TWI480099B - Photocatalyst coating body - Google Patents

Photocatalyst coating body Download PDF

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TWI480099B
TWI480099B TW100110396A TW100110396A TWI480099B TW I480099 B TWI480099 B TW I480099B TW 100110396 A TW100110396 A TW 100110396A TW 100110396 A TW100110396 A TW 100110396A TW I480099 B TWI480099 B TW I480099B
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photocatalyst
coated body
body according
group
layer
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TW100110396A
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TW201210695A (en
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Hiroshi Terasaki
Takeshi Ikeda
Ritsuko Nose
Osamu Ura
Junji Kameshima
Makoto Hayakawa
Mitsuyoshi Kanno
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Toto Ltd
Toto Okitsumo Coatings Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B01J37/0219—Coating the coating containing organic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/024—Multiple impregnation or coating
    • B01J37/0244—Coatings comprising several layers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1693—Antifouling paints; Underwater paints as part of a multilayer system
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C09D7/67—Particle size smaller than 100 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Catalysts (AREA)
  • Paints Or Removers (AREA)
  • Laminated Bodies (AREA)

Description

光觸媒塗裝體Photocatalyst coating body

[相關連申請案][Related application]

本申請案係主張2010年3月25日提出申請之日本國專利申請案2010-070197號及2010年10月18日提出申請之國際申請案PCT/JP2010/068790號之優先權者，藉由引用此等申請案之說明書，作為本案揭示之一部分。The present application claims the priority of the Japanese Patent Application No. 2010-070197, filed on March 25, 2010, and the priority of the International Application No. PCT/JP2010/068790, filed on Oct. 18, 2010. The description of these applications is part of the disclosure of this case.

本發明係關於光觸媒塗裝體，更詳細係有關隨著降雨所產生之自行清淨機能及有害氣體分解機能優異，長期具有良好耐候性的光觸媒塗裝體。The present invention relates to a photocatalyst-coated body, and more particularly relates to a photocatalyst-coated body which is excellent in self-cleaning function and harmful gas decomposition function due to rainfall, and has good weather resistance for a long period of time.

近年，氧化鈦等之光觸媒被用於建築物之外裝材等許多的用途上。利用光觸媒藉由光能量而被激發的活性，以分解各種有害物質，或使被塗佈有光觸媒的基材表面產生親水化，可容易以水輕易洗去附著於表面之汙垢。可得到塗佈有這種光觸媒之光觸媒塗裝體的技術，例如有下述者。In recent years, photocatalysts such as titanium oxide have been used in many applications such as building materials. By utilizing the activity of the photocatalyst excited by the light energy to decompose various harmful substances or to hydrophilize the surface of the substrate coated with the photocatalyst, the dirt adhering to the surface can be easily washed away with water. A technique of obtaining a photocatalyst coated body coated with such a photocatalyst can be obtained, for example, as follows.

形成於光觸媒親水機能優異之複合材上的光觸媒被膜，例如有國際公開第98/03607號說明書(專利文獻1)所示，由金屬氧化物所構成之光觸媒粒子；及選自由氧化矽微粒子、可形成矽氧樹脂皮膜之矽氧樹脂皮膜前驅物、及可形成氧化矽皮膜之氧化矽皮膜前驅物所成群之至少1種所構成的被膜。由塗膜形成初期開始呈現親水性來看，氧化矽微粒子或可形成氧化矽皮膜之氧化矽皮膜前驅物之硬化物，作為光觸媒皮膜的成分是非常優異的。The photocatalyst film which is formed on the composite material having a photocatalyst hydrophilic function is, for example, a photocatalyst particle composed of a metal oxide as shown in International Publication No. 98/03607 (Patent Document 1); and is selected from the group consisting of cerium oxide microparticles. A film composed of at least one of a group of a silicone resin film precursor forming a silicone resin film and a cerium oxide film precursor capable of forming a cerium oxide film. In view of the hydrophilicity at the initial stage of the formation of the coating film, the cerium oxide fine particles or the cured product of the cerium oxide film precursor which can form the cerium oxide film are excellent as a component of the photocatalyst film.

又，有機基材上形成光觸媒親水性被膜時，如國際公開第97/00134號說明書(專利文獻2)所示，為了解決因光觸媒之光觸媒活性，使有機材料被分解或劣化的問題時，因而使用矽氧等具有光觸媒耐蝕性之中間層介於基材與光觸媒親水性被膜之間的技術。Further, when a photocatalyst hydrophilic film is formed on an organic substrate, as described in the specification of International Publication No. 97/00134 (Patent Document 2), in order to solve the problem that the organic material is decomposed or deteriorated due to the photocatalytic activity of the photocatalyst, A technique in which an intermediate layer having photocatalytic corrosion resistance such as xenon is interposed between a substrate and a photocatalyst hydrophilic film is used.

又，提案防止於基材與光觸媒粒子之間的中間層所具有對光觸媒之耐蝕性之光觸媒層龜裂的技術。例如特開2007-168135號公報(專利文獻3)所示，揭示窯業系之基材1的表面依有機塗膜2、無機塗膜3、含有光觸媒之無機塗膜4的順序形成塗膜的塗裝體，其中無機塗膜3之破壞延伸率設定為0.8~3.0%的複合材。含有光觸媒之無機塗膜4中，無機塗佈劑使用調配有光觸媒之可形成矽氧樹脂皮膜之矽氧樹脂皮膜前驅物，對於含有光觸媒之無機塗膜，可選擇不會比可形成氧化矽微粒子或氧化矽皮膜之氧化矽皮膜前驅物更脆的素材。Further, a technique for preventing cracking of a photocatalyst layer having corrosion resistance to a photocatalyst in an intermediate layer between a substrate and photocatalyst particles has been proposed. For example, JP-A-2007-168135 (Patent Document 3) discloses that the surface of the substrate 1 of the kiln system is coated with the organic coating film 2, the inorganic coating film 3, and the inorganic coating film 4 containing the photocatalyst. The package, wherein the inorganic coating film 3 has a fracture elongation of 0.8 to 3.0%. In the inorganic coating film 4 containing a photocatalyst, the inorganic coating agent uses a cerium oxide resin film precursor which can form a cerium oxide resin film which is prepared with a photocatalyst, and for the inorganic coating film containing a photocatalyst, it is possible to select no cerium oxide microparticles. Or a more brittle material of the cerium oxide film precursor of the cerium oxide film.

又，將光觸媒粒子固定於彈性素材之表面的技術，例如有特開平10-202794號公報(專利文獻4)所示，揭示一種以矽氧彈性體塗佈的薄片狀物，且該矽氧彈性體表層部黏固著具有光觸媒能之氧化鈦粉末為特徵的矽氧彈性體塗佈薄片狀物。其製法較獨特，在片狀物上塗佈矽氧彈性體組成物，接著在其表面載持具有光觸媒能之氧化鈦粉末後，使矽氧彈性體組成物硬化的方法。In addition, as disclosed in Japanese Laid-Open Patent Publication No. Hei 10-202794 (Patent Document 4), a sheet-like material coated with a silicone elastomer is disclosed, and the silicone elastic property is disclosed. The surface layer portion is adhered to a silicone elastomer coated sheet characterized by photocatalytic titanium oxide powder. The method for producing the cerium oxygen elastomer composition is characterized in that the cerium oxide elastomer composition is coated on the sheet, and then the titanium oxide powder having photocatalytic energy is supported on the surface thereof.

[先前技術文獻][Previous Technical Literature]

[專利文獻][Patent Literature]

[專利文獻1]　國際公開第98/03607號說明書[Patent Document 1] International Publication No. 98/03607

[專利文獻2]　國際公開第97/00134號說明書[Patent Document 2] International Publication No. 97/00134

[專利文獻3]　特開2007-168135號公報[Patent Document 3] JP-A-2007-168135

[專利文獻4]　特開平10-202794號公報[Patent Document 4] Japanese Patent Publication No. Hei 10-202794

[專利文獻5]　特開2008-272718號公報[Patent Document 5] JP-A-2008-272718

本發明人等如今藉由將特定物性的層接觸設置於光觸媒下方，得到可實現具有良好彈性之光觸媒塗裝體的見解。此外，也發現此光觸媒塗裝體同時可滿足光觸媒塗裝體所要求之基本性能。本發明係基於此見解而完成者。The present inventors have now obtained the knowledge that a photocatalyst coated body having good elasticity can be obtained by providing a layer of a specific physical property under the photocatalyst. In addition, it has been found that the photocatalyst coating body can simultaneously satisfy the basic properties required for the photocatalyst coating body. The present invention has been completed based on this finding.

因此，本發明的目的係提供具有要求的基本性能，且具有優異的耐候性，具有良好彈性之光觸媒塗裝體。Accordingly, it is an object of the present invention to provide a photocatalyst-coated body which has the required basic properties and which has excellent weather resistance and good elasticity.

本發明之光觸媒塗裝體，其係具備：基材；含有光觸媒所成之光觸媒層；介於前述基材及前述光觸媒層之間，且被設定為與前述光觸媒層下方接觸的中間層所成的光觸媒塗裝體，其特徵係前述中間層為含有樹脂成分所成，前述樹脂成分為含有矽氧成分與柔軟之非矽氧成分所成，且前述中間層之25℃下藉由依據JIS K7244-4之固體黏彈性測定裝置所測定的損失正切超過0.2，未達1.5，前述中間層之藉由依據JIS K7244-4之固體黏彈性測定裝置所測定之損失彈性率之溫度變化曲線中之光譜波峰之至少1個超過-80度，且30度以下。The photocatalyst coated body of the present invention comprises: a substrate; a photocatalyst layer comprising a photocatalyst; and an intermediate layer interposed between the substrate and the photocatalyst layer and disposed in contact with the underside of the photocatalyst layer; The photocatalyst coated body is characterized in that the intermediate layer is made of a resin component, and the resin component is made of a non-oxygen component and a soft non-oxygen component, and the intermediate layer is formed at 25 ° C according to JIS K7244. The loss tangent measured by the solid viscoelasticity measuring device of -4 is more than 0.2, which is less than 1.5, and the spectrum of the intermediate layer by the temperature change curve of the loss elastic modulus measured by the solid viscoelasticity measuring apparatus of JIS K7244-4 At least one of the peaks exceeds -80 degrees and is less than 30 degrees.

