+

WO2004067447A1 - Procede pour produire un dispersoide presentant des liaisons metal-oxygene et dispersoide - Google Patents

Procede pour produire un dispersoide presentant des liaisons metal-oxygene et dispersoide Download PDF

Info

Publication number
WO2004067447A1
WO2004067447A1 PCT/JP2004/000882 JP2004000882W WO2004067447A1 WO 2004067447 A1 WO2004067447 A1 WO 2004067447A1 JP 2004000882 W JP2004000882 W JP 2004000882W WO 2004067447 A1 WO2004067447 A1 WO 2004067447A1
Authority
WO
WIPO (PCT)
Prior art keywords
metal
dispersoid
temperature
bis
producing
Prior art date
Application number
PCT/JP2004/000882
Other languages
English (en)
Japanese (ja)
Inventor
Shinji Abe
Kazuki Hasegawa
Original Assignee
Nippon Soda Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Soda Co., Ltd. filed Critical Nippon Soda Co., Ltd.
Priority to JP2005504757A priority Critical patent/JPWO2004067447A1/ja
Publication of WO2004067447A1 publication Critical patent/WO2004067447A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/14—Methods for preparing oxides or hydroxides in general
    • C01B13/32—Methods for preparing oxides or hydroxides in general by oxidation or hydrolysis of elements or compounds in the liquid or solid state or in non-aqueous solution, e.g. sol-gel process
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/22—Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability

