Paint composite film comprising anatase-type titanium oxide, and method for manufacturing same
Abstract
Provided is a paint composite film which comprises anatase-type titanium oxide, exhibits photocatalytic activity and generates active oxygen even in visible light and weak light rays, has a self-cleaning effect, and effectively blocks the invasive action of activated oxygen on interior surfaces. Also provided is a method for manufacturing the paint composite film comprising anatase-type titanium oxide. The present invention, in which a peroxotitanic acid solution serves as an A solution and an anatase-type titanium oxide dispersion solution obtained by heating the A solution to 70-200°C serves as a B solution, is characterized by providing: an exterior-use composite film having a photocatalyst layer and obtained by applying and drying the B solution, which has photocatalytic activity, on an undercoat layer formed by applying and drying the A solution, to which reinforcing particles have been added; and an interior-use composite film having antimicrobial activity even in dark places and obtained by applying and drying the B solution, to which a precious metal has been added, on an undercoat layer formed by applying and drying the A solution.

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38 claims: 15 independent, 23 dependent
- 1ペルオキソチタン酸水溶液をA液とし、 前記A液を70乃至200°Cに加熱して製造したアナターゼ型酸化チタン分散液に、貴金属の塩又はナノコロイドを加えた液をB液とし、 建築物の塗装面に、前記A液を塗布し乾燥させた上に、前記B液を塗布し乾燥させて形 成したことを特徴とするアナターゼ型酸化チタンを含有する塗装用複合膜。
- 2前記A液のペルオキソチタン酸の含有率は、ペルオキソチタン酸の重量を酸化チタンの重量に換算し、A液の重量を100重量部とした場合に、0.1乃至10重量部の範囲内であることを特徴とする請求項1に記載のアナターゼ型酸化チタンを含有する塗装用複合膜。
- 3前記B液のアナターゼ型酸化チタン含有率は、B液の重量を100重量部とした場合に、0.1乃至10重量部の範囲内であることを特徴とする請求項1に記載のアナターゼ型酸化チタンを含有する塗装用複合膜。
- 4前記A液の含有するペルオキソチタン酸の重量を酸化チタンの重量に換算した重量と、前記B液の含有する酸化チタンの重量と、の比が、10:1乃至1:10の範囲内であることを特徴とする請求項1に記載のアナターゼ型酸化チタンを含有する塗装用複合膜。
- 5前記貴金属の塩又はナノコロイドが、銅、銀、金、及び白金の塩又はナノコロイドからなる群のうちの1以上であることを特徴とする請求項1に記載のアナターゼ型酸化チタンを含有する塗装用複合膜。
- 6前記B液の前記貴金属の塩又はナノコロイドの含有率は、貴金属の塩又はナノコロイドの重量を金属の重量に換算し、B液の重量を100重量部とした場合に、1×10 -4 乃至1×10 -9 重量部の範囲内であることを特徴とする請求項5に記載のアナターゼ型酸化チタンを含有する塗装用複合膜。
- 7前記A液の塗装面に対する塗布量が1乃至100g/m 2 であり、前記B液の塗布量が1乃至100g/m 2 であることを特徴とする請求項1乃至6の何れか1項に記載のアナターゼ型酸化チタンを含有する塗装用複合膜。
- 8前記塗装面が、建造物内部の壁、天井、床、仕切部材、家具、及び照明器具を含む内装面であることを特徴とする請求項1乃至7の何れか1項に記載のアナターゼ型酸化チタンを含有する塗装用複合膜。
- 9建築物の内装面に形成された非結晶性の酸化チタンから成るアンダーコート層と、該アンダーコート層上に形成された貴金属の塩又はナノコロイド、及びアナターゼ型酸化チタンから成る光触媒層と、を有し、 前記貴金属の塩又はナノコロイドの含有量は、貴金属の塩又はナノコロイドの重量を金属の重量に換算し、前記アナターゼ型酸化チタンの重量を100重量部とした場合に、1×10 -1 乃至1×10 -8 重量部の範囲内であることを特徴とするアナターゼ型酸化チタンを含有する塗装用複合膜。
- 10前記非結晶性の酸化チタン層の重量と、前記アナターゼ型酸化チタン層の重量と、の比が、10:1乃至1:10の範囲内であることを特徴とする請求項9に記載のアナターゼ型酸化チタンを含有する塗装用複合膜。
- 11前記貴金属の塩又はナノコロイドが、銅、銀、金、及び白金の塩又はナノコロイドからなる群のうちの1以上であることを特徴とする請求項9に記載のアナターゼ型酸化チタンを含有する塗装用複合膜。
- 12前記内装面が、建造物内部の壁、天井、床、仕切部材、家具、及び照明器具を含むことを特徴とする請求項9乃至11の何れか1項に記載のアナターゼ型酸化チタンを含有する塗装用複合膜。
- 13建築物の内装面に形成したペルオキソ基を含む非晶質固体層と、該非晶質固体層の上に形成した貴金属の塩又はナノコロイドを含むアナターゼ型酸化チタン層と、を有し、 前記貴金属の塩又はナノコロイドの含有量は、貴金属の塩又はナノコロイドの重量を金属の重量に換算し、前記アナターゼ型酸化チタンの重量を100重量部とした場合に、1×10 -1 乃至1×10 -8 重量部の範囲内であることを特徴とするアナターゼ型酸化チタンを含有する塗装用複合膜。
- 14前記非晶質固体の重量を酸化チタンの重量に換算した重量と、前記アナターゼ型酸化チタンの重量と、の比が、10:1乃至1:10の範囲内であることを特徴とする請求項13に記載のアナターゼ型酸化チタンを含有する塗装用複合膜。
- 15前記貴金属の塩又はナノコロイドが、銅、銀、金、及び白金の塩又はナノコロイドからなる群のうちの1以上であることを特徴とする請求項13に記載のアナターゼ型酸化チタンを含有する塗装用複合膜。
- 16前記内装面が、建造物内部の壁、天井、床、仕切部材、家具、及び照明器具を含むことを特徴とする請求項13乃至15の何れか1項に記載のアナターゼ型酸化チタンを含有する塗装用複合膜。
- 17非結晶性酸化チタン及び平均粒径が5乃至500μmでありモース硬度が5以上である強化粒子を含むアンダーコート層と、 前記アンダーコート層の上に形成されたアナターゼ型酸化チタンを含む光触媒層と、 を有し、 前記非結晶性酸化チタンの質量を100質量部としたときに、前記強化粒子の質量が、1乃至100質量部であることを特徴とするアナターゼ型酸化チタンを含有する塗装用複合膜。
- 18前記強化粒子が、長石、硅石、シリカゲル、アルミナ、又はチタニアの粒子中の1以上であることを特徴とする請求項17に記載のアナターゼ型酸化チタンを含有する塗装用複合膜。
- 19前記アンダーコート層の前記非結晶性酸化チタンの塗布量は、0.1乃至100g/m 2 であることを特徴とする請求項17又は18に記載のアナターゼ型酸化チタンを含有する塗装用複合膜。
- 20前記光触媒層のアナターゼ型酸化チタンの塗布量は、0.1乃至50g/m 2 であることを特徴とする請求項17乃至19の何れか1項に記載のアナターゼ型酸化チタンを含有する塗装用複合膜。
- 21前記光触媒層が、更に前記非結晶性酸化チタンを含むことを特徴とする請求項17乃至9の何れか1項に記載のアアナターゼ型酸化チタンを含有する塗装用複合膜。
- 22前記光触媒層の塗布量は、アナターゼ型酸化チタンの塗布量と、非結晶性酸化チタンの塗布量と、を合計した塗布量が、0.1乃至50g/m 2 であり、アナターゼ型酸化チタンの質量と、非結晶性酸化チタンの質量と、の比率が、1:0乃至1:2の範囲(但し0は除く)であることを特徴とする請求項21に記載のアナターゼ型酸化チタンを含有する塗装用複合膜。
- 23ペルオキソチタン酸水溶液をA液とし、 該A液を70乃至200°Cに加熱して製造したアナターゼ型酸化チタン分散液に、貴金属の塩又はナノコロイドを加えた液をB液とし、 建築物の内装面に、前記A液を塗布し乾燥させた上に、前記B液を塗布し乾燥させて形成することを特徴とするアナターゼ型酸化チタンを含有する塗装用複合膜の製造方法。
- 24前記A液のペルオキソチタン酸の含有率は、ペルオキソチタン酸の重量を酸化チタンの重量に換算し、A液の重量を100重量部とした場合に、0.1乃至10重量部の範囲内であることを特徴とする請求項23に記載のアナターゼ型酸化チタンを含有する塗装用複合膜の製造方法。
- 25前記B液のアナターゼ型酸化チタン含有率は、B液の重量を100重量部とした場合に、0.1乃至10重量部の範囲内であることを特徴とする請求項23に記載のアナターゼ型酸化チタンを含有する塗装用複合膜の製造方法。
- 26前記A液の含有するペルオキソチタン酸の重量を酸化チタンの重量に換算した重量と、前記B液の含有する酸化チタンの重量と、の比が、10:1乃至1:10の範囲内であることを特徴とする請求23に記載のアナターゼ型酸化チタンを含有する塗装用複合膜の製造方法。
- 27前記貴金属の塩又はナノコロイドが、銅、銀、金、及び白金の塩又はナノコロイドからなる群のうちの1以上であることを特徴とする請求項23に記載のアナターゼ型酸化チタンを含有する塗装用複合膜の製造方法。
- 28前記B液の前記貴金属の塩又はナノコロイドの含有率は、貴金属の塩又はナノコロイドの重量を金属の重量に換算し、B液の重量を100重量部とした場合に、1×10 -4 乃至1×10 -9 重量部の範囲内であることを特徴とする請求項27に記載のアナターゼ型酸化チタンを含有する塗装用複合膜の製造方法。
- 29前記A液の塗装面に対する塗布量が1乃至100g/m 2 であり、前記Bの塗布量が1乃至100g/m 2 であることを特徴とする請求項23に記載のアナターゼ型酸化チタンを含有する塗装用複合膜の製造方法。
- 30前記塗装面が、建造物内部の壁、天井、床、仕切部材、家具、及び照明器具を含むことを特徴とする請求項23に記載のアナターゼ型酸化チタンを含有する塗装用複合膜の製造方法。
- 31チタン原料からペルオキソチタン酸水溶液を製造するペルオキソチタン酸水溶液製造工程と、 前記ペルオキソチタン酸水溶液に含まれるペルオキソチタン酸の質量を酸化チタンの質量に換算して100質量部とし、前記ペルオキソチタン酸水溶液に平均粒径が5乃至500μmでありモース硬度が5以上である強化粒子を1乃至100質量部加えてアンダーコート液を製造するアンダーコート液製造工程と、 前記アンダーコート液を基体表面に塗布し乾燥して非結晶性酸化チタンと前記強化粒子を含むアンダーコート層を形成するアンダーコート層形成工程と、 前記ペルオキソチタン酸水溶液を加熱してアナターゼ型酸化チタン分散液を含む光触媒液を製造する光触媒液製造工程と、 前記光触媒液を、前記アンダーコート層の上に塗布し乾燥して光触媒層を形成する光触媒層形成工程と、 を有することを特徴とするアナターゼ型酸化チタンを含有する塗装用複合膜の製造方法。
- 32前記強化粒子が、長石、硅石、シリカゲル、アルミナ、又はチタニアの粒子の中の1以上であることを特徴とする請求項31に記載のアナターゼ型酸化チタンを含有する塗装用複合膜の製造方法。
- 33前記ペルオキソチタン酸水溶液に含まれるペルオキソチタン酸の含有量は、ペルオキソチタン酸の質量を酸化チタンの質量に換算し、前記ペルオキソチタン酸水溶液の質量を100質量部とした場合に、0.1乃至20質量部であることを特徴とする請求項7又は8に記載のアナターゼ型酸化チタンを含有する塗装用複合膜の製造方法。
- 34前記アンダーコート液の塗布量は、ペルオキソチタン酸の質量を酸化チタンの質量に換算して、0.1乃至500g/m 2 になるように前記アンダーコート液を基材に塗布することを特徴とする請求項7乃至9の何れか1項に記載のアナターゼ型酸化チタンを含有する塗装用複合膜の製造方法。
- 35前記光触媒液に含まれるアナターゼ型酸化チタンの含有量は、前記光触媒液の質量を100質量部とした場合に、0.1乃至20質量部であることを特徴とする請求項7乃至9の何れか1項に記載のアナターゼ型酸化チタンを含有する塗装用複合膜の製造方法。
- 36前記光触媒液の塗布量は、酸化チタンの質量が0.1乃至250g/m 2 になるように前記光触媒液を前記アンダーコート層に塗布することを特徴とする請求項35に記載のアナターゼ型酸化チタンを含有する塗装用複合膜の製造方法。
- 37前記光触媒液が、更に前記ペルオキソチタン酸水溶液を含むことを特徴とする請求項31乃至34の何れか1項に記載のアナターゼ型酸化チタンを含有する塗装用複合膜の製造方法。
- 38前記光触媒液の質量を100質量部とし、前記光触媒溶液に含まれるペルオキソチタン酸の質量を酸化チタンの質量に換算した場合に、アナターゼ型酸化チタンの質量と、ペルオキソチタン酸の質量との合計が0.1乃至20質量部であり、アナターゼ型酸化チタンの質量とペルオキソチタン酸の質量の比率が、1:0乃至1:2の範囲であることを特徴とする請求項37に記載のアナターゼ型酸化チタンを含有する塗装用複合膜の製造方法。
Independent claims38
61 paragraphs, as filed
A composite membrane for paint containing Anatase type titanium oxide, and a manufacturing method for the same
