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WO2005090067A1 - Produit stratifie et procédé de fabrication de celui-ci - Google Patents

Produit stratifie et procédé de fabrication de celui-ci Download PDF

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Publication number
WO2005090067A1
WO2005090067A1 PCT/JP2005/005400 JP2005005400W WO2005090067A1 WO 2005090067 A1 WO2005090067 A1 WO 2005090067A1 JP 2005005400 W JP2005005400 W JP 2005005400W WO 2005090067 A1 WO2005090067 A1 WO 2005090067A1
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WO
WIPO (PCT)
Prior art keywords
layer
metal
water absorption
doped
titanium
Prior art date
Application number
PCT/JP2005/005400
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English (en)
Japanese (ja)
Inventor
Shiro Ogata
Original Assignee
Sustainable Titania Technology Inc.
Dow Corning Toray 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 Sustainable Titania Technology Inc., Dow Corning Toray Co., Ltd. filed Critical Sustainable Titania Technology Inc.
Priority to JP2006511323A priority Critical patent/JP4527112B2/ja
Publication of WO2005090067A1 publication Critical patent/WO2005090067A1/fr

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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
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
    • C23C28/3455—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer with a refractory ceramic layer, e.g. refractory metal oxide, ZrO2, rare earth oxides or a thermal barrier system comprising at least one refractory oxide layer

Definitions

  • the present invention relates to a waterproof and stain resistant laminate, and to a method of manufacturing the laminate.
  • the surface of the building material is coated in advance with a water repellent substance such as a silicone compound and an antifungal agent or an antibacterial agent to prevent the penetration of water into the building material.
  • a water repellent substance such as a silicone compound and an antifungal agent or an antibacterial agent to prevent the penetration of water into the building material.
  • JP 2002-138243 A proposes a method of forming a photocatalyst layer on a primer layer containing an acrylic resin having an alkoxysilyl group and a hydroxyl group.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2000-135442
  • Patent Document 2 Japanese Patent Application Laid-Open No. 2002-138243
  • Patent Document 3 International Publication 2004Z041723 pamphlet
  • the photocatalytic layer may be hydrolyzed by the action of an alkali metal silicate.
  • an object of the present invention is to provide a laminate capable of being optionally colored while maintaining a good waterproof function and a pollution preventing function, and a construction material and a structure provided with the laminate.
  • a substrate having pores on the surface A substrate having pores on the surface
  • a colorless, transparent, or colored, transparent, translucent, or opaque, water absorption-preventing layer comprising a silicon-containing compound, which is formed on the substrate, and
  • the invention is achieved by a laminate comprising:
  • the laminate of the present invention is particularly preferable as a decorative material, which is preferable as a building material. Therefore, The laminate of the present invention can be suitably used in a construction.
  • the metal-doped titanate oxide-containing layer be made of amorphous titanium oxide.
  • the metal-doped titanium oxide-containing layer preferably further contains a silicone oil, particularly a polyether-modified silicone oil.
  • a photocatalytic functional layer may be formed on the metal-doped titanate oxide-containing layer.
  • the photocatalytic function layer also becomes anatase type titanium dioxide.
  • the water absorption preventing layer containing the above-mentioned cheese-containing compound is made of a water absorption inhibitor comprising a cheese-containing compound and water.
  • the laminate of the present invention is a laminate of the present invention.
  • a water-repellent or colored transparent, semi-transparent or opaque water absorption layer containing a silicon-containing compound Forming on the substrate having pores on the surface a water-repellent or colored transparent, semi-transparent or opaque water absorption layer containing a silicon-containing compound, and It can manufacture through the process of forming a metal dope titanium oxide containing layer.
  • FIG. 1 schematically shows an example of a first method for producing metal-doped titanium oxide.
  • the substrate constituting the laminate of the present invention is an inorganic or organic substrate having pores on the surface.
  • the substrate having pores on the surface includes, in addition to a porous substrate, a substrate having a porous film layer on the substrate surface, and a substrate having essentially porous defects on the surface.
  • Such a substrate has a rough surface and a relatively high water absorption rate, so that rainwater infiltrates into the substrate together with contaminants such as contaminants in the air and dust, or stagnates on the surface of the substrate or becomes dirty.
  • the inorganic base having pores on the surface for example, a base made of a substance such as concrete, mortar, clay, stone or the like, or a metal on which a porous film such as metal oxide or ceramic is formed on the surface A substrate is mentioned. More specifically, concrete PC plates, concrete members having a solid surface, ALC plates, mortar members having a finished surface, bricks, tiles, in particular ceramic tiles, tiles, marble, granite, ceramic coated metal plates, etc. It is illustrated. Further, examples of the organic substrate having pores on the surface include substrates made of substances such as wood and paper. The shape of the substrate is not particularly limited, and any shape such as a cube, a rectangular parallelepiped, a sphere, or a sheet can be adopted.
