WO2007077712A1 - 基体の保護方法 - Google Patents
基体の保護方法 Download PDFInfo
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- WO2007077712A1 WO2007077712A1 PCT/JP2006/324455 JP2006324455W WO2007077712A1 WO 2007077712 A1 WO2007077712 A1 WO 2007077712A1 JP 2006324455 W JP2006324455 W JP 2006324455W WO 2007077712 A1 WO2007077712 A1 WO 2007077712A1
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- Prior art keywords
- substrate
- positively charged
- titanium
- substrate surface
- dielectric
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/16—Anti-static materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B17/00—Methods preventing fouling
- B08B17/02—Preventing deposition of fouling or of dust
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B6/00—Cleaning by electrostatic means
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/06—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects
Definitions
- the present invention relates to a method for achieving prevention or reduction of contamination and protection of a surface by imparting a positive charge to the surface of a substrate.
- a method for forming a film having an antifouling function or a self-cleaning function on the substrate surface has been developed in order to prevent and remove contaminants from the substrate surface.
- this method for example, there is a method of forming a photocatalyst layer using anatase-type oxidite described in JP-A-9-2622481.
- Patent Document 1 Japanese Patent Laid-Open No. 9-262481
- the ultraviolet absorbent when an ultraviolet absorbent is mixed in the substrate, the ultraviolet absorbent may be decomposed by the action of components in the substrate and may not exhibit a sufficient ultraviolet absorbing effect.
- the substrate When the photocatalytic function is imparted to the substrate surface, the substrate itself may be decomposed and deteriorated by the photocatalytic action depending on the type of the substrate. In addition, since it has a negative charge, there is a problem of electrostatically adsorbing contaminants having a positive charge.
- An object of the present invention is to provide a new technique for preventing or reducing fading or discoloration of a substrate over time and at the same time preventing or reducing the adhesion of contaminants.
- An object of the present invention is to provide a substrate surface or a substrate surface layer.
- the organic or inorganic substance is preferably in the form of a film, particularly preferably water-repellent or hydrophilic polymer force.
- an intermediate layer may be formed between the surface of the substrate and the positively charged substance layer.
- the above self-cleaning action is added to the substrate while maintaining the water-repellent or hydrophilic surface characteristics.
- the characteristics of the substrate surface can be changed to water repellency and hydrophilicity by controlling the irradiation of electromagnetic waves onto the substrate surface. Therefore, it is possible to prevent or reduce the adhesion of contaminants to the substrate surface over a long period of time.
- an antifogging function can be imparted to the substrate.
- the substrate treated by the method of the present invention has high resistance to the action itself of sunlight and the like, and the light degradation ability by sunlight or the like can be well protected.
- the present invention can prevent or reduce fading or discoloration of the substrate over a long period of time.
- FIG. 1 is a conceptual diagram showing a positive charge imparting mechanism by a composite used in the present invention.
- FIG. 2 is a schematic diagram showing an example of a first method for producing metal-doped titanium titanium
- FIG. 3 is a conceptual diagram showing a first mode for applying a positive charge to a substrate.
- FIG. 4 is a conceptual diagram showing a second mode in which a positive charge is imparted to a substrate.
- FIG. 5 is a conceptual diagram showing a third mode for applying a positive charge to a substrate.
- FIG. 6 Conceptual diagram showing a fourth mode for applying a positive charge to a substrate.
- FIG. 7 Schematic diagram showing the mechanism for removing contaminants on a positively charged substrate surface.
- Contaminants that are one of the causes of fading or discoloration of the substrate surface are that inorganic substances such as carbon and organic substances such as Z or oil floating in the atmosphere gradually accumulate on the substrate surface. To adhere to the substrate surface.
- the present invention removes these contaminants by means of electrostatic repulsion, or
- the present invention is characterized in that adhesion of these contaminants to the substrate is avoided or reduced.
- pollutants especially oil, which are mainly suspended in the outdoor air, are in an "oxidized” state due to the so-called photooxidation reaction caused by various electromagnetic waves including sunlight. .
- the photo-oxidation reaction refers to the moisture (H 0), oxygen (O
- the organic or inorganic material is naturally separated from the surface of the substrate using electrostatic repulsion.
- the present invention uses a cation; a conductor or dielectric having a positive charge; a composite of a conductor and a dielectric or semiconductor; or a mixture thereof.
- the cation is not particularly limited, but aluminum, tin, and cesium.
- Ions of metal elements such as indium, cerium, selenium, chromium, nickel, antimony, iron, copper, manganese, tandastene, zirconium and zinc are preferred.
- SiO nya key is not particularly limited, but aluminum, tin, and cesium.
- Bimetallic non-metal ions can also be used.
- the valence of the ion is not particularly limited.
- a monovalent to tetravalent cation can be used.
- a metal salt may be used as a source of the metal ions.
- metal salts such as cerium, selenium tetrachloride, cupric chloride, manganese salt, tungsten tetrachloride, tungsten oxydichloride, potassium tungstate, oxysalt salt and zirconium chloride.
- hydroxides or oxides such as indium hydroxide and key tungstic acid can be used.
- Examples of positively charged conductors or dielectrics include conductors or dielectrics that generate positive charges other than the above-mentioned cations.
- a battery made of various conductors described later.
- positive dielectrics such as wool and nylon that are positively charged by friction.
- FIG. 1 is a conceptual diagram in which a combination of a conductor, a dielectric, or a semiconductor conductor is arranged on the surface of a substrate (not shown) or in a surface layer.
- the conductor can have a positively charged state on the surface by the presence of a high concentration of free electrons that can move freely inside.
- a conductive substance containing a cation may be used as the conductor.
- the dielectric or semiconductor adjacent to the conductor is dielectrically polarized due to the influence of the surface charge state of the conductor.