0001the present invention relates to a composite membrane for paint containing Anatase type titanium oxide, and a manufacturing method for the same -- more -- detailed It excels in photocatalyst activity and antibacterial activity, and film formation ability is high, and adhesion nature with a painted surface is strong, and it is related with a composite membrane for paint containing the Anatase type titanium oxide in which the invasion to the inner wall surface by the active oxygen generated by a photochemical reaction was reduced, and a manufacturing method for the same.
0002Titanium oxide has a Anatase type and a rutile type crystallized type. In this, Anatase type titanium oxide has the catalyst activity of a strong photochemical reaction, Active oxygen which had and generated the photocatalyst function which absorbs the light which has larger energy than a band gap in response to irradiation of light, and changes oxygen into active oxygen, A powerful oxidization operation is shown, oxidization decomposition of the various objects is carried out, and having a self-pure operation, a powerful antibacterial action, etc. is known (see the patent documents 1 and 2).
0003For example, a photocatalyst transfers the energy which absorbed and absorbed light energy to oxygen, and the self-pure operation by a photocatalyst film generates active oxygen, Generated active oxygen carries out oxidization decomposition of the adhesive organic Dirty dyed goods adhering to the outside of an outer wall or a windowpane, and it is based on a mechanism of flushing a contaminant rain water becomes easy to flush, and keeping an outer wall and a windowpane of a building pure. It is already put in practical use.
0004The Anatase type titanium oxide film formed on the surface of glass will carry out decomposition removal of the contaminant which generated active oxygen and adhered on the surface of glass, if light is received. Since the glass from which the contaminant was removed regains original hydrophilicity (hydrophilicity-ized operation), it spreads without the water adhering to the surface becoming a dot, and does not produce cloudy weather (the antifog effect). The Anatase type titanium oxide tunic is applied to an automobile mirror or the surface of a traffic-control sign using this operation. Since, as for the active oxygen generated from a photocatalyst coat, an oxidized part understands gas like nitrogen oxide (NOX) or a bad smell substance, the Anatase type titanium oxide tunic is used for air purification of the sound insulating wall of a highway, home electronics, etc., a deodorization operation, etc.
0005The conventional formation method of a Anatase type titanium oxide tunic, Slurry of a titanium oxide granular material, or the applying method for applying solution of a titanium chloride or titanium sulfate to a base, and calcinating it, A sol gel process which applies to a base the sol produced by hydrolysis of metal Alkoxide, and calcinates it, The sputtering method which carries out sputtering of the target of an oxide in a high vacuum, and forms membranes on a base, There are plasma spray coating etc. which are fused in the CVD method which volatilizes an organic metallic compound and a halogenation thing, decomposes in a heating furnace, and produces a film on a base, and the plasma which generated solid particles in the atmosphere and with which the base surface is irradiated. However, since the applying method needs the temperature of hundreds of times or more for formation of a Anatase type titanium oxide film, A base has the problem of being restricted to what bears high temperature, and a sol gel process also has the problem of needing to be heated more than 400 degreeC, although calcination removal of acid or the organic substance is carried out into materials sol.
0006Solution of the peroxotitanic acid hydrate which processes and generates titanium materials with hydrogen peroxide as a manufacturing method of Anatase type titanium oxide in recent years, It was indicated only by applying and drying the underwater dispersion liquid of the Anatase type titanium oxide particle obtained by heating to about 100 degreeC that formation of a Anatase type titanium oxide photocatalyst film is possible (see the patent documents 3~7).
0007The Anatase type titanium oxide photocatalyst film obtained with this manufacturing method can form a coat only by applying to a substrate and drying, and has the feature that visible light can also show photocatalyst activity. It has the problem that film strength and adhesion nature are a little inferior to a photocatalyst printed and carried out at the conventional high temperature on the other hand.
0008The active oxygen emitted from a photocatalyst has the problem of also invading a base. That is, it is although a photocatalyst film can be formed on the base which is not invaded by active oxygen like glass, metal, and concrete, For example, if a photocatalyst is applied on the base invaded by active oxygen like a paint painted surface, a base will be invaded with a contaminant and degradation of a base will be promoted. For this reason, in order to form a Anatase type titanium oxide film in the surface of the base disassembled into active oxygen, the under coat which intercepts active oxygen is required.
0009The amorphous titanium oxide film produced by on the other hand applying and drying the peroxotitanic acid hydrate which is an intermediate of Anatase type titanium oxide, Although it does not have a photocatalyst operation, film strength is excellent, and it has the feature that adhesion Nature is excellent to many substrates containing a Anatase type titanium oxide film.
0010A photocatalyst does not have light, or although sufficient activity cannot be demonstrated at the weak place of light, there is a problem that a bacillus breeds easily in a dark place, especially concerning antibacterial activity. Since the endurance over the long period of time of several year~about ten is required under a very severe environmental condition, even if the coat of the outer wall of a building is [ a certain grade ] effective, just its it may not be enough as providing the undercoat layer of amorphous titanium oxide. Therefore, development of the method of further strengthening membranous intensity and adhesion nature was desired, holding the catalyst activity of Anatase type titanium oxide.
