CN1155468C - Hydrophilic member - Google Patents
Hydrophilic member Download PDFInfo
- Publication number
- CN1155468C CN1155468C CNB998159875A CN99815987A CN1155468C CN 1155468 C CN1155468 C CN 1155468C CN B998159875 A CNB998159875 A CN B998159875A CN 99815987 A CN99815987 A CN 99815987A CN 1155468 C CN1155468 C CN 1155468C
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- Prior art keywords
- film
- hydrophilic member
- mentioned
- record
- oxide
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
- B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
- C03C17/3417—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials all coatings being oxide coatings
Abstract
A hydrophilic member comprising a glass plate (1) as a substrate, a tin(II)oxide (SnO2) film (2) formed on the glass plate and a silicon oxide (SiO2) film (3) formed on the tin(II)oxide (SnO2) film (2) as an overcoat layer thereof, wherein the glass plate (1) is made from a soda glass containing SiO2 as the main component thereof, the tin(II)oxide (SnO2) film (2) is formed, for example, by the CVD method and has a thickness of 10 to 800 nm and an average surface roughness (Ra) of 0.5 to 25 nm and the silicon oxide (SiO2) film (3) is formed by using sputtering deposition and has a thickness of 0.1 to 100 nm and an average surface roughness (Ra) of 0.5 to 25 nm. The average surface roughness (Ra) of the silicon oxide (SiO2) film (3) is the same as that of the tin(II)oxide (SnO2) film (2), since the silicon oxide (SiO2) film (3) is formed on the tin(II)oxide (SnO2) film (2), which results in that the irregularity of the tin(II)oxide (SnO2) film (2) is transferred, as it is, to the silicon oxide (SiO2) film (3). The hydrophilic properties of the member has advantages in that, after washing operation, it can be recovered in an extremely short time and also the hydrophilic properties thus recovered are durable for a long period of time.
Description
Technical field
The present invention relates to hydrophily, particularly hydrophilic restorative good hydrophilic member.
Background technology
Become hydrophily as substrate material surfaces such as making glass and have the prior art of antifog property, known have the spy to open flat 9-278431 communique, spy to open that flat 9-295363 communique, spy are opened flat 10-36144 communique, the spy opens flat 10-231146 communique.
Disclose in the Te Kaiping 9-278431 communique, coating contains the surface conditioning agent of phosphoric acid or its salt, deliquescent aluminium compound, water-soluble silicate, surfactant and solvent formation on substrate surface, simultaneously, the average surface roughness of its hydrophilic membrane is 0.5-500nm.
Te Kaiping 9-295363 communique discloses, and forms oxidation titanium film and tin oxide film at substrate material surface, and simultaneously, the surface average roughness of oxidation titanium film and tin oxide film is more than the 1 μ m.
Te Kaiping 10-36144 communique discloses, and forms titanium oxide (TiO at glass baseplate surface
2) wait photocatalyst film, form silica (SiO on the surface of this photocatalyst film
2) wait the porous, inorganic oxide-film.
Te Kaiping 10-231146 communique discloses, and on the glass baseplate surface, forms alkaline barrier film and photocatalyst film, and simultaneously, the surface average roughness of photocatalyst film is 1.5-80nm.
Open in the disclosed technology of flat 9-278431 communique above-mentioned spy,, can not actually use because the chemical durability of hydrophilic film and resistance to abrasion are low.In addition, above-mentioned spy opens in the disclosed technology of flat 9-295363 communique, and the surface roughness of hydrophilic film (Ra) is more than the 1 μ m, it is desirable to more than the 4 μ m, and its transparency low (haze is big) is unsuitable for using at transparent base material surfaces such as glass plates.In addition, open in the disclosed technology of flat 10-36144 communique above-mentioned spy, hydrophilic film is a porous material, and resistance to abrasion is low, and when pollutants such as grease entered in the hole, the hydrophily defunctionalization was difficult to recover.And, open in the disclosed technology of flat 10-231146 communique above-mentioned spy, because hydrophilic film is formed by multilayer, manufacturing needs the time.
In addition, above-mentioned any prior art all is to form hydrophilic film at substrate material surface, simultaneously, its surface is made into trickle matsurface, so, hydrophily is further enhanced, yet, when substrate material surface is made dirty, during with the detergent washing surface, thereafter it is slow that hydrophily is recovered, and this is a shortcoming.