本發明之光觸媒塗裝體係具有優異的耐候性，且具有良好的彈性。具體而言，本發明之光觸媒塗裝體，例如即使在屋外施工，隨著季節變動等、塗膜表面之溫度變化，而在光觸媒被膜上產生龜裂，也可確保基材與光觸媒層之密著性，可抑制所產生之龜裂在表面側或基材側傳播或發展。此外，依據較佳之態樣時，本發明之光觸媒塗裝體係由塗膜形成初期呈現親水性，結果實質上從塗膜隨後，可發揮優異之隨著降雨之自行清淨機能，可長期維持其親水性的優點。The photocatalyst coating system of the invention has excellent weather resistance and good elasticity. Specifically, in the photocatalyst-coated body of the present invention, for example, even if it is applied outdoors, the temperature of the surface of the coating film changes due to seasonal changes, and cracks occur in the photocatalyst film, thereby ensuring the denseness of the substrate and the photocatalyst layer. The property can suppress the propagation or development of cracks generated on the surface side or the substrate side. Further, according to a preferred aspect, the photocatalyst coating system of the present invention exhibits hydrophilicity at the initial stage of formation of the coating film, and as a result, it can exhibit excellent self-cleaning function with rainfall from the coating film, and can maintain its hydrophilicity for a long period of time. The advantage of sex.

[實施發明之形態][Formation of the Invention]

光觸媒塗裝體Photocatalyst coating body

本發明之光觸媒塗裝體基本上係具備：基材；含有光觸媒所成之光觸媒層；介於前述基材及前述光觸媒層之間，且被設定為與前述光觸媒層下方接觸的中間層；所成的構造。前述中間層為含有樹脂成分所成，樹脂成分為含有矽氧成分與柔軟之非矽氧成分，且中間層之25℃下藉由依據JIS K7244-4之固體黏彈性測定裝置所測定的損失正切超過0.2，未達1.5。本發明之光觸媒塗裝體係具有優異的耐候性，且具有良好的彈性。具體而言，即使在光觸媒被膜上產生龜裂，也可確保基材與光觸媒層之密著性，可抑制所產生之龜裂往基材側傳播或發展，同時對於氣體分解機能等之光觸媒機能也具有優異的性能。因此，本發明之塗裝體不限於以下者，例如可以下(1)~(6)之構件為基材來形成。換言之，(1)橋梁等之施加振動的構造物、(2)無釉之陶磁器、混凝土、水泥板、木材、石材等之多孔質材料，且處於氣溫為0℃以下之氣氛的構件、(3)金屬材料、橡膠、可撓性薄膜樹脂等具有可撓性的材料所構成，其上形成光觸媒層後，被施予彎曲加工的構件、(4)即使一天氣溫變化為20℃以上之較大的場所所使用的構件、(5)金屬、樹脂、橡膠、矽氧密封膠、密封塗層等之線膨脹率10-5 K-1 以上之熱膨脹率較大的材料所構成之構件、(6)氣溫之年溫差為30℃以上之環境下使用的構件。此等構件的表面被太陽光等可光激發光觸媒之光源的光照射。The photocatalyst coated body of the present invention basically comprises: a substrate; a photocatalyst layer comprising a photocatalyst; an intermediate layer interposed between the substrate and the photocatalyst layer and disposed in contact with the underside of the photocatalyst layer; The structure of the formation. The intermediate layer is composed of a resin component, and the resin component is a non-oxygen component containing a cerium oxide component and a soft non-oxygen component, and the loss tangent measured by the solid viscoelasticity measuring apparatus according to JIS K7244-4 at 25 ° C of the intermediate layer. More than 0.2, less than 1.5. The photocatalyst coating system of the invention has excellent weather resistance and good elasticity. Specifically, even if cracks are formed in the photocatalyst film, the adhesion between the substrate and the photocatalyst layer can be ensured, and the generated cracks can be prevented from propagating or developing toward the substrate side, and the photocatalytic function for the gas decomposition function or the like can be suppressed. It also has excellent performance. Therefore, the coated body of the present invention is not limited to the following, and for example, the members (1) to (6) can be formed as a base material. In other words, (1) a structure such as a bridge that vibrates, (2) an unglazed ceramic, a concrete, a cement board, a wood, a stone, or the like, and a member having an atmosphere having a temperature of 0 ° C or less, (3) a material made of a flexible material such as a metal material, a rubber or a flexible film resin, which is subjected to a bending process after forming a photocatalyst layer, and (4) a large temperature change of 20 ° C or more per day. (a) a member made of a material used in a place, (5) a metal, a resin, a rubber, a silicone sealant, a sealant, or the like, which has a linear expansion coefficient of 10 -5 K -1 or more and a material having a large thermal expansion coefficient, (6) The member used in an environment where the temperature difference is 30 °C or more. The surface of such members is illuminated by light such as sunlight that is photoexcitable to the source of the photocatalyst.

依據本發明之較佳態樣時，前述光觸媒層其粒子成分含有光觸媒粒子與無機氧化物粒子，且前述粒子成分係相對於前述光觸媒層為70質量%以上，較佳為90質量%以上。光觸媒層以此種構成時，由塗膜形成初期容易呈現親水性，實質上，從塗膜隨後可發揮優異之伴隨降雨所得之自行清淨機能。此態樣時，特別是光觸媒層為脆性時，可進一步抑制龜裂之傳播或發展。According to a preferred aspect of the present invention, the photocatalyst layer contains photocatalyst particles and inorganic oxide particles, and the particle component is 70% by mass or more, preferably 90% by mass or more based on the photocatalyst layer. When the photocatalyst layer has such a configuration, it is easy to exhibit hydrophilicity at the initial stage of formation of the coating film, and substantially, the coating film can then exhibit excellent self-cleaning performance due to rainfall. In this aspect, especially when the photocatalyst layer is brittle, the propagation or development of cracks can be further suppressed.

一般光觸媒層、特別是以無機成分構成之光觸媒層因為脆性，因此隨著季節變動、溫度變化有時會產生龜裂。但是本發明之光觸媒塗裝體時，此龜裂係因以下所示之2的理由之相乘效果，使得龜裂之影響不會傳播至表面側及基材側。但是以下的理由為假設，但是本發明不限於具有此等作用效果者。其一係與光觸媒層下方接觸之中間層之25℃的損失正切超過0.2，藉此中間層吸收傳播能量者。又，依據本發明之一態樣，光觸媒層70%以上為光觸媒粒子、無機氧化物粒子等之粒子狀物質所構成時，光觸媒層存在著粒子間隙，因該間隙而抑制龜裂之發展。因此等效果，在光觸媒層所產生之龜裂不易往其表面或剖面方向傳播或發展，表面不會產生伴隨龜裂之白濁等的外觀不良，又中間層、基材不易破損。與光觸媒層下方接觸之中間層之25℃的損失正切未達1.5時，光觸媒層表面可長期維持親水性未達20°。此外，調配矽氧成分作為中間層之樹脂成分，可抑制因光觸媒造成基材之劣化。In general, a photocatalyst layer, particularly a photocatalyst layer composed of an inorganic component, is brittle, and therefore cracks may occur depending on seasonal changes and temperature changes. However, in the case of the photocatalyst-coated body of the present invention, the crack is caused by the multiplication effect of the two reasons shown below, so that the influence of the crack does not propagate to the surface side and the substrate side. However, the following reasons are assumed, but the present invention is not limited to those having such effects. The loss of a 25 ° C tangent of the intermediate layer in contact with the underlying photocatalyst layer exceeds 0.2, whereby the intermediate layer absorbs the energy. Further, according to one aspect of the present invention, when 70% or more of the photocatalyst layer is composed of a particulate material such as photocatalyst particles or inorganic oxide particles, a particle gap exists in the photocatalyst layer, and the development of cracks is suppressed by the gap. Therefore, the crack generated in the photocatalyst layer is less likely to propagate or develop on the surface or the cross-section, and the surface does not have an appearance defect such as white turbidity accompanying the crack, and the intermediate layer and the substrate are not easily broken. When the loss tangent of 25 ° C of the intermediate layer in contact with the underside of the photocatalyst layer is less than 1.5, the surface of the photocatalyst layer can maintain hydrophilicity of less than 20 ° for a long period of time. Further, by disposing the oxygen-containing component as the resin component of the intermediate layer, deterioration of the substrate due to the photocatalyst can be suppressed.

本發明之光觸媒塗裝體中之前述光觸媒層的表面係接受前述光觸媒的光激發，呈現換算成與水之接觸角為未達20°之親水性較佳。藉此可發揮優異之伴隨降雨之自行清淨機能。The surface of the photocatalyst layer in the photocatalyst coating body of the present invention is preferably subjected to photoexcitation of the photocatalyst, and is preferably hydrophilic in a contact angle with water of less than 20°. This provides excellent self-cleaning performance with rainfall.

