Member having photocatalytic activity and multilayered glass

Specification

The member and double-glazed glass which have a photocatalyst function

Technical field

[0001] The present invention relates to the double-glazed glass incorporating the member in which the photocatalyst layer was formed on the surface, and this member.

Background art

[0002] It is known that photocatalysts, such as Anatase type titanium oxide, will demonstrate the antifouling effect, antibacterial properties, and hydrophilicity which disassemble an organic matter by irradiation of ultraviolet rays. Good these days The photocatalyst which exhibits a catalyst function by Visibility light also attracts attention.

for forming the layer of the photocatalyst mentioned above in the member surfaces, such as glass, -- sputtering and vapor deposition etc. -- it is based on the vacuum forming-membranes method or the decompression forming-membranes method in many cases.

[0003] In forming a photocatalyst layer in the substrate surfaces, such as glass, there is no proposal which provides a foundation layer between a substrate and a photocatalyst layer in patent documents 1, patent documents 2, patent documents 3, and patent documents 4. Being done.

It is Ah for forming the medium which becomes patent documents 1 from a photocatalyst constituent on the surface of a glass board material. In order to prevent the functional fall of the medium by the alkali which it is sufficient for and is eluted from glass, Glass board material Providing one layer of barriers between photocatalyst constituents (medium) is indicated, A Consider it as a rear layer. As for The, oxidization Ginole Conium and using especially amorphous oxidization Ginole Conium are proposed. In patent documents 2, Making a ground film intervene and forming a photocatalyst layer on a substrate, especially under Contents use a zirconium dioxide as a ground film and using titanium oxide as a photocatalyst layer are indicated. It is.

In patent documents 3, it is gold, such as a zirconium dioxide, between a substrate (aluminum) and a photocatalyst layer. Genus oxide layer is made to intervene and it is oxygen from a photocatalyst layer to a substrate by this metal oxide layer. The contents which control diffusion are indicated.

Oxidization Ginole Conium is mentioned to patent documents 4 as a photocatalyst substance, and it is this oxidization Zirco. The contents in which the titanium oxide layer was formed on the outside of 2 Um are indicated. [0004] In the relation of the membranous film thickness and the optical characteristic which laminated a zirconium dioxide and titanium oxide As a prior art which made reference, there are patent documents 5 and patent documents 6.

In patent documents 5, 10 nm or less-thick SnO and ZrO are as an alkali nonproliferation layer.

2 it is Mentioned Two -- Case Where 20 Nm or Less is Mentioned as TiO, and also Transparency is Given to Article

2

being alike -- it is indicated that it is necessary to make thickness of a tunic thin.

In patent documents 6, it is high temperature stable type a cubic system or Orthorhombic between a substrate and a titanium oxide layer. It is indicated that the oxidization Ginole Conium layer of a system is formed, and also it is light at an automotive application. It is indicated that the thickness of a catalyst bed must be a grade which it can keep seeing.

[0005] Patent documents 1 : Provisional Publication No. 9 - No. 227167 gazette

Patent documents 2: Provisional Publication No. 10 - No. 66878 gazette

Patent documents 3: Provisional-publication-of-a-patent No. 312830 [ 2000 to ] gazette

Patent documents 4: Provisional-publication-of-a-patent No. 205094 [ 2001 to ] gazette

Patent documents 5: Provisional-publication-of-a-patent No. 513695 [ 2000 to ] gazette, The 12 page 8 line

Patent documents 6 : A PCT international publication (WO 02/40417), The 10 page 9 line

The indication of an invention

Object of the Invention

[0006] literature 11 -- if a photocatalyst layer is formed by the method indicated to 5 If the function as a photocatalyst may not be exhibited or thickness of a photocatalyst layer is not thickened, it is Depart about the function as a photocatalyst. Vienna is not carried out, but the reflectance of an article is large, a Summer interference color appears, and they are desirable reflectance and a color. There was a case where coexistence of a tone and photocatalyst activity was difficult.

[0007] It is crystalline oxidization Di as a foundation layer of a photocatalyst layer (TiO) so that it may be indicated by patent documents 6.

2

If a Luconium layer is provided, the photocatalyst layer excellent in photocatalyst activity can be formed, but it is necessary to form the oxidization Ginole Conium layer of a high temperature stable type cubic system or an ortho rhombic system. Resin with low heat resistance, etc. cannot be used for a case as a substrate. big The since heating uniformly is technically difficult for the substrate of A -- big sizes for construction etc. it is difficult to obtain a light catalytic member -- etc. -- question which nonuniformity produces to a color tone other than a problem There is a title.