- negative charges are generated in the dielectric or semiconductor on the side adjacent to the conductor and positive charges are generated on the non-adjacent side.
- the surface of the combination of the conductor dielectric or the semiconductor conductor is positively charged, and a positive charge is imparted to the substrate surface.
- the size of the complex (referring to the length of the longest axis passing through the complex) is 1 nm to 100 ⁇ m, preferably lnm to 10 ⁇ m, more preferably lnm to 1 m, more preferably lnm to lOOnm. It can be a range.
- the conductor used in the present invention is preferably a metal from the viewpoint of durability.
- Metal tin, cesium, indium, cerium, selenium, chromium, nickel, antimony, iron , Silver, copper, manganese, platinum, tungsten, zirconium, zinc, and other metals.
- the shape of the conductor is not particularly limited, and can be any shape such as particulate, flake, and fiber.
- metal salts of some metals can also be used. Specifically, aluminum chloride, 1st and 2nd tin chloride, chromium chloride, nickel chloride, 1st and 2nd antichloride, 1st and 2nd ferrous chloride, silver nitrate, cesium chloride, indium trichloride, salt ⁇ Cerium chloride, selenium tetrachloride, cupric chloride, manganese chloride, platinum chloride, tungsten tetrachloride, tungsten chloride, tungsten oxide, potassium tungstate, gold chloride chloride, oxychloride And various metal salts such as salt and zinc.
- hydroxides or acids such as indium hydroxide and ketandastenoic acid can also be used.
- Examples of the semiconductor include C, Si, Ge, Sn, GaAs, Inp, GeN, ZnSe, and PbSnTe.
- Semiconductor metal oxide, photo semiconductor metal, and photo semiconductor metal oxide can also be used.
- MoS, InSb, RuO, CeO, etc. are used, but the photocatalytic activity is deactivated with Na.
- Dielectrics include barium titanate (PZT) V, so-called SBT, BLT, and the following PZT, PLZT— (Pb, La) (Zr ⁇ Ti) 0, SBT, SBTN— SrBi (Ta, Nb)
- Composite metals such as O 2 and BSO—Bi 2 SiO can be used. Also, with organic key compounds
- silane compounds silicone compounds, so-called organically modified silica compounds,
- Various low dielectric materials such as Limer insulating film, arylene ether polymer, benzocyclobutene, fluorine polymer parylene N or F, and fluorinated amorphous carbon can be used.
- any combination of a conductor and a dielectric or a semiconductor can be used as long as it can impart a positive charge to the surface of the base.
- metal-doped titanium oxide As the metal, a group power consisting of copper, manganese, nickel, conoleto, iron and zinc is preferred. At least one of the selected metal elements is preferred.
- oxides and peroxides such as TiO, TiO, and TiO ZnH 2 O can be used.
- TiO, TiO, and TiO ZnH 2 O can be used.
- Titanium peroxide having a peroxo group is preferred.
- the titanium oxide may be any of amorphous type, anatase type, brookite type and rutile type, and these may be mixed, but amorphous type titanium oxide is preferred.
- Amorphous type titanium oxide does not have a photocatalytic function.
- anatase-type, wurtzite-type and rutile-type titanium oxides have a photocatalytic function.
- the photocatalytic function is lost when copper, manganese, nickel, cobalt, iron or zinc is combined at a certain concentration or more. . Therefore, the metal-doped titanic acid oxide does not have a photocatalytic function.
- Amorphous acid titanium is a force that can be converted to anatase acid titanium over time by heating with sunlight etc. When combined with copper, manganese, nickel, conoreto, iron or zinc, anatase acid titanium Since titanium loses its photocatalytic function, after all, the metal-doped titanate oxide does not exhibit a photocatalytic function over time.
- a method for producing the metal-doped titanate a production method based on a hydrochloric acid method or a sulfuric acid method, which is a general method for producing titanium dioxide powder, may be employed. Various methods for producing a liquid dispersion titer solution may be employed. The metal can be composited with titanate regardless of the production stage.
- specific methods for producing the metal-doped titanate oxide include the following first to third production methods and the conventionally known sol-gel method.
- a tetravalent titanium compound such as tetrasalt and titanium is reacted with a base such as ammonia.
- a base such as ammonia.
- this titanium hydroxide is peroxo-oxidized with an oxidizing agent to form an ultra-fine particle amorphous peroxy titanium.
- This reaction is preferably carried out in an aqueous medium. Furthermore, it can be transferred to anatase-type peroxytitan by optionally heat treatment.
- at least one of copper, manganese, nickel, cobalt, iron, zinc, or a compound thereof is mixed.
- the peroxidation oxidizing agent is not particularly limited, and a peroxygenation product of titanium, that is, a peroxygenated hydrogen peroxide that can be used as long as it can form peroxytitanium is preferred.
- a peroxygenation product of titanium that is, a peroxygenated hydrogen peroxide that can be used as long as it can form peroxytitanium is preferred.
- the concentration of hydrogen peroxide is not particularly limited, but 30 to 40% is preferable. It is preferable to cool the titanium hydroxide before peroxotization.
- the cooling temperature is preferably 1-5 ° C.
- FIG. 2 shows an example of the first manufacturing method.
- an aqueous solution of titanium tetrachloride and aqueous ammonia are mixed in the presence of at least one compound of copper, manganese, nickel, cobalt, iron, and zinc, and the hydroxide of the metal and titanium are mixed.
- the concentration and temperature of the reaction mixture at that time are not particularly limited, but it is preferably dilute and normal temperature.
- This reaction is a neutralization reaction, and it is preferable that the pH of the reaction mixture is finally adjusted to around 7.