For example, the glass pane that automobile is used and the mirror of use in toilet etc. because of its surface is easy to make dirty, need frequently to wash with washing agent., it is slow that the hydrophily after the washing is recovered, and trickle water droplet easily adheres to from the teeth outwards, and anti-fog effect is reduced.
Summary of the invention
In order to solve above-mentioned problem; the hydrophilic member that the present invention relates to is directly or by alkalescence to stop that the underlying membrane of usefulness forms stannic oxide layer on substrate material surface; forming protective layer on the surface of this stannic oxide layer constitutes; above-mentioned protective layer is select from silica, aluminium oxide, zirconia, cerium oxide and titanium oxide at least a; and the most surperficial surface average roughness (Ra) is 0.5～25nm.
The scope of desirable surface average roughness (Ra) is 0.5～25nm, and that better is 5～15nm.In this scope, the long-time stability of hydrophilicity are better.
Only form stannic oxide layer (SnO at substrate material surface
2), with this stannic oxide layer (SnO
2) when the surface made matsurface, also same prior art (spy opens flat 9-295363 communique) was disclosed like that, hydrophily can be brought into play., in case during with the bath soap washing surface, become 70 °～80 ° with the contact angle of water.
On the other hand, at above-mentioned stannic oxide layer (SnO
2) form thin silicon oxide film (SiO on the surface
2) when waiting, after the washing, with the contact angle of water less than 10 °.
Can think that this is because stannic oxide layer (SnO
2) and silicon oxide film (SiO
2) have opposite polarity, and bath soap is an anionic species, so, after the washing, present super hydrophilic.
Above-mentioned tin oxide film (SnO
2), have Rutile structure, be desirable.Because above-mentioned tin oxide film (SnO
2) have rutile-type crystalline texture, it is possible forming the polycrystalline thin-film with suitable concave-convex surface shape.
In addition, by making tin oxide film (SnO
2) surface roughness (Ra) reach 0.5～25nm, and should concavo-convexly be transferred to the most surperficial on, then making the most surperficial surface average roughness (Ra) reach 0.5～25nm becomes possibility.
When the mean roughness (Ra) on above-mentioned surface during less than 0.5nm, can not form the raising of the long-term retentivity of water-wet behavior and performance effectively concavo-convexly, be unfavorable.In addition, concavo-convex excessive when surface average roughness (Ra) during greater than 25nm, the transparency was lost, the long-time stability of hydrophilicity are reduced, be unfavorable.
In addition, it is desirable that above-mentioned concavo-convex equispaced (Sm) reaches 4～300nm, even concavo-convex equispaced is littler than 4nm, even perhaps big than 300nm, the long-time stability of hydrophilicity and anti-fog performance reduce, and are unfavorable.The better scope in this equispaced (sm) is 5～150nm.In this scope, the long-time stability of hydrophilic nmature are better.
Here, as the method for the above-mentioned surface average roughness of expression (Ra), can adopt the arithmetic average roughness (Ra) of definition among the JISB0601 (1994).The value of arithmetic average roughness (nm) is obtained according to following formula with " from the absolute value of the deviation of average line " expression.
(mathematical formulae 1)
L in the formula: datum length
In addition, also same to concavo-convex equispaced (Sm) with above-mentioned surface average roughness (Ra), defined with JIS B 0601 (1994).That is to say that concavo-convex equispaced value (nm) is represented with " interval averages of peak value one-period that the intersection point that intersects from roughness curve and average line is obtained ", obtains according to following formula.
In the formula: Smi: concavo-convex interval (mm)
N: in the datum length scope, the number at concavo-convex interval
In addition, as above-mentioned tin oxide film (SnO
2) thickness be that 10～800nm is desirable, as silicon oxide film (SiO
2) to wait the thickness of protective layer be that 0.1～100hm is desirable.
When oxygen is littler or bigger than it than it than tin film, can't obtain desirable concavo-convex.That is to say, the thickness of tin oxide film than it hour, can not form uniform tunicle, when bigger than it, the concavo-convex interval on surface is strengthened, and is unfavorable.