Definitions

  • the present invention relates to a method for producing a dispersoid having a metal-oxygen bond, which is stably dispersed without aggregation in an organic solvent.
  • the metal oxide sol is useful as a material for forming a metal oxide film, an inorganic component of an organic-inorganic composite, and the like, and a method for producing rebeck is known.
  • Japanese Patent Application Laid-Open No. 2001-233604 discloses that, in an organic solvent containing an alkoxy alcohol, a metal alkoxide or a mixture of a metal alkoxide and a metal salt is added in an amount of 0 to the total number of moles thereof. It describes a method for producing a coating solution that is hydrolyzed with 1 to 10 water, preferably 3 to 10 water.
  • An object of the present invention is to provide a method for producing a dispersoid having a metal-oxygen bond which can be applied to various metals and is stably dispersed without aggregation.
  • the present inventors have conducted intensive studies to solve the above problems, and as a result, in an organic solvent containing one or two or more alkoxy alcohols, one or more metal compounds were added to the total molar amount of the metal compounds. Dispersoids with a metal-oxygen bond that are stable, transparent, and homogeneously dispersed without aggregation because they can be applied to various types of metals by adding water that is at least 1/2 mole and less than 2 moles of the number. The present inventors have found a method for producing the compound, and have completed the present invention.
  • the present invention is as follows.
  • one or two or more metal compounds are added in a molar amount equal to or more than 1/2 times the mole and less than 2 times the total number of moles of the metal compounds.
  • the metal compound has the formula (I)
  • ⁇ represents a metal atom
  • X represents a hydrolyzable group
  • R represents an organic group which may have a functional group capable of forming a bond with the metal atom via an oxygen atom
  • a + b m
  • b represents an integer from l to m
  • m represents the valency of a metal atom.
  • the metal is at least one selected from the group consisting of titanium, zirconium, aluminum, gay, germanium, indium, tin, tantalum, zinc, tungsten, lead, magnesium, lanthanum, tantalum, and barium.
  • the method for producing a dispersoid having a monooxygen bond according to any one of (1) to (11).
  • the dispersoid in the present invention is characterized by being stably dispersed without aggregation.
  • the dispersoid means fine particles dispersed in a dispersion system, and specific examples thereof include colloid particles.
  • the state of being stably dispersed without aggregation in the present invention means a state in which a dispersoid having a metal-oxygen bond in a solvent does not coagulate and is not separated inhomogeneously, and is preferably transparent and homogeneous.
  • the term “transparent” refers to a state in which the transmittance of visible light is high. Specifically, the concentration of the dispersoid is oxidized. 0.5% by weight in terms of material, the optical path length of the quartz cell is 1 cm, the target sample is an organic solvent, and the wavelength of light is 550 nm. This refers to a state representing a transmittance of 80 to 100%.
  • the particle size of the dispersoid of the present invention is not particularly limited, but in order to obtain a high transmittance in visible light, the particle size is preferably in the range of 1 to 100 nm, and 1 to 5 nm.
  • the thickness is preferably 0 nm, more preferably in the range of 1 to 10 nm.
  • Alkoxy alcohols used as solvents include 2-methoxyethanol, 2-ethoxyethanol, 2-propoxyethanol, 2-butoxyethanol, 1-methoxy-2-propanol, 3-methoxypropanol, 3-ethoxypropanol, and 3-ethoxypropanol.
  • Examples include, but are not particularly limited to, alkyl alcohols having 1 to 4 alkoxy and 1 to 4 carbon atoms, such as propoxypropanol, 4-methoxybutanol, 4-ethoxybutanol, and 4-propoxybutanol. . These alkoxy alcohols are used alone or in combination of two or more.
  • 2-methoxyethanol, 2-ethoxyethanol or 1-methoxy-2-propanol is used as solvent, more preferably 2-methoxyethanol.
  • other organic solvents compatible with the alkoxy alcohol can be added within a range that does not affect the reactivity, but usually the alkoxy alcohol is the main component.
  • the organic solvent is distilled off from the reaction solution containing the alkoxy alcohol to a high concentration state, and a homogeneous and transparent dispersion can be obtained by adding the organic solvent again.
  • the organic solvent depends on the type of the metal compound.
  • alcohol solvents such as methanol and ethanol
  • chlorinated solvents such as methylene chloride and chloroform
  • hexane cyclohexane
  • benzene toluene
  • xylene Hydrocarbon solvents
  • chlorobenzene ether solvents such as tetrahydrofuran, dimethyl ether, dioxane, etc.
  • ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, dimethylformamide, dimethyl sulfoxide
  • Aprotic polar solvents such as methylpolysiloxane and octamethylcyclotetrasiloxane used as a dispersion medium of a titanium dioxide dispersion described in JP-A-9-120838.
  • Decamethylcyclopentanesiloxane methylphenol Silicones such as enylpolysiloxane can be
  • Examples of the metal compound used in the present invention include a compound represented by the formula (I).
  • M represents a metal atom
  • specific examples of the metal atom used in the present invention include an alkali metal element, an alkaline earth metal element and an alkali metal element from the second period to the sixth period of the periodic table.
  • 3 Group B element one of the elements selected from the group consisting of Group 4B element and Group 5B element from the third period to the sixth period of the periodic table, the transition metal element, and the lanthanide element
  • a combination of two or more metals can be exemplified.
  • the metal is titanium, zirconium, aluminum, silicon, germanium
  • Preference is given to indium, tin, tantalum, zinc, tungsten, lead, magnesium, lanthanum, tantalum and barium.
  • magnesium, lanthanum, tantalum, and barium which are hardly soluble in common organic solvents, can be produced.
  • X represents a hydrolyzable group, specifically, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, an acyloxy group having 1 to 6 carbon atoms, a halogen atom, an isocyanate group, an amino group, Or an amide group, etc.
  • b represents an integer of 1 to m, which may be the same or different, and particularly include a hydroxyl group and a carbon number which may have a substituent.
  • Preferred are 1 to 6 alkoxy groups, halogen atoms, or isocyanate groups.
  • R represents an organic group which may have a functional group capable of forming a bond with a metal atom via an oxygen atom.
  • R represents a monovalent hydrocarbon group, A monovalent hydrocarbon group, a monovalent halogenated hydrocarbon group, a monovalent halogenated hydrocarbon group having a substituent, a monovalent hydrocarbon group containing a linking group, or a monovalent halogenated hydrocarbon group containing a linking group.
  • a represents an integer of any one of lb, and when a is 2 or more, they may be the same or different.
  • Specific examples of the functional group capable of forming a bond with a metal atom via an oxygen atom include a hydroxyl group, an active halogen atom, a propyloxyl group, and an ester group.