  • a water absorption preventing layer containing a che containing compound is present on a substrate having pores on the surface.
  • the water absorption preventing layer containing the cheyne-containing compound has a function of preventing the penetration of water into the substrate, and in particular, it is preferable to be composed of a water absorption inhibitor composed of the keir-containing compound and water.
  • a water absorption preventing agent consisting of a silica-containing composite and water can also penetrate into pores of a substrate to form a water absorption preventing layer, and therefore effectively preventing the penetration of water into the substrate. Can.
  • silane-based water absorption inhibitors comprising hydrolyzable silane, water, and surfactant are preferable because they are excellent in permeability to the substrate, water absorption prevention performance, durability of the water absorption prevention layer, handling, and workability. .
  • hydrolyzable silane various alkoxysilanes can be used. Specifically, tetraalkoxysilane, alkyltrialkoxysilane, dialkyldialkoxysilane, and trialkylalkoxysilane can be mentioned. Among these, one hydrolyzable silane may be used alone, or two or more hydrolyzable silanes may be mixed and used as needed. In addition, these hydrolyzable silanes may be blended with the hydrolyzate thereof and various organopolysiloxanes.
  • the surfactant is not particularly limited, and any anionic surfactant, cationic surfactant, nonionic surfactant, and a mixture thereof can be used.
  • silane water absorption inhibitor compositions disclosed in JP-A-62-197369, JP-A-6-3 13167, etc. can be suitably used.
  • silane-based water absorption inhibitor is commercially available as Dry Seal S (manufactured by Toray 'Dow Co-Jung' Silicone Co., Ltd.).
  • an aqueous solution of an alkali metal salt of alkyl siliconate an aqueous solution of sodium methyl siliconate and an aqueous solution of potassium methyl siliconate are exemplified.
  • aqueous solutions of alkali metal salts of rusiliconate include Dry Seal C and Dry Seal E (manufactured by Toray Dow Co., Ltd. Silicone Co., Ltd.).
  • the water absorption preventing layer containing the cheese-containing compound may be colorless and transparent, or may be colored and transparent, translucent or opaque.
  • the coloring here includes not only colors such as red, blue and green but also white.
  • it is preferable to mix various coloring agents such as inorganic or organic pigments or dyes in the water absorption preventing layer.
  • examples of the inorganic pigment include carbon black, graphite, yellow lead, iron oxide yellow, red iron oxide, red iron oxide, red iron oxide, green oxide, chromium oxide green, iron oxide and the like.
  • organic pigments organic organic pigments, phthalocyanic organic pigments, organic organic pigments, organic organic pigments, quinotalidone organic pigments, organic pigments of dioxazine organic pigments, organic pigments of isoindolinone organic pigments, diketopyrrolopyrrole and various metal complexes are used. Although it is possible, it is desirable to have excellent light resistance.
  • light-resistant organic pigments examples include insoluble azo organic pigments such as Hansaello, toluidine red, phthalocyanine organic pigments such as phthalocyanine blue B, phthalocyanine greens, and quinacridone organic pigments such as quinacridone red and the like. Can be mentioned.
  • the dye examples include basic dyes, direct dyes, acid dyes, vegetable dyes and the like, and those excellent in light resistance are preferred.
  • direct scarlet, loccerin, azolin and orange Particularly preferred are direct orange R conc, orange orange, chrysophenin NS, methanyl ello, in brown, direct brown KGG, green brown R, blue in direct blue B, and black in direct black GX, nigg in tin BHL, etc.
  • the water absorption preventing layer containing a cheyne-containing compound is constituted of a chew-containing compound and water
  • the water absorption preventing agent and pigment containing a caiose-containing compound and a hydrophobe are constituted.
  • the mixing ratio (weight ratio) with is preferably in the range of 1: 2: 1: 0.5.
  • the range of 1: 11: 0.1 is more preferable.
  • additives such as a dispersant, a stabilizer, and a leveling agent may be further added to the water absorption preventing layer containing the silica-containing compound. These additives have the function of facilitating the formation of the water absorption preventing layer. Furthermore, when a colorant such as pigment 'dye is blended, it is also possible to add a binder for adhesion promotion of the colorant.
