CN103992042A - ITO powder, ITO painting for conductive film and manufacture method for transparent conductive film - Google Patents
ITO powder, ITO painting for conductive film and manufacture method for transparent conductive film Download PDFInfo
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- CN103992042A CN103992042A CN201410049873.1A CN201410049873A CN103992042A CN 103992042 A CN103992042 A CN 103992042A CN 201410049873 A CN201410049873 A CN 201410049873A CN 103992042 A CN103992042 A CN 103992042A
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Abstract
The invention provides ITO powder, ITO painting for conductive film and a manufacture method for transparent conductive film. When the painting containing the polycrystal ITO particles is used to manufacture the transparent conductive film constituted by the ITO conductive films and reduce the resistance of the conductive films. The ITO powder comprises first powder (11) and second powder. The first powder is constituted by the anisotropic polycrystal ITO particles; the cluster of the polycrystal ITO particles are formed by a plurality of rod-shaped bodies (11b) which are shorter than the central cores (11a) surrounding the rod-shaped cores along the length direction of the rod-shaped center cores. The second powder is constituted by the ITO particles which are finer than the first powder. The average long shaft axis of the firs powder and the average short axis diameter are L1 and S1, wherein the L1 is 200-5000nm and the LA/S1 is 2-20; the average long axis diameter of the second powder and the average short axis diameter are L2 and the S2, wherein the L2 is 10-100nm and the L2/S2 1-3. The second powder is mixed in a mass ratio of 0.01-0.5 relative to total mass of the first powder and the second powder
Description
Technical field
The present invention relates to a kind of ito powder that comprises the 1st powder being formed by the aggregate of the poly-ITO with shape anisotropy (Indium Tin Oxide) particle and the 2nd powder being formed by the ITO particle that is narrower than the 1st powder.More specifically, relate to the ito powder for the raw material of nesa coating.
Background technology
In recent years, popularize ITO conducting film as nesa coating.This ITO conducting film is generally by carrying out the physical film deposition method of sputter or the coating film forming method of the organic compound that coating is dispersed with the dispersion liquid of ITO particle or contains ITO is carried out film forming to ITO.Wherein, use coating film forming method more favourable than using physical film deposition method.This is owing to comparing with the ITO conducting film forming by physical film deposition method, although the electroconductibility of the ITO conducting film forming by coating film forming method is slightly low, but in coating film forming method, in the time of coating film forming without using the device that vacuum unit etc. is expensive, and can tackle like a cork the film forming of big area and complicated shape, its result, can reduce manufacturing cost.Especially, in this coating film forming method, the dispersion liquid that is dispersed with ITO particle is attracted attention as the method for coating.Its reason is, the method with by the organic compound that contains ITO as compared with the method for coating, without making coated film thermolysis, thus can be with lower temperature film forming, and can obtain good electroconductibility.And, also improve and propose following technology from the viewpoint of ITO particle, by the shape that is scattered in the ITO particle in dispersion liquid is made as bar-shaped, thereby in the time forming conductive path, improve particle order of contact each other, and overcome the lower this point of electroconductibility that the ITO conducting film based on coating film forming method has.This be due to, as long as bar-shaped ITO particle can be adjacent to arrange along lengthwise direction on the substrate that forms ITO conducting film, reduce at particle interface each other, therefore particle contact area each other increases, its result resistance declines.
This bar-shaped ITO particle and the coating that is dispersed with this ITO particle are for example disclosed in patent documentation 1.In this patent documentation 1, disclose the manufacture method of following stanniferous Indium sesquioxide micropowder: after the pH of reactive system being adjusted into 2.0～4.0 by pink salt and the solution of indium salt and the neutralization reaction of alkali aqueous solution, further in 15～80 DEG C, at least spend 30 minutes and add alkali aqueous solution until final pH becomes 5.0～9.0 the temperature of reactive system is remained, and the hydrate of thus obtained bar-shaped oxidation pink salt and Indium sesquioxide is carried out to heat treated.In the manufacture method of this stanniferous Indium sesquioxide micropowder, the minor axis diameter of stanniferous Indium sesquioxide (ITO) micropowder is in the scope of 0.02～0.10 μ m, and major diameter is in the scope of 0.2～0.95 μ m.The stanniferous Indium sesquioxide micropowder of manufacturing is by this method bar-shaped, when therefore preparing coating and be coated with it, can form on a small quantity excellent electric conductivity and the good film of the transparency.In addition, above-mentioned patent documentation 1 is recited as needle-like by the shape of ITO micropowder but not is bar-shaped, but formed by the aggregate with anisotropic poly-ITO particle owing to being recited as the 1st powder in this specification sheets and these claims, the aggregate of this poly-ITO particle is integrally formed with the direction along identical with the length direction of bar-shaped centronucleus and the mode of surrounding bar-shaped centronucleus around this centronucleus by the multiple rhoptrys that are shorter than bar-shaped centronucleus, therefore, in the narration of patent documentation 1, be also recited as bar-shaped but not needle-like.
Patent documentation 1: Japanese Patent Publication 6-80422 communique (claim 1 and 2, [0029] section)
But, in the manufacture method of the stanniferous Indium sesquioxide micropowder shown in above-mentioned patent documentation 1 in the past, bar-shaped stanniferous Indium sesquioxide (ITO) micropowder is arranged in parallel along the real estate that forms ITO conducting film all the time, but has the unfavorable condition vertically erecting with respect to real estate.This unfavorable condition can be by overcoming from pressurization with the coating machines such as roller coating machine etc. in the time that the coating that is dispersed with bar-shaped ITO micropowder is coated on real estate.
But, in the manufacture method of the stanniferous Indium sesquioxide micropowder shown in above-mentioned patent documentation 1 in the past, exist bar-shaped ITO micropowder to tangle in dispersion liquid and be jam (ジ ャ system) state and between bar-shaped ITO micropowder, easily produce the problem in space.Therefore, the resistance of the nesa coating being made up of the ITO conducting film of manufacturing by aforesaid method rises, the problem that for example exists the performance of the optics such as the thin-film solar cells that makes to contain nesa coating to worsen.
