WO2015046572A1 - Ito powder and method for producing same - Google Patents

Ito powder and method for producing same Download PDF

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WO2015046572A1
WO2015046572A1 PCT/JP2014/076104 JP2014076104W WO2015046572A1 WO 2015046572 A1 WO2015046572 A1 WO 2015046572A1 JP 2014076104 W JP2014076104 W JP 2014076104W WO 2015046572 A1 WO2015046572 A1 WO 2015046572A1
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ito
surface treatment
particles
treatment agent
polycrystalline
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PCT/JP2014/076104
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French (fr)
Japanese (ja)
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岳洋 米澤
山崎　和彦
愛 竹之下
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三菱マテリアル株式会社
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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/1884—Manufacture of transparent electrodes, e.g. TCO, ITO
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C01P2002/54—Solid solutions containing elements as dopants one element only
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer

Definitions

  • the present invention relates to an ITO powder for forming an ITO conductive film capable of suppressing an increase in electrical resistance value of an ITO conductive film under high temperature and high humidity, and a method for producing the ITO powder.
  • ITO refers to indium tin oxide.
  • Transparent electrodes are used in display devices such as LCD (Liquid Crystal Display), PDP (Plasma Display Panel), organic EL (ElectroLuminescence), and touch panel.
  • This transparent electrode is often composed of a transparent conductive material made of ITO or the like.
  • Such a transparent electrode is usually formed into a film by a sputtering method or the like (see, for example, Patent Document 1).
  • the sputtering apparatus is expensive and has a problem that the film formation efficiency is low and the film is easily cracked.
  • a method of forming an ITO conductive film excellent in flexibility, which is less prone to cracking a method of applying an ITO conductive film forming coating to a substrate instead of the sputtering method has been proposed.
  • the transparent electrode obtained by the coating method is placed under high temperature and high humidity, the electrical resistance value tends to increase due to oxygen and moisture in the atmosphere. It was.
  • a surface-treated conductive powder and a curable compound obtained by treating the surface of a conductive powder such as ITO powder having water resistance with a surface treatment agent Proposed transparent conductive material (for example, see Patent Document 2) and transparent conductive material containing transparent conductive particles such as resin, ITO powder, silica material, and silane coupling agent (for example, see Patent Document 3) has been.
  • JP 2004-315951 A (paragraph [0002]) JP 2006-59772 A (summary, claim 1) JP 2009-135044 (Abstract, Claim 1)
  • the transparent electrode of the ITO conductive film formed of the transparent conductive material disclosed in Patent Documents 2 and 3 can suppress an increase in electrical resistance value due to the influence of moisture even under high temperature and high humidity.
  • the conventional high temperature and high humidity shown here is, for example, a temperature of 60 ° C., a humidity of 95% RH, and 750 hours.
  • the use of transparent electrodes has become more diverse, and it has formed an ITO conductive film that can suppress an increase in the electrical resistance value of transparent electrodes under high temperature and high humidity even under severer conditions than before. There is a need for ITO particles for this purpose.
  • An object of the present invention is to provide an ITO powder capable of forming an ITO conductive film which is a transparent electrode capable of suppressing an increase in electrical resistance value under high temperature and high humidity even under severer conditions than before, It is in providing the manufacturing method.
  • a surface treatment agent comprising a silicate ester having 4 alkoxy groups having 2 or less carbon atoms or an oligomer of the silicate ester, or 2 alkoxy groups having 2 or less carbon atoms.
  • 2nd viewpoint of this invention is invention based on 1st viewpoint, Comprising: Silicate ester has tetramethoxysilane which has a C1-C1 alkyl group, or C2-C2 alkyl group. Tetraethoxysilane.
  • a third aspect of the present invention is the invention based on the first aspect, wherein the silane coupling agent is N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxy.
  • the silane coupling agent is N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxy.
  • polycrystalline ITO particles are obtained by including the vapor of the surface treatment agent for ITO powder according to any one of the first to third aspects in a carrier gas composed of an inert gas. It is characterized by being the manufacturing method of the ITO powder which surface-treats the said polycrystal ITO particle with the said surface treating agent by distribute
  • polycrystalline ITO particles are obtained by including the surface treatment agent vapor of the ITO powder according to any one of the first to third aspects in a carrier gas composed of an inert gas. It is characterized by being the manufacturing method of the ITO powder which surface-treats the said polycrystal ITO particle with the said surface treating agent by distribute
  • an ITO conductive film forming coating material comprising the ITO powder according to any one of the first to third aspects and a dispersion medium, wherein the dispersion medium is an alcoholic solution. It is characterized by that.
  • a seventh aspect of the present invention is a method for forming an ITO conductive film using the ITO conductive film forming paint described in the sixth aspect.
  • the main component of ITO In 2 O 3
  • has a Bixbyite structure and can be expressed as a structure in which oxygen is regularly removed from the fluorite structure.
  • This structure has a structure in which oxygen is easily taken in between lattices when the amount of Sn as a dopant is increased. For this reason, when ITO powder is placed under high temperature and high humidity, water adsorbed on the powder surface binds as —OH between oxygen vacancies and lattices on the ITO powder surface and traps carrier electrons. Reduces electrical conductivity.
  • the ITO powder according to the first aspect of the present invention is treated with the specific surface treatment agent described above.
  • the surface treatment agent is the silicate ester
  • the stability to water is greatly improved by bonding the silicate ester between oxygen vacancies and lattices on the surface of the polycrystalline ITO particles.
  • the silane coupling agent it is considered that the stability to water is greatly improved by bonding an amino group or a mercapto group between oxygen vacancies and lattices on the surface of the polycrystalline ITO particles.
  • —OH already exists on the particle surface. That is, —OH exists on the surface of the polycrystalline ITO particles constituting the ITO powder.
  • tetramethoxysilane having an alkyl group having 1 carbon atom or tetraethoxysilane having an alkyl group having 2 carbon atoms is selected as the silicate ester. Since these silicate esters have a small number of carbon atoms, the reactivity increases. As a result, the silicate is easily bonded to the surface of the polycrystalline ITO particles.
  • N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane is used as a silane coupling agent. Any one selected from the group consisting of 3-mercaptopropyltrimethoxysilane, trifluoropropyltrimethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, and decyltrimethoxysilane.
  • These silane coupling agents have an effect of inhibiting H 2 O from approaching the surface of the polycrystalline ITO particles because of the steric hindrance and polarity of the end groups.
  • an ITO conductive film is formed using the paint according to the sixth aspect of the present invention, an increase in electrical resistance value of the ITO conductive film under high temperature and high humidity can be suppressed.
  • the ITO conductive film formed by the method of the seventh aspect of the present invention can suppress an increase in electrical resistance value under high temperature and high humidity.
  • the ITO powder of the present invention comprises polycrystalline ITO particles 10 surface-treated with a surface treatment agent.
  • the polycrystalline ITO particles 10 are composed of a rod-shaped central core 11 and a plurality of rod-shaped bodies 12, and are integrally formed with the rod-shaped body 12 so as to surround the rod-shaped central core 11 along the same direction in the longitudinal direction of the rod-shaped central core 11.
  • Is formed. 2A and 2B in the polycrystalline ITO particles, a plurality of short rods are observed as twigs, and these short rods are adjacent to each other while surrounding the rod-shaped central core. It is observed that they stick to the rod-shaped central core side by side in the same direction.
  • the diameters and lengths of the plurality of rod-shaped bodies are not necessarily the same, and the cross-sectional shape and the surface shape are not necessarily the same.
  • the average length L in the longitudinal direction of the rod-shaped central core 12 of the polycrystalline ITO particle 10 is in the range of 0.2 to 5.0 ⁇ m, preferably 1.0 to 5.0 ⁇ m.
  • L / D is in the range of 2 to 20, preferably 3 to 10. It is in.
  • L is less than 0.2 ⁇ m, it becomes easy to stand perpendicular to the substrate surface on which the ITO conductive film is formed, and the effect of being easily overturned like a rugby ball cannot be obtained.
  • L exceeds 5.0 ⁇ m the packing between the particles is deteriorated. If L / D is less than 2, the effect of improving conductivity due to anisotropy cannot be obtained. If L / D is more than 20, the rod-like particles are broken and shortened when the coating film is produced.
  • the polycrystalline ITO particles of the ITO powder of the present invention have the above-mentioned shape, for example, when a coating-type ITO film is produced using the polycrystalline ITO particles, when a paint containing the ITO powder is applied to a resin film, When the coating surface of the paint is pressed, the polycrystalline ITO particles are easily oriented on the resin film surface along the coating direction. That is, the polycrystalline ITO particles are liable to roll and lie on the resin film surface. Moreover, since the ITO particles of the present invention are polycrystalline, an appropriate shift occurs at the grain boundary. As a result, voids between the particles are easily filled, and the polycrystalline ITO particles are dense.
  • the ITO particles of the present invention when used for a material such as a transparent electrode, the electrical resistance of the transparent electrode or the like can be further reduced, and good conductivity can be obtained.
  • the coating layer becomes a dense structure. The light transmittance of the transparent electrode or the like of the optical device can be improved, and the haze can be reduced.
  • a tin salt and an indium salt are weighed and mixed at a predetermined ratio, the mixture is dissolved in pure water to obtain a mixed solution of a tin salt and an indium salt, and the mixed solution and an alkali are mixed. React to produce a suspension of tin-containing indium hydroxide.
  • a mixing method a method of adding an alkali such as ammonia to a mixed aqueous solution of a tin salt and an indium salt and reacting them is preferable.
  • anisotropic particles are likely to be generated, and the generated water is controlled by controlling the temperature, the addition rate and / or the particle concentration during the addition of the alkali.
  • the size and axial ratio of the oxide particles can be controlled.
  • the reaction liquid being mixed is irradiated with ultrasonic waves having a predetermined frequency.
  • a plurality of ITO rods shorter than the ITO rod-shaped central core are arranged around the ITO rod-shaped central core along the same direction as the longitudinal direction of the ITO rod-shaped central core and surround the ITO rod-shaped central core.
  • An ITO powder composed of integrally formed polycrystalline ITO particles can be produced.
  • the frequency of the ultrasonic wave is 20 to 10,000 kHz. If the frequency is less than 20 kHz, the ultrasonic stirring effect is weak. On the other hand, if it exceeds 10,000 kHz, the output of the ultrasonic wave is lowered and a sufficient effect cannot be obtained.
  • the frequency is further preferably 20 to 1000 kHz.
  • the predetermined time for applying the ultrasonic wave to the suspension is necessary to appropriately adjust the predetermined time for applying the ultrasonic wave to the suspension according to the frequency, the volume of the neutralizing solution, and the like.
  • the frequency of the ultrasonic wave is 100 kHz and the volume of the reaction solution is 1 L
  • the time for dropping the alkali while irradiating the ultrasonic wave is preferably 20 to 600 minutes. If the application time of the ultrasonic wave is too short, there is a problem that the effect of ultrasonic irradiation cannot be sufficiently obtained, and if it is too long, there is a problem that the particles become too long.
  • the liquid level of the reaction liquid is set to be the same as the liquid level of the ultrasonic irradiation apparatus (medium for transmitting ultrasonic waves from the irradiation apparatus to the reactor) so that the ultrasonic waves are uniformly applied to the reaction liquid.
  • This ultrasonic wave By applying this ultrasonic wave, agglomeration of single pieces of anisotropic ITO particles is prevented, and at the same time, a plurality of ITO rods shorter than the central core around the ITO rod central core are the same as the longitudinal direction of the ITO rod central core. Polycrystalline ITO particles fixed along the direction and surrounding the ITO rod-like central core can be obtained.
  • hydrochloride As the salt of tin and indium, there are hydrochloride, sulfate, nitrate, etc., but hydrochloride is generally preferable.
  • alkali ammonia, caustic soda, caustic potash, or a carbonate thereof is used, but ammonia is preferably used from the viewpoint of reducing impurities after the slurry formation of tin-containing indium hydroxide.
  • the produced tin-containing indium hydroxide slurry is collected by solid-liquid separation of the suspension, and the impurities are washed with pure water to obtain a tin-containing indium hydroxide cake with increased purity.
  • the obtained cake is dried at a temperature of room temperature or higher, preferably 80 ° C. or higher, whereby a dry powder of tin-containing indium hydroxide is obtained.
  • tin may be substituted for indium in indium hydroxide, but may be co-precipitated with indium hydroxide as tin oxide and / or tin hydroxide.
  • the mixture is in the form of indium hydroxide and amorphous as tin hydroxide.
  • the particle diameter of the tin-containing indium hydroxide is determined in the step of obtaining a hydroxide.
  • the reaction temperature is in the range of 40 to 90 ° C.
  • the reaction time is in the range of 20 to 600 minutes
  • the final particle concentration is in the range of 0.01 to 3 mol / liter.
  • the reaction temperature is 60 ° C.
  • the reaction time The time required for total neutralization
  • the final particle concentration may be 0.5 mol / liter.
  • the reaction temperature may be set low, the reaction rate may be shortened, or the particle concentration may be increased.
  • the size of the finally produced polycrystalline ITO particles is substantially determined by the size of the tin-containing hydroxide. That is, when the tin-containing hydroxide changes to ITO particles, both the average length L and the average diameter D shrink about 70 to 80%.
  • this firing step is to generate ITO as an oxide from tin-containing indium hydroxide and to give oxygen deficiency to the resulting ITO crystals. Therefore, this firing step is performed in a weak reducing atmosphere in which an inert gas and a reducing gas are mixed to give oxygen deficiency to the ITO crystal.
  • a weak reducing atmosphere a mixed gas in which hydrogen, carbon monoxide, ammonia gas, or alcohol is mixed with an inert gas such as nitrogen, helium, or argon is used.
  • the mixing ratio of each gas in the mixed gas is appropriately determined by the amount of oxygen deficiency to be imparted to the ITO crystal. However, if the reducing power of the mixed gas is too strong, the tin-containing indium hydroxide becomes InO, metal In, or the like.
  • the mixing ratio of hydrogen, carbon monoxide, or the like is desirably set to such a concentration that the mixed gas does not exceed the explosion limit in the atmosphere.
  • the firing step firing is performed first, followed by reduction treatment.
  • the tin-containing indium hydroxide is dehydrated into indium oxide.
  • the firing temperature is 300 to 1000 ° C.
  • a complete oxide can be obtained at 300 ° C. or higher, and intense sintering between ITO particles can be avoided at 1000 ° C. or lower.
  • a preferable firing temperature is 350 to 800 ° C. or less.
  • the firing time may be 0.1 hours or longer, but is not necessary once the dehydration reaction is completed.
  • the atmosphere is air.
  • the reduction treatment after calcination is preferably performed at a temperature of 200 to 500 ° C. in the reducing atmosphere described above. If it is 200 degreeC or more, an oxygen deficiency can be provided, and if it is less than 500 degreeC, since an appropriate reduction power is obtained, insulating InO is not produced
  • the reduction treatment time is 0.5 to 5 hours. If it is less than 0.5 hours, oxygen deficiency is not sufficiently formed, and no significant change is observed even if it exceeds 5 hours.