  • the resistance is Binders for various paints having acrylic acid esters and acrylic acid ester copolymer resin having excellent weatherability as main components can be used, for example, Polysol AP-3720 (manufactured by Showa High Molecular Co., Ltd.), Polysol AP — 609 (manufactured by Showa Highpolymer Co., Ltd.) and the like.
  • the water absorption preventing layer containing the carbon-containing composite can be formed, for example, as follows.
  • a solution containing a water absorption inhibitor comprising a binder-containing mixture and water, and optionally, the coloring agent, the additive, and the binder, is provided in a depth of about 2-5 mm in the surface layer of the substrate. Apply to penetrate.
  • the substrate is heated, if necessary, to evaporate the solvent, thereby forming a water absorption preventing layer containing the compound containing kei on the substrate.
  • the water absorption preventing layer containing the kei-containing compound can impart the water absorption preventing property and the coloring property to the substrate by being integrated with the substrate.
  • the thickness of the water absorption preventing layer containing the carbon-containing composite formed as described above is not particularly limited force 0.10. 05-0.3 m force is preferred. Moreover, when a coloring agent, an additive, and a binder are added, 1.0 m-100 / z m is preferable 10 m-50 m is more preferable.
  • any known method can be used.
  • a spray coating method dip coating method Flow coating, spin coating, roll coating, brushing, sponge coating, etc. are possible.
  • At least one of the metal elements selected from copper, manganese, nickel, cobalt, iron and zinc is selected on the water absorption preventing layer containing the kei-containing compound.
  • a metal-doped titanate-containing layer comprising doped titanate.
  • titanium oxide Various oxides such as TiO, TiO, TiO, TiO ZnH O, Peroxidation
  • the substance may be any of amorphous, anatase, brookite and rutile types.
  • the metal-doped titanate oxide includes one or more of copper, manganese, nickel, cobalt, iron and zinc, and a selected metal element, preferably peroxo It also becomes a titanate having a group and its property is fine particles or powder.
  • the titanium oxide having a peroxo group may be an amorphous type, anatase type, brookite type or rutile type, or may be offset, or a mixture of these! / ,.
  • Amorphous titanium oxide does not have a photocatalytic function.
  • anatase type, Brutzite type and rutile type titanium dioxide has a photocatalytic function but loses the photocatalytic function when copper, manganese, nickel, cobalt, iron, or zinc is compounded to a certain concentration or more.
  • the metal-doped titanate used in the present invention does not have a photocatalytic function.
  • the power of amorphous titanium oxide is converted to anatase titanium oxide over time by heating with sunlight, etc.
  • the metal-doped titanium oxide exhibits a non-photocatalytic unique antifouling function. This prevents or reduces the deterioration or contamination of the surface of the metal-doped titanium oxide-containing layer.
  • the mechanism of action is unknown, it is considered to be due to a combined action based on photoacidic reaction caused by short wavelength electromagnetic waves such as ultraviolet light (sunlight).
  • the photooxidation reaction is the generation of oxygen and oxygen in the air or organic matter, or active oxygen such as hydroxyl group radical ( ⁇ ), (singlet oxygen), etc. by short wavelength electromagnetic waves.
  • the metal-doped titanate oxide layer according to the present invention is positively charged as a whole since the doped metal has a positive charge. Therefore, the positively charged organic matter and the metal-doped titanate oxide layer having the same positive charge as the inorganic matter or the inorganic matter react electrically, and the organic matter and the soot or the inorganic matter are subjected to the action of an external force such as running water or weather.
  • the metal-doped titanate oxide layer surface force is relatively easily removed. This is considered to be able to suppress or reduce the contamination on the surface of the metal-doped titanate oxide layer.
  • general titanium dioxide can be used as a method for producing a metal-doped titanate according to the present invention.
  • a production method based on a hydrochloric acid method or a sulfuric acid method, which is a production method of powder powder, may be adopted, or various production methods of liquid dispersed titanium solution may be adopted.
  • the metal can be combined with the titanate at any manufacturing stage.
  • specific methods for producing the metal-doped titanate include the following first to third production methods, as well as sol-gel methods which are conventionally known.
  • a compound of tetravalent titanium such as tetrabasic titanium is reacted with a base such as ammonia to form titanium hydroxide.
  • this titanium hydroxide is peroxidized with an oxidizing agent to form ultrafine particles of amorphous titanium oxide.
  • the reaction is preferably carried out in an aqueous medium.
  • the oxidizing agent for peroxo formation is not particularly limited, and peroxo compounds of titanium are preferable, that is, hydrogen peroxide which can be used various kinds of peroxy titanium which can form titanium dioxide.