<p num="0011"><patcit num="1"><text>JP,7-155598,A</text></patcit><patcit num="2"><text>JP,9-225319,A</text></patcit><patcit num="3"><text>The patent No. 2875993 gazette</text></patcit><patcit num="4"><text>The patent No. 3490012 gazette</text></patcit><patcit num="5"><text>The patent No. 3490013 gazette</text></patcit><patcit num="6"><text>The patent No. 2938376 gazette</text></patcit><patcit num="7"><text>The patent No. 3122658 gazette</text></patcit><patcit num="8"><text>The patent No. 4452689 gazette</text></patcit></p>
<p num="0012">It is made in order that the present invention may solve the above problems, Invasion of the active oxygen to a substrate is covered effectively, membrane formation nature and adhesion nature are good, catalyst efficiency is high, and a manufacturing method makes it a subject to provide a composite membrane for interiors containing easy and cheap Anatase type titanium oxide, and a manufacturing method for the same. A first embodiment of the present invention has photocatalyst activity, even if it is visible light and weak light, generates active oxygen, has a self-detergent action, and it makes it a subject to provide the composite membrane for interiors containing the Natase type titanium oxide which has strong antibacterial activity also in a dark place.</p><p num="0013">A second embodiment of the present invention is while having the strong adhesion nature and coat intensity of , which can also bear the severe environmental condition to which the exterior of a building is put and having a powerful self-detergent action by photocatalyst operation, It is in providing the composite membrane for the exterior containing the Anatase type titanium oxide which covered invasion of the active oxygen to a substrate effectively.</p>
<p num="0014">The composite membrane for interiors containing Anatase type titanium oxide for solving this subject, To the Anatase type titanium oxide dispersion liquid which used peroxotitanic acid solution as A liquid, and heated and manufactured A liquid to 70 thru/or 200 degreeC, The liquid which added the salt or nanocolloid of the precious metals was used as B liquid, the interior side of the building was made to apply and dry the above-mentioned A liquid, and also the above-mentioned B liquid was applied and dried, and it formed.</p><p num="0015">The content of the peroxotitanic acid of the above-mentioned A liquid can be within the limits of 0.1 thru/or 10 weight sections, when the weight of peroxotitanic acid is converted into the weight of titanium oxide and the weight of A liquid is 100 weight sections. The Anatase type titanium oxide content of the above-mentioned B liquid can be within the limits of 0.1 thru/or 10 weight sections, when the weight of B liquid is 100 weight sections.</p><p num="0016">It is preferred that the ratio of the weight which converted into the weight of titanium oxide the weight of the peroxotitanic acid which the above-mentioned A liquid contains, and the weight of the titanium oxide which the above-mentioned B liquid contains to , is within the limits of 10:1 thru/or 1:10. It is preferred that the salt or nanocolloid of the above-mentioned precious metals is one or more [ of the groups which consist of the salt or nanocolloid of copper, silver, gold, and platinum ].</p><p num="0017">The salt of the above-mentioned precious metals of the above-mentioned B liquid or the content of nanocolloid is 1x10, when the salt of the precious metals or the weight of nanocolloid is converted into metaled weight and the weight of B liquid is 100 weight sections.<sup>-4</sup>Or 1x10<sup>-9</sup>It is within the limits of a weight section. The amount of applications to the painted surface of the above-mentioned A liquid is 1 thru/or 100g/m.<sup>2</sup>Come out, it is and the amount of applications of the above-mentioned B liquid is 1 thru/or 100g/m.<sup>2</sup>It comes out and a certain thing is preferred. It is preferred that the above-mentioned painted surface is an interior side containing the wall inside a building, a ceiling, a floor, a partition member, furniture, and a light.</p><p num="0018">The composite membrane for paint containing Anatase type titanium oxide of the present invention, The undercoat layer which comprises titanium oxide of the amorphous nature formed in the interior side of a building, It has a photocatalyst layer which comprises the salt or nanocolloid, and Anatase type titanium oxide of the precious metals formed on the undercoat layer, and they are salt of the above-mentioned precious metals, or the content of nanocolloid, When the salt of the precious metals or the weight of nanocolloid is converted into metaled weight and the weight of the above-mentioned Anatase type titanium oxide is 100 weight sections, it is 1x10.<sup>-1</sup>Or 1x10<sup>-8</sup>It is within the limits of a weight section.</p><p num="0019">The composite membrane for paint containing Anatase type titanium oxide of the present invention, The noncrystalline-solid layer containing the Pell oxo group formed in the interior side of a building, and the Anatase type titanium oxide layer containing the salt or nanocolloid of the precious metals formed on the above-mentioned noncrystalline-solid layer, When it With, the salt of the above-mentioned precious metals or the content of nanocolloid converts the salt of the precious metals, or the weight of nanocolloid into metaled weight and the weight of the above-mentioned Anatase type titanium oxide is 100 weight sections, it is 1x10.<sup>-1</sup>Or 1x10<sup>-8</sup>It is within the limits of a weight section.</p><p num="0020">The composite membrane for paint containing Anatase type titanium oxide of the present invention, The undercoat layer in which amorphous titanium oxide and average particle diameter are 5 thru/or 500 micrometers, and Mohs hardness contains the strengthening particles which are five or more, When it has a photocatalyst layer containing the Anatase type titanium oxide formed on the above-mentioned undercoat layer and the mass of the above-mentioned amorphous titanium oxide is 100 mass parts, the mass of the above-mentioned strengthening particles is 1 thru/or 100 mass parts.</p><p num="0021">It is preferred that the above-mentioned strengthening particles are one or more [ of an in / feldspar, a silica stone, silica gel, alumina, or Chita Near's particles ]. The amount of applications of the above-mentioned amorphous titanium oxide of the above-mentioned undercoat layer is 0.1 thru/or 100g/m.<sup>2</sup>It comes out and a certain thing is made. The amount of applications of Anatase type titanium oxide of the above-mentioned photocatalyst layer is 0.1 thru/or 50g/m.<sup>2</sup>It comes out and a certain thing is preferred.</p><p num="0022">The above-mentioned photocatalyst layer can contain the above-mentioned amorphous titanium oxide further. As for the amount of applications of the above-mentioned photocatalyst layer, the amount of applications which totaled the amount of applications of Anatase type titanium oxide and the amount of applications of amorphous titanium oxide is 0.1 thru/or 50g/m.<sup>2</sup>It comes out, and it is and the ranges (however, 0 removes) of the mass of Anatase type titanium oxide, the mass of amorphous titanium oxide, and the ratio of , are 1:0 thru/or 1:2.</p><p num="0023">A manufacturing method of the composite membrane for paint which contains Anatase type titanium oxide of the present invention again, To the Anatase type titanium oxide dispersion liquid which used peroxotitanic acid solution as A liquid, and heated and manufactured the above-mentioned A liquid to 70 thru/or 200 degreeC, The liquid which added the salt or nanocolloid of the precious metals is used as B liquid, the interior side of the building was made to apply and dry the above-mentioned A liquid, and also the above-mentioned B liquid is applied and dried, and it forms.</p><p num="0024">The content of the peroxotitanic acid of the above-mentioned A liquid can be within the limits of 0.1 thru/or 10 weight sections, when the weight of peroxotitanic acid is converted into the weight of titanium oxide and the weight of A liquid is 100 weight sections. The Anatase type titanium oxide content of the above-mentioned B liquid can be within the limits of 0.1 thru/or 10 weight sections, when the weight of B liquid is 100 weight sections.</p><p num="0025">The ratio of the weight which converted into the weight of titanium oxide the weight of the peroxotitanic acid which the above-mentioned A liquid contains, and the weight of the titanium oxide which the above-mentioned B liquid contains to , is within the limits of 10:1 thru/or 1:10. It is preferred that the salt or nanocolloid of the above-mentioned precious metals is one or more [ of the groups which consist of the salt or nanocolloid of copper, silver, gold, and platinum ].</p><p num="0026">The salt of the above-mentioned precious metals of the above-mentioned B liquid or the content of nanocolloid is 1x10, when the salt of the precious metals or the weight of nanocolloid is converted into metaled weight and the weight of B liquid is 100 weight sections.<sup>-4</sup>Or 1x10<sup>-9</sup>It is within the limits of a weight section. The amount of applications to the painted surface of the above-mentioned A liquid is 1 thru/or 100g/m.<sup>2</sup>Come out, it is and the amount of applications of the above-mentioned B is 1 thru/or 100g/m.<sup>2</sup>It comes out and a certain thing is preferred. The above-mentioned painted surface contains the wall inside a building, a ceiling, a floor, a partition member, furniture, and a light.</p><p num="0027">A manufacturing method of the composite membrane for paint which contains Natase type titanium oxide of the present invention again, The peroxotitanic acid solution manufacturing process which manufactures peroxotitanic acid solution from titanium materials, The mass of the peroxotitanic acid contained in the above-mentioned peroxotitanic acid solution is converted into the mass of titanium oxide, and it may be 100 mass parts, The under coat liquid manufacturing process which adds 1 thru/or 100 mass parts of strengthening particles whose average particle diameter is 5 thru/or 500 micrometers, and whose Mohs hardness is five or more to the above-mentioned peroxotitanic acid solution, and manufactures under coat liquid, The undercoat layer formation process which forms the undercoat layer which applies the above-mentioned under coat liquid to the base surface, dries, and contains amorphous titanium oxide and the above-mentioned strengthening particles, It has a photocatalyst liquid manufacturing process which manufactures the photocatalyst liquid which heats the above-mentioned peroxotitanic acid solution and contains Anatase type titanium oxide dispersion liquid, and a photocatalyst layer formation process which applies the above-mentioned photocatalyst liquid on the above-mentioned undercoat layer, dries, and forms a photocatalyst layer.</p><p num="0028">It is preferred that the above-mentioned strengthening particles are one or more [ of an in / the particles of feldspar, a silica stone, silica gel, alumina, or Chita Near ]. The content of the peroxotitanic acid contained in the above-mentioned peroxotitanic acid solution can be 0.1 thru/or 20 mass parts, when the mass of peroxotitanic acid is converted into the mass of titanium oxide and the mass of the above-mentioned peroxotitanic acid solution is 100 mass parts.</p><p num="0029">The amount of applications of the above-mentioned under coat liquid converts the mass of peroxotitanic acid into the mass of titanium oxide, and is 0.1 thru/or 500g/m.<sup>2</sup>It is preferred for it to be alike, and to apply the above-mentioned under coat liquid to a substrate so that it may become. The content of the Anatase type titanium oxide contained in the above-mentioned photocatalyst liquid is 0.1 thru/or 20 mass parts, when the mass of the above-mentioned photocatalyst liquid is 100 mass parts.</p><p num="0030">The mass of titanium oxide of the amount of applications of the above-mentioned photocatalyst liquid is 0.1 thru/or 250g/m.<sup>2</sup>It is preferred for it to be alike, and to apply the above-mentioned photocatalyst liquid to the above-mentioned undercoat layer so that it may become. The above-mentioned photocatalyst liquid contains the above-mentioned peroxotitanic acid solution further.</p><p num="0031">When the mass of the peroxotitanic acid which makes mass of the above-mentioned photocatalyst liquid 100 mass parts, and is contained in the above-mentioned photocatalyst solution is converted into the mass of titanium oxide, it is the mass of Anatase type titanium oxide, The sum total with the mass of peroxotitanic acid is 0.1 thru/or 20 mass parts, and the ranges of the ratio of the mass of Anatase type titanium oxide and the mass of peroxotitanic acid are 1:0 thru/or 1:2.</p>
<p num="0032">The composite membrane for paint containing Anatase type titanium oxide of the present invention, A liquid (peroxotitanic acid solution) is manufactured from titanium materials and hydrogen peroxide solution, The precious metals are added to the Anatase type titanium oxide dispersion liquid which heated and manufactured A liquid by 70 thru/or 200 degreeC to make B liquid, The interior side was made to apply and dry A liquid, and also B liquid was able to be applied and dried, and it could manufacture easily and cheaply, and was also able to manufacture the heating temperature of A liquid at low temperature farther than a sol-gel method and the titanium oxide applying method.</p><p num="0033">A substrate is water and the photocatalyst composite membrane of the present invention also manufactures under coat liquid and photocatalyst liquid below by the boiling point of water, and since under coat liquid carries out application dryness one by one, and it can form photocatalyst liquid, it has the feature that manufacture is easy.</p><p num="0034">The titanium oxide layer of the amorphous nature formed by drying after applying A liquid of the present invention, While forming the good high-density film of various bases, film formation nature, and adhesiveness, The Anatase type titanium oxide layer formed from Anatase type titanium oxide dispersion liquid (B liquid) has good adhesiveness, and compensated adhesive shortage of a Anatase type titanium oxide layer, and the operation of the good undercoat layer to the active oxygen generated by the photocatalytic reaction was shown.</p><p num="0035">The photocatalyst composite membrane of the present invention has a powerful photocatalyst operation, and has a photocatalyst operation also by indoor light again. A photochemistry active catalyst function is shown in response to irradiation of light, generate active oxygen, and it has a self-consecration operation, antibacterial properties, anti-mold, and antiviral activity, and a deodorization operation and formaldehyde disintegration are shown.</p><p num="0036">The Anatase type titanium oxide layer which according to a first embodiment of the present invention added and applied the precious metals to B liquid, and dried and formed them in it, Even if it is visible light and weak light, while a photochemistry active catalyst function is shown in response to irradiation of light, generating active oxygen and having a strong self-consecration operation, strong antibacterial properties, anti-mold, and antiviral activity, A deodorization operation and formaldehyde disintegration were shown, and also in the dark place, strong antibacterial properties, anti-mold, and antiviral activity were shown, and the contained precious metals compensated the weak point of the photocatalyst in which activity is not shown, and showed the feature outstanding as a composite membrane for paint for interiors in the dark place.</p><p num="0037">To the undercoat layer of the amorphous titanium oxide which was excellent in film strength and adhesiveness according to a second embodiment of the present invention, The intensity of a photocatalyst layer and abrasion resistance improved, and by having blended the strengthening particles whose average particle diameter is 5~500 micrometers and whose Mohs hardness is five or more, having formed the crevice among strengthening particles, and having protected the photocatalyst layer showed the feature outstanding as a composite membrane for paint for the exterior. The intensity of a photocatalyst layer and abrasion resistance improved further by adding amorphous titanium oxide to a photocatalyst layer.</p>
0038<figref num="1">It is a schematic cross section of the photocatalyst composite membrane of the present invention, (a) is a figure immediately after the application of a photocatalyst composite membrane, and (b) is a figure showing the state where a part of convex part of the photocatalyst composite membrane wore out and exfoliated.</figref><figref num="2">It is a top view showing the state of Drawing 1 (b).</figref>
0039Below, a composite membrane for paint containing Anatase type titanium oxide concerning the embodiment of the present invention and a manufacturing method for the same are explained in detail. The composite membrane for paint containing Anatase type titanium oxide of the [composite membrane for paint] present invention, Let peroxotitanic acid solution be A liquid, and let the Anatase type titanium oxide dispersion liquid which heated and manufactured A liquid by 70 thru/or 200 degreeC be B liquid, It has a stage which apply A liquid to a substrate, dry it, make the good undercoat layer of membrane formation nature and adhesiveness form, and a substrate and a photocatalyst layer are pasted up, and protects a substrate from active oxygen, and a photocatalyst layer which applies and dries B liquid on an undercoat layer, and carries out Anatase type titanium oxide content.