  • a silicate ester or a silane coupling agent which is a surface treatment agent described later, is this OH. Since it is easy to couple
  • the polycrystalline ITO particles are surface-treated with a surface treatment agent.
  • a surface treatment agent comprising a silicate ester having 4 alkoxy groups having 2 or less carbon atoms or an oligomer of the silicate ester, or two or more alkoxy groups having 2 or less carbon atoms.
  • a surface treatment agent comprising a silane coupling agent having one or more alkyl groups of any one of a long-chain alkyl group or an alkyl group partially substituted with fluorine is used.
  • R, R 1 and R 2 are each an alkyl group.
  • the surface treatment agent comprising the silicate ester or the silicate ester oligomer
  • a structure in which a silicate ester or a silicate hydrolyzate is bonded to the surface of the polycrystalline ITO conductive film is obtained.
  • the surface treatment agent comprising the silane coupling agent a structure in which an amino group or a mercapto group is bonded to the surface of the polycrystalline ITO conductive film, or the surface of the polycrystalline ITO conductive film (an alkoxy group of the silane coupling agent).
  • Or sianol group generated by hydrolysis of alkoxy group
  • the bonding configuration between the hydroxyl group on the surface of the polycrystalline ITO conductive film and the surface treatment agent is via —OH on the surface of the ITO conductive film.
  • Examples of the silicic acid ester having four alkoxy groups having 2 or less carbon atoms include tetramethoxysilane (carbon number 1) or tetraethoxysilane (carbon number 2). Examples are silane (carbon number 1) trimer to pentamer or tetraethoxysilane (carbon number 2) trimer to pentamer.
  • a silane coupling agent having two or more alkoxy groups having 2 or less carbon atoms and one or more alkyl groups having an amino group or a mercapto group as a terminal group includes N-2- (aminoethyl) Examples are -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, or 3-mercaptopropyltrimethoxysilane.
  • silane coupling agent having two or more alkoxy groups having 2 or less carbon atoms and one or more long-chain alkyl groups having 6 or more carbon atoms
  • examples of the silane coupling agent having two or more alkoxy groups having 2 or less carbon atoms and one or more long-chain alkyl groups having 6 or more carbon atoms include hexyltrimethoxysilane and hexyltriethoxysilane. Or decyltrimethoxysilane.
  • trifluoropropyltrimethoxysilane is exemplified as the silane coupling agent having two or more alkoxy groups having 2 or less carbon atoms and one or more alkyl groups partially substituted with fluorine.
  • the silicate ester of the present invention is preferably one having a plurality of ester bonds that can easily form a network as SiO 2 after being bonded to the surface of the polycrystalline ITO particles.
  • Examples of the surface treatment furnace used for the surface treatment of the polycrystalline ITO particles include a batch type small rotary kiln (manufactured by Motoyama Co., Ltd .: inner diameter 70 mm ⁇ length 1000 mm) or a tubular furnace (inner diameter 100 mm ⁇ length 1200 mm).
  • the kiln is filled with a predetermined amount of polycrystalline ITO particles and preheated to a processing temperature as an inert gas (for example, nitrogen gas, argon gas) as a carrier gas.
  • an inert gas for example, nitrogen gas, argon gas
  • the kiln After flowing through 0.5 to 10 liters / minute for 60 to 300 minutes so as to have an inert atmosphere at the treatment temperature, the kiln is started, that is, the kiln is rotated at a rotational speed of 0.5 to 60 rpm. At the same time, the carrier gas containing the surface treatment agent vapor is circulated in the kiln by bubbling.
  • a metal tray containing a predetermined amount of polycrystalline ITO particles is placed in the tubular furnace, and after performing gas replacement in the same manner as in the case of using the kiln as a surface treatment furnace. The steam containing the surface treatment agent is circulated.
  • the conditions for surface treatment of polycrystalline ITO particles using the kiln or tubular furnace are as follows: the temperature of the carrier gas containing the surface treatment agent vapor (treatment temperature) is 10 to 150 ° C., preferably 50 to 120 ° C. the amount 10-1000 liters preferably 50 and ⁇ 250 liters, 1 ⁇ 10 0 ⁇ 1 ⁇ 10 6 ppm the concentration of the surface treatment agent contained in the carrier gas, preferably a 1 ⁇ 10 2 ⁇ 1 ⁇ 10 5 ppm To do.
  • the vapor pressure of the surface treatment agent is low when the treatment temperature is less than the lower limit value, the surface treatment does not proceed and the effect of suppressing the increase in resistance value of the target ITO conductive film under high temperature and high humidity is obtained.
  • the gas flow rate is set to 0.1 to 1 m / min.
  • the ITO powder (surface-treated polycrystalline ITO particles) is mixed so as to have a ratio of 1 to 70% by mass with respect to 100% by mass of the alcoholic solution of the dispersion medium, and stirred with a mixer. A coating for film formation is prepared.
  • the ITO powder dispersion medium include alcohol-based solutions such as ethanol, 2-butanol, and 1-propanol.
  • the ITO powder may be added and mixed in the range of 1 to 70% by mass with respect to 100% by mass of the alcoholic solution. If the amount is less than 1% by mass, it is difficult to form a film having a sufficient thickness on the conductive film.
  • the ITO conductive film forming coating material is put in a homogenizer, a bead mill pulverizer or the like, and the ITO powder in the coating material is pulverized. Furthermore, if necessary, a binder such as silica sol gel or acrylic resin can be added to the ITO conductive film forming paint within a range not deteriorating the resistance.
  • the ITO conductive film is manufactured as follows, for example.
  • a base material for forming the ITO conductive film is prepared in advance.
  • This base material is a first film such as polyethylene terephthalate (PET) coated with polyurethane on one side, and the surface of the first film not coated with polyurethane is coated on a glass substrate with a double-sided adhesive tape or the like.
  • PET polyethylene terephthalate
  • an ITO conductive film forming coating material is applied to a base material fixed on a glass substrate by a bar coating method, a die coating method, a doctor blade method, or the like, and then dried.
  • the base material coated with the ITO conductive film forming coating material is peeled off from the glass substrate, and a second film such as PET is superimposed on the surface of the base material on which the ITO conductive film forming coating material is applied.
  • a second film such as PET is superimposed on the surface of the base material on which the ITO conductive film forming coating material is applied.
  • Example 1 By the method described above, needle-like particles of tin-containing indium hydroxide having an average length L of polycrystalline ITO particles of 1 ⁇ m and an average diameter D of 0.2 ⁇ m were prepared.
  • the frequency of the ultrasonic wave described above is 34 kHz
  • the application time is 60 minutes
  • the salt of tin and indium is hydrochloride
  • the alkali is ammonia.
  • the resulting cake was dried at 110 ° C. Firing was performed in a nitrogen gas atmosphere at 600 ° C. for 3 hours.
  • the reduction treatment after firing was performed at 300 ° C. for 2 hours in a nitrogen gas atmosphere to which 3% by mass of hydrogen gas was added.
  • a batch type small rotary kiln (manufactured by Motoyama Co., Ltd .: inner diameter 70 mm ⁇ length 1000 mm) is filled with the polycrystalline ITO particles subjected to the firing and reduction treatment, and a carrier gas containing tetramethoxysilane vapor as a surface treatment agent is used.
  • the polycrystalline ITO particles were surface-treated by flowing through the kiln. Specifically, first, 500 g of polycrystalline ITO particles before surface treatment were filled in a kiln. Subsequently, nitrogen gas preheated to 100 ° C. was circulated for 60 minutes at a flow rate of 5 liters / minute as a carrier gas.
  • the inside of the kiln became an inert gas atmosphere (nitrogen gas atmosphere) at 80 ° C.
  • the kiln was rotated at a rotation speed of 2 rpm, and at the same time, the carrier gas containing the surface treatment agent vapor was circulated in the kiln by bubbling.
  • the total gas amount at this time was 1000 liters, and the concentration of tetramethoxysilane (surface treatment agent) contained in the carrier gas was about 100 ppm.
  • the gas flow rate was set to 1 m / min to prevent the polycrystalline ITO particles and the ITO powder from being rolled up. As a result, an ITO powder made of surface-treated polycrystalline ITO particles was obtained.
  • Example 2 Polycrystalline ITO particles after the firing and reduction treatment of Example 1 but before the surface treatment were filled in a tubular furnace (inner diameter 100 mm ⁇ length 1200 mm), and tetramethoxysilane 3 was used as a surface treatment agent.
  • the polycrystalline ITO particles were surface-treated by passing a carrier gas containing vapor of ⁇ 5-mer (tetramethoxysilane oligomer) through a tubular furnace. Specifically, after placing a metal tray containing 500 g of polycrystalline ITO particles before surface treatment in a tubular furnace and performing gas replacement as in the case of using a kiln as the surface treatment furnace of Example 1.
  • a vapor containing tetramethoxysilane trimer to pentamer (tetramethoxysilane oligomer) was circulated as a surface treatment agent.
  • the treatment conditions at this time are as follows: gas temperature (treatment temperature) is 80 ° C., total gas amount is 100 liters, and the concentration of tetramethoxysilane trimer to pentamer (surface treatment agent) contained in the carrier gas is 50 ppm. did.
  • gas temperature treatment temperature
  • total gas amount is 100 liters
  • concentration of tetramethoxysilane trimer to pentamer (surface treatment agent) contained in the carrier gas is 50 ppm. did.
  • an ITO powder made of surface-treated polycrystalline ITO particles was obtained.
  • Example 3 Example except that tetraethoxysilane was used as a surface treatment agent instead of tetramethoxysilane in Example 1 and that the tubular path of Example 2 was used instead of the batch type small rotary kiln in Example 1. In the same manner as in Example 1, an ITO powder comprising surface-treated polycrystalline ITO particles was obtained.
  • Example 4 In place of the tetramethoxysilane of Example 1, tetraethoxysilane trimer to pentamer (tetraethoxysilane oligomer) was used as a surface treatment agent, and the batch type small rotary kiln of Example 1 was used instead of Example 1. An ITO powder made of surface-treated polycrystalline ITO particles was obtained in the same manner as in Example 1 except that 2 tubular paths were used.
  • Example 5 Surface treatment was carried out in the same manner as in Example 1 except that N-2- (aminoethyl) -3-aminopropyltrimethoxysilane was used as a surface treatment agent instead of tetramethoxysilane in Example 1. An ITO powder composed of polycrystalline ITO particles was obtained.
  • Example 6> Instead of tetramethoxysilane of Example 1, 3-aminopropyltrimethoxysilane was used as a surface treatment agent, and the tubular path of Example 2 was used instead of the batch type small rotary kiln of Example 1. Obtained ITO powder made of surface-treated polycrystalline ITO particles in the same manner as in Example 1.
  • Example 7 An ITO powder made of surface-treated polycrystalline ITO particles was prepared in the same manner as in Example 1 except that 3-mercaptopropylmethyldimethoxysilane was used as the surface treatment agent instead of tetramethoxysilane in Example 1. Obtained.
  • Example 8 An ITO powder made of surface-treated polycrystalline ITO particles was prepared in the same manner as in Example 1 except that 3-mercaptopropyltrimethoxysilane was used as the surface treatment agent instead of tetramethoxysilane in Example 1. Obtained.
  • Example 9 Aside from using the trifluoropropyltrimethoxysilane as a surface treatment agent in place of the tetramethoxysilane of Example 1 and using the tubular path of Example 2 instead of the batch type small rotary kiln of Example 1. In the same manner as in Example 1, an ITO powder comprising surface-treated polycrystalline ITO particles was obtained.
  • Example 10 An ITO powder composed of surface-treated polycrystalline ITO particles was obtained in the same manner as in Example 1 except that hexyltrimethoxysilane was used as the surface treatment agent instead of tetramethoxysilane in Example 1.
  • Example 11 In place of using the decyltrimethoxysilane as a surface treatment agent instead of the tetramethoxysilane of Example 1, and using the tubular path of Example 2 instead of the batch type small rotary kiln of Example 1. In the same manner as in Example 1, an ITO powder comprising surface-treated polycrystalline ITO particles was obtained.
  • Example 12 An ITO powder composed of surface-treated polycrystalline ITO particles was obtained in the same manner as in Example 1 except that hexyltriethoxysilane was used as the surface treating agent instead of tetramethoxysilane in Example 1.
  • Example 3 An ITO powder made of surface-treated polycrystalline ITO particles was obtained in the same manner as in Example 1, except that p-styrylmethoxysilane was used as the surface treatment agent instead of tetramethoxysilane in Example 1. .
  • Example 4 Instead of tetramethoxysilane in Example 1, hexamethyldisilazane was used as a surface treatment agent, and in place of the batch type small rotary kiln in Example 1, except that the tubular path in Example 2 was used. In the same manner as in Example 1, an ITO powder comprising surface-treated polycrystalline ITO particles was obtained.
  • Example 5 An ITO powder composed of surface-treated polycrystalline ITO particles was obtained in the same manner as in Example 1 except that phenyltrimethoxysilane was used as the surface treatment agent instead of tetramethoxysilane in Example 1.
  • Example 6 Example except that dimethyldimethoxysilane was used as a surface treating agent instead of tetramethoxysilane in Example 1 and that the tubular path of Example 2 was used in place of the batch-type small rotary kiln in Example 1. In the same manner as in Example 1, an ITO powder comprising surface-treated polycrystalline ITO particles was obtained.
  • a coating for forming an ITO conductive film was prepared using the ITO powder comprising the surface-treated polycrystalline ITO particles of Examples 1 to 12 and Comparative Examples 1 to 6, and an ITO conductive film was formed on the PET film using this coating. Formed. Specifically, 2 g of ITO powder composed of the above-mentioned surface-treated polycrystalline ITO particles is added to 6 g of ethanol as a dispersion medium, and dispersed for 30 minutes with an ultrasonic homogenizer to prepare a paint for forming an ITO conductive film. did.
  • This ITO conductive film forming coating is formed on a PET film by a bar coating method in accordance with the method for producing a transparent conductive film described above, and pressure is applied to this film at a roll pressure of 700 kg / cm and a delivery speed of 30 cm / min.
  • a roll pressure of 700 kg / cm and a delivery speed of 30 cm / min thus, an ITO conductive film was obtained.
  • the initial electrical resistance value and the electrical resistance value after humidification were measured for every film
  • the electric resistance value after humidification is reduced to 2152 to 7477 ⁇ / sq, and the rate of change from the initial electric resistance value to the electric resistance value after humidification is reduced to 5.1 to 9.8 times. It was.
  • ITO composed of polycrystalline ITO particles surface-treated by a surface treatment agent comprising a silicate ester having four alkoxy groups having 2 or less carbon atoms or a surface treatment agent comprising an oligomer of these silicate esters. It has been found that when an ITO conductive film is formed using powder, the electrical resistance value after humidification is relatively low and the increase in electrical resistance value can be sufficiently suppressed even under high temperature and high humidity.