In addition, stop the underlying membrane of usefulness as above-mentioned alkalescence, generally speaking, using with silica is suitable as the film of main component.In addition, as required, both can add P (phosphorus), B additives such as (boron), also can make composite oxides with tin oxide etc.
Also have, above-mentioned alkalescence stops the underlying membrane of usefulness, can form with existent method, for example, sol-gal process, liquid phase deposition method, vacuum film formation method, baking, spraying process and CVD method etc.
In addition, above-mentioned alkalescence stops the underlying membrane of usefulness, and 10nm～300nm is desirable.When thickness during less than 10nm, alkaline blocking effect is insufficient, and during greater than 300nm, and is remarkable from the interference colours of film, is difficult to control the optical characteristics of glass plate, is unfavorable.
In addition, as above-mentioned matrix material, with silica (SiO
2) be suitable as glass, ceramic tile, pottery or the metallic plate of main component, and, as the hydrophilic member that the present invention relates to, for example, can be used as mirror.
Description of drawings
Fig. 1 (a) reaches the profile that (b) is respectively the hydrophilic member amplification that the present invention relates to.
The specific embodiment
With reference to the accompanying drawings embodiment of the present invention are illustrated below.Fig. 1 here (a) reaches the amplification profile that (b) is respectively the hydrophilic member that the present invention relates to.
In the embodiment that is shown in (a), hydrophilic member is to form tin oxide (SnO on the surface as the glass plate 1 of matrix material
2) film 2, at this tin oxide film (SnO
2) 2 surface forms the silica (SiO as protective layer
2) film 3.
In the embodiment that is shown in (b), at glass plate 1 and tin oxide film (SnO
2) between 2, insert underlying membrane 4, leach from glass plate 1 to prevent alkali metal such as Na.
Also have, the Ra presentation surface mean roughness among Fig. 1, Sm represents concavo-convex equispaced.
As glass plate 1, be with SiO
2As the soda-lime glass of main component, tin oxide film (SnO
2) 2, for example can use known in the past method such as sol-gal process, liquid phase deposition method, vacuum film formation method, baking, spraying process, CVD method and sputtering method to form, its thickness is 10～800nm, the mean roughness (Ra) on surface is 0.5～25nm.In addition, tin oxide film (SnO
2) film 2 has rutile-type crystalline texture.
In addition, silica (SiO
2) film 3, for example, can use original known method such as sol-gal process, liquid phase deposition method, vacuum film formation method, baking, spraying process, CVD method and sputtering method to form, its thickness is 0.1～100nm.Yet, silicon oxide film (SiO
2) 3 at above-mentioned tin oxide film (SnO
2) form on 2, so, tin oxide film (SnO
2) 2 concavo-convex by the former state transfer printing, silicon oxide film (SiO
2) 3 surface average roughness (Ra) is 0.5～25nm.
In addition, about concavo-convex equispaced (Sm), the scope that reaches 4～300nm is suitable.Equispaced (Sm) is littler or bigger than 300nm than 4nm, and hydrophilic long-time stability are low, is unfavorable.
Therefore, owing to form trickle concavo-convexly from the teeth outwards, then the hydrophily of hydrophilic surface improves more.
That is to say,, when surface area reaches r times, with the contact angle θ of water, form when concavo-convex and the contact angle θ ' of water during smooth surface, cos θ '=rcos θ (90 °＞θ＞θ ') establishment that obtains from the Wenzel formula because that the surface go up to form is trickle concavo-convex.But,, not limit by this when contact angle during greater than 90 °.
For example, during smooth surface, reach at contact angle and to form concavo-convexly on 30 ° the component surface, when reaching 1.1 times of surface areas, obtain cos θ '=1.1cos30 °=0.935 from following formula to water, therefore, θ '=17.7 °.Equally, when surface area reached 1.15 times, θ ' was 5.2 °.
But in the little occasion of θ, this formula may not be set up, yet concavo-convex by being provided with as tendency, it is littler that θ ' can become.
That is to say that owing to form trickle concavo-convexly from the teeth outwards, hydrophilic surface becomes and has bigger hydrophily.
On the other hand, stop underlying membrane 4 with alkalescence, can use stack membrane that constitutes as the film of main component as the film of main component with silica as the silicon oxide film of the film of main component and the complex oxide film that constitutes by silica and tin oxide, carbon containing or with tin oxide with silica etc. as purpose.