本發明之光觸媒塗裝體中之前述光觸媒層中之光觸媒的比例，較佳為1質量%以上，未達20質量%，更佳為5質量%以上15質量%以下。本發明之一態樣中，光觸媒層中之光觸媒之調配比例為遠少於無機氧化物粒子所構成之上述範圍內時，可以最小限度使光觸媒粒子與基材之直接接觸，藉此可抑制基材(特別是有機基材)之侵蝕。同時，藉此構成，可防止光觸媒對基材(特別是有機基材)之侵蝕，同時可得到有害氣體分解性、及所要之各種被膜特性(透明性、膜強度等)優異的光觸媒塗裝體。The ratio of the photocatalyst in the photocatalyst layer in the photocatalyst coating body of the present invention is preferably 1% by mass or more, less than 20% by mass, and more preferably 5% by mass or more and 15% by mass or less. In one aspect of the invention, when the proportion of the photocatalyst in the photocatalyst layer is much smaller than the above range of the inorganic oxide particles, the photocatalyst particles can be directly contacted with the substrate, thereby suppressing the base. Erosion of materials (especially organic substrates). At the same time, it is possible to prevent the photocatalyst from being attacked on the substrate (especially the organic substrate), and at the same time, it is possible to obtain a photocatalyst-coated body excellent in decomposing harmful gases and various desired film properties (transparency, film strength, etc.). .

本發明中，光觸媒為粒子時，光觸媒塗裝體中之前述光觸媒粒子之平均粒徑，較佳為10nm以上，未達1000nm，更佳為10nm以上，未達100nm，最佳為10nm以上60nm以下。本說明書中，此光觸媒粒子之平均粒徑係藉由掃描型電子顯微鏡，測定進入2萬倍~20萬倍之視野中之任意100個粒子的長度，以個數平均值計算得到。粒子的形狀最佳為真球，也可為略圓形或橢圓形，此時，粒子的長度係以((長徑+短徑)/2)概略計算得到。光觸媒粒子之平均粒徑在上述範圍時，可充分發揮光觸媒層中之通氣量、氣體分解活性，而顯示充分的光觸媒分解活性，同時也可平衡發揮耐候性等之各種被膜特性。此外，光觸媒粒子之平均粒徑在上述範圍時，光觸媒層顯示良好的透明性。In the present invention, when the photocatalyst is a particle, the average particle diameter of the photocatalyst particles in the photocatalyst-coated body is preferably 10 nm or more, less than 1000 nm, more preferably 10 nm or more, less than 100 nm, and most preferably 10 nm or more and 60 nm or less. . In the present specification, the average particle diameter of the photocatalyst particles is measured by a scanning electron microscope to determine the length of any 100 particles in a field of view of 20,000 to 200,000 times, and is calculated as a number average. The shape of the particles is preferably a true sphere or a slightly circular or elliptical shape. In this case, the length of the particles is roughly calculated as ((long diameter + short diameter)/2). When the average particle diameter of the photocatalyst particles is within the above range, the amount of aeration and the gas decomposition activity in the photocatalyst layer can be sufficiently exhibited, and sufficient photocatalyst decomposition activity can be exhibited, and various film properties such as weather resistance can be balanced. Further, when the average particle diameter of the photocatalyst particles is in the above range, the photocatalyst layer exhibits good transparency.

本發明之光觸媒塗裝體中之前述無機氧化物粒子的平均粒徑，較佳為5nm以上，未達100nm，更佳下限值為10nm，更佳之上限值為40nm。本說明書中，此無機氧化物粒子之平均粒徑係與上述光觸媒粒子之平均粒徑同樣，係藉由掃描型電子顯微鏡，測定進入20萬倍之視野中之任意100個粒子的長度，並以個數平均值計算得到。無機氧化物粒子之平均粒子徑在上述範圍時，可提高光觸媒層中之通氣性，提高氣體分解反應性，同時可提高耐磨耗性、耐龜裂。The average particle diameter of the inorganic oxide particles in the photocatalyst-coated body of the present invention is preferably 5 nm or more, less than 100 nm, more preferably 10 nm, and more preferably 40 nm. In the present specification, the average particle diameter of the inorganic oxide particles is the same as the average particle diameter of the photocatalyst particles, and the length of any 100 particles entering the field of view of 200,000 times is measured by a scanning electron microscope. The average of the numbers is calculated. When the average particle diameter of the inorganic oxide particles is in the above range, the air permeability in the photocatalyst layer can be improved, the gas decomposition reactivity can be improved, and the abrasion resistance and crack resistance can be improved.

本發明之光觸媒塗裝體中之前述光觸媒層的膜厚，較佳為3μm以下。光觸媒層之膜厚為3μm以下時，可得到透明性、膜強度優異的特性，可明顯抑制龜裂不會往表面側進展而造成外觀不良的效果。依據本發明之較佳態樣時，光觸媒層之膜厚較佳為0.2μm以上，更佳為0.5μm以上。光觸媒層之膜厚為0.2μm以上，可發揮良好的親水性。此外，到達光觸媒層與基材之界面的紫外線被充分衰減，因此可得到提高耐候性的效果。The film thickness of the photocatalyst layer in the photocatalyst coating body of the present invention is preferably 3 μm or less. When the film thickness of the photocatalyst layer is 3 μm or less, the transparency and the film strength are excellent, and the effect that the crack does not progress to the surface side and the appearance is poor can be remarkably suppressed. According to a preferred embodiment of the present invention, the film thickness of the photocatalyst layer is preferably 0.2 μm or more, more preferably 0.5 μm or more. The film thickness of the photocatalyst layer is 0.2 μm or more, and it exhibits good hydrophilicity. Further, the ultraviolet rays reaching the interface between the photocatalyst layer and the substrate are sufficiently attenuated, so that the effect of improving the weather resistance can be obtained.

本發明之一態樣係光觸媒塗裝體之前述光觸媒層中存在著粒子間隙。藉此，可提高藉由光觸媒之有害氣體分解機能，同時可抑制龜裂往表面側及剖面側進展。In one aspect of the invention, there is a particle gap in the photocatalyst layer of the photocatalyst coating body. Thereby, the decomposition function of the harmful gas by the photocatalyst can be improved, and the progress of the crack on the surface side and the cross-sectional side can be suppressed.

本發明之光觸媒塗裝體中之粒子間隙，較佳為存在20體積%以上35體積%以下。空隙率在上述範圍時，其有害氣體與光觸媒粒子以高機率接觸。因此，進一步提高有害氣體之分解活性。夾雜此程度的間隙，可充分抑制龜裂往表面側及剖面側進展。The particle gap in the photocatalyst-coated body of the present invention is preferably 20% by volume or more and 35% by volume or less. When the void ratio is in the above range, the harmful gas and the photocatalyst particles are in contact with each other at a high probability. Therefore, the decomposition activity of the harmful gas is further improved. When the gap is mixed, the progress of the crack on the surface side and the cross section side can be sufficiently suppressed.

本說明書中，空隙率較佳為使用大塚電子股份公司製之反射分光膜厚計：FE-3000，每1試料測定5點以上，較佳為測定10點以上，求其平均值所得之數值。其順序如下所示。In the present specification, it is preferable to use a reflection spectroscopic film thickness meter: FE-3000 manufactured by Otsuka Electronics Co., Ltd., and to measure 5 points or more per sample, preferably 10 points or more, and obtain the average value. The order is as follows.

順序1.玻璃板之折射率決定Sequence 1. The refractive index of the glass plate is determined

1-1.依以下條件計測玻璃板之波長230~800nm的反射率。1-1. Measure the reflectance of the glass plate at a wavelength of 230 to 800 nm according to the following conditions.

測定方法　絕對反射率Measuring method Absolute reflectance

透鏡　Refrec.25XLens Refrec.25X

標準反射板　A1-S-13Standard reflector A1-S-13

濾鏡　無Filter

細縫　0.2mm×2mmSlit 0.2mm×2mm

取樣時間　1000msecSampling time 1000msec

累積次數　9次Accumulated 9 times

增益　正常Gain normal

1-2.藉由構成介質=空氣、玻璃板、光之入射角Φ =0°，使由空氣側入射之光以玻璃板反射時之空氣/玻璃板界面的Fresnel振幅反射係數與n-Cauchy之分散式，計算得到玻璃板之波長230~800nm的反射率。前述n-Cauchy之分散式中，常數(Cm1 、Cm2 、Cm3 )之初期值分別為Cm1 =1.5、Cm2 =0、Cm3 =0，空氣之折射率為1，空氣之消光係數(extinction coefficient )為0(小檜山光信，“光學薄膜之基礎理論”p20~65，(2003，optronics公司))。1-2. The Fresnel amplitude reflection coefficient of the air/glass plate interface when the light incident from the air side is reflected by the glass plate and n-Cauchy by the medium = air, glass plate, and light incident angle Φ =0° The dispersion method calculates the reflectance of the glass plate at a wavelength of 230 to 800 nm. In the above-mentioned n-Cauchy dispersion formula, the initial values of the constants (C m1 , C m2 , C m3 ) are C m1 =1.5, C m2 =0, C m3 =0, the refractive index of air is 1, and the extinction of air The extinction coefficient is 0 (Mr. Xiaoshan, “Basic Theory of Optical Films” p20~65, (2003, optronics)).

1-3.實測反射率(1-1)與計算反射率(1-2)進行比較，求出殘差平方和(sum ofsquared residuals )成為最小時的Cm1 、Cm2 、Cm3 。此時，殘差平方和之上限為0.02。1-3. The measured reflectance (1-1) is compared with the calculated reflectance (1-2), and C m1 , C m2 , and C m3 when the sum of squared residuals is minimized are obtained. At this time, the upper limit of the sum of squares of the residuals is 0.02.

1-4.將以1-3所求得之Cm1 、Cm2 、Cm3 代入n-Cauchy之分散式中，決定玻璃板之折射率nm。1-4. Substituting C m1 , C m2 , and C m3 obtained in 1-3 into the dispersion of n-Cauchy, the refractive index nm of the glass plate is determined.