  • the surface treatment is performed by the surface treatment agent comprising a silane coupling agent having at least two alkoxy groups having 2 or less carbon atoms and at least one alkyl group having an amino group or a mercapto group as a terminal group.
  • the surface treatment agent comprising a silane coupling agent having at least two alkoxy groups having 2 or less carbon atoms and at least one alkyl group having an amino group or a mercapto group as a terminal group.
  • the surface treatment was performed with vinyltrimethoxysilane, p-styrylmethoxysilane, phenyltrimethoxysilane, and dimethyldimethoxysilane having no long-chain alkyl group having 6 or more carbon atoms.
  • Comparative Examples 2, 3, 5 and 6 in which an ITO conductive film was formed using ITO powder made of crystalline ITO particles the electric resistance value after humidification increased from 12233 to 18753 ⁇ / sq, and the electric resistance after humidification was increased from the initial electric resistance value. The rate of change to the resistance value increased from 25.7 to 60.3 times.
  • ITO conductive using ITO powder composed of polycrystalline ITO particles surface-treated with hexyltrimethoxysilane, decyltrimethoxysilane, and hexyltriethoxysilane having a long-chain alkyl group having 6 or more carbon atoms.
  • the electric resistance value after humidification was reduced to 1393 to 1937 ⁇ / sq, and the rate of change from the initial electric resistance value to the electric resistance value after humidification was 3.6 to 4.1 times. It has become smaller.
  • the surface treatment is performed by the surface treatment agent comprising a silane coupling agent having two or more alkoxy groups having 2 or less carbon atoms and one or more long-chain alkyl groups having 6 or more carbon atoms.
  • the surface treatment agent comprising a silane coupling agent having two or more alkoxy groups having 2 or less carbon atoms and one or more long-chain alkyl groups having 6 or more carbon atoms.
  • an ITO conductive film was formed using ITO powder made of polycrystalline ITO particles surface-treated with trifluoropropyltrimethoxysilane having an alkyl group partially substituted with fluorine.
  • the electric resistance value after humidification was reduced to 1407 ⁇ / sq, and the rate of change from the initial electric resistance value to the electric resistance value after humidification was reduced to 3.1 times.
  • the surface treatment with the surface treatment agent comprising a silane coupling agent having two or more alkoxy groups having 2 or less carbon atoms and one or more alkyl groups partially substituted with fluorine is performed. It was found that when an ITO conductive film is formed using ITO powder composed of crystalline ITO particles, the electrical resistance value is relatively low after humidification, and the increase in electrical resistance value can be sufficiently suppressed even under high temperature and high humidity. .

Abstract

ITO particles comprise polycrystalline ITO particles, each of which has a surface treated with a surface-treating agent that comprises a silicic acid ester having four alkoxy groups each having 2 or less carbon atoms or an oligomer of the silicic acid ester or a surface-treating agent that comprises a silane coupling agent having at least two alkoxy groups each having 2 or less carbon atoms and also having at least one alkyl group selected from an alkyl group having an amino group or a mercapto group as an terminal group, a long-chain alkyl group having 6 or more carbon atoms and an alkyl group partially substituted by fluorine atoms.

Description

ＩＴＯ粉末及びその製造方法ITO powder and method for producing the same
　本発明は、高温高湿下においてＩＴＯ導電膜の電気抵抗値の上昇を抑制し得るＩＴＯ導電膜を形成するためのＩＴＯ粉末と、このＩＴＯ粉末の製造方法に関する。本明細書において、ＩＴＯとはインジウム錫酸化物(Indium Tin Oxide)をいう。
　本願は、２０１３年９月３０日に、日本に出願された特願２０１３－２０５０７１号に基づき優先権を主張し、その内容をここに援用する。 The present invention relates to an ITO powder for forming an ITO conductive film capable of suppressing an increase in electrical resistance value of an ITO conductive film under high temperature and high humidity, and a method for producing the ITO powder. In this specification, ITO refers to indium tin oxide.
This application claims priority based on Japanese Patent Application No. 2013-205071 filed in Japan on September 30, 2013, the contents of which are incorporated herein by reference.
　ＬＣＤ(Liquid Crystal Display)やＰＤＰ(Plasma Display Panel)、有機ＥＬ(ElectroLuminescence)、タッチパネル等の表示装置には、透明電極が用いられている。この透明電極は、ＩＴＯ等からなる透明導電材料によって構成されることが多い。このような透明電極は、通常スパッタリング法などで膜状に形成される（例えば、特許文献１参照）。しかしながらスパッタリング装置は高価であり、かつ、成膜の効率が悪く、また、その膜はひび割れし易い等の問題がある。このひび割れの起こりにくい屈曲性に優れたＩＴＯ導電膜を形成する方法として、スパッタリング法に代わって、ＩＴＯ導電膜形成用塗料を基板に塗布する方法が提案されている。しかしながら、塗布方式で得られた透明電極は、高温高湿下におかれると、雰囲気中の酸素や水分に起因して電気抵抗値が上昇する傾向にあり、これが信頼性を低下させる一因となっていた。 Transparent electrodes are used in display devices such as LCD (Liquid Crystal Display), PDP (Plasma Display Panel), organic EL (ElectroLuminescence), and touch panel. This transparent electrode is often composed of a transparent conductive material made of ITO or the like. Such a transparent electrode is usually formed into a film by a sputtering method or the like (see, for example, Patent Document 1). However, the sputtering apparatus is expensive and has a problem that the film formation efficiency is low and the film is easily cracked. As a method of forming an ITO conductive film excellent in flexibility, which is less prone to cracking, a method of applying an ITO conductive film forming coating to a substrate instead of the sputtering method has been proposed. However, when the transparent electrode obtained by the coating method is placed under high temperature and high humidity, the electrical resistance value tends to increase due to oxygen and moisture in the atmosphere. It was.
  この問題を解決するために、塗布方式によるＩＴＯ導電膜形成用塗料として、耐水性を有するＩＴＯ粉末のような導電粉の表面を表面処理剤で処理してなる表面処理導電粉と硬化性化合物を含む透明導電材料（例えば、特許文献２参照。）や、樹脂とＩＴＯ粉末のような透明導電粒子とシリカ材料とシランカップリング剤とを含有する透明導電材料（例えば、特許文献３参照）が提案されている。 In order to solve this problem, as a coating for forming an ITO conductive film by a coating method, a surface-treated conductive powder and a curable compound obtained by treating the surface of a conductive powder such as ITO powder having water resistance with a surface treatment agent Proposed transparent conductive material (for example, see Patent Document 2) and transparent conductive material containing transparent conductive particles such as resin, ITO powder, silica material, and silane coupling agent (for example, see Patent Document 3) Has been.
特開２００４－３１５９５１号公報（段落［０００２］）JP 2004-315951 A (paragraph [0002]) 特開２００６－５９７７２号公報（要約、請求項１）JP 2006-59772 A (summary, claim 1) 特開２００９－１３５０４４号公報（要約、請求項１）JP 2009-135044 (Abstract, Claim 1)
　上記特許文献２及び３に示される透明導電材料により形成されたＩＴＯ導電膜の透明電極は、高温高湿下であっても水分の影響による電気抵抗値の上昇を抑制することが可能である。
　ここで示す従来の高温高湿下とは、例えば、温度６０℃、湿度９５％ＲＨ、７５０時間等である。
　しかしながら、近年では、透明電極の用途が一層多岐にわたっており、従来にも増して厳しい条件下であっても、高温高湿下における透明電極の電気抵抗値の上昇を抑制できる、ＩＴＯ導電膜を形成するためのＩＴＯ粒子が求められている。 The transparent electrode of the ITO conductive film formed of the transparent conductive material disclosed in Patent Documents 2 and 3 can suppress an increase in electrical resistance value due to the influence of moisture even under high temperature and high humidity.
The conventional high temperature and high humidity shown here is, for example, a temperature of 60 ° C., a humidity of 95% RH, and 750 hours.
However, in recent years, the use of transparent electrodes has become more diverse, and it has formed an ITO conductive film that can suppress an increase in the electrical resistance value of transparent electrodes under high temperature and high humidity even under severer conditions than before. There is a need for ITO particles for this purpose.
　本発明の目的は、従来にも増して厳しい条件下であっても、高温高湿下における電気抵抗値の上昇を抑制可能な透明電極であるＩＴＯ導電膜を形成することができる、ＩＴＯ粉末及びその製造方法を提供することにある。 An object of the present invention is to provide an ITO powder capable of forming an ITO conductive film which is a transparent electrode capable of suppressing an increase in electrical resistance value under high temperature and high humidity even under severer conditions than before, It is in providing the manufacturing method.
　本発明の第１の観点は、炭素数が２以下であるアルコキシ基を４つ有する珪酸エステル又はこの珪酸エステルのオリゴマー体からなる表面処理剤により、或いは炭素数が２以下であるアルコキシ基を２つ以上有し、かつアミノ基若しくはメルカプト基を末端基に有するアルキル基、炭素数が６以上である長鎖のアルキル基、又は一部がフッ素で置換されたアルキル基のいずれか１種のアルキル基を１つ以上有するシランカップリング剤からなる表面処理剤により、表面処理された多結晶ＩＴＯ粒子からなるＩＴＯ粉末である。 According to a first aspect of the present invention, a surface treatment agent comprising a silicate ester having 4 alkoxy groups having 2 or less carbon atoms or an oligomer of the silicate ester, or 2 alkoxy groups having 2 or less carbon atoms. An alkyl group having at least one amino group or mercapto group as a terminal group, a long-chain alkyl group having 6 or more carbon atoms, or an alkyl group partially substituted with fluorine. It is an ITO powder composed of polycrystalline ITO particles that have been surface treated with a surface treatment agent comprising a silane coupling agent having one or more groups.
　本発明の第２の観点は、第１の観点に基づく発明であって、更に珪酸エステルが、炭素数が１であるアルキル基を有するテトラメトキシシラン、又は炭素数が２であるアルキル基を有するテトラエトキシシランである。 2nd viewpoint of this invention is invention based on 1st viewpoint, Comprising: Silicate ester has tetramethoxysilane which has a C1-C1 alkyl group, or C2-C2 alkyl group. Tetraethoxysilane.
　本発明の第３の観点は、第１の観点に基づく発明であって、更にシランカップリング剤が、Ｎ－２－(アミノエチル)－３－アミノプロピルトリメトキシシラン、３－アミノプロピルトリメトキシシラン、３－メルカプトプロピルメチルジメトキシシラン、３－メルカプトプロピルトリメトキシシラン、トリフルオロプロピルトリメトキシシラン、ヘキシルトリメトキシシラン、ヘキシルトリエトキシシラン、及びデシルトリメトキシシランからなる群より選択される何れか一つである。 A third aspect of the present invention is the invention based on the first aspect, wherein the silane coupling agent is N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxy. Any one selected from the group consisting of silane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, trifluoropropyltrimethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, and decyltrimethoxysilane. One.
　本発明の第４の観点は、第１ないし第３の観点のいずれか１つの観点に記載のＩＴＯ粉末の表面処理剤の蒸気を不活性ガスからなるキャリアガスに含ませて、多結晶ＩＴＯ粒子を充填したロータリキルン内に流通させることにより前記多結晶ＩＴＯ粒子を前記表面処理剤で表面処理するＩＴＯ粉末の製造方法であることを特徴とする。 According to a fourth aspect of the present invention, polycrystalline ITO particles are obtained by including the vapor of the surface treatment agent for ITO powder according to any one of the first to third aspects in a carrier gas composed of an inert gas. It is characterized by being the manufacturing method of the ITO powder which surface-treats the said polycrystal ITO particle with the said surface treating agent by distribute | circulating in the rotary kiln filled with.
　本発明の第５の観点は、第１ないし第３の観点のいずれか１つの観点に記載のＩＴＯ粉末の表面処理剤の蒸気を不活性ガスからなるキャリアガスに含ませて、多結晶ＩＴＯ粒子を充填した管状炉内に流通させることにより前記多結晶ＩＴＯ粒子を前記表面処理剤で表面処理するＩＴＯ粉末の製造方法であることを特徴とする。 According to a fifth aspect of the present invention, polycrystalline ITO particles are obtained by including the surface treatment agent vapor of the ITO powder according to any one of the first to third aspects in a carrier gas composed of an inert gas. It is characterized by being the manufacturing method of the ITO powder which surface-treats the said polycrystal ITO particle with the said surface treating agent by distribute | circulating in the tubular furnace filled with.
　本発明の第６の観点は、第１ないし第３の観点のいずれか１つの観点に記載のＩＴＯ粉末と分散媒とを含み、分散媒がアルコール系溶液であるＩＴＯ導電膜形成用塗料であることを特徴とする。 According to a sixth aspect of the present invention, there is provided an ITO conductive film forming coating material comprising the ITO powder according to any one of the first to third aspects and a dispersion medium, wherein the dispersion medium is an alcoholic solution. It is characterized by that.
　本発明の第７の観点は、第６の観点に記載されたＩＴＯ導電膜形成用塗料を用いてＩＴＯ導電膜を形成する方法であることを特徴とする。 A seventh aspect of the present invention is a method for forming an ITO conductive film using the ITO conductive film forming paint described in the sixth aspect.
　元来、ＩＴＯの主たる構成要素であるＩｎ２Ｏ３は、Bixbyite構造をなし、蛍石構造から規則的に酸素が抜けた構造と表現できる。この構造はドーパントであるＳｎの量が増えるなどすると、格子間に酸素を取り込みやすい構造になっている。このためＩＴＯ粉末が高温高湿下におかれると、粉末表面に吸着した水がＩＴＯ粉末表面の酸素空孔や格子間に、－ＯＨとして結合し、キャリア電子をトラップすることから、ＩＴＯ粉末の導電性を低下させる。 Originally, the main component of ITO, In 2 O 3, has a Bixbyite structure, and can be expressed as a structure in which oxygen is regularly removed from the fluorite structure. This structure has a structure in which oxygen is easily taken in between lattices when the amount of Sn as a dopant is increased. For this reason, when ITO powder is placed under high temperature and high humidity, water adsorbed on the powder surface binds as —OH between oxygen vacancies and lattices on the ITO powder surface and traps carrier electrons. Reduces electrical conductivity.