- the metal and titanium hydroxides thus obtained are washed with pure water, cooled to about 5 ° C before and after, and then peroxolated with hydrogen peroxide water.
- an aqueous dispersion containing fine titanium oxide particles having amorphous peroxo groups doped with metal that is, an aqueous dispersion containing metal-doped titanium oxide can be produced.
- a tetravalent titanium compound such as tetrasalt-titanium is peroxoated with an oxidizing agent, and this is reacted with a base such as ammonia to form ultrafine particles of amorphous peroxytitanium.
- This reaction is preferably carried out in an aqueous medium. Furthermore, it can be transferred to anatase-type peroxytitanium by optionally heat-embedding. ! / Of each process above In force, at least one of copper, manganese, nickel, cobalt, iron, zinc or their compounds is mixed.
- Tetravalent titanium compounds such as tetrasalt and titanium are reacted simultaneously with the oxidizing agent and base to form titanium hydroxide and its peroxo group at the same time to form amorphous titanium peroxide with ultrafine particles. .
- This reaction is preferably carried out in an aqueous medium. Further, it can be transferred to anatase-type titanium peroxide by optionally heat-treating.
- at least one of copper, manganese, nickel, conoret, iron, zinc, or a compound thereof is mixed.
- the titanium alkoxide is mixed and stirred with a solvent such as water or alcohol, an acid or a base catalyst, and the titanium alkoxide is hydrolyzed to form a sol solution of ultrafine titanium oxide. Either before or after this hydrolysis is mixed with at least one of copper, manganese, nickel, cobalt, iron, zinc or their compounds.
- the titanium oxide thus obtained is an amorphous type having a peroxo group.
- the titanium alkoxide is represented by the general formula: Ti (OlT) (wherein alkyl group).
- titanium alkoxide examples include Ti (0—isoC H), Ti (0—nC H),
- Tetravalent titanium compound As a tetravalent titanium compound used in the production of metal-doped titanate, titanium hydroxide, also called orthotitanic acid (H TiO), can be formed when reacted with a base.
- H TiO orthotitanic acid
- various titanium compounds can be used, for example, water-soluble inorganic acid salts of titanium such as titanium tetrachloride, titanium sulfate, titanium nitrate, and titanium phosphate.
- water-soluble organic acid salts of titanium such as titanium oxalate can be used.
- water solubility is particularly excellent, and no component other than titanium remains in the dispersion of the metal-doped titanic acid compound. I like it.
- the concentration of the solution is not particularly limited as long as a gel of titanium hydroxide and titanium can be formed.
- a dilute solution is preferred.
- the solution concentration of the tetravalent titanium compound is preferably 5 to 0.3% by weight, more preferably 0.9 to 0.3% by weight.
- bases to be reacted with the tetravalent titanium compound various bases can be used as long as they can react with the tetravalent titanium compound to form hydroxyaluminum titanium, including ammonia, caustic soda, Ability to illustrate sodium carbonate, caustic potash, etc. Ammonia is preferred
- the concentration of the solution is not particularly limited as long as a titanium hydroxide gel can be formed, but a relatively dilute solution may be used. preferable.
- the concentration of the base solution is preferably 10 to 0.01%, more preferably 1.0 to 0.1 wt%.
- the ammonia concentration is preferably 10 to 0.01 wt%, more preferably 1.0 to 0.1 lwt%.
- Examples of the compound of copper, manganese, nickel, cobalt, iron or zinc are as follows.
- Ni compound Ni (OH), NiCl
- Co compounds Co (OH) NO, Co (OH), CoSO, CoCl
- Cu compounds Cu (OH), Cu (NO), CuSO, CuCl,
- Mn compounds MnNO, MnSO, MnCl
- Fe compounds Fe (OH), Fe (OH), FeCl
- Zivf compound Zn (NO), ZnSO, ZnCl
- the concentration of titanium peroxide in the aqueous dispersion obtained by the first to third production methods is 0.05 to 15 wt%. Is preferably 0.1 to 5 wt%.
- 1: 1 is preferable from the present invention in terms of the molar ratio of titanium to the metal component, but from the stability of the aqueous dispersion, 1 : 0. 01 to 1: 0.5 force S, preferably 1: 0. 03 to 1: 0.1.
- the substrate to which the present invention is applied is not particularly limited, and various inorganic substrates and organic substrates, or combinations thereof can be used.
- Examples of the inorganic substrate include a substrate made of a material such as transparent or opaque glass, metal, metal oxide, ceramics, concrete, mortar, and stone.
- Examples of the organic substrate include substrates having physical strength such as organic resin, wood, and paper.
- Specific examples of organic resin include polyethylene, polypropylene, polycarbonate, polyacrylate, polyester, polyamide, polyurethane, ABS resin, poly salt resin, silicone, melamine resin, urea resin, Examples include silicone resin, fluorine resin, cellulose, and epoxy-modified resin.
- the shape of the substrate is not particularly limited, and may be any shape such as a cube, a rectangular parallelepiped, a sphere, a sheet, and a fiber.
- the substrate may be porous.
- an architectural substrate or a sealing material, an apparatus, a body for conveying an apparatus, and a display screen are preferable.
- the coating material on which the surface of the substrate may be coated is alkyd resin, acrylic resin, amino resin, polyurethane resin, epoxy resin, silicone resin, fluorine resin, acrylic silicon resin.
- Suitable for paints that contain synthetic resins and colorants such as fats, unsaturated polyester resins, UV-cured resins, phenol resins, salt resin resins, and synthetic resin emulsions. Can be used for
- the thickness of the coating film is preferably from 0.01 to 100 ⁇ m, more preferably from 0.1 to 50 ⁇ m, and particularly preferably from 0.5 to 10 m.
- a spray coating method, a dip coating method, a flow coating method, a spin coating method, a roll coating method, a brush coating, a sponge coating or the like can be applied.