0040(Manufacture of peroxotitanic acid solution) If there is no trouble in operation of the present invention, what was manufactured by which method can be used for the peroxotitanic acid solution used as A liquid by the present invention. Water hydrogen oxide water more superfluous than reaction this quantity is added to titanium materials content solution as indicated in patent documents 5, subsequently -- if neglect the yellow solution obtained by adding an ammonia solution and neutralizing, settle peroxotitanic acid salt, Filter and wash precipitation, water is made suspended and hydrogen peroxide solution is added -- yellow -- transparent peroxotitanic acid solution (A liquid) is obtained. It is applied and dried A liquid forms the amorphous solid which has the Pell oxo group.
0041The titanium hydroxide gel which made titanium materials content solution add and generate an alkali component can be used as indicated in patent documents 6. Fully washing is preferred until the substance used for precipitation formation is no longer detected here. If the substance used for precipitation formation remains, condensation of gradual Anatase type titanium oxide dispersion liquid will take place at the manufactured peroxotitanic acid solution (A liquid) and the time, The size of the titanium oxide particles of the generated Anatase type titanium oxide dispersion liquid may become large, an ointment may become unstable, and adhesion nature or density may be inferior. If hydrogen peroxide solution is added to the obtained titanium hydroxide gel and is made to react to it overnight, peroxotitanic acid solution (A liquid) of a yellow viscous liquid object will be obtained. In addition, the manufacturing method of various peroxotitanic acid solution (A liquid) is indicated in patent documents 7.
0042As for the concentration of peroxotitanic acid solution (A liquid), when the weight of A liquid is 100 weight sections, it is preferred that the weight which converted peroxotitanic acid into titanium oxide is 0.1 thru/or 10 weight sections. The content converted into the titanium oxide weight of peroxotitanic acid may be unable to form the undercoat layer of thickness sufficient in 0.1 weight section or less, in 10 weight sections or more, the viscosity of peroxotitanic acid solution may increase and handling may become difficult.
0043If it hardens by drying after applying peroxotitanic acid solution (A liquid), a peroxy titanic acid layer will be obtained. However, as for peroxy titanic acid (titanium peroxide acid), according to chemicals great dictionary 2 (KYORITSU SHUPPAN Co., Ltd., Showa 38 issue), "molecular formula is TiO.<sub>3</sub>3H<sub>2</sub>It is O, and when it heats, it is" thing which emits oxygen and water and changes to titanium oxide. Peroxy titanic acid is an unstable compound, also in normal temperature, emits oxygen and water temporally, and actually changes to amorphous titanium oxide. In the actual type of usage, the composite membrane for interiors concerning the invention in this application is also not a peroxy titanic acid layer but a titanium oxide layer of amorphous nature.
0044(Manufacture of Anatase type titanium oxide dispersion liquid) Peroxotitanic acid solution (A liquid) is set to 70degreeC thru/or 200 degreeC, It is preferred to carry out heat-treatment for 5 thru/or 20 hours by 90degreeC thru/or less than 100 degreeC as most desirable example for 3 thru/or 30 hours by 1 hour thru/or 40 hours, preferably 80 thru/or 120 degreeC, and to manufacture Anatase type titanium oxide dispersion liquid. Even if heating temperature requires time for a reaction too much and heats undesirably below by 70 degreeC more than 200 degreeC, a reaction becomes quick too much, control becomes difficult, and there is no effect of balancing it only by a device becoming large-scale. The X ray analysis spectrum of the film which applies the liquid which heat-treated peroxotitanic acid solution, solidified, and was formed has a peak based on Anatase type titanium oxide as indicated in patent documents 5 and 6.
0045A 1st embodiment of the [1st embodiment] present invention is related with the composite membrane for interiors containing the precious metals and Anatase type titanium oxide. Here, especially if interiors are the equipment and the member provided in the inside of the building, it will not be restricted, but a wall, a ceiling, a floor, a door, a partition, furniture, a light, a kitchen counter, a bathroom, a rest room, etc. can be included, for example.
0046Since many materials which beautiful is required more and are easy to receive invasion of active oxygen are used although the interior of a building is not generally put to severe open air conditions like the exterior and the intensity of a coat is not required so much, the measure is required. Since the quantity of the visible light which ultraviolet rays do not enter substantially but receives them also has few insides of a building than the exterior, the Anatase type titanium oxide composite membrane which has activity higher than the conventional photocatalyst is required. As a contaminant which should be processed by interior, there are smoke of a bad smell, formaldehyde, and a cigarette other than the usual contaminant, etc., and antibacterial activity, especially the strong antibacterial activity in a dark place are required.
0047For this reason, the composite membrane for interiors containing Anatase type titanium oxide of the present invention, Peroxotitanic acid solution is used as A liquid, and the precious metals are added to the Anatase type titanium oxide dispersion liquid which heated and manufactured A liquid by 70 thru/or 200 degreeC to make B liquid, Make the substrate of an interior side apply and dry A liquid, make the good undercoat layer of membrane formation nature and adhesiveness form, and a substrate and a photocatalyst layer are pasted up, and a substrate is protected from active oxygen, Apply B liquid on it, it was made to dry, and the composite membrane for interiors which contains Anatase type titanium oxide and the precious metals, and has a photocatalyst operation and a bactericidal action was formed.
0048A 1st embodiment of the present invention adds the salt or nanocolloid of the precious metals to Anatase type titanium oxide dispersion liquid, and is taken as B liquid. As for the precious metals to be used, it is preferred that one or more [ of the groups chosen from copper, silver, gold, and platinum ] is included, and they can mention a silver salt and platinum salts as a more desirable example. These precious metals show powerful antibacterial properties, anti-mold, and antiviral activity.
0049(Manufacture of peroxotitanic acid solution) If there is no trouble in operation of the present invention, what was manufactured by which method can be used for the peroxotitanic acid solution used as A liquid by the present invention. Water hydrogen oxide water more superfluous than reaction this quantity is added to titanium materials content solution as indicated in patent documents 5, subsequently -- if neglect the yellow solution obtained by adding an ammonia solution and neutralizing, settle peroxotitanic acid salt, Filter and wash precipitation, water is made suspended and hydrogen peroxide solution is added -- yellow -- transparent peroxotitanic acid solution (A liquid) is obtained. It is applied and dried A liquid forms the amorphous solid which has the Pell oxo group.
0050It can fully wash and can use the titanium hydroxide gel which made titanium materials content solution add and generate an alkali component until the substance used for precipitation formation is no longer detected, as indicated in patent documents 6. If the substance used for precipitation formation remains, condensation of gradual Anatase type titanium oxide dispersion liquid will take place at the manufactured peroxotitanic acid solution (A liquid) and the time, There was a case where the size of the titanium oxide particles of the generated Anatase type titanium oxide dispersion liquid became large, an ointment became unstable, and adhesion nature or density was inferior. If hydrogen peroxide solution is added to the obtained titanium hydroxide gel and is made to react to it overnight, peroxotitanic acid solution (A liquid) of a yellow viscous liquid object will be obtained. In addition, the manufacturing method of various peroxotitanic acid solution (A liquid) is indicated in patent documents 7.
0051As for the concentration of peroxotitanic acid solution (A liquid), when the weight of A liquid is 100 weight sections, it is preferred that the weight which converted peroxotitanic acid into titanium oxide is 0.1 thru/or 10 weight sections. The content converted into the titanium oxide weight of peroxotitanic acid may be unable to form the under coat film of thickness sufficient in 0.1 weight section or less, in 10 weight sections or more, the viscosity of peroxotitanic acid solution may increase and handling may become difficult.