[0008] Although the composition which provided the Heat wire reflection film (low radiation rate film: Low -- E film) in the indoor side surface of the outdoors side glass board is publicly known to double-glazed glass, green the glass board which provided this Heat wire reflection film It becomes the cut color tone and the subject exists in the flexibility of a color tone.

Means for solving problem

[0009] The member which has a photocatalyst function concerning the present invention in order to solve the above-mentioned subject, Transparent substrate table The oxide, oxynitride which contain at least 1 side of silicon and tin in a field, And they are the main ingredients and To about a nitriding thing. A Peeling off prevention layer is provided, a crystalline foundation layer is passed on this exfoliation prevention layer, and it is a photocatalyst layer. It is a member which has the formed photocatalyst function, The thickness of the above-mentioned crystalline foundation layer was 2 nm or more, 40 nm or less, preferably 3 nm or more and 20 nm or less, and the thickness of the above-mentioned photocatalyst layer was 2 nm or more, 15 nm or less, preferably 3 nm or more and 10 nm or less.

[0010] As oxidization silicon amorphous as the above-mentioned exfoliation prevention layer, and the above-mentioned crystalline foundation layer, crystalline titanium oxide can be illustrated as a zirconium dioxide and the above-mentioned photocatalyst layer. It is especially the bottom of crystallinity. The monoclinic system zirconium dioxide crystal of a stratum is preferred.

[0011] Namely, Les [ exhibit / by the photocatalyst layer (TiO) of the same membrane formation thickness / a photocatalyst function ], a thing

2

This which has the difference in the crystallinity of a photocatalyst layer when Section structure is observed by an electron microscope It became clear. That is, pillar-shaped particle structure continues clearly from an interface with a substrate to the surface of a layer. The photocatalyst layer (TiO) by which Formed is carried out is a boundary with a substrate, although a remarkable photocatalyst effect is demonstrated.

2

Pillar-shaped particle structure is not accepted near a field, and the photocatalyst layer in which an amorphous layer (a dead layer is called below) exists does not demonstrate sufficient photocatalyst effect.

[0012] Here, the feature [ being amorphous (amorphous) ] is the layer which came out strongly, and a dead layer is an electron. A line diffraction pattern serves as a halo pattern, and is observed. A diffraction spot is observed when it is not a dead layer.

[0013] Since particle structure is continuously formed from a foundation layer to a photocatalyst layer when the above-mentioned dead layer has composition which does not exist substantially, Spare time of these particle structures (pillar-shaped structure) Ion with a small ion radius like the surface to chlorine ion which passes along between, and moisture power Glass machine It may be spread in the direction (substrate) of a board. Such a diffusion molecule reaches even to a glass substrate. Al power, such as sodium in which negative ion, such as chlorine ion, exists in a glass substrate in a It was case It reacts to Lion, and salt may generate, and a film may exfoliate or it may become a fault.

[0014] These artificers made the present invention based on the following knowledge. That is, it is if a photocatalyst layer is formed via the foundation layer which promotes growth of the crystalline particles of a photocatalyst, Appearance of the above-mentioned dead layer If expression can be controlled and an exfoliation prevention layer is provided between a foundation layer and a glass substrate, Glass substrate Exfoliation of a power thing film and generating of a fault can be controlled, and the fall of photocatalyst performance is controlled. It can do, By and the thing for which a layer including a monoclinic system oxidization Ginole Conium crystal is used as a foundation layer The effect which promotes growth of the crystalline particles of a photocatalyst further increases, and -- further -- crystalline foundation layer limiting thickness and the thickness of a photocatalyst layer to the specific range, respectively -- reflectance -- low -- a reflected-colors tone is thin -- specific [ it is blue, and / invigoration ], since reflectance nonuniformity and color tone nonuniformity are also lost It is preferably applicable to the structural glass of the large area which thought the design as important.