For example, the complex oxide film that constitutes by silica and tin oxide, and the silicon oxide film of carbon containing, its refractive index is between the refractive index of the refractive index of glass plate 1 and tin oxide film 2, can obtain better outward appearance.That is, adopt underlying membrane, can suppress interference colours variations (color spot is refuted), simultaneously, can seek the reflected colour modulation and become neutralc tint from the thickness chromatic dispersion generation of tin oxide film with middle refractive index.
In addition, underlying membrane, for example, with tin oxide as the film of main component with constitute the occasion of laminated body as the film of main component with silica, by adjusting the thickness of this each film of laminated body, owing to be in as the apparent refractive index of laminated body between the refractive index of the refractive index of glass plate 1 and tin oxide film 2, can obtain having the same effect of underlying membrane of above-mentioned middle refractive index.
Also have, the hydrophilic member of above-mentioned formation is used for the occasion of mirror, in the inside of glass plate 1, perhaps between glass plate 1 and the underlying membrane 4; Or in the occasion of no underlying membrane, at glass plate 1 and tin oxide film (SnO
2) between 2, for example, form the metallic film of silver and so on.
Secondly, the formation method to film in the embodiment of the invention and comparative example is illustrated.Concrete is, the sample of embodiment 1 is by adopting above-mentioned film formation device (not shown) on glass pane surface, forms tin oxide film successively, silicon oxide film is made.The sample of embodiment 2～4,6 then is the method that adopts similarly to Example 1, by on glass pane surface, form tin oxide film successively, silicon oxide film is made.The sample of embodiment 5 adopts method similarly to Example 1, forms tin oxide film, silicon oxide film, tin oxide film, silicon oxide film successively and make on glass pane surface.
The sample of comparative example 1 adopts method similarly to Example 1, forms tin oxide film successively on glass pane surface, silicon oxide film is made.The sample of comparative example 2, be that common glass plate is immersed in in the aqueous solution of fluosilicic hydracid as main component, glass pane surface is carried out etch processes, by forming in glass pane surface with perforated membrane was constituted trickle concavo-convex the making of silica as main component.The sample of comparative example 4,5 adopts method similarly to Example 1, makes by formation tin oxide film on glass pane surface.
Secondly, to the sample determination average surface roughness (Ra) of the foregoing description and comparative example and concavo-convex equispaced (Sm).The mensuration of these values is to adopt AFM (AFM) and electron microscope is observed, calculate from the section curve that records.
In addition, clean sample with bathing with soaping, confirm the wetability of water to sample surfaces, carry out the mensuration that contact angle changes.With the contact angle of water, be after the surface of sample is cleaned at once, measure after 2 hours and after 200 hours.
Tabulate down 1 and table 2 list hydrophilic member and the comparative example that the present invention relates to, after cleaning with washing agent, the comparative result that changes with the contact angle of water.
Table 1
Table 2
As shown in Table 1, the hydrophilic member that the present invention relates to just become below 10 ° with the contact angle of water at once after cleaning, and after long-time, hydrophily continues to keep.
In contrast, as known from Table 2, general glass plate (comparative example 3) is about 10 ° with the contact angle of water after cleaning at once, and As time goes on, contact angle slowly strengthens.Can think that this is because concavo-convex little (the Ra ≈ 1nm) on surface can't guarantee that hydrophily continues due to the maintenance.In addition, by etching, be about 10 ° with the contact angle of water at once on the surface after to form trickle concavo-convex glass plate (comparative example 2) also be to clean, and As time goes on, contact angle slowly strengthen.Can infer, this is owing to compare with concave-convex surface, concavo-convex interval too small, and durability worsens, simultaneously, due to hydrophilic maintenance performance also reduces.
In addition, tin oxide (SnO
2) thickness of film, when the thickness (comparative example 1) of its formation when exceeding scope of the present invention, (Sm＞300nm), silica (SiO are strengthened in the concavo-convex interval on film surface
2) the concavo-convex interval of film also strengthens, therefore, hydrophilic retentivity can't be guaranteed.In addition, on glass plate, only form tin oxide (SnO
2) occasion (comparative example 4 and comparative example 5) of film, then with tin oxide (SnO
2) thickness of film is irrelevant, is more than 70 ° with the contact angle of water at once after cleaning, no hydrophily.Can think that this and surface configuration have nothing to do, but by tin oxide (SnO
2) film self character determined.