0052(Manufacture of Anatase type titanium oxide dispersion liquid) Peroxotitanic acid solution (A liquid) is set to 70degreeC thru/or 200 degreeC, Heat-treatment for 5 thru/or 20 hours can be carried out by 90degreeC thru/or less than 100 degreeC as most desirable example for 3 thru/or 30 hours by 40 hours thru/or 2 hours, preferably 80 thru/or 120 degreeC, and Anatase type titanium oxide dispersion liquid can be manufactured. Heating temperature requires time for a reaction too much, and is not preferred at below 70 degreeC. Even if it heats more than 200 degreeC, a reaction becomes quick too much, control becomes difficult, and there is no effect of balancing it only by a device becoming large-scale. The X ray analysis spectrum of the film which applies the liquid which heat-treated peroxotitanic acid solution, solidified, and was formed has a peak based on Anatase type titanium oxide as indicated in patent documents 5 and 6.
0053(Salt of the precious metals, or addition of nanocolloid) The present invention adds the salt or nanocolloid of the precious metals to Anatase type titanium oxide dispersion liquid, and uses it as B liquid. As for the precious metals to be used, it is preferred that one or more [ of the groups chosen from copper, silver, gold, and platinum ] is included, and they can mention a silver salt and platinum salts as a more desirable example. These precious metals show powerful antibacterial properties, anti-mold, and antiviral activity.
0054Although the negative ion of the precious-metals salt which makes the precious metals a positive ion can illustrate chloride salt, a nitrate, perchloric acid salt, sulfate, an phosphate, tetra-Fluorophore acid chloride, and Hexafluoroline acid chloride as salt of strong acid and acetate, formate, and carbonate can be illustrated as salt of weak acid, It is not limited to these. As platinum salts, hexachloroplatinic acid, tetra-chloro platinic acid, and those salts can be included. If precious-metals nanocolloid is a possible thing, it can use a publicly known thing for the object of the present invention.
0055As for the concentration of Anatase type titanium oxide in B liquid, when the weight of B liquid is 100 weight sections, it is preferred that the weight of titanium oxide is 0.1 thru/or 10 weight sections. The weight of titanium oxide becomes difficult to form the photocatalyst film of thickness sufficient in 0.1 weight section or less, in 10 weight sections or more, the viscosity of Anatase type titanium oxide may increase and handling may become difficult.
0056The salt of the precious metals in B liquid or the concentration of nanocolloid is 1x10, when the salt of the precious metals or the weight of nanocolloid is converted into metaled weight and the weight of B liquid is 100 weight sections.<sup>-4</sup>Or 1x10<sup>-9</sup>It is preferred that it is within the limits of a weight section. The quantity of the precious metals is 1x10.<sup>-9</sup>Antibacterial activity sufficient in the concentration below a weight section may be unable to be shown, and it is 1x10.<sup>-4</sup>Even if it adds above, an effect is not enhanced compared with the applied quantity. Here, the salt of the precious metals or the content of nanocolloid is 1x10, when the salt of the precious metals or the weight of nanocolloid is converted into metaled weight and the weight of the above-mentioned Anatase type titanium oxide is 100 weight sections.<sup>-1</sup>Or 1x10<sup>-8</sup>It is within the limits of a weight section.
0057(Process which applies peroxotitanic acid solution (A liquid) and it dries) As long as the coating method of the process which applies peroxotitanic acid solution (A liquid) and it dries meets the object of the present invention, which method may be sufficient as it. Especially the amount of applications is 1.0 thru/or 100ml/m, although not restricted.<sup>2</sup>It comes out and a certain thing is made. 1.0ml/m<sup>2</sup>Below the thickness of a peroxotitanic acid film may become insufficient, and it is 100ml/m.<sup>2</sup>Since an effect does not increase even if it applies thickly above, it is disadvantageous. It can also perform performing an application at once in two or more steps. It is preferred that drying temperature carries out below, for example by 40 degreeC since peroxotitanic acid changes to a Anatase type crystal above 70 degreeC.
0058As long as the coating method of the process which applies B liquid and it dries meets the object of the present invention, which method may be sufficient as it. Especially the amount of applications is 1.0 thru/or 100ml/m, although not restricted.<sup>2</sup>It comes out and a certain thing is made. 1.0ml/m<sup>2</sup>The below of the thickness of a Anatase type titanium oxide film is sometimes insufficient as an inner wall, and it is 100ml/m.<sup>2</sup>Since an effect does not increase even if it applies thickly above, it is disadvantageous. It can also perform performing an application at once in two or more steps. It is preferred to perform dryness below by 60 degreeC.
0059As for the ratio of A liquid to B liquid, it is preferred that the ratio of the titanic acid weight which converted into the weight of titanium oxide the weight of the peroxotitanic acid which A liquid contains, and the titanic acid weight which the above-mentioned B liquid contains to , is within the limits of 10:1 thru/or 1:10, and it is more preferred that it is within the limits of 4:1 thru/or 1:4. B liquid may be unable to show activity with a Anatase type titanium oxide film sufficient as a photoactive catalyst or less [ of A liquid ] by 1/10, and A liquid is or less [ of B liquid ] in 1/10, The peroxotitanic acid film may be unable to show sufficient coating operation to the active oxygen which a Anatase type titanium oxide film generates, and may be unable to show the feature as a composite membrane.
0060Even if the [2nd embodiment] artificer is a trial product of Photocatalytic equipment with the insufficient intensity and adhesion nature of an examination developmental stage in the durability test process of a trial product, The photocatalyst layer applied on the substrate which has a rough side, It found out having the abrasion resistance which was intentionally superior to the photocatalyst layer applied to the smooth field, the hint was obtained to this, and when the photocatalyst composite membrane which has an undercoat layer which has a rough side was made as an experiment, it found out having the effect that abrasion resistance increases beyond anticipation.
0061Drawing 1 is a schematic cross section of a photocatalyst composite membrane of the present invention, and (a) is a figure immediately after an application of a photocatalyst composite membrane. (b) is a figure showing the state where a part of convex part of a photocatalyst composite membrane wore out and exfoliated, and Drawing 2 is a top view showing a state of Drawing 1 (b). On substrate 6, as shown in Drawing 1 (a), after carrying out application dryness of the undercoat layer 2 containing strengthening particles 3, photocatalyst composite membrane 10 of the present invention carries out application dryness of the photocatalyst layer 1, and is formed.
0062Photocatalyst composite membrane 10 is a thin film, and if the wear advances, as shown in Drawing 1 (b), a part of photocatalyst layer 1 of the top part of convex part 4 will be worn out, and it will turn into photocatalyst composite membrane 20 in which undercoat layer 2 was exposed to and exposed part 7 was formed. However, as shown in Drawing 2, the rate of the area of exposed part 7 of photocatalyst composite membrane 20 is small, and since active oxygen is diffused and moved, it is presumed that the contaminant of exposed part 7 may also be disassembled.
0063Since convex part 4 formed from hard particles and amorphous titanium oxide will protect Anatase type titanium oxide of crevice 5 if an applicant will be in the state which shows in Drawing 1 (b), That for which advance of wear of photocatalyst composite membrane 20 beyond it is delayed was presumed, strengthening particles 3 were blended with undercoat layer 2, and it thought out to form a rough side in undercoat layer 2, and completed the present invention. Usually, in order to form the undercoat layer which has a rough side, it is necessary to make it newly increase one process but, and since what is necessary is just to already have undercoat layer 2 and to add strengthening particles 3, when it is the present invention, there is an advantage of not needing the increase in the number of processes.
0064Below, a photocatalyst composite membrane concerning a second embodiment and a manufacturing method for the same are explained. Photocatalyst composite membrane 10 of the present invention has undercoat layer 2 containing amorphous titanium oxide and strengthening particles 3 and photocatalyst layer 1 containing the Anatase type titanium oxide applied on undercoat layer 2.
0065A mean particle size (JIS Z 8901:2006 3.1) of strengthening particles 3 used by the present invention is 5~500 micrometers. Or more by five, if Mohs hardness can form a rough side in undercoat layer 2, it can use any particle. Although it can illustrate that it is one or more [ of an in / the natural mineral containing feldspar and a silica stone, silica gel, alumina, or inorganic powder including Chita Near ] as an example of the strengthening particles which can be used preferably, the strengthening particles of the present invention are not limited to this. The shape of strengthening particles will not be limited especially if it is a thing of the shape which can form a rough side in undercoat layer 2, but any particle of shape can be used for it.
0066As for the size of strengthening particles 3, it is preferred that a mean particle size is a range which is 5~500 micrometers, it is more preferred that it is 10~300 micrometers, and it is most preferred that it is 15~200 micrometers. It may become difficult, as for the particles to which the particles below 5 micrometers have too small [ to fully protect photocatalyst layer 1 but ] a size of convex part 4 formed, and a mean particle size exceeds 500 micrometers, for a mean particle size to adhere to substrate 6 by undercoat layer 2, and strengthening particles 3 may exfoliate. When the mass of the amorphous titanium oxide which forms undercoat layer 2 is 100 mass parts, as for the content of strengthening particles 3, it is preferred that the mass of strengthening particles 3 is 1~100 mass parts, it is more preferred that it is 2~50 mass parts, and it is most preferred that it is 5~20 mass parts. If mass of strengthening particles 3 cannot form convex part 4 sufficient in less than 1 mass part but exceeds 100 mass parts, the area of the crevice protected becomes small and is not preferred.
0067Since the photocatalyst composite membrane of the present invention is a thin film formed in the rough side, it is difficult to real-measure the film thickness and the amount of applications of a coat. Therefore, titanium oxide which applied the amount of applications to the substrate of a unit area in the example of the present invention (SiO)<sub>2</sub>Mass of the calculation as molar mass 80, or mass of the peroxotitanic acid converted into the mass of titanium oxide (henceforth, "conversion SiO)<sub>2</sub>It shall be based on describing it as mass", and shall calculate.
0068Conversion SiO applied to undercoat layer 2 of the present invention<sub>2</sub>Mass is 0.1~100g/m.<sup>2</sup>It comes out, a certain thing is preferred, and it is 0.2~50g/m.<sup>2</sup>It comes out, a certain thing is more preferred, and it is 0.5~20g/m.<sup>2</sup>It comes out and a certain thing is the most preferred. The above-mentioned conversion SiO of undercoat layer 2<sub>2</sub>Mass is 0.1g/m.<sup>2</sup>The shield mechanism of adhesion nature sufficient in the following and/or active oxygen cannot be exhibited, but it is 100g/m.<sup>2</sup>Beyond -- even if it thickens, since the increase in the shield mechanism of the adhesion nature beyond it and/or active oxygen is not accepted, it is not economically preferred.