順序2.光觸媒層之空隙率之決定Sequence 2. Determination of void ratio of photocatalyst layer

2-1.依以下條件計測光觸媒層之波長230~800nm的反射率。2-1. Measure the reflectance of the photocatalyst layer at a wavelength of 230 to 800 nm according to the following conditions.

測定方法　絕對反射率Measuring method Absolute reflectance

透鏡　Refrec.25XLens Refrec.25X

標準反射板　Al-S-13Standard reflector Al-S-13

濾鏡　無Filter

細縫　0.2mm×2mmSlit 0.2mm×2mm

取樣時間　1000msecSampling time 1000msec

累積次數　9次Accumulated 9 times

增益　正常Gain normal

2-2.構成介質=空氣、光觸媒層=單層薄膜、玻璃板，光之入射角Φ =0°，由空氣側入射之光以單層薄膜反射的光與、單層薄膜內部透過之光在單層薄膜之上下面(空氣/單層薄膜界面、單層薄膜/玻璃板界面)進行多重重複反射的光合計時之空氣/單層薄膜界面的Fresnel振幅反射係數與Bruggeman之近似式，藉此計算得到光觸媒層之波長230~800nm的反射率(小檜山光信，“光學薄膜之基礎理論”p20~65，(2003，optronics公司)、D. E. A spnes，Thin Solid Films，89，249(1982))。C1 (SiO2 之體積分率)、C2 (TiO2 之體積分率)、C3 (空氣之體積分率)之初期值係分別為0.70、0.05、0.25。此外，空氣之折射率為1，空氣之消光係數為0。SiO2 、TiO2 之折射率(n1 、n2 )、消光係數(k1 、k2 )係引用E. D. Palik，“Handbook of Optical Constants of Solids”，(1998，Academic Press，San Diego)。2-2. Composition medium = air, photocatalyst layer = single-layer film, glass plate, incident angle of light Φ =0°, light reflected by a single layer of film incident on the air side, and light transmitted through a single layer of film The Fresnel amplitude reflection coefficient of the air/single-film interface of the photo-timed multiple photoreactions on the underside of the single-layer film (air/single-film interface, single-layer film/glass plate interface) and Bruggeman's approximation This calculation yields a reflectance of the photocatalyst layer at a wavelength of 230 to 800 nm (Mr. Xiaoshan, "Basic Theory of Optical Films" p20~65, (2003, optronics), DE A spnes, Thin Solid Films, 89, 249 (1982)) . The initial values of C 1 (volume fraction of SiO 2 ), C 2 (volume fraction of TiO 2 ), and C 3 (volume fraction of air) were 0.70, 0.05, and 0.25, respectively. In addition, the refractive index of air is 1, and the extinction coefficient of air is zero. The refractive indices (n 1 , n 2 ) and extinction coefficients (k 1 , k 2 ) of SiO 2 and TiO 2 are cited in ED Palik, "Handbook of Optical Constants of Solids", (1998, Academic Press, San Diego).

2-3.改變膜厚d、SiO2 、TiO2 、空氣之體積分率C1 、C2 、C3 之值，實測反射率(2-1)與計算反射率(2-2)進行比較，求出殘差平方和成為最小時之C1 、C2 、C3 。殘差平方和未達0.02，且成為最小時之C3 作為空隙率。其他條件如下述。2-3. Changing the film thickness d, SiO 2 , TiO 2 , the volume fraction of air C 1 , C 2 , C 3 , the measured reflectance (2-1) and the calculated reflectance (2-2) Find C 1 , C 2 , and C 3 when the sum of squared residuals becomes minimum. The sum of the squares of the residuals is less than 0.02, and C 3 is the smallest when it becomes the void ratio. Other conditions are as follows.

膜厚檢索方法　最佳化法Film thickness retrieval method optimization method

檢索範圍(波長)　400~800nmSearch range (wavelength) 400~800nm

檢索範圍(膜厚)　0~2000nmSearch range (film thickness) 0~2000nm

膜厚階段　10nmFilm thickness stage 10nm

此處所求得之C3 作為本發明之光觸媒層中的空隙率(體積%)。C 3 obtained herein is used as the void ratio (% by volume) in the photocatalyst layer of the present invention.

本發明之光觸媒塗裝體之前述樹脂成分中之柔軟非矽氧樹脂的比例，較佳為超過1%，未達99.5%，更佳為超過10%，未達99.5%，最佳為超過50%，未達99.5%。柔軟非矽氧樹脂的比例在上述範圍時，可抑制中間層之因光觸媒的劣化，提高中間層與光觸媒層之密著性。The proportion of the soft non-oxygen resin in the resin component of the photocatalyst coating body of the present invention is preferably more than 1%, less than 99.5%, more preferably more than 10%, less than 99.5%, and most preferably more than 50. %, less than 99.5%. When the ratio of the soft non-oxygen resin is in the above range, the deterioration of the photocatalyst in the intermediate layer can be suppressed, and the adhesion between the intermediate layer and the photocatalyst layer can be improved.

本發明之光觸媒塗裝體之前述樹脂成分中之矽氧成分的比例，以SiO2 換算，較佳為0.5%以上，30%以下。樹脂成分中之矽氧成分的比例在此範圍時，可更能抑制中間層之光觸媒的劣化。The ratio of the oxygen component in the resin component of the photocatalyst-coated body of the present invention is preferably 0.5% or more and 30% or less in terms of SiO 2 . When the ratio of the oxygen component in the resin component is within this range, deterioration of the photocatalyst in the intermediate layer can be more suppressed.

光觸媒層Photocatalyst layer

本發明中，光觸媒層於基材表面若存在光觸媒，較佳為光觸媒粒子時，除了完全膜狀以外，亦包含例如部分成為膜狀的狀態。此外，亦可在基材表面上以島狀離散狀態存在。依據本發明之較佳樣態時，此光觸媒層係使用塗佈液所得者。In the present invention, when a photocatalyst is present on the surface of the substrate, preferably a photocatalyst particle, in addition to a completely film shape, a state in which a portion is formed into a film shape, for example. Further, it may exist in an island-like discrete state on the surface of the substrate. In accordance with a preferred aspect of the invention, the photocatalyst layer is obtained using a coating liquid.

依據本發明之較佳形態時，光觸媒塗裝體所具有的光觸媒層係含有作為粒子成分之光觸媒粒子與無機氧化物粒子，且前述粒子成分係相對於前述光觸媒層為70質量%，較佳為75質量%，更佳為80質量%，更佳為90質量%以上。According to a preferred embodiment of the present invention, the photocatalyst layer of the photocatalyst-coated body contains photocatalyst particles and inorganic oxide particles as a particle component, and the particle component is 70% by mass based on the photocatalyst layer, preferably 75 mass%, more preferably 80 mass%, still more preferably 90 mass% or more.

本發明中，粒子成分係指伴隨形狀的成分。粒子成分係以光觸媒粒子及無機氧化物粒子作為必須成分，也可含有作為任意成分之後述其他的粒子。粒子成分的形狀無特別限定，可為球狀、棒狀、纖維狀、晶鬚狀、平板狀、不定形。In the present invention, the particle component means a component accompanying the shape. The particle component is composed of photocatalyst particles and inorganic oxide particles as essential components, and may be contained as an optional component. The shape of the particle component is not particularly limited, and may be a spherical shape, a rod shape, a fibrous shape, a whisker shape, a flat shape, or an amorphous shape.

本發明中，光觸媒可使用例如有銳鈦礦型氧化鈦、金紅石型氧化鈦、板鈦礦型氧化鈦等的結晶性氧化鈦、ZnO、SnO2 、SrTiO3 、WO3 、Bi2 O3 、Fe2 O3 之金屬氧化物中之至少一種。可僅使用一種類或可組合複數種使用。複數種之較佳組合，例如有結晶性氧化鈦與SnO2 、結晶性氧化鈦與WO3 等。此處所例示之任一金屬氧化物也適合於後述各構成組合。In the present invention, for example, crystalline titanium oxide such as anatase titanium oxide, rutile titanium oxide or brookite-type titanium oxide, ZnO, SnO 2 , SrTiO 3 , WO 3 or Bi 2 O 3 can be used. And at least one of metal oxides of Fe 2 O 3 . It is possible to use only one type or a combination of a plurality of types. A preferred combination of plural kinds includes, for example, crystalline titanium oxide and SnO 2 , crystalline titanium oxide, and WO 3 . Any of the metal oxides exemplified herein is also suitable for each constituent combination described later.

光觸媒粒子較佳為結晶性氧化鈦粒子。結晶性氧化鈦相較於ZnO時，具有較佳之耐水性。又，與SnO2 比較時，更能以太陽光中含許多之380nm~420nm之波長的光，發揮氣體分解等的光觸媒機能。又相較於SrTiO3 時，較容易得到奈米等級的微粒子，因此具有較大的比表面積，容易得到實用上充分的光觸媒活性。此外，相較於WO3 、Bi2 O3 、Fe2 O3 時，能帶隙較大，因此具有充分的氧化力，同時光激發後，不易產生傳導電子與電洞之再結合，氣體分解具有充分的活性化能。結晶性氧化鈦係無害，且化學性安定，可廉價取得。又，結晶性氧化鈦係能帶隙能較高，因此光激發時需要紫外線，光激發過程不會吸收可見光，因此不會因補色成分而產生發色。The photocatalyst particles are preferably crystalline titanium oxide particles. The crystalline titanium oxide has better water resistance than ZnO. Further, when compared with SnO 2 , it is possible to exhibit photocatalytic function such as gas decomposition in a large amount of light having a wavelength of 380 nm to 420 nm in sunlight. Further, in comparison with SrTiO 3 , it is easier to obtain nano-sized fine particles, and therefore has a large specific surface area, and it is easy to obtain practically sufficient photocatalytic activity. In addition, compared to WO 3 , Bi 2 O 3 , and Fe 2 O 3 , the band gap is large, so that it has sufficient oxidizing power, and at the same time, after photoexcitation, recombination of conduction electrons and holes is less likely to occur, and gas decomposition Has sufficient activation energy. The crystalline titanium oxide is harmless and chemically stable, and can be obtained at low cost. Further, since the crystalline titanium oxide has a high band gap energy, ultraviolet rays are required for photoexcitation, and visible light is not absorbed by the photoexcitation process, so that color development is not caused by the complementary color component.