  • hydrogen peroxide solution is used as the oxidizing agent, the concentration of hydrogen peroxide is not particularly limited, but preferably 30 to 40%. It is preferred to cool the hydroxy titanium before peroxy. The cooling temperature at that time is preferably 15 ° C.
  • FIG. 1 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 of a compound of copper, manganese, nickel, cobalt, iron, zinc, and the hydroxide of the metal and titanium of Produce a mixture of hydroxides.
  • concentration and temperature of the reaction mixture at that time are not particularly limited, but it is preferable to use dilute and normal temperature.
  • This reaction is a neutralization reaction, and it is preferable that the pH of the reaction mixture be finally adjusted to around 7.
  • the hydroxide of metal and titanium thus obtained is washed with pure water, cooled at 5 ° C., and then peroxidized with hydrogen peroxide water.
  • the metal-doped titanium oxide fine particles having amorphous type peroxo group are contained.
  • An aqueous dispersion, ie an aqueous dispersion containing the metal-doped titanium oxide according to the present invention can be prepared.
  • a compound of tetravalent titanium such as tetrabasic titanium is peroxidized with an oxidizing agent, which is reacted with a base such as ammonia to form ultrafine particles of amorphous type titanium peroxide.
  • the reaction is preferably carried out in an aqueous medium.
  • it is possible to transfer to anatase type titanium dioxide by heat treatment optionally.
  • At least one of copper, manganese, nickel, cobalt, iron, zinc or their compounds is mixed at the force of each step of the above-mentioned steps.
  • a compound of tetravalent titanium such as tetrabasic titanium is reacted simultaneously with an oxidizing agent and a base to simultaneously form titanium hydroxide and its peroxolation to form ultrafine particles of amorphous titanium peroxide.
  • the reaction is preferably carried out in an aqueous medium.
  • at least one of copper, manganese, nickel, cobalt, iron, zinc and compounds thereof is mixed.
  • a mixture of amorphous titanium peroxide and anatase titanium peroxide obtained by heating this titanium oxide is a metal-doped titanium oxide of the present invention. It goes without saying that it can be used as a gift.
  • a solvent such as water or alcohol, an acid or a base catalyst is mixed and stirred in titanium alkoxide to hydrolyze the titanium alkoxide, thereby forming a sol solution of ultrafine particle titanium oxide.
  • an acid or a base catalyst is mixed and stirred in titanium alkoxide to hydrolyze the titanium alkoxide, thereby forming a sol solution of ultrafine particle titanium oxide.
  • at least one of copper, manganese, nickel, cobalt, iron, zinc or compounds thereof is mixed.
  • the titanium oxide thus obtained is an amorphous type having a peroxo group.
  • titanium alkoxide is represented by the general formula: Ti (OR ′) (however, alkyl group)
  • titanium alkoxide examples include Ti (0-iso C H), Ti (0-n C H), T
  • titanium hydroxide also called orthotitanic acid (H TiO) when reacted with a base
  • Any titanium complex can be used as long as it can form a titanium oxide, and examples thereof include water-soluble inorganic acid salts of titanium such as titanium tetrabasic, titanium sulfate, titanium nitrate and titanium phosphate. Besides these, water-soluble organic acid salts of titanium such as titanium borate can also be used. Among these various titanium compounds, tetrachloride titanium is preferred in that it is particularly excellent in water solubility, and components other than titanium do not remain in the metal-doped titanium oxide dispersion. .
  • the concentration of the solution is not particularly limited as long as a gel of hydroxide titanium can be formed.
  • a dilute solution is preferred.
  • the solution concentration of the compound of tetravalent titanium is preferably 0.9-0. 0 wt%, which is preferably 5-0.
  • the base to be reacted with the compound of tetravalent titanium various bases can be used as long as they can react with the compound of tetravalent titanium to form titanium dioxide, and ammonia, caustic soda, and so on can be used. Sodium carbonate, caustic potash, etc. can be exemplified. Ammonia is preferred.
  • the concentration of the solution is not particularly limited as long as a gel of titanium hydroxide can be formed, but a relatively dilute solution is used.
  • the concentration of the base solution is preferably 10-0.01 wt%, more preferably 1.0-0.lwt%.
  • the concentration of ammonia is preferably 10-0. 1 wt%, more preferably 1.0-0. 1 wt%.