Summary of the invention
The object of the present invention is to provide following a kind of ito powder: in the time utilizing ito powder to prepare ITO conducting film to use coating, can prevent the 1st powder from dispersion liquid, tangling and be jam state, and in the time of the nesa coating that utilizes the manufacture of ITO conducting film coating to be formed by ITO conducting film, by filling the 2nd powder in the space between the 1st powder, can reduce the resistance of nesa coating.
What the inventor etc. furtherd investigate found that, when the dispersion liquid that contains bar-shaped poly-ITO particle is used to coating as ITO conducting film, need to make bar-shaped poly-ITO particle can not become easy entanglement simple bar-shaped, make bar-shaped poly-ITO particle be difficult to stand on real estate, poly-ITO particle contacted each other all the time tight and increase poly-ITO particle contact area each other, and find, by the particles filled fine poly-ITO resistance that makes in bar-shaped poly-ITO particle gap is each other declined, until completed the present invention.
The 1st viewpoint of the present invention is a kind of ito powder, this ito powder comprises: the 1st powder, be made up of the aggregate with anisotropic poly-ITO particle, the aggregate of this poly-ITO particle is integrally formed with the direction along identical with the length direction of bar-shaped centronucleus and the mode of surrounding bar-shaped centronucleus around this centronucleus by the multiple rhoptrys that are shorter than bar-shaped centronucleus; And the 2nd powder, formed by the ITO particle that is narrower than the 1st powder, wherein, the average major axis diameter of the 1st powder and average minor axis diameter are made as respectively to L
1and S
1time, L
1be 200～5000nm and L
1/ S
1be 2～20; The average major axis diameter of the 2nd powder and average minor axis diameter are made as respectively to L
2and S
2time, L
2be 10～100nm and L
2/ S
2be that the 1～3,2nd powder mixes taking the total amount 100 quality % with respect to the 1st powder and the 2nd powder as the ratio of 1～50 quality %.
The ITO conducting film coating that the 2nd viewpoint of the present invention is the ito powder that comprises claim 1 and record.
The 3rd viewpoint of the present invention is manufactured the method for nesa coating for the ITO conducting film coating that utilizes claim 2 and record.
In the ito powder of the 1st viewpoint of the present invention, the aggregate with anisotropic poly-ITO particle is used as to the 1st powder.The aggregate of this poly-ITO particle is integrally formed with the direction along identical with the length direction of bar-shaped centronucleus and the mode of surrounding bar-shaped centronucleus around this centronucleus by the multiple rhoptrys that are shorter than bar-shaped centronucleus and has an anisotropy, therefore, be difficult for vertically erecting with respect to the real estate that forms ITO conducting film, as rugby, easily fall down on the contrary, therefore can stop the 1st powder to tangle in dispersion liquid and be jam state.And, in above-mentioned the 1st powder, around formed by multiple rhoptrys, therefore the aggregate of poly-ITO particle contacts with each other, recess between claval protuberance and rhoptry engages as gear, can increase thus contact area, and it is less to result from space between the aggregate of poly-ITO particle.On the other hand, the ITO particle that is narrower than the 1st powder is used as to the 2nd powder, therefore in ITO conducting film, the 2nd powder is filled in the space producing between the aggregate of the poly-ITO particle of the 1st powder, and the aggregate of the poly-ITO particle of the 1st powder is electrically connected by the 2nd powder each other.Its result, comprise if utilize the 1st and the ito powder of the 2nd powder manufacture ITO conducting film coating, and utilize this coating to manufacture nesa coating, the resistance of this conducting film declines to a great extent.
In the manufacture method of the ITO conducting film of the of the present invention the 2nd and the 3rd viewpoint with coating and nesa coating, the ITO conducting film that utilization comprises above-mentioned ito powder is coated substrate with coating, can reduce thus the resistance of formed nesa coating, and the opacity that can make nesa coating is that mist degree declines, and can also improve the transmissivity of nesa coating.
Brief description of the drawings
In Fig. 1, be (a) schematic isometric of the 1st powder that formed by the aggregate of the poly-ITO particle of embodiment of the present invention, (b) be the schematic, cross-sectional diagram of the 1st powder.
Fig. 2 is the schematic diagram of the 2nd powder that is made up of the ITO particle of embodiment of the present invention.
In Fig. 3, (a) be 10 of the 1st powder that forms of the aggregate by poly-ITO particle of the present invention taken by scanning electronic microscope (SEM), the photo figure of 000 times, (b) is the photo figure of 50,000 times with the 1st powder of scanning electronic microscope (SEM) shooting.
Fig. 4 is scanning electronic microscope (SEM) the photo figure that represents the nesa coating surface of comparative example 1.
Fig. 5 is scanning electronic microscope (SEM) the photo figure that represents the nesa coating surface of comparative example 2.
Fig. 6 is scanning electronic microscope (SEM) the photo figure that represents the nesa coating surface of embodiment 1.
Fig. 7 is the photo figure of vial wall while becoming transparent after representing the dispersion liquid of embodiment and comparative example (ITO conducting film coating) to put into vial and sway and leave standstill.
Fig. 8 is the opaque and photo figure while being jam state of vial wall after representing the dispersion liquid of comparative example (ITO conducting film coating) to put into vial and sway and leave standstill.
Nomenclature
11-the 1st powder, the bar-shaped centronucleus of 11a-, 11b-rhoptry, 12-the 2nd powder.