  • R is a monovalent hydrocarbon group
  • an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 1 to 30 carbon atoms, or an aryl group is preferable.
  • R is a monovalent halogenated hydrocarbon group
  • the group means a group in which one or more of the hydrogen atoms in the hydrocarbon group has been replaced with a halogen atom, and
  • a group in which two or more are substituted with a halogen atom is preferred.
  • the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom, and a fluorine atom is preferable.
  • R is a monovalent hydrocarbon group having a substituent
  • R refers to a group in which a hydrogen atom of the monovalent hydrocarbon group is substituted with a substituent
  • R is a monovalent halogenated hydrocarbon group having a substituent.
  • R refers to a group in which a hydrogen atom or a halogen atom in a monovalent halogenated hydrocarbon group is substituted with a substituent.
  • substituent in these groups include a hydroxyl group, an amide group, an imide group, an ester group, and a hydroxyl group. Further, the number of substituents in these groups is preferably 1 to 3.
  • R is a carbon-carbon bond between the monovalent hydrocarbon group or the monovalent halogenated hydrocarbon.
  • examples include a group containing a linking group, or a group in which a linking group is bonded to a terminal of a monovalent hydrocarbon group or a monovalent halogenated hydrocarbon group bonded to a metal atom.
  • the linking group is preferably — ⁇ , —S—, —COO— or —CONR — (R i is a hydrogen atom or an alkyl group).
  • the metal compound represented by the formula (I) is particularly preferably a metal alkoxide.
  • the partial hydrolyzate of the metal alkoxide exemplified above is also included in the metal alkoxide used in the present invention.
  • the element is a composite alkoxide obtained by a reaction between two or more metal alkoxides, or a compound alkoxide obtained by a reaction of one or more metal alkoxides with one or more metal salts. It may be a complex alkoxide. Furthermore, these can be used in combination.
  • a complex alkoxide as a complex salt obtained by a combination of Group 3B elements can be exemplified.
  • chloride examples thereof include compounds obtained by reacting a metal salt such as nitrate, sulfate, acetate, formate, and oxalate with an alkoxide.
  • the number of carbon atoms in the alkoxy group of the metal alkoxide is not particularly limited, but is preferably 1 to 4 carbon atoms in view of the concentration of the contained oxide, the ease of desorption of organic substances, the availability, and the like.
  • an acyloxy group such as an acetoxy group, which can be more easily hydrolyzed, can also be used.
  • An organic solvent containing one or two or more alkoxy alcohols Producing a dispersoid having a metal-oxygen bond that can be stably dispersed without aggregation in an organic solvent by a method using 0.5 to 2 moles of water relative to the metal compound in a medium. Can be.
  • the water used in the present invention is not particularly limited as long as it is neutral, but it is preferable to use distilled water or ion-exchanged water, and particularly preferable is ion-exchanged water having an electric conductivity of 2 s / cm or less.
  • the amount is not particularly limited as long as it is in the range specified above, and can be arbitrarily selected depending on the dispersoid having the desired properties.
  • the method of adding water to a metal compound includes a method of adding water diluted with an organic solvent to an organic solvent solution containing an alkoxy alcohol of a metal compound, and a method of adding an alkoxy alcohol of a metal alkoxide in an organic solvent in which water is suspended or dissolved. Any method can be used to add an organic solvent containing, but a method of adding water later is preferable. Further, the addition of water may be performed once or may be performed in plural times.
  • the concentration of the metal compound in the organic solvent is not particularly limited as long as it can suppress rapid heat generation and has a fluidity that allows stirring, but is usually preferably 5 to 30% by weight.
  • the temperature at which water is added to the metal compound is not particularly limited, but is preferably equal to or lower than the hydrolysis start temperature, and more preferably 150 ° C. to 110 ° C.
  • the hydrolysis start temperature indicates the lowest temperature at which hydrolysis proceeds when the metal compound comes into contact with water.
  • the method for measuring the hydrolysis initiation temperature is not particularly limited, and specifically, the method described in JP-A-1-234007, and measurement of 1 H NMR at elevated temperature from a low temperature state Thus, a method of measuring a change in signal of the hydrolyzable group of the metal compound and the like can be exemplified.
  • water is added to the metal compound at a predetermined temperature, it is preferable to add water or an organic solvent solution containing water at the same predetermined temperature.
  • the temperature can be raised from room temperature to the reflux temperature of the solvent used.
  • this dispersion a gel film, gel fiber, parc gel, etc., having a low content of organic substances can be obtained.
  • the organic substances are desorbed from the gel by heat treatment or the like, the fine structure of the obtained molded body is obtained. And the amount of residual pores can be reduced.
  • the present invention provides a solution containing a dispersoid having a metal monooxide bond obtained by treating a metal compound with water in a solvent prepared as described above, wherein the weight concentration of the dispersoid in terms of metal oxide is reduced. It is characterized in that it is stably dispersed in a solvent even if it is at least 1.2 times, more preferably at least 1.4 times, the metal oxide equivalent weight concentration of the metal compound before the treatment. This is because a solution in which a dispersoid having a metal-oxygen bond is dispersed in an organic solvent at a high concentration is further concentrated at room temperature or higher, preferably at 80 ° C or lower, by distilling off the organic solvent.
  • the state of high concentration includes a state in which there is no solvent, and the state at that time can take any one of a solid state, a liquid state, a gel state, or a mixed state thereof, depending on the metal.
  • the dispersoid of the present invention is sufficiently stable, but a dispersion stabilizer can be added.
  • the dispersion stabilizer refers to a component added to disperse the dispersoid in the dispersion medium in a stable manner, and includes anticoagulants such as deflocculants, protective colloids, and surfactants.
  • the compound having such an action include chelating compounds.
  • the compound has at least one hydroxyl group in the molecular skeleton, and has a strong chelating effect on metal.
  • such compounds include glycolic acid, dalconic acid, lactic acid, tartaric acid, citric acid, malic acid, polycarboxylic acids such as succinic acid, and hydroxycarboxylic acids. Examples thereof include pyrophosphoric acid and tripolyphosphoric acid.
  • polydentate conjugates having strong chelating ability for metal atoms include acetylacetone, methyl acetoacetate, ethyl acetoacetate, acetoacetate-n-propyl, acetoacetate-i-propyl.