  • Ni alloy Ni (OH), NiCl
  • Co compound Co (OH) NO, Co (OH), CoSO, CoCl
  • Cu compounds Cu (OH), Cu (NO), CuSO, CuCl, Cu (CH 3 COO)
  • Mn compounds MnNO, MnSO, MnCl
  • Fe compounds Fe (OH), Fe (OH), FeCl
  • Zivf compound Zn (NO), ZnSO, ZnCl
  • the concentration of titanium peroxide (total amount containing coexistent copper, manganese, nickel, cobalt, iron or zinc) in the aqueous dispersion obtained by the first to third production methods is 0.05 to 15 wt%. Is preferable 0.15 wt% is more preferable.
  • the molar ratio of titanium to the metal component is preferably 1: 0.01-1: 0.5, 1: 1: 0-1 0.1 is more preferable.
  • an additive such as a leveling agent or a dispersing agent which facilitates layer formation is compounded. Is preferred.
  • silicone oil various types can be used.
  • polyether modified silicone oil is preferable.
  • organopolysiloxanes having the following structure.
  • an organopolysiloxane in which a polyethylene oxide, polypropylene oxide or polyethylene oxide copolymer block is bonded to a silicon atom through an alkylene group is preferable.
  • Such polyether-modified silicone oil can be produced by a known method, for example, as disclosed in JP-A-9-165318. It can manufacture by the method as described in a gazette.
  • polyether modified silicone oil for example, TSF 4445, TSF 4446 (above, manufactured by GE Toshiba Silicone Co., Ltd.), KF-352, KF- 353 (above, manufactured by Shin-Etsu Kagaku Kogyo Co., Ltd.), SH3746 Toray 'Dow Co-Jung ⁇ Silicone Co., Ltd.).
  • aqueous dispersion it is effective to improve the stability of the aqueous dispersion by blending a mixture of a dispersant containing an anionic surfactant as the main component and sodium tripolyphosphate.
  • silane coupling compound having an amino group, an epoxy group and a methacryloxy group
  • silane coupling agent makes it possible to improve the hardness of the metal-doped titanium oxide-containing layer and the adhesion to the adjacent layer.
  • silicone rubber, silicone powder, silicone resin, etc. may be blended.
  • the mixing ratio (wt%) of the metal-doped titanium oxide according to the present invention and the additive such as the leveling agent and the dispersing agent is preferably 1: 0.2-1: 20, 1: 0. More preferred is 05-1: 10.
  • the metal-doped titanate oxide-containing layer in the laminate of the present invention can be produced by applying an aqueous dispersion containing a metal-doped titanate on the water absorption preventing layer and drying it.
  • the thickness of the metal-doped titanium oxide-containing layer is preferably 0.01 ⁇ m ⁇ 2.0 / z m, more preferably 0.1 m ⁇ 1.O / z m.
  • general-purpose film forming methods such as brush coating, roller coating, spray coating and the like can be used.
  • the mixing ratio of metal-doped titanium oxide to silicone oil is 1: 0. 1: 0. 05-1: 10 is more preferred.
  • the thickness of the metal-doped titanic acid-containing layer is preferably 0.010 to 0.15m / m, and preferably 0.050 to 0.13.
  • the constituent material of the adjacent layer in particular the organic substance, is deteriorated by the photocatalytic function even if it receives light energy such as ultraviolet light. I have not.
  • an organic resin such as an acrylic resin, a polyester resin, or a polycarbonate resin can also be mixed with the metal-doped titanate-containing layer itself as required.
  • the metal-doped titanate oxide-containing layer is a silicone oil, particularly, polyether-modified
  • silicone oil is contained, the effect of suppressing or reducing deterioration of the metal-doped titanium oxide-containing layer, color deterioration (fading), or contamination of the surface of the layer by organic or inorganic substances is particularly enhanced.
  • a photocatalytic functional layer can be further provided on the metal-doped titanate oxide layer in the laminate of the present invention.
  • the photocatalytic functional layer is a layer having a function of oxidizing and decomposing organic and Z 2 or inorganic compounds on the surface of a specific metal compound by photoexcitation.
  • the principle of photocatalyst is that a specific metal compound is photoexcited from water or oxygen in the air to radical species of OH-or O-
  • the organic and Z inorganic compounds having a positive charge generated by the reaction with the above-mentioned radial species have an electrostatic force on the surface of the photocatalytic function layer. Adhere by Then, the organic species and Z or the inorganic compound are further decomposed by the radical species, and at the stage where the electrostatic force of the decomposition product is reduced by its action, the decomposition product is removed by an external force such as flowing water and wind and rain.
  • metal compound examples include typical titanium oxide (TiO 2), ZnO, SrTiOP, and Cd.
  • the photocatalytic functional layer is coated, on the metal-doped titanium oxide-containing layer, an aqueous dispersion containing fine particles (about 2 nm to about 20 nm) of these metal compounds, together with various additives as necessary. It can be formed by drying.
