CN1927474A - Antifouling member and antifouling coating composition - Google Patents

Antifouling member and antifouling coating composition Download PDF

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Publication number
CN1927474A
CN1927474A CNA2006100934524A CN200610093452A CN1927474A CN 1927474 A CN1927474 A CN 1927474A CN A2006100934524 A CNA2006100934524 A CN A2006100934524A CN 200610093452 A CN200610093452 A CN 200610093452A CN 1927474 A CN1927474 A CN 1927474A
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China
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mentioned
record
oxide
layer
hydrophobic resin
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Chinese (zh)
Inventor
渡部俊也
早川信
町田光义
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Toto Ltd
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Toto Ltd
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F1/00—Tubular elements; Assemblies of tubular elements
    • F28F1/10—Tubular elements and assemblies thereof with means for increasing heat-transfer area, e.g. with fins, with projections, with recesses
    • F28F1/12—Tubular elements and assemblies thereof with means for increasing heat-transfer area, e.g. with fins, with projections, with recesses the means being only outside the tubular element
    • F28F1/24—Tubular elements and assemblies thereof with means for increasing heat-transfer area, e.g. with fins, with projections, with recesses the means being only outside the tubular element and extending transversely
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24F—AIR-CONDITIONING; AIR-HUMIDIFICATION; VENTILATION; USE OF AIR CURRENTS FOR SCREENING
    • F24F8/00—Treatment, e.g. purification, of air supplied to human living or working spaces otherwise than by heating, cooling, humidifying or drying
    • F24F8/20—Treatment, e.g. purification, of air supplied to human living or working spaces otherwise than by heating, cooling, humidifying or drying by sterilisation
    • F24F8/22—Treatment, e.g. purification, of air supplied to human living or working spaces otherwise than by heating, cooling, humidifying or drying by sterilisation using UV light
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F19/00—Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01Q—ANTENNAS, i.e. RADIO AERIALS
    • H01Q1/00—Details of, or arrangements associated with, antennas
    • H01Q1/02—Arrangements for de-icing; Arrangements for drying-out ; Arrangements for cooling; Arrangements for preventing corrosion
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01Q—ANTENNAS, i.e. RADIO AERIALS
    • H01Q1/00—Details of, or arrangements associated with, antennas
    • H01Q1/40—Radiating elements coated with or embedded in protective material
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F2245/00—Coatings; Surface treatments
    • F28F2245/02—Coatings; Surface treatments hydrophilic
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F2245/00—Coatings; Surface treatments
    • F28F2245/04—Coatings; Surface treatments hydrophobic

Abstract

Disclosed is a member having an antifouling surface on which the so-called stains, such as deposits and contaminants, are less likely to be deposited. The surface of the member has both a hydrophobic portion, and a hydrophilic portion induced by a photocatalyst, the hydrophobic portion and the hydrophilic portion being present in a microscopically dispersed and exposed state on the surface.

Description

Antifouling member and antifouling coating composition
The application be that February 6, application number in 1997 are 200410057892.5 the applying date, denomination of invention divides an application for the application for a patent for invention of " antifouling member and antifouling coating composition ".
Technical field
The present invention relates to material and be difficult to member, more particularly, relate to that dirts such as conglomerate, pollutant are difficult to adhere to, have the member on the surface of antifouling property in its surface attachment, and the composition that is used to make the member with this surface.In addition, the surface that the present invention relates to give desirable member is difficult to the method for the character of attachment material, more particularly, relates to the method for giving the character that is difficult to adhere to dirts such as conglomerate, pollutant.
Background technology
In building and paint field, because environmental pollution makes the exterior finishing material of building and the surface contamination of outdoor architecture thing become problem.
The coal dust and the particle that float in the atmosphere are accumulated on the roof and exterior wall of building when fine.Conglomerate flows with rainwater when rainfall, flows down along the exterior wall of building.And, the coal dust that floats in the air is trapped in the rainwater, the rainwater that has captured coal dust flows down along the exterior wall of building and the outer surface of outdoor architecture thing.The result is to adhere to polluter along the zone of rainwater process from the teeth outwards.Then, when such dry tack free, present the contamination of striated from the teeth outwards.
Construction exterior exterior material and the contamination of filming are made of inorganic pollutions such as combustion products such as carbon black, city coal dust and clay particles.It is believed that, such pollutant qualitative diversity makes the countermeasure of preventing and remedying pollution become complicated (tangerine Gao Yidian work " the promotion test method of the pollution of material on the outer wall bodyguard ", Architectural Institute of Japan's structure porism literary composition report collection, No. 404, in October, 1989, p.15～24).
Originally, it is believed that in order to prevent the contamination of above-mentioned building appearance etc., it was desirable adopting hydrophobicity coating such as polytetrafluoroethylene (PTFE).Yet recently, people consider, for containing the many city coal dusts of hydrophobicity composition, should make film coated surface have hydrophily (macromolecule, 44 volumes, May nineteen ninety-five number, 307 pages) as far as possible.Therefore, the someone proposes to come decorative constructure (news " chemical industry daily paper ", January 30 nineteen ninety-five) with hydrophilic graft polymers.It is reported that this is filmed to have to be converted into and reaches 30～40 ° hydrophily with the contact angle of water.
Therefore, with the clay mineral is that the inorganic dust of representative and the contact angle of water are 20 °～50 °, so to the contact angle with water is that 30 °～40 ° graft polymers has compatibility, thereby easily adheres in its surface, can not prevent the contamination of inorganic dust so can think that this graft polymers is filmed.
Thereby someone proposes by making above-mentioned component surface obtain the way that hydrophobicity or hydrophily are maintained in the clean condition the surface, yet its activity still has the leeway of improvement.
Summary of the invention
The inventor has now found that, hydrophobic parts and by the simultaneous surface of hydrophilic parts that photochemical catalyst causes shows fabulous antifouling property.Finish the present invention according to this discovery.
Therefore, the purpose of this invention is to provide member with the surface that is difficult to attachment material.
In addition, the purpose of this invention is to provide and have the member that the antifouling property surface is arranged that is difficult to adhere to dirts such as conglomerate, pollutant.
Hydrophobic parts that member of the present invention has and the hydrophilic parts that is caused by photochemical catalyst are disperseed at the component surface microcosmic, and exist with exposed state.
Therefore, according to first embodiment of the present invention, provide a kind of member, the superficial layer that comprises photocatalytic oxide, polyorganosiloxane resin or silica and hydrophobicity fluororesin that wherein contains matrix material and be provided with on this matrix material, above-mentioned polysiloxanes or silica and hydrophobicity fluororesin disperse and exist with exposed state at the outmost surface microcosmic of this superficial layer.
In addition,, provide a kind of member, the superficial layer that contains hydrophobic resin and photocatalytic oxide that this member has matrix material and is provided with on this matrix material according to second embodiment of the present invention.
Above-mentioned hydrophobic resin that exists on the outmost surface of this superficial layer and above-mentioned photocatalytic oxide disperse with microcosmic and exposed state exists, and, above-mentioned photocatalytic oxide, the photocatalysis that generates by optical excitation, this photocatalytic oxide self produces hydrophily, or makes near the photocatalytic oxide that exists this photocatalytic oxide produce hydrophily.
According to first and second two embodiments of the present invention, from the hydrophobic parts of hydrophobic resin and the hydrophilic parts that is caused by photochemical catalyst, microcosmic disperses and is present in the outmost surface of member.The result of this hydrophobic parts and the adjacent existence of hydrophilic parts is, easily with the hydrophily attachment of hydrophilic parts, at adjacent hydrophobic but affinity not partly.In addition, easily and the hydrophobicity attachment of hydrophobic parts, in adjacent hydrophilic parts also affinity not.Therefore, hydrophily attachment and hydrophobicity attachment all can not be attached on the component surface.And even adhere to, this adheres to also is unsettled, and this attachment breaks away from easily, and component surface is maintained in the clean condition.But above-mentioned explanation is a supposition purely, and the present invention is not subjected to the qualification of this mechanism.
Description of drawings
Fig. 1 is the structural map of expression first embodiment of the invention member.According to the present invention, member 1 is made of matrix material 2 and top formed superficial layer 3 thereof, superficial layer 3 contains polysiloxane or silica layer 4, the hydrophobicity fluororesin 5 and the photocatalytic oxide 6 that disperse in this layer 4 expose a part of hydrophobicity fluororesin 5 in the outmost surface of this polysiloxanes or silica layer 4.
Fig. 2 is the method to set up of tested test sample among the expression embodiment 3.According to member 1 of the present invention, be arranged in the figure on the wall surface in house 11, be under the sun-exposed state from the sun 10.
Fig. 3 is the structural map of the member of expression second embodiment of the invention.According to member 21 of the present invention, be on matrix material 22, to form superficial layer 23, the photocatalytic oxide 25 that superficial layer 23 contains hydrophobic resin layer 24 and disperses in this layer 24, and photocatalytic oxide 25 is to exist on the outermost surface that is exposed to layer 24.
Fig. 4 is expression, and under state shown in Figure 3, superficial layer 23 contains the state diagram of inorganic oxide 26 again.
Fig. 5 is the second desirable concrete example of expression second embodiment of the invention.According to member 21 of the present invention comprise that the layer 24 that is made of the photocatalytic oxide and the hydrophobic resin that forms constitute thereon layers 28.Here, the layer 28 of hydrophobic resin formation is laminated on the part layer 24.The result is that hydrophobic resin and photocatalytic oxide microcosmic are dispersed in the outermost layer of superficial layer 23, exist with exposed state.
Fig. 6 represents that under state shown in Figure 5, the layer 24 that comprises photocatalytic oxide contains inorganic oxide 29 formed states again.
The specific embodiment
Definition
In the present invention, so-called " soil resistance " reaches " antifouling activity ", is meant that certain surface is an inertia to adhering to of material, and perhaps, certain surface is gone up various materials and is difficult to adhere to, and, also mean, in case adhere to the character that material is also easily removed.
In addition, in the present invention, hydrophobic parts and hydrophilic parts exist with " microcosmic dispersion " state from the teeth outwards, and the unit are that means the existence of hydrophobic parts and hydrophilic parts homogeneous is less than about 0.1mm 2
And, in the present invention, so-called photochemical catalyst means when using light (exciting light) irradiation of the energy bigger than the energy between its crystallization conduction band and the valence band (being the short wavelength), electron production in the valence band excites (optical excitation), generates the material in conduction and hole.In addition,, can enumerate as the photocatalytic oxide, for example, oxides such as the titanium oxide of Detitanium-ore-type, Titanium Dioxide Rutile Top grade, zinc oxide, tin oxide, iron oxide, bismuth oxide, tungstic acid and strontium titanates.
