CN103693678B - Ito powder and the manufacture method of manufacture method and dispersion liquid and ito film thereof - Google Patents
Ito powder and the manufacture method of manufacture method and dispersion liquid and ito film thereof Download PDFInfo
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- CN103693678B CN103693678B CN201310287607.8A CN201310287607A CN103693678B CN 103693678 B CN103693678 B CN 103693678B CN 201310287607 A CN201310287607 A CN 201310287607A CN 103693678 B CN103693678 B CN 103693678B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G19/00—Compounds of tin
- C01G19/02—Oxides
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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
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G15/00—Compounds of gallium, indium or thallium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
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Abstract
The present invention provides the ito powder of a kind of surface modification demonstrating high conductivity when under low pressure becoming pressed compact and the manufacture method of manufacture method and dispersion liquid and ito film thereof.The ito powder of the surface modification of the present invention, resistivity to the described pressed compact during pressure of the pressed compact applying 0.98MPa being made up of this ito powder is below 0.50 Ω cm, the specific insulation of described pressed compact when applying the pressure of 0.196～29.42MPa to described pressed compact is set to Y and when described pressure is set to X, the relation approximation Y=aX between described pressure and described specific insulationn, a is less than 5.00, and n is less than 0.500.
Description
Technical field
The present invention relates to a kind of surface modification demonstrating high conductivity when under low pressure becoming pressed compact ito powder and
Manufacture method.In this specification, ITO refers to indium tin oxide (Indium Tin Oxide).
Background technology
ITO is In2O3In doped with the compound of tin (Sn), have 1020～1021cm-3High carrier concentration,
In ito film with vapor phase method film forming such as sputtering methods, 1 × 10 can be obtained-4The low-resistivity of Ω about cm.By this ITO
In the ito film made, there is in visible region high transparent (such as referenced patent document 1).Therefore, ito film
It is widely used in the transparency electrode (such as referenced patent document 2) of liquid crystal display or the heat that heat ray shielding effect is higher
Radiation shielding material (such as referenced patent document 3) etc. requires in the field of excellent optical characteristics.As this ITO
The film build method of film, is studying the membrane formation process based on simplicity coating and is replacing relatively costly vacuum vapour deposition and sputtering
The physical film deposition methods such as method (such as referenced patent document 4).
Patent document 1: Japanese Patent Publication 2009-032699 publication ([0009] section)
Patent document 2: Japanese Patent Publication 2005-054273 publication ([0006] section)
Patent document 3: Japanese Patent Publication 2011-116623 publication ([0002] section)
Patent document 4: Japanese Patent Publication 2011-034708 publication ([0002] section)
As the film build method of the application type of the method for film forming ito film have material utilization ratio and productivity ratio is higher,
Bendability is excellent and the advantage such as less-restrictive for the substrate being coated.But, compared with physical film deposition method,
The electric conductivity of particle itself is relatively low, and particle contact resistance each other is higher, therefore there is the relatively low shortcoming of electric conductivity on the contrary.
Content of the invention
It is an object of the invention to provide a kind of can reduction and obtain height with resistivity during coating method film forming ito film
The ito powder of electric conductivity and manufacture method thereof.
1st viewpoint of the present invention is the ito powder of surface modification, which is following ito powder: to by described ITO powder
The pressed compact that end is constituted applies 0.98MPa(10kgf/cm2) pressure when the specific insulation of described pressed compact be 0.50 Ω
Below cm, will apply 0.196～29.42MPa(2～300kgf/cm to described pressed compact2) pressure when described pressure
The specific insulation of base is set to Y and when described pressure is set to X, the relation between described pressure and described specific insulation
Approximating following formula (1), in this formula (1), a is less than 5.00, and n is for below-0.500.
Y=aXn(1)
Further, the 2nd viewpoint of the present invention is the invention based on the 1st viewpoint, which is the manufacture ITO including following operation
The improvement of powder method: the mixed-alkali aqueous solution comes in the mixed aqueous solution of trivalent indium compound and divalent tin compound
Generate the co-precipitation hydroxide of indium and tin；Clean described sediment with pure water or ion exchange water；Remove described precipitation
The slurry being dispersed with indium tin hydroxide particle prepared by the supernatant of thing；It is dried described slurry；And burn till described drying
Indium tin hydroxide obtain indium tin oxide, wherein, in described matting, clean to described supernatant
Resistivity is at least up to 5000 Ω cm, in the preparation section of described slurry, will eliminate the slurry of described supernatant
It is diluted so that after the concentration of described hydroxide particles becomes the scope of 10～30 mass % with water, same in stirring
When in described slurry, add having relative to the scope that described hydroxide particles 100 mass % is 0.1～5 mass %
Machine protective agent, after described firing process, pulverizes the aggregation of the ito powder having burnt till, by the ITO of this pulverizing
Powder infusion is after surface treatment liquid, in a nitrogen atmosphere, heats 0.5～5 hour the scopes of 200～400 DEG C.
3rd viewpoint of the present invention is the invention based on the 2nd viewpoint, which is the following method manufacturing ito powder: described
Organic protective agent is palmityl dimethyl ethyl QAE quaternary aminoethyl sulfate, polyvinyl alcohol or octyldimethyl ethyl ammonium ethyl sulphur
Hydrochlorate.