光觸媒粒子例如在結晶性氧化鈦粒子中，較佳為銳鈦礦型氧化鈦。銳鈦礦型氧化鈦相較於金紅石型氧化鈦，其氧化力較強，因此可發揮更強的氣體分解等之光觸媒機能。作為光觸媒粒子之銳鈦礦型氧化鈦粒子可與上述各構成適當組合，且不會妨礙其效果，可發揮上述的作用效果。The photocatalyst particles are preferably anatase-type titanium oxide, for example, among the crystalline titanium oxide particles. The anatase type titanium oxide has a stronger oxidizing power than the rutile type titanium oxide, and thus exhibits a photocatalytic function such as gas decomposition. The anatase-type titanium oxide particles as the photocatalyst particles can be appropriately combined with each of the above-described respective components, and the above-described effects can be exhibited without impeding the effects.

無機氧化物粒子可使用氧化矽粒子、氧化鋁粒子、氧化鋯粒子、氧化鈰粒子等。較佳為氧化矽粒子。光觸媒層除光觸媒粒子、無機氧化物粒子(氧化矽粒子)外，在不影響光觸媒親水機能的量，較佳為30質量%以下，更佳為10質量%以下的範圍內添加無機黏結劑或金屬或金屬化合物、界面活性劑等。As the inorganic oxide particles, cerium oxide particles, alumina particles, zirconia particles, cerium oxide particles or the like can be used. Preferred is cerium oxide particles. In addition to the photocatalyst particles and the inorganic oxide particles (cerium oxide particles), the photocatalyst layer is added to the inorganic binder or the metal in an amount of preferably 30% by mass or less, more preferably 10% by mass or less, without affecting the amount of the photocatalyst hydrophilic function. Or a metal compound, a surfactant, or the like.

光觸媒層含有可作為任意成分之其他的粒子，例如有氟樹脂粒子、乳膠‧丙烯酸球等的樹脂粒子、著色顏料粒子、晶鬚‧纖維‧填料等之體質顏料粒子、雲母‧滑石‧玻璃球等之創意材粒子等。The photocatalyst layer contains other particles which can be used as an optional component, for example, resin particles such as fluororesin particles, latex, acrylic beads, coloring pigment particles, whiskey fibers, fillers, and the like, mica, talc, glass balls, etc. Creative material particles and so on.

依據本發明之較佳態樣時，光觸媒層可含有無機黏結劑，例如有無定形氧化鈦、無定形氧化矽；鹼矽酸鹽、烷基矽酸鹽等可形成氧化矽皮膜之前驅物的硬化物；無定形氧化鋯；碳酸鋯銨、乙酸鋯、甲酸鋯等可形成氧化鋯皮膜之前驅物的硬化物等。According to a preferred aspect of the present invention, the photocatalyst layer may contain an inorganic binder such as amorphous titanium oxide or amorphous cerium oxide; alkali silicate, alkyl silicate or the like which hardens the precursor before formation of the cerium oxide film. Amorphous zirconia; zirconium carbonate, zirconium acetate, zirconium formate, etc., which can form a cured product of a precursor of a zirconia film.

依據本發明之較佳態樣時，光觸媒層可含有金屬或金屬化合物，例如有Cu或Cu2 O、CuO等之Cu化合物、Ag或Ag2 O等之Ag化合物、Pt或Pt化合物、Fe或Fe化合物、Pd或Pd化合物等。According to a preferred aspect of the present invention, the photocatalyst layer may contain a metal or a metal compound such as a Cu compound such as Cu or Cu 2 O, CuO or the like, an Ag compound such as Ag or Ag 2 O, a Pt or Pt compound, Fe or Fe compound, Pd or Pd compound, and the like.

本發明之光觸媒塗裝體所具有的光觸媒層係使用將上述成分分散於溶劑後之塗佈液，藉由乾燥或燒成來形成。依據本發明之較佳態樣時，形成光觸媒層時之塗佈液，從光觸媒或無機氧化物粒子之分散安定性、塗佈於中間層上時之潤濕性的觀點，可含有界面活性劑。界面活性劑可自非離子性界面活性劑、陰離子性界面活性劑、陽離子性界面活性劑、兩性離子性界面活性劑中適當選擇。較佳為非離子性界面活性劑，更佳為醚型非離子性界面活性劑、酯型非離子性界面活性劑、聚烷二醇非離子性界面活性劑、氟系非離子性界面活性劑、聚矽氧系非離子性界面活性劑。The photocatalyst layer of the photocatalyst-coated body of the present invention is formed by drying or baking a coating liquid obtained by dispersing the above components in a solvent. According to a preferred aspect of the present invention, the coating liquid in forming the photocatalyst layer may contain a surfactant from the viewpoint of dispersion stability of the photocatalyst or inorganic oxide particles and wettability when applied to the intermediate layer. . The surfactant can be appropriately selected from a nonionic surfactant, an anionic surfactant, a cationic surfactant, and a zwitterionic surfactant. Preferably, it is a nonionic surfactant, more preferably an ether type nonionic surfactant, an ester type nonionic surfactant, a polyalkylene glycol nonionic surfactant, a fluorine-based nonionic surfactant. , polyoxynity nonionic surfactant.

本發明中使用之光觸媒接受光激發之親水化係1晚未經光照射可產生之往疏水方向之與水之接觸角的變動，藉由日光碳弧燈式耐候性試驗24小時可回復的程度即可。日光碳弧燈式耐候性試驗係使用SUGA試驗機股份公司製(條件：光照射30W/m2 、氣氛溫度60℃，120分鐘光照射中，水噴霧18分鐘、水溫16±5℃)。其中與水之接觸角係以JIS R1703-1所記載的方法測定。The photocatalyst used in the present invention receives photoexcitation of the hydrophilized system for 1 night without light irradiation, and the change in the contact angle with the water in the hydrophobic direction can be recovered by the solar carbon arc lamp type weather resistance test for 24 hours. Just fine. The daylight carbon arc lamp type weather resistance test was carried out by SUGA Test Machine Co., Ltd. (conditions: light irradiation 30 W/m 2 , atmospheric temperature 60 ° C, water irradiation for 120 minutes, water spray for 18 minutes, water temperature 16 ± 5 ° C). The contact angle with water was measured by the method described in JIS R1703-1.

中間層middle layer

本發明之光觸媒塗佈物所具有的中間層係介於基材及光觸媒層之間，且設置為與光觸媒層下方接觸。此中間層含有樹脂成分，此樹脂成分含有矽氧成分及柔軟非矽氧樹脂，且在25℃之損失正切超過0.2未達1.5，較佳為超過0.2未達1.0者。The photocatalyst coating of the present invention has an intermediate layer interposed between the substrate and the photocatalyst layer and is placed in contact with the underside of the photocatalyst layer. The intermediate layer contains a resin component containing a cerium oxide component and a soft non-oxygenated resin, and the loss tangent at 25 ° C exceeds 0.2 and does not reach 1.5, preferably exceeds 0.2 and does not reach 1.0.

「介於基材及光觸媒層之間，且設置於與光觸媒層下方接觸」的狀態，只要是接觸光觸媒層下方與中間層上方即可，其界面可為實質上直線的狀態，亦可為一部份交錯狀態之任一種。The state of "between the substrate and the photocatalyst layer and being placed under the photocatalyst layer" may be a state in which the interface is substantially straight or may be one as long as it is above the contact photocatalyst layer and above the intermediate layer. Any of a number of interlaced states.

本說明書中，光觸媒塗佈物所具有之中間層的損失正切係將中間層設置於依據JIS K7244-4(「塑膠動態機械特性之試驗方法-第4部：拉伸振動-非共振法」)之固體黏彈性測定裝置上，以拉伸模式在頻率數1Hz下測定所得之值。In the present specification, the loss of the intermediate layer of the photocatalyst coating material is such that the intermediate layer is provided in accordance with JIS K7244-4 ("Testing Method for Dynamic Mechanical Properties of Plastics - Part 4: Tensile Vibration - Non-Resonance Method") The obtained value was measured in a tensile mode at a frequency of 1 Hz on a solid viscoelasticity measuring apparatus.

本發明中，中間層係含有樹脂成分所成。此樹脂成分係含有矽氧成分與柔軟非矽氧成分。此處，矽氧成分可使用矽氧樹脂或矽氧片段，而柔軟之非矽氧成分可使用柔軟之非矽氧樹脂或柔軟之非矽氧片段。又，樹脂成分可僅由上述兩種成分所構成，或可含有上述兩種成分以外之樹脂或片段。樹脂成分係使上述兩種成分或上述兩種成分及其他樹脂或片段進行聚合、混合、交聯而得。In the present invention, the intermediate layer contains a resin component. This resin component contains a neon component and a soft non-oxygen component. Here, the oxygen-enhancing component may use a silicone resin or a helium oxygen moiety, and the soft non-oxygen component may use a soft non-oxygen resin or a soft non-oxygen moiety. Further, the resin component may be composed only of the above two components, or may contain a resin or a fragment other than the above two components. The resin component is obtained by polymerizing, mixing, and crosslinking the above two components or the above two components and other resins or fragments.