  • the thickness of the photocatalytic functional layer is preferably 0.01 ⁇ m-2. 0 m, more preferably 0.1 l m-1. m.
  • the use of an aqueous dispersion is preferred for the formation of the photoaming agent functional layer, but it is also possible to use an alcohol as a solvent.
  • the aqueous dispersion for forming a photocatalytic function layer can be produced, for example, by the following method.
  • the peroxytitanium in the aqueous dispersion can be converted to titanium dioxide in a dry film-forming state.
  • titanium hydroxide is peroxidized with an oxidizing agent such as hydrogen peroxide to form ultrafine particles of amorphous titanium peroxide. Furthermore, it is transferred to an anatase-type titanium oxide by heat treatment.
  • the tetravalent titanium compound described above is peroxidized with an oxidizing agent such as hydrogen peroxide, and then reacted with a base such as ammonia to form ultrafine particles of amorphous titanium peroxide.
  • an oxidizing agent such as hydrogen peroxide
  • a base such as ammonia
  • the reaction of the tetravalent titanium compound described above with an oxidizing agent such as hydrogen peroxide or the like and a base such as ammonia simultaneously forms hydroxylated titanium and peroxo formation, and the amorphous fine particles of ultrafine particles are produced. Form titanium oxide. Furthermore, it is transferred to anatase type titanium peroxide by heat treatment.
  • Metals that improve the photocatalytic performance may be added to the photocatalytic function layer.
  • various substances such as metal salts can be added within the range not to inactivate 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, tungsten, zirconium, zinc and the like.
  • hydroxides or oxides for some metals or non-metals.
  • examples of compounds other than metal salts include indium hydroxide, caustic tungstic acid, silica sol, calcium hydroxide and the like.
  • indium hydroxide caustic tungstic acid
  • silica sol silica sol
  • calcium hydroxide and the like.
  • Contaminants on the surface of the laminate of the present invention are decomposed by the action of the photocatalytic functional layer, so that the contamination of the surface of the laminate can be prevented and the appearance of the laminate can be favorably maintained over time. Ru.
  • the photocatalytic function layer is formed directly on the substrate, there is a risk that the photocatalytic function layer may be peeled off from the substrate with time, but by interposing the metal-doped titanate oxide containing layer, the photocatalytic function layer becomes excellent as the substrate. Can be integrated into
  • the silicon-containing compound which is the water absorption preventing agent is degraded by the oxidative decomposition of the photocatalytic function layer, but in the laminate of the present invention, Since the metal-doped titanium oxide-containing layer having no photocatalytic function is interposed between the water absorption preventing layer and the photocatalytic function layer, the water absorption preventing layer is not deteriorated.
  • the laminate of the present invention can be used in any field where various design properties and high !, waterproofness and stain resistance are required, and glass, metal, ceramics, concrete, wood, Stone materials, sealants, etc. or combinations of these materials, such as building materials; air conditioning outdoor equipment; kitchen equipment; sanitary equipment; lighting equipment; automobiles; bicycles; motorcycles; aircraft; trains; It is suitably used for manufacture.
  • the laminate of the present invention is suitable as a building material, and buildings such as houses and buildings built using the building materials, and civil engineering works such as roads and tunnels have high waterproofing and dirt resistance over time. The stain preventing effect can be exhibited.
  • Pollux white (PC-CRH: manufactured by Sumika Color Co., Ltd.) 100 parts by weight as an inorganic pigment and Pollux binder (PM-FD: manufactured by Sumika Color Inc.) as a binder 5
  • PM-FD manufactured by Sumika Color Inc.
  • a mixture of parts by weight and a 10-fold water dilution of DRYSEAL S Toray 'Dow Coyung' Silicone-based water absorption inhibitor manufactured by Toray Silicone Co., Ltd.
  • DRYSEAL S Toray 'Dow Coyung' Silicone-based water absorption inhibitor manufactured by Toray Silicone Co., Ltd.
  • Dry seal is a mixture of 100 parts by weight of Pollux Yellow (PC-LD: manufactured by Sumika Color Co., Ltd.) as an organic pigment and 5 parts by weight of Pollux Binder (PM-FD: manufactured by Sumika Color Co., Ltd.) as a binder S: A 10-fold diluted water solution of S (Toray 'Dow Coyung' Silicone-based water absorption inhibitor manufactured by Silicone Co., Ltd.) was mixed and stirred at a weight ratio of 1:10 to obtain a water absorption preventing coloring solution.