Further, the 4th viewpoint of the present invention is the invention based on the 1st viewpoint, which is the manufacture ITO including following operation
The improvement of powder method: the mixed-alkali aqueous solution comes in the mixed aqueous solution of trivalent indium compound and divalent tin compound
Generate the co-precipitation hydroxide of indium and tin；Clean described sediment with pure water or ion exchange water；Remove described precipitation
The slurry being dispersed with indium tin hydroxide particle prepared by the supernatant of thing；It is dried described slurry；And burn till described drying
Indium tin hydroxide obtain indium tin oxide.Wherein, in described matting, clean to described supernatant
Resistivity is at least up to 5000 Ω cm, in the preparation section of described slurry, will eliminate the slurry of described supernatant
It is diluted so that after the concentration of described hydroxide particles becomes the scope of 10～30 mass % with water, same in stirring
When in described slurry, add having relative to the scope that described hydroxide particles 100 mass % is 0.1～5 mass %
Machine protective agent, in described drying process, to the slurry being added with described organic protective agent and be dispersed with indium tin hydroxide
Material is dried, and in described firing process, the microwave with 2.45GHz～28GHz carries out heating and burns till in an atmosphere,
After described firing process, pulverize the aggregation of the ito powder having burnt till, the ito powder of this pulverizing be impregnated in
After surface treatment liquid, in a nitrogen atmosphere, the scope at 200～400 DEG C heats 0.5～5 hour.
5th viewpoint of the present invention is the invention based on the 4th viewpoint, which is the following method manufacturing ito powder: described
Organic protective agent is palmityl dimethyl ethyl QAE quaternary aminoethyl sulfate, polyvinyl alcohol or octyldimethyl ethyl ammonium ethyl sulphur
Hydrochlorate.
Further, the 6th viewpoint of the present invention is the invention based on the 1st viewpoint, which is the manufacture ITO including following operation
The improvement of powder method: the mixed-alkali aqueous solution comes in the mixed aqueous solution of trivalent indium compound and divalent tin compound
Generate the co-precipitation hydroxide of indium and tin；Clean described sediment with pure water or ion exchange water；Remove described precipitation
The slurry being dispersed with indium tin hydroxide particle prepared by the supernatant of thing；It is dried described slurry；And burn till described drying
Indium tin hydroxide obtain indium tin oxide.Wherein, in described matting, clean to described supernatant
Resistivity is at least up to 5000 Ω cm, in the preparation section of described slurry, will eliminate the slurry of described supernatant
It is diluted so that after the concentration of described hydroxide particles becomes the scope of 1～5 mass % with alcohol, while stirring
That adds relative to the scope that described hydroxide particles 100 mass % is 0.1～5 mass % in described slurry is organic
Protective agent, in described firing process, to the inside of the tube furnace of the scope being heated to 250～800 DEG C, makes nitrogen
In the state of with the linear velocity circulation of the scope of 0.5～5m/s, will dilute with described alcohol and be added with described organic protection
Agent and be dispersed with the slurry of indium tin hydroxide particle and spray, thus thermally decompose in described tube furnace and burn till
Indium tin hydroxide particle obtains indium tin oxide particles.
7th viewpoint of the present invention is the invention based on the 6th viewpoint, which is the following method manufacturing ito powder: described
Alcohol is ethanol, methyl alcohol or propyl alcohol, and described organic protective agent is palmityl dimethyl ethyl QAE quaternary aminoethyl sulfate, polyethylene
Alcohol or octyldimethyl ethyl ammonium sulfovinate.
Further, the 8th viewpoint of the present invention is for by the ito powder of the 1st viewpoint or by any one side in the 2nd～the 7th
The ito powder that method produces is scattered in solvent the method manufacturing dispersion liquid.
Further, the 9th viewpoint of the present invention for being manufactured the method for ito film by the dispersion liquid of the 8th viewpoint.
The ito powder of the 1st viewpoint of the present invention, applies 0.98MPa(10kgf/cm2) pressure when ito powder
The specific insulation of pressed compact be below 0.50 Ω cm, described pressed compact will be applied 0.196～29.42MPa(2～
300kgf/cm2) pressure when the specific insulation of described pressed compact when being set to Y and described pressure is set to X, approximation
A in above-mentioned formula (1), formula (1) is less than 5.00 and n is below-0.500, therefore, it is possible to reduce profit
Obtain high conductivity with this ito powder with resistivity during coating method film forming ito film.
Further, in the manufacture method of the ito powder of the 2nd viewpoint of the present invention, in matting, clean to supernatant
The resistivity of liquid is at least up to 5000 Ω cm, in the preparation section of slurry, will eliminate the slurry of supernatant with water
It is diluted so that after the concentration of hydroxide particles becomes the scope of 10～30 mass %, to described while stirring
Slurry adds the organic protective agent relative to the scope that described hydroxide particles 100 mass % is 0.1～5 mass %,
After firing process, pulverize the aggregation of the ito powder having burnt till, the ito powder of this pulverizing be impregnated in surface
After treatment fluid, in a nitrogen atmosphere, the scope at 200～400 DEG C heats 0.5～5 hour.Hydroxide particles is divided
Solving the higher organic protective agent cladding of temperature, therefore in sintering process, the contact each other of ITO particle is prevented from,
Particle growth difficulty.This organic protective agent is finally thermally decomposed by burning till.Thus, the surface of ito powder is modified,
This ito powder can be reduced by and obtain high conductivity with resistivity during coating method film forming ito film.