本發明中，中間層中之樹脂成分的量，較佳為10質量%以上100質量%以下，更佳為50質量%以上100質量%以下，更佳為55質量%以上100質量%以下，更佳為60質量%以上100質量%以下。In the present invention, the amount of the resin component in the intermediate layer is preferably 10% by mass or more and 100% by mass or less, more preferably 50% by mass or more and 100% by mass or less, still more preferably 55% by mass or more and 100% by mass or less. It is preferably 60% by mass or more and 100% by mass or less.

本發明中，柔軟非矽氧成分係指柔軟非矽氧樹脂或柔軟非矽氧片段，較佳為一藉由依據JIS K7244-4之固體黏彈性測定裝置所測定之損失彈性率之溫度變化曲線中之光譜波峰為超過-80度且在30度以下的成分。中間層中所含之柔軟非矽氧成分藉由具有如上述性質時，中間層之藉由依據JIS K7244-4之固體黏彈性測定裝置所測定之損失彈性率之溫度變化曲線中，發現光譜波峰之至少一個超過-80度且在30度以下。In the present invention, the soft non-oxygenated component means a soft non-oxygenated resin or a soft non-oxygenated component, preferably a temperature change curve of loss elastic modulus measured by a solid viscoelasticity measuring apparatus according to JIS K7244-4. The spectral peak in the middle is a component exceeding -80 degrees and below 30 degrees. The soft non-oxygen component contained in the intermediate layer is found to have a spectral peak in the temperature profile of the intermediate layer by the loss elastic modulus measured by the solid viscoelasticity measuring apparatus according to JIS K7244-4. At least one of them exceeds -80 degrees and is below 30 degrees.

又，柔軟非矽氧成分之量係相對於矽氧成分中之Si的量，較佳為20質量%以上100,000質量%以下，更佳為100質量%以上20,000質量%以下，更佳為200質量%以上16,000質量%以下。Further, the amount of the soft non-oxygen component is preferably 20% by mass or more and 100% by mass or less, more preferably 100% by mass or more and 20,000% by mass or less, and more preferably 200% by mass based on the amount of Si in the cerium oxide component. % or more is 16,000 mass% or less.

柔軟非矽氧樹脂可利用例如胺基甲酸酯聚醚、胺基甲酸酯聚酯、胺基甲酸酯聚碳酸酯、聚醚、聚酯、聚丙烯酸酯、聚甲基丙烯酸酯、聚丙烯酸、聚甲基丙烯酸、聚乙烯、該等之複合物、使該等經矽氧改質或鹵素改質者。Soft non-oxygenated resins may utilize, for example, urethane polyethers, urethane polyesters, urethane polycarbonates, polyethers, polyesters, polyacrylates, polymethacrylates, poly Acrylic acid, polymethacrylic acid, polyethylene, composites of these, such as those modified by oxime or halogen.

柔軟非矽氧片段可使用例如胺基甲酸酯聚醚片段、胺基甲酸酯聚酯片段、胺基甲酸酯聚碳酸酯片段、聚醚片段、聚酯片段、聚丙烯酸酯片段、聚甲基丙烯酸酯片段、聚丙烯酸片段、聚甲基丙烯酸片段、聚乙烯片段、使該等經矽氧改質或鹵素改質的片段。Soft non-oxygenated fragments can be used, for example, urethane polyether fragments, urethane polyester fragments, urethane polycarbonate fragments, polyether fragments, polyester fragments, polyacrylate fragments, poly a methacrylate fragment, a polyacrylic acid fragment, a polymethacrylic acid fragment, a polyethylene fragment, a fragment which is modified by oxime or halogen.

又，矽氧樹脂較佳為使用以下述平均組成式(1)表示的矽氧：Further, the oxime resin preferably uses argon which is represented by the following average composition formula (1):

R1 p Si(OR2 )q O(4-p-q)/2 　...(1)R 1 p Si(OR 2 ) q O (4-pq)/2 (1)

(式中，R1 為未取代或取代之一價烴基，R2 係選自由氫原子、碳數1~6之未取代之一價烴基或碳數1~6之烷氧基取代之一價烴基，p及q為滿足0<p<4，0<q<4，0<(p+q)<4之數)。Wherein R 1 is an unsubstituted or substituted monovalent hydrocarbon group, and R 2 is selected from the group consisting of a hydrogen atom, an unsubstituted one-valent hydrocarbon group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms; The hydrocarbon group, p and q are those satisfying 0 < p < 4, 0 < q < 4, 0 < (p + q) < 4.

上述式中，R1 之未取代或經取代之一價烴基，較佳為碳數1~18者，未經取代之一價烴基例如有甲基、乙基、丙基、異丙基、丁基、第三丁基、己基、環己基、辛基、癸基等烷基，乙烯基、烯丙基、5-己烯基、9-癸烯基等烯基，苯基等芳基，苄基、苯基乙基等芳烷基等。又，經取代之一價烴基係未經取代之一價烴基之氫原子之一部分或全部經取代基取代者，而取代基可使用1)氟、氯等鹵素原子，2)縮水甘油氧基、環氧基環己基等環氧官能基，3)甲基丙烯酸基、丙烯酸基等(甲基)丙烯酸官能基，4)胺基、胺基乙基胺基、苯基胺基、二丁胺基等胺基官能基，5)巰基、四硫醚基等含硫官能基，6)(聚氧伸烷基)烷基醚基等烷基醚基，7)羧基、磺醯基等陰離子性基，8)含有四級銨鹽構造之基團等，但作為反應基以2)、3)者為佳，特別是以具有環氧官能基者為佳。此經取代之一價烴基的具體例有三氟丙基、全氟丁基乙基、全氟辛基乙基、3-氯丙基、2-(氯甲基苯基)乙基、3-縮水甘油氧基丙基、2-(3,4-環氧基環己基)乙基、3-(甲基)丙烯氧基丙基、(甲基)丙烯氧基甲基、3-胺基丙基、N-(2-胺基乙基)胺基丙基、3-(N-苯基胺基)丙基、3-二丁胺基丙基、3-巰基丙基、聚氧伸乙基氧基丙基、3-羥基羰基丙基、3-三丁基銨丙基等。此等中以甲基、丙基、己基、苯基較佳。In the above formula, the unsubstituted or substituted one-valent hydrocarbon group of R 1 is preferably a carbon number of 1 to 18, and the unsubstituted one-valent hydrocarbon group is, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group or a butyl group. An alkyl group such as a tributyl group, a hexyl group, a cyclohexyl group, an octyl group or a decyl group; an alkenyl group such as a vinyl group, an allyl group, a 5-hexenyl group or a 9-nonenyl group; an aryl group such as a phenyl group; An aralkyl group such as a phenylethyl group or the like. Further, a part or all of a hydrogen atom substituted with a monovalent hydrocarbon group which is an unsubstituted one-valent hydrocarbon group is substituted with a substituent, and the substituent may be 1) a halogen atom such as fluorine or chlorine, 2) a glycidyloxy group, An epoxy functional group such as an epoxycyclohexyl group; 3) a (meth)acrylic acid functional group such as a methacrylic group or an acrylic group; 4) an amine group, an aminoethylamino group, a phenylamino group, and a dibutylamino group. An amine functional group, 5) a sulfur-containing functional group such as a mercapto group or a tetrasulfide group, an alkyl ether group such as 6) a polyoxyalkylene alkyl ether group, and 7 an anionic group such as a carboxyl group or a sulfonyl group. 8) A group containing a quaternary ammonium salt structure, etc., preferably 2) or 3) as the reactive group, particularly preferably having an epoxy functional group. Specific examples of the substituted one-valent hydrocarbon group are trifluoropropyl, perfluorobutylethyl, perfluorooctylethyl, 3-chloropropyl, 2-(chloromethylphenyl)ethyl, 3-shrinkable Glyceryloxypropyl, 2-(3,4-epoxycyclohexyl)ethyl, 3-(meth)acryloxypropyl, (meth)acryloxymethyl, 3-aminopropyl , N-(2-Aminoethyl)aminopropyl, 3-(N-phenylamino)propyl, 3-dibutylaminopropyl, 3-mercaptopropyl, polyoxyethyloxy A propyl group, a 3-hydroxycarbonylpropyl group, a 3-tributyl ammonium propyl group or the like. Among these, a methyl group, a propyl group, a hexyl group, and a phenyl group are preferred.

R2 之碳數1~6之未取代或經取代之一價烴基之例有包含甲基、乙基、丙基、異丙基、丁基、第二丁基、第三丁基等烷基，異丙烯基等烯基，苯基等芳基之未取代一價烴基，或甲氧基甲基、乙氧基乙基、乙氧基甲基、甲氧基乙基等烷氧基烷基等之經烷氧基取代之一價烴基。Examples of the unsubstituted or substituted one-valent hydrocarbon group having 1 to 6 carbon atoms of R 2 include an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a second butyl group, and a third butyl group. An alkenyl group such as an isopropenyl group, an unsubstituted monovalent hydrocarbon group of an aryl group such as a phenyl group, or an alkoxyalkyl group such as a methoxymethyl group, an ethoxyethyl group, an ethoxymethyl group or a methoxyethyl group. The alkoxy group is substituted with a monovalent hydrocarbon group.