Embodiment
Below, with reference to the accompanying drawings to describing for implementing mode of the present invention.Ito powder of the present invention comprises the 1st powder being made up of the aggregate of poly-ITO particle and the 2nd powder being made up of the ITO particle that is narrower than the 1st powder.As shown in the schematic diagram of Fig. 1, the 1st powder 11 is made up of bar-shaped centronucleus 11a and multiple rhoptry 11b, and the mode of substantially surrounding bar-shaped centronucleus 11a along equidirectional with multiple rhoptry 11b on the length direction of bar-shaped centronucleus 11a is integrally formed.And, if with reference to the photo figure of figure 3, can be observed in the 1st powder multiple shorter rhoptrys as twig, and can be observed that these are adjacent to each other and arrange and be fixed on bar-shaped centronucleus in identical direction in surrounding bar-shaped centronucleus compared with short rhoptry.In addition, as shown in Figure 3, diameter separately of multiple rhoptrys and length are without necessarily identical, and its cross-sectional shape, surface shape are also without necessarily identical.And the 2nd powder 12 is as shown in the schematic diagram of Fig. 2, the state of the state disperseing with its primary particle or the cohesion of multiple primary particle exists.
On the other hand, as shown in Figure 1, the average major axis diameter of the 1st powder 11 and average minor axis diameter are made as respectively to L
1and S
1time, L
1be 200～5000nm, be preferably 1500～3000nm, and L
1/ S
1be 2～20, be preferably 3～10.At this, by the average major axis diameter L of the 1st powder 11
1the reason that is defined in the scope of 200～5000nm is, while being less than 200nm, easily vertically erect and cannot obtain the effect of easily falling down as rugby with respect to the real estate that forms ITO conducting film, if exceed the packing variation each other of aggregate of poly-ITO particle of 5000nm.And, by L
1/ S
1the reason that is set in 2～20 scope is, be less than at 2 o'clock, cannot obtain based on anisotropic electroconductibility and improve effect, if exceed 20 dispersion liquid described later (ITO conducting film coating) be jam shape, and cause being difficult to increase the filling ratio of ITO conducting film, and cause the aggregate of the poly-ITO particle being formed by bar-shaped centronucleus and rhoptry in the time making film rupture and shorten.In addition, utilize scanning electronic microscope (SEM) to take the 1st powder 11, and with the vernier callipers average major axis diameter L of the aggregate of the poly-ITO particle to 50 formation the 1st powder 11 on this SEM photo respectively
1survey, their measured value is carried out after times rate conversion divided by 50, the value obtaining i.e. the average major axis diameter L of the 1st powder 11
1.And, utilize scanning electronic microscope (SEM) to take the 1st powder 11, and with the vernier callipers average minor axis diameter S of the aggregate of the poly-ITO particle to 50 formation the 1st powder 11 on this SEM photo respectively
1survey, their measured value is carried out after times rate conversion divided by 50, the value obtaining i.e. the average minor axis diameter S of the 1st powder 11
1.
And, as shown in Figure 2, the average major axis diameter of the 2nd powder 12 and average minor axis diameter are made as respectively to L
2and S
2time, L
2be 10～100nm, be preferably 10～50nm, and L
2/ S
2be 1～3, be preferably 1～1.5.At this, by the average major axis diameter L of the 2nd powder
2the reason that is defined in the scope of 10～100nm is, if being less than in theory 10nm cannot stably manufacture with existing operation, if exceed 100nm the 2nd powder 12 cannot fill up well between aforesaid the 1st powder 11, thereby become the major cause of scattering of light, and cause mist degree to raise.And, by L
2/ S
2the reason that is defined in 1～3 scope is, is less than the 1 i.e. average major axis diameter L of the 2nd powder 12
2be shorter than average minor axis diameter S
2be can not be getable, if exceed 3 powder easy entanglement each other, between powder, produce space, cannot realize object and the effect of the script of filling up powder space each other.In addition, utilize scanning electronic microscope (SEM) to take the 2nd powder 12, and with the vernier callipers average major axis diameter L of the ITO particle to 50 formation the 2nd powder 12 on this SEM photo respectively
2survey, their measured value is carried out after times rate conversion divided by 50, the value obtaining i.e. the average major axis diameter L of the 2nd powder 12
2.And, utilize scanning electronic microscope (SEM) to take the 2nd powder 12, and with the vernier callipers average minor axis diameter S of the ITO particle to 50 formation the 2nd powder 12 on this SEM photo respectively
2survey, their measured value is carried out after times rate conversion divided by 50, the value obtaining i.e. the average minor axis diameter S of the 2nd powder 12
2.
And, the 2nd powder taking the total amount 100 quality % with respect to the 1st powder and the 2nd powder as 1～50 quality %, the ratio that is preferably 5～30 quality % mixes.At this, the reason that the 2nd powder is defined in to the scope of 1～50 quality % with respect to the blending ratio of the 1st powder 100 quality % is, while being less than 1 quality %, the blending ratio of the 2nd powder is very few, cannot obtain by the 2nd powder being filled in to the effect that reduces the resistance of nesa coating between the 1st powder, cause interface increase and the density of powder to decline if exceed 50 quality %, resistance increases on the contrary.
As shown in Figure 1, in the ito powder so forming, because the 1st powder 11 is formed as above-mentioned shape, because the 1st powder 11 is made up of bar-shaped centronucleus 11a and multiple rhoptry 11b, and the mode of substantially surrounding bar-shaped centronucleus 11a along equidirectional with multiple rhoptry 11b on the length direction of bar-shaped centronucleus 11a is integrally formed, therefore while for example manufacturing application type ito thin film, to pressurize containing the coating of this ito powder while coat while manufacturing nesa coating on resin film, easily be oriented in resin film face along being coated with direction.The aggregate that, forms the poly-ITO particle of the 1st powder easily rolls and accumbency at resin film face.And forming the ITO particle of the 1st powder is polycrystalline, therefore produce the result of appropriateness skew at grain circle, result from void ratio between the aggregate of poly-ITO particle less.And the 2nd powder that is narrower than the 1st powder is filled in the space producing between the aggregate of the poly-ITO particle of the 1st powder, the aggregate of the poly-ITO particle of the 1st powder is electrically connected by the 2nd powder each other.Its result, utilizes the resistance of the nesa coating of ito powder of the present invention to decline to a great extent, and can obtain thus the nesa coating with good electroconductibility.And moreover,, because the 2nd powder being made up of ITO particle is filled between the aggregate of the poly-ITO particle that forms the 1st powder, therefore, in the time coating on transparency carrier or film, organizing of coating layer is careful.Its result, the transmittance of the sensitive surface of thin-film solar cells or the transparency electrode of optics etc. improves, and can to make the opacity of above-mentioned sensitive surface and transparency electrode etc. be that mist degree declines.