- Figures 3-6 show the above cations; a positively charged conductor or dielectric; a conductor dielectric or semiconductor composite; or a mixture thereof to attach a positive charge to the substrate surface. It is a conceptual diagram which shows the aspect of how many force to give.
- FIG. 3 shows an insulating organic or inorganic substance in which a positively charged substance composed of a positive ion, a positively charged conductor or dielectric, or a mixture of these and the above composite is placed on the surface of the substrate.
- a positively charged substance composed of a positive ion, a positively charged conductor or dielectric, or a mixture of these and the above composite is placed on the surface of the substrate.
- An embodiment in which the surface of a positively charged substance is coated with a quality film is shown.
- a positive electrode made of a positive electrode, a conductor or dielectric having a positive charge, or a mixture of these and the above composite is used.
- Charged material is placed.
- the arrangement of the positively charged substance shown in FIG. 3 (1) is, for example, that a metal film made of the above metal element and having a positive charge is placed on the substrate, or a salt, hydroxide or metal ion of the above metal ion.
- an uncured liquid of a substance constituting the substrate is added to the positively charged metal having a higher or lower specific gravity than the liquid, or a salt, hydroxide or oxide of the metal ion. It is also possible to place a positively charged substance in the surface layer of the substrate by mixing a predetermined amount of the substance and allowing the liquid to harden after being left for a predetermined time. When the substrate is painted, the positively charged substance may be included in the paint.
- the positively-charged material may be a force multi-layer arranged as a single layer.
- the thickness of the layer is from ⁇ , preferably ⁇ to 0.01 / ⁇ ⁇ to 2. O ⁇ m, and more preferably to ⁇ to 0.03 / ⁇ ⁇ to 1. O / z m.
- the layer of the positively charged substance on the substrate need not be a continuous layer as shown in FIG.
- the positively charged substance may be discontinuously dispersed on the substrate as a cluster (an aggregate of positively charged substances).
- a positively charged substance is covered with a film of an insulating organic or inorganic substance.
- the thickness of the membrane is from 0.01 to: LOO m force S preferred, 0.05 to 50 In particular, 0.1 to: LO / zm is preferable.
- the type of the insulating organic substance is not particularly limited as long as it has a behavior as a dielectric, but is made of a polymer material that is water-repellent or hydrophilic and exhibits remarkable properties with respect to water. It is preferable.
- water-repellent polymer materials include polyethylene, polypropylene, polystyrene and other polyolefins; polyacrylates, acrylonitrile / styrene copolymers (AS), acrylonitrile, acrylic resins such as butadiene.styrene copolymers (ABS), etc.
- Fluororesin is preferred as a water-repellent polymer material, and in particular, a polyvinylidene fluoride trifluorethylene copolymer and polyvinylidene fluoride having ferroelectricity and water repellency.
- the type crystal and the one containing it are preferred.
- Commercially available fluorine resin can be used, and examples of commercially available products include HIREC 1550 manufactured by NTT-AT Corporation.
- a copolymer having two or more kinds of olefins containing fluorine atoms a copolymer of olefin containing fluorine atoms and a hydrocarbon monomer, and two or more kinds of olefins containing fluorine atoms are also provided.
- hydrophilic polymer materials include polyethylene glycol, polypropylene glycol, polyethylene glycol such as polypropylene glycol block copolymer; polybulu alcohol; polyacrylic acid (alkali metal salt, ammonium salt, etc.) Salts), polymethacrylic acid (including salts such as alkali metal salts and ammonium salts), polyacrylate-polymethacrylic acid (including salts such as alkali metal salts and ammonium salts) copolymers; Polyacrylamide; polyvinylpyrrolidone; hydrophilic celluloses such as carboxymethylcellulose (CMC) and methylcellulose (MC); natural hydrophilic polymer compounds such as polysaccharides.
- CMC carboxymethylcellulose
- MC methylcellulose
- the type of the insulating inorganic substance is not particularly limited as long as it has a behavior as a dielectric! /, But it is preferable that it has a water repellent or hydrophilic inorganic compound power.
- Examples of the water repellent inorganic material include a silane water repellent and a fluorine water repellent.
- fluorine-based water repellents include fluorine-containing compounds or fluorine-containing compound-containing compositions such as perfluoroalkyl group-containing compounds. If a fluorine-containing compound with high adsorptivity to the substrate surface is selected, after applying to the substrate surface, the chemical component of the water repellent or water absorption inhibitor reacts with the substrate to form a chemical bond. Or the chemical components need to be cross-linked.
- the fluorine-containing compound that can be used as such a fluorine-based water repellent is a compound having a molecular weight of 1,000 to 20,000 containing a perfluoroalkyl group in the molecule.
- Perfluorosulfonic acid salt, perfluorosulfonic acid ammonium salt, perfluorocarboxylic acid salt, perfluoroalkyl betaine, perfluoroalkylethylene carbonate oxide, perfluoro Examples include loalkylamine oxides, perfluoroalkyl phosphate esters, and perfluoroalkyltrimethylammonium salts.
- perfluoroalkyl phosphate ester and perfluoroalkyltrimethyl ammonium salt are preferred because of their excellent adsorptivity to the substrate surface.
- Surflon S-112 and Surflon S-121 are commercially available.
- the substrate surface characteristics can be changed from water repellent to hydrophilic by controlling irradiation of electromagnetic waves such as ultraviolet rays and sunlight (particularly ultraviolet rays) to the substrate surface. It can be changed to sex. As a result, the protection mode can be freely changed according to the characteristics required of the substrate. Therefore, when both the contact angle characteristics of water and oil and the surface charge characteristics are utilized, the use of a fluorine-based water repellent is used. Is particularly preferred.