Further, in the manufacture method of the ito powder of the 4th viewpoint of the present invention, in matting, clean to supernatant
The resistivity of liquid is at least up to 5000 Ω cm, in the preparation section of slurry, will eliminate the slurry of supernatant with water
It is diluted so that after the concentration of hydroxide particles becomes the scope of 10～30 mass %, to described while stirring
Slurry adds the organic protective agent relative to the scope that described hydroxide particles 100 mass % is 0.1～5 mass %,
In drying process, to being added with organic protective agent and being dispersed with the slurry of indium tin hydroxide and be dried, burning till
In operation, the microwave with 2.45GHz～28GHz carries out heating and burns till in an atmosphere, after firing process, pulverizes
The aggregation of the ito powder having burnt till, after the ito powder of this pulverizing be impregnated in surface treatment liquid, at nitrogen atmosphere
Under, heat 0.5～5 hour the scopes of 200～400 DEG C.Hydroxide particles is decomposed the higher organic guarantor of temperature
Protecting agent cladding, therefore in sintering process, the contact each other of ITO particle is prevented from, particle growth difficulty.This is organic
Protective agent is finally thermally decomposed by burning till.Thus, the surface of ito powder is modified, and can be reduced by this ITO
Powder obtains high conductivity with resistivity during coating method film forming ito film.
Further, in the manufacture method of the ito powder of the 6th viewpoint of the present invention, in matting, clean to supernatant
The resistivity of liquid is at least up to 5000 Ω cm, in the preparation section of slurry, will eliminate the slurry of supernatant with alcohol
It is diluted so that after the concentration of hydroxide particles becomes the scope of 1～5 mass %, to described slurry while stirring
Material adds the organic protective agent relative to the scope that hydroxide particles 100 mass % is 0.1～5 mass %, in institute
State in firing process, to the inside of the tube furnace of the scope being heated to 250～800 DEG C, so that nitrogen is with 0.5～5m/s
Scope linear velocity circulation in the state of, will with alcohol dilute and be added with organic protective agent and be dispersed with indium tin hydrogen-oxygen
The slurry of chalcogenide particles is sprayed, thus thermally decomposes and burn till indium tin hydroxide particle in tube furnace and obtain indium
Tin oxide granule.Hydroxide particles be decomposed temperature higher organic protective agent cladding, therefore at sintering process
In, the contact each other of ITO particle is prevented from, particle growth difficulty.This organic protective agent is by burning till and final heat point
Solve.Thus, the surface of ito powder is modified, and can be reduced by this ito powder with coating method film forming ito film
When resistivity obtain high conductivity.
Brief description
Fig. 1 is the schematic diagram of the device of the resistivity of the pressed compact measuring ito powder.
Fig. 2 is the figure of the relation between the resistivity of the pressed compact representing impressed pressure and ito powder.
Detailed description of the invention
Then, detailed description of the invention is illustrated.
The resistivity of ito powder is the weight when evaluating the characteristic of the ito film being made up of this ito powder
Want index.Especially when ito film is used as conductive sheet or electrode, it is desirable to high conductivity i.e. low-resistivity.
The resistivity of this ito powder is obtained by measuring its specific insulation after making ito powder and becoming the form of pressed compact.
On the other hand, the specific insulation of pressed compact changes with additional pressure.Therefore, although a certain both constant-pressures
Under the specific insulation of pressed compact become tentative benchmark, if but by the shape of ito powder and specific surface area,
Obtain specific insulation in the state of changing over high pressure from low pressure and it is set to the resistivity of ito powder, then may be used
Obtain the resistivity of the better ito powder of accuracy.The present invention completes based on this opinion.
The ito powder of the present invention is the ito powder of surface modification, applies the pressed compact being made up of this ito powder
0.98MPa(10kgf/cm2) pressure when the specific insulation of pressed compact be below 0.50 Ω cm, will be to pressed compact
Apply 0.196～29.42MPa(2～300kgf/cm2) pressure when the specific insulation of pressed compact be set to Y and
The following formula (1) of relation approximation when pressure is set to X, between pressure and specific insulation.Wherein, formula (1)
A be less than 5.00, and n is for below-0.500.
Y=aXn(1)
This formula is to survey with the state of pressed compact according to the ito powder relatively low to surface modification and specific insulation
Fixed result is derived.If above-mentioned a is more than 5.00 or n exceedes-0.500, even if outside then existing to powder
Plus-pressure becomes big, i.e. strengthens the trend that particle contact each other is also difficult to improve electric conductivity, there is unfavorable condition.
Ito powder for manufacturing the ito film of the present invention changes for the surface that carries out being produced by following 3 kinds of methods
Property process ito powder.By carrying out surface modification treatment, it is possible to increase utilize this ito powder to produce
The electric conductivity of ito film.
(1) the 1st manufacture method
In the mixed aqueous solution of trivalent indium compound and divalent tin compound the mixed-alkali aqueous solution generate indium with
The co-precipitation hydroxide of tin, after this precipitation is dried, is burnt till, pulverizes obtained indium tin oxide and obtains
Ito powder.As trivalent indium compound, indium trichloride (InCl can be enumerated3), indium nitrate (In(NO3)3),
Indium acetate (In(CH3COO)3) etc., as divalent tin compound, stannous chloride (SnCl can be enumerated2·2H2O),
STANNOUS SULPHATE CRYSTALLINE (SnSO4), stannic bromide (SnBr2) etc..As alkaline aqueous solution, ammonia (NH can be enumerated3) water,
Ammonium hydrogen carbonate (NH4HCO3) water etc..By by reaction solution when making the hydroxide with tin for the indium be co-precipitated
Final pH is adjusted to 3.5～9.3, is preferably regulated as pH5.0～8.0, and solution temperature is adjusted to more than 5 DEG C,
It is preferably regulated as solution temperature 10 DEG C～80 DEG C, the co-precipitation hydroxide precipitation of indium and tin can be made.Alkaline water
Alkaline aqueous solution can be instilled and be adjusted to above-mentioned pH scope in above-mentioned mixed aqueous solution by the mixing of solution
Carry out simultaneously, or also above-mentioned mixed aqueous solution can be instilled with alkaline aqueous solution simultaneously and be adjusted in water
Carry out while above-mentioned pH scope.