[0015] It is possible to apply the member which has the above-mentioned photocatalyst function as an outdoors side glass board of double-glazed glass especially among structural glass. In this case, the oxide which contains at least 1 side of , silicon, and tin on the outdoors side surface of the outdoors side glass board, Peel which makes an oxynitride and a nitriding thing the main ingredients Release prevention layer is provided and 25 nm or less of 2 nm or more in thickness, preferably crystalline 3-nm or more foundation layer of 5 nm or less are passed on this exfoliation prevention layer, It is [ 2 nm or more 15 nm or less thickness ] desirable. 3-nm or more a photocatalyst layer of 5 nm or less is formed, and it is on the indoor side surface of the outdoors side glass board. It has composition in which the Heat wire reflection film was formed.

[0016] In the member or double-glazed glass which has the still more nearly above-mentioned photocatalyst function, the thickness of an exfoliation prevention layer is 2 nm. -- It is 200 nm and preferably is 5 nm. -- It is lOOnm. Thickness of an exfoliation prevention layer When thinner than power S2nm, they are film exfoliation and Les that the control effect of generating of a fault is not enough, and desirable. Up the control effect of the above-mentioned film exfoliation and generating of a fault of the intermediary in which This is thicker than 200 nm -- large -- Toward since it does not carry out the upper -- the maximum of the thickness of an economic viewpoint to an exfoliation prevention layer -- 200 nm -- good -- better -- Les, If the thickness of an exfoliation prevention layer is thicker than 5 nm, the interception effect of moisture increases and they are a substrate and a film. Generating of the water-soluble salt in an interface comes to be controlled completely, and is more preferred. This effect Since the thickness of the above-mentioned exfoliation prevention layer is demonstrated enough below by lOOnm, Result is more desirable Peel. The maximum of the thickness of Release prevention layer is lOOnm. However, it is a refractive index of a substrate as an exfoliation prevention layer. In selecting the thing of a greatly different refractive index, it can do as [ produce / to a color tone / change ]. It is preferred to make only To thin.

[0017] Since the above-mentioned exfoliation prevention layer intercepts the ion and moisture with a small ion radius like chlorine ion from the surface, it prevents these ion and a molecule reaching even to a glass substrate (substrate) and generating of water-soluble reaction salt is prevented, It is Depression about exfoliation of the foundation layer from the substrate which this melts into water and happens. A system can be carried out.

moreover -- the case where the glass substrate produced with the float process is selected as a substrate -- glass machine the tin deterioration layer or amorphous tin oxide layer formed in a contact surface with the tin bath of a board -- exfoliation prevention layer thing power S it carries out -- it can do.

[0018] If it is in the present invention, the above-mentioned foundation layer and a photocatalyst layer consist of a crystalline metal oxide or metal oxynitride, the distance between the oxygen atoms under crystal which constitutes the above-mentioned foundation layer -- few -- Even if there is nothing, one approximates with one of the distance between the oxygen atoms under crystal which constitutes a photocatalyst layer. To is preferred. It is on a foundation layer in case of the combination of a foundation layer and a photocatalyst layer by which this condition is fulfilled. When forming a photocatalyst layer, an oxygen atom is used as a common portion, and it is a crystalline photocatalyst layer immediately. It is easy to grow up.

When the interval of an oxygen atom is observed, they are a single Diagonal zirconium dioxide and Anatase type titanium oxide. It approximates in a certain portion (90 -- it is in 110% of range), and is Connection of a monoclinic system as a foundation layer. If a Crystallinity zirconium compound is selected, The crystal of Anatase type titanium oxide on it It is thought that it is easy to be formed.

As a foundation layer, a small amount of tin, nitrogen, and carbon besides the above-mentioned single Diagonal zirconium dioxide are Attach Callot. The zirconium dioxide carried out and oxynitriding Ginole Conium are used preferably.

moreover -- as a photocatalyst layer -- tin, nitrogen, and carbon besides the above-mentioned Anatase type titanium oxide -- fine -- Titanium oxide and the titanium oxynitride by which quantity addition was carried out are used preferably.

[0019] As the electron diffraction image obtained by glaring from a rectangular cross to the layer section of zirconium dioxide single Diagonal desirable as a foundation layer in addition, (111) diffraction from a field or a field (1 111) there is an image -- the field interval of an orientation surface (111) -- 2. 6-3. 0A and the field interval of an orientation surface (1 111) -- 3.0 -- 1 -- it is 3. 4A.

Since distortion has occurred during a crystal, the zirconium dioxide of the field interval besides this range is a film. Stress tends to cause size Listen film peeling. The oxygen position of a crystal face shifts by distortion. The compatibility of the oxide which constitutes photocatalyst layers, such as titanium oxide, and an oxygen position which will not carry out The is low. Since it becomes, the desirable crystal growth of a photocatalyst layer is no longer seen.