　本発明の第１の観点のＩＴＯ粉末は、上述した特定の表面処理剤で処理される。表面処理剤が上記珪酸エステルの場合には、多結晶ＩＴＯ粒子表面の酸素空孔や格子間に珪酸エステルが結合することで、水に対する安定性が大幅に改善されると考えられる。また上記シランカップリング剤の場合には、上記多結晶ＩＴＯ粒子表面の酸素空孔や格子間にアミノ基若しくはメルカプト基などが結合することで、水に対する安定性が大幅に改善されると考えられる。また、ＩＴＯの表面には、既に粒子表面に－ＯＨが存在する。即ち、ＩＴＯ粉末を構成する多結晶ＩＴＯ粒子表面に－ＯＨが存在する。この－ＯＨに上記珪酸エステル又は上記シランカップリング剤が結合することによって、トラップされた電子が開放され、導電性が向上する効果も得られる。この結果、本発明のＩＴＯ粉末を用いて形成されるＩＴＯ導電膜の高温高湿下における電気抵抗値の上昇を抑制することができる。 The ITO powder according to the first aspect of the present invention is treated with the specific surface treatment agent described above. In the case where the surface treatment agent is the silicate ester, it is considered that the stability to water is greatly improved by bonding the silicate ester between oxygen vacancies and lattices on the surface of the polycrystalline ITO particles. In the case of the silane coupling agent, it is considered that the stability to water is greatly improved by bonding an amino group or a mercapto group between oxygen vacancies and lattices on the surface of the polycrystalline ITO particles. . Further, on the surface of ITO, —OH already exists on the particle surface. That is, —OH exists on the surface of the polycrystalline ITO particles constituting the ITO powder. By bonding the silicate ester or the silane coupling agent to this —OH, the trapped electrons are released, and the effect of improving the conductivity is also obtained. As a result, an increase in electrical resistance value of the ITO conductive film formed using the ITO powder of the present invention under high temperature and high humidity can be suppressed.
　本発明の第２の観点のＩＴＯ粉末では、珪酸エステルとして、炭素数が１であるアルキル基を有するテトラメトキシシラン、又は炭素数が２であるアルキル基を有するテトラエトキシシランを選択する。これら珪酸エステルは、炭素数が小さいため、反応性が高くなる。この結果、珪酸エステルが多結晶ＩＴＯ粒子表面に結合し易くなる。 In the ITO powder of the second aspect of the present invention, tetramethoxysilane having an alkyl group having 1 carbon atom or tetraethoxysilane having an alkyl group having 2 carbon atoms is selected as the silicate ester. Since these silicate esters have a small number of carbon atoms, the reactivity increases. As a result, the silicate is easily bonded to the surface of the polycrystalline ITO particles.
　本発明の第３の観点のＩＴＯ粉末では、シランカップリング剤として、Ｎ－２－(アミノエチル)－３－アミノプロピルトリメトキシシラン、３－アミノプロピルトリメトキシシラン、３－メルカプトプロピルメチルジメトキシシラン、３－メルカプトプロピルトリメトキシシラン、トリフルオロプロピルトリメトキシシラン、ヘキシルトリメトキシシラン、ヘキシルトリエトキシシラン、及びデシルトリメトキシシランからなる群より選択される何れか一つを選択する。これらのシランカップリング剤は、末端基の持つ立体障害や極性のため、多結晶ＩＴＯ粒子表面にＨ２Ｏが接近することを阻害する効果がある。 In the ITO powder of the third aspect of the present invention, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane is used as a silane coupling agent. Any one selected from the group consisting of 3-mercaptopropyltrimethoxysilane, trifluoropropyltrimethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, and decyltrimethoxysilane. These silane coupling agents have an effect of inhibiting H 2 O from approaching the surface of the polycrystalline ITO particles because of the steric hindrance and polarity of the end groups.
　本発明の第６の観点の塗料を用いてＩＴＯ導電膜を形成すると、このＩＴＯ導電膜の高温高湿下における電気抵抗値の上昇を抑制することができる。 When an ITO conductive film is formed using the paint according to the sixth aspect of the present invention, an increase in electrical resistance value of the ITO conductive film under high temperature and high humidity can be suppressed.
　本発明の第７の観点の方法で形成されたＩＴＯ導電膜は、高温高湿下における電気抵抗値の上昇を抑制することができる。 The ITO conductive film formed by the method of the seventh aspect of the present invention can suppress an increase in electrical resistance value under high temperature and high humidity.
本発明のＩＴＯ粉末の多結晶ＩＴＯ粒子の模式斜視図である。It is a model perspective view of the polycrystalline ITO particle | grains of the ITO powder of this invention. 本発明のＩＴＯ粉末の多結晶ＩＴＯ粒子の模式断面図である。It is a schematic cross section of the polycrystalline ITO particles of the ITO powder of the present invention. 本発明の多結晶ＩＴＯ粒子、ＩＴＯ粉末の一形態をＴＥＭによって撮像した１００００倍の写真図である。It is a 10,000 times photograph figure which imaged one form of the polycrystalline ITO particle of the present invention, and ITO powder by TEM. 本発明の多結晶ＩＴＯ粒子、ＩＴＯ粉末の一形態をＴＥＭによって撮像した５００００倍の写真図である。It is a 50000 times photograph figure which imaged one form of the polycrystalline ITO particle of the present invention, and ITO powder by TEM.
　次に本発明を実施するための形態を図面に基づいて説明する。 Next, modes for carrying out the present invention will be described with reference to the drawings.
　＜ＩＴＯ粉末＞
　図１Ａ及び図１Ｂに模式的に示されているように、本発明のＩＴＯ粉末は、表面処理剤で表面処理された多結晶ＩＴＯ粒子１０からなる。多結晶ＩＴＯ粒子１０は、棒状中心核１１と複数の棒状体１２からなり、棒状中心核１１の長手方向に基本的に同じ向きに沿って棒状中心核１１を囲むようにして棒状体１２と一体的に形成されている。更に図２Ａ及び図２Ｂの写真図に示すように、多結晶ＩＴＯ粒子では、複数の短い棒状体が小枝のように観察され、これらの短い棒状体が棒状中心核の周囲を囲みながら互いに隣接し合いながら同様の方向に並んで棒状中心核に固着していることが観察される。なお、図２Ａ及び図２Ｂに示すように複数の棒状体のそれぞれの径及び長さは必ずしも同一である必要はなく、その断面形状、表面形状も必ずしも同一である必要はない。 <ITO powder>
As schematically shown in FIGS. 1A and 1B, the ITO powder of the present invention comprises polycrystalline ITO particles 10 surface-treated with a surface treatment agent. The polycrystalline ITO particles 10 are composed of a rod-shaped central core 11 and a plurality of rod-shaped bodies 12, and are integrally formed with the rod-shaped body 12 so as to surround the rod-shaped central core 11 along the same direction in the longitudinal direction of the rod-shaped central core 11. Is formed. 2A and 2B, in the polycrystalline ITO particles, a plurality of short rods are observed as twigs, and these short rods are adjacent to each other while surrounding the rod-shaped central core. It is observed that they stick to the rod-shaped central core side by side in the same direction. As shown in FIGS. 2A and 2B, the diameters and lengths of the plurality of rod-shaped bodies are not necessarily the same, and the cross-sectional shape and the surface shape are not necessarily the same.
　図１Ａで示される、上記多結晶ＩＴＯ粒子１０の棒状中心核１２の長手方向の平均長さＬは、０．２～５．０μｍ、好ましくは１．０～５．０μｍの範囲にある。図１Ａ及び図１Ｂで示される、多結晶ＩＴＯ粒子１０の前記長手方向に対して垂直な方向の断面における平均直径をＤとするとき、Ｌ／Ｄが２～２０、好ましくは３～１０の範囲にある。Ｌは０．２μｍ未満では、ＩＴＯ導電膜を形成する基板面に対して垂直に立ち易くなり、ラグビーボールのように倒れやすい効果が得られない。Ｌが５．０μｍを越えると、粒子同士のパッキングが悪くなる。またＬ／Ｄが２未満では異方性による導電性向上の効果が得られず、２０を越えると塗膜作製時に棒状粒子が破断し、短くなってしまうという不具合を生じる。 1A, the average length L in the longitudinal direction of the rod-shaped central core 12 of the polycrystalline ITO particle 10 is in the range of 0.2 to 5.0 μm, preferably 1.0 to 5.0 μm. When the average diameter in the cross section perpendicular to the longitudinal direction of the polycrystalline ITO particles 10 shown in FIGS. 1A and 1B is D, L / D is in the range of 2 to 20, preferably 3 to 10. It is in. When L is less than 0.2 μm, it becomes easy to stand perpendicular to the substrate surface on which the ITO conductive film is formed, and the effect of being easily overturned like a rugby ball cannot be obtained. When L exceeds 5.0 μm, the packing between the particles is deteriorated. If L / D is less than 2, the effect of improving conductivity due to anisotropy cannot be obtained. If L / D is more than 20, the rod-like particles are broken and shortened when the coating film is produced.
　本発明のＩＴＯ粉末の多結晶ＩＴＯ粒子は、上記の形状を持つため、例えば上記多結晶ＩＴＯ粒子を用いて塗布型ＩＴＯフィルムを製造すると、樹脂フィルムに当該ＩＴＯ粉末を含む塗料を塗布したときや、前記塗料の塗布面を加圧したときに、多結晶ＩＴＯ粒子が塗布方向に沿って樹脂フィルム面に配向し易い。即ち、多結晶ＩＴＯ粒子は樹脂フィルム面に転がって横たわり易い。また、本発明のＩＴＯ粒子は多結晶であるため、粒界で適度なずれが生じる。その結果、粒子間の空隙が充填され易くなり、多結晶ＩＴＯ粒子間が密になる。従って、本発明のＩＴＯ粒子を透明電極等の材料に用いたときに、より透明電極等の電気抵抗を下げ、良好な導電性が得られる。またそればかりでなく、多結晶ＩＴＯ粒子間が充填される結果、当該ＩＴＯ粉末を含む塗料を透明基板やフィルム上に塗布したとき塗布層が緻密組織になり、これにより薄膜太陽電池の受光面やオプティカルデバイスの透明電極等の光透過率を良好とし、かつヘーズを低下させることができる。 Since the polycrystalline ITO particles of the ITO powder of the present invention have the above-mentioned shape, for example, when a coating-type ITO film is produced using the polycrystalline ITO particles, when a paint containing the ITO powder is applied to a resin film, When the coating surface of the paint is pressed, the polycrystalline ITO particles are easily oriented on the resin film surface along the coating direction. That is, the polycrystalline ITO particles are liable to roll and lie on the resin film surface. Moreover, since the ITO particles of the present invention are polycrystalline, an appropriate shift occurs at the grain boundary. As a result, voids between the particles are easily filled, and the polycrystalline ITO particles are dense. Therefore, when the ITO particles of the present invention are used for a material such as a transparent electrode, the electrical resistance of the transparent electrode or the like can be further reduced, and good conductivity can be obtained. In addition, as a result of filling the space between the polycrystalline ITO particles, when the paint containing the ITO powder is applied on a transparent substrate or film, the coating layer becomes a dense structure. The light transmittance of the transparent electrode or the like of the optical device can be improved, and the haze can be reduced.
　＜ＩＴＯ粉末の製造方法＞
　先ず、第１の工程として、スズ塩とインジウム塩とを所定の割合で秤量混合し、当該混合物を純水に溶解してスズ塩とインジウム塩との混合溶液とし、当該混合溶液とアルカリとを反応させて、スズ含有水酸化インジウムの懸濁液を生成させる。混合の方法としては、スズ塩とインジウム塩との混合水溶液へ、アンモニア等のアルカリを添加して反応させる方法が好ましい。スズ塩とインジウム塩との混合水溶液へ、アルカリを添加すると、異方性粒子が生成し易い上に、アルカリ添加の際の温度、添加速度及び／又は粒子濃度を制御することによって、生成する水酸化物粒子の大きさや軸比を制御できる。 <Production method of ITO powder>
First, as a first step, a tin salt and an indium salt are weighed and mixed at a predetermined ratio, the mixture is dissolved in pure water to obtain a mixed solution of a tin salt and an indium salt, and the mixed solution and an alkali are mixed. React to produce a suspension of tin-containing indium hydroxide. As a mixing method, a method of adding an alkali such as ammonia to a mixed aqueous solution of a tin salt and an indium salt and reacting them is preferable. When an alkali is added to a mixed aqueous solution of a tin salt and an indium salt, anisotropic particles are likely to be generated, and the generated water is controlled by controlling the temperature, the addition rate and / or the particle concentration during the addition of the alkali. The size and axial ratio of the oxide particles can be controlled.
　更に、本発明では、所定周波数の超音波を混合中の上記反応液に照射する。この超音波の付与により、ＩＴＯ棒状中心核の周囲にこのＩＴＯ棒状中心核より短い複数のＩＴＯ棒状体が、ＩＴＯ棒状中心核の長手方向と同様の向きに沿いかつＩＴＯ棒状中心核を囲むように一体的に形成された多結晶ＩＴＯ粒子からなるＩＴＯ粉末を製造することができる。超音波の周波数は２０～１００００ｋＨｚとする。周波数が、２０ｋＨｚ未満では超音波の攪拌効果が弱く、一方、１００００ｋＨｚを越えると超音波の出力が落ちて、十分な効果が得られない。周波数は更に２０～１０００ｋＨｚとすることが好ましい。 Furthermore, in the present invention, the reaction liquid being mixed is irradiated with ultrasonic waves having a predetermined frequency. By applying this ultrasonic wave, a plurality of ITO rods shorter than the ITO rod-shaped central core are arranged around the ITO rod-shaped central core along the same direction as the longitudinal direction of the ITO rod-shaped central core and surround the ITO rod-shaped central core. An ITO powder composed of integrally formed polycrystalline ITO particles can be produced. The frequency of the ultrasonic wave is 20 to 10,000 kHz. If the frequency is less than 20 kHz, the ultrasonic stirring effect is weak. On the other hand, if it exceeds 10,000 kHz, the output of the ultrasonic wave is lowered and a sufficient effect cannot be obtained. The frequency is further preferably 20 to 1000 kHz.
　超音波を上記の懸濁液に付与する所定時間は、周波数や中和液の容量等によって適宜調整する必要がある。例えば、超音波の周波数が１００ｋＨｚのときで、反応液の容量が１Ｌのときには超音波を照射しながら、アルカリを滴下する時間は、２０～６００分が好ましい。超音波の付与時間は短すぎると、超音波照射の効果が十分に得られない不具合があり、長すぎると、粒子が長くなりすぎる不具合がある。超音波が反応液に均一に付与されるように、反応液の液面は超音波照射装置の液面（照射装置から反応器へ超音波を伝える媒体）と同一になるようにする。この超音波の付与によって、異方性ＩＴＯ粒子の単体同士の凝集を防ぐと同時に、ＩＴＯ棒状中心核の周囲に中心核より短い複数のＩＴＯ棒状体が、ＩＴＯ棒状中心核の長手方向と同様の向きに沿いかつＩＴＯ棒状中心核を囲むように固着された多結晶ＩＴＯ粒子を得ることができる。 It is necessary to appropriately adjust the predetermined time for applying the ultrasonic wave to the suspension according to the frequency, the volume of the neutralizing solution, and the like. For example, when the frequency of the ultrasonic wave is 100 kHz and the volume of the reaction solution is 1 L, the time for dropping the alkali while irradiating the ultrasonic wave is preferably 20 to 600 minutes. If the application time of the ultrasonic wave is too short, there is a problem that the effect of ultrasonic irradiation cannot be sufficiently obtained, and if it is too long, there is a problem that the particles become too long. The liquid level of the reaction liquid is set to be the same as the liquid level of the ultrasonic irradiation apparatus (medium for transmitting ultrasonic waves from the irradiation apparatus to the reactor) so that the ultrasonic waves are uniformly applied to the reaction liquid. By applying this ultrasonic wave, agglomeration of single pieces of anisotropic ITO particles is prevented, and at the same time, a plurality of ITO rods shorter than the central core around the ITO rod central core are the same as the longitudinal direction of the ITO rod central core. Polycrystalline ITO particles fixed along the direction and surrounding the ITO rod-like central core can be obtained.