  • PC-LD manufactured by Sumika Color Co., Ltd.
  • PM-FD manufactured by Sumika Color Co., Ltd.
  • S A 10-fold diluted water solution of S (Toray 'Dow Coyung' Silicone-based water absorption inhibitor manufactured by Silicone Co., Ltd.) was mixed and stirred at a weight ratio of 1:10 to obtain a water absorption preventing coloring solution.
  • a solution in which 3 g was completely dissolved was further added with 10 g of a 50% titanium tetrachloride solution (manufactured by Sumitomo Sittics Co., Ltd.), and pure water was added to make the total volume 1000 ml.
  • a 50% titanium tetrachloride solution manufactured by Sumitomo Sittics Co., Ltd.
  • the precipitate was washed with pure water until the conductivity of the supernatant liquid reached 0.8 mSZm or less, and when the conductivity reached 0.80 mSZm, the washing was finished. As a result, 340 g of a hydroxide-containing solution having a concentration of 0.81 wt% was prepared.
  • An anatase type titanium peroxide aqueous dispersion (Sustainable Technology Co., Ltd. B56) was used as a photocatalyst function imparting solution.
  • a commercially available pre-cast concrete substrate (width 300 mm, length 300 mm, thickness 30 mm) was coated twice with the paint-preventing coloring solution of Example 1-1 with a paint brush and dried well at room temperature
  • Reference Example 1 A evaluation substrate was obtained by the same method as in Example 1 except that Reference Example 1 2 was used in place of 1).
  • Reference Example 1 A evaluation substrate was obtained by the same method as in Example 1 except that Reference Example 1 3 was used instead of 1).
  • Reference Example 1 A evaluation substrate was obtained by the same method as in Example 1 except that Reference Example 1 4 was used instead of 1.
  • Comparative Example 5 The copper-doped amorphous type titanium peroxide dispersion prepared in Reference Example 2-1 was coated on the same substrate as in Example 1 using a paint spray gun at an air pressure of 2 kgz m 2 in an amount of lOg z m 2 Thus, Comparative Example 5 was obtained.
  • Example 1-14 and Comparative Example 1-15 were exposed outdoors in Chiba Prefecture and Saga Prefecture from the middle of May 2003 to the beginning of October, and the contamination status of the evaluation substrates was visually evaluated. did .
  • the results are shown in Table 1.
  • Reference Example 2 3 Reference Example 2-1 Copper-doped amorphous type titanium peroxide dispersion 0.85 wt% with polyether-modified silicone oil SH3746 (Toray 'Dow Co-Jung' Silicone Co., Ltd.) 0.4 wt% is added and mixed The mixture was stirred to obtain a copper-doped amorphous type titanium-polyether-modified silicone mixed dispersion.
  • Example 1-5 On a commercially available precast concrete substrate (width 300 mm, length 300 mm, thickness 30 mm), the water absorption preventing liquid of Example 1-5 was applied twice with a paint brush and thoroughly dried at normal temperature.
  • Reference Example 15 An evaluation substrate was obtained by the same method as Example 5, except that the liquid for water absorption preventing coloring of Reference Example 16 was used instead of 5.
  • Example 5 On the evaluation substrate of Example 5, the photocatalytic function imparting solution of Reference Example 3-1 was applied three times with a paint brush, and dried at normal temperature.
  • the photocatalytic function imparting solution of Reference Example 3-1 was coated 3 times with a paint brush on the evaluation substrate of Example 6 and dried at normal temperature.
  • An evaluation substrate was obtained by the same method as in Example 5 except that the mixed liquid of copper-doped amorphous type peroxytitanium polyether-modified silicone according to Reference Example 2-3 was not used.
  • An evaluation substrate was obtained by the same method as in Example 6 except that the mixed liquid of copper-doped amorphous type peroxytitanium polyether-modified silicone according to Reference Example 2-3 was not used.
  • the evaluation substrates of Examples 5 to 8 and Comparative Examples 6 to 7 were exposed outdoors in Saga Prefecture from October 2003 to the end of January 2004, and evaluation of contamination of the evaluation substrate with the naked eye, Evaluation of fixation by the Cellotape (registered trademark) peeling test described above, evaluation of hydrophilicity by the naked eye, and evaluation of water absorption by the naked eye were performed.
  • Evaluation of absorbency after sprinkling tap water on the surface of each evaluation substrate, a part of the evaluation substrate was cut, and the water absorption state of the cross section was visually evaluated. The results are shown in Table 2.
  • the laminate of the present invention by arbitrarily coloring the water absorption preventing layer containing the silica-containing composite, it is possible to give a free design while activating the texture of the substrate itself.