Embodiment 6, inside paste on the glass pane surface of silver, form the mirror that has the film of identical formation with embodiment 3.The surface of this mirror even blow, does not produce any mist spots yet, in addition, be below 10 ° with the contact angle of water at once after cleaning, and hydrophily continues to keep for a long time.Therefore, the mirror hydrophily height of embodiment 6, and have good hydrophilic retentivity.
As mentioned above, according to the 1st feature formation of hydrophilic member of the present invention, its contact angle to water is little, can obtain better hydrophily long-time stability.
The 2nd feature according to above-mentioned hydrophilic member of the present invention constitutes, Yi Bian bring into play the action effect that above-mentioned the 1st feature constitutes, Yi Bian can form polycrystalline thin-film with suitable concave-convex surface shape.
The 3rd feature according to above-mentioned hydrophilic member of the present invention constitutes, can bring into play the action effect that above-mentioned the 1st feature constitutes and the 2nd feature constitutes on one side, can obtain the most lip-deep hydrophily is on one side given full play to, and, hydrophily after cleaning reaches recovery in the extremely short time, have high hydrophily lasting effect.
The 4th feature according to above-mentioned hydrophilic member constitutes, during any feature the above-mentioned the 1st～3 constitutes, can bring into play various action effects on one side, can keep long-term hydrophilicity on one side.
The 5th feature according to above-mentioned hydrophilic member constitutes, during any feature the above-mentioned the 1st～4 constitutes, Yi Bian bring into play various action effects, Yi Bian may obtain desirable hydrophilic film.
The 6th feature according to above-mentioned hydrophilic member constitutes, during any feature the above-mentioned the 1st～5 constitutes, Yi Bian bring into play various action effects, Yi Bian can obtain desirable concavo-convex.
The 7th feature according to above-mentioned hydrophilic member constitutes, during any feature the above-mentioned the 1st～6 constitutes, bring into play various action effects on one side, be in the middle of glass plate refractive index and the tin oxide film refractive index owing to the underlying membrane refractive index on one side, when suppressing interference colours variations (color spot is refuted), can seek to reflect tone and reach muted color.
The 8th feature according to above-mentioned hydrophilic member constitutes, during any feature the above-mentioned the 1st～7 constitutes, bring into play various action effects on one side, on one side owing to the apparent refractive index as laminated body is between glass plate refractive index and the tin oxide film refractive index, when suppressing interference colours variations (color spot is refuted), can seek to reflect tone and reach muted color.
The 9th feature according to above-mentioned hydrophilic member constitutes, during any feature the above-mentioned the 1st～8 constitutes, bring into play various action effects on one side, can effectively be used for purposes such as mirror, window glass for automobile, for building antifog antifouling glass, glasses, lens, ceramic tile or metallic plate on one side.
Constitute according to the 10th feature of above-mentioned hydrophilic member, during any feature the above-mentioned the 1st～9 constitutes, bring into play various action effects on one side, Yi Bian can be used as the peephole that automobile use, the mirror that the bathroom is used etc. effectively.
Claims (9)
1. hydrophilic member; this hydrophilic member be on substrate material surface directly; perhaps stop that by alkalescence the underlying membrane of usefulness forms stannic oxide layer; on this stannic oxide layer surface, form the hydrophilic member of protective layer; it is characterized in that; above-mentioned protective layer is by at least aly constituting of selecting from silica, aluminium oxide, zirconia, cerium oxide and titanium oxide; and; the most surperficial surface average roughness (Ra) is 0.5～25nm, and above-mentioned tin oxide has the crystalline texture of rutile-type.
2. according to the hydrophilic member of record in the claim 1, it is characterized in that the surface average roughness of above-mentioned tin oxide (Ra) is 0.5～25nm, so the most surperficial surface average roughness (Ra) also is 0.5～25nm.
3. according to the hydrophilic member of record in the claim 1, it is characterized in that its most surperficial concavo-convex equispaced (Sm) is 4～300nm.
4. according to the hydrophilic member of record in the claim 1, it is characterized in that the thickness of above-mentioned stannic oxide layer is 10～800nm.