　ここで、スズ及びインジウムの塩としては、塩酸塩、硫酸塩、又は硝酸塩などがあるが、一般的には塩酸塩が好ましい。また、アルカリとしては、アンモニア、苛性ソーダ、苛性カリ、又はそれらの炭酸塩が用いられるが、スズ含有水酸化インジウムのスラリー生成後における不純物を削減する観点からアンモニアを用いることが好ましい。 Here, as the salt of tin and indium, there are hydrochloride, sulfate, nitrate, etc., but hydrochloride is generally preferable. As the alkali, ammonia, caustic soda, caustic potash, or a carbonate thereof is used, but ammonia is preferably used from the viewpoint of reducing impurities after the slurry formation of tin-containing indium hydroxide.
　生成したスズ含有水酸化インジウムのスラリーを前記懸濁液の固液分離により採集し、純水により不純物を洗浄することで、純度を高めたスズ含有水酸化インジウムのケーキが得られる。得られたケーキを、室温以上、望ましくは８０℃以上の温度で乾燥することにより、スズ含有水酸化インジウムの乾燥粉が得られる。 The produced tin-containing indium hydroxide slurry is collected by solid-liquid separation of the suspension, and the impurities are washed with pure water to obtain a tin-containing indium hydroxide cake with increased purity. The obtained cake is dried at a temperature of room temperature or higher, preferably 80 ° C. or higher, whereby a dry powder of tin-containing indium hydroxide is obtained.
　スズ含有水酸化インジウム中において、スズは水酸化インジウムのインジウムと置換している場合もあるが、酸化スズ及び／又は水酸化スズとして水酸化インジウムと共沈している場合もあり、酸化スズ及び／又は水酸化スズとして水酸化インジウムと非晶質の混合体となっている場合もある。 In tin-containing indium hydroxide, tin may be substituted for indium in indium hydroxide, but may be co-precipitated with indium hydroxide as tin oxide and / or tin hydroxide. In some cases, the mixture is in the form of indium hydroxide and amorphous as tin hydroxide.
　上述したように、スズ含有水酸化インジウムの粒子径は、水酸化物を得る工程で決定される。具体的には、反応温度を４０～９０℃の範囲に、反応時間（全中和にかかる時間）を２０～６００分の範囲に、最終粒子濃度を０．０１～３ｍｏｌ／リットルの範囲にそれぞれ制御することで所望の粒径を有するスズ含有水酸化インジウムを得ることができる。 As described above, the particle diameter of the tin-containing indium hydroxide is determined in the step of obtaining a hydroxide. Specifically, the reaction temperature is in the range of 40 to 90 ° C., the reaction time (total neutralization time) is in the range of 20 to 600 minutes, and the final particle concentration is in the range of 0.01 to 3 mol / liter. By controlling, tin-containing indium hydroxide having a desired particle size can be obtained.
　ここで、例えば多結晶ＩＴＯ粒子の平均長さＬが１μｍ、平均直径Ｄが０．２μｍであるスズ含有水酸化インジウムの針状粒子を合成する場合には、反応温度を６０℃、反応時間（全中和にかかる時間）を７５分、最終粒子濃度を０．５ｍｏｌ／リットルとすれば良い。一方、上記スズ含有水酸化インジウムの針状粒子より平均長さの小さな粒子を製造する場合は、反応温度を低く設定するか、反応速度を短くするか又は粒子濃度を高くすればよい。なお、最終的に生成される多結晶ＩＴＯ粒子のサイズは、当該スズ含有水酸化物のサイズによりほぼ決定される。即ち、当該スズ含有水酸化物はＩＴＯ粒子へ変化する際、平均長さＬ及び平均直径Ｄ共に７０～８０％程度収縮する。 Here, for example, when synthesizing needle-like particles of tin-containing indium hydroxide having an average length L of polycrystalline ITO particles of 1 μm and an average diameter D of 0.2 μm, the reaction temperature is 60 ° C., the reaction time ( The time required for total neutralization) may be 75 minutes, and the final particle concentration may be 0.5 mol / liter. On the other hand, when producing particles having an average length smaller than the needle-like particles of tin-containing indium hydroxide, the reaction temperature may be set low, the reaction rate may be shortened, or the particle concentration may be increased. Note that the size of the finally produced polycrystalline ITO particles is substantially determined by the size of the tin-containing hydroxide. That is, when the tin-containing hydroxide changes to ITO particles, both the average length L and the average diameter D shrink about 70 to 80%.
　次に、第２の工程である、得られたスズ含有水酸化インジウムを焼成する工程について説明する。この焼成工程の目的は、スズ含有水酸化インジウムから、酸化物であるＩＴＯを生成させること及び得られるＩＴＯの結晶に酸素欠損を与えることである。従って、この焼成工程はＩＴＯの結晶に酸素欠損を与えるために不活性ガスと還元性ガスとを混合した弱還元雰囲気下で行われる。通常、弱還元雰囲気として、窒素やヘリウム、アルゴン等の不活性ガスに、水素や一酸化炭素、アンモニアガス、アルコールを混合した混合ガスが用いられる。混合ガスにおける各ガスの混合比率はＩＴＯの結晶に付与しようとする酸素欠損量により適宜決定される。但し混合ガスの還元力が強すぎると、スズ含有水酸化インジウムはＩｎＯ、金属Ｉｎ等になってしまう。また、水素や一酸化炭素等の混合比率は、混合ガスが大気中で爆発限界を越えない程度の濃度にすることが望ましい。 Next, the step of firing the obtained tin-containing indium hydroxide, which is the second step, will be described. The purpose of this firing step is to generate ITO as an oxide from tin-containing indium hydroxide and to give oxygen deficiency to the resulting ITO crystals. Therefore, this firing step is performed in a weak reducing atmosphere in which an inert gas and a reducing gas are mixed to give oxygen deficiency to the ITO crystal. Usually, as a weak reducing atmosphere, a mixed gas in which hydrogen, carbon monoxide, ammonia gas, or alcohol is mixed with an inert gas such as nitrogen, helium, or argon is used. The mixing ratio of each gas in the mixed gas is appropriately determined by the amount of oxygen deficiency to be imparted to the ITO crystal. However, if the reducing power of the mixed gas is too strong, the tin-containing indium hydroxide becomes InO, metal In, or the like. In addition, the mixing ratio of hydrogen, carbon monoxide, or the like is desirably set to such a concentration that the mixed gas does not exceed the explosion limit in the atmosphere.
　焼成工程では、初めに焼成が行われ、続いて還元処理が行われる。焼成は、スズ含有水酸化インジウムを脱水して酸化インジウムにする。焼成温度は３００～１０００℃である。３００℃以上で完全な酸化物を得ることができ、１０００℃以下でＩＴＯ粒子間同士の激しい焼結を回避できる。好ましい焼成温度は３５０～８００℃以下である。焼成時間は０．１時間以上であればよいが、脱水反応が終了すれば、それ以上は不要である。雰囲気は大気とする。 In the firing step, firing is performed first, followed by reduction treatment. In the baking, the tin-containing indium hydroxide is dehydrated into indium oxide. The firing temperature is 300 to 1000 ° C. A complete oxide can be obtained at 300 ° C. or higher, and intense sintering between ITO particles can be avoided at 1000 ° C. or lower. A preferable firing temperature is 350 to 800 ° C. or less. The firing time may be 0.1 hours or longer, but is not necessary once the dehydration reaction is completed. The atmosphere is air.
　焼成後の還元処理は、好ましくは２００～５００℃未満の温度で上述した還元雰囲気下で行われる。２００℃以上あれば酸素欠損を付与でき、５００℃未満であれば、適当な還元力が得られるので絶縁性のＩｎＯが生成されない。還元処理時間は０．５～５時間である。０．５時間未満では酸素欠損の形成が不十分であり、５時間を越えても優位な変化が見られない。以上の工程を経て、本発明の多結晶ＩＴＯ粒子からなるＩＴＯ粉末を得ることができる。このように不活性ガスにアルコールを混合した混合ガスで焼成したＩＴＯ粉末では、多結晶ＩＴＯ粒子表面にＯＨ基が多いことから、後述する表面処理剤である珪酸エステル又はシランカップリング剤がこのＯＨ基と結合しやすいため、珪酸エステル又はシランカップリング剤による表面処理の効果がより高く、高温高湿下におけるＩＴＯ導電膜の電気抵抗値の上昇をより一層抑制することができる。 The reduction treatment after calcination is preferably performed at a temperature of 200 to 500 ° C. in the reducing atmosphere described above. If it is 200 degreeC or more, an oxygen deficiency can be provided, and if it is less than 500 degreeC, since an appropriate reduction power is obtained, insulating InO is not produced | generated. The reduction treatment time is 0.5 to 5 hours. If it is less than 0.5 hours, oxygen deficiency is not sufficiently formed, and no significant change is observed even if it exceeds 5 hours. Through the above steps, an ITO powder composed of the polycrystalline ITO particles of the present invention can be obtained. In the ITO powder baked with a mixed gas in which an alcohol is mixed with an inert gas in this way, since there are many OH groups on the surface of the polycrystalline ITO particles, a silicate ester or a silane coupling agent, which is a surface treatment agent described later, is this OH. Since it is easy to couple | bond with a group, the effect of the surface treatment by a silicate ester or a silane coupling agent is higher, and it can suppress further the raise of the electrical resistance value of the ITO electrically conductive film under high temperature, high humidity.
　＜多結晶ＩＴＯ粒子の表面処理方法＞
　上記多結晶ＩＴＯ粒子は表面処理剤により表面処理される。ここで、表面処理剤としては、炭素数が２以下であるアルコキシ基を４つ有する珪酸エステル又はこの珪酸エステルのオリゴマーからなる表面処理剤、或いは炭素数が２以下であるアルコキシ基を２つ以上有し、かつアミノ基（-Ｒ-ＮＨ２、-Ｒ-ＮＨＲ、-Ｒ-ＮＲ１Ｒ２）若しくはメルカプト基（-Ｒ-ＳＨ）を末端基に有するアルキル基、炭素数が６以上である長鎖のアルキル基、又は一部がフッ素で置換されたアルキル基のいずれか１種のアルキル基を１つ以上有するシランカップリング剤からなる表面処理剤が用いられる。ここでＲ、Ｒ１、Ｒ２はそれぞれアルキル基である。
　前記珪酸エステル又は珪酸エステルのオリゴマー体からなる表面処理剤によれば、多結晶ＩＴＯ導電膜表面に珪酸エステル又は珪酸エステルの加水分解体が結合した構成が得られる。また、前記シランカップリング剤からなる表面処理剤によれば、多結晶ＩＴＯ導電膜表面基にアミノ基又はメルカプト基が結合した構成、若しくは多結晶ＩＴＯ導電膜表面に（シランカップリング剤のアルコキシ基）又は（アルコキシ基の加水分解で生じたシラノール基）が結合した構成が得られる。多結晶ＩＴＯ導電膜表面の水酸基と表面処理剤との結合構成は、ＩＴＯ導電膜表面の－ＯＨを介するものである。 <Polycrystalline ITO particle surface treatment method>
The polycrystalline ITO particles are surface-treated with a surface treatment agent. Here, as the surface treatment agent, a surface treatment agent comprising a silicate ester having 4 alkoxy groups having 2 or less carbon atoms or an oligomer of the silicate ester, or two or more alkoxy groups having 2 or less carbon atoms. And an alkyl group having an amino group (—R—NH 2 , —R—NHR, —R—NR 1 R 2 ) or a mercapto group (—R—SH) as a terminal group, and having 6 or more carbon atoms A surface treatment agent comprising a silane coupling agent having one or more alkyl groups of any one of a long-chain alkyl group or an alkyl group partially substituted with fluorine is used. Here, R, R 1 and R 2 are each an alkyl group.
According to the surface treatment agent comprising the silicate ester or the silicate ester oligomer, a structure in which a silicate ester or a silicate hydrolyzate is bonded to the surface of the polycrystalline ITO conductive film is obtained. Further, according to the surface treatment agent comprising the silane coupling agent, a structure in which an amino group or a mercapto group is bonded to the surface of the polycrystalline ITO conductive film, or the surface of the polycrystalline ITO conductive film (an alkoxy group of the silane coupling agent). ) Or (silanol group generated by hydrolysis of alkoxy group) is bonded. The bonding configuration between the hydroxyl group on the surface of the polycrystalline ITO conductive film and the surface treatment agent is via —OH on the surface of the ITO conductive film.
　炭素数が２以下であるアルコキシ基を４つ有する珪酸エステルとしては、テトラメトキシシラン（炭素数１）、又はテトラエトキシシラン（炭素数２）が例示され、上記珪酸エステルのオリゴマーとしては、テトラメトキシシラン（炭素数１）の３～５量体、又はテトラエトキシシラン（炭素数２）の３～５量体が例示される。 Examples of the silicic acid ester having four alkoxy groups having 2 or less carbon atoms include tetramethoxysilane (carbon number 1) or tetraethoxysilane (carbon number 2). Examples are silane (carbon number 1) trimer to pentamer or tetraethoxysilane (carbon number 2) trimer to pentamer.
　また炭素数が２以下であるアルコキシ基を２つ以上有し、かつアミノ基若しくはメルカプト基を末端基に有するアルキル基を１つ以上有するシランカップリング剤としては、Ｎ－２－(アミノエチル)－３－アミノプロピルトリメトキシシラン、３－アミノプロピルトリメトキシシラン、３－メルカプトプロピルメチルジメトキシシラン、又は３－メルカプトプロピルトリメトキシシランが例示される。 A silane coupling agent having two or more alkoxy groups having 2 or less carbon atoms and one or more alkyl groups having an amino group or a mercapto group as a terminal group includes N-2- (aminoethyl) Examples are -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, or 3-mercaptopropyltrimethoxysilane.
　また炭素数が２以下であるアルコキシ基を２つ以上有し、かつ炭素数が６以上の長鎖のアルキル基を１つ以上有するシランカップリング剤としては、ヘキシルトリメトキシシラン、ヘキシルトリエトキシシラン、又はデシルトリメトキシシランが例示される。 Examples of the silane coupling agent having two or more alkoxy groups having 2 or less carbon atoms and one or more long-chain alkyl groups having 6 or more carbon atoms include hexyltrimethoxysilane and hexyltriethoxysilane. Or decyltrimethoxysilane.