  • Acetoacetate-n-butyl, acetoacetate-sec-butyl, acetoacetate-t-butyl, 2,4-hexane-dione, 2,4-heptanedione, 3,5-heptanedione, 2,4 Mono-octane-dione, 2,4-nonanedione, 5-methyl-hexanedione and the like can be exemplified.
  • Dimethylpolysiloxane-methyl (polysiloxyalkylene) siloxane copolymer trimethylsiloxycyanic acid, carboxy-modified silicone described in JP-A-438-38 and JP-A-2000-53421 Examples include oils, silicone compounds such as amine-modified silicones, and the like.
  • a metal oxide thin film and an organic-inorganic composite can be produced from a dispersoid having a metal-oxygen bond prepared as described above and / or an inorganic polymer using the dispersoid as a starting material. .
  • the solution containing the dispersoid is applied and then dried at a temperature of 200 ° C. or less.
  • concentration of the dispersoid in the solution containing the dispersoid varies depending on the coating method and the target film thickness, but is not particularly limited as long as it can be applied on the substrate.
  • the range of 5 to 50% by weight in terms of the converted weight is preferable.
  • the solvent used for the solution include the same solvents as those used for dispersing the dispersoid. Particularly, it is preferable to use the same solvent as the solvent used for dispersing the dispersoid. Although preferred, a different solvent can be used as long as it does not affect the dispersibility of the dispersoid.
  • Other components can be added to the solution containing the dispersoid as needed.
  • other components include water glass, colloidal silica, silicon compounds such as polyorganosiloxane, phosphates such as zinc phosphate and aluminum phosphate, heavy phosphates, cement, lime, gypsum, and the like.
  • Inorganic binders such as frit for enamel, glaze for glass lining, plaster, fluorine Organic binders such as polymers, silicone polymers, acrylic resins, epoxy resins, polyester resins, melamine resins, urethane resins, alkyd resins, etc., and these binders may be used alone or in combination of two or more. These can be used in combination.
  • an inorganic binder, a fluorine-based polymer, and a silicon-based polymer are preferable.
  • cement include Portland cement such as early-strength cement, ordinary cement, moderate heat cement, sulfate resistant cement, white cement, oil well cement, geothermal well cement, fly ash cement, high sulfate cement, and silica.
  • Cement, mixed cement such as blast furnace cement, and alumina cement can be used.
  • Secco Plus Plus, lime plaster, dolomite plaster, etc. can be used as plus plus one.
  • fluorine-based polymer examples include polyvinyl fluoride, polyvinylidene fluoride, polychlorinated trifluorene, polytetrafluoroethylene, polytetrafluoroethylene, hexafluoropropylene copolymer, and ethylene-polytetrafluoroethylene copolymer.
  • Crystalline fluoroplastics such as ethylene monochloride trifluoride ethylene copolymer, tetrafluoroethylene-perfluoroalkylpier ether copolymer, perfluorocyclopolymer, pinyl ether-fluoroolefin polymer, Amorphous fluororesins such as vinyl ester-fluorofluorin copolymers and various fluorine-based rubbers can be used.
  • a fluoropolymer mainly composed of a bier ether-fluorofluorin copolymer and a vinyl ester-fluorofluorin copolymer is preferred because it is less likely to decompose and deteriorate and is easy to handle.
  • a silicon-based polymer a silicon-modified resin such as a straight-chain silicone resin, an ataryl-modified silicone resin, an acryloyl silicone resin, an epoxy-silicon resin, and various silicone rubbers can be used.
  • the ratio of the dispersoid to the other components exemplified above is 5 to 98% by weight, preferably 20 to 98%, more preferably 50 to 98%, and most preferably 70 to 9%. 8%.
  • a heat stabilizer, an antioxidant, an ultraviolet absorber, an antistatic agent, a coloring agent, a surfactant, a crosslinking agent, a dispersant, a filler, and the like may be added to the solution containing the dispersoid.
  • a cross-linking agent a normal cross-linking agent such as an isocyanate-based or melamine-based one can be used, and as a dispersing agent, a force coupling agent or the like can be used.
  • any of known methods such as spin coating, dip coating, spray coating, roll coating, and screen printing may be used. it can.
  • roll coating is preferred.
  • a method using a par and a method using a gas are preferable methods.
  • a screen printing method and an offset printing method are preferable because patterning can be performed at the time of coating.
  • the coating amount varies depending on the use of the obtained thin film, but is generally 0.1 to 10 ml / m2 as the coating amount of the active ingredient other than the solvent. More preferred details, a 0. 2 ⁇ 7ml / m 2, more preferably from 0. 4 ⁇ 5 ml / m 2 .
  • Substrates include articles made of inorganic materials such as ceramics and glass, plastic, rubber, wood, and paper. Any organic material, metal such as aluminum, and metal material such as an alloy such as steel can be used.
  • the size and shape of the substrate are not particularly limited, and any of a flat plate, a three-dimensional object, a film, and the like can be used. It can also be used for painted articles.
  • plastic films are preferred, and examples include cellulose triacetate, cellulose diacetate, nitrocellulose, polystyrene, polyethylene terephthalate, polyethylene naphthate, syndiotactic polystyrene, polyethylene-coated paper, polyether sulfone, and polyarylate.
  • Polyvinylidene fluoride, Teflon (registered trademark) and the like can be used.
  • these supports may be provided with a waterproof layer containing a polyvinylidene chloride-based polymer for the purpose of improving the so-called dimensional stability, in which dimensions change due to changes in temperature and humidity.
  • a thin film of an organic and / or inorganic compound may be provided for the purpose of gas barrier.
  • the organic thin film include polyvinyl alcohol and poly (ethylene-co-biel alcohol).
  • the inorganic compound include silica, alumina, talc, permikulite, kaolinite, mica, and synthetic mica. No.
  • various organic and / or inorganic additives may be added to the substrate for other functions.
  • the applied film can be subjected to a heat treatment as needed while distilling off the solvent.
  • Heating after coating can be performed at a low temperature of 200 ° C. or less, preferably 20 to 100 ° C., and more preferably 30 to 80 ° C.
  • the heating time is not particularly limited, but is usually from 1 minute to 120 hours.
  • a metal oxide-containing seed crystal which is supposed to be formed after film formation is added to the coating solution containing the metal compound.
  • the addition ratio of the seed crystals of the metal oxide fine particles is preferably from 10 w to 90 w, more preferably from 10 w to 80 wt% of the sol weight when the sol is formed from the dispersoid.
  • the metal oxide may be crystallized by light irradiation. In this case, the crystallization of the metal oxide is further promoted by the addition of the seed crystal. I do.
  • the size of the seed crystal is arbitrary, but is preferably not more than 0.1 ⁇ in terms of sphere from the viewpoint of transmittance.
  • the seed crystal to be added is not limited to the target metal oxide itself, but may be any one that is suitable for heteroepitaxy, such as a crystal having the same crystal form and / or having a value close to the lattice constant.