依據本發明之一樣態時，為了對矽氧樹脂賦予柔軟性，可含有二官能基矽烷衍生物單體(每分子具有兩個水解性基X，各矽原子上鍵結兩個氧原子形成二官能基矽氧烷鍵的單體)。較佳之水解性二官能基矽烷衍生物單體，例如有二苯基二氯矽烷、二苯基二溴矽烷、二苯基二甲氧基矽烷、二苯基二乙氧基矽烷、苯基甲基二氯矽烷、苯基甲基二溴矽烷、苯基甲基二甲氧基矽烷、苯基甲基二乙氧基矽烷、γ-縮水甘油氧基丙基甲基二甲氧基矽烷、γ-縮水甘油氧基丙基甲基二乙氧基矽烷、γ-(甲基)丙烯氧基丙基甲基二甲氧基矽烷、γ-(甲基)丙烯氧基丙基甲基二乙氧基矽烷、γ-胺基丙基甲基二甲氧基矽烷、γ-胺基丙基甲基二乙氧基矽烷、十七氟辛基甲基二甲氧基矽烷、十七氟辛基甲基二乙氧基矽烷。According to the same aspect of the present invention, in order to impart flexibility to the oxime resin, a difunctional decane derivative monomer may be contained (having two hydrolyzable groups X per molecule, and two oxygen atoms bonded to each ruthenium atom form two Functional siloxane-bonded monomer). Preferred hydrolyzable difunctional decane derivative monomers, for example, diphenyldichlorodecane, diphenyldibromodecane, diphenyldimethoxydecane, diphenyldiethoxydecane, phenylmethyl Dichlorodecane, phenylmethyldibromodecane, phenylmethyldimethoxydecane, phenylmethyldiethoxydecane, γ-glycidoxypropylmethyldimethoxydecane, γ - glycidoxypropylmethyldiethoxydecane, γ-(meth)acryloxypropylmethyldimethoxydecane, γ-(meth)acryloxypropylmethyldiethoxy Baseline, γ-aminopropylmethyldimethoxydecane, γ-aminopropylmethyldiethoxydecane, heptafluorooctylmethyldimethoxydecane, heptadecafluorooctyl Diethoxy decane.

另外，矽氧片段也與與上述相同，較佳為使用以下述平均組成式(1)表示之矽氧：Further, the oxygen-containing fragment is also the same as described above, and it is preferred to use the oxygen which is represented by the following average composition formula (1):

R1 p Si(OR2 )q O(4-p-q)/2 　...(1)R 1 p Si(OR 2 ) q O (4-pq)/2 (1)

(式中，R1 為未取代或經取代之一價烴基，R2 係選自由氫原子、碳數1~6之未取代一價烴基或碳數1~6之烷氧基取代之一價烴基，p及q為滿足0<p<4，0<q<4，0<(p+q)<4之數)。(wherein R 1 is an unsubstituted or substituted one-valent hydrocarbon group, and R 2 is selected from the group consisting of a hydrogen atom, an unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms; The hydrocarbon group, p and q are those satisfying 0 < p < 4, 0 < q < 4, 0 < (p + q) < 4.

上述式中，R1 之未取代或經取代之一價烴基較佳為碳數1~18者，未取代之一價烴基之具體例有甲基、乙基、丙基、異丙基、丁基、第三丁基、己基、環己基、辛基、癸基等烷基，乙烯基、烯丙基、5-己烯基、9-癸烯基等烯基，苯基等芳基，苄基、苯基乙基等芳烷基等。又，經取代之一價烴基為未取代之一價烴基之氫原子之一部分或全部經取代基取代者，而取代基可使用1)氟、氯等鹵素原子，2)縮水甘油氧基、環氧基環己基等環氧官能基，3)甲基丙烯酸基、丙烯酸基等(甲基)丙烯酸官能基，4)胺基、胺基乙基胺基、苯基胺基、二丁基胺基等胺基官能基，5)巰基、四硫醚基等含硫官能基，6)(聚氧伸烷基)烷基醚基等烷基醚基，7)羧基、磺醯基等陰離子性基，8)含有四級銨鹽構造之基團等，但作為反應基以2)、3)者為佳，尤其以具有環氧官能基者為佳。此經取代一價烴基之具體例有三氟丙基、全氟丁基乙基、全氟辛基乙基、3-氯丙基、2-(氯甲基苯基)乙基、3-縮水甘油氧基丙基、2-(3,4-環氧基環己基)乙基、3-(甲基)丙烯氧基丙基、(甲基)丙烯氧基甲基、3-胺基丙基、N-(2-胺基乙基)胺基丙基、3-(N-苯基胺基)丙基、3-二丁胺基丙基、3-巰基丙基、聚氧伸乙基氧基丙基、3-羥基羰基丙基、3-三丁基銨丙基等。此等中以甲基、丙基、己基、苯基為佳。In the above formula, the unsubstituted or substituted monovalent hydrocarbon group of R 1 is preferably a carbon number of 1 to 18, and specific examples of the unsubstituted one-valent hydrocarbon group are a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group. An alkyl group such as a tributyl group, a hexyl group, a cyclohexyl group, an octyl group or a decyl group; an alkenyl group such as a vinyl group, an allyl group, a 5-hexenyl group or a 9-nonenyl group; an aryl group such as a phenyl group; An aralkyl group such as a phenylethyl group or the like. Further, the substituted one-valent hydrocarbon group is partially or wholly substituted with one or more of the hydrogen atoms of the unsubstituted one-valent hydrocarbon group, and the substituent may be 1) a halogen atom such as fluorine or chlorine, 2) a glycidyloxy group or a ring. An epoxy functional group such as an oxycyclohexyl group; 3) a (meth)acrylic acid functional group such as a methacrylic group or an acrylic group; 4) an amine group, an aminoethylamino group, a phenylamino group, and a dibutylamino group. An amine functional group, 5) a sulfur-containing functional group such as a mercapto group or a tetrasulfide group, an alkyl ether group such as 6) a polyoxyalkylene alkyl ether group, and 7 an anionic group such as a carboxyl group or a sulfonyl group. 8) A group containing a quaternary ammonium salt structure, etc., preferably 2) or 3) as the reactive group, particularly preferably having an epoxy functional group. Specific examples of the substituted monovalent hydrocarbon group are trifluoropropyl, perfluorobutylethyl, perfluorooctylethyl, 3-chloropropyl, 2-(chloromethylphenyl)ethyl, 3-glycidol. Oxypropyl, 2-(3,4-epoxycyclohexyl)ethyl, 3-(meth)acryloxypropyl, (meth)acryloxymethyl, 3-aminopropyl, N-(2-Aminoethyl)aminopropyl, 3-(N-phenylamino)propyl, 3-dibutylaminopropyl, 3-mercaptopropyl, polyoxyethyloxy Propyl, 3-hydroxycarbonylpropyl, 3-tributylammoniumpropyl and the like. Among them, a methyl group, a propyl group, a hexyl group or a phenyl group is preferred.

R2 之碳數1~6之未取代或經取代之一價烴基之例有包含甲基、乙基、丙基、異丙基、丁基、第二丁基、第三丁基等烷基，異丙烯基等烯基，苯基等芳基之未取代一價烴基，或甲氧基甲基、乙氧基乙基、乙氧基甲基、甲氧基乙基等烷氧基烷基等經烷氧基取代之一價烴基。Examples of the unsubstituted or substituted one-valent hydrocarbon group having 1 to 6 carbon atoms of R 2 include an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a second butyl group, and a third butyl group. An alkenyl group such as an isopropenyl group, an unsubstituted monovalent hydrocarbon group of an aryl group such as a phenyl group, or an alkoxyalkyl group such as a methoxymethyl group, an ethoxyethyl group, an ethoxymethyl group or a methoxyethyl group. The alkoxy group is substituted with a monovalent hydrocarbon group.

依據本發明之一樣態時，為了對矽氧片段賦予柔軟性，亦可含有二官能基矽烷衍生物單體(每分子具有兩個水解性基X，且各矽原子上鍵結兩個氧原子形成二官能基矽氧烷鍵之單體)。較佳之水解性二官能基矽烷衍生物單體，例如有二苯基二氯矽烷、二苯基二溴矽烷、二苯基二甲氧基矽烷、二苯基二乙氧基矽烷、苯基甲基二氯矽烷、苯基甲基二溴矽烷、苯基甲基二甲氧基矽烷、苯基甲基二乙氧基矽烷、γ-縮水甘油氧基丙基甲基二甲氧基矽烷、γ-縮水甘油氧基丙基甲基二乙氧基矽烷、γ-(甲基)丙烯氧基丙基甲基二甲氧基矽烷、γ-(甲基)丙烯氧基丙基甲基二乙氧基矽烷、γ-胺基丙基甲基二甲氧基矽烷、γ-胺基丙基甲基二乙氧基矽烷、十七氟辛基甲基二甲氧基矽烷、十七氟辛基甲基二乙氧基矽烷。According to the same aspect of the present invention, in order to impart flexibility to the oxygen-containing fragment, a difunctional decane derivative monomer (having two hydrolyzable groups X per molecule and two oxygen atoms bonded to each of the ruthenium atoms) may be contained. A monomer forming a difunctional siloxane chain). Preferred hydrolyzable difunctional decane derivative monomers, for example, diphenyldichlorodecane, diphenyldibromodecane, diphenyldimethoxydecane, diphenyldiethoxydecane, phenylmethyl Dichlorodecane, phenylmethyldibromodecane, phenylmethyldimethoxydecane, phenylmethyldiethoxydecane, γ-glycidoxypropylmethyldimethoxydecane, γ - glycidoxypropylmethyldiethoxydecane, γ-(meth)acryloxypropylmethyldimethoxydecane, γ-(meth)acryloxypropylmethyldiethoxy Baseline, γ-aminopropylmethyldimethoxydecane, γ-aminopropylmethyldiethoxydecane, heptafluorooctylmethyldimethoxydecane, heptadecafluorooctyl Diethoxy decane.

本發明中，中間層可含有之上述兩種以外之樹脂，例如有聚酯、聚丙烯酸酯、聚甲基丙基酸酯、聚丙烯酸、聚甲基丙烯酸、聚苯乙烯、聚乙烯、環氧樹脂、聚碳酸酯、聚丙烯醯胺、聚醯胺、多元胺、多元醇、聚胺基甲酸酯、聚醚、聚硫醚、聚酚、該等之複合物、該等經矽氧改質、或鹵素改質的樹脂等。In the present invention, the intermediate layer may contain resins other than the above two, such as polyester, polyacrylate, polymethyl propyl ester, polyacrylic acid, polymethacrylic acid, polystyrene, polyethylene, epoxy. Resin, polycarbonate, polypropylene decylamine, polyamine, polyamine, polyol, polyurethane, polyether, polythioether, polyphenol, composites of these, etc. A resin that has been modified by halogen or halogen.