　更に炭素数が２以下であるアルコキシ基を２つ以上有し、かつ一部にフッ素で置換されたアルキル基を１つ以上有するシランカップリング剤としては、トリフルオロプロピルトリメトキシシランが例示される。なお、本発明の珪酸エステルは、多結晶ＩＴＯ粒子表面に結合した後、ＳｉＯ２としてネットワークを組みやすい、複数のエステル結合を持つものが好ましい。 Further, trifluoropropyltrimethoxysilane is exemplified as the silane coupling agent having two or more alkoxy groups having 2 or less carbon atoms and one or more alkyl groups partially substituted with fluorine. . The silicate ester of the present invention is preferably one having a plurality of ester bonds that can easily form a network as SiO 2 after being bonded to the surface of the polycrystalline ITO particles.
　上記多結晶ＩＴＯ粒子の表面処理に用いられる表面処理炉としては、バッチ式小型ロータリーキルン(株式会社モトヤマ製：内径７０ｍｍ×長さ１０００ｍｍ)、又は管状炉(内径１００ｍｍ×長さ１２００ｍｍ)が挙げられる。バッチ式小型ロータリーキルンを用いる場合には、キルン内に所定量の多結晶ＩＴＯ粒子を充填し、処理温度に予熱した不活性ガス（例えば、窒素ガス、アルゴンガス等）をキャリアガスとして、キルン内が処理温度の不活性雰囲気になるように、０．５～１０リットル／分で６０～３００分間流通させた後、キルンの運転を開始する、即ちキルンを０．５～６０ｒｐｍの回転速度で回転させると同時に、バブリングによって表面処理剤の蒸気を含ませたキャリアガスをキルン内に流通させる。一方、管状炉を用いる場合には、所定量の多結晶ＩＴＯ粒子を入れた金属製トレーを管状炉内に設置し、表面処理炉として上記キルンを用いた場合と同様にガス置換を行った後に、表面処理剤を含んだ蒸気を流通させる。 Examples of the surface treatment furnace used for the surface treatment of the polycrystalline ITO particles include a batch type small rotary kiln (manufactured by Motoyama Co., Ltd .: inner diameter 70 mm × length 1000 mm) or a tubular furnace (inner diameter 100 mm × length 1200 mm). In the case of using a batch type small rotary kiln, the kiln is filled with a predetermined amount of polycrystalline ITO particles and preheated to a processing temperature as an inert gas (for example, nitrogen gas, argon gas) as a carrier gas. After flowing through 0.5 to 10 liters / minute for 60 to 300 minutes so as to have an inert atmosphere at the treatment temperature, the kiln is started, that is, the kiln is rotated at a rotational speed of 0.5 to 60 rpm. At the same time, the carrier gas containing the surface treatment agent vapor is circulated in the kiln by bubbling. On the other hand, when a tubular furnace is used, a metal tray containing a predetermined amount of polycrystalline ITO particles is placed in the tubular furnace, and after performing gas replacement in the same manner as in the case of using the kiln as a surface treatment furnace. The steam containing the surface treatment agent is circulated.
　上記キルン又は管状炉を用いて多結晶ＩＴＯ粒子を表面処理する条件は、表面処理剤の蒸気を含むキャリアガスの温度（処理温度）を１０～１５０℃、好ましくは５０～１２０℃とし、総ガス量を１０～１０００リットル、好ましくは５０～２５０リットルとし、キャリアガスに含まれる表面処理剤の濃度を１×１００～１×１０６ｐｐｍ、好ましくは１×１０２～１×１０５ｐｐｍとする。ここで、上記処理温度は、下限値未満では表面処理剤の蒸気圧が低いために、表面処理が進まず目的とするＩＴＯ導電膜の高温高湿下における抵抗値の上昇を抑制する効果が得られない問題点があり、上限値より高い場合には、逆に処理が進みすぎ、表面処理剤がＩＴＯ粒子同士の接触を阻害し、初期の表面抵抗が大きくなってしまう問題点がある。また総ガス量は、下限値未満では、処理量が少ないため、目的とするＩＴＯ導電膜の高温高湿下における抵抗値の上昇を抑制する効果が得られない問題点があり、上限値より大きい場合には処理が進みすぎる問題点がある。更にキャリアガスに含まれる表面処理剤の濃度は、下限値未満では多結晶ＩＴＯ粒子表面への表面処理剤の結合が起こり難いという問題点があり、上限値より高い場合には、多結晶ＩＴＯ粒子同士が結合してしまい、多結晶ＩＴＯ粒子が分散し難くなるという問題点がある。なお、多結晶ＩＴＯ粒子やＩＴＯ粉末が巻き上げられるのを防止するためにガスの流速は０．１～１ｍ／分とする。 The conditions for surface treatment of polycrystalline ITO particles using the kiln or tubular furnace are as follows: the temperature of the carrier gas containing the surface treatment agent vapor (treatment temperature) is 10 to 150 ° C., preferably 50 to 120 ° C. the amount 10-1000 liters preferably 50 and ~ 250 liters, 1 × 10 0 ~ 1 × 10 6 ppm the concentration of the surface treatment agent contained in the carrier gas, preferably a 1 × 10 2 ~ 1 × 10 5 ppm To do. Here, since the vapor pressure of the surface treatment agent is low when the treatment temperature is less than the lower limit value, the surface treatment does not proceed and the effect of suppressing the increase in resistance value of the target ITO conductive film under high temperature and high humidity is obtained. There is a problem that cannot be achieved, and when the value is higher than the upper limit value, the process progresses too much, and the surface treatment agent interferes with the contact between the ITO particles, and the initial surface resistance increases. Also, if the total gas amount is less than the lower limit value, the amount of treatment is small, so there is a problem that the effect of suppressing the increase in resistance value of the target ITO conductive film under high temperature and high humidity cannot be obtained, and it is larger than the upper limit value. In such a case, there is a problem that the process proceeds too much. Furthermore, if the concentration of the surface treatment agent contained in the carrier gas is less than the lower limit value, there is a problem that the surface treatment agent does not easily bind to the surface of the polycrystalline ITO particles. There is a problem that they are bonded to each other and the polycrystalline ITO particles are difficult to disperse. In order to prevent the polycrystalline ITO particles and ITO powder from being rolled up, the gas flow rate is set to 0.1 to 1 m / min.
　＜ＩＴＯ導電膜形成用塗料の製造方法＞
　上記ＩＴＯ粉末（表面処理された多結晶ＩＴＯ粒子）を、分散媒のアルコール系溶液１００質量％に対して１～７０質量％の割合となるように混合し、ミキサーで攪拌することにより、ＩＴＯ導電膜形成用塗料を調製する。ＩＴＯ粉末の分散媒としては、エタノール、２－ブタノール、１－プロパノール等のアルコール系溶液が例示される。ＩＴＯ粉末はこのアルコール系溶液１００質量％に対して１～７０質量％の範囲で添加混合するとよい。１質量％未満では導電膜に十分な厚さの膜を形成するのが困難となり、７０質量％を越えると分散液の粘度が高く、塗布が困難となる。また必要に応じて上記ＩＴＯ導電膜形成用塗料をホモジェナイザーやビーズミル粉砕機等に入れて、この塗料中のＩＴＯ粉末を粉砕処理する。更に必要に応じて、抵抗を悪化させない範囲で、シリカゾルゲルやアクリル樹脂等のバインダを上記ＩＴＯ導電膜形成用塗料に添加することができる。 <Method for producing ITO conductive film forming paint>
The ITO powder (surface-treated polycrystalline ITO particles) is mixed so as to have a ratio of 1 to 70% by mass with respect to 100% by mass of the alcoholic solution of the dispersion medium, and stirred with a mixer. A coating for film formation is prepared. Examples of the ITO powder dispersion medium include alcohol-based solutions such as ethanol, 2-butanol, and 1-propanol. The ITO powder may be added and mixed in the range of 1 to 70% by mass with respect to 100% by mass of the alcoholic solution. If the amount is less than 1% by mass, it is difficult to form a film having a sufficient thickness on the conductive film. If necessary, the ITO conductive film forming coating material is put in a homogenizer, a bead mill pulverizer or the like, and the ITO powder in the coating material is pulverized. Furthermore, if necessary, a binder such as silica sol gel or acrylic resin can be added to the ITO conductive film forming paint within a range not deteriorating the resistance.
　＜ＩＴＯ導電膜の製造方法＞
　ＩＴＯ導電膜は、例えば次のようにして製造される。予めＩＴＯ導電膜を形成するための基材を作製しておく。この基材は、片面にポリウレタンが塗布されたポリエチレンテレフタレート（ＰＥＴ）等の第１のフィルムであって、この第１のフィルムのうちポリウレタンが塗布されていない面をガラス基板上に両面粘着テープ等を用いて貼付けて作製される。先ず、ＩＴＯ導電膜形成用塗料を、ガラス基板上に固定された基材上にバーコート法、ダイコート法、ドクターブレード法等により塗布した後に、乾燥させる。次にＩＴＯ導電膜形成用塗料が塗布された基材をガラス基板から剥離し、基材のうちＩＴＯ導電膜形成用塗料の塗布面にＰＥＴ等の第２のフィルムを重ね合せ、この状態でロールプレス機にてロール圧力１００～２０００ｋｇ／ｃｍ、送り出し速度１０～５０ｃｍ／分の条件で圧力を加えた後に、第２のフィルムを剥離する。これによりフィルム上にＩＴＯ導電膜が形成される。 <Method for producing ITO conductive film>
The ITO conductive film is manufactured as follows, for example. A base material for forming the ITO conductive film is prepared in advance. This base material is a first film such as polyethylene terephthalate (PET) coated with polyurethane on one side, and the surface of the first film not coated with polyurethane is coated on a glass substrate with a double-sided adhesive tape or the like. Affixed using First, an ITO conductive film forming coating material is applied to a base material fixed on a glass substrate by a bar coating method, a die coating method, a doctor blade method, or the like, and then dried. Next, the base material coated with the ITO conductive film forming coating material is peeled off from the glass substrate, and a second film such as PET is superimposed on the surface of the base material on which the ITO conductive film forming coating material is applied. After applying pressure with a press machine under conditions of a roll pressure of 100 to 2000 kg / cm and a delivery speed of 10 to 50 cm / min, the second film is peeled off. Thereby, an ITO conductive film is formed on the film.
　＜ＩＴＯ導電膜の評価方法＞
　上記のようにして得られた透明導電膜について、以下のようにして表面抵抗の評価を行った。即ち、上記のようにして得られた透明導電膜の予め定められた測定点につき、三菱油化製ＬｏｒｅｓｔａＡＰ ＭＣＰ－Ｔ４００を用いて表面の電気抵抗を測定し、その測定値を初期電気抵抗値とした。その後、８５℃、相対湿度８５％ＲＨに制御された恒温恒湿槽内に、２０００時間透明導電膜を保管した後に、初期抵抗測定時に定めた測定点において再度表面の電気抵抗の値を測定し、これを加湿後電気抵抗値とした。そして、下記式に基づいて変化率を算出した。なお、ここで相対湿度は大気圧下、８５℃／温度８５℃における相対湿度である。
　　　　　　変化率 ＝ [加湿後電気抵抗値／ 初期電気抵抗値] <Evaluation method of ITO conductive film>
About the transparent conductive film obtained as mentioned above, surface resistance was evaluated as follows. That is, for a predetermined measurement point of the transparent conductive film obtained as described above, the electrical resistance of the surface was measured using LorestaAP MCP-T400 manufactured by Mitsubishi Yuka, and the measured value was regarded as the initial electrical resistance value. did. Then, after storing the transparent conductive film for 2000 hours in a constant temperature and humidity chamber controlled to 85 ° C. and relative humidity 85% RH, the value of the electrical resistance of the surface is measured again at the measurement point determined at the time of initial resistance measurement. This was used as the electric resistance value after humidification. And the rate of change was computed based on the following formula. Here, the relative humidity is relative humidity at 85 ° C./temperature 85 ° C. under atmospheric pressure.
Rate of change = [electric resistance value after humidification / initial electric resistance value]
　次に本発明の実施例を比較例とともに詳しく説明する。 Next, examples of the present invention will be described in detail together with comparative examples.
　＜実施例１＞
　前述した方法で、多結晶ＩＴＯ粒子の平均長さＬが１μｍ、平均直径Ｄが０．２μｍであるスズ含有水酸化インジウムの針状粒子を作製した。この針状粒子の作製に際し、前述した超音波の周波数は３４ｋＨｚであり、その付与時間は６０分であり、スズ及びインジウムの塩は塩酸塩であり、アルカリはアンモニアである。得られたケーキを１１０℃で乾燥した。焼成は窒素ガス雰囲気で、６００℃、３時間行った。焼成後の還元処理は、水素ガスを３質量％添加した窒素ガス雰囲気で３００℃で、２時間行った。 <Example 1>
By the method described above, needle-like particles of tin-containing indium hydroxide having an average length L of polycrystalline ITO particles of 1 μm and an average diameter D of 0.2 μm were prepared. In producing the acicular particles, the frequency of the ultrasonic wave described above is 34 kHz, the application time is 60 minutes, the salt of tin and indium is hydrochloride, and the alkali is ammonia. The resulting cake was dried at 110 ° C. Firing was performed in a nitrogen gas atmosphere at 600 ° C. for 3 hours. The reduction treatment after firing was performed at 300 ° C. for 2 hours in a nitrogen gas atmosphere to which 3% by mass of hydrogen gas was added.
　上記焼成及び還元処理を行った多結晶ＩＴＯ粒子をバッチ式小型ロータリーキルン(株式会社モトヤマ製：内径７０ｍｍ×長さ１０００ｍｍ)に充填し、表面処理剤としてテトラメトキシシランの蒸気を含ませたキャリアガスをキルン内に流通させることにより、多結晶ＩＴＯ粒子を表面処理した。具体的には、先ず表面処理前の多結晶ＩＴＯ粒子５００ｇをキルンに充填した。次いで１００℃に予熱した窒素ガスをキャリアガスとして５リットル／分の流速で６０分間流通させた。これによりキルン内が８０℃の不活性ガス雰囲気（窒素ガス雰囲気）になった。次にキルンを２ｒｐｍの回転速度で回転させると同時に、バブリングによって表面処理剤の蒸気を含ませたキャリアガスをキルン内に流通させた。このときの総ガス量は１０００リットルであり、キャリアガスに含まれるテトラメトキシシラン（表面処理剤）の濃度は約１００ｐｐｍであった。また多結晶ＩＴＯ粒子やＩＴＯ粉末が巻き上げられるのを防止するためにガスの流速を１ｍ／分とした。これにより表面処理された多結晶ＩＴＯ粒子からなるＩＴＯ粉末を得た。 A batch type small rotary kiln (manufactured by Motoyama Co., Ltd .: inner diameter 70 mm × length 1000 mm) is filled with the polycrystalline ITO particles subjected to the firing and reduction treatment, and a carrier gas containing tetramethoxysilane vapor as a surface treatment agent is used. The polycrystalline ITO particles were surface-treated by flowing through the kiln. Specifically, first, 500 g of polycrystalline ITO particles before surface treatment were filled in a kiln. Subsequently, nitrogen gas preheated to 100 ° C. was circulated for 60 minutes at a flow rate of 5 liters / minute as a carrier gas. As a result, the inside of the kiln became an inert gas atmosphere (nitrogen gas atmosphere) at 80 ° C. Next, the kiln was rotated at a rotation speed of 2 rpm, and at the same time, the carrier gas containing the surface treatment agent vapor was circulated in the kiln by bubbling. The total gas amount at this time was 1000 liters, and the concentration of tetramethoxysilane (surface treatment agent) contained in the carrier gas was about 100 ppm. Further, the gas flow rate was set to 1 m / min to prevent the polycrystalline ITO particles and the ITO powder from being rolled up. As a result, an ITO powder made of surface-treated polycrystalline ITO particles was obtained.