- hydrophilic inorganic material examples include SiO, a silicon compound, and a photocatalytic function.
- the photocatalytic substance contains a specific metal compound and has a function of oxidizing and decomposing organic and Z or inorganic compounds on the surface of the layer by photoexcitation.
- the principle of photocatalysis is that specific metal compounds generate radical species such as water in the air or oxygen power OH— or O— by photoexcitation.
- this radical species is a redox degradation of organic and Z or inorganic compounds.
- metal compound in addition to typical titanium oxide (TiO), ZnO, SrTiOP, Cd
- an aqueous dispersion containing fine particles of these metal compounds (about 2 ⁇ ! To about 20nm) together with various additives as required is coated on a positively charged substance and dried. Can be formed.
- the thickness of the membrane is preferably from 0.01 ⁇ m to 2.0 m, more preferably from 0.1 / ⁇ ⁇ to 1. O / z m.
- An aqueous dispersion is preferably used for forming the photocatalytic material film, but alcohol can also be used as a solvent.
- the aqueous dispersion for forming a photocatalytic substance film can be produced, for example, by the following method.
- peroxy titanium in the aqueous dispersion can be changed to acid titanium in a dry film-forming state.
- Titanium hydroxide is formed by reacting the tetravalent titanium compound described above with a base such as ammonia. Next, this titanium hydroxide is peroxoated with an oxidizing agent such as hydrogen peroxide to form amorphous fine titanium peroxide particles. Further, it is transferred to anatase type peroxytitanium by heat treatment.
- the tetravalent titanium compound described above is peroxoated with an oxidizing agent such as hydrogen peroxide and then reacted with a base such as ammonia to form an ultrafine particleed amorphous titanium peroxide.
- the tetravalent titanium compound described above is reacted with an oxidizing agent such as hydrogen peroxide or hydrogen and a base such as ammonia to simultaneously form hydroxide and titanium and peroxo, thereby forming amorphous fine particles.
- an oxidizing agent such as hydrogen peroxide or hydrogen and a base such as ammonia to simultaneously form hydroxide and titanium and peroxo, thereby forming amorphous fine particles.
- a base such as ammonia
- Metals (Ag, Pt) that improve the photocatalytic performance may be added to the photocatalytic material film.
- various substances such as metal salts can be added within a range that does not deactivate the photocatalytic function.
- the metal salt include metal salts such as aluminum, tin, chromium, nickel, antimony, iron, silver, cesium, indium, cerium, selenium, copper, manganese, calcium, platinum, tandastene, zirconium, and zinc.
- a hydroxide or an acid can be used for some metals or non-metals.
- Various metal salts such as salty zirconium and salty zinc can be exemplified.
- Examples of compounds other than metal salts include indium hydroxide, key tungstic acid, silica sol, calcium hydroxide, and the like.
- an amorphous type titanium oxide titanium In order to improve the adhesion of the photocatalytic material film, it is also possible to add an amorphous type titanium oxide titanium.
- Contaminants on the surface of the substrate are decomposed by the action of the photocatalytic material film. Contamination can be prevented and the cosmetic properties of the substrate can be maintained over time. If the photocatalytic material film is directly formed on the substrate, the photocatalytic material film may be peeled off from the substrate over time. However, by interposing a positively charged material, the photocatalytic material film can be well integrated with the substrate. I'll do it.
- FIG. 4 shows an embodiment in which a positively charged substance made of a combination of a conductor dielectric or a semiconductor is arranged on the surface of a substrate, and the positively charged substance is covered with an insulating organic or inorganic substance film.
- the embodiment of FIG. 4 differs from the embodiment of FIG. 3 only in that a layer of a conductor dielectric or a semiconductor composite, preferably a metal-doped titanium oxide titanium layer, is formed on the substrate.
- the particle size of the composite of the conductor and the dielectric or semiconductor can be in the range of several nm to several tens of ⁇ m.
- the combination ratio of the conductive fine particles and the dielectric or semiconductor fine particles in the composite is preferably 1: 1.
- the thickness of the composite layer can be in the range of lOnm to 100 m.
- the composite layer can be produced, for example, by performing at least one step of applying an aqueous dispersion of the metal-doped titanate on the substrate surface and then drying it.
- a general film forming method such as brush coating, roller coating, spray coating or the like can be used.
- FIG. 5 shows a case where a positively charged substance, which is a positive ion, a conductor or dielectric having a positive charge, a composite of a conductor dielectric or a semiconductor, or a mixture thereof, is disposed on the surface of the substrate.
- a positively charged substance which is a positive ion, a conductor or dielectric having a positive charge, a composite of a conductor dielectric or a semiconductor, or a mixture thereof.
- an organic or inorganic substance atom or atomic group is formed on the surface of the positively charged substance by grafting or the like.
- the method of scientific modification is mentioned.
- the atom or atomic group to be chemically modified preferably contains a fluorine atom.
- fluoroalkyl acrylate copolymer is preferred as the fluorine compound for chemical modification.
- GM-101 and GM-105 Commercially available as GM-101 and GM-105.
- the above chemical modification can be produced by performing a drying step at least once after the solution of the fluorine compound is applied to the substrate surface.
- the coating method methods such as brush coating, roller coating, and spray coating can be used.
- FIG. 6 shows a positively charged substance which is an insulating organic or inorganic substance, a cation, a positively charged conductor or insulator, a conductor dielectric or semiconductor composite, or a mixture thereof. And an insulating organic or inorganic material film is formed on the substrate surface. Thickness of film: 0.1 to LOO / z m force S, preferably 0.1 to 50 / z m force S, more preferably 0.5 to 10 m. All of the positively charged material may be present in the membrane without having to be exposed on the surface of the membrane.