0069The amount of applications of photocatalyst layer 1 of the present invention is 0.1~50g/m as titanium oxide.<sup>2</sup>It comes out, a certain thing is preferred, and it is 0.2~20g/m.<sup>2</sup>It comes out, a certain thing is more preferred, and it is 1~10g/m.<sup>2</sup>It comes out and a certain thing is the most preferred. The amount of applications of photocatalyst layer 1 is 0.1g/m.<sup>2</sup>When it is the following, sufficient photocatalyst activity may be unable to be shown, and it may wear out easily. The amount of applications of photocatalyst layer 1 is 50g/m.<sup>2</sup>Even if it carries out a Beyond application, since there are few photocatalyst activities and increases in strong, they are not economically preferred.
0070The present invention can blend amorphous titanium oxide with photocatalyst layer 1 further, and can make the intensity of photocatalyst composite membrane 10 increase. When the amount of applications of photocatalyst layer 1 in other examples is totaled with the mass of amorphous titanium oxide, and the mass of Anatase type titanium oxide (following and "conversion sum total SiO)<sub>2</sub>It is 0.1~50g/m for describing it as mass."<sup>2</sup>It comes out, a certain thing is preferred, and it is 0.2~20g/m.<sup>2</sup>It comes out, a certain thing is more preferred, and it is 1~10g/m.<sup>2</sup>It comes out and a certain thing is the most preferred. "Conversion sum total SiO<sub>2</sub>Mass" is 0.1g/m.<sup>2</sup>When it is the following, sufficient photocatalyst activity cannot be shown, and it may wear out easily, and is 50g/m.<sup>2</sup>Since Beyond also has few photocatalyst activities and increases in strong, it is not economically desirable. As for the mass of the Anatase type titanium oxide which photocatalyst liquid contains, and the mass ratio with amorphous titanium oxide, it is preferred that it is the range of 1:0~1:2 (however, 0 removes), it is more preferred that it is 4:1~2:3, and it is most preferred that it is 3:2~1:1. If a mass ratio with amorphous titanium oxide to Anatase type titanium oxide exceeds 1:2, the photocatalyst activity of a photocatalyst composite membrane falls and it is not desirable.
0071Since a present invention article does not absorb visible light substantially when a present invention article is applied to the outer wall surface which has gloss, when the mean particle size of strengthening particles 3 contained in an undercoat layer is small, it is rare to spoil the gloss of the substrate applied to the outer wall surface. However, it comes to have a lusterless effect by diffused reflection as the mean particle size of strengthening particles 3 becomes large.
0072(Manufacturing method) Below, the manufacturing method of the photocatalyst composite membrane concerning two embodiments of the present invention is explained. Photocatalyst composite membrane 10 of a first embodiment of the present invention, The peroxotitanic acid solution manufacturing process which manufactures peroxotitanic acid solution from titanium materials, The under coat liquid manufacturing process which manufactures the under coat liquid containing peroxotitanic acid solution and strengthening particles 3, The undercoat layer formation process which makes the surface of base 6 apply and dry under coat liquid, and forms undercoat layer 2, It can have a photocatalyst liquid manufacturing process which manufactures the photocatalyst liquid which heats peroxotitanic acid solution and contains Anatase type titanium oxide dispersion liquid, and a photocatalyst layer formation process which applies photocatalyst liquid on undercoat layer 2, dries it, and forms photocatalyst layer 1. When using a photocatalyst composite membrane in a very cruel environment, peroxotitanic acid solution can be added to Anatase type titanium oxide dispersion liquid, and photocatalyst layer 1 can further be strengthened to them.
0073It is the same as the first example of a <peroxotitanic acid solution manufacturing process>.
0074Average particle diameter is 5~500 micrometers, and Mohs hardness adds strengthening particles 3 which are five or more in <under coat liquid manufacturing process> peroxotitanic acid solution, and it manufactures under coat liquid in it. When the mass of peroxotitanic acid solution is 100 mass parts, as for the quantity of strengthening particles 3 contained in under coat liquid, it is preferred that it is 0.01~20 mass parts, and it is more preferred that it is 0.02~10 mass parts. When the content of strengthening particles 3 is less than 0.01 mass part, When the field which has sufficient coarseness for undercoat layer 2 cannot be formed but 20 mass parts is exceeded, It becomes difficult for the mobility of under coat liquid to fall and apply, or the content of strengthening particles 3 increases too much relatively, and the intensity of undercoat layer 2 may fall.
0075<Undercoat layer formation process> under coat liquid is applied in the specified quantity, and an undercoat layer is formed. Although the layer of peroxotitanic acid is formed, an undercoat layer emits oxygen and water temporally and changes to the layer of amorphous titanium oxide at the beginning. As long as it meets the object of the present invention, which method may be sufficient as the method of applying under coat liquid, and it may be applied at once or two coats of it may be given in two or more steps. As for drying temperature, since peroxotitanic acid may change to a Anatase type crystal gradually above 70 degreeC and intensity and adhesion nature may fall, it is preferred to carry out below by 40 degreeC.
0076The peroxotitanic acid in which under coat liquid contains the amount of applications of under coat liquid "conversion SiO<sub>2</sub>Mass" is 0.1~500g/m.<sup>2</sup>It is preferred for it to be alike, and to apply so that it may become. "Conversion SiO<sub>2</sub>Mass" is 0.1g/m.<sup>2</sup>Undercoat layer 2 of sufficient thickness cannot be formed, and adhesive strength with photocatalyst layer 1 cannot fully be strengthened with the following, and active oxygen may fully be unable to be intercepted from substrate 6 generated with the photocatalyst. "conversion SiO<sub>2</sub>Mass" is 500g/m.<sup>2</sup>Even if it applies the quantity to exceed, since there are few increases in an effect as compared with the expense and the labor which are taken to apply increasing, it is not desirable.
0077<Photocatalyst liquid manufacturing process> peroxotitanic acid solution is set to 70 degreeC~200-degreeC, The photocatalyst liquid which carries out heat-treatment for 1~20 hours by less than 90 degrees C~100 degreeC as most desirable example by 0.2~40 hours, preferably 80~120 degreeC for 1~30 hours, and contains Anatase type titanium oxide dispersion liquid can be manufactured. Heating temperature requires time for a reaction too much, and is not preferred at less than 70 degreeC. Even if it exceeds and heats 200 degreeC, a reaction becomes quick too much, control becomes difficult, and a high pressure cooker etc. are needed and the effect of balancing it only by a device becoming large-scale may not be acquired.
0078When the mass of photocatalyst liquid is 100 mass parts, as for the Anatase type titanium oxide concentration of photocatalyst liquid, it is preferred that the mass of titanium oxide is 0.1~20 mass parts, and it is more preferred that it is 0.5~10 mass parts. When the mass of titanium oxide becomes difficult to form the photocatalyst film of thickness sufficient in less than 0.1 mass part and exceeds 20 mass parts, the viscosity of Anatase type titanium oxide may increase and handling may become difficult. The X ray diffraction spectrum of the film which applies the liquid which heat-treated peroxotitanic acid solution, solidified, and was formed has a peak based on Anatase type titanium oxide the same with being indicated in patent documents 1 and 2.
0079<Photocatalyst layer formation process> photocatalyst liquid is applied on an undercoat layer, is dried, and a photocatalyst layer is formed. As long as a coating method meets the object of the present invention, which method may be sufficient as it. It can also perform performing an application at once in two or more steps. Although a drying method in particular is not restricted, it is preferred to carry out below by 60 degreeC. As for the amount of applications of photocatalyst layer 1 of the present invention, the quantity of Anatase type titanium oxide is 0.1~250g/m.<sup>2</sup>It comes out and a certain thing is preferred. The amount of applications of photocatalyst layer 1 is 0.1g/m.<sup>2</sup>In the following, the photocatalyst layer of sufficient thickness may be unable to be formed, and it is 250g/m.<sup>2</sup>Even if it carries out a Beyond application, since there are few photocatalyst activities and increases in strong as compared with the expense and the labor which are taken to apply increasing, it is not desirable.
0080Photocatalyst layer 1 of the present invention can contain amorphous titanium oxide further. Photocatalyst Solution of other embodiments is "conversion SiO of the mass of Anatase type titanium oxide, and peroxotitanic acid, when the mass of photocatalyst solution is 100 mass parts.<sub>2</sub>It is preferred that the sum total mass of mass" is 0.1~20 mass parts, and it is more preferred that it is 0.5~5 mass parts. When the undercoat layer of thickness sufficient when the above-mentioned sum total mass is less than 0.1 mass part may be unable to be formed and it exceeds 20 mass parts, the viscosity of photocatalyst liquid may increase and handling may become difficult.
0081The amount of applications of catalyst bed 1 in this embodiment, "conversion sum total SiO<sub>2</sub>Mass" is 0.1~250g/m.<sup>2</sup>It comes out and a certain thing is preferred. "Conversion sum total SiO<sub>2</sub>Mass" is 0.1g/m.<sup>2</sup>In the following, the photocatalyst layer of sufficient thickness may be unable to be formed, and it is 250g/m.<sup>2</sup>Even if it carries out a Beyond application, since there are few photocatalyst activities and increases in strong as compared with the expense and the labor which are taken to apply increasing, it is not desirable. The mass of the Anatase type titanium oxide which photocatalyst liquid contains and peroxotitanic acid "conversion SiO<sub>2</sub>As for the ratio of mass" to ,, it is preferred that it is the range of 1:0~1:2, it is more preferred that it is 4:1~2:3, and it is most preferred that it is 3:2~1:1.