  • indium oxide can be used as a seed crystal.
  • a commercially available product or a synthesized product may be used.
  • the metal oxide thin film is IT0
  • commercially available products such as those manufactured by Mitsubishi Materials and Sumitomo Metal Mining can be used.
  • the synthesis method include a sol-gel method, hydrothermal synthesis, and ordinary sintering.
  • sol-gel method science soluhana S., Agune Jyofusha, 1988
  • Sol-gel method for thin film coating technology Technical Information Association, 1994
  • Sol-gel method Sol-gel method.
  • the outlook supervised by Masayuki Yamane, Technical Information Service Roundtable [ATIS] Sol-Gel Report Publications, 1992 ”.
  • the light source that irradiates the coating film with ultraviolet light or visible light is 150 ⁇ ! Any material may be used as long as it emits light having a wavelength of 700 nm.
  • a transparent conductive pattern can be formed by using a photomask in combination.
  • a laser oscillator can be used.
  • the laser-oscillator include an excimer laser, an argon laser, a helium-neon laser, a semiconductor laser, a YAG laser, a carbon dioxide laser, and a dye laser.
  • a laser beam is used, a metal oxide is not formed except for an irradiated portion, so that a pattern can be formed without using a screen printing or the like at the time of coating.
  • Synchrotron radiation can also be used. These devices can be selected in consideration of the wavelength to be irradiated.
  • a metal hydroxide is generated together with the generation of the metal oxide, but in consideration of the absorption of the metal-10H bond, light including ultraviolet light of 400 nm or less is considered. It is advisable to use a device that generates this. Furthermore, when the metalloxane network is formed by the progress of the dehydration reaction, the absorption of the metal-10-metal bond is shorter than that of the metal-10H bond, but the metal-10-metal bond must be activated. By irradiating light having a wavelength that allows the crystallization, crystallization of the metal oxide is promoted. Although the irradiation time is not particularly limited, it is usually appropriately set between 1 minute and 120 hours.
  • the atmosphere in the light irradiation process is free, but it is preferable to perform the reduction in a certain reduction atmosphere. It is considered that under a certain reducing atmosphere, an increase in carrier density due to an increase in oxygen vacancies and / or adsorption of oxygen molecules to grain boundaries was suppressed.
  • a high boiling point low molecular weight solvent that decomposes by light irradiation may be used.
  • examples include isophorone and benzyl acetate.
  • a resin made of photolysis can be used.
  • quinone diazides polymethyl methacrylate, polyphenylmethylsilane, and polymethylisopropenyl ketone.
  • the dispersoid of the present invention is, in particular, a fine particle that is stably dispersed in an organic solvent without using an acid, a base, and / or a dispersion stabilizer, and has high transparency. Polymers and organic-inorganic composites Coalescence can be formed.
  • Examples of the known polymer include an acrylic resin, a poly (thio) urethane-based resin, a resin mainly containing getyldaricol bisacrylcarbonate, and a resin obtained from an epoxy group-containing compound. Specifically, the following can be exemplified.
  • acrylic resin examples include those obtained by polymerizing a monomer described below as a raw material.
  • Monofunctional methacrylates include methyl methacrylate, ethyl methacrylate, n-butyl methyl methacrylate, ethyl methacrylate, benzyl methyl acrylate, phenyl methacrylate, cyclohexyl methyl acrylate, Examples include isopolnyl methacrylate and adamantyl methacrylate.
  • polyfunctional methacrylates include ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, propylene dimethyl ether, and 1,4-butanediol dimethyl.
  • the monofunctional acrylate include methyl acrylate, ethyl acrylate, n-butyl acrylate, ethyl hexyl acrylate, cyclohexyl acrylate, benzyl acrylate, phenyl acrylate, and isopolnyl acrylate.
  • ethylene glycol diacrylate triethylene glycol diacrylate, 1,6-hexanediol diatalylate, trimethylolpropane triacrylate, pen-erythri 1-triacrylate And the like.
  • styrene methylstyrene, dimethylstyrene, chlorostyrene, dichlorostyrene, bromostyrene, p-chloromethylstyrene, di-substituted styrene such as divinylbenzene, and a-methylstyrene Acrylonitrile, methacrylonitrile, maleic anhydride, N-substituted maleimide, and the like, and the copolymers of these with the acrylic or methacrylic compounds also fall under the category of acrylic resins.
  • an organic monomer capable of radical or cationic polymerization is preferable, and an organic monomer containing at least one bond selected from an amide bond, an imide bond, a urethane bond, and a urea bond is particularly preferable.
  • specific examples of the radically polymerizable organic monomer include (meth) acrylamide, (meth) acrylamide derivatives, (meth) acryloylmorpholine, N-vinylpyrrolidone, (meth) urethane And acrylates and adducts of aminoalkyl (meth) acrylate and isocyanate.
  • (meth) acrylamide refers to both methacrylamide and acrylamide
  • (meth) acrylate refers to both methacrylate and acrylate.
  • examples of the cationically polymerizable monomer include compounds having an epoxy ring, a vinyl ether bond, or an orthospiro ring as a polymerization functional group.
  • an optional organic monomer may be used for modifying the obtained polymer, and this kind of optional organic monomer has an amide bond, a urethane bond, and a urea bond. You don't have to. However, this arbitrary organic monomer must have the same polymerization mode (radical polymerization, cationic polymerization) as the above-mentioned essential monomer.
  • optional organic monomers include, when the essential monomer is a radically polymerizable monomer, methyl (meth) acrylate, 1, licyclo [5,2,1,0] decanyl (meth) acrylate, Pentyldaricol di (meth) acrylate, 3,3,3-trifluoroethyl (meth) acrylate, etc.
  • the essential monomer is a cationically polymerizable monomer, ethylene glycol-diglycidyl ether, propylene dalicol diglycidyl ether, water And bisphenol A diglycidyl ether.
  • the poly (thio) urethane resin refers to a polythiourethane or polyurethane resin obtained by reacting a polyisocyanate compound with a polythiol compound or a polyhydroxy compound.
  • the polyisocyanate compound is not particularly limited, and specific examples thereof include the following.
  • meta and paraphenylene diisocyanate 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, meta And isocyanate compounds having an aromatic ring such as para-xylylene diisocyanate, meta and para-tetramethyl xylylene diisocyanate, 2,6-naphthalene diisocyanate, and 1,5-naphthalene diisocyanate (preferable These include 2,4- and 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, meta-xylylene diisocyanate, meta-tetramethyl xylylene diisocyanate, 2 , 6-naphthalene diisocyanate),
  • diphenyldisulphide-1,4,4'-diisocyanate 2,2'-dimethyldiphenyldisulfide-1,5,5'-diisocyanate, 3,3'-dimethyldiphenyldisulphide-1,5, 5'-Diisocyanate, 3, 3'-Dimethyldiphenyldisulphide-1,6,6'-diisocyanate, 4,4'-Dimethyldiphenyldisulphide-1,5,5'-Diisocyanate, 3,3 '—Dimethoxydiphenyl disulphide-1,4' —Diisocyanate, 4, 4 'Dimethoxydiphenyldisulphide-1,3' —Diisocyanate, diphenylsulfone-1,4,4 '—Diisocyana 1,3'-diisocyanate, benzylidenesulfone 4,4'-diisocyanate, diphenylmethane