[0020] There is a diffraction pattern from (101) a field as an electron diffraction image obtained by glaring from a rectangular cross to the layer section of Anatase type titanium oxide desirable as a photocatalyst layer, and the field interval of an orientation surface (10 1) is 3. 3-3. 7 A.

Since distortion has occurred during a crystal, membrane stress titanium oxide of the field interval besides this range It is large, film peeling is caused and it is Easy. moreover -- the oxygen position of a crystal face shifts by distortion -- stripes The compatibility of the oxide which constitutes foundation layers, such as Les and a zirconium dioxide, and an oxygen position is low. a To sake -- titanium oxide -- good -- better -- Les and Les [ have ] which crystal growth looks at,

[0021] As a formation method of the above-mentioned foundation layer and a photocatalyst layer, it is under right Tooth with any methods, such as a liquid phase method (a sol gel process, liquid phase deposition) and a gaseous phase method (the sputtering method, a vacuum evaporation method, and a CVD method). Although the crystalline improvement effect of the photocatalyst layer by a ground film is accepted, since it is accompanied by crystal growth -- from book Gaseous phase methods a big effect is especially accepted in Ming, such as the sputtering method and the vapor-depositing method , -- it is suitable.

[0022] Into the above-mentioned photocatalyst layer, generating of a career can be promoted with doping metal and a photocatalyst effect can be heightened.

As a dope metal, Zn, Mo, Fe, etc. are highly suitable for the photocatalyst activity improvement effect. Z It is preferably that more than 0. 1 mass % and below 1 mass % carry out the amount of addition about n and Mo. Below 0. 5 mass % makes [ more than 0. 2 mass % ] it still more desirable. About Fe, it is a photocatalyst layer. It is made for inner content to become [ more than 0. 001 mass % ] below in 0. 5 mass %. It is Limit to these. That of To is disorder of the crystal structure of a photocatalyst, if too large [ when there are few amounts of addition, an effect is too small, and ]. It is because it becomes a cause of recombination center generation and photocatalyst activity falls.

[0023] The hydrophilic effect can be heightened by forming in the surface of the above-mentioned photocatalyst layer the thin film which has hydrophilicity. The thin films which have hydrophilicity are oxidization silicon, a zirconium dioxide, and oxidization gel Maniu. At least one sort of oxides chosen from the group which consists of Beam and an aluminum oxide are preferred. This the inside of Re and others -- oxidization silicon -- from a viewpoint of the hydrophilic improvement effect and endurance -- further -- desirable -- using -- To be. As for the thin film which has hydrophilicity, it is preferred that it is porosity-like. It is porosity-like. With Frenzy in which whose hydrophilic maintenance performance the water retention effect increases and is increasing To an ultraviolet exposure It is because activated species, such as active oxygen which occurred on the Photocatalytic layer surface, can reach to the surface of an article, so the photocatalyst activity of and a photocatalyst layer is not spoiled greatly.

[0024] as the method of forming a porous hydrophilic thin film -- a liquid phase method (a sol gel process, liquid phase deposition) and a gaseous phase method (the sputtering method, a vacuum evaporation method, and a CVD method) -- business -- Les and To be. If the sol gel process generally known is applied, a porous thin film can produce easily, but it is sol gel. By adding organic polymers and higher alcohol in the materials liquid of a method, it is porosity still more easily. A nature thin film can be obtained. gaseous phase methods, such as the sputtering method, -- gas at the time of sputtering the dangling bond of an oxide, such as reducing the quantity of the oxygen in gas which increases pressure, is increased -- as -- By adjusting membrane formation conditions, a porous thin film is producible.

[0025] The thickness of the thin film which has the above-mentioned hydrophilicity, more than lnm, and 30 nm or less are preferred. lnm -- thin -- If There and hydrophilic grant are thicker than 30 nm which comes out enough and drops off, the photocatalyst activity of a photocatalyst layer will be spoiled. It is not desirable at that. With the still more desirable range of this thickness, more than lnm, and 20 nm or less It is. In this range, hydrophilic maintenance performance in case light does not hit is high.