Antifouling member according to first embodiment of the invention
Member according to first embodiment of the invention is made of the superficial layer that contains photocatalytic oxide, polyorganosiloxane resin or silica and hydrophobicity fluororesin that contains matrix material and be provided with on this matrix material.And polysiloxanes or silica and hydrophobicity fluororesin disperse with microcosmic and exist with exposed state in the outmost surface of this superficial layer.
In this scheme, because the hydrophobicity fluororesin exists with the form of exposing outmost surface, so at first in the outmost surface formation hydrophobic parts of this member.
In addition, polysiloxanes or silica expose in its outmost surface.According to the present invention, when the surface irradiation light time of this member, because polysiloxanes or silica hydrophily will be further given in the effect of the photocatalytic oxide that exists in the superficial layer, and this hydrophily continues just can continue as long as illumination is penetrated.And, in case stop illumination, and when beginning illumination once more and penetrating, hydrophily will produce once again.The mechanism of action of hydrophiling is also determined, it is believed that the organic group of combination on the silicon atom in the polysiloxane molecule is replaced by hydroxyl to small part and just to present hydrophily.By such hydrophiling, on member outmost surface of the present invention, form hydrophilic parts.
As mentioned above, hydrophobic parts and the hydrophilic parts that caused by the photochemical catalyst effect at outermost surface and the result that deposits are simultaneously, in component surface of the present invention, hydrophily attachment and hydrophobicity attachment all can not adhere to, and even adhere to, it adheres to also unstable, this attachment breaks away from easily, the state that component surface keeps clean.
The desirable particular instantiation of the present embodiment is in Fig. 1.In Fig. 1, member 1 is to reach the superficial layer 3 that forms in the above by matrix material 2 to constitute, superficial layer 3 contains polysiloxane or silica layer 4, the hydrophobicity fluororesin 5 and the photocatalytic oxide 6 that disperse in this layer 4 expose the part of hydrophobicity fluororesin 5 in the outmost surface of this polysiloxanes or silica layer 4.In the embodiment depicted in fig. 1, polysiloxanes or silica are as layer structure, and hydrophobicity fluororesin and photocatalytic oxide are as granular.
In the embodiment of the present invention, the photocatalytic oxide can be with above-mentioned photocatalytic oxide.When the photocatalytic oxide was anatase-type titanium oxide, Titanium Dioxide Rutile Top grade, zinc oxide, strontium titanates, doing irradiation with sunlight, indoor illumination, fluorescent lamp, mercury lamp, incandescent lamp, xenon lamp, high-pressure mercury lamp, metal halide compound lamp, BLB lamp was desirable with light.In addition, in the occasion of making the photocatalytic oxide with tin oxide, be desirable with sunlight bactericidal lamp and BLB lamp etc.And the exposure intensity of irradiates light also can wait suitably according to composition of member and uses thereof and select, yet for the hydrophilic parts that makes substrate material surface has highly hydrophilic and remains under this state, the exposure intensity of exciting light is at 0.001mW/cm 2More than be desirable, that better is 0.01mW/cm 2More than, it would be desirable 0.1mW/cm 2More than.
In the present embodiment, so-called polyorganosiloxane resin it is desirable to represent with a following average group accepted way of doing sth (I)
R PSiO (4-P)/2 (I)
In the formula, the group of R for selecting constitute from hydrogen atom and one or two or more kinds organic group one group; X is alkoxyl or halogen atom; P is for satisfying the number of 0＜p＜2.
Here, when R represents organic group, mean alkyl (be more preferably the not substituted alkyl of 1～18 of carbon number, best is the alkyl of 3～18 of carbon numbers) or aryl (it is desirable to phenyl).
Desirable object lesson as polyorganosiloxane resin, can enumerate, MTMS, MTES, methyl trichlorosilane, the methyl tribromosilane, methyl three isopropoxy silane, methyl three tert-butoxy silane, ethyl trimethoxy silane, ethyl triethoxysilane, ethyl trichlorosilane, the ethyl tribromosilane, ethyl three isopropoxy silane, ethyl three tert-butoxy silane, the n-pro-pyl trimethoxy silane, the n-pro-pyl triethoxysilane, n-propyltrichlorosilan, the n-pro-pyl tribromosilane, n-pro-pyl three isopropoxy silane, n-pro-pyl three tert-butoxy silane, the n-hexyl trimethoxy silane, the n-hexyl triethoxysilane, the n-hexyl trichlorosilane, the n-hexyl tribromosilane, n-hexyl three isopropoxy silane, n-hexyl three tert-butoxy silane, positive decyl trimethoxy silane, positive decyl triethoxysilane, positive decyltrichlorosilane, positive decyl tribromosilane, positive decyl three isopropoxy silane, positive decyl three tert-butoxy silane, the n-octyl trimethoxy silane, the n-octyl triethoxysilane, the n-octyl trichlorosilane, the n-octyl tribromosilane, n-octyl three isopropoxy silane, n-octyl three tert-butoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane, phenyl trichlorosilane, the phenyl tribromosilane, phenyl three isopropoxy silane, phenyl three tert-butoxy silane, dimethyldichlorosilane, dimethyl two bromo-silicanes, dimethyldimethoxysil,ne, dimethyldiethoxysilane, diphenyl dichlorosilane, dibromodiphenyl silane, dimethoxydiphenylsilane, the diphenyl diethoxy silane, phenylmethyldichloroislane, phenyl methyl two bromo-silicanes, phenyl methyl dimethoxy silane, the phenyl methyl diethoxy silane, vinyl trichlorosilane, the vinyl tribromosilane, vinyltrimethoxy silane, VTES, vinyl silane triisopropoxide, vinyl three tert-butoxy silane, the trifluoro propyl trichlorosilane, the trifluoro propyl tribromosilane, the trifluoro propyl trimethoxy silane, the trifluoro propyl triethoxysilane, trifluoro propyl three isopropoxy silane, trifluoro propyl three tert-butoxy silane, γ-glycidoxy propyl group methyl dimethoxysilane, γ-glycidoxy propyl group methyl diethoxy alkane, γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxy propyl-triethoxysilicane, γ-glycidoxy propyl group three isopropoxy silane, γ-glycidoxy propyl group three tert-butoxy silane, γ-metacryloxy propyl group methyl dimethoxysilane, γ-metacryloxy propyl group methyldiethoxysilane, γ-metacryloxy propyl trimethoxy silicane, γ-metacryloxy propyl-triethoxysilicane, γ-metacryloxy propyl group three isopropoxy silane, γ-metacryloxy propyl group three tert-butoxy silane, gamma-amino propyl group methyl dimethoxysilane, gamma-amino propyl group methyldiethoxysilane, the gamma-amino propyl trimethoxy silicane, γ-An Jibingjisanyiyangjiguiwan, gamma-amino propyl group three isopropoxy silane, gamma-amino propyl group three tert-butoxy silane, γ-sulfydryl propyl group methyl dimethoxysilane, γ-sulfydryl propyl group methyldiethoxysilane, γ-Qiu Jibingjisanjiayangjiguiwan, γ-sulfydryl propyl-triethoxysilicane, γ-sulfydryl propyl group triisopropyl TMOS, γ-sulfydryl propyl group three tert-butoxy silane, β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, the hydrolysate of β-(3, the 4-epoxycyclohexyl) ethyl triethoxysilane, the dehydration condensation polymer.In the present embodiment, the preferred amorphous silica of silica.
In addition, in the present embodiment, as the hydrophobic fluorine resin, for example, can enumerate polytetrafluoroethylene (PTFE), Kynoar, polyvinyl fluoride, polychlorostyrene is for trifluoro-ethylene, tetrafluoroethene one hexafluoropropylene copolymer, ethylene-tetrafluoroethylene copolymer, ethene-chloro trifluoro-ethylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, perfluor ring polymers, vinyl ethers-fluoroolefin copolymer, vinyl esters-fluoroolefin copolymer, tetrafluoroethene-vinyl ether co-polymer, chloro trifluoro-ethylene-vinyl ether co-polymer, the crosslinked body of tetrafluoroethene carbamate, tetrafluoroethene epoxy cross-linking body, the crosslinked body of tetrafluoroethene acrylic, fluoro-containing group polymer such as the crosslinked body of tetrafluoroethene melamine.In the present invention, the hydrophobicity degree of hydrophobic fluorine resin can suitably determine in the scope that can bring into play effect of the present invention.Yet for example, the hydrophobicity degree it is desirable to, with the contact angle of water greater than 80 °, better is 120 °.In above-mentioned fluororesin, tetrafluoroethene considers it is desirable from the persistence of high hydrophobic and high hydrophobic.
And, matrix material is not particularly limited, for example, can use metal, pottery, glass, plastics, timber, stone material, cement, concrete, fiber, fabric, can be used in combination or use its layered product.Matrix material can be determined according to the purposes of member.
The amount of hydrophobic fluorine resin can wait suitably according to the composition of superficial layer and purposes and determine that still, it is desirable that the amount in superficial layer reaches 20～60% (weight) in the superficial layer of the present embodiment, and better is 25～50% (weight).
In addition, the amount of the photocatalytic oxide of superficial layer is not particularly limited yet, still, the amount in superficial layer is that 10～80% (weight) are desirable, and better is 20～50% (weight).
According to the desirable embodiment of the present invention, the thickness of superficial layer can wait suitably according to the composition of superficial layer and purposes to be determined, still, for example wants to it is desirable to the occasion that makes superficial layer transparent less than about 0.4 μ m.Thus, can prevent the caused whiting of irregular reflection of light, so superficial layer comes down to transparent.And, it is desirable to can prevent effectively that less than about 0.2 μ m color from appearring in the superficial layer that the interference of light causes.If superficial layer is thinner, its transparency improves, still, consider from wearability, and obviously be that it is desirable having certain thickness.
Embodiment as shown in Figure 1 is such, in hydrophobicity fluororesin and photocatalytic oxide occasion with granular use, its particle diameter can suitably be selected, yet, the main particle diameter of hydrophobicity fluororesin is desirable about 10nm～10 μ m, better is that photocatalytic oxide crystallization particle diameter is desirable about 1nm～100nm about 100nm～1 μ m, and better is about 5nm～20nm.