After generating above-mentioned co-precipitation indium tin hydroxide, clean this sediment with pure water or ion exchange water, clean
It is at least up to 5000 Ω cm to the resistivity of supernatant, preferably at least reach 50000 Ω cm.If supernatant
Resistivity is less than 5000 Ω cm, then the impurity such as chlorine are not fully removed, it is impossible to obtain the oxidation of highly purified indium tin
Thing powder.Remove resistivity and reach the above-mentioned sedimentary supernatant of more than 5000 Ω cm, it is thus achieved that be dispersed with indium
The higher slurry of the viscosity of tin hydroxide particles.With pure water or ion exchange water, this slurry is diluted so that
The concentration of hydroxide particles becomes the scope of 10～30 mass %, preferably becomes the scope of 15～25 mass %,
Afterwards, while stirring, in slurry, interpolation improves this particle for being adsorbed in hydroxide particles surface
The organic protective agent of dispersiveness.Above-mentioned dilution range less than lower limit when, exist in the drying of slurry time-consuming not
Good situation, if exceeding higher limit, then can mix organic protective agent, therefore in the state of the viscosity of slurry is higher
There is the unfavorable condition of organic protectant undercompounding.Relative to hydroxide particles 100 mass %, this has
The protectant addition of machine is the scope of 0.1～5 mass %.ITO after the suppression thermal decomposition of this organic protective agent
From the viewpoint of the sintering of powder, preferably the decomposition temperature of organic protective agent is in the range of 250～500 DEG C.Make
For this organic protective agent, palmityl dimethyl ethyl QAE quaternary aminoethyl sulfate, polyvinyl alcohol or octyl group diformazan can be enumerated
Base ethyl ammonium sulfovinate etc..When the addition of organic protective agent is less than the lower limit of above-mentioned scope, it is impossible to fill
Dividing the protection carrying out hydroxide particles surface, the dispersiveness of particle is poor.Further, if exceeding higher limit, then
A part for organic matter or the unfavorable condition of the carbon component residual from organic matter can occur.
In an atmosphere, preferably under the inert gas atmosphere such as nitrogen or argon, adsorption is had the indium of organic protective agent
Tin hydroxide is after the scope of 100～200 DEG C is dried 2～24 hours, in an atmosphere at the model of 250～800 DEG C
Enclose and burn till 0.5～6 hour with firing furnace.Utilize hammer-mill or ball mill etc., formed poly-will be burnt till by this
Collective pulverizes and decomposes to obtain ito powder.This ito powder is put into and is mixed with the anhydrous of 50～95 mass %
After the surface treatment liquid of the distilled water of ethanol and 5～50 mass % is dipped into, put in glass dish, at nitrogen
Under gas atmosphere, the scope at 200～400 DEG C heats 0.5～5 hour, then can obtain the ITO carrying out surface modification treatment
Powder.
(2) the 2nd manufacture methods
The solid-liquid separating method of slurry and heating process for calcining and the 1st manufacture method are different.First, to the 1st
Organic protective agent that what manufacture method obtained be added with and be dispersed with the slurry of indium tin hydroxide and be dried.As
Slurry is pressed into the mud cake obtaining hydroxide in pressure filter by one case of this drying means with force (forcing) pump, dry
This mud cake dry.Then the dried object microwave with 2.45GHz～28GHz in an atmosphere is carried out heating to burn till.Should
Above-mentioned mud cake is for example filled in the micro-wave oven of CMC technological development Co., Ltd by microwave heating treatment, and profit
Carry out by the microwave heating treatment of the 2.45GHz of the μ-reactor of four countries' measurement industry system.
Heating using microwave is in the range of 250～800 DEG C, preferably in the range of 350～600 DEG C, with 10
The speed intensification reaching target temperature within Fen Zhong is carried out, and burns till by keeping 5～120 minutes at target temperature
Scope, preferably keep the scope of 10～60 minutes to carry out.When heating-up temperature is less than lower limit, there is hydrogen-oxygen
Compound incomplete decomposing becomes the unfavorable condition of oxide, if exceeding higher limit, then there is ITO particle coarsening
Unfavorable condition.If more than 10 minutes, then there is the effect heating up rapidly and disappear in the heating-up time to target temperature
The unfavorable condition lost.If the retention time under target temperature is less than lower limit, then there is hydroxide incomplete
Resolving into the unfavorable condition of oxide, if exceeding higher limit, then there is the unfavorable condition of ITO particle coarsening.
Utilize hammer-mill or ball mill etc. to pulverize burned material and decompose and obtain ito powder.Hereinafter, manufacture with the 1st
Method similarly obtains the ito powder carrying out surface modification treatment.
(3) the 3rd manufacture methods
Without pulverizing indium tin oxide, this point and the 1st and the 2nd manufacture method after burning till indium tin hydroxide
Different.