  • 1,3,5-tris (mercaptomethyl) benzene, 1,2,3-tris (mercaptoethyl) benzene, 1,2,4-tris (mercaptoethyl) benzene, 1,3,5-trimethyl (Mercaptoethyl) benzene, 1,2,3-tris (mercaptomethoxy) benzene, 1,2,4-tris (mercaptomethoxy) benzene, 1,3,5-tris (mercaptomethoxy) benzene , 1,
  • V bis (mercaptomethyl) sulfide, bis (mercaptoethyl) sulfide, bis (meth Lecaptopropyl) sulfide, bis (mercaptomethylthio) methane, bis (2-mercaptoethylthio) methane, bis (3-mercaptopropylthio) methane, 1,2-bis (mercaptomethylthio) ethane, 1,2- (2 —Mercaptoethylthio) ethane, 1,2— (3-Mercaptopyl pill) ethane, 1,3-bis (mercaptomethylthio) propane, 1,3-bis (2-mercabutethylthio) propane, 1,3— Bis (3-mercaptopropylthio) propane, 1,2-bis (2-mercaptoethylthio) -1,3-mercaptopropane, 2-mercaptoethylthio-1,3-propanedithiol, 1,2,3-tris (Mercaptapt
  • Yl triethylene glycol, polyethylene glycol, tris (2-hydroxyethyl) isocyanurate, cyclobutanediol, cyclopentanediol, cyclohexanediol, cycloheptanediol, cyclooctanediol, bicyclo [4,3,0] —Nonanediol, dicyclohexanediol, tricyclo
  • (2-hydroxyethyl) sulfide 1,2-bis- (2-hydroxyethyl mercapto) ethane, bis (2-hydroxyethyl) disulphide, 1,4-dithiane-1,5-diol, bis (2,3-dihydroxypropyl) sulfide, tetrakis (4-hydroxy-12-thiaptyl) methane, bis (4-hydroxyphenyl) sulfone (trade name: bisphenol S), tetrabromobisphenol S, tetramethylbisphenol S Polyols containing sulfur atoms, such as 4,4'-thiopis (6-tert-butyl 3-methylphenol) and 1,3-bis (2-hydroxyethylthioethyl) -cyclohexane.
  • sulfur atoms such as 4,4'-thiopis (6-tert-butyl 3-methylphenol
  • poly (thio) urethane resins those used as lens base materials have been conventionally known.
  • Specific examples of known publications that disclose the following are, for example, JP-A-58-127914, JP-A-57-136601, JP-A-01-163012, and JP-A-03-236386.
  • polyisocyanate compounds, polythiol compounds and polyhydroxy compounds disclosed in these publications correspond to the raw material monomers for producing the poly (thio) urethane resin according to the present invention. .
  • Examples of the resin containing diethylene glycol bisaryl carbonate as a main component include a homopolymer of diethylene glycol bisaryl carbonate and dimethylene glycol bisaryl carbonate. And a copolymer obtained by reacting a copolymerizable monomer with a copolymerizable monomer.
  • Monomers copolymerizable with dimethylene glycol bisaryl carbonate include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, ethyl methacrylate, benzyl methacrylate, phenyl methacrylate, and cyclomethacrylate.
  • Monofunctional methacrylates such as hexyl, isopolnyl methacrylate, and adamantyl methacrylate can be mentioned.
  • Examples of polyfunctional methacrylates include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, and triethylene glycol.
  • Dimethacrylate tripropylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, trimethylolpropane trimethacrylate, Erythritol trimethacrylate, glycerin dimethacrylate, 2,2-bis [4- (methacryloxy) phenyl] propane, 2,2-bis [4- (methacryloxyethoxy) phenyl] propane, etc. .
  • Substituted styrene or a- methyl styrene Atari Ronitoriru, main evening Krilo nitriles, maleic anhydride, N- substituted maleimides, di ⁇ Lil phthalate, di ⁇ Lil isophthalate, Jiariruterefu evening rate, and the like.
  • Copolymers of diethylene glycol bisaryl carbonate and other monomers are known, and examples thereof include Japanese Patent Application Laid-Open Nos. 54-41965 and 51-125254 And Japanese Unexamined Patent Application Publication No. 2001-509380.
  • the resin obtained from the epithio group-containing compound is a resin obtained by polymerizing a monomer having an epithio group or a monomer mixture containing the monomer as a raw material, and specific examples of the monomer having an epithio group include: The following are mentioned.
  • a radical polymer having a (thio) urethane structure in the molecule can be exemplified.
  • a straight-chain polymer having 3 to 6 carbon atoms having at least two mercapto groups in the molecule can be exemplified.
  • a radical polymer using a monomer obtained by reacting a linear alkane compound with a compound having at least one isocyanate group and at least one (meth) acryloyl group in a molecule can be exemplified.
  • the (meth) acryloyl group means both an acryloyl group and a methacryloyl group.
  • Examples of the linear alkane compound having 3 to 6 carbon atoms and having at least two mercapto groups in the molecule which is one of the raw materials of the radical polymerizable compound having a thiourethane bond as described above, include: 2,3-trimercaptopropane, 1,2,3-trimercaptobutane, 1,2,4-trimercaptobutane, 1,2,3,4-tetramercaptobutane, 1,2,3-trimercaptopentane, 1,2,4-trimercaptopentane, 1,2,3,4-tetramercaptopentane, 1,2,3-trimercaptohexane, 1,2,4-trimercaptohexane, 1,2, 5-trimercaptohexane, 2, 3, 4-trimercaptohexane, 2, 3, 5-trimercaptohexane, 3,4,5-trimercaptohexane, 1, 2, 3, 4-tetramercapto Kisane, 1, 2, 3,5-tetramercaptohexane,
  • Examples of other raw materials having at least one isocyanate group and at least one (meth) acryloyl group in a molecule include acryloyl isocyanate, methacryloyi succinate, and 2-isocyanatoethyla. Acrylate and 2-isocyanatoethyl methyl acrylate are preferred. Among them, 2-isocyanatoethyl methacrylate is preferred in view of the performance and availability of the obtained optical material.
  • the one exemplified above has one isocyanate group and one (meth) acryloyl group, but may have two or more isocyanate groups, and may have two or more (meth) acryloyl groups. May be provided.
  • the organic-inorganic composite is used as an optical material, in order to appropriately improve the physical properties, in addition to the polymerizable compound, for example, when a radical polymerizable organic monomer is used, a radical polymerizable group is used. And may contain one or more kinds of radically polymerizable compounds copolymerizable with the above compounds.
  • the radically polymerizable compound examples include methyl (meth) acrylate, Ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, butoxysyl (meth) acrylate, cyclohexyl (meth) Acrylate, 2-hydroxyethyl (methyl) acrylate, glycidyl (meth) acrylate, Hue Kishetil (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene diglycol di (meth) acrylate, polyethylene glycol di (Meth) acrylate, neopentyl glycol (meth) acrylate, ethylene glycol bisglycidyl (meth)
  • the (meth) acrylate means both acrylate and methacrylate
  • the (meth) acryloxy group means both atalyloxy group and methacryloxy group.
  • a known radical or cationic polymerization initiator is used
  • the organic monomer is an organic monomer capable of polyaddition or polycondensation, Ethylenediamine, hexamethylenetetramine, N, N-dimethyloctylamine, N, N, ⁇ ', ⁇ '-tetramethyl-1,6-diaminohexane, 4,4'-trimethylenebis (1-methylbiperidine), 1 , 8-Diazapiciclo- [5,4,0] —Amine compounds such as 7-indene, or dimethyltin dichloride, dimethyltinbis (isooctylthio
  • benzophenone 4,4-dimethylaminobenzophenone, 1-hydroxycyclohexylphenylketone, isoamyl ⁇ -dimethylaminobenzoate, methyl 4-dimethylaminobenzoate, benzoin, benzoin Well-known such as butyl ether, benzoin isobutyl ether, benzoin isopropyl ether, 2,2-diethoxyacetophenone, methyl ⁇ -benzoylbenzoate, 2-hydroxy-2-methyl-1-phenylpropanone, and acylphosphinoxide.
  • a sensitizer may be added.