In the member of first embodiment of the invention, do not observe the showy coal smoke in the atmosphere, be difficult to adhere to water droplet, snowflake yet, and then be difficult to boiomacromolecule, biology and microorganisms etc. such as attachment protein matter.Therefore, can aspect following, use according to member of the present invention.That is building materials,, building external decorative, the interior trim of building, window frame, glass pane, the member that structure is used, sheet material, the outer decoration and the coating of means of transport, the extraneous adornment of mechanical device and parts, dust cover and coating, the reflecting plate that road sign is used, various exhibiting devices, advertising tower, the sound-proof wall that road is used, the sound-proof wall that railway is used, the decorative panel that road is used, the light source cover that semaphore is used, outdoor Graphic Panel, bridge, the outer decoration and the coating of guardrail, the upholstery in tunnel and coating, the tunnel interior lighting device, glass, the solar cell cover, solar water heater's collector mat, the vinyon greenhouse, for motor vehicle illuminating lamp shade, the road mirror, vehicle-use mirror, two-wheel vehicle used instrument mask and instrument board, glass lens, plastic lens, welders' mask, the glass pane of house and automobile and rolling stock, show window, the insulation show window, membrane structure material, the fin that heat exchange is used, the glass surface in various places, curtain, tire, roof Material, antenna, power transmission line, residential equipment, urinal, bathing pool, the platform of washing one's face, ligthing paraphernalia, the illumination cover, kitchen articles, tableware, cupboard, tableware washer, tableware dryer, sink, cooking lattice, air discharge hood for kitchen, ventilation fan, nonthrombogenic material, anti-albumen tack material, hull bottom and be applied to film on the above-mentioned article.
According to the desirable specific embodiments of the present invention, hydrophobic parts and hydrophilic parts have a degree, can be in addition suitably selected according to its purposes.
For example, on the outmost surface of superficial layer, every 10nm 2～100nm 2,, at least respectively exist the member at a place to have the high molecular character of the aufwuch of being difficult to from the hydrophobic parts of above-mentioned hydrophobicity fluororesin with from the hydrophilic parts of above-mentioned polysiloxanes or silica.Therefore, such member can be used for the antithrombotic material, anti-protein tack material and prevent the material that lipid adheres to, more particularly, can be used for haptic lens, catheter and subcutaneous device, various man-made organ, blood bag, adopt the disposable medical appliance of pipe of connecting between urinal, lung drain means and these members etc.
In addition, in the outmost surface of superficial layer, every 10nm 2～1 μ m 2, at least respectively exist the member at a place to have the character that is difficult to aufwuch from the hydrophobic parts of above-mentioned hydrophobicity fluororesin with from the hydrophilic parts of above-mentioned polysiloxanes or silica.Therefore, such member can be used as, and hull bottom material, outer wall materials, bathroom material, bathing pool material, views and admires the pond material of usefulness, on facilities such as recirculated water utilization (for example, the artificial pond in park) surfacing that contacts with recirculated water (for example, the patch block of facility) etc.
And, in the outmost surface of superficial layer, every 0.1mm 2At least respectively exist the member at a place to be difficult to adhere to the coal smoke dirt that floats from the atmosphere from above-mentioned hydrophobic parts of hating property fluororesin not with from the hydrophilic parts of above-mentioned polysiloxanes or silica, perhaps, in case have and adhere to the character that above-mentioned dirt is also removed easily.Therefore, can be used as the casing part of the vehicles such as road structure, plate washer, glass, wheel disc, automobile such as decorative panel that outdoor use construction material, solar cell cover, solar water heater heat-collecting device cover, bridge floor railing, tunnel inwall, sound-proof wall, anti-sound wall, guard rail, road are used.
The member of the present embodiment, because of it has antifouling activity, so the contact angle of its superficial layer and water do not limit substantially, yet, in the scope of apparent contact angle about 10～120 ° of itself and water.
In addition, people are known, and the photocatalytic oxide has antifouling, the antibiotic and deodorization function based on its oxygenolysis.Can think that member of the present invention can keep this effect.Such photocatalyst oxidizes decomposition is when at the every 0.1mm of the outmost surface of superficial layer 2, at least respectively there is the occasion at a place from the hydrophobic parts of above-mentioned hydrophobicity fluororesin with from the hydrophilic parts of above-mentioned polysiloxanes or silica, can obtain desirable performance.
And member of the present invention can prevent to adhere to the growth of water droplet effectively, and in addition, the water droplet that adheres to breaks away from from the surface easily owing to the effect of slight force is rotated.In addition, member of the present invention is even ice and snow can not easily adhere in its surface.That is, member of the present invention has the effect that prevents that water droplet from growing up, water droplet adheres to and ice and snow adheres to.
Having the result who prevents water droplet growth effect is, for example, the present invention can be applicable to glass and mirror, can prevent effectively that water droplet from growing to the degree of energy scattered light.Specifically, it is applied to prevent that glass, mirror, lens, prism etc. are fuzzy and guarantees the visual field.More particularly, can be as eyeglass, welders' mask, goggles and the insulation show window etc. of the glass pane of building, the glass pane of the vehicles, for motor vehicle reflective mirror, road mirror, the mirror of washing one's face, instrument board cover, glasses.Verified, on the outmost surface of superficial layer, per 0.2 μ m 2, when at least respectively having a place from the hydrophobic parts of hydrophobicity fluororesin with from the hydrophilic parts of polysiloxanes or silica, such effect can be brought into play ideally.
In addition, member of the present invention, because of it has the effect that prevents that water droplet from adhering to and ice and snow adheres to, so, member of the present invention can be used for, prevent in the heat exchanger decrease in efficiency that causes of adhering to of water droplet between the aluminium radiator fin, the generation that the weld pool surface insulating properties that prevents to cause owing to adhering to of (salt) water descends on insulator surface, prevent that bathing pool revetment part is owing to the decline that causes sight adhering to of water droplet, prevent the ice and snow accumulation on roof, prevent that icicle from forming, prevent antenna accumulation ice and snow, prevent the communication obstacle, prevent transmission line of electricity accumulation ice and snow and prevent point discharge etc.More particularly, can be used as the estrade of the fin of heat exchanger, bathing pool, the usefulness that washes one's face, culinary estrade, roof Material, roof rain water mouth, antenna, transmission line of electricity etc.According to the desirable embodiment of the present invention, such water droplet that prevents adheres to and prevents the ice and snow adhewsive action, and is verified, in the outmost surface of superficial layer, and every 1mm 2,, when respectively having at least one place, can better be brought into play from the hydrophobic parts of above-mentioned hydrophobicity fluororesin with from the hydrophilic parts of above-mentioned polysiloxanes or silica.
And according to the desirable embodiment of the present invention, adding metals such as Ag, Cu and Zn at superficial layer is desirable.Added this metallic surface layer,, therefore, soil resistance has been improved more even in the dark also can become extinct attached to lip-deep bacterium and mould.
According to another desirable embodiment of the present invention, can add platinums group metal such as Pt, Pd, Ru, Rh, Ir and Os at superficial layer.Add this metallic surface layer, can strengthen the redox active of photochemical catalyst, can improve the decomposability of decomposability, raising pernicious gas and the stench of organic dirt.
According to the manufacturing of the antifouling member of first embodiment of the invention and composition for this reason
According to the member of first embodiment of the invention, be that coating is used to form the composition of superficial layer on substrate material surface basically, form superficial layer and produced.
As according to the desirable embodiment of the present invention, be used for the composition of this manufacturing, contain:
(a) the polyorganosiloxane resin coating precursor that can form the polyorganosiloxane resin coating maybe can form the silica coating precursor of silica coating;
(b) be dispersed in photocatalytic compound in above-mentioned (a) coating precursor;
(c) be dispersed in hydrophobicity fluororesin in above-mentioned (a) coating precursor.
Here, as the desirable example of polyorganosiloxane resin coating precursor, can enumerate the siloxanes that a following average group accepted way of doing sth is represented:
R pSiX qO (4-p-q)/2
In the formula, the implication of R is identical with the definition of above-mentioned formula (I), and X represents alkoxyl or halogen atom, and p is the number that satisfies 0＜q＜4 for satisfied 0＜p＜2, q, and p+q＜4.
In addition, as another desirable example of polyorganosiloxane resin coating precursor, can enumerate the hydrolyzable silane derivative of representing with following formula:
R pSiX 4-p
In the formula, the implication of R is identical with the definition of above-mentioned formula (I), and X is alkoxyl or halogen atom, and p is 1 or 2.
Object lesson as the water-disintegrable silane derivative of this tool, can enumerate MTMS, MTES, methyl tripropoxy silane, methyl three butoxy silanes, ethyl trimethoxy silane, ethyl triethoxysilane, ethyl tripropoxy silane, ethyl three butoxy silanes, phenyltrimethoxysila,e, phenyl triethoxysilane, phenyl tripropoxy silane, phenyl three butoxy silanes, dimethyldimethoxysil,ne, dimethyldiethoxysilane, dimethyl dipropoxy silane, dimethyl dibutoxy silane, diethyl dimethoxy silane, the diethyl diethoxy silane, diethyl dipropoxy silane, diethyl dibutoxy silane, phenyl methyl dimethoxy silane, the phenyl methyl diethoxy silane, phenyl methyl dibutoxy silane, the n-pro-pyl trimethoxy silane, the n-pro-pyl triethoxysilane, n-pro-pyl tripropoxy silane, n-pro-pyl three butoxy silanes, γ-glycosides oxygen propyl trimethoxy silicane, γ-propylene oxygen propyl trimethoxy silicane etc.
In addition, as above-mentioned siloxanes, the partial hydrolysis and the dehydration polycondensation of silane derivative that can be by above-mentioned tool hydrolysis property, or the dehydration polycondensation of the partial hydrolysate of the partial hydrolysate of the silane derivative by above-mentioned tool hydrolysis property and tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, four butoxy silanes, diethoxy dimethoxy silane etc. is made.
In addition, as the desirable example of silica coating precursor, can enumerate the silicate of representing with an average group accepted way of doing sth:
SiX qO (4-q)/2
In the formula, X is alkoxyl or halogen atom, and q is for satisfying the number of 0＜q＜4.
In addition, as another desirable example of silica coating precursor, can enumerate following general formula have four-functional group can hydrolysis silane derivative:
SiX 4
In the formula, X is alkoxyl or halogen atom.
As the desirable object lesson of the water-disintegrable silane derivative of the tool of above-mentioned four-functional group, can enumerate tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, four butoxy silanes, diethoxy dimethoxy silane etc.
As the desirable object lesson of above-mentioned silicates, can enumerate the partial hydrolysis of the silane derivative that the tool of above-mentioned four-functional group is water-disintegrable and dehydration condensation polymer etc.
In order to form superficial layer, composition it is desirable to make (a) and (b) and (c) dissolves or be dispersed in the solvent, and desirable solvent comprises water, ethanol and propyl alcohol etc.
In addition, in order to form this superficial layer, composition can contain additive again, for example, hydrochloric acid, nitric acid, acetic acid, maleic acid etc. can promote the catalyst of silicone precursor hydrolysis, alkali compounds classes such as tri-n-butylamine, hexylamine, acid compound classes such as three isopropoxy aluminium, tetra isopropyl titanate etc. can make the catalyst of silicone precursor sclerosis, silane coupling agents etc. can make the dispersed surfactant that improves of masking liquid, levelling agents such as diacetone alcohol, cellosolve, sprays such as dimethyl ether etc.