EFFECT OF THE INVENTION

[0026] As explained above, according to the present invention, it hits forming a photocatalyst layer on the surface of a substrate, It is Light touch directly about the photocatalyst layer which provides a crystalline foundation layer and is formed on this foundation layer. It is made for the crystal of intermediation to grow continuously to the surface. It is Peel prevention between a substrate and a foundation layer. Since generating of film exfoliation, a fault, etc. was controlled by providing Pinning layer, Window for construction Glass, the glass board for a display, and glass substrate for DNA analysis, an information portable device and Hygiene equipment, medical facilities, electronic equipment, the inspection chip for living body and medical science, and hydrogen and the charge of oxygen generator material etc. -- the material which has high photocatalyst activity to all members can be provided. the function of the especially optical feature of a certain kind, and the varying smallness and a photocatalyst -- synthetic -- both -- An article with film composition which carries out Stand can be provided.

[0027] Furthermore, according to the present invention, by having stored the thickness of the crystalline foundation layer and the photocatalyst layer in predetermined thickness, a reflected-colors tone can be made blue, commodity value can be raised, and the application to double-glazed glass is expected.

Brief explanation of the drawings

[0028] [Drawing 1] Sectional view of a member which has a photocatalyst function concerning the present invention

[figure 2] The sectional view of the double-glazed glass concerning the present invention

[figure 3] setting film thickness of a ZrO layer and TiO layer to lOnm -- the film thickness of a SiO layer -- a 10-nm pitch -- change

2 2 2

figure showing change of the color tone of the penetration light of a Did case setting film thickness of a [Drawing 4] ZrO layer and a TiO layer to lOnm -- the film thickness of a SiO layer -- a lOnm pitch -- change

2 2 2

The figure showing change of the color tone of the catoptric light of a Did case

[figure 5] Change the film thickness of a TiO layer in a 5-nm pitch by setting film thickness of SiO layer and a ZrO layer to lOnm.

2 2 2

The figure showing the rate of a visible light reflex of a It was case

[figure 6] Change the film thickness of a ZrO layer in a 5-nm pitch by setting film thickness of SiO layer and a TiO layer to lOnm.

2 2 2

The figure showing the rate of a visible light reflex of a It was case

[figure 7] Change the film thickness of a TiO layer in a 5-nm pitch by setting film thickness of SiO layer and a ZrO layer to lOnm.

2 2 2

The figure showing the rate of a visible light reflex of the double-glazed glass (with a Low - E film) of a It was case

[figure 8] Change the film thickness of a ZrO layer in a 5-nm pitch by setting film thickness of SiO layer and a TiO layer to lOnm.

2 2 2

The figure showing the rate of a visible light reflex of the double-glazed glass (with a Low - E film) of a It was case

[figure 9] Change the film thickness of a TiO layer in a 5-nm pitch by setting film thickness of SiO layer and a ZrO layer to lOnm.

2 2 2

The figure showing change of the distance between chromaticity coordinates of a It was case (D)

The reflected-colors tone the distance between chromaticity coordinates (D) indicates 3.5 or less range to be corresponding to garden 10] figure 9 is strange. Figure showing-izing

[Drawing l l] -- setting film thickness of SiO layer and a TiO layer to lOnm -- the film thickness of a ZrO layer -- a 5-nm pitch -- change

2 2 2

The figure showing change of the distance between chromaticity coordinates of a Did case (D)

The reflected-colors tone the distance between chromaticity coordinates (D) indicates 3.5 or less range to be corresponding to garden 12] figure 11 is strange. Figure showing-izing

[figure 13] setting film thickness of SiO layer and a ZrO layer to lOnm -- the film thickness of a TiO layer -- a 5-nm pitch -- change

2 2 2

The figure showing change of the distance between chromaticity coordinates of the double-glazed glass of a Did case (D)

The reflected-colors tone the distance between chromaticity coordinates (D) indicates 3.5 or less range to be corresponding to garden 14] figure 13 is strange. Figure showing-izing

[figure 15] setting film thickness of SiO layer and a TiO layer to lOnm -- the film thickness of a ZrO layer -- a 5-nm pitch -- change

2 2 2

The figure showing change of the distance between chromaticity coordinates of the double-glazed glass of a Did case (D)

The reflected-colors tone the distance between chromaticity coordinates (D) indicates 3.5 or less range to be corresponding to garden 16] figure 15 is strange. Figure showing-izing

[figure 17] Use the glass board which made equal all film thickness of SiO layer, the ZrO layer, and TiO layer, and it is double layer Gala.