　＜実施例２＞
　実施例１の焼成及び還元処理を行った後であって表面処理を行う前の多結晶ＩＴＯ粒子を、管状炉(内径１００ｍｍ×長さ１２００ｍｍ)に充填し、表面処理剤としてテトラメトキシシランの３～５量体（テトラメトキシシランのオリゴマー）の蒸気を含ませたキャリアガスを管状炉内に流通させることにより、多結晶ＩＴＯ粒子を表面処理した。具体的には、表面処理前の多結晶ＩＴＯ粒子５００ｇを入れた金属製トレーを管状炉内に設置し、実施例１の表面処理炉としてキルンを用いた場合と同様にガス置換を行った後に、表面処理剤としてテトラメトキシシランの３～５量体（テトラメトキシシランのオリゴマー）を含んだ蒸気を流通させた。このときの処理条件は、ガス温度（処理温度）を８０℃とし、総ガス量を１００リットルとし、キャリアガスに含まれるテトラメトキシシランの３～５量体（表面処理剤）の濃度を５０ｐｐｍとした。これにより表面処理された多結晶ＩＴＯ粒子からなるＩＴＯ粉末を得た。 <Example 2>
Polycrystalline ITO particles after the firing and reduction treatment of Example 1 but before the surface treatment were filled in a tubular furnace (inner diameter 100 mm × length 1200 mm), and tetramethoxysilane 3 was used as a surface treatment agent. The polycrystalline ITO particles were surface-treated by passing a carrier gas containing vapor of ˜5-mer (tetramethoxysilane oligomer) through a tubular furnace. Specifically, after placing a metal tray containing 500 g of polycrystalline ITO particles before surface treatment in a tubular furnace and performing gas replacement as in the case of using a kiln as the surface treatment furnace of Example 1. Then, a vapor containing tetramethoxysilane trimer to pentamer (tetramethoxysilane oligomer) was circulated as a surface treatment agent. The treatment conditions at this time are as follows: gas temperature (treatment temperature) is 80 ° C., total gas amount is 100 liters, and the concentration of tetramethoxysilane trimer to pentamer (surface treatment agent) contained in the carrier gas is 50 ppm. did. As a result, an ITO powder made of surface-treated polycrystalline ITO particles was obtained.
　＜実施例３＞
　実施例１のテトラメトキシシランに代えて、テトラエトキシシランを表面処理剤として用いるとともに、実施例１のバッチ式小型ロータリキルンに代えて、実施例２の管状路を用いたこと以外は、実施例１と同様にして、表面処理された多結晶ＩＴＯ粒子からなるＩＴＯ粉末を得た。 <Example 3>
Example except that tetraethoxysilane was used as a surface treatment agent instead of tetramethoxysilane in Example 1 and that the tubular path of Example 2 was used instead of the batch type small rotary kiln in Example 1. In the same manner as in Example 1, an ITO powder comprising surface-treated polycrystalline ITO particles was obtained.
　＜実施例４＞
　実施例１のテトラメトキシシランに代えて、テトラエトキシシランの３～５量体（テトラエトキシシランのオリゴマー）を表面処理剤として用いるとともに、実施例１のバッチ式小型ロータリキルンに代えて、実施例２の管状路を用いたこと以外は、実施例１と同様にして、表面処理された多結晶ＩＴＯ粒子からなるＩＴＯ粉末を得た。 <Example 4>
In place of the tetramethoxysilane of Example 1, tetraethoxysilane trimer to pentamer (tetraethoxysilane oligomer) was used as a surface treatment agent, and the batch type small rotary kiln of Example 1 was used instead of Example 1. An ITO powder made of surface-treated polycrystalline ITO particles was obtained in the same manner as in Example 1 except that 2 tubular paths were used.
　＜実施例５＞
　実施例１のテトラメトキシシランに代えて、Ｎ－２－(アミノエチル)－３－アミノプロピルトリメトキシシランを表面処理剤として用いたこと以外は、実施例１と同様にして、表面処理された多結晶ＩＴＯ粒子からなるＩＴＯ粉末を得た。 <Example 5>
Surface treatment was carried out in the same manner as in Example 1 except that N-2- (aminoethyl) -3-aminopropyltrimethoxysilane was used as a surface treatment agent instead of tetramethoxysilane in Example 1. An ITO powder composed of polycrystalline ITO particles was obtained.
　＜実施例６＞
　実施例１のテトラメトキシシランに代えて、３－アミノプロピルトリメトキシシランを表面処理剤として用いるとともに、実施例１のバッチ式小型ロータリキルンに代えて、実施例２の管状路を用いたこと以外は、実施例１と同様にして、表面処理された多結晶ＩＴＯ粒子からなるＩＴＯ粉末を得た。 <Example 6>
Instead of tetramethoxysilane of Example 1, 3-aminopropyltrimethoxysilane was used as a surface treatment agent, and the tubular path of Example 2 was used instead of the batch type small rotary kiln of Example 1. Obtained ITO powder made of surface-treated polycrystalline ITO particles in the same manner as in Example 1.
　＜実施例７＞
　実施例１のテトラメトキシシランに代えて、３－メルカプトプロピルメチルジメトキシシランを表面処理剤として用いたこと以外は、実施例１と同様にして、表面処理された多結晶ＩＴＯ粒子からなるＩＴＯ粉末を得た。 <Example 7>
An ITO powder made of surface-treated polycrystalline ITO particles was prepared in the same manner as in Example 1 except that 3-mercaptopropylmethyldimethoxysilane was used as the surface treatment agent instead of tetramethoxysilane in Example 1. Obtained.
　＜実施例８＞
　実施例１のテトラメトキシシランに代えて、３－メルカプトプロピルトリメトキシシランを表面処理剤として用いたこと以外は、実施例１と同様にして、表面処理された多結晶ＩＴＯ粒子からなるＩＴＯ粉末を得た。 <Example 8>
An ITO powder made of surface-treated polycrystalline ITO particles was prepared in the same manner as in Example 1 except that 3-mercaptopropyltrimethoxysilane was used as the surface treatment agent instead of tetramethoxysilane in Example 1. Obtained.
　＜実施例９＞
　実施例１のテトラメトキシシランに代えて、トリフルオロプロピルトリメトキシシランを表面処理剤として用いるとともに、実施例１のバッチ式小型ロータリキルンに代えて、実施例２の管状路を用いたこと以外は、実施例１と同様にして、表面処理された多結晶ＩＴＯ粒子からなるＩＴＯ粉末を得た。 <Example 9>
Aside from using the trifluoropropyltrimethoxysilane as a surface treatment agent in place of the tetramethoxysilane of Example 1 and using the tubular path of Example 2 instead of the batch type small rotary kiln of Example 1. In the same manner as in Example 1, an ITO powder comprising surface-treated polycrystalline ITO particles was obtained.
　＜実施例１０＞
　実施例１のテトラメトキシシランに代えて、ヘキシルトリメトキシシランを表面処理剤として用いたこと以外は、実施例１と同様にして、表面処理された多結晶ＩＴＯ粒子からなるＩＴＯ粉末を得た。 <Example 10>
An ITO powder composed of surface-treated polycrystalline ITO particles was obtained in the same manner as in Example 1 except that hexyltrimethoxysilane was used as the surface treatment agent instead of tetramethoxysilane in Example 1.
　＜実施例１１＞
　実施例１のテトラメトキシシランに代えて、デシルトリメトキシシランを表面処理剤として用いるとともに、実施例１のバッチ式小型ロータリキルンに代えて、実施例２の管状路を用いたこと以外は、実施例１と同様にして、表面処理された多結晶ＩＴＯ粒子からなるＩＴＯ粉末を得た。 <Example 11>
In place of using the decyltrimethoxysilane as a surface treatment agent instead of the tetramethoxysilane of Example 1, and using the tubular path of Example 2 instead of the batch type small rotary kiln of Example 1. In the same manner as in Example 1, an ITO powder comprising surface-treated polycrystalline ITO particles was obtained.
　＜実施例１２＞
　実施例１のテトラメトキシシランに代えて、ヘキシルトリエトキシシランを表面処理剤として用いたこと以外は、実施例１と同様にして、表面処理された多結晶ＩＴＯ粒子からなるＩＴＯ粉末を得た。 <Example 12>
An ITO powder composed of surface-treated polycrystalline ITO particles was obtained in the same manner as in Example 1 except that hexyltriethoxysilane was used as the surface treating agent instead of tetramethoxysilane in Example 1.
　＜比較例１＞
　表面処理剤を用いなかったこと以外は、実施例１と同様にして、表面処理された多結晶ＩＴＯ粒子からなるＩＴＯ粉末を得た。 <Comparative Example 1>
An ITO powder made of surface-treated polycrystalline ITO particles was obtained in the same manner as in Example 1 except that the surface treatment agent was not used.
　＜比較例２＞
　実施例１のテトラメトキシシランに代えて、ビニルトリメトキシシランを表面処理剤として用いたこと以外は、実施例１と同様にして、表面処理された多結晶ＩＴＯ粒子からなるＩＴＯ粉末を得た。 <Comparative example 2>
An ITO powder composed of surface-treated polycrystalline ITO particles was obtained in the same manner as in Example 1 except that vinyltrimethoxysilane was used as the surface treatment agent in place of the tetramethoxysilane of Example 1.
　＜比較例３＞
　実施例１のテトラメトキシシランに代えて、ｐ－スチリルメトキシシランを表面処理剤として用いたこと以外は、実施例１と同様にして、表面処理された多結晶ＩＴＯ粒子からなるＩＴＯ粉末を得た。 <Comparative Example 3>
An ITO powder made of surface-treated polycrystalline ITO particles was obtained in the same manner as in Example 1, except that p-styrylmethoxysilane was used as the surface treatment agent instead of tetramethoxysilane in Example 1. .
　＜比較例４＞
　実施例１のテトラメトキシシランに代えて、ヘキサメチルジシラザンを表面処理剤として用いるとともに、実施例１のバッチ式小型ロータリキルンに代えて、実施例２の管状路を用いたこと以外は、実施例１と同様にして、表面処理された多結晶ＩＴＯ粒子からなるＩＴＯ粉末を得た。 <Comparative example 4>
Instead of tetramethoxysilane in Example 1, hexamethyldisilazane was used as a surface treatment agent, and in place of the batch type small rotary kiln in Example 1, except that the tubular path in Example 2 was used. In the same manner as in Example 1, an ITO powder comprising surface-treated polycrystalline ITO particles was obtained.
　＜比較例５＞
　実施例１のテトラメトキシシランに代えて、フェニルトリメトキシシランを表面処理剤として用いたこと以外は、実施例１と同様にして、表面処理された多結晶ＩＴＯ粒子からなるＩＴＯ粉末を得た。 <Comparative Example 5>
An ITO powder composed of surface-treated polycrystalline ITO particles was obtained in the same manner as in Example 1 except that phenyltrimethoxysilane was used as the surface treatment agent instead of tetramethoxysilane in Example 1.
　＜比較例６＞
　実施例１のテトラメトキシシランに代えて、ジメチルジメトキシシランを表面処理剤として用いるとともに、実施例１のバッチ式小型ロータリキルンに代えて、実施例２の管状路を用いたこと以外は、実施例１と同様にして、表面処理された多結晶ＩＴＯ粒子からなるＩＴＯ粉末を得た。 <Comparative Example 6>
Example except that dimethyldimethoxysilane was used as a surface treating agent instead of tetramethoxysilane in Example 1 and that the tubular path of Example 2 was used in place of the batch-type small rotary kiln in Example 1. In the same manner as in Example 1, an ITO powder comprising surface-treated polycrystalline ITO particles was obtained.
　＜比較試験１及び評価＞
　実施例１～１２及び比較例１～６の表面処理された多結晶ＩＴＯ粒子からなるＩＴＯ粉末を用いて、ＩＴＯ導電膜形成用塗料を調製し、この塗料を用いてＰＥＴフィルム上にＩＴＯ導電膜を形成した。具体的には、上記表面処理された多結晶ＩＴＯ粒子からなるＩＴＯ粉末２ｇを、分散媒のエタノール６ｇに添加し、超音波ホモジェナイザーで３０分間分散して、ＩＴＯ導電膜形成用塗料を調製した。このＩＴＯ導電膜形成用塗料を前述した透明導電膜の製造方法に従って、ＰＥＴフィルム上に、バーコート法で成膜し、この膜にロール圧力７００ｋｇ／ｃｍ、送り出し速度３０ｃｍ／分で圧力を加えることで、ＩＴＯ導電膜を得た。そして、前述した評価方法に基づいて、各膜毎に初期電気抵抗値と加湿後電気抵抗値を測定した。そのうえで、加湿後電気抵抗値を初期電気抵抗値で除して変化率を求めた。その結果を表１に示す。なお、表１には、表面処理剤の種類と表面処理炉の種類も記載した。 <Comparative test 1 and evaluation>
A coating for forming an ITO conductive film was prepared using the ITO powder comprising the surface-treated polycrystalline ITO particles of Examples 1 to 12 and Comparative Examples 1 to 6, and an ITO conductive film was formed on the PET film using this coating. Formed. Specifically, 2 g of ITO powder composed of the above-mentioned surface-treated polycrystalline ITO particles is added to 6 g of ethanol as a dispersion medium, and dispersed for 30 minutes with an ultrasonic homogenizer to prepare a paint for forming an ITO conductive film. did. This ITO conductive film forming coating is formed on a PET film by a bar coating method in accordance with the method for producing a transparent conductive film described above, and pressure is applied to this film at a roll pressure of 700 kg / cm and a delivery speed of 30 cm / min. Thus, an ITO conductive film was obtained. And based on the evaluation method mentioned above, the initial electrical resistance value and the electrical resistance value after humidification were measured for every film | membrane. Then, the rate of change was determined by dividing the electrical resistance value after humidification by the initial electrical resistance value. The results are shown in Table 1. Table 1 also shows the type of surface treatment agent and the type of surface treatment furnace.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１から明らかなように、表面処理なしの多結晶ＩＴＯ粒子からなるＩＴＯ粉末を用いてＩＴＯ導電膜を形成した比較例１では、加湿後電気抵抗値が２０６９６Ω／sq (ohms per square)と大きくなり、初期電気抵抗値から加湿後電気抵抗値への変化率が５１．１倍と大きくなった。これに対し、テトラメトキシシラン、テトラメトキシシランの３～５量体、テトラエトキシシラン及びテトラエトキシシランの３～５量体で表面処理した多結晶ＩＴＯ粒子からなるＩＴＯ粉末を用いてＩＴＯ導電膜を形成した実施例１～４では、加湿後電気抵抗値が２１５２～７４７７Ω／sqと小さくなり、初期電気抵抗値から加湿後電気抵抗値への変化率が５．１～９．８倍と小さくなった。これにより炭素数が２以下であるアルコキシ基を４つ有する珪酸エステルからなる表面処理剤により、又はこれらの珪酸エステルのオリゴマー体からなる表面処理剤により、表面処理された多結晶ＩＴＯ粒子からなるＩＴＯ粉末を用いてＩＴＯ導電膜を形成すると、加湿後電気抵抗値が比較的低く、かつ高温高湿下であっても、電気抵抗値の上昇を十分に抑制できることが判った。 As is clear from Table 1, in Comparative Example 1 in which the ITO conductive film was formed using ITO powder composed of polycrystalline ITO particles without surface treatment, the electric resistance value after humidification was as large as 20696 Ω / sq (ohms per square). Thus, the rate of change from the initial electrical resistance value to the electrical resistance value after humidification was as large as 51.1 times. On the other hand, an ITO conductive film was formed using ITO powder made of polycrystalline ITO particles surface-treated with tetramethoxysilane, tetramethoxysilane trimer to pentamer, tetraethoxysilane and tetraethoxysilane trimer to pentamer. In the formed Examples 1 to 4, the electric resistance value after humidification is reduced to 2152 to 7477 Ω / sq, and the rate of change from the initial electric resistance value to the electric resistance value after humidification is reduced to 5.1 to 9.8 times. It was. Thus, ITO composed of polycrystalline ITO particles surface-treated by a surface treatment agent comprising a silicate ester having four alkoxy groups having 2 or less carbon atoms or a surface treatment agent comprising an oligomer of these silicate esters. It has been found that when an ITO conductive film is formed using powder, the electrical resistance value after humidification is relatively low and the increase in electrical resistance value can be sufficiently suppressed even under high temperature and high humidity.