According to first embodiment of the invention, use the member of said composition, be by said composition is coated on the matrix material, and make the matrix material that has been coated with said composition make reaction that polyorganosiloxane resin coating precursor in the composition or silica coating precursor be transformed into polysiloxane coating or silica coating and produced.
As the method for coating above-mentioned composition on matrix material, can suitably utilize methods such as spraying process, infusion process, The tape casting, rotary process, drum process, spread coating and sponge rubbing method.
In addition, polysiloxane coating precursor or silica coating precursor become the reaction of polysiloxane coating or silica coating, can suitably determine according to the character of used precursor, for example, can make precursor polymeric with heat treated, room temperature placement, ultraviolet ray irradiation, moistening processing etc.The advantage of method therefor of the present invention is by choice reaction, can make member under lower reaction condition.Concrete is, for example, only place and just can make in room temperature, and in addition, can be to make under the room temperature substantially also with ultraviolet the irradiation.
And, pass through the above-mentioned composition supplied with, be provided at the method for giving soil resistance on the desirable surface, comprise according to method of the present invention: be coated with above-mentioned composition planning to give on the surface of soil resistance, make silicone precursor or silica precursor in the composition be transformed into polysiloxane coating or silica coating.
Antifouling member according to second embodiment of the invention
Member according to second embodiment of the invention is provided with the superficial layer that comprises hydrophobic resin and photocatalytic oxide on matrix material.And above-mentioned hydrophobic resin and above-mentioned photocatalytic oxide exist with form and the exposed state that microcosmic disperses in the outmost surface of this superficial layer.
The member of second embodiment of the invention, same with the member of first embodiment of the invention, its hydrophobic parts and the hydrophilic parts that caused by photochemical catalyst in outmost surface and the result that deposits are simultaneously, hydrophily attachment and hydrophobicity attachment all can not be attached on the component surface, in addition, even adhere to, this adheres to also unstable, attachment breaks away from easily, the state that component surface keeps clean.Therefore, also has same substantially purposes according to the member of second embodiment of the invention with the member of first embodiment of the invention.
In addition, as according to the desirable embodiment of the present invention, superficial layer of the present invention can contain inorganic oxide again.This inorganic oxide exists with microcosmic dispersion and exposed state in the outmost surface of superficial layer with hydrophobic resin and photocatalytic oxide.In addition, the photocatalysis that the optical excitation by photocatalytic oxide produces makes the inorganic oxide hydrophiling.That is the hydrophilic parts that inorganic oxide is further caused by photochemical catalyst in superficial layer.
Desirable first object lesson of second embodiment of the invention as shown in Figure 3.Member 21 shown in this figure is included in and forms superficial layer 23, the photocatalytic oxide 25 that superficial layer 23 contains hydrophobic resin layer 24 and disperses on the matrix material 22 in this layer 24.And this photocatalytic oxide 25 exists with the state that exposes layer 24 outmost surface.In the embodiment shown in this figure, the photocatalytic oxide provides as granular.
In addition, in the embodiment depicted in fig. 3, superficial layer 23 can contain inorganic oxide, and its embodiment is shown in Fig. 4.In the embodiment of this figure, photocatalytic oxide 25 and particulate inorganic oxides 26 disperse in hydrophobic resin layer 24 simultaneously.And this inorganic oxide 26 is also to expose the outmost surface that state is present in layer 23.
Desirable second object lesson of second embodiment of the invention as shown in Figure 5.Member 21 shown in this figure comprises layer 24 that the photocatalytic oxide constitutes and the layer 28 that is made of hydrophobic resin that forms on this layer, here, hydrophobic layer 28 is laminated on the part layer 24.The result is, disperses with microcosmic and the state that exposes exists at the outmost surface hydrophobic resin of superficial layer 23 and photocatalytic oxide.
In the embodiment of this Fig. 5, the layer 24 by the photocatalytic oxide constitutes can further contain inorganic oxide, and its embodiment is shown in Fig. 6.In the embodiment of this figure, particulate inorganic oxides 29 disperses in the layer that the photocatalytic inorganic oxide constitutes.And this inorganic oxide 29 also exists with the state that exposes layer 23 outmost surface.
In the present embodiment, the photocatalytic oxide can be with above-mentioned those.In addition, the irradiation usefulness light source and exposure intensity thereof, with illustrate in the invention described above first embodiment basic identical.
In second embodiment of the invention, so-called hydrophobic resin means fluororesin, acrylic resin, polyurethanes resin, mylar, vinyl resins, PET and polyorganosiloxane resin, for example, and propylene polysiloxanes, rubber etc.
As according to the desirable embodiment of the present invention, consider from light resistance, be desirable with fluororesin.As desirable fluororesin, can enumerate polytetrafluoroethylene (PTFE), Kynoar, polyvinyl fluoride, polychlorostyrene is for trifluoro-ethylene, tetrafluoraoethylene-hexafluoropropylene copolymer, ethylene-tetrafluoroethylene copolymer, ethene-chloro trifluoro-ethylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, the perfluor cyclopolymer, vinyl ethers-fluoroolefin copolymer, vinyl esters-fluoroolefin copolymer, tetrafluoroethene-vinyl ether co-polymer, chloro tetrafluoroethene-vinyl ether co-polymer, the crosslinked body of tetrafluoroethene urethane, the epoxy crosslinked body of tetrafluoroethene, the crosslinked body of tetrafluoroethene propylene, the crosslinked body of tetrafluoroethene melamine etc. contains fluorine-based polymer.
In addition, according to other desirable embodiment of the present invention, the also object lesson of operable polyorganosiloxane resin, can enumerate, MTMS, MTES, methyl trichlorosilane, the methyl tribromosilane, methyl three isopropoxy silane, methyl three tert-butoxy silane, ethyl trimethoxy silane, ethyl triethoxysilane, ethyl trichlorosilane, the ethyl tribromosilane, ethyl three isopropoxy silane, ethyl three tert-butoxy silane, the n-pro-pyl trimethoxy silane, the n-pro-pyl triethoxysilane, n-propyltrichlorosilan, the n-pro-pyl tribromosilane, n-pro-pyl three isopropoxy silane, n-pro-pyl three tert-butoxy silane, the n-hexyl trimethoxy silane, the n-hexyl triethoxysilane, the n-hexyl trichlorosilane, the n-hexyl tribromosilane, n-hexyl three isopropoxy silane, n-hexyl three tert-butoxy silane, positive decyl trimethoxy silane, positive decyl three butoxy silanes, positive decyltrichlorosilane, positive decyl tribromosilane, positive decyl three isopropoxy silane, positive decyl three tert-butoxy silane, the n-octyl trimethoxy silane, the n-octyl triethoxysilane, the n-octyl trichlorosilane, the n-octyl tribromosilane, n-octyl three isopropoxy silane, n-octyl three tert-butoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane, phenyl trichlorosilane, the phenyl tribromosilane, phenyl three isopropoxy silane, phenyl three tert-butoxy silane, dimethyldichlorosilane, dimethyl two bromo-silicanes, dimethyldimethoxysil,ne, dimethyldiethoxysilane, diphenyl dichlorosilane, dibromodiphenyl silane, dimethoxydiphenylsilane, the diphenyl diethoxy silane, phenylmethyldichloroislane, phenyl methyl two bromo-silicanes, phenyl methyl dimethoxy silane, the phenyl methyl diethoxy silane, vinyl three aminopropyl silanes, the vinyl tribromosilane, vinyltrimethoxy silane, VTES, vinyl silane triisopropoxide, vinyl three tert-butoxy silane, the trifluoro propyl trichlorosilane, the trifluoro propyl tribromosilane, the trifluoro propyl trimethoxy silane, the trifluoro propyl triethoxysilane, trifluoro propyl three isopropoxy silane, trifluoro propyl three tert-butoxy silane, γ-glycidoxy propyl group methyl dimethoxysilane, γ-glycidoxy propyl group methyldiethoxysilane, γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxy propyl-triethoxysilicane, γ-glycidoxy propyl group three isopropoxy silane, γ-glycidoxy propyl group three tert-butoxy silane, γ-methylpropenyl oxygen propyl group methyl dimethoxysilane, γ-methylpropenyl oxygen propyl group methyldiethoxysilane, γ-methylpropenyl oxygen propyl trimethoxy silicane, γ-methylpropenyl oxygen propyl-triethoxysilicane, γ-methylpropenyl oxygen propyl group three isopropoxy silane, γ-methylpropenyl oxygen propyl group three tert-butoxy silane, gamma-amino propyl group methyl dimethoxysilane, gamma-amino propyl group methyldiethoxysilane, the gamma-amino propyl trimethoxy silicane, γ-An Jibingjisanyiyangjiguiwan, gamma-amino propyl group three isopropoxy silane, gamma-amino propyl group three tert-butoxy silane, γ-sulfydryl propyl group methyldiethoxysilane, γ-sulfydryl propyl group MTMS, γ-sulfydryl propyl group MTES, γ-sulfydryl propyl group triisopropyl TMOS, γ-sulfydryl propyl group three tert-butoxy silane, β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, the hydrolysis of β-(3, the 4-epoxycyclohexyl) ethyl triethoxysilane etc. is herded, the dehydration condensation polymer.Also have, these polyorganosiloxane resins are used as the material that hydrophilic parts is provided in first embodiment of the invention, in first embodiment of the invention, because the photocatalysis of photocatalytic oxide and by hydrophiling.Can think that in second embodiment of the invention, the polyorganosiloxane resin that exists is by hydrophiling near the photocatalytic oxide.Yet, in second embodiment of the present invention, to compare with the photocatalytic oxide, polyorganosiloxane resin exists in a large number, comes down to as hydrophobic resin.Therefore, the contradiction of the first embodiment of the invention and second embodiment does not occur.
In the present invention, the hydrophobicity degree of this hydrophobic resin can suitably determine in the scope of performance effect of the present invention, its degree, and for example the contact angle with water is desirable greater than 60 degree, better is greater than 120 degree.
In addition, the desirable inorganic oxide that adds in the present embodiment, as long as can be by the photocatalysis of photocatalytic oxide by hydrophiling, be not particularly limited, for example, can enumerate metal oxides such as silica, alumina, sodium metasilicate, silicate, alumino-silicate, zirconia, ceria, tin oxide, calcium oxide, magnesia ore, unbodied titanium dioxide.Especially silica or alumina keep hydrophilic viewpoint to consider from the dark hydrophilic parts, are desirable.
In addition, matrix material is not particularly limited, same with the occasion of first embodiment of the invention, can suitably determine according to the purposes of member, and its object lesson and first embodiment of the present invention are same.