<p num="0082">Below an example is shown and the present invention is explained to it in detail. [Example 1] Manufacture of the <1st process> peroxotitanic acid solution (A liquid) An ammonia solution and 440 ml were dropped at the solution which set 39.6 ml of 60% (weight/capacity) solution of titanium tetrachloride to 4000 ml with distilled water 2.5% (weight/capacity), and titanium hydroxide was settled. The sediment was Filter(ed), and 30% (weight/capacity) of hydrogen peroxide solution and 80 ml were added and agitated after washing with distilled water to the titanium hydroxide suspension for which distilled water was added to make 720 ml. In 7 degreeC, neglected it for 24 hours, excessive hydrogen peroxide solution was made to decompose, and 1000 ml of yellow viscosity fluids were obtained.</p><p num="0083"><the 2nd process> -- manufacture of B liquid the place which sealed the peroxotitanic acid solution obtained at the first process to the resisting pressure glass container, and was boiled in bathing for 12 hours (98~100degreeC) -- light yellow -- 1.00% (weight/capacity) of translucent Anatase type titanium oxide dispersion liquid generated. 0.1 ml of silver nitrate solution which contains 0.1% (weight/capacity) of silver as metal silver is added to 1.00% (weight/capacity) of Anatase type titanium oxide dispersion liquid [ 100 ml of ], and it is 1x10.<sup>-6</sup>% (Weight/capacity) B liquid containing the silver agitated and mixed was created.</p><p num="0084">The <3rd process> Process which applies peroxotitanic acid solution (A liquid) to an interior side, and it dries An injection spray is used for the peroxotitanic acid solution (A liquid) manufactured at the 1st process, and it is 10ml/m on slide glass.<sup>2</sup>The peroxotitanic acid layer was manufactured by applying in the amount of of and drying by 25 degreeC.</p><p num="0085">The [4th process] Process which applies B liquid and it dries It is 10ml/m about B liquid manufactured at the 2nd process on the slide glass board which applied A liquid manufactured at the 3rd process, and was dried.<sup>2</sup>The sample which applied the composite membrane for interiors containing Anatase type titanium oxide concerning a first embodiment of Example 1 was obtained by applying in the amount of of and drying by 40 degreeC.</p><p num="0086">[Example 2] 60% (weight/capacity) of manufacture titanium tetrachloride solution of <1st process> A liquid, adding hydrogen peroxide solution and 20 ml to the solution which diluted 5.00 ml with distilled water to 500 ml 30% (weight/capacity), agitating, producing a brown transparent fluid, and an ammonia solution (dark Ammoquia water 1 capacity part: water 9 capacity part) being dropped at this solution 10%, and setting pH to seven -- yellow -- transparent solution was produced. The obtained solution was neglected by 25 degreeC one whole day and night, and the yellow precipitation sediment was made to generate. This is Filter(ed), distilled water is added after washing to make about 150 ml for it, and it is cationic exchange resin (Amberlite IR-120B). It throws in H type and 25g of anion exchange resin (Amberlite IRA-410, OH type) at a time, respectively, and they are neglected for 30 minutes, After filtering and removing ion-exchange resin, A liquid of a transparent yellow fluid and 200 ml were obtained 1 hour afterward by being referred to as about 180 ml with distilled water, cooling with ice water, adding hydrogen peroxide solution and 20 ml 30% (weight/capacity), and cooling. The 2nd process~4th process obtained the sample which applied the composite membrane for interiors which carries out like Example 1 and contains Anatase type titanium oxide of Example 2.</p><p num="0087">[Example 3] Manufacture of <1st process> A liquid A liquid was obtained like Example 1. <the 2nd process> -- the place which sealed hermetically the peroxotitanic acid solution obtained at the first process of manufacture of B liquid in the resisting pressure glass container, and was boiled in bathing for 12 hours (98~100degreeC) -- light yellow -- 1.00% (weight/capacity) of translucent Anatase type titanium oxide dispersion liquid were obtained. 0.1 ml of solution which contains 0.001% (weight/capacity) of platinum nanocolloid (see the patent documents 8) as metal platinum is added to 1.00% (weight/capacity) of Anatase type titanium oxide dispersion liquid [ 100 ml of ], and it is 1x10.<sup>-8</sup>1.00% (weight/capacity) of B liquid containing the platinum nanocolloid of a weight section (weight/capacity) was created. The 3rd process and the 4th process obtained the sample which applied the composite membrane for interiors which carries out like Example 1 and contains Anatase type titanium oxide of Example 3.</p><p num="0088">About B liquid obtained at the 2nd process of [comparative example 1] example 1, it is 10ml/m on slide glass.<sup>2</sup>The sample which the Anatase type titanium oxide composite layer of comparative example 1 applied was obtained by applying the amount of of, and drying and heat-treating by 40 degreeC.</p><p num="0089">About the peroxotitanic acid solution (A liquid) obtained at the 1st process of [comparative example 2] example 1, it is 10ml/m on slide glass.<sup>2</sup>The sample which applied the comparative example 2 Anatase type titanium oxide composite membrane was obtained by applying the amount of of and drying by 40 degreeC.</p><p num="0090">The sample which applied the Anatase type titanium oxide composite membrane like [comparative example 3] example 1 without adding silver nitrate at the 2nd process was obtained.</p><p num="0091">[Example 4] Manufacture of <1st process> under coat liquid An ammonia solution and 440 ml were dropped at the solution which set 39.6 ml of 60% (mass/capacity) solution of titanium tetrachloride to 4000 ml with distilled water 2.5% (mass/capacity), and titanium hydroxide was settled. The sediment was Filter(ed), and 30% (mass/capacity) of hydrogen peroxide solution and 80 ml were added and agitated after washing with distilled water to the titanium hydroxide suspension for which distilled water was added to make 720 ml. It was neglected in 7 degreeC for 24 hours, water was added for excessive hydrogen peroxide solution after decomposition Sata, and 1.00 kg of peroxotitanic acid solution of the yellow viscosity fluid was obtained. The "conversion titanic acid mass" of the peroxotitanic acid in 100 mass parts of peroxotitanic acid solution is 1.00 mass parts. In 100 mass parts of this peroxotitanic acid solution, the mean particle size added and agitated 0.1 mass part of powder of the silica stone which is 20 micrometers, and obtained under coat liquid in it.</p><p num="0092">The <2nd process> Manufacturing process of an undercoat layer An injection spray is used, agitating the under coat liquid manufactured at the 1st process, and it is 20g/m on a melamine coated plywood board.<sup>2</sup>The undercoat layer which has a rough side was manufactured by applying in the amount of of and drying by 25 degreeC. The mass of the silica stone when the "conversion titanic acid mass" of the peroxotitanic acid in an undercoat layer is 100 mass parts was 10 mass parts.</p><p num="0093"><the 3rd process> -- manufacturing process of photocatalyst liquid the place which sealed the peroxotitanic acid solution obtained at the first process to the resisting pressure glass container, and was boiled in bathing for 12 hours (98~100degreeC) -- light yellow -- translucent photocatalyst liquid was obtained. When the mass of photocatalyst liquid was 100 mass parts, the mass of Anatase type titanium oxide was 1.0 mass part.</p><p num="0094">The <4th process> Photocatalyst composite membrane manufacturing process It is 10ml/m on the undercoat layer which obtained the photocatalyst liquid manufactured at the 3rd process at the 2nd process.<sup>2</sup>The sample of Example 1 which applied the photocatalyst composite membrane containing Anatase type titanium oxide of Example 1 was obtained by applying in the amount of of and drying by 40 degreeC. The amount of applications of Anatase type titanium oxide of the photocatalyst layer of the manufactured sample is 1.0g/m.<sup>2</sup>It comes out.</p><p num="0095">They are the under coat liquid obtained at the 1st process of Example 1 in the 4th process, and the optical medium obtained at the 3rd process like [Example 5] example 1 (mass and mass of strengthening particles 3) 1:1 since it is little -- having ignored -- it mixed, and it applied on the under coat obtained at the 2nd process, it dried, and manufactured the photocatalyst composite membrane of Example 2.</p><p num="0096">Like [comparative example 4] example 1, the photocatalyst composite membrane of comparative example 1 which does not have a rough side was manufactured without adding strengthening particles to an undercoat layer. Like [comparative example 5] example 5, although it did not have a rough side, the photocatalyst composite membrane of comparative example 2 which contains amorphous titanium oxide in a photocatalyst layer was manufactured, without adding strengthening particles to an undercoat layer.</p><p num="0097">On [comparative example 6] melamine coated plywood board, it is 10ml/m.<sup>2</sup>Only Photocatalyst liquid was applied and it dried. On [comparative example 7] melamine coated plywood board, only under coat liquid was applied and dried and the undercoat layer was formed.</p><p num="0098">[Example 1 of an examination] Nitric oxide removal examination Sample : Specimen of Example 1~3 and comparative examples 1 and 2, And piece of glass Test method: JIS R 1701-1:2004, fine-ceramics photocatalyst material Air-cleaning performance-testing-method-part I: Removal performance 6.1 of nitrogen oxide, 6.2 testing body: Incorporated company Environmental Technical Laboratory</p><p num="0099">The measurement result of the sample of Example 1~3 of a 1st embodiment and a comparative example is shown in Table 1. It was shown that Example 1~3 which has a photocatalyst layer and an undercoat layer has the outstanding nitric oxide removal operation. Although comparative example 1 has a photocatalyst layer of Anatase type titanium oxide, since membrane formation nature is not good, it is inferior to Example 1~3 in a nitric oxide removal operation. Comparative example 2 and the piece of glass which do not have a photocatalyst layer do not have a nitric oxide removal operation.<tables num="1"><img file="WO2016148108A4_D0001.tif" /></tables></p><p num="0100">The measurement result of the sample of Examples 4 and 5 of a 2nd embodiment and comparative example 4~7 is shown in Table 2. As shown in Example 4 of Table 2, the photocatalyst composite membrane of a 2nd embodiment of the present invention showed the photoactive catalyst function (NO removal operation) equivalent to the sample of only the photocatalyst layer shown in the photocatalyst composite membrane and comparative example 6 containing the amorphous type titanium oxide shown in the conventional photocatalyst composite membrane and comparative example 4 which are shown in comparative example 4. As for the photocatalyst composite membrane of the sample which contains an undercoat layer in the photocatalyst layer of Example 5 concerning other embodiments of the present invention, the fall of the photoactive catalyst function was seen.