The manufacture method of above-mentioned ito powder is then described.
The manufacture method > of < the 1st powder
First, as the 1st operation, take and mix pink salt and indium salt with predetermined proportion, this mixture being dissolved in to the mixing solutions that is used as pink salt and indium salt in pure water, making this mixing solutions and alkali reaction generate the suspension of stannic hydroxide and indium hydroxide.As blending means, preferably the alkali such as ammonia are made an addition to the method that makes them react in the mixed aqueous solution of pink salt and indium salt.If add alkali in the mixed aqueous solution of pink salt and indium salt, easily generate anisotropic particle, and temperature can add alkali by control time, at least one in speed or the granule density of alkali of adding are controlled size and the axial ratio of generated hydroxide particles.
Then, the above-mentioned reaction solution in mixing is irradiated the ultrasonic wave of preset frequency.By this hyperacoustic giving, as shown in Figure 1, can manufacture the 1st powder 11 being made up of the aggregate with anisotropic poly-ITO particle, the aggregate of this poly-ITO particle is integrally formed with the direction along identical with the length direction of bar-shaped centronucleus 11a and the mode of surrounding bar-shaped centronucleus 11a around this bar-shaped centronucleus 11a by the multiple rhoptry 11b that are shorter than bar-shaped centronucleus 11a.Hyperacoustic calibration is set in the scope of 20～10000kHz.The reason that hyperacoustic frequency is defined in to the scope of 20～10000kHz is, while being less than 20kHz, hyperacoustic mixing effect weakens, if exceed 10000kHz hyperacoustic output decline, cannot obtain sufficient effect.Hyperacoustic frequency is more preferably made as 20～1000kHz.
The time that ultrasonic wave is imparted to above-mentioned suspension need to suitably be adjusted according to the capacity of frequency and neutralizer etc.For example, hyperacoustic frequency is the capacity of 100kHz and reaction solution while being 1 liter, irradiates ultrasonic wave while time of splashing into alkali is preferably 20～600 minutes.At this, if give ultrasonic wave while make pink salt and the mixing solutions of indium salt and the time of alkali reaction too short, there is the effect unfavorable condition not fully of ultrasonic irradiation, if give ultrasonic wave while make pink salt and the mixing solutions of indium salt and the overlong time of alkali reaction, can cause particle elongated.In order to give equably ultrasonic wave to reaction solution, the liquid level of reaction solution is made as identical with the liquid level (transmitting hyperacoustic medium from irradiating unit to reactor) of ultrasonic wave irradiation device.By giving this ultrasonic wave, can be in the aggregate that prevents the anisotropic poly-ITO particle that forms the 1st powder cohesion each other, obtain the 1st powder being formed by the aggregate of poly-ITO particle, in the aggregate of this poly-ITO particle, the multiple rhoptrys that are shorter than bar-shaped centronucleus are fixed with the direction along identical with the length direction of bar-shaped centronucleus and the mode of surrounding bar-shaped centronucleus around this centronucleus.
At this, as the salt of tin and indium, can enumerate hydrochloride, vitriol or nitrate etc., but conventionally preferably utilize hydrochloride.And, as alkali, use ammonia, caustic soda, Pian Zhuan caustic potash flakes or their carbonate, but conventional base metal and alkaline-earth metal reduce the characteristic of the transparent conductive oxides taking ITO as representative, therefore preferably use ammonia.
Gather the slurry of the above-mentioned stannic hydroxide having generated and indium hydroxide by solid-liquid separation, and clean impurity with pure water, thereby can obtain the block of carrying highly purified stanniferous indium hydroxide.Obtained block is dried with the above preferably 80 DEG C of above temperature of room temperature, thereby obtains the xeraphium of stanniferous indium hydroxide.
In stanniferous indium hydroxide, although tin can replace the indium of indium hydroxide sometimes, but also there is the situation of any or two in stannic oxide and stannic hydroxide and indium hydroxide co-precipitation, also have any or two in stannic oxide and stannic hydroxide and indium hydroxide to become the situation of amorphous mixture.
As mentioned above, the particle diameter of stanniferous indium hydroxide is determined in the operation that obtains oxyhydroxide.Particularly, by temperature of reaction being controlled in the scope of 40～90 DEG C, reaction times (all neutralization spend time) is controlled in the scope of 20～600 minutes, final granule density is controlled in the scope of 0.01～3mol/ liter, can obtains the stanniferous indium hydroxide with desirable particle diameter.
At this, when synthesis example is the rod-shpaed particle of 1000nm and the average minor axis diameter stanniferous indium hydroxide that is 200nm as formed the average major axis diameter of bar-shaped centronucleus in the aggregate of poly-ITO particle of the 1st powder, temperature of reaction is made as to 60 DEG C, reaction times (time that all neutralization spends) is made as to 75 minutes, final granule density is made as to 0.5mol/ and rises.On the other hand, when manufacturing average major axis diameter and being less than the particle of rod-shpaed particle of above-mentioned stanniferous indium hydroxide, temperature of reaction is set as lower, or Reaction time shorten, or improve granule density.In addition, the size of the aggregate of the final poly-ITO particle generating almost depends on the size of the rod-shpaed particle of above-mentioned stanniferous indium hydroxide.That is, the rod-shpaed particle of above-mentioned stanniferous indium hydroxide in the time becoming poly-ITO particle, average major axis diameter L
1and average minor axis diameter S
1all shorten 70～80% left and right.