  • the polymerization reaction can be performed by either solution polymerization or bulk polymerization, and can be performed by heating or irradiating a mixture of an organic component and an inorganic component.
  • the method (i i) or the method (i i i) is preferable.
  • the organic-inorganic composite of the present invention is preferably used as an optical material because it has a high refractive index and a high visible light transmittance.
  • the optical material may include an ultraviolet absorber, a dye or a pigment, etc. to improve light absorption properties, an antioxidant, an anti-coloring agent, etc., to improve weather resistance, and a molding processability, A release agent or the like can be appropriately added as desired.
  • the ultraviolet absorber for example, benzotriazole type, benzophenone type, salicylic acid type and the like can be mentioned
  • the dye and pigment for example, anthraquinone type and azo type can be mentioned.
  • Antioxidants and anti-coloring agents include, for example, monophenol-based, bisphenol-based, high-molecular-weight phenol-based, sulfur-based, and phosphorus-based agents.
  • Release agents include, for example, fluorine-based surfactants and silicone-based surfactants. Agents, acidic phosphates, higher fatty acids and the like.
  • a uniform mixture containing the dispersoid having an oxygen-metal bond, the organic monomer, a monomer copolymerizable with the monomer, an additive and a catalyst may be used.
  • the monomer is a radical polymerizable monomer
  • it is injected into a mold that is a known casting polymerization method, that is, a combination of a glass or resin mold and a resin gasket that transmits ultraviolet light, and is irradiated with ultraviolet light. It is cured, and if it is a polyaddition or polycondensation monomer, it is cured by heating.
  • the mold may be subjected to a mold release treatment in advance to facilitate removal of the resin after molding, or a release agent may be contained in the uniform mixed solution.
  • heating is preferably performed to complete the polymerization or to reduce the stress generated inside the material.
  • the heating temperature and time at this time vary depending on the amount of energy of ultraviolet irradiation and the like, but are generally 30 to 150 ° C. and 0.2 to 24 hours, respectively.
  • the initial temperature is preferably in a relatively low temperature range of 5 to 40 ° C.
  • a high temperature of 30 is used.
  • the optical material obtained by the production method as described in (1) or (4), in which the production of the organic polymer has already been completed can be molded by casting the solution with a mold or the like. You.
  • the optical material of the present invention thus obtained usually has a refractive index of 1.6 or more.
  • the optical material of the present invention can be easily dyed in water or an organic solvent by using a usual disperse dye. At this time, in order to further facilitate the dyeing, a carrier is added or heated. Is also good.
  • the present invention also provides an optical product comprising the optical material obtained as described above.
  • the optical product is not particularly limited, and may be, for example, an optical plastic lens such as an eyeglass lens. Examples thereof include lenses, prisms, optical fibers, recording medium substrates, filters, glasses, vases, etc. Among them, optical plastic lenses, particularly, spectacle lenses are preferred.
  • the optical material of the present invention is applied to the surface of a lens or glass without casting polymerization, and is cured by performing an operation such as light irradiation as necessary, and a hard coat film for protecting the surface is provided. It can also be used as a raw material of a multilayer antireflection film for preventing reflection.
  • the coating method is not particularly limited, but any of dip coating, spin coating, flow coating, roller coating, brush coating and the like can be employed.
  • this precursor sol solution was concentrated under reduced pressure at a pass temperature of 60 ° C. using a monotally evaporator.
  • 12.2 g of a colorless, transparent, high-concentration precursor sol having a concentration of 41 weight in terms of zirconium oxide was obtained. Table 1 summarizes the results.
  • a colorless and transparent precursor sol solution having a concentration of 5 wt.% In terms of intartar oxide was obtained in the same manner as in Example 1, except that tantalum pentaethoxide was used as a starting material and the molar ratio was set to 0 / Ta 1.875.
  • the particle size distribution of this precursor sol solution was monodisperse with a particle size of 5 mn. The results are summarized in Table 1.
  • Table 1 shows examples of the production in the same manner as in Example 1 except that the starting materials and the amount of added water were changed.
  • the zirconium precursor sol solution prepared in Example 1 was concentrated under reduced pressure until it became a solid.
  • the resulting white salt became a homogeneous, transparent dispersion upon addition of 2-methoxyethanol, toluene, THF, xylene or isoamyl alcohol.
  • the tantalum-enriched precursor sol solution prepared in Example 2 (concentration in terms of oxide weight: 51 »2. Og was diluted with 5.8 g of 2-methoxyethanol to a concentration of 13%. This solution was placed on a glass substrate (5 cm ⁇ 5 cm). ) was dropped at room temperature and a rotation speed of 3000 rpm for 30 seconds, and the coated film was dried at a temperature of 100 ° C. and then heated at 400 ° C. for 30 minutes. As a result, a transparent film having a thickness of 260 nm was obtained When the haze ratio and the like were measured using standard white light, the haze ratio H 0.79, the total transmittance T 89.42%, and the linear transmittance P 88. 71% (glass substrate: haze ratio H 0.07, total transmittance T 92.0, linear transmittance P 91.95 Colour
  • Hydrolysis was performed in the same manner as in Example 1, except that the amount of water added to zirconium was 2.0 and 4.0 (3 ⁇ 40 / M molar ratio).
  • the amount of water added was 2.0 (3 ⁇ 40 / M molar ratio)
  • the solution after hydrolysis maintained transparency, but became cloudy when refluxed.
  • the amount of water added was 40 (3 ⁇ 40 / M molar ratio)
  • the solution after hydrolysis was already cloudy, and a white wet gel was formed when refluxed. The gel did not form a homogeneous, transparent dispersion upon addition of 2-methoxyethanol, toluene, THF, xylene or isoamyl alcohol.
  • the solution was refluxed at 120 to obtain 100 g of a colorless and transparent precursor sol solution having a zirconium oxide concentration of 5 wt%, and a light transmittance (400) of 96%. there were.
  • This precursor sol solution was concentrated under reduced pressure at a bath temperature of 60 ° C. using a rotary evaporator. As a result, 12.2 g of a yellow, transparent, high-concentration precursor sol solution having a concentration of 41% by weight in terms of zirconium oxide was obtained.
  • a stable, uniform, and transparent dispersoid having a metal-oxygen bond can be produced. From this dispersoid, an organic-inorganic composite and a metal oxide film can be produced, and since these can be widely used as optical materials and the like, it can be said that the industrial utility value of the present invention is high.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Inorganic Chemistry (AREA)
  • Oxygen, Ozone, And Oxides In General (AREA)
  • Paints Or Removers (AREA)