Slurry higher for the viscosity being dispersed with indium tin hydroxide particle obtaining with the 1st manufacture method is entered with alcohol
Row dilution, so that the concentration of hydroxide particles becomes the scope of 1～5 mass %, preferably becomes 1～3 mass %
Scope, and add in slurry while stirring and be used for being adsorbed in hydroxide particles surface and improve this particle
Dispersiveness organic protective agent.Relative to hydroxide particles 100 mass %, the addition of this organic protective agent
It is the scope of 0.1～5 mass %.Specify addition scope each of above-mentioned dilution range and above-mentioned organic protective agent
The reason of lower limit and each higher limit is identical with the 1st manufacture method.After the suppression thermal decomposition of this organic protective agent
From the viewpoint of the sintering of ito powder, preferably the decomposition temperature of organic protective agent is in the range of 250～500 DEG C.
As this alcohol, ethanol, propyl alcohol or methyl alcohol etc. can be enumerated, as organic protective agent, palmityl dimethyl can be enumerated
Ethyl ammonium sulfovinate, polyvinyl alcohol or octyldimethyl ethyl ammonium sulfovinate etc..
To the inside of the vertical tube furnace being heated to 250～800 DEG C of scopes configuring of the long side direction making pipe,
Making the nitrogen as carrier gas with the linear velocity of 0.5～5m/s scope, the preferably linear velocity with 1～3m/s scope circulates
In the state of, the slurry that will dilute with alcohol and be added with organic protective agent and be dispersed with indium tin hydroxide particle
Utilize two-fluid spray nozzle to spray, be together directed in tube furnace with nitrogen.Linear velocity is less than ITO during lower limit
The harvest yield of powder reduces, if exceeding higher limit, then cannot fully heat the slurry sprayed.Thus, indium
Tin hydroxide particles thermally decomposes in tube furnace and burns till, and can obtain from the outlet of tube furnace and carry out surface and change
Property process ito powder.
[embodiment]
Then, embodiments of the invention are together described in detail with comparative example.
＜ embodiment 1 ＞
The method of ito powder of surface modification treatment [manufacture carry out]
At the inidum chloride (InCl that In metal concentration is 24 mass %3) in aqueous solution 163g, add mixing dichloro
Change tin powder (SnCl2·2H2O powder) 4g, after stirring is all dissolved to tin dichloride powder, by all of
Amount joins in the pure water of 1000ml and is used as material solution.By the ammonia (NH of 25 mass %3) aqueous solution is to this
Material solution instills 90 minutes.Now reaction temperature is adjusted to 80 DEG C, the pH of end reaction solution is adjusted
It is 8.0.The indium tin co-precipitation hydroxide i.e. sediment being generated is repeated gradient by ion exchange water clear
Wash.When the resistivity of supernatant reaches more than 5000 Ω cm, remove above-mentioned sedimentary supernatant and obtain
It is dispersed with the higher slurry of the viscosity of indium tin hydroxide particle.
It while stirring this slurry, is diluted this slurry so that the concentration of hydroxide particles becomes with pure water
After 20 mass %, add the organic protective agent i.e. polyvinyl alcohol of 1.3g.The addition of this organic protective agent is relative
It is 1.0 mass % in indium tin hydroxide.By this slurry in an atmosphere after 110 DEG C of dryings 10 hours, at air
In burn till 2 hours at 700 DEG C, and aggregation pulverized and decompose, thus obtaining the ito powder of about 70g.Will
The ito powder of this 70g is put into and is mixed with the surface treatment liquid of absolute ethyl alcohol and distilled water (blending ratio is, phase
For alcohol 95 quality %, distilled water is 5 mass %) in be dipped into after, put in glass dish, at nitrogen
Heat 2 hours at 330 DEG C under gas atmosphere, thus obtain the ito powder carrying out surface modification treatment.
[manufacture of ito film]
This ito powder 20g carrying out surface modification treatment is put into distilled water (0.020g), two (2-ethyl hexyls
Acid) triglycol ester [3G] (23.8g), absolute ethyl alcohol (2.1g), phosphoric acid polyester (1.0g), 2 ethyl hexanoic acid
(2.0g) and the mixed liquor of 2,4-pentane diketone (0.5g) make it disperse.By prepared dispersion liquid with nothing
Water-ethanol is diluted to the solid content i.e. content of ito powder becomes 10 mass %.This dispersion liquid being diluted is led to
Cross spin coating and coat film forming on quartz glass plate, thus obtain the ito film that thickness is 0.2 μm.
＜ embodiment 2 ＞
At the inidum chloride (InCl that In metal concentration is 24 mass %3) in aqueous solution 135g, add mixing dichloro
Change tin powder (SnCl2·2H2O powder) 16g, after stirring is all dissolved to tin dichloride powder, by all of
Amount joins in the pure water of 1000ml and is used as material solution.By the ammonia (NH of 25 mass %3) aqueous solution is to this
Material solution instills 90 minutes.Now reaction temperature is adjusted to 60 DEG C, the pH of end reaction solution is adjusted
It is 5.0.The indium tin co-precipitation hydroxide i.e. sediment being generated is repeated gradient by ion exchange water clear
Wash.When the resistivity of supernatant reaches more than 5000 Ω cm, remove above-mentioned sedimentary supernatant, thus
Obtain and be dispersed with the higher slurry of the viscosity of indium tin hydroxide particle.While stirring this slurry, by this slurry
It is diluted with pure water so that after the concentration of hydroxide particles becomes 15 mass %, adding organic protective agent is palm fibre
Palmitic acid base dimethyl ethyl QAE quaternary aminoethyl sulfate (70 mass %) 4.5g.The addition of this organic protective agent is relative to indium
Tin hydroxide is 3.0 mass %.