2 2 2

Figure showing change of the color tone at the time of considering it as A The best form for inventing

[0029] Describe an embodiment of the invention based on an accompanying drawing below. here -- a figure -- the typical sectional view of a member which has a photocatalyst function which requires 1 for the present invention, and a figure -- 2 has a photocatalyst function It is a sectional view of the double-glazed glass which used the member as the outdoors side glass board.

[0030] a figure -- if it is in the member which has a photocatalyst function shown in 1, a SiO layer is provided in the surface of transparent substrates 1, such as a glass board, as exfoliation prevention layer 1 -- this exfoliation prevention layer 1 top -- crystalline foundation layer 2

2

It carries out, a ZrO layer is provided, this crystalline foundation layer 2 is passed, and a TiO layer is Establishment as photocatalyst layer 3.

2 Two It is kicked. 2 nm or more, 200 mn or less, and the ZrO layer of the thickness of each class are [ SiO layer ] 2 nm or more.

2 2

40 or less mn and TiO layer are 2 nm or more and 15 nm or less.

2

[0031] a figure -- the double-glazed glass shown in 2 -- outdoors side glass board 10 and indoor side glass board 20 -- spacer 30 Countering arrangement is carried out so that it may pass and precise space may be made in between. And a SiO layer is provided in the outdoors side surface of outdoors side glass board 10 as exfoliation prevention layer 1, and it crystallizes on this exfoliation prevention layer 1.

2

A ZrO layer is provided as sex foundation layer 2, this crystalline foundation layer 2 is passed, and it is as photocatalyst layer 3.

2

The TiO layer is provided. It is low radiation rate film 4 to the indoor side surface of outdoors side glass board 10.

2

Low-Ell is formed and they are Les and To.

[0032] a figure -- 3 and a figure -- 4 sets film thickness of ZrO and TiO to 10 nm, and is strange in a 10-nm pitch in the film thickness of SiO

2 2 2

It is a figure showing change of the color tone of the penetration light at the time of making it turn, and catoptric light, and even if these figures to glass and a refractive index omit, and are and it changes film thickness about SiO, a color tone hardly changes,

2

It turns out that a rate of change also becomes large, so that change of a color tone becomes so large that the difference of a refractive index with glass becomes large and film thickness moreover becomes large.

Speak by which the color tone (a*, b*) was obtained from the spectrum photometer here based on CIE1976UCS It computed from Toru.

[0033] a figure -- 5 thru/or a figure -- 8 is a figure showing the relation between class film thickness and the rate of a visible light reflex (R) -- a figure -- 5 -- SiO

2 When Film Thickness of Layer and ZrO Layer was 10 Nm and Film Thickness of TiO Layer is Changed in 5-Nm Pitch

2 2

the rate of a visible light reflex -- a figure -- 6 sets film thickness of SiO layer and a TiO layer to 10 nm -- the film thickness of a ZrO layer -- 5n

2 2 2

the rate of a visible light reflex at the time of making it change in m pitch -- a figure -- 7 -- the film thickness of a SiO layer and ZrO layer -- 10 eta

2 2

Double-glazed glass at the time of changing the film thickness of TiO layer in a 5-nm pitch as m (Low -- with E film)

2

the rate of a visible light reflex -- a figure -- 8 sets film thickness of a SiO layer and TiO layer to 10 nm -- the film thickness of ZrO layer

2 2 2 From the result of having measured the rate of a visible light reflex with the spectrum photometer here where the rate of a visible light reflex of the double-glazed glass (Low -- with E film) at the time of making it changing in a 5-nm pitch is shown based on JIS R3106 to * mountain Les

As for these figures to the rate of a visible light reflex, the film thickness of TiO layer and ZrO layer is 50. When it is 60 nm

2 2

It turns out that it is alike and becomes high, and the rate of a visible light reflex will fall if it is smaller than this range or large. As and a rate of a visible light reflex (R), they are 20% or less, preferably 15% or less.

Drawing 9 thru/or figure 16 is a figure showing change of the distance between chromaticity coordinates (D), and the reflected-colors tone corresponding to this. It is, Drawing 9 sets film thickness of a SiO layer and ZrO layer to 10 nm, and it is in a 5-nm pitch about the film thickness of TiO layer.