The amount of photocatalytic oxide is not particularly limited in the superficial layer of the present embodiment, and for example, it is desirable that the amount in superficial layer reaches about 10～80% (weight), and better is about 20～50% (weight).
According to the desirable embodiment of the present invention, the thickness of superficial layer can be according to suitably decision such as the composition of superficial layer and purposes.The desirable scope also occasion with first embodiment of the invention is identical.
And, with the embodiment shown in the figure, can be with granular photocatalytic oxide.Its particle diameter
(crystallization particle diameter) can suitably determine, but the size about 1nm～100nm is desirable, and better is about 5nm～20nm.
In addition, even in the occasion of using particulate inorganic oxides, its particle diameter can determine suitably that also the size about 1nm～1 μ m is desirable, and better is about 5nm～100nm.
In object lesson as shown in the figure, desirable condition is as described below.
At first, in the embodiment depicted in fig. 3, the thickness of hydrophobic resin layer 24 it is desirable to 10nm～10 μ m, and that better is 100nm～1 μ m.The amount of the photocatalytic oxide particle in the layer 24, desirable is 10～80% (weight), better is 20～50% (weight).In addition, in the embodiment depicted in fig. 4, the amount of photocatalytic oxide particle, desirable is 1～80% (weight), better is 20～50% (weight); The amount of inorganic oxide particle, desirable is 1～70% (weight), better is 5～55% (weight).
In the embodiment depicted in fig. 5, the thickness of photocatalytic oxide skin(coating) 27, that desirable is 10nm～1 μ m, that better is 50nm～400nm.In addition, the thickness of the hydrophobic resin layer of Cun Zaiing in the above, that desirable is 1nm～100nm, that better is 5～50nm.In the embodiment depicted in fig. 6, the amount of photocatalytic oxide particle, desirable is 10～99% (weight), better is 50～99% (weight); The amount of inorganic oxide particle, desirable is 50～90% (weight), better is 5～50% (weight).
The member of second embodiment of the invention, as implied above, its purposes member with first embodiment of the invention basically is identical.The ratio that hydrophobic parts and hydrophilic parts exist, same with the occasion of first embodiment of the invention, can suitably determine according to its purposes, and the object lesson of its size and purposes is also identical with first embodiment of the present invention.
That is, in the outmost surface of superficial layer, every 10nm 2～100nm 2At least respectively there are the member at a place in hydrophobic parts and hydrophilic parts, have the high molecular character of the aufwuch of being difficult to.Therefore, such member might be applied to antithrombotic material, anti-protein tack material, prevent lipid tack material etc.More particularly, can be used as haptic lens, catheter and subcutaneous device, various man-made organ, blood bag, adopt disposable medical apparatus such as pipe that connect between urinal, lung drain means and these members etc.
In addition, in the outmost surface of superficial layer, every 10nm 2～1 μ m 2, hydrophobic parts and hydrophilic parts respectively exist the member at least one place to have the character that is difficult to aufwuch.Therefore, but such member purposes hull bottom material, outer wall materials, bathroom material, bathing pool material, view and admire usefulness the pond material, (for example utilize on the facility at recirculated water, the artificial pond in park) surfacing that contacts with recirculated water (for example, the patch block of facility) etc.
And at the outmost surface of superficial layer, every 1mm 2, at least respectively there are the member at a place in hydrophobic parts and hydrophilic parts, are difficult to adhere to the dirt from the coal smoke that floats in the atmosphere, perhaps, adhere to the character that above-mentioned dirt is also removed easily in case have.Therefore, the casing that can be used as the vehicles such as structure that the heat collector cover, bridge floor railing, tunnel inwall of room External building material, solar-electricity pool cover, solar water heater, anti-sound wall, sound insulation wall, guard rail, road decorative panel and road use, plate washer, glass, wheel disc, automobile.
According to the member of the present embodiment, same with first embodiment of the invention, as long as it has antifouling activity, and its surface contact angle with water is not limited substantially, generally, with the apparent contact angle of water in 10～120 scopes of spending.
In addition, the photocatalytic oxide, known its of people has antifouling, antibiotic and deodorization function based on oxygenolysis, it is believed that in member of the present invention, this effect can keep.The oxygenolysis of such photochemical catalyst, at the outermost layer of superficial layer, every 0.1mm 2, from the hydrophobic parts of above-mentioned hydrophobicity fluororesin with from the hydrophilic parts of above-mentioned polysiloxanes or silica one place is arranged at least respectively, could bring into play this oxygenolysis better.
Member of the present invention, the growth that can prevent to adhere to water droplet effectively, under oligodynamic action, the water droplet that adheres to rolls from the teeth outwards, breaks away from the surface easily.In addition, even member ice and snow of the present invention can not easily adhere in its surface.That is, member of the present invention has and prevents that water droplet from growing up, preventing that water droplet from adhering to and prevent the effect that ice and snow adheres to.
Have and prevent that the result that water droplet is grown up from being, for example, when the present invention is applied to glass and mirror etc., can prevent effectively water droplet grow to can scattered light degree.More particularly, prevent the fuzzy of glass, mirror, lens, prism etc., and guarantee its visual field.In particular, can be as lens, welders' mask, goggles and the insulation show window of the glass pane of the glass pane of building, the vehicles, Vehicular reflecting mirror, road mirror, the mirror of washing one's face, instrument board cover, glasses.Can think, on the outmost surface of superficial layer, per 0.2 μ m 2, above-mentioned hydrophobic parts and above-mentioned hydrophilic parts from polysiloxanes or silica from the hydrophobicity fluororesin at least respectively has a place, and this effect can be brought into play preferably.
In addition, member of the present invention has and prevents that water droplet from adhering to and prevent the effect that ice and snow adheres to, so, member of the present invention can be used for, prevent in the heat exchanger that water droplet between the aluminium radiator fin adheres to and the decrease in efficiency that causes, prevent the generation that the weld pool surface insulating properties that causes owing to adhering to of (salt) water descends on insulator surface, prevent that bathing pool revetment part is owing to the decline that causes sight adhering to of water droplet, prevent the ice and snow accumulation on roof, prevent the formation of icicle, prevent antenna accumulation ice and snow, prevent the communication obstacle, prevent transmission line of electricity accumulation ice and snow, prevent point discharge.More particularly, can be as fin, the bathing pool of heat exchanger, the estrade of the usefulness that washes one's face, culinary estrade, roof Material, roof rain water mouth, antenna, power transmission line etc.
According to the desirable embodiment of the present invention, such water droplet that prevents adheres to and prevents the ice and snow adhewsive action, can think, and in the outmost surface of superficial layer, every 1mm 2, at least respectively there is the occasion at a place from the hydrophobic parts of above-mentioned hydrophobicity fluororesin with from the hydrophilic parts of above-mentioned polysiloxanes or silica, can bring into play this effect better.
And same with the occasion of first embodiment of the invention in second embodiment of the present invention, adding metals such as Ag, Cu, Zn at superficial layer is desirable.Added such metallic surface layer, though the bacterium and the mould that adhere on the surface of in the dark also can becoming extinct, thereby, more improved antifouling property.Can add platinums group metal such as Pt, Pd, Ru, Rh, Ir, Os at superficial layer.Add this metallic surface layer, can strengthen the redox active of photochemical catalyst, improved the decomposability of decomposability, pernicious gas and the stench of dirt.
Manufacturing according to the second embodiment antifouling member
According to the member of second embodiment of the invention, it is desirable to be made with laxative remedy.
At first, as the member of Fig. 3 or structure shown in Figure 4, can make with the layer lining matrix material that comprises the hydrophobic resin that contains photocatalytic oxide that is dispersed in wherein and the inorganic oxide that can also have.More particularly, hydrophobic resin is dissolved in the solvent that can dissolve this resin, and photocatalytic oxide and the inorganic oxide that can also have are dispersed in this solvent, be made into coating fluid, it is coated on the matrix material.Then, evaporating solvent obtains the dried resin layer, forms superficial layer on matrix material.
Photocatalytic oxide and inorganic oxide are present in the outmost surface of superficial layer with exposed state, photocatalytic oxide and inorganic oxide in the degree of exposure of the outmost surface of superficial layer basically with to be coated with in the feed liquid concentration of photocatalytic oxide and inorganic oxide proportional.Yet under some occasion, when the concentration of these materials increased in being coated with feed liquid, they also were difficult to be exposed on the surface.In such occasion, behind the formation resin bed, the surface of removing formed layer can make inner photocatalytic oxide and inorganic oxide expose desirable amount from the teeth outwards.
The member of Fig. 3 and structure shown in Figure 4, available following method manufacturing.That is, on matrix material, be coated with the hydrophobic resin precursor composition that can form the hydrophobic resin layer earlier.As the example of this precursor composition, can enumerate the hydrophobic resin solution that in the solvent of energy solubilizing hydrophobic resin, forms.In other words, inorganic oxide and above-mentioned photocatalytic oxide surface carry out hydrophobization with water-repelling agent.As the object lesson of water-repelling agent, for example, can enumerate silane coupling agent.This hydrophobization photocatalytic oxide and inorganic oxide, be coated on being coated with on the rete of the hydrophobic resin precursor composition that forms on the matrix material.Because of photocatalytic oxide and inorganic oxide, its surface is by hydrophobization, so, easily and hydrophobic resin be coated with the rete affinity, and be present on the surface equably.Then, remove water-repelling agent from photocatalytic oxide and photocatalytic oxide surface.This is removed operation and can suitably determine according to the water-repelling agent kind.Yet silane coupling agent can easily be removed with ultraviolet ray irradiation or etch processes.Then, precursor composition is solidified or drying, obtain the reaction of hydrophobic resin layer, obtain member as shown in the figure.
In addition, the member of tool Fig. 5 and structure shown in Figure 6, for example, on matrix material, form and contain the photocatalytic oxide, also can contain the layer of inorganic oxide according to circumstances again, on this layer of part, employing can form the hydrophobic resin precursor composition of hydrophobic resin layer, and part forms cover layer, makes cover layer stand reaction, generate the hydrophobic resin layer, make this member.More particularly, prepare to contain the composition of photocatalytic oxide particle, close also the visual field can contain adhesive simultaneously, then, it is coated on the matrix material.React, combine by adhesive between the photocatalytic oxide particle, form the layer that constitutes by the photocatalytic oxide.And on the photocatalytic oxide skin(coating), part applies the solution of the precursor composition that is dissolved with hydrophobic resin.As the means that apply of part, for example, can enumerate, the slit of the opening by having special pattern applies precursor composition.Then, make this precursor composition reaction, obtain member to be transformed into the hydrophobic resin layer.