- the insulating film as in FIGS. 3 to 5 due to dielectric polarization, a negative charge is generated on the side in contact with the positively charged material, and the positively charged material force is also separated. A positive charge is generated on the surface of the side film.
- FIG. 7 shows a mechanism for removing contaminants from the positively charged substrate surface.
- Contaminants accumulate on the substrate surface and are photooxidized by the action of electromagnetic waves such as sunlight. In this way, a positive charge is also given to the pollutant (Fig. 7 (2)).
- Contaminants are easily removed from the substrate by physical action such as wind and rain (Fig. 7 (4)).
- the substrate is self-cleaned.
- the substrate surface has been protected by coating the substrate surface with an organic or inorganic substance having excellent water repellency or hydrophilicity.
- the organic or inorganic substance is generally negative. Due to the electric charge, there was a problem that contaminants adhered over time and their protective properties were significantly lost.
- the surface of the substrate is present in this way. Such a problem does not occur because a positive charge is imparted to the existing organic or inorganic substance.
- the self-cleaning property can be imparted while maintaining the chemical properties such as water repellency and hydrophilicity of the organic or inorganic substance on the surface of the substrate or by appropriately changing the properties.
- the positive charge imparted to the surface of the substrate is utilized to make use of the functionality of the organic or inorganic substance itself on the substrate and at the same time, to make use of the continuous “antifouling / antifogging function”.
- Product becomes possible.
- this technology can be applied to any substrate, it can maintain its function for a long time by applying a positive charge to the surface of an organic substance having excellent water repellency and hydrophilicity. Application to a substrate is preferred. This makes “dirty, plastic” possible.
- the positive charge on the surface of the substrate can reduce deterioration of the substrate due to electromagnetic waves. That is, the oxidation deterioration of the substrate is caused by the generation of radicals such as' ⁇ , ⁇ ⁇ , etc. due to electromagnetic waves such as ultraviolet rays on the surface of the substrate or in the substrate to cause an oxidative decomposition reaction.
- the positively charged surface of the substrate makes these radicals stable molecules. Therefore, it is considered that the oxidative deterioration of the substrate is prevented or reduced.
- the same process force can reduce the generation of wrinkles.
- surfactant or dispersant various organic silicon compounds can be used.
- Various organosilane compounds and various silicone oils, silicone rubbers, silicone rubbers and silicone resins can be used. Those having an alkyl silicate structure or a polyether structure in the molecule, or an alkyl silicate structure and a polyether. Desired to have both of the structure.
- the alkyl silicate structure refers to a structure in which an alkyl group is bonded to a silicon atom of a siloxane skeleton.
- the polyether structure is not limited to these.
- polyethylene oxide, polypropylene oxide, polytetramethylene oxide, polyethylene oxide-polypropylene oxide block copolymer examples thereof include molecular structures such as polyethylene polytetramethylene glycol copolymer and polytetramethylene glycol-polypropylene oxide copolymer.
- a polyethylene oxide polypropylene oxide block copolymer is more preferable from the viewpoint of controlling wettability depending on the block degree and molecular weight.
- polyether-modified silicone such as polyether-modified polydimethylsiloxane is suitable.
- polyether-modified silicone such as polyether-modified polydimethylsiloxane is suitable.
- This can be produced by a known method. For example, it can be produced by the method described in Synthesis Example 1, 2, 3, 4 of JP-A-4 242499 or the reference example of JP-A-9-165318. Can do.
- polyethylene oxide / polypropylene oxide block copolymer-modified polydimethylsiloxane obtained by reacting methallyl polyethylene oxide / polypropylene oxide block copolymer with dihydropolydimethylsiloxane is preferred.
- TSF4445, TSF4446 manufactured by GE Toshiba Silicone Co., Ltd.
- SH200 manufactured by Dow Cowing Silicone Co., Ltd.
- KP series manufactured by Shin-Etsu Chemical Co., Ltd.
- DC3PA, ST869A Toray 'Dowcoung' manufactured by Silicone Co., Ltd.
- an intermediate layer may exist between the substrate surface and the positively charged substance layer.
- an intermediate layer containing a silane compound it is preferable to form an intermediate layer containing a silane compound on the substrate in advance. Since this intermediate layer contains a large amount of SiO 2 bonds, it is possible to improve the strength of the positively charged material layer and the adhesion to the substrate.
- the intermediate layer has a moisture content to the substrate. It also has a function to prevent intrusion.
- Examples of the silane compound include hydrolyzable silanes, hydrolysates thereof, and mixtures thereof.
- Various alkoxysilanes can be used as the hydrolyzable silane, and specific examples include tetraalkoxysilane, alkyltrialkoxysilane, dialkyldialkoxysilane, and trialkylalkoxysilane.
- one type of hydrolyzable silane may be used alone, or two or more types of hydrolyzable silanes may be mixed and used as necessary.
- Various organopolysiloxanes may be blended with these silanic compounds.
- As an intermediate layer forming agent containing such a Silane compound there is Dryeal S (manufactured by Dowco Jung Silicone Co., Ltd.).
- room temperature curable silicone resins such as methyl silicone resin and methylphenyl silicone resin may be used as the intermediate layer forming agent.
- room temperature curable silicone resins include AY42-170, SR2510, SR2406, SR2410, SR2405, SR241 1 (manufactured by Toray “Dowcoung” Silicone Co., Ltd.).
- the intermediate layer may be colorless and transparent, or may be colored transparent, translucent or opaque. Coloring here includes not only red, blue, green, etc. but also white. In order to obtain a colored intermediate layer, it is preferable to mix various colorants such as inorganic or organic pigments or dyes in the intermediate layer.
- Examples of the inorganic pigment include carbon black, graphite, yellow lead, iron oxide yellow, red lead, bengara, ultramarine, chromium oxide green, iron oxide and the like.