2 2 2

the figure and figure showing change of the distance between chromaticity coordinates at the time of making it change (D) -- 10 -- a figure -- corresponding to 9 -- color Figure showing change of the reflected-colors tone the distance between degree coordinates (D) indicates 3.5 or less range to be, Figure When 11 set film thickness of a SiO layer and a TiO layer to 10 nm and the film thickness of a ZrO layer is changed in a 5-nm pitch

2 2 2

change of the distance between chromaticity coordinates (D) is shown -- a figure -- 12 -- a figure -- the figure and figure showing change of the reflected-colors tone the distance between chromaticity coordinates (D) indicates 3.5 or less range to be corresponding to 11 -- 13 -- the film thickness of SiO layer and a ZrO layer

2 Color Degree Seat of Double-glazed Glass at the time of 2 being 10 Nm and Changing Film Thickness of TiO Layer in 5-Nm Pitch

2

change of the distance between marks (D) is shown -- a figure -- 14 -- a figure -- corresponding to 13 -- the distance between chromaticity coordinates (D) -- 3.5 -- with -- the figure and figure showing change of the reflected-colors tone which shows the lower range -- 15 -- the film thickness of a SiO layer and a TiO layer -- 10 eta

2 2

Between the chromaticity coordinates of the double-glazed glass at the time of changing the film thickness of ZrO layer in a 5-nm pitch as m

2

change of distance (D) is shown -- a figure -- 16 -- a figure -- corresponding to 15 -- the distance between chromaticity coordinates (D) -- 3.5 or less It is a figure showing change of the reflected-colors tone which shows the range. If D is 3.5 or less, it is in the case of manufacture. Even if there is change of film thickness, color nonuniformity does not become large but is preferred on quality control. here -- the size of D value -- coming as for To, it is clear that the ease of carrying out of a color change is shown -- within the limits in which the present invention has the value but -- Depression A film Atsunori enclosure of each layer which is obtained is found out this time.

Between chromaticity coordinates when the distance between chromaticity coordinates changes 5 nm of film thickness film thickness change before here Distance is shown. A formula is shown below.

*

D = {(a * n-- a * n-- 1)²+ 2 (b * n -- b * n_l) 0.5 having summarized more than [0035] -- the following -- (-- it is table 1)} this (table 1) -- from -- if the rate of a color change, reflected colors (blue example enclosure), the rate of a visible light reflex, and hydrophilicity are taken into consideration about a single film single plate (what formed the photocatalyst layer only in the 1 side side of a glass board) -- a ZrO layer -- 2 nm -- 40 nm -- good -- better

2

To are 15 nm, preferably 3 nm 2 nm about 20 nm and TiO layer 3 nm. -- It is 10 nm.

2

the double-glazed glass (with a Low_E film) using the above-mentioned single plate glass -- a ZrO layer -- just

2 The is 2 Nm. -- 25 Nm, Preferably 3 Nm -- About 5 Nm and TiO Layer, it is 2 Nm. -- Desirable 15 Nm

2

3 nm of Is -- It can be said that it is 5 nm.

A photocatalyst activity (hydrophilicity) valuation method is a light source about a black lamp (main wavelength of 365 nm). It uses and is illumination lmW/cm²it carries out -- measuring the angle of contact of the water 60 minutes after UV irradiation -- hydrophilicity-ized criticism Value was performed.

[0036] [-- table 1]

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a figure -- 17 should use the glass board which made equal all film thickness of SiO layer, the ZrO layer, and TiO layer

2 2 2

It is a figure showing change of the color tone at the time of considering it as double-glazed glass. a figure -- it sets to 17 -- a glass layer is laminated and G shows Les and To

AKM5 and G/SiO/(5 nm) ZrO /(5 nm) TiO (5 nm)

AKM10 and G/SiO/(10 nm) ZrO /(10 nm) TiO (lOnm)

AKM15 and G/SiO/(15 nm) ZrO /(15 nm) TiO (15 nm)

AKM20 and G/SiO/(20 nm) ZrO /(20 nm) TiO (20 nm)

Composition of low radiation rate film 4,

It is Low-E = G/ZnO(35.2 nm)/Ag(6.3 nm)/ZnO(85.2 nm)/Ag(12.1 nm)/ZnO (35.2 nm).

this figure -- comparing only with a Low - E film from 17 -- the 1st page (outdoor side) of The of the outdoors side glass board -- book If it is in the double-glazed glass in which the photocatalyst layer of A request was formed, the reflected colors observed from the outdoors side are green. Power also changes to a blue color tone and understands Les and To.