Below, as the 2nd operation, the operation of burning till above-mentioned acquired stanniferous indium hydroxide is described.At this, the object that stanniferous indium hydroxide is burnt till is to be generated and given oxygen defect as the ITO of oxide compound and to the crystallization of this ITO having generated by stanniferous indium hydroxide.Therefore, for the crystallization of ITO is given oxygen defect and carry out this firing process in the weakly reducing atmosphere that is mixed with inactive gas and reducing gas.Conventionally,, as weakly reducing atmosphere, use the mixed gas that is mixed with hydrogen, carbon monoxide, ammonia, alcohol in the inactive gas such as nitrogen or helium, argon.The blending ratio of the each gas in mixed gas suitably determines according to the oxygen defect amount of wanting the crystallization of giving ITO.But if the reducing power of mixed gas is excessively strong, stanniferous indium hydroxide can become InO, metal In etc.And the blending ratio of hydrogen or carbon monoxide etc. is preferably the concentration that mixed gas can not exceed the degree of explosion limits in atmosphere.
In firing process, first burn till, then reduce processing.By burning till, stanniferous indium hydroxide dewaters and becomes indium tin.Firing temperature is set in the scope of 300～1000 DEG C.At this, the reason that firing temperature is defined in to the scope of 300～1000 DEG C is, more than 300 DEG C, can obtain oxide compound completely, can avoid ITO particle fierce sintering each other below 1000 DEG C.Firing temperature is preferably below 350～800 DEG C.And, firing time be 0.1 hour above, once but dehydration reaction end no longer need to burn till.In addition atmosphere is made as to atmosphere.
Reduction after burning till is processed preferably above with 200 DEG C and be less than the temperature of 500 DEG C and carry out under above-mentioned reducing atmosphere.At this, be reducing the temperature limit processed reason above due to 200 DEG C and that be less than the scope of 500 DEG C, if 200 DEG C can be given oxygen defect above, if thereby be less than 500 DEG C of InO that can obtain suitable reducing power and can not generate insulativity.And the reduction treatment time is 0.5～5 hour.At this, the reason that the reduction treatment time is defined in to the scope of 0.5～5 hour is, while being less than 0.5 hour the formation of oxygen defect insufficient, there will not be superior variation if exceed 5 hours.Through above operation, can obtain the 1st powder being formed by the aggregate of poly-ITO particle.
The manufacture method > of < the 2nd powder
Indium ion and tin ion precipitate and the co-precipitation oxyhydroxide of generation indium and tin in solution under the existence of alkali.Now, by the pH of solution is adjusted into 3.5～10.0, be preferably adjusted into pH6.0～8.0, and solution temperature is adjusted into more than 5 DEG C, preferably solution temperature is adjusted into 10 DEG C～40 DEG C, thereby can make the co-precipitation precipitation of hydroxide of indium and tin.For the acid-basicity in when reaction is adjusted into pH3.5～10.0, preference is as used Indium-111 chloride (InCl
3) and tin protochloride (SnCl
22H
2o) mixed aqueous solution or Indium-111 chloride (InCl
3) and Tin tetrachloride pentahydrate (SnCl
45H
2o) mixed aqueous solution, and this mixed aqueous solution and alkali aqueous solution are splashed into Yu Shuizhong be simultaneously adjusted into above-mentioned pH scope.Or, above-mentioned mixed solution is splashed in alkali aqueous solution.As alkali aqueous solution, use ammonia (NH
3) water, ammonium hydrogencarbonate (NH
4hCO
3) water etc.
Generate after above-mentioned co-precipitation indium tin hydroxide, clean this throw out with pure water, more than cleaning and becoming 5000 Ω cm to the resistivity of supernatant liquor, more than preferably becoming 50000 Ω cm.If the resistivity of supernatant liquor cannot fully be removed the impurity such as chlorine lower than 5000 Ω cm, cannot obtain highly purified indium tin hydroxide powder.Removing resistivity becomes above-mentioned sedimentary supernatant liquors more than 5000 Ω cm, becomes full-bodied pulp-like.In atmosphere, preferably under the inactive gas such as nitrogen or argon atmosphere, the indium tin hydroxide of this pulp-like, is burnt till in the scope of 250～800 DEG C 0.5～6 hour after 2～24 hours at the scope inner drying of 100～200 DEG C in atmosphere.To burn till the polymer forming and utilize beater grinder or ball mill to pulverize and evacuate by this, thereby obtain ito powder.If this ito powder is put into the surface treatment liquid that is mixed with the dehydrated alcohol of 50～95 mass parts and the distilled water of 5～50 mass parts to be made after its dipping, put into glass dish, under nitrogen atmosphere and in the scope of 200～400 DEG C, heat 0.5～5 hour, can obtain by surface and carry out the 2nd powder that the ITO particle of modification forms., can obtain average major axis diameter L
2be 10～100nm and L
2/ S
2it is 1～3 the 2nd powder.
The blending means > of < the 1st powder and the 2nd powder
Above-mentioned the 1st powder is mixed with the ratio of being scheduled to above-mentioned the 2nd powder.Particularly, taking with respect to the 1st powder 100 quality % as 1～50 quality %, be preferably 5～30 quality % ratio mix the 2nd powder.Can obtain thus ito powder of the present invention.In addition, as the blending means of the 1st powder and the 2nd powder, can utilize the dry type blending means of carrying out with mixing machine etc.But, the 1st powder is mixed in the alcoholic solvents such as ethanol, sec-butyl alcohol, n-propyl alcohol and prepares the 1st coating, the 2nd powder is mixed in the alcoholic solvents such as ethanol, sec-butyl alcohol, n-propyl alcohol and prepares the 2nd coating, and can be mixed to get when these coating are mixed with liquid state more even, therefore preferred.