The member of tool Fig. 5 and structure shown in Figure 6, also available manufactured down.That is, earlier at substrate material surface, use and above-mentioned same method, form and contain the photocatalytic oxide, the layer that can contain inorganic oxide is again closed in the visual field.On above-mentioned layer, apply and be included in the composition that contains light decomposability lyophobic dust and hydrophobic resin that can dissolve in the specific solvent, form cover layer, use up irradiation, decompose and remove this light decomposability lyophobic dust, and make cover layer stand reaction, make it be transformed into the hydrophobic resin layer, make member.
The member of tool Fig. 5 and structure shown in Figure 6, also available manufactured down.That is, at first, use and above-mentioned same method, substrate material surface is formed contain the photocatalytic oxide, the layer that can contain inorganic oxide is again closed in the visual field.On this layer, apply again and contain the lyophobic dust that is dissolved in specific solvent and the composition of hydrophobic resin, form cover layer, make above-mentioned specific solvent contact by film surface, remove lyophobic dust, make cover layer become the hydrophobic resin layer, make member.The lyophobic dust that is dissolvable in water specific solvent is known, and for example, lyophobic dust and the combination that can make the specific solvent of its dissolving can be enumerated polyethylene, polystyrene and petroleum-type; Polyacetals, polyamide and highly basic; Polyacetals, ABS, propylene and strong acid; Low density polyethylene (LDPE), poly-p-phenylene oxide, polystyrene, polysulfones, polyvinyl chloride and chlorine compound solvent; Polyacetals, ABS, polystyrene, polyvinyl chloride and amines; Propylene, polystyrene, polysulfones, polyvinyl chloride and ketone, ester, ether; ABS, propylene, poly-p-phenylene oxide, polystyrene, polyvinyl chloride and aromatic acid compound solvent.
Embodiment
Embodiment 1
Anatase-type titanium oxide colloidal sol (Japan's chemistry, TA-15, nitric acid peptization type, pH=1), Ludox (Japanese synthetic rubber, グ ラ ス カ A liquid, pH=4), MTMS (Japanese synthetic rubber, グ ラ ス カ B liquid) and ethanol mix, stirred 2～3 minutes, obtain being coated with feed liquid.Use spraying process, this is coated with on the glazed tile matrix material that feed liquid is coated on 5 * 10cm rectangle (eastern pottery machine, AB 02 E11).In 200 ℃, heat treated 15 minutes comprises the superficial layer of anatase-type titanium oxide particle 11 parts (weight), silica 6 parts (weight), 5 parts of (weight) (being the purchase volume benchmark) of polysiloxanes with formation, obtains the member of antifouling activity.With it as sample 1.
Sample 1 is 85 ° with the contact angle of water.Measure 30 seconds after dripping from the microsyringe water droplet, the contact angle of mensuration sample 1 and water with the contact angle contact angle determination device (consonance interface science, CA-X 150) of water.
Then, on sample 1 surface, with ultraviolet light source (three common-battery gas, black light indigo plant (Block ラ ッ Network ラ イ ト Block Le)-(BLB) fluorescent lamp), with 0.3mW/cm 2Ultraviolet irradiation intensity irradiation one day.With this member that obtains as sample 2.Sample 2 is reached 0 ° by hydrophiling up to the contact angle with water.
Then, with Raman spectral analysis sample 1 surface.In addition, to sample 1, use mercury lamp at 22.8mW/cm 2The following 2 hours ultraviolet lights of irradiation of ultraviolet irradiation intensity.With this member that obtains as sample 3.The Raman spectrum analysis is also carried out on surface to this sample 3.The result is at the methyl peak that sample 1 surface is found, not find that on sample 3 what replace it is the broad peak of hydroxyl.
Thus, can think because as the optical excitation of the anatase-type titanium oxide of photochemical catalyst, the organic group of combination on the silicon atom is replaced by hydroxyl under the photochemical catalyst effect in the polysiloxane molecule of overlay film surface, and by hydrophiling.
Embodiment 2
Anatase-type titanium oxide colloidal sol (Japan's chemistry, TA-15), Ludox (Japanese synthetic rubber, グ ラ ス カ A liquid), MTMS (Japanese synthetic rubber, グ ラ ス カ B liquid), polytetrafluoroethylene (PTFE) particle (industry of ダ イ キ Application, Le Block ロ Application L-5) and ethanol mixes, stir and be coated with feed liquid with preparation in 2～3 minutes, the feed liquid that is coated with that obtains, with spraying process (spray diameter 0.5mm), be coated on 5 * 10cm and become on the rectangle glazed tile matrix material (eastern pottery machine, AB 02E11).In 200 ℃ of heat treatments 15 minutes, comprise the superficial layer of anatase-type titanium oxide particle 33 parts (weight), polytetrafluoroethylparticle particle 66 parts (weight), silica 6 parts (weight), 5 parts of (weight) (being the purchase volume benchmark) of polysiloxanes with formation, obtain sample 4.This sample 4 is 110 ° with the contact angle of water.
Then, on sample 4 surfaces, with ultraviolet light source (three common-battery gas, black light indigo plant (Block ラ Star Network ラ イ ト Block Le)-(BLB) fluorescent lamp), with 0.3mW/cm 2Ultraviolet irradiation intensity irradiation one day.The member that obtains as sample 5.Sample 5 is 97.4 ° with the contact angle of water, slightly descends than pre-irradiation.The organic group of combination on the silicon atom is replaced by hydroxyl owing to photocatalysis in the expection polysiloxane molecule, and by hydrophiling, because this hydrophilic influence is some with the contact angle minimizing of water.Promptly can think on sample 5 surfaces, because the photocatalysis organic group replaced by hydroxyl, the polysiloxanes of hydrophiling expose in the air externally and present hydrophilic part and hydrophobicity fluororesin expose in the air externally and present hydrophobicity part the two all microcosmic be dispersed with structure and form.
Embodiment 3
The sample 5 that embodiment 2 is obtained is placed on outdoor, and application form keeps performance in the face of the cleaning of conglomerate and pollutant.For comparing, be placed on the glazed tile plate outdoor equally.
The surface is the sample that is provided with in grid bottom, the top on building roof as shown in Figure 2 to the cleaning retentivity of conglomerate and pollutant, exposes 4 months and studies.
The result is, can be observed some dirts with the glazed tile plate, then do not observe with sample 5.
In addition, investigation exposes the variation of 4 months front and back component surface aberration.According to JIS (JIS) H 0201, measure aberration with colour difference meter, use Δ E *Expression.The result is, uses glazed tile, and exposing that aberration before and after the experiment changes is 2, and with sample 5, aberration changes less than 0.5.
Embodiment 4
Make 1,3,5, the 7-tetramethyl-ring tetrasiloxane is with photocatalytic TiO 2 particles (the former industry of stone, ST-41) gas phase contact, the photocatalytic TiO 2 particles 5g that has been coated with at particle surface, ボ Application コ-ト of big Japanese イ Application キ chemical industry (vinyl acetate-propylene copolymer 0.6g) and water 25ml paint agitator and are mixed, and are coated on the aluminium base.At this moment, the ratio of resinous principle and titanium dioxide is a volume ratio 1.Above-mentioned coating obtains sample 19 120 ℃ of curing.
The contact angle that records sample 19 and water is 70 °.
In addition, handle this specimen surface with the sodium hydrate aqueous solution of pH 10, handle with watery hydrochloric acid, then, irradiation sunlight obtains sample 20.
The contact angle that records sample 20 and water is for being low to moderate 56 °.
At the surface of this sample 20 coating aqueous solution of methylene blue, when using solar radiation equally, color fades away after 1 day, can confirm the anti-fouling effect of photocatalysis Decomposition.
Embodiment 5
Anatase-type titanium oxide colloidal sol (the former industry of stone, STS-11), polytetrafluoroethylene (PTFE) particle (ダ イ キ Application industry, D-1) and distilled water mix, stirred 30 minutes, obtain being coated with feed liquid, be coated on 10cm with spraying process and become on the soda-lime glass matrix material of rectangle,, form the superficial layer that comprises anatase-type titanium oxide particle 4 parts (weight), polytetrafluoroethylparticle particle 6 parts (weight) in 380 ℃ of heat treatments 3 minutes.Then,, use vacuum evaporation, form the reflectance coating of aluminium, obtain mirror sample 11 at the back side of this glass plate.
The observation on the surface by sample 11, can confirm to have formed superficial layer with following structure, that is, the photocatalytic oxide particle expose with atmosphere join be hydrophilic part and hydrophobicity fluororesin expose with the part hydrophobic in nature of joining with atmosphere the two from the teeth outwards microcosmic disperse to exist.
Then, measure the contact angle of sample 11 surfaces and water.Measure the contact angle (interface science of coordinating, CA-X 150) of sample and water with the contact angle determination device, after dripping 30 seconds with water droplet, the contact angle evaluation of itself and water.The result is, the contact angle of sample and water is 120 °, and it is greater than 90 °.In addition, when sample 11 tilted, water droplet rotated, falls.
Then, with ultraviolet light source (three common-battery gas, black light indigo plant (Block ラ ッ Network ラ イ ト Block Le)-(BLB) fluorescent lamp), with 0.5mW/cm 2Surperficial about 1 day of ultraviolet irradiation intensity irradiation sample 11, obtain sample 12.Measure the contact angle of sample 12 and water, the result is, with the contact angle of water be 110 °.In addition, when sample 12 tilted, water droplet rotated, falls.
Embodiment 6
Anatase-type titanium oxide colloidal sol (the former industry of stone, STS-11), polytetrafluoroethylene (PTFE) particle (ダ イ キ Application industry, D-1) and distilled water mix, stirred 30 minutes, obtain coating solution, be coated on the matrix material with spraying process,, formed and contained the superficial layer that anatase-type titanium oxide particle 4 parts (weight), polytetrafluoroethylparticle particle 6 parts (weight) constitute in 380 ℃ of heat treatments 3 minutes.Obtain sample 21.
By observation to the surface of sample 21, can confirm to have formed superficial layer with following structure, that is, the photocatalytic oxide particle reveals, and doing well reveals with the hydrophilic parts of joining with atmosphere and hydrophobicity part fluororesin does well that the two disperses to exist with microcosmic from the teeth outwards with the hydrophobicity part of joining with atmosphere.
Then, measure the surface of sample 21 and the contact angle of water.Measure contact angle surperficial and water with contact angle determination device (consonance interface science, CA-X 150), water droplet dripped back 30 seconds, used with the contact angle of water and estimated.The result is, with the contact angle of water be 120 °, greater than 90 ° value.In addition, when sample 21 tilted, water droplet rotated, falls.