<tables num="2"><img file="WO2016148108A4_D0002.tif" /></tables></p><p num="0101">[Example 2 of an examination] Active oxygen cover examination Sample : To the piece of wood which polished the surface (10 cm x 10 cm), it is 0.1-mol methylene blue. The ethanol solution was sprayed evenly and the active oxygen cover specimen was created. The method of Example 1~3 and comparative examples 1 and 2 is followed, however it is a top instead of the piece of glass. The sample for an active oxygen cover examination is created using the active oxygen cover specimen of an account, and it is a dark place. It dried for two days by 25 degreeC. Solution diluted test method 10.1-mol methylene blue, it twice, and 4 times The applied piece of a standard color tone was created. 2) Carry out 10 cm Separation from a sample using the above-mentioned active oxygen cover specimen, glare instead of the piece of glass by a fluorescent light with an illumination of 5000 luxs, and it is change of the hue of a specimen. It observed and evaluated according to the following evaluation term. 4: 1 which became a color tone equivalent to the piece of a standard color tone diluted 2:4 times which became a color tone equivalent to the piece of a standard color tone diluted to 3:2 time without change: 0 in which blue almost disappeared : blue disappeared completely.</p><p num="0102">The measurement result of the sample of Example 1~3 of a 1st embodiment and a comparative example is shown in Table 3. Methylene blue faded quickly and, as for comparative example 1 which has a catalyst bed and does not have a under coat, it was shown that active oxygen has reached the substrate. Example 1~3 which has a catalyst bed and a under coat had a slow fading speed of methylene blue, and it was shown that the under coat has prevented invasion of active oxygen.<tables num="3"><img file="WO2016148108A4_D0003.tif" /></tables></p><p num="0103">The measurement result of the sample of Example 4~6 of a 2nd embodiment and a comparative example is shown in Table 4. Each sample of Example 4~6 showed the invasion prevention effect of outstanding active oxygen.<tables num="4"><img file="WO2016148108A4_D0004.tif" /></tables></p><p num="0104">[Example 3 of an examination] Examination [ antibacterial ] test method: Light irradiation film contact printing Sample : Specimen of Examples 1 and 3 and comparative example 3 (light condition) Testing body: The Kyoto microorganism research institute Dark-condition test-organism stock: Staphylococcus aureus NBRC-12732 In accordance with "light irradiation film contact printing of an antibacterial technical conference", the viable cell count was measured 24 hours afterward about the fungus liquid in the fungus liquid dropped on fluorescent light irradiation (550lx, 10 cm) / non-glaring specimen.</p><p num="0105">Result A result is shown in Table 5. the specimen of Example 1 containing a catalyst bed, a under coat, and the precious metals -- a light condition -- and -- Don't show [ in antibacterial activity ] under a dark condition, although it has antibacterial activity also in any under a dark condition and the specimen of comparative examples 1 and 3 which do not contain the precious metals has antibacterial activity under a light condition.<tables num="5"><img file="WO2016148108A4_D0005.tif" /></tables></p><p num="0106">[Abrasion resistant test] A melamine resin coated plywood board with a <manufacture of specimen> thickness of 1.5 mm is used as a substrate, The red photocatalyst layer which added 0.01-mass part red dyes to 100 mass parts of photocatalyst liquid at the 2nd process was manufactured like Example 1, and it pierced with the circular punching machine after an application and dryness, and presented the abrasion resistant test. (Wear-resistant measurement) Although the abrasion resistant test was done based on JIS K 5600 (wear ring method), The coat was too thin, and since measurement was not able to do the exact amount of change of mass, the number of rotations of the wear ring until the red photocatalyst layer powder discharged from the scanning portion of a wear ring stops being red in viewing was measured. It examined 10 times, the arithmetic average of measured value was performed, and that of 1 rounded off.</p><p num="0107">The abrasion resistant test and the nitric oxide removal examination were done about Examples 4 and 5 and comparative example 1~4 concerning the 2nd example of the present invention. A result is shown in Table 6.<tables num="6"><img file="WO2016148108A4_D0006.tif" /></tables></p><p num="0108">(Examination of the mean particle size of strengthening particles) Like <example 6~9>> example 1, as shown in Table 2, the mean particle size of the silica stone contained in an undercoat layer was changed, and the photocatalyst composite membrane of Example 4~6 was manufactured. Like comparative example 8 and <9>> example 1, as shown in Table 2, the mean particle size of the silica stone contained in an undercoat layer was changed, and the photocatalyst composite membrane of comparison 5 and 6 was manufactured.</p><p num="0109">The abrasion resistant test and the nitric oxide removal examination were done about Example 4, 6~9, and comparative examples 8 and 9. A result is shown in Table 7.<tables num="7"><img file="WO2016148108A4_D0007.tif" /></tables></p><p num="0110">As shown in Table 7, the mean particle size of strengthening particles cannot strengthen abrasion resistance with 1 micrometer enough like comparative example 8, but as shown in Example 4 and 6~9, the mean particle size of strengthening particles shows the significant wear-resistant strengthening operation with 5~500 micrometers. In the diameter of a particle of strengthening particles, lack of strengthening particles took place in 1000 micrometers (comparative example 9), and the wear-resistant fall took place.</p><p num="0111">(Examination of the amount of strengthening particles) Like <example 10~12>> example 1, as shown in Table 3, the quantity of the silica stone contained in an undercoat layer was changed, and the photocatalyst composite membrane of Example 7~9 was manufactured. Like comparative example 10 and <11>> example 1, as shown in Table 3, the quantity of the silica stone contained in an undercoat layer was changed, and the photocatalyst composite membrane of comparative examples 7 and 8 was manufactured.</p><p num="0112">The abrasion resistant test and the nitric oxide removal examination were done about Example 7~9 and comparative examples 7 and 8. A result is shown in Table 3.<tables num="8"><img file="WO2016148108A4_D0008.tif" /></tables></p><p num="0113">As shown in Table 8, when the mass of an undercoat layer is 100 mass parts, Although wear-resistant strengthening operation with mass of strengthening particles sufficient at 0.5 mass part or less [comparative example 10] is not seen, if a strengthening particle of 1~100 mass parts or more is added as shown in Example 1 and 10~12, a wear-resistant significant strengthening operation will be seen. However, when the quantity of strengthening particles became 200 mass parts or more (comparative example 11), strengthening particles were not fully able to adhere, and a wear-resistant examination was not able to be done. Although at least 100 mass parts of large strengthening particles could not fully adhere, average particle diameter was judged to be usable by the collection of small strengthening particles and the strengthening particles which have a large and small diameter of a particle, when there were few openings.</p>
01141 Photocatalyst Layer 2 Undercoat-Layer 3 Strengthening Particle 4 Crevice 5 Convex Part 6 Substrate 7 Exposed-Part 10 Photocatalyst Composite Membrane 20 Photocatalyst Composite Membrane (Partial Wear)
11 sheets
Sheet 1 Sheet 2 Sheet 3 Sheet 4 Sheet 5 Sheet 6 Sheet 7 Sheet 8 Sheet 9 Sheet 10 Sheet 11
10 members in 3 offices; this record represents the family
Members10
| Document | Office | Kind | |
|---|---|---|---|
| JP5936735B1 | Japan | B1 | |
| WO2016148108A2 | World Intellectual Property Organization (WIPO) | A2 | |
| JP2016168587A | Japan | A | |
| JP2016168777A | Japan | A | |
| WO2016148108A3 | World Intellectual Property Organization (WIPO) | A3 | |
| JP6067825B1 | Japan | B1 | |
| JP6067899B2 | Japan | B2 | |
| WO2016148108A4This record | World Intellectual Property Organization (WIPO) | A4 | |
| JP2017094256A | Japan | A | |
| TW201800238A | Taiwan Province of China | A |
Numbers
- Publication
- 2016/148108
- Application
- 57999
Titles5
- English
- PAINT COMPOSITE FILM COMPRISING ANATASE-TYPE TITANIUM OXIDE, AND METHOD FOR MANUFACTURING SAME
- French
- FILM DE PEINTURE COMPOSITE COMPRENANT UN OXYDE DE TITANE DE TYPE ANATASE, ET SON PROCÉDÉ DE FABRICATION
- Japanese
- アナターゼ型酸化チタンを含有する塗装用複合膜及びその製造方法
- Unlabeled
- アナターゼ型酸化チタンを含有する塗装用複合膜及びその製造方法
- Unlabeled
- A composite membrane for paint containing Anatase type titanium oxide, and a manufacturing method for the same
Classification
- CPC, 11
- B01J23/42
- B05D5/00
- B05D7/00
- B05D7/24
- B01J23/50
- B05D1/36
- B32B9/00
- C09D1/00
- B01J35/36
- B01J2235/15
- B01J35/38
- IPC, 11
- B01J35 02
- B01J23 42
- B01J23 50
- B05D1 36
- B05D5 00
- B05D7 00
- B05D7 24
- B32B9 00
- C09D1 00
- B01J35 36
- B01J35 38
Designated states146
- Regional, 80
- Albania
- Austria
- Belgium
- Bulgaria
- Switzerland
- Cyprus
- Czechia
- Germany
- Denmark
- Estonia
- Spain
- Finland
- France
- United Kingdom
- Greece
- Croatia
- Hungary
- Ireland
- Iceland
- Italy
- Lithuania
- Luxembourg
- Latvia
- Monaco
and 56 moreShow fewer
- North Macedonia
- Malta
- Netherlands (Kingdom of the)
- Norway
- Poland
- Portugal
- Romania
- Serbia
- Sweden
- Slovenia
- Slovakia
- San Marino
- Türkiye
- Burkina Faso
- Benin
- Central African Republic
- Congo
- Côte d’Ivoire
- Cameroon
- Gabon
- Guinea
- Equatorial Guinea
- Guinea-Bissau
- Comoros
- Mali
- Mauritania
- Niger
- Senegal
- Chad
- Togo
- Botswana
- Ghana
- Gambia
- Kenya
- Liberia
- Lesotho
- Malawi
- Mozambique
- Namibia
- Rwanda
- Sudan
- Sierra Leone
- Sao Tome and Principe
- Eswatini
- United Republic of Tanzania
- Uganda
- Zambia
- Zimbabwe
- Armenia
- Azerbaijan
- Belarus
- Kyrgyzstan
- Kazakhstan
- Russian Federation
- Tajikistan
- Turkmenistan
- National, 66
- United Arab Emirates
- Antigua and Barbuda
- Angola
- Australia
- Bosnia and Herzegovina
- Barbados
- Bahrain
- Brunei Darussalam
- Brazil
- Belize
- Canada
- Chile
- China
- Colombia
- Costa Rica
- Cuba
- Dominica
- Dominican Republic
- Algeria
- Ecuador
- Egypt
- Grenada
- Georgia
- Guatemala
and 42 moreShow fewer
- Honduras
- Indonesia
- Israel
- India
- Iran (Islamic Republic of)
- Saint Kitts and Nevis
- Democratic People’s Republic of Korea
- Republic of Korea
- Lao People’s Democratic Republic
- Saint Lucia
- Sri Lanka
- Libya
- Morocco
- Republic of Moldova
- Montenegro
- Madagascar
- Mongolia
- Mexico
- Malaysia
- Nigeria
- Nicaragua
- New Zealand
- Oman
- Panama
- Peru
- Papua New Guinea
- Philippines
- Qatar
- Saudi Arabia
- Seychelles
- Singapore
- El Salvador
- Syrian Arab Republic
- Thailand
- Tunisia
- Trinidad and Tobago
- Ukraine
- United States of America
- Uzbekistan
- Saint Vincent and the Grenadines
- Viet Nam
- South Africa