  • the unique contamination preventing function exerted by the metal-doped titanium oxide-containing layer itself can prevent contamination of the surface of the laminate.
  • the antifouling effect can be further improved by incorporating a silicone oil, particularly a polyether-modified silicone oil, into the metal-doped titanate-containing layer.
  • the metal-doped titanate oxide-containing layer does not have a photocatalytic function, it does not cause oxidative decomposition of a water absorption preventing layer containing a carbon-containing binder.
  • the laminate of the present invention can provide an optional design while maintaining good waterproofness and stain resistance over time, and is particularly suitable as a building material for outdoor construction. It is.
  • the water absorption preventing layer may be degraded by oxidation by the action of the photocatalytic function layer.
  • the photocatalytic functional layer is not hydrolyzed.
  • the laminate can provide an arbitrary design while maintaining good waterproofness and contamination resistance over time, for example, a house (including an outer wall, a bathroom, a kitchen, a toilet), a building, etc. It is suitably used as a building material for outdoor structures such as waterways, dams, roads, tunnels, bridges, airports and port facilities.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Laminated Bodies (AREA)
  • Catalysts (AREA)

Abstract

Il est prévu un produit stratifié comprenant un substrat ayant des pores à la surface de celui-ci, une couche transparente ou colorée, évitant l'absorption d'eau, contenant un composé contenant du silicium, formée sur ledit substrat, et une couche contenant un oxyde de titane dopé avec au moins un élément de métal sélectionné parmi le groupe consistant en cuivre, manganèse, nickel, cobalt, fer et zinc, formé sur ladite couche évitant l'absorption d'eau. Le produit stratifié ci-dessus peut être coloré de manière arbitraire, tout en conservant une bonne propriété hydrofuge et une bonne résistance aux taches.
PCT/JP2005/005400 2004-03-24 2005-03-24 Produit stratifie et procédé de fabrication de celui-ci WO2005090067A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102448584A (zh) * 2009-05-29 2012-05-09 萨斯堤那普尔科技股份有限公司 气体的除去或无害化方法
EP2045025A4 (fr) * 2006-07-25 2013-01-02 Sustainable Titania Technology Inc Procédé de protection d'un corps de base
WO2020129456A1 (fr) * 2018-12-19 2020-06-25 富士フイルム株式会社 Matériau composite de photocatalyseur, élément de protection d'affichage de signalisation, élément de protection de panneau tactile, élément de protection de cellule solaire, élément de protection de capot de capteur, affichage de signalisation, panneau tactile, cellule solaire et capot de capteur

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997000134A1 (fr) * 1995-06-19 1997-01-03 Nippon Soda Co., Ltd. Structure porteuse de photocatalyseur et materiau de revetement photocatalytique
JPH11319709A (ja) * 1998-05-15 1999-11-24 Mitsubishi Materials Corp 有機系基材への光触媒膜の形成方法とその用途
JP2003252625A (ja) * 2001-12-28 2003-09-10 Shinto Paint Co Ltd 変性チタニアゾル組成物

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW200422260A (en) * 2002-11-07 2004-11-01 Sustainable Titania Technology Titania-metal complex and method for preparation thereof, and film forming method using dispersion comprising the complex

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997000134A1 (fr) * 1995-06-19 1997-01-03 Nippon Soda Co., Ltd. Structure porteuse de photocatalyseur et materiau de revetement photocatalytique
JPH11319709A (ja) * 1998-05-15 1999-11-24 Mitsubishi Materials Corp 有機系基材への光触媒膜の形成方法とその用途
JP2003252625A (ja) * 2001-12-28 2003-09-10 Shinto Paint Co Ltd 変性チタニアゾル組成物

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2045025A4 (fr) * 2006-07-25 2013-01-02 Sustainable Titania Technology Inc Procédé de protection d'un corps de base
CN102448584A (zh) * 2009-05-29 2012-05-09 萨斯堤那普尔科技股份有限公司 气体的除去或无害化方法
EP2436436A4 (fr) * 2009-05-29 2012-10-10 Sustainable Titania Technology Inc Procédé d'extraction ou de détoxication de gaz
WO2020129456A1 (fr) * 2018-12-19 2020-06-25 富士フイルム株式会社 Matériau composite de photocatalyseur, élément de protection d'affichage de signalisation, élément de protection de panneau tactile, élément de protection de cellule solaire, élément de protection de capot de capteur, affichage de signalisation, panneau tactile, cellule solaire et capot de capteur

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JPWO2005090067A1 (ja) 2008-05-08
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