Then, with fluorescent lamp (three common-battery gas, black light indigo plant (Block ラ ッ Network ラ イ ト Block Le)-(BLB) fluorescent lamp), with 0.5mW/cm 2Ultraviolet irradiation intensity, irradiation surperficial about 1 day of sample 21 obtains sample 22.Measure the contact angle of sample 22 surfaces and water, the result is, with the contact angle of water be 110 °.In addition, when sample 22 tilted, water droplet rotated, falls.

Claims (70)

1. member, this member comprises, matrix material, with the superficial layer that contains photocatalytic oxide, polyorganosiloxane resin or silica and hydrophobicity fluororesin that is provided with on this matrix material, above-mentioned polysiloxanes or silica and hydrophobicity fluororesin disperse and exist with exposed state at the outmost surface microcosmic of this superficial layer.
2. the member of record in the claim 1, wherein, above-mentioned photocatalytic oxide is to select from anatase-type titanium oxide, Titanium Dioxide Rutile Top grade, zinc oxide, tin oxide, iron oxide, bismuth oxide, tungstic acid and strontium titanates one group.
3. the member of record in the claim 1 or 2, wherein, above-mentioned photocatalytic oxide makes the polyorganosiloxane resin or the silica hydrophiling that exist in this member outmost surface by the photocatalysis that optical excitation produces.
In the claim 1 or 2 record member, wherein, above-mentioned polyorganosiloxane resin can be represented with a following average group accepted way of doing sth (I):
R pSiO (4-p)/2 (I)
In the formula, R is for from hydrogen atom and a kind of organic group or group that organic group constitutes more than two kinds selects one group; X is alkoxyl or halogen atom; P is for satisfying the number of 0＜p＜2.
In the claim 4 record member, wherein, above-mentioned organic group is an alkyl or aryl.
6. the member of any one record in the claim 1～5, wherein, above-mentioned silica is an amorphous silica.
7. the member of any one record in the claim 1～6, wherein, from the hydrophobic parts of hydrophobic resin with from the hydrophilic parts of polysiloxanes or silica, disperse with microcosmic and exist in outmost surface with the state that exposes, hydroaropic substance and lyophobic dust all can not be attached on the component surface, therefore, can keep cleaning surfaces.
8. the member of any one record in the claim 1～7, wherein, in the outmost surface of above-mentioned superficial layer, every 10nm 2～100nm 2, respectively have at least one place from the hydrophobic parts of above-mentioned hydrophobicity fluororesin with from the hydrophilic parts of above-mentioned polysiloxanes or silica.
9. the member of claim 8 record, it has the high molecular character of the aufwuch of being difficult to.
10. the member of claim 9 record, it can be used as the antithrombotic material, anti-protein tack material and anti-lipid attachment material.
11. the member of claim 10 record can be used as haptic lens, catheter, subcutaneous device, man-made organ, blood bag, adopts urinal, lung drain means or their tube connector.
12. the member of any one record in the claim 1～7, wherein, in the outmost surface of above-mentioned superficial layer, every 10nm 2～1 μ m 2, respectively have at least one place from the hydrophobicity of above-mentioned hydrophobicity fluororesin part with from the hydrophilic parts of above-mentioned polysiloxanes or silica.
13. the member of claim 10 record, it has the character that is difficult to aufwuch.
14. the member of claim 13 record, it can be used as hull bottom material, outer wall materials, bathroom material, bathing pool material, views and admires the millpond material, recirculated water utilizes in the facility and the surfacing of recirculated water contact portion.
15. the member of any one record in the claim 1～7, wherein, on the outmost surface of above-mentioned superficial layer, every 1mm 2, respectively have at least one place from the hydrophobic parts of above-mentioned hydrophobicity fluororesin with from the hydrophilic parts of above-mentioned polysiloxanes or silica.
16. the member of claim 15 record, it has the dirt that is difficult to adhere to from the coal smoke that floats in the atmosphere, perhaps, also is easy to the character of removing in case adhere to.
17. the member of claim 16 record, it can be used as the casing of room external application construction material, solar-electricity pool cover, solar water heater heat-collecting device cover, bridge floor railing, tunnel inwall, anti-sound wall, sound insulation wall, guard rail, road structure, plate washer, glass insulator, wheel disc, the vehicles.
18. the member of any one record in the claim 1～7, it has the character that can not grow at the water droplet of its surface attachment.
19. the member of claim 18 record, it can be used for lens, welders' mask, goggles or the insulation show window of glass pane, the vehicles perspex of glass pane, the vehicles of building, for motor vehicle reflective mirror, road mirror, the mirror of washing one's face, instrument board cover, glasses.
20. the member of any one record in the claim 1～7 is difficult to adhere to water droplet or ice and snow in its surface, also breaks away from easily even perhaps adhere to its water droplet.
21. the member of record in the claim 20, it can be used as the estrade of heat exchanger fin, glass insulator, bathing pool, the usefulness that washes one's face, culinary estrade, roof Material, roof rain water mouth, antenna or power transmission line.
22. the member of record in the claim 1～16, wherein, above-mentioned superficial layer also contains Ag, Cu or Zn, or the platinum group metal.
23. one kind is applied to form the composition with antifouling activity superficial layer on the matrix material thereon, said composition contains:
(a) the polyorganosiloxane resin coating precursor that can form the polyorganosiloxane resin coating maybe can form the silica coating the silica coating precursor and
(b) be dispersed in above-mentioned (a) coating precursor the photocatalytic oxide and
(c) be dispersed in hydrophobicity fluororesin in above-mentioned (a) coating precursor.
24. the composition of record in the claim 23, wherein, above-mentioned polyorganosiloxane resin coating precursor is the siloxanes of representing with an average group accepted way of doing sth:
R pSiX qO (4-p-q)/2
In the formula, R is identical with the definition of above-mentioned formula (I), and X represents alkoxyl or halogen atom, and p is the number that satisfies 0＜p＜2, and q is the number that satisfies 0＜q＜4.
25. the composition of record in the claim 18, wherein, the hydrolyzable silane derivative of above-mentioned polyorganosiloxane resin coating precursor for representing with general formula:
R pSiX 4-p
In the formula, R is identical with the definition of above-mentioned formula (I), and X is alkoxyl or halogen atom, and p is 1 or 2.
26. the composition of record in the claim 23, wherein, the silicate of above-mentioned silica coating precursor for representing with an average group accepted way of doing sth:
SiX qO (4-q)/2
In the formula, X is alkoxyl or halogen atom, and q is for satisfying the number of 0＜q＜4.
27. the composition of record in the claim 23, wherein, the four-functional group hydrolyzable silane derivative of above-mentioned silica coating precursor for representing with general formula:
SiX 4
In the formula, R is identical with the definition of above-mentioned formula (I), and X is alkoxyl or halogen atom.
28. the composition of any one record in the claim 23～27, wherein, above-mentioned photocatalytic oxide is to select from anatase-type titanium oxide, Titanium Dioxide Rutile Top grade, zinc oxide, tin oxide, iron oxide, bismuth oxide, tungstic acid and strontium titanates one group.
29. the method for manufacturing component of record in the claim 1～22, may further comprise the steps: the composition that on matrix material, adopts any one record in the claim 23～28, above-mentioned polyorganosiloxane resin coating precursor or silica coating precursor stand to become the reaction of polysiloxane coating or silica coating, thereby, on matrix material, form the soil resistance coating, above-mentioned polysiloxanes or silica and above-mentioned hydrophobicity fluororesin that the outmost surface that this soil resistance coating is included in this superficial layer is disperseed with microcosmic and existed with the state that exposes.
30. on desirable surface, give the method for antifouling property, this method may further comprise the steps: the composition of any one record is applied in and wishes to give on the surface of soil resistance in the employing claim 22～28, above-mentioned polyorganosiloxane resin coating precursor or silica coating precursor are solidified, thereby, on matrix material, form the soil resistance coating, above-mentioned polysiloxanes or silica and above-mentioned hydrophobicity fluororesin that the outmost surface that this soil resistance coating is included in this superficial layer is disperseed with microcosmic and existed with the state that exposes.
31. the antifouling member made from the methods of claim 29 or 30 records.
32. member, it contains matrix material, with the superficial layer that contains hydrophobic resin and photocatalytic oxide that on this matrix material, is provided with, on the outmost surface of this superficial layer, above-mentioned hydrophobic resin and above-mentioned photocatalytic oxide disperse with microcosmic and exist with exposed state, and,, make the hydrophiling of this photocatalytic oxide own or make near the photocatalytic oxide hydrophiling that exists this photocatalytic oxide owing to the photocatalysis that optical excitation produces by above-mentioned photocatalytic oxide.
33. the member of claim 32 record, wherein, above-mentioned superficial layer can contain inorganic oxide again, and, outmost surface at this superficial layer, this inorganic oxide and above-mentioned hydrophobic resin and above-mentioned photocatalytic oxide disperse with microcosmic simultaneously and exposed state exists, and owing to the photocatalysis that optical excitation produces, make above-mentioned inorganic oxide hydrophiling by above-mentioned catalysed oxidation thing.
34. the member of record in the claim 32, wherein, above-mentioned superficial layer is the layer that comprises above-mentioned hydrophobic resin, above-mentioned photocatalytic divided oxide is dispersed in this layer, and, in the outmost surface of this superficial layer, above-mentioned hydrophobic resin and above-mentioned photocatalytic oxide disperse with microcosmic and exist with exposed state.
35. the member of record in the claim 32, wherein, above-mentioned superficial layer also contains inorganic oxide, and, this inorganic oxide with above-mentioned hydrophobic resin and above-mentioned photocatalytic oxide, disperses with microcosmic and exists with exposed state in the outmost surface of this superficial layer, owing to the photocatalysis that optical excitation produces, make above-mentioned inorganic oxide hydrophiling by above-mentioned photocatalytic oxide.
36. the member of record in the claim 31, wherein, above-mentioned superficial layer comprise by above-mentioned photocatalytic oxide constitute the layer and this layer top lamination by hydrophobic resin constitute the layer, and, this hydrophobic resin layer in the result of the layer top lamination that is made of above-mentioned photocatalytic oxide is, in the outmost surface of this superficial layer, above-mentioned hydrophobic resin and above-mentioned photocatalytic oxide disperse with microcosmic and exist with exposed state.
37. the member of record in the claim 32, wherein, the layer that is made of above-mentioned photocatalytic oxide also contains inorganic oxide, and, on the outmost surface of this superficial layer, this inorganic oxide and above-mentioned hydrophobic resin and above-mentioned photocatalytic oxide disperse with microcosmic together and exist with exposed state, owing to the photocatalysis that optical excitation produces, make above-mentioned inorganic oxide hydrophiling by above-mentioned photocatalytic oxide.
38. the member of any one record in the claim 32～37, wherein, above-mentioned photocatalytic oxide is to select from anatase-type titanium oxide, Titanium Dioxide Rutile Top grade, zinc oxide, tin oxide, iron oxide, bismuth oxide, tungstic acid and strontium titanates one group.