By this slurry in an atmosphere after 110 DEG C of dryings 10 hours, burn till 3 hours at 800 DEG C in an atmosphere,
And aggregation pulverized and decomposes, thus obtain the ito powder of about 75g.The ito powder of this 75g is put into
It is mixed with the surface treatment liquid (blending ratio: relative to alcohol 95 quality %, distillation of absolute ethyl alcohol and distilled water
Water is 5 mass %) in be dipped into after, put in glass dish in a nitrogen atmosphere, 2 little 330 DEG C of heating
When, thus obtain the ito powder carrying out surface modification treatment.Further, this ito powder and embodiment 1 are utilized
Similarly produce ito film.
＜ embodiment 3 ＞
At the inidum chloride (InCl that In metal concentration is 24 mass %3) in aqueous solution 154g, add mixing dichloro
Change tin powder (SnCl2·2H2O powder) 8g, after stirring is all dissolved to tin dichloride powder, by all of
Amount joins in the pure water of 1000ml and is used as material solution.By the ammonia (NH of 25 mass %3) aqueous solution is to this
Material solution instills 90 minutes.Now reaction temperature is adjusted to 20 DEG C, the pH of end reaction solution is adjusted
It is 7.0.The indium tin co-precipitation hydroxide i.e. sediment being generated is repeated gradient by ion exchange water clear
Wash.When the resistivity of supernatant reaches more than 5000 Ω cm, remove above-mentioned sedimentary supernatant, thus
Obtain and be dispersed with the higher slurry of the viscosity of indium tin hydroxide particle.While stirring this slurry, by this slurry
It is diluted with ethanol so that after the concentration of hydroxide particles becomes 1.0 mass %, adding organic protective agent is
Octyldimethyl ethyl ammonium sulfovinate (50 mass %) 10g.The addition of this organic protective agent is relative to indium
Tin hydroxide is 5.0 mass %.
To the inside of the vertical tube furnace being heated to 500 DEG C configuring of the long side direction making pipe, make as carrier gas
Nitrogen in the state of circulate with the linear velocity of 1m/s scope, utilize two-fluid spray nozzle to spray in this slurry,
And be together directed in tube furnace with nitrogen.Thus, indium tin hydroxide particle thermally decomposes in tube furnace and burns
Become, obtain the ito powder carrying out surface modification treatment from the outlet of tube furnace.And utilize this ito powder
Produce ito film similarly to Example 1.
＜ comparative example 1 ＞
At the inidum chloride (InCl that In metal concentration is 24 mass %3) in aqueous solution 245g, add melting concn
It is the butter of tin (SnCl of 55 mass %4) aqueous solution 11.5g, prepare InCl3-SnCl4Mixed solution.Connect
, by ammonium hydrogen carbonate (NH4HCO3) water 500g is dissolved in ion exchange water, being prepared as total amount is 1000ml
And temperature is 70 DEG C.In this aqueous solution, by above-mentioned InCl3-SnCl4It is same that all of amount of mixed solution stirs
When instill within 20 minutes, generate indium tin co-precipitation hydroxide.It is stirred for 30 minutes with this state.Now anti-
The final pH answering solution is 9.0.Reclaim sediment i.e. indium tin hydroxide, after centrifuge dewatering, add from
Sub-exchanged water is centrifuged while cleaning filtering, and the resistivity filtrate reaches knot during more than 5000 Ω cm
Bundle centrifugal filtration.Then by this sediment at 100 DEG C dried overnight after, burn till 3 hours at 600 DEG C, and will be poly-
Collective pulverizes and decomposes, thus obtains the ito powder of 75g.
The ito powder of this 75g is put into the surface treatment liquid (blending ratio being mixed with absolute ethyl alcohol and distilled water
For relative to alcohol 95 quality %, distilled water is 5 mass %) in be dipped into after, put in glass dish,
Heat 3 hours at 330 DEG C in a nitrogen atmosphere, thus obtain the ito powder carrying out surface modification treatment.Further,
This ito powder is utilized to produce ito film similarly to Example 1.
＜ comparative test ＞
[evaluation of ito powder]
0.98MPa will be applied to the pressed compact being made up of each ito powder obtaining in embodiment 1～3 and comparative example 1
(10kgf/cm2) pressure when the specific insulation of this pressed compact be shown in table 1 below.Utilize the mensuration shown in Fig. 1
Device (Mitsubishi Chemical Analytech Co., Ltd. MCP-PD51) measures in this embodiment 1～3
And the specific insulation of each ito powder obtaining in comparative example 1.Specifically, it at the internal diameter φ shown in Fig. 1 is
The ito powder of filling 2.00g in the cylinder body 1 of 25mm, at 0.196～29.42MPa(2～300kgf/cm2)
In the range of change pressure, measure respectively at the same time in embodiment 1～3 and comparative example 1 obtain ito powder
In resistivity and the test portion thickness of more than 10.Pressure by not shown determination of pressure sensor, resistivity with
Direct current four-terminal method measures.In FIG, the pressed compact that 2 is ito powder.
The pressure (transverse axis) and the ITO that are converted into power according to unit are of test portion powder is put on shown in Fig. 2
Relation between the specific insulation (longitudinal axis) of the pressed compact of powder.This relation is similar to by least squares method
The formula (1) of following power.In addition, the specific insulation of powder is by by correction coefficient attached for the system that measures
It is multiplied by the value determining to calculate.The approximate formula obtaining in embodiment 1～3 and comparative example 1 shown in table 1
(1) value of a and n.