The manufacture method > of coating for < ITO conducting film
Mix above-mentioned ito powder with the ratio that becomes 1～70 quality % with respect to alcohol 100 quality %, and stir to prepare ITO conducting film coating with mixing machine.At this, the reason that ito powder is defined in to 1～70 quality % with respect to the blending ratio of alcohol 100 quality % is, be difficult to form thickness sufficient conducting film if be less than 1 quality %, if exceed 70 quality %, the viscosity of dispersion liquid (ITO conducting film coating) is higher, and it is difficult that coating becomes.In addition, as alcohol, can enumerate ethanol, sec-butyl alcohol, n-propyl alcohol etc.And, as required above-mentioned ITO conducting film is put in ball mill pulverizer etc. the ito powder in this coating is carried out to pulverization process with coating.And, in the scope that does not make resistance worsen, can as required the tackiness agent such as silica sol gel and acrylic resin be added to above-mentioned ITO conducting film with in coating.
The manufacture method > of < nesa coating
Nesa coating is for example to manufacture as follows.Make in advance the base material that is used to form ITO conducting film.This base material is the film of polyethylene terephthalate (PET) that is coated with urethane in one side etc., and it is by sticking on the uncoated one side that has urethane in this film on glass substrate and make with double sticky tape etc.First, be coated with after method, mould painting method, scraper plate method etc. are coated on the base material being fixed on glass substrate by ITO conducting film coating and make it dry by rod.Then, the base material that is coated with ITO conducting film coating is peeled off from glass substrate, make the overlay films such as PET be overlapped in the one side that is coated with ITO conducting film coating in base material, after exerting pressure with the rate of delivery of the roller pressure of 100～2000kg/cm and 10～50cm/ minute with roll squeezer, peel off overlay film under this state.On film, form thus ITO conducting film.
[embodiment]
Below, describe embodiments of the invention and comparative example in detail.
< embodiment 1 >
In order to make the 1st powder, first taking indium concentration is the indium chloride aqueous solution (InCl of 18.5 quality %
3) 100g and tin chloride (SnCl
45H
2o) 6.3g, is dissolved in the pure water of 2000ml, prepares the mixing solutions of indium chloride and tin chloride.The concentration of the tin of this mixing solutions is adjusted into Sn/In taking molar ratio computing as 0.10.The mixing solutions of this indium chloride and tin chloride is heated to 60 DEG C, and spend the ammoniacal liquor that slowly adds 29 quality % for 160 minutes, be used as the suspension of stanniferous indium hydroxide with this.Then, in this suspension, adding ammoniacal liquor, during generating precipitation, is the ultrasonic wave that prevents that the aggregate of cohesion and making poly-ITO particle from giving 34kHz to above-mentioned suspension.Filtration is collected the suspension of this stanniferous indium hydroxide and is cleaned with pure water, thereby obtains the block of stanniferous indium hydroxide.The block of this stanniferous indium hydroxide is dried in 100 DEG C.From the block that this has been dried, reclaim coprecipitate and with after separating centrifuge dehydration, add ion exchanged water to clean while carry out ion filter, reach 5000 Ω cm at the ratio resistance of filtrate and finish centrifuging when above.And, the stanniferous indium hydroxide as above-mentioned coprecipitate is arranged in firing furnace, at N
2after keeping burning till for 2 hours with 800 DEG C in atmosphere, at H
2the N of concentration 1 volume %
2in atmosphere, within 3 hours, burn till (reduction is processed) with 250 DEG C of maintenances.Obtain thus the 1st powder being formed by the aggregate of poly-ITO particle.The average major axis diameter of the 1st powder and average minor axis diameter are made as respectively to L
1and S
1time, L
1for 1500nm, L
1/ S
1be 6.
In order to make the 2nd powder, first mix the indium chloride (InCl of the In metal that contains 18g
3) 50 milliliters of the aqueous solution and tin protochloride (SnCl
22H
2o) 3.6g, by this mixed aqueous solution and ammonia (NH
3) aqueous solution splashes into simultaneously in the water of 500 milliliters and be adjusted into pH7.Under the state that solution temperature is made as to 30 DEG C, react 30 minutes.Then be, that throw out carries out Ramped rinsing repeatedly by ion exchanged water to generated indium tin co-precipitation oxyhydroxide.When the resistivity of supernatant liquor becomes 50000 Ω cm when above, remove above-mentioned sedimentary supernatant liquor and become the slurry that viscosity is higher.And, after the indium tin hydroxide of this pulp-like is kept being dried with 110 DEG C in atmosphere an evening, in atmosphere, within 3 hours, burn till with 550 DEG C of maintenances, and pulverize evacuation polymer, thereby obtain the ito powder of about 25g.This ito powder of 25g is put in the surface treatment liquid that is mixed with dehydrated alcohol and distilled water (blending ratio is is distilled water 5 mass parts with respect to alcohol 95 mass parts) and made after its dipping, put into glass dish, by keep obtaining for 2 hours with 330 DEG C the 2nd powder being formed by the ITO particle that carries out surface modification treatment under nitrogen atmosphere.The average major axis diameter of the 2nd powder and average minor axis diameter are made as respectively to L
2and S
2time, L
2for 30nm, L
2/ S
2be 1.2.And, by the 2nd powder with respect to the 1st and the total amount 100 quality % of the 2nd powder mode that becomes 20 quality % mix to obtain ito powder.Utilize this ito powder to prepare ITO conducting film coating, after being coated with method and this ITO conducting film coating is coated to PET film and being dried with rod, exert pressure with the roller pressure of 700kg/cm and the rate of delivery of 30cm/ minute, thereby obtain the nesa coating being formed by ITO conducting film.This nesa coating is made as to embodiment 1.
< comparative example 1 >
Utilize the ito powder only being formed by the 1st powder of embodiment 1, coat on PET film and after dry with rod painting method similarly to Example 1, exert pressure to obtain nesa coating with roll squeezer, set it as comparative example 1.
< comparative example 2 >
Utilize the ito powder only being formed by the 2nd powder of embodiment 1, coat on PET film and after dry with rod painting method similarly to Example 1, exert pressure to obtain nesa coating with roll squeezer, set it as comparative example 2.
< comparison test 1 and evaluation >
Take respectively the surface of the nesa coating of embodiment 1, comparative example 1 and comparative example 2 by scanning electronic microscope (SEM), by their photo illustration in Fig. 4～Fig. 6.