　また、表１から明らかなように、アミノ基を末端基ではなく中央に有するヘキサメチルジシラザンで表面処理した多結晶ＩＴＯ粒子からなるＩＴＯ粉末を用いてＩＴＯ導電膜を形成した比較例４では、加湿後電気抵抗値が１９１０３Ω／sqと大きくなり、初期電気抵抗値から加湿後電気抵抗値への変化率が４１．８倍と大きくなった。これに対し、アミノ基を末端基に有するＮ－２－(アミノエチル)－３－アミノプロピルトリメトキシシラン、及び３－アミノプロピルトリメトキシシランで表面処理した多結晶ＩＴＯ粒子からなるＩＴＯ粉末を用いてＩＴＯ導電膜を形成した実施例５及び６では、加湿後電気抵抗値が２９６０Ω／sq及び１２５３Ω／sqと小さくなり、初期電気抵抗値から加湿後電気抵抗値への変化率が４．９倍及び２．５倍と小さくなった。またメルカプト基を末端基に有する３－メルカプトプロピルメチルジメトキシシラン、及び３－メルカプトプロピルトリメトキシシランで表面処理した多結晶ＩＴＯ粒子からなるＩＴＯ粉末を用いてＩＴＯ導電膜を形成した実施例７及び８では、加湿後電気抵抗値が１０５８Ω／sq及び７４６Ω／sqと小さくなり、初期電気抵抗値から加湿後電気抵抗値への変化率が３．６倍及び２．４倍と小さくなった。これにより炭素数が２以下であるアルコキシ基を２つ以上有し、かつアミノ基若しくはメルカプト基を末端基に有するアルキル基を１つ以上有するシランカップリング剤からなる表面処理剤により、表面処理された多結晶ＩＴＯ粒子からなるＩＴＯ粉末を用いてＩＴＯ導電膜を形成すると、加湿後電気抵抗値が比較的低く、かつ高温高湿下であっても、電気抵抗値の上昇を十分に抑制できることが判った。 Further, as apparent from Table 1, in Comparative Example 4 in which an ITO conductive film was formed using ITO powder made of polycrystalline ITO particles surface-treated with hexamethyldisilazane having an amino group at the center instead of a terminal group, The electric resistance value after humidification was as large as 19103 Ω / sq, and the rate of change from the initial electric resistance value to the electric resistance value after humidification was as large as 41.8 times. In contrast, ITO powder comprising N-2- (aminoethyl) -3-aminopropyltrimethoxysilane having an amino group as a terminal group and polycrystalline ITO particles surface-treated with 3-aminopropyltrimethoxysilane was used. In Examples 5 and 6 in which the ITO conductive film was formed, the electric resistance values after humidification were reduced to 2960 Ω / sq and 1253 Ω / sq, and the rate of change from the initial electric resistance value to the electric resistance value after humidification was 4.9 times. And 2.5 times smaller. Examples 7 and 8 in which an ITO conductive film was formed using ITO powder composed of 3-mercaptopropylmethyldimethoxysilane having a mercapto group as a terminal group and polycrystalline ITO particles surface-treated with 3-mercaptopropyltrimethoxysilane Then, the electrical resistance values after humidification were reduced to 1058 Ω / sq and 746 Ω / sq, and the rate of change from the initial electrical resistance value to the electrical resistance value after humidification was reduced to 3.6 times and 2.4 times. Thus, the surface treatment is performed by the surface treatment agent comprising a silane coupling agent having at least two alkoxy groups having 2 or less carbon atoms and at least one alkyl group having an amino group or a mercapto group as a terminal group. When an ITO conductive film is formed using ITO powder made of polycrystalline ITO particles, the electrical resistance value is relatively low after humidification, and the increase in electrical resistance value can be sufficiently suppressed even under high temperature and high humidity conditions. understood.
　また、表１から明らかなように、炭素数が６以上である長鎖のアルキル基を有しないビニルトリメトキシシラン、ｐ－スチリルメトキシシラン、フェニルトリメトキシシラン、及びジメチルジメトキシシランで表面処理した多結晶ＩＴＯ粒子からなるＩＴＯ粉末を用いてＩＴＯ導電膜を形成した比較例２、３、５及び６では、加湿後電気抵抗値が１２２３３～１８７５３Ω／sqと大きくなり、初期電気抵抗値から加湿後電気抵抗値への変化率が２５．７～６０．３倍と大きくなった。これに対し、炭素数が６以上である長鎖のアルキル基を有するヘキシルトリメトキシシラン、デシルトリメトキシシラン、及びヘキシルトリエトキシシランで表面処理した多結晶ＩＴＯ粒子からなるＩＴＯ粉末を用いてＩＴＯ導電膜を形成した実施例１０～１２では、加湿後電気抵抗値が１３９３～１９３７Ω／sqと小さくなり、初期電気抵抗値から加湿後電気抵抗値への変化率が３．６～４．１倍と小さくなった。これにより炭素数が２以下であるアルコキシ基を２つ以上有し、かつ炭素数が６以上である長鎖のアルキル基を１つ以上有するシランカップリング剤からなる表面処理剤により、表面処理された多結晶ＩＴＯ粒子からなるＩＴＯ粉末を用いてＩＴＯ導電膜を形成すると、加湿後電気抵抗値が比較的低く、かつ高温高湿下であっても、電気抵抗値の上昇を十分に抑制できることが判った。 Further, as is apparent from Table 1, the surface treatment was performed with vinyltrimethoxysilane, p-styrylmethoxysilane, phenyltrimethoxysilane, and dimethyldimethoxysilane having no long-chain alkyl group having 6 or more carbon atoms. In Comparative Examples 2, 3, 5 and 6 in which an ITO conductive film was formed using ITO powder made of crystalline ITO particles, the electric resistance value after humidification increased from 12233 to 18753 Ω / sq, and the electric resistance after humidification was increased from the initial electric resistance value. The rate of change to the resistance value increased from 25.7 to 60.3 times. On the other hand, ITO conductive using ITO powder composed of polycrystalline ITO particles surface-treated with hexyltrimethoxysilane, decyltrimethoxysilane, and hexyltriethoxysilane having a long-chain alkyl group having 6 or more carbon atoms. In Examples 10 to 12 in which the film was formed, the electric resistance value after humidification was reduced to 1393 to 1937 Ω / sq, and the rate of change from the initial electric resistance value to the electric resistance value after humidification was 3.6 to 4.1 times. It has become smaller. Thus, the surface treatment is performed by the surface treatment agent comprising a silane coupling agent having two or more alkoxy groups having 2 or less carbon atoms and one or more long-chain alkyl groups having 6 or more carbon atoms. When an ITO conductive film is formed using ITO powder made of polycrystalline ITO particles, the electrical resistance value is relatively low after humidification, and the increase in electrical resistance value can be sufficiently suppressed even under high temperature and high humidity conditions. understood.
　更に、表１から明らかなように、一部がフッ素で置換されたアルキル基を有するトリフルオロプロピルトリメトキシシランで表面処理した多結晶ＩＴＯ粒子からなるＩＴＯ粉末を用いてＩＴＯ導電膜を形成した実施例９では、加湿後電気抵抗値が１４０７Ω／sqと小さくなり、初期電気抵抗値から加湿後電気抵抗値への変化率が３．１倍と小さくなった。これにより炭素数が２以下であるアルコキシ基を２つ以上有し、かつ一部がフッ素で置換されたアルキル基を１つ以上有するシランカップリング剤からなる表面処理剤により、表面処理された多結晶ＩＴＯ粒子からなるＩＴＯ粉末を用いてＩＴＯ導電膜を形成すると、加湿後電気抵抗値が比較的低く、かつ高温高湿下であっても、電気抵抗値の上昇を十分に抑制できることが判った。 Further, as is apparent from Table 1, an ITO conductive film was formed using ITO powder made of polycrystalline ITO particles surface-treated with trifluoropropyltrimethoxysilane having an alkyl group partially substituted with fluorine. In Example 9, the electric resistance value after humidification was reduced to 1407 Ω / sq, and the rate of change from the initial electric resistance value to the electric resistance value after humidification was reduced to 3.1 times. As a result, the surface treatment with the surface treatment agent comprising a silane coupling agent having two or more alkoxy groups having 2 or less carbon atoms and one or more alkyl groups partially substituted with fluorine is performed. It was found that when an ITO conductive film is formed using ITO powder composed of crystalline ITO particles, the electrical resistance value is relatively low after humidification, and the increase in electrical resistance value can be sufficiently suppressed even under high temperature and high humidity. .
　１０　　多結晶ＩＴＯ粒子
　１１　　棒状中心核
　１２　　棒状体 10 Polycrystalline ITO particles 11 Rod-shaped central core 12 Rod-shaped body

Claims (7)

  1. 　炭素数が２以下であるアルコキシ基を４つ有する珪酸エステル又はこの珪酸エステルのオリゴマー体からなる表面処理剤により、或いは炭素数が２以下であるアルコキシ基を２つ以上有し、かつアミノ基若しくはメルカプト基を末端基に有するアルキル基、炭素数が６以上である長鎖のアルキル基、又は一部がフッ素で置換されたアルキル基のいずれか１種のアルキル基を１つ以上有するシランカップリング剤からなる表面処理剤により、表面処理された多結晶ＩＴＯ粒子からなるＩＴＯ粉末。 By a surface treatment agent comprising a silicic acid ester having 4 or less alkoxy groups having 2 or less carbon atoms or an oligomer of this silicic acid ester, or having 2 or more alkoxy groups having 2 or less carbon atoms, and an amino group or Silane coupling having one or more alkyl groups of any one of an alkyl group having a mercapto group as a terminal group, a long-chain alkyl group having 6 or more carbon atoms, or an alkyl group partially substituted with fluorine ITO powder made of polycrystalline ITO particles surface-treated with a surface treatment agent made of an agent.
  2. 　前記珪酸エステルが、炭素数が１であるアルキル基を有するテトラメトキシシラン、又は炭素数が２であるアルキル基を有するテトラエトキシシランである請求項１に記載のＩＴＯ粉末。 The ITO powder according to claim 1, wherein the silicate ester is tetramethoxysilane having an alkyl group having 1 carbon atom or tetraethoxysilane having an alkyl group having 2 carbon atoms.
  3. 　前記シランカップリング剤が、Ｎ－２－(アミノエチル)－３－アミノプロピルトリメトキシシラン、３－アミノプロピルトリメトキシシラン、３－メルカプトプロピルメチルジメトキシシラン、３－メルカプトプロピルトリメトキシシラン、トリフルオロプロピルトリメトキシシラン、ヘキシルトリメトキシシラン、ヘキシルトリエトキシシラン、及びデシルトリメトキシシランからなる群より選択される何れか一つである請求項１に記載のＩＴＯ粉末。 The silane coupling agent is N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, trifluoro The ITO powder according to claim 1, which is any one selected from the group consisting of propyltrimethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, and decyltrimethoxysilane.
  4. 　請求項１ないし３のいずれか１項に記載のＩＴＯ粉末の表面処理剤の蒸気を不活性ガスからなるキャリアガスに含ませて、多結晶ＩＴＯ粒子を充填したロータリキルン内に流通させることにより多結晶ＩＴＯ粒子を前記表面処理剤で表面処理するＩＴＯ粉末の製造方法。 The surface treatment agent vapor of the ITO powder according to any one of claims 1 to 3 is contained in a carrier gas composed of an inert gas, and is circulated in a rotary kiln filled with polycrystalline ITO particles. A method for producing ITO powder, wherein crystal ITO particles are surface-treated with the surface treatment agent.
  5. 　請求項１ないし３のいずれか１項に記載のＩＴＯ粉末の表面処理剤の蒸気を不活性ガスからなるキャリアガスに含ませて、多結晶ＩＴＯ粒子を充填した管状炉内に流通させることにより多結晶ＩＴＯ粒子を前記表面処理剤で表面処理するＩＴＯ粉末の製造方法。 The surface treatment agent vapor of the ITO powder according to any one of claims 1 to 3 is contained in a carrier gas composed of an inert gas, and is circulated in a tubular furnace filled with polycrystalline ITO particles. A method for producing ITO powder, wherein crystal ITO particles are surface-treated with the surface treatment agent.
  6. 　請求項１ないし３のいずれか１項に記載のＩＴＯ粉末と分散媒とを含み、前記分散媒がアルコール系溶液であるＩＴＯ導電膜形成用塗料。 A coating for forming an ITO conductive film comprising the ITO powder according to any one of claims 1 to 3 and a dispersion medium, wherein the dispersion medium is an alcohol-based solution.
  7. 　請求項６に記載されたＩＴＯ導電膜形成用塗料を用いてＩＴＯ導電膜を形成する方法。 A method for forming an ITO conductive film using the ITO conductive film forming paint according to claim 6.
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