- organic pigments azo organic pigments, phthalocyanine organic pigments, selenium organic pigments, quinotalidone organic pigments, dioxazine organic pigments, isoindolinone organic pigments, diketopyrrolopyrrole and various metal complexes are used. Although it is possible, it should have excellent light resistance.
- light-resistant organic pigments include, for example, Hansa Yellow, toluidine red, which is an insoluble azo organic pigment, phthalocyanine blue, which is a phthalocyanine organic pigment, phthalocyanine green, quinacridone red, which is a quinacridone organic pigment, and the like. Is mentioned.
- Examples of the dye include basic dyes, direct dyes, acid dyes, vegetable dyes, and the like, but those having excellent light resistance are preferred. , Direct Orange R Conch, Acid Orange, Yellow, Chryso For Phenine NS, Methanil Yellow, and Brown, Direct Brown KGG and Acid Brown R are particularly preferable.
- Direct Blue B is used for Blue.
- Black Direct Black GX and Nigguchi Shin BHL are particularly preferable.
- the mixing ratio (weight ratio) of these silane compound or silicone resin and pigment is in the range of 1: 2 to 1: 0.05.
- the range of 1: 1 to 1: 0.1 is more preferable.
- the intermediate layer may further contain additives such as a dispersant, a stabilizer, and a leveling agent. These additives have an effect of facilitating the formation of the intermediate layer. Furthermore, when a coloring agent such as a pigment 'dye is blended, a binder for fixing the coloring agent can be added. As binders in this case, binders for various paints mainly composed of acrylic acid ester and acrylic acid ester copolymerized resin having excellent weather resistance can be used. For example, Polysol AP-3720 (Showa Polymer Co., Ltd.) Company), Polysol AP-609 (Showa Polymer Co., Ltd.), and the like.
- the intermediate layer can be formed, for example, as follows.
- An intermediate layer forming agent comprising a silane compound or silicone resin in a volatile solvent, and, if necessary, the colorant.
- the solution containing the additive and the binder is applied to the surface of the substrate so as to have a thickness of about 2 to 5 mm. If necessary, the intermediate layer is formed on the substrate by heating and evaporating the volatile solvent.
- the colored intermediate layer can be imparted with a colored cosmetic by being integrated with the substrate.
- the thickness of the intermediate layer formed as described above is not particularly limited, but is preferably 0.0 1 to 1.0 ⁇ m force, more preferably 0.05 to 0.3 ⁇ m force ⁇ I like it!
- a colorant, a calorie additive, and a binder are added, 1.0 m to 100 m force S is preferable, and 10 m to 50 m force S is more preferable.
- any known method can be used.
- a spray coating method, a dip coating method, a flow coating method, a spin coating method, a roll coating method, Brush painting, sponge painting, etc. are possible.
- the present invention can be used in various fields where various design properties and high waterproof / antifouling performance are required. Glass, metal, ceramics, concrete, wood, stone, polymer resin cover, high Molecular resin sheets, fibers (clothing, curtains, etc.), sealing agents, etc., or combinations thereof, building materials; air-conditioning outdoor units; kitchen equipment; sanitary equipment; lighting equipment; automobiles; bicycles; ; Trains; Goods used for indoor and outdoor goods such as ships, and for face panels of various machines, electronic devices, televisions, etc.
- buildings such as houses, buildings, roads, and tunnels constructed using the building materials preferred for building materials can exhibit a high waterproof / antifouling effect over time.
- the amount of 12gZm 2 is sprayed on the surface of a commercially available transparent float glass plate (length 100mm, width 100mm, thickness 4mm) with STi Chitar 'Hicoat Z (Z18-1000A), a metal-doped titanium oxide-containing liquid. And dried at 80 ° C for 15 minutes. Thereafter, HIREC1550 (manufactured by NTT-AT Co., Ltd.), which is a fluorine-based super-water-repellent resin solution, was brushed and dried at 80 ° C. for 15 minutes to prepare an evaluation substrate.
- HIREC1550 manufactured by NTT-AT Co., Ltd.
- HIR EC1550 (manufactured by NTT-AT Co., Ltd.) was brushed on the surface of a commercially available transparent float glass plate (length 100 mm, width 100 mm, thickness 4 mm), and dried at 80 ° C. for 15 minutes to prepare an evaluation substrate.
- STi hose on the surface of a commercially available transparent float glass plate (length 100mm, width 100mm, thickness 4mm) Apply Tania-Noise Coat Z (Z18-1000A) by spraying in an amount of 12g / m 2 , 80.
- An evaluation substrate was prepared by drying at C for 15 minutes. The thickness of the film on the substrate surface was about 80 nm.
- STi Chita-Nano Coat Z (Z18-1000A) was sprayed on the surface of a commercially available transparent float glass plate (length 100mm, width 100mm, thickness 4mm) at a temperature of 12gZm 2 at 80 ° C. Dry for 5 minutes.
- the fluorine-based water repellency imparting liquid obtained by diluting FTONE GM-101 (Daikin Kogyo Co., Ltd.) to 10 times volume with mineral oil was applied by spray at an amount of 12 g / m 2.
- the substrate for evaluation was prepared by drying at 80 ° C. for 15 minutes.
- Fluorine series obtained by diluting F-tone GM-101 (Daikin Industries Co., Ltd.) to 10 times the volume with mineral oil on the surface of a commercially available transparent float glass plate (length 100mm, width 100mm, thickness 4mm)
- a water repellency imparting solution was applied in an amount of 12 gZm 2 by spraying and dried at 80 ° C. for 15 minutes to produce an evaluation substrate.
- the following operation was performed to determine the charge state of the surface of the evaluation substrate.