Abstract

La présente invention concerne un procédé pour produire un dispersoïde qui présente une ou plusieurs liaisons métal-oxygène et qui peut être dispersé de manière stable, sans formation d'agrégat. Ce procédé peut s'appliquer à divers métaux. Le procédé pour produire ce dispersoïde consiste à hydrolyser un ou plusieurs composés métalliques dans un solvant organique contenant un ou plusieurs alcools alkoxy, en utilisant de l'eau avec un rapport molaire d'eau par rapport à l'ensemble des composés métalliques qui s'élève de 0,5 à moins de 2. Le dispersoïde selon cette invention permet de produire des films minces d'oxyde métallique à basse température et donne des composites organiques-inorganiques homogènes.
PCT/JP2004/000882 2003-01-31 2004-01-30 Procede pour produire un dispersoide presentant des liaisons metal-oxygene et dispersoide WO2004067447A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2005504757A JPWO2004067447A1 (ja) 2003-01-31 2004-01-30 金属−酸素結合を有する分散質の製造方法および分散質

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2003024024 2003-01-31
JP2003-024024 2003-01-31

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US11/333,766 Continuation US7631718B2 (en) 2003-07-16 2006-01-17 Saddle-type vehicle and engine

Publications (1)

Publication Number Publication Date
WO2004067447A1 true WO2004067447A1 (fr) 2004-08-12

Family

ID=32820750

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2004/000882 WO2004067447A1 (fr) 2003-01-31 2004-01-30 Procede pour produire un dispersoide presentant des liaisons metal-oxygene et dispersoide

Country Status (2)

Country Link
JP (1) JPWO2004067447A1 (fr)
WO (1) WO2004067447A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7000427B2 (en) 2002-08-15 2006-02-21 Velocys, Inc. Process for cooling a product in a heat exchanger employing microchannels
JP2009203222A (ja) * 2008-01-29 2009-09-10 Kojundo Chem Lab Co Ltd 希土類オキソイソプロポキシドの合成方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01230407A (ja) * 1987-11-17 1989-09-13 Japan Synthetic Rubber Co Ltd 微粒子状金属化合物の製造方法
JPH0959022A (ja) * 1995-08-23 1997-03-04 Nippon Steel Corp Ｍｎ系ペロフスカイト酸化物薄膜の製造方法
JPH10298769A (ja) * 1997-04-18 1998-11-10 Kansai Shin Gijutsu Kenkyusho:Kk 金属酸化物前駆体ゾルの製造方法および金属酸化物成形体の製造方法
JP2001026421A (ja) * 1999-07-14 2001-01-30 Fukuoka Prefecture ゾル・ゲル法による結晶性薄膜の形成方法
JP2001233604A (ja) * 2000-02-24 2001-08-28 Kansai Research Institute 酸化物薄膜形成用塗布液およびその製造方法ならびに酸化物薄膜の製造方法
JP2001342018A (ja) * 2000-05-31 2001-12-11 Japan Carlit Co Ltd:The 金属酸化物前駆体溶液及び金属酸化物薄膜
WO2003014022A1 (fr) * 2001-08-03 2003-02-20 Nippon Soda Co., Ltd. Substance dispersee contenant des liaisons metal-oxygene

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01230407A (ja) * 1987-11-17 1989-09-13 Japan Synthetic Rubber Co Ltd 微粒子状金属化合物の製造方法
JPH0959022A (ja) * 1995-08-23 1997-03-04 Nippon Steel Corp Ｍｎ系ペロフスカイト酸化物薄膜の製造方法
JPH10298769A (ja) * 1997-04-18 1998-11-10 Kansai Shin Gijutsu Kenkyusho:Kk 金属酸化物前駆体ゾルの製造方法および金属酸化物成形体の製造方法
JP2001026421A (ja) * 1999-07-14 2001-01-30 Fukuoka Prefecture ゾル・ゲル法による結晶性薄膜の形成方法
JP2001233604A (ja) * 2000-02-24 2001-08-28 Kansai Research Institute 酸化物薄膜形成用塗布液およびその製造方法ならびに酸化物薄膜の製造方法
JP2001342018A (ja) * 2000-05-31 2001-12-11 Japan Carlit Co Ltd:The 金属酸化物前駆体溶液及び金属酸化物薄膜
WO2003014022A1 (fr) * 2001-08-03 2003-02-20 Nippon Soda Co., Ltd. Substance dispersee contenant des liaisons metal-oxygene

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7000427B2 (en) 2002-08-15 2006-02-21 Velocys, Inc. Process for cooling a product in a heat exchanger employing microchannels
JP2009203222A (ja) * 2008-01-29 2009-09-10 Kojundo Chem Lab Co Ltd 希土類オキソイソプロポキシドの合成方法

Also Published As

Publication number Publication date
JPWO2004067447A1 (ja) 2006-05-18

Similar Documents

Publication Publication Date Title
JP5133815B2 (ja) 金属−酸素を有する分散質
JP5008869B2 (ja) 金属−酸素結合を有する分散質、金属酸化物膜、及び単分子膜
CN110869355B (zh) 苯并吡喃化合物、含有该化合物的固化性组合物、及含有由该固化性组合物形成的固化物的光学物品
JP6929930B2 (ja) 光学材料のための芳香族ポリチオール化合物
JP6034997B1 (ja) 重合性組成物および新規なアルキン化合物
JP4139701B2 (ja) 有機−無機複合体
WO2004067447A1 (fr) Procede pour produire un dispersoide presentant des liaisons metal-oxygene et dispersoide
KR101813258B1 (ko) 광학 재료용 실록산 티올 올리고머
JP5441975B2 (ja) 有機−無機複合体
JP2020132773A (ja) 硬化性複合材料及びそれを用いたインプリント方法
JP7492703B2 (ja) 微粒子分散型重合性組成物の製造方法および該製造方法により作製された微粒子分散型重合性組成物
KR101883811B1 (ko) 광학 재료용 실록산 티올 올리고머
KR101890332B1 (ko) 광학 재료용 실록산 티올 올리고머
JP2024035465A (ja) 微粒子分散型重合性組成物の製造方法および該製造方法により作製された微粒子分散型重合性組成物
JP2006299049A (ja) 有機−無機複合体およびシリル化誘導体
JP2000044648A (ja) 光学製品
JP2001083301A (ja) プラスチックレンズ及びその製造方法

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): BW GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 2005504757

Country of ref document: JP

122 Ep: pct application non-entry in european phase
点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载