As from Fig. 4～Fig. 6 clearly, in the nesa coating of comparative example 1 that only uses the 1st powder, between the 1st powder, be formed with space (Fig. 4), in the nesa coating of comparative example 2 that only uses the 2nd powder, between the 2nd powder, be also formed with space (Fig. 5), with respect to this, by the 1st and the nesa coating of the embodiment 1 that forms of the mixed powder of the 2nd powder in, in the space between the 1st powder, be filled with the 2nd powder and become fine and close (Fig. 6).
< embodiment 2 >
Except the average major axis diameter L of the 1st powder
1beyond 200nm, make similarly to Example 1 nesa coating.Using this nesa coating as embodiment 2.
< embodiment 3 >
Except changing, suspension is irradiated to ultrasonic wave so that the average major axis diameter L of the 1st powder
1become beyond the total reaction time of 3000nm, make in the same manner nesa coating with embodiment 1.Using this nesa coating as embodiment 3.
< embodiment 4 >
Except changing, suspension is irradiated to ultrasonic wave so that the average major axis diameter L of the 1st powder
1become beyond the total reaction time of 5000nm, make in the same manner nesa coating with embodiment 1.Using this nesa coating as embodiment 4.
< embodiment 5 >
Except changing hyperacoustic frequency that suspension is given so that the average major axis diameter of the 1st powder and average minor axis diameter ratio L
1/ S
1become beyond 2, make in the same manner nesa coating with embodiment 1.Using this nesa coating as embodiment 5.
< embodiment 6 >
Except changing hyperacoustic frequency that suspension is given so that the average major axis diameter of the 1st powder and average minor axis diameter ratio L
1/ S
1become beyond 3, make in the same manner nesa coating with embodiment 1.Using this nesa coating as embodiment 6.
< embodiment 7 >
Except changing hyperacoustic frequency that suspension is given so that the average major axis diameter of the 1st powder and average minor axis diameter ratio L
1/ S
1become beyond 10, make in the same manner nesa coating with embodiment 1.Using this nesa coating as embodiment 7.
< embodiment 8 >
Except changing hyperacoustic frequency that suspension is given so that the average major axis diameter of the 1st powder and average minor axis diameter ratio L
1/ S
1become beyond 20, make in the same manner nesa coating with embodiment 1.Using this nesa coating as embodiment 8.
< embodiment 9 >
Temperature when changing the reaction of suspension is so that the average major axis diameter L of the 2nd powder
2become beyond 10nm, make in the same manner nesa coating with embodiment 1.Using this nesa coating as embodiment 9.
< embodiment 10 >
Temperature when changing the reaction of suspension is so that the average major axis diameter L of the 2nd powder
2become beyond 50nm, make in the same manner nesa coating with embodiment 1.Using this nesa coating as embodiment 10.
< embodiment 11 >
Temperature when changing the reaction of suspension is so that the average major axis diameter L of the 2nd powder
2become beyond 100nm, make in the same manner nesa coating with embodiment 1.Using this nesa coating as embodiment 11.
< embodiment 12 >
PH when changing the reaction of suspension is so that the average major axis diameter of the 2nd powder and average minor axis diameter ratio L
2/ S
2become beyond 1.0, make in the same manner nesa coating with embodiment 1.Using this nesa coating as embodiment 12.
< embodiment 13 >
PH when changing the reaction of suspension is so that the average major axis diameter of the 2nd powder and average minor axis diameter ratio L
2/ S
2become beyond 1.5, make in the same manner nesa coating with embodiment 1.Using this nesa coating as embodiment 13.
< embodiment 14 >
PH when changing the reaction of suspension is so that the average major axis diameter of the 2nd powder and average minor axis diameter ratio L
2/ S
2become beyond 3.0, make in the same manner nesa coating with embodiment 1.Using this nesa coating as embodiment 14.
< embodiment 15 >
Except with respect to the 1st and the total amount 100 quality % of the 2nd powder mix the 2nd powder of 1 quality %, make in the same manner nesa coating with embodiment 1.Using this nesa coating as embodiment 15.
< embodiment 16 >
Except with respect to the 1st and the total amount 100 quality % of the 2nd powder mix the 2nd powder of 5 quality %, make in the same manner nesa coating with embodiment 1.Using this nesa coating as embodiment 16.
< embodiment 17 >
Except with respect to the 1st and the total amount 100 quality % of the 2nd powder mix the 2nd powder of 30 quality %, make in the same manner nesa coating with embodiment 1.Using this nesa coating as embodiment 17.
< embodiment 18 >
Except with respect to the 1st and the total amount 100 quality % of the 2nd powder mix the 2nd powder of 50 quality %, make in the same manner nesa coating with embodiment 1.Using this nesa coating as embodiment 18.
< comparative example 3 >
Except changing hyperacoustic frequency that suspension is given so that the average major axis diameter L of the 1st powder
1become beyond 150nm, make in the same manner nesa coating with embodiment 1.By this nesa coating as a comparative example 3.
< comparative example 4 >
Except changing, suspension is irradiated to ultrasonic wave so that the average major axis diameter L of the 1st powder
1become beyond the total reaction time of 5200nm, make in the same manner nesa coating with embodiment 1.By this nesa coating as a comparative example 4.
< comparative example 5 >
Except changing hyperacoustic frequency that suspension is given so that the average major axis diameter of the 1st powder and average minor axis diameter ratio L
1/ S
1become beyond 1, make in the same manner nesa coating with embodiment 1.By this nesa coating as a comparative example 5.
< comparative example 6 >
Except changing hyperacoustic frequency that suspension is given so that the average major axis diameter of the 1st powder and average minor axis diameter ratio L
1/ S
1become beyond 22, make in the same manner nesa coating with embodiment 1.By this nesa coating as a comparative example 6.
< comparative example 7 >
Temperature when changing the reaction of suspension is so that the average major axis diameter L of the 2nd powder
2become beyond 110nm, make in the same manner nesa coating with embodiment 1.By this nesa coating as a comparative example 7.