39. the member of any one record in the claim 27～33, wherein, above-mentioned inorganic oxide is to select from silica, alumina, sodium metasilicate, silicate, alumino-silicate, zirconia, ceria, tin oxide, calcium oxide, magnesia ore and amorphous titania one group.
40. the member of any one record in the claim 27～34, wherein, above-mentioned hydrophobic resin is to select from fluororesin, propylene resin, polyurethane resin, polyester resin, vinyl resins, PET and acrylic acid polysiloxanes one group.
41. the member of any one record in the claim 27～35, wherein, disperse with microcosmic and exist in outmost surface from the hydrophobic parts of hydrophobic resin with from the hydrophilic parts of above-mentioned photocatalytic oxide or above-mentioned inorganic oxide with exposed state, so, hydroaropic substance and lyophobic dust are even can not surface attached to member on, thereby its surface can keep clean.
42. the member of any one record in the claim 27～36, wherein, in the outmost surface of above-mentioned superficial layer, every 10nm 2～100nm 2, respectively have at least one place from the hydrophobic parts of above-mentioned hydrophobicity resin with from the hydrophilic parts of above-mentioned photocatalytic oxide or above-mentioned inorganic oxide.
43. the member of record in the claim 42, it has the high molecular character of difficult aufwuch.
44. the member of record in the claim 43, it can be used as nonthrombogenic material, anti-protein attachment material and anti-lipid attachment material.
45. the member of record can be used as haptic lens or catheter, subcutaneous device, man-made organ, blood bag, adopts urinal, lung drain means or their tube connector in the claim 44.
46. the member of any one record in the claim 32～41, in the outmost surface of above-mentioned superficial layer, every 10nm 2～1 μ m 2, respectively have at least one place from the hydrophobic parts of above-mentioned hydrophobicity resin with from the hydrophilic parts of above-mentioned photocatalytic oxide or above-mentioned inorganic oxide.
47. the member of record in the claim 46, it can be used as hull bottom material, outer wall materials, bathroom material, bathing pool material, views and admires the millpond material, utilize in the facility surfacing with the recirculated water contact portion at recirculated water.
48. the member of any one record in the claim 32～41, on the outmost surface of its superficial layer, every 1mm 2, respectively have at least one place from the hydrophobic parts of above-mentioned hydrophobicity fluororesin with from the hydrophilic parts of above-mentioned polysiloxanes and silica.
49. the member of record in the claim 43, it has the dirt that is difficult to adhere to from the coal smoke that floats in the atmosphere, perhaps in case adhere to the character that this dirt is also removed easily.
50. the member of record in the claim 49 can be used as room external application construction material, solar-electricity pool cover, the solar water heater heat-collecting device casing with cover, bridge floor railing, tunnel inwall, anti-wall, sound insulation wall, guard rail, road structure, plate washer, glass insulator, wheel disc, the vehicles.
51. the member of any one record in the claim 32～41, it has the character that can not grow at the water droplet of its surface attachment.
52. the member of record in the claim 18, can be used for preventing that glass, mirror, lens, prism etc. are fuzzy and guarantee the visual field, more particularly, the lens, welders' mask, goggles or insulation show window, heat exchanger fin, glass insulator, bathing pool, the estrade of the usefulness that washes one's face, culinary estrade, roof Material, roof rain water mouth, antenna or the power transmission line that can be used for glass pane, the vehicles perspex of building window glass, the vehicles, for motor vehicle reflective mirror, road mirror, the mirror of washing one's face, instrument board cover, glasses.
53. the member of any one record in the claim 32～41 is difficult to adhere to water droplet or ice and snow in its surface, perhaps, in a single day even adhere to, this water droplet also breaks away from easily.
54. the member of record in the claim 53, can be used for preventing that glass, mirror, lens, prism etc. are fuzzy and guarantee the visual field, more particularly, the lens, welders' mask, goggles or insulation show window, heat exchanger fin, glass insulator, bathing pool, the estrade of the usefulness that washes one's face, culinary estrade, roof Material, roof rain water mouth, antenna or the power transmission line that can be used for glass pane, the vehicles perspex of building window glass, the vehicles, for motor vehicle reflective mirror, road mirror, the mirror of washing one's face, instrument board cover, glasses.
55. the member of record in the claim 32～54, wherein, above-mentioned superficial layer also contains Ag, Cu or Zn, perhaps platinum group metal.
56. the method for manufacturing component of record in the claim 34, this method comprise with comprising the layer covering matrix material that above-mentioned photocatalytic divided oxide is dispersed in above-mentioned hydrophobic resin wherein.
57. the method for record in the claim 56 wherein, also comprises: after covering matrix material, remove the operation on surface of the layer of formation with the layer that comprises above-mentioned hydrophobic resin.
58. the method for manufacturing component of record in the claim 35, this method comprises: the operation that covers matrix material with the layer that comprises the hydrophobic resin that wherein contains inorganic oxide and photocatalytic oxide.
59. the method for record in the claim 58 also comprises:, after covering matrix material, remove the operation on the surface of gained layer with the layer that contains above-mentioned hydrophobic resin.
60. the method for manufacturing component of record in the claim 34, it comprises following operation:
Make above-mentioned photocatalytic oxide surface hydrophobization with water-repelling agent, on substrate material surface, use the hydrophobic resin precursor composition that can form the hydrophobic resin layer;
Before said composition forms the hydrophobic resin layer, coating surface used above-mentioned water-repelling agent hydrophobization the photocatalytic oxide;
Remove above-mentioned water-repelling agent from above-mentioned photocatalytic oxide surface;
Make above-mentioned precursor composition stand to become the reaction of hydrophobic resin layer.
61. the member autofrettage of record in the claim 35, this method comprises:
Make the surface-hydrophobicized of above-mentioned inorganic oxide and/or above-mentioned photocatalytic oxide with water-repelling agent;
Use the hydrophobic resin precursor composition that can form the hydrophobic resin layer at substrate material surface;
Before above-mentioned composition becomes the hydrophobic resin layer, the coating used above-mentioned water-repelling agent hydrophobization the photocatalytic oxide;
Remove above-mentioned water-repelling agent from the surface of above-mentioned photocatalytic oxide and/or above-mentioned photocatalytic oxide;
And, make above-mentioned precursor composition stand to become the reaction of hydrophobic resin layer.
62. the manufacture method of the member of record in the claim 36, this method comprises:
On substrate material surface, form the layer that comprises above-mentioned photocatalytic oxide;
Use the hydrophobic resin precursor composition that can form the hydrophobic resin layer on this layer top, form cover layer;
Make above-mentioned cover layer stand to become the reaction of hydrophobic resin layer.
63. the method for record in the claim 53, this method is the slit by the opening with particular style, forms above-mentioned precursor composition on the layer of the above-mentioned photocatalytic oxide that partly contains the above-mentioned inorganic oxide of dual-purpose.
64. the method for manufacturing component of record in the claim 37, this method may further comprise the steps:
On substrate material surface, form the layer that contains above-mentioned inorganic oxide and above-mentioned photocatalytic oxide;
The hydrophobic resin precursor composition that certain applications in the above can form the hydrophobic resin layer forms cover layer;
Make above-mentioned cover layer stand to become the reaction of hydrophobic resin layer.
65. the method for record in the claim 64, the slit of the opening of this method by having particular style comprises in part on the layer of above-mentioned photocatalytic oxide of the above-mentioned inorganic oxide of dual-purpose and forms above-mentioned composition.
66. the method for manufacturing component of record in the claim 36, this method comprises:
On matrix material, form the layer that comprises above-mentioned photocatalytic oxide;
Use the composition that contains light decomposability lyophobic dust and hydrophobic resin in the above, form cover layer;
Penetrate, decompose the lyophobic dust of removing above-mentioned smooth decomposability by illumination;
And, make above-mentioned cover layer stand to become the reaction of hydrophobic resin layer.
67. the method for manufacturing component of record in the claim 37, this method comprises:
On substrate material surface, form the layer that comprises above-mentioned inorganic oxide and above-mentioned photocatalytic oxide;
Use the composition that contains light decomposability lyophobic dust and hydrophobic resin in the above and form cover layer;
Penetrate by illumination, decompose and remove above-mentioned smooth decomposability lyophobic dust, make above-mentioned lining cap rock become the hydrophobic resin layer.
68. the method for manufacturing component of record in the claim 36, this method comprises:
On substrate material surface, form the layer that comprises above-mentioned photocatalytic oxide;
Using in the above to contain has the composition of deliquescent lyophobic dust and hydrophobic resin to form cover layer to specific solvent;
Make above-mentioned specific solvent contact by the surface of rete, remove lyophobic dust, make above-mentioned cover layer become the hydrophobic resin layer.
69. the method for manufacturing component of record in the claim 37, this method comprises:
On substrate material surface, form the layer that comprises above-mentioned inorganic oxide and above-mentioned photocatalytic oxide;
Use in the above and contain the composition that specific solvent is had deliquescent lyophobic dust and hydrophobic resin, form cover layer;
Make that the contact of above-mentioned specific solvent is above-mentioned is removed lyophobic dust by the surface of rete, make above-mentioned cover layer become the hydrophobic resin layer.
70. a member wherein contains in its surface with hydrophobic parts that microcosmic disperses and exposed state exists and the hydrophilic parts that is caused by photochemical catalyst.
CNA2006100934524A 1996-05-31 1997-06-02 Antifouling member and antifouling coating composition Pending CN1927474A (en)

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JPH1051214A (en) 1998-02-20
JPH1045433A (en) 1998-02-17
JPH1046952A (en) 1998-02-17
JPH1043013A (en) 1998-02-17
JPH1050111A (en) 1998-02-20
JPH1050159A (en) 1998-02-20
JPH1043078A (en) 1998-02-17
JPH1044302A (en) 1998-02-17
JPH1046759A (en) 1998-02-17
JPH1045431A (en) 1998-02-17
JPH1043024A (en) 1998-02-17
JPH1043682A (en) 1998-02-17
JPH1045428A (en) 1998-02-17
JPH1051014A (en) 1998-02-20
JPH1047890A (en) 1998-02-20
JPH1050118A (en) 1998-02-20
JPH1043019A (en) 1998-02-17
JPH1046989A (en) 1998-02-17
JPH1046534A (en) 1998-02-17
JPH1046526A (en) 1998-02-17
JPH1046054A (en) 1998-02-17
JPH1044301A (en) 1998-02-17
JPH1046527A (en) 1998-02-17
JPH1046530A (en) 1998-02-17
JPH1046522A (en) 1998-02-17
JPH1045432A (en) 1998-02-17
JPH1043069A (en) 1998-02-17
JPH1048578A (en) 1998-02-20

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