Y=aXn(1)
Determined in embodiment 1～3 by Instrument of Electrical Resistivity Measurement (oiling company of Mitsubishi MCP-T400) and
The surface resistivity (Ω/) of each ito film obtaining in comparative example 1.The results are shown in table 1.
[table 1]
＜ evaluates ＞
As seen from Table 1, be less than 5.00 to a by formula (1) and n for-0.500 below example 1～
The pressed compact that the ito powder of 3 is constituted applies 0.98MPa(10kgf/cm2) pressure when this pressed compact volume electricity
Resistance rate is below 0.500 Ω cm.Further, the surface resistivity of the ito film being made up of these ito powders is
1.0×106Ω/below.In contrast, to being less than 5.00 by a of formula (1) but n exceedes-0.500
The pressed compact that the ito powder of comparative example 1 is constituted applies 0.98MPa(10kgf/cm2) pressure when this pressed compact
Specific insulation is more than 0.5 Ω cm.Further, the surface electricity of the ito film being made up of the ito powder of comparative example 1
Resistance rate has exceeded 1.0 × 106Ω/□.More than demonstrate the embodiment 1～3 with the relation being similar to formula (1),
Reduce and obtain high conductivity with resistivity during coating method film forming ito film.
Claims (6)
1. a manufacture method for ito powder, it includes following operation:
In the mixed aqueous solution of trivalent indium compound and divalent tin compound, the mixed-alkali aqueous solution generates indium and tin
Co-precipitation hydroxide；Clean described co-precipitation hydroxide with pure water or ion exchange water；Remove described co-precipitation hydrogen
The slurry being dispersed with indium tin hydroxide particle prepared by the supernatant of oxide；It is dried described slurry；And burn till described
The indium tin hydroxide being dried obtains indium tin oxide,
The method of described manufacture ito powder is characterised by,
In the operation of described cleaning, the resistivity cleaning extremely described supernatant is at least up to 5000 Ω cm,
It in the preparation section of described slurry, is diluted so that described hydrogen with water by eliminating the slurry of described supernatant
After the concentration of oxide particle becomes the scope of 10～30 mass %, add relatively in described slurry while stirring
In the organic protective agent of the scope that described hydroxide particles 100 mass % is 0.1～5 mass %,
Have the indium tin hydroxide of described organic protective agent to be dried to adsorption after, in the described operation burnt till,
Scope firing furnace at 250～800 DEG C burns till 0.5～6 hour in an atmosphere,
After the described operation burnt till, pulverize the aggregation of the ito powder having burnt till, by the ito powder of this pulverizing
After impregnated in the surface treatment liquid of the distilled water being mixed with the absolute ethyl alcohol of 50～95 mass % and 5～50 mass %,
Under nitrogen atmosphere, heat 0.5～5 hour the scopes of 200～400 DEG C,
Described organic protective agent is palmityl dimethyl ethyl QAE quaternary aminoethyl sulfate, polyvinyl alcohol or octyldimethyl ethyl
QAE quaternary aminoethyl sulfate,
Described ito powder is the ito powder of surface modification, applies 0.98MPa to the pressed compact being made up of described ito powder
Pressure when the specific insulation of described pressed compact be below 0.50 Ω cm, will apply 0.196 to described pressed compact～
The specific insulation of the described pressed compact during pressure of 29.42MPa is set to Y and when described pressure is set to X, described pressure
And the relation between described specific insulation carrys out matching with following formula (1), in this formula (1), a is 5.00
Hereinafter, and n is for below-0.500,
Y=aXn (1)。
2. a manufacture method for ito powder, it includes following operation:
In the mixed aqueous solution of trivalent indium compound and divalent tin compound, the mixed-alkali aqueous solution generates indium and tin
Co-precipitation hydroxide；Clean described co-precipitation hydroxide with pure water or ion exchange water；Remove described co-precipitation hydrogen
The slurry being dispersed with indium tin hydroxide particle prepared by the supernatant of oxide；It is dried described slurry；And burn till described
The indium tin hydroxide being dried obtains indium tin oxide,
The method of described manufacture ito powder is characterised by,
In the operation of described cleaning, the resistivity cleaning extremely described supernatant is at least up to 5000 Ω cm,
It in the preparation section of described slurry, is diluted so that described hydrogen with water by eliminating the slurry of described supernatant
After the concentration of oxide particle becomes the scope of 10～30 mass %, add relatively in described slurry while stirring
In the organic protective agent of the scope that described hydroxide particles 100 mass % is 0.1～5 mass %,
In described drying process, to being added with described organic protective agent and be dispersed with the slurry of indium tin hydroxide and carry out
It is dried,
In the described operation burnt till, the microwave with 2.45GHz～28GHz in an atmosphere, at the model of 250～800 DEG C
In enclosing, after heating up with the speed reaching target temperature within 10 minutes, keep 5～120 points at described target temperature
The scope of clock carries out heating and burns till,
After the described operation burnt till, pulverize the aggregation of the ito powder having burnt till, by the ito powder of this pulverizing
After impregnated in the surface treatment liquid of the distilled water being mixed with the absolute ethyl alcohol of 50～95 mass % and 5～50 mass %,