5. according to the hydrophilic member of record in the claim 1, it is characterized in that the thickness of above-mentioned protective layer is 0.1～100nm.
6. according to the hydrophilic member of record in the claim 1, it is characterized in that above-mentioned alkalescence stops that the refractive index of the underlying membrane of usefulness is the median of matrix material refractive index and tin oxide refractive index.
7. according to the hydrophilic member of record in the claim 1, it is characterized in that above-mentioned underlying membrane is the laminated body of tin oxide and silica.
8. according to the hydrophilic member of record in the claim 1, it is characterized in that above-mentioned matrix material is with glass, ceramic tile, pottery or the metallic plate of silica as main component.
9. according to the hydrophilic member of record in the claim 1, it is characterized in that this hydrophilic member is between matrix material the inside, matrix material and stannic oxide layer or forms the mirror of metallic film between underlying membrane and the stannic oxide layer.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34368898 | 1998-12-03 | ||
| JP343688/1998 | 1998-12-03 | ||
| JP11095014A JP2000226234A (en) | 1998-12-03 | 1999-04-01 | Hydrophilic member |
| JP95014/1999 | 1999-04-01 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1334769A CN1334769A (en) | 2002-02-06 |
| CN1155468C true CN1155468C (en) | 2004-06-30 |
Family
ID=26436283
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB998159875A Expired - Fee Related CN1155468C (en) | 1998-12-03 | 1999-11-30 | Hydrophilic member |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JP2000226234A (en) |
| KR (1) | KR100633767B1 (en) |
| CN (1) | CN1155468C (en) |
| AU (1) | AU1412400A (en) |
| DE (1) | DE19983784T1 (en) |
| GB (1) | GB2361246B (en) |
| WO (1) | WO2000032391A1 (en) |
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| CN1815686B (en) * | 2004-12-17 | 2010-06-23 | 株式会社半导体能源研究所 | Semiconductor device and manufacturing method thereof |
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| WO2009110236A1 (en) * | 2008-03-04 | 2009-09-11 | 株式会社 東芝 | Hydrophilic member and hydrophilic articles made by using the same |
| CN103718230B (en) * | 2011-08-05 | 2016-05-18 | Hoya株式会社 | Cover-plate glass and manufacture method thereof for portable set |
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|---|---|---|---|---|
| JPH09231821A (en) * | 1995-12-22 | 1997-09-05 | Toto Ltd | Luminaire and method for maintaining illuminance |
| JPH09278431A (en) * | 1996-04-18 | 1997-10-28 | Central Glass Co Ltd | Hydrophilic film and its production |
| JP2901550B2 (en) * | 1996-07-26 | 1999-06-07 | 株式会社村上開明堂 | Anti-fog element |
| JP3700358B2 (en) * | 1996-12-18 | 2005-09-28 | 日本板硝子株式会社 | Antifogging and antifouling glass articles |
-
1999
- 1999-04-01 JP JP11095014A patent/JP2000226234A/en active Pending
- 1999-11-30 KR KR1020017006837A patent/KR100633767B1/en not_active IP Right Cessation
- 1999-11-30 GB GB0113886A patent/GB2361246B/en not_active Expired - Fee Related
- 1999-11-30 WO PCT/JP1999/006675 patent/WO2000032391A1/en active IP Right Grant
- 1999-11-30 CN CNB998159875A patent/CN1155468C/en not_active Expired - Fee Related
- 1999-11-30 AU AU14124/00A patent/AU1412400A/en not_active Abandoned
- 1999-11-30 DE DE19983784T patent/DE19983784T1/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1815686B (en) * | 2004-12-17 | 2010-06-23 | 株式会社半导体能源研究所 | Semiconductor device and manufacturing method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| GB0113886D0 (en) | 2001-08-01 |
| JP2000226234A (en) | 2000-08-15 |
| KR100633767B1 (en) | 2006-10-16 |
| AU1412400A (en) | 2000-06-19 |
| KR20010101110A (en) | 2001-11-14 |
| GB2361246A (en) | 2001-10-17 |
| CN1334769A (en) | 2002-02-06 |
| GB2361246B (en) | 2003-09-17 |
| DE19983784T1 (en) | 2001-11-08 |
| WO2000032391A1 (en) | 2000-06-08 |
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