< comparative example 8 >
PH when changing the reaction of suspension is so that the average major axis diameter of the 2nd powder and average minor axis diameter ratio L
2/ S
2become beyond 3.2, make in the same manner nesa coating with embodiment 1.By this nesa coating as a comparative example 8.
< comparative example 9 >
Except with respect to the 1st and the total amount 100 quality % of the 2nd powder mix the 2nd powder of 0.8 quality %, make in the same manner nesa coating with embodiment 1.By this nesa coating as a comparative example 9.
< comparative example 10 >
Except with respect to the 1st and the total amount 100 quality % of the 2nd powder mix the 2nd powder of 52 quality %, make in the same manner nesa coating with embodiment 1.By this nesa coating as a comparative example 10.
< comparison test 2 and evaluation >
Measure the proterties of coating for the ITO conducting film of embodiment 1～18 and comparative example 1～10, and measure the ratio resistance of the nesa coating of embodiment 1～18 and comparative example 1～10.Proterties about ITO conducting film with coating, after the vial of 1/3 dispersion liquid (ITO conducting film coating) of putting into volume is swayed to (rocking intensely) and leaving standstill, if the wall of vial in 1 minute, become transparent for " well " (Fig. 7), if become jam state be " bad " (Fig. 8).And, about surface resistivity (Ω/: ohms per square), utilize tester (Mitsubishi chemical Co., Ltd, trade(brand)name: Loresta HP type, MCP-T410, probe: series connection 1.5mm pitch) in 25 DEG C of atmosphere, measure by the four terminal four probe methods that apply based on continuous current.The results are shown in table 1.
[table 1]
As seen from Table 1, only use in the comparative example 1 of the 1st powder, it is 1969 Ω/ that the surface resistivity of nesa coating raises, and only use in the comparative example 2 of the 2nd powder, the surface resistivity of nesa coating becomes high 9473 Ω/, with respect to this, be mixed with the 1st and the embodiment 1～18 of the 2nd powder in, the surface resistivity of nesa coating is reduced to 1211～1897 Ω/.Hence one can see that, and by mixing the 1st powder and the 2nd powder, the surface resistivity of nesa coating reduces.And, in the very few comparative example 9 of the blending ratio of the 2nd powder, it is 1984 Ω/ that the surface resistivity of nesa coating raises, in the too much comparative example 10 of the blending ratio of the 2nd powder, it is 3591 Ω/ that the surface resistivity of nesa coating raises, with respect to this, in the embodiment 15～18 of the blending ratio of the 2nd powder in the scope of 1～50 quality %, the surface resistivity of nesa coating is reduced to 1409～1889 Ω/.And known, do not change embodiment 15～18 nesa coating surface resistivity and while increasing the blending ratio of the 2nd powder, although surface resistivity reduces gradually, start to increase from a certain lighting, and if exceed 50 quality % the resistance when not mixing be higher.And in the proterties of dispersion liquid (ITO conducting film coating) is bad comparative example 4,6 and 8, it is 4865～6784 Ω/ that the surface resistivity of nesa coating raises.Hence one can see that, if the dispersion state of dispersion liquid (ITO conducting film coating) is bad, after film forming, also can carry out the filling of the powder in nesa coating, thereby become high resistance.
Utilizability in industry
Ito powder of the present invention can be used in application type nesa coating of optics of the transparency electrode of the panel switch that contains contact panel etc. etc. etc.
Claims (3)
1. an ito powder, it comprises:
The 1st powder, be made up of the aggregate with anisotropic poly-ITO particle, the aggregate of this poly-ITO particle is integrally formed with the direction along identical with the length direction of bar-shaped centronucleus and the mode of surrounding bar-shaped centronucleus around described centronucleus by the multiple rhoptrys that are shorter than bar-shaped centronucleus; And
The 2nd powder, is made up of the ITO particle that is narrower than described the 1st powder, and described ito powder is characterised in that,
The average major axis diameter of described the 1st powder and average minor axis diameter are made as respectively to L
1and S
1time, L
1be 200～5000nm and L
1/ S
1be 2～20,
The average major axis diameter of described the 2nd powder and average minor axis diameter are made as respectively to L
2and S
2time, L
2be 10～100nm and L
2/ S
2be 1～3,
Described the 2nd powder mixes taking the total amount 100 quality % with respect to described the 1st powder and the 2nd powder as the ratio of 1～50 quality %.
2. an ITO conducting film coating, wherein,
Described ITO conducting film comprises ito powder claimed in claim 1 with coating.
3. a manufacture method for nesa coating, wherein,
Described manufacture method utilizes the ITO conducting film coating described in claim 2 to manufacture nesa coating.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013-030578 | 2013-02-20 | ||
| JP2013030578A JP2014159346A (en) | 2013-02-20 | 2013-02-20 | ITO powder |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103992042A true CN103992042A (en) | 2014-08-20 |
Family
ID=51306420
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410049873.1A Pending CN103992042A (en) | 2013-02-20 | 2014-02-13 | ITO powder, ITO painting for conductive film and manufacture method for transparent conductive film |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP2014159346A (en) |
| CN (1) | CN103992042A (en) |
| TW (1) | TW201434753A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111378298A (en) * | 2018-12-27 | 2020-07-07 | 苏州锦艺新材料科技有限公司 | Powder material, preparation method thereof and powder coating |
-
2013
- 2013-02-20 JP JP2013030578A patent/JP2014159346A/en active Pending
- 2013-11-29 TW TW102143766A patent/TW201434753A/en unknown
-
2014
- 2014-02-13 CN CN201410049873.1A patent/CN103992042A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111378298A (en) * | 2018-12-27 | 2020-07-07 | 苏州锦艺新材料科技有限公司 | Powder material, preparation method thereof and powder coating |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201434753A (en) | 2014-09-16 |
| JP2014159346A (en) | 2014-09-04 |
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Application publication date: 20140820 |