- a polypropylene sheet strip (width 2 mm, length 15 Omm, weight 0.005 g) was prepared in an atmosphere with an air temperature of 18 ° C and a humidity of 40%, and the strip was rubbed against a cotton cloth. Negative static electricity was charged on the surface.
- the evaluation board is placed vertically using a polystyrene book stand, and the distance from the strip is lOmn! After setting the thickness to ⁇ 20 mm, it was observed whether the strip adsorbed or repelled on the evaluation substrate. When adsorbing, it was determined that the substrate surface was positively charged, and when it was repelled, it was determined that the substrate surface was negatively charged. (The same operation was performed with a Teflon rod (known to be negatively charged)) and repulsion was confirmed). The results are shown in the table.
- the following operations were performed to determine the hydrophilicity / water repellency of the evaluation substrate surface.
- One drop (0.028 to 0.029 g) of pure water was dropped onto an evaluation substrate placed horizontally using a dropper with a height force within 10 mm.
- the contact angle formed by the dropped water droplet on the surface of the evaluation substrate was visually observed, and when the contact angle was 40 ° or less, it was determined to be hydrophilic, and when it was 80 ° or more, it was determined to be water repellent. The results are shown in the table.
- substrate of Example 2 and Comparative Examples 1 and 2 the exposure test was conducted in Saga Prefecture, and the contamination state of each board
- Table 3 shows the results.
- strong water repellency means that the contact angle with water is 100 ° or more and 120 ° or less
- water repellency means that the contact angle with water is 80 ° or more and 100 It means that the contact angle with water is 20 ° or less and 5 ° or more.
- the contact angle was visually measured with a manual goniometer.
- contaminated a state in which many white spots were attached on the substrate surface
- no white spots were attached was designated as “no contamination”. There were three rainfalls during the exposure test period.
- Comparative Examples 1 and 2 have strong water repellency regardless of the exposure test. Examples 1 and 2 become hydrophilic when exposed to sunlight, while water repellent when not exposed to sunlight. It becomes. Therefore, the results shown in Table 3 indicate that the water repellency and hydrophilicity of the substrate surface can be controlled by arranging a positively charged substance coated with a fluorine-based water repellent on the substrate surface. In Evaluation 2, the same results were obtained for the two forces performed twice.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
Description
Claims
Priority Applications (3)
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JP2007552890A JP4995738B2 (ja) | 2005-12-27 | 2006-12-07 | 基体の保護方法 |
EP06834210A EP1967285A4 (en) | 2005-12-27 | 2006-12-07 | PROCESS FOR PROTECTING A BASE |
US12/086,375 US20090267015A1 (en) | 2005-12-27 | 2006-12-07 | Method for Protecting Substrate |
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JP2005-374511 | 2005-12-27 | ||
JP2005374511 | 2005-12-27 |
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WO2007077712A1 true WO2007077712A1 (ja) | 2007-07-12 |
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PCT/JP2006/324455 WO2007077712A1 (ja) | 2005-12-27 | 2006-12-07 | 基体の保護方法 |
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US (1) | US20090267015A1 (ja) |
EP (1) | EP1967285A4 (ja) |
JP (1) | JP4995738B2 (ja) |
KR (1) | KR20080074194A (ja) |
CN (1) | CN101346191A (ja) |
WO (1) | WO2007077712A1 (ja) |
Cited By (1)
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JP5624458B2 (ja) * | 2008-04-11 | 2014-11-12 | 中央精機株式会社 | 基体の保護方法 |
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TWI285566B (en) * | 2004-05-06 | 2007-08-21 | Sustainable Titania Technology | Method for protecting substrate |
JP4926176B2 (ja) * | 2006-07-25 | 2012-05-09 | サスティナブル・テクノロジー株式会社 | 基体の保護方法 |
US10754067B2 (en) | 2017-05-18 | 2020-08-25 | GM Global Technology Operations LLC | Textured self-cleaning film system and method of forming same |
US10583428B2 (en) | 2017-05-18 | 2020-03-10 | GM Global Technology Operations LLC | Self-cleaning film system and method of forming same |
US10556231B2 (en) | 2017-05-18 | 2020-02-11 | GM Global Technology Operations LLC | Self-cleaning film system and method of forming same |
US10533249B2 (en) | 2017-05-18 | 2020-01-14 | GM Global Technology Operations LLC | Method of forming a self-cleaning film system |
US10429641B2 (en) * | 2017-05-31 | 2019-10-01 | GM Global Technology Operations LLC | Light-enhanced self-cleaning film system and method of forming same |
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- 2006-12-07 JP JP2007552890A patent/JP4995738B2/ja not_active Expired - Fee Related
- 2006-12-07 EP EP06834210A patent/EP1967285A4/en not_active Withdrawn
- 2006-12-07 KR KR1020087015463A patent/KR20080074194A/ko not_active Application Discontinuation
- 2006-12-07 CN CNA2006800490979A patent/CN101346191A/zh active Pending
- 2006-12-07 US US12/086,375 patent/US20090267015A1/en not_active Abandoned
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JP5624458B2 (ja) * | 2008-04-11 | 2014-11-12 | 中央精機株式会社 | 基体の保護方法 |
US8906298B2 (en) | 2008-04-11 | 2014-12-09 | Central Motor Wheel Co., Ltd. | Method for protecting substrate |
Also Published As
Publication number | Publication date |
---|---|
EP1967285A4 (en) | 2011-05-04 |
JPWO2007077712A1 (ja) | 2009-06-11 |
US20090267015A1 (en) | 2009-10-29 |
KR20080074194A (ko) | 2008-08-12 |
EP1967285A1 (en) | 2008-09-10 |
JP4995738B2 (ja) | 2012-08-08 |
CN101346191A (zh) | 2009-01-14 |
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