive oxide particulate.
8. be with the base material of transparent conductivity overlay film, it is characterized in that to require 1 or 2 described indiums be that the transparent conductivity particulate layer of metal particle, the low transparent overlay film of this transparent conductivity particulate layer of refractive index ratio on this transparent conductivity particulate layer that is laid in constitute by the right that contains on base material, the base material.
9. display unit is characterized in that, possesses the front panel that the base material by the described band transparent conductivity of claim 8 overlay film constitutes, and the transparent conductivity overlay film is formed at the outside surface of this front panel.
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|---|---|---|---|
| JP2002146717 | 2002-05-21 | ||
| JP2002146717A JP4002469B2 (en) | 2002-05-21 | 2002-05-21 | Manufacturing method of indium metal fine particles, coating liquid for forming transparent conductive film containing indium metal fine particles, dispersion sol, substrate with transparent conductive film, display device |
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|---|---|
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| CN1278805C CN1278805C (en) | 2006-10-11 |
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|---|---|
| JP (1) | JP4002469B2 (en) |
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| CN102554261A (en) * | 2005-11-10 | 2012-07-11 | 住友金属矿山株式会社 | Indium nanowire, oxide nanowire, conductive oxide nanowire and manufacturing methods thereof |
| CN103990810A (en) * | 2014-05-30 | 2014-08-20 | 洛阳理工学院 | Technology for preparing nanometer indium powder |
| CN104540777A (en) * | 2013-07-19 | 2015-04-22 | Lg化学株式会社 | Core-shell nanoparticles for transparent electrically-conductive thin film formation, and production method for transparent electrically-conductive thin film using same |
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| JP4814491B2 (en) * | 2004-02-24 | 2011-11-16 | 株式会社アルバック | Method for forming transparent conductive film and transparent electrode |
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| JP3563236B2 (en) * | 1996-09-26 | 2004-09-08 | 触媒化成工業株式会社 | Coating liquid for forming transparent conductive film, substrate with transparent conductive film, method for producing the same, and display device |
-
2002
- 2002-05-21 JP JP2002146717A patent/JP4002469B2/en not_active Expired - Lifetime
-
2003
- 2003-05-12 KR KR1020030029737A patent/KR100986628B1/en active IP Right Grant
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Also Published As
| Publication number | Publication date |
|---|---|
| CN1278805C (en) | 2006-10-11 |
| KR100986628B1 (en) | 2010-10-08 |
| KR20030041940A (en) | 2003-05-27 |
| JP2003342602A (en) | 2003-12-03 |
| JP4002469B2 (en) | 2007-10-31 |
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