Under nitrogen atmosphere, heat 0.5～5 hour the scopes of 200～400 DEG C,
Described organic protective agent is palmityl dimethyl ethyl QAE quaternary aminoethyl sulfate, polyvinyl alcohol or octyldimethyl ethyl
QAE quaternary aminoethyl sulfate,
Described ito powder is the ito powder of surface modification, applies 0.98MPa to the pressed compact being made up of described ito powder
Pressure when the specific insulation of described pressed compact be below 0.50 Ω cm, will apply 0.196 to described pressed compact～
The specific insulation of the described pressed compact during pressure of 29.42MPa is set to Y and when described pressure is set to X, described pressure
And the relation between described specific insulation carrys out matching with following formula (1), in this formula (1), a is 5.00
Hereinafter, and n is for below-0.500,
Y=aXn(1)。
3. a manufacture method for ito powder, it includes following operation:
In the mixed aqueous solution of trivalent indium compound and divalent tin compound, the mixed-alkali aqueous solution generates indium and tin
Co-precipitation hydroxide；Clean described co-precipitation hydroxide with pure water or ion exchange water；Remove described co-precipitation hydrogen
The slurry being dispersed with indium tin hydroxide particle prepared by the supernatant of oxide；It is dried described slurry；And burn till described
The indium tin hydroxide being dried obtains indium tin oxide,
The method of described manufacture ito powder is characterised by,
In the operation of described cleaning, the resistivity cleaning extremely described supernatant is at least up to 5000 Ω cm,
It in the preparation section of described slurry, is diluted so that described hydrogen with alcohol by eliminating the slurry of described supernatant
After the concentration of oxide particle becomes the scope of 1～5 mass %, stirring while add in described slurry relative to
Described hydroxide particles 100 mass % is the organic protective agent of the scope of 0.1～5 mass %,
In the described operation burnt till, to the inside of the tube furnace of the scope being heated to 250～800 DEG C, make nitrogen with
In the state of the linear velocity of the scope of 0.5～5m/s circulates, will dilute with described alcohol and be added with described organic protective agent simultaneously
And the slurry being dispersed with indium tin hydroxide particle sprays, thus thermally decompose in described tube furnace and burn till indium tin
Hydroxide particles obtains indium tin oxide particles,
Described organic protective agent is palmityl dimethyl ethyl QAE quaternary aminoethyl sulfate, polyvinyl alcohol or octyldimethyl ethyl
QAE quaternary aminoethyl sulfate,
Described ito powder is the ito powder of surface modification, applies 0.98MPa to the pressed compact being made up of described ito powder
Pressure when the specific insulation of described pressed compact be below 0.50 Ω cm, will apply 0.196 to described pressed compact～
The specific insulation of the described pressed compact during pressure of 29.42MPa is set to Y and when described pressure is set to X, described pressure
And the relation between described specific insulation carrys out matching with following formula (1), in this formula (1), a is 5.00
Hereinafter, and n is for below-0.500,
Y=aXn (1)。
4. manufacture method according to claim 3, wherein,
Described alcohol is ethanol, methyl alcohol or propyl alcohol.
5. manufacture a method for dispersion liquid, wherein,
It is scattered in the ito powder being produced by the method according to any one of Claims 1 to 4 in solvent and manufacture
Dispersion liquid.
6. manufacture a method for ito film, wherein,
Dispersion liquid described in claim 5 is manufactured ito film.
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| KR102454200B1 (en) * | 2017-12-14 | 2022-10-14 | 엘티메탈 주식회사 | Manufacturing method of Indium-Tin-Oxide powder and Indium-Tin-Oxide powder using it |
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| EP1967495A1 (en) * | 2007-02-21 | 2008-09-10 | Sumitomo Metal Mining Co., Ltd. | Manufacturing method for antimony-containing tin oxide fine particles for forming solar radiation shielding body, dispersion for forming solar radiation shielding body, solar radiation sheilding body, and solar radiation shielding base material |
| CN102015538A (en) * | 2008-05-06 | 2011-04-13 | 赢创德固赛有限公司 | Indium tin oxide powder and dispersion thereof |
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| EP1113992B1 (en) * | 1998-09-06 | 2006-06-21 | Leibniz-Institut für Neue Materialien gemeinnützige GmbH | Method for preparing suspensions and powders based on indium tin oxide and the use thereof |
| JP4389368B2 (en) * | 1999-12-02 | 2009-12-24 | 三菱マテリアル株式会社 | Conductive pigment powder and transparent conductive film made using the same |
| JP2004123523A (en) | 2002-09-11 | 2004-04-22 | Sumitomo Chem Co Ltd | Method for producing indium oxide-tin oxide powder |
| GB0411949D0 (en) * | 2004-05-28 | 2004-06-30 | Ici Plc | Mixed metal oxides |
| KR100787635B1 (en) | 2007-01-22 | 2007-12-21 | 삼성코닝 주식회사 | Indium tin oxide target, method of manufacturing the same and transparent electrode manufactured by using the same |
| JP2010059040A (en) * | 2008-08-07 | 2010-03-18 | Idemitsu Kosan Co Ltd | Method for producing microparticle and heat-ray-shielding microparticle obtained thereby |
| JP5726728B2 (en) * | 2009-05-12 | 2015-06-03 | Ｄｏｗａエレクトロニクス株式会社 | ITO powder, ITO paint, and transparent conductive film formed using ITO paint |
| JP2011246305A (en) * | 2010-05-26 | 2011-12-08 | Hiroshima Univ | Method for producing powder by solid phase reaction |
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