又，本發明中，中間層可含有之上述兩種以外之片段，例如有聚酯片段(segment)、聚丙烯酸酯片段、聚甲基丙基酸酯片段、聚丙烯酸片段、聚甲基丙烯酸片段、聚苯乙烯片段、聚乙烯片段、聚碳酸酯片段、聚丙烯醯胺片段、聚醯胺片段、多元胺片段、多元醇片段、聚胺基甲酸酯片段、聚醚片段、聚硫醚片段、聚酚片段、該等經矽氧改質或鹵素改質之片段等。Further, in the present invention, the intermediate layer may contain fragments other than the above two, such as a polyester segment, a polyacrylate segment, a polymethyl acrylate fragment, a polyacrylic acid fragment, and a polymethacrylic acid fragment. , polystyrene fragments, polyethylene fragments, polycarbonate fragments, polyacrylamide fragments, polyamine fragments, polyamine fragments, polyol fragments, polyurethane fragments, polyether fragments, polythioether fragments , polyphenol fragments, such oxime-modified or halogen-modified fragments, and the like.

本發明中，中間層除上述樹脂成分外，亦可含有著色料、體質顏料、亮光調整劑、紫外線吸收劑、光安定化劑、造膜助劑、硬化劑、界面活性劑、黏度調整劑、消泡劑、pH調整劑等。In the present invention, the intermediate layer may contain, in addition to the above resin component, a coloring material, an extender pigment, a bright light adjusting agent, an ultraviolet absorber, a light stabilizer, a film forming aid, a hardener, a surfactant, a viscosity adjuster, Defoamer, pH adjuster, etc.

著色料可使用無機顏料、有機顏料、染料等。As the coloring material, an inorganic pigment, an organic pigment, a dye, or the like can be used.

無機顏料可使用氧化鈦、鋅白、紅色氧化鐵、氧化鉻、鈷藍、鐵黑等金屬氧化物系，氧化鋁白、黃色氧化鐵等金屬氫氧化物系、普魯士藍等亞鐵氰化合物系、黃鉛、鉻酸鋅、鉬紅等鉻酸鉛系、硫化鋅、朱紅、鎘黃、鎘紅等硫化物、硒化合物、重晶石(Barite)、沉降性硫酸鋇等硫酸鹽系、碳酸氫鈣、沉降性碳酸鈣等碳酸鹽系、含水矽酸鹽、灰石、群青等矽酸鹽系、碳黑等碳系、鋁粉、青銅(bronze)粉、鋅粉等金屬粉系、雲母‧氧化鈦系等珍珠顏料系等。As the inorganic pigment, a metal oxide such as titanium oxide, zinc white, red iron oxide, chromium oxide, cobalt blue or iron black, a metal hydroxide such as alumina white or yellow iron oxide, or a ferrocyanide compound such as Prussian blue can be used. Lead, such as lead, zinc sulfide, vermilion, cadmium yellow, cadmium red, sulphate, barite, barium sulfate Carbonate such as calcium hydride or sedimentary calcium carbonate, metal silicate such as hydrous citrate, limestone or ultramarine, carbonaceous such as carbon black, aluminum powder, bronze powder, zinc powder, and mica ‧Pearl pigments such as titanium oxide.

有機顏料可使用萘酚綠B等亞硝基系顏料、萘酚S等之硝基顏料系、立索爾紅(LitholRed)、金光紅(Lake Red)C、耐曬黃(FAST YELLOW)、萘酚紅等偶氮顏料系，鹼藍(Alkali blue)紅、羅丹明(Rhodamine)紅、喹吖啶酮紅(Quinacridone Red)、二噁嗪紫(Dioxazine violet)、異吲哚啉酮黃等之縮合多環顏料系。As the organic pigment, a nitroso pigment such as naphthol green B, a nitro pigment system such as naphthol S, Lithhol Red, Lake Red C, FAST YELLOW, naphthalene can be used. Azo pigments such as phenol red, Alkali blue red, Rhodamine red, Quinacridone Red, Dioxazine violet, isoindolinone yellow, etc. Condensed polycyclic pigment system.

染料可使用分散染料、鹼性染料、直接染料、酸性染料。Disperse dyes, basic dyes, direct dyes, acid dyes can be used as the dye.

體質顏料可使用例如氧化鈦晶鬚、碳酸鈣晶鬚、鈦酸鉀晶鬚、硼酸鋁晶鬚、雲母、滑石、硫酸鋇、碳酸鉀、矽砂、矽藻土、高嶺土、灰石、陶土、碳酸鋇等。As the extender pigment, for example, titanium oxide whiskers, calcium carbonate whiskers, potassium titanate whiskers, aluminum borate whiskers, mica, talc, barium sulfate, potassium carbonate, barium sand, diatomaceous earth, kaolin, limestone, clay, Barium carbonate and the like.

亮光調整劑可使用例如無機系之亮光調整劑、有機系之亮光調整劑等。無機系之亮光調整劑可使用例如乾式氧化矽、濕式氧化矽、碳酸鈣、雲母、氮化硼、氧化鈦。有機系之亮光調整劑可使用例丙烯酸樹脂球、胺基甲酸酯樹脂球、矽氧樹脂粉、氟素樹脂粉等之樹脂球。As the brightening adjuster, for example, an inorganic bright light adjusting agent, an organic bright light adjusting agent, or the like can be used. As the inorganic light brightening agent, for example, dry cerium oxide, wet cerium oxide, calcium carbonate, mica, boron nitride, or titanium oxide can be used. As the organic light modulating agent, a resin ball such as an acrylic resin ball, a urethane resin ball, a silicone resin powder, or a fluororesin powder can be used.

紫外線吸收劑可使用二苯甲酮系、苯并***系、三嗪系紫外線吸收劑。As the ultraviolet absorber, a benzophenone type, a benzotriazole type, or a triazine type ultraviolet absorber can be used.

上述二苯甲酮系之紫外線吸收劑，具體而言可適當地使用2,4-二羥基二苯甲酮、2-羥基-4-甲氧基二苯甲酮、2-羥基-4-甲氧基二苯甲酮-5-磺酸、2-羥基-4-正辛氧基二苯甲酮、2-羥基-4-正十二烷氧基二苯甲酮、2-羥基-4-苄氧基二苯甲酮、雙(5-苯甲醯基-4-羥基-2-甲氧基苯基)甲烷、2,2'-二羥基-4-甲氧基二苯甲酮、2,2'-二羥基-4,4'-二甲氧基二苯甲酮、2,2',4,4'-四羥基二苯甲酮、4-十二烷氧基-2-羥基二苯甲酮、2-羥基-4-甲氧基-2'-羧基二苯甲酮、2-羥基-4-硬脂氧基二苯甲酮、辛苯酮(octabenzone)、及2-羥基-4-丙烯氧基二苯甲酮、2-羥基-4-甲基丙烯氧基二苯甲酮、2-羥基-5-丙烯氧基二苯甲酮、2-羥基-5-甲基丙烯氧基二苯甲酮、2-羥基-4-(丙烯氧基-乙氧基)二苯甲酮、2-羥基-4-(丙烯氧基-乙氧基)二苯甲酮、2-羥基-4-(甲基丙烯氧基-二乙氧基)二苯甲酮、2-羥基-4-(丙烯氧基-三乙氧基)二苯甲酮等聚合性二苯甲酮系紫外線吸收劑或彼等之(共)聚合物等。The above benzophenone-based ultraviolet absorber, specifically, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methyl can be suitably used. Oxybenzophenone-5-sulfonic acid, 2-hydroxy-4-n-octyloxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4- Benzyloxybenzophenone, bis(5-benzylidene-4-hydroxy-2-methoxyphenyl)methane, 2,2'-dihydroxy-4-methoxybenzophenone, 2 , 2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 4-dodecyloxy-2-hydroxyl Benzene, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2-hydroxy-4-stearyloxybenzophenone, octabenzone, and 2-hydroxy- 4-propoxy benzophenone, 2-hydroxy-4-methylpropoxy benzophenone, 2-hydroxy-5-propoxy benzophenone, 2-hydroxy-5-methyl propylene oxide Benzophenone, 2-hydroxy-4-(acryloxy-ethoxy)benzophenone, 2-hydroxy-4-(acryloxy-ethoxy)benzophenone, 2-hydroxy- 4-(Methacryloxy-diethoxy)benzophenone, 2-hydroxy-4-(acryloxy-triethoxy)diphenyl And other polymerizable benzophenone ultraviolet absorbers or their (co) polymer.

上述苯并***系紫外線吸收劑，具體而言例如有2-(2'-羥基-5'-甲基苯基)苯并***、2-(2'-羥基-5'-第三丁基苯基)苯并***、2-(2'-羥基-3',5'-二第三丁基苯基)苯并***、2-(2-羥基-5-第三辛基苯基)苯并***、2-(2-羥基-3,5-二第三辛基苯基)苯并***、2-[2'-羥基-3',5'-雙(α,α'-二甲基苄基)苯基]苯并***、甲基-3-[3-第三丁基-5-(2H-苯并***-2-基)-4-羥基苯基]丙酸酯與聚乙二醇(分子量300)之縮合物，異辛基-3-[3-(2H-苯并***-2-基)-5-第三丁基-4-羥基苯基]丙酸酯、2-(3-十二烷基-5-甲基-2-羥基苯基)苯并***、2-(2'-羥基-3'-第三丁基-5'-甲基苯基)-5-氯苯并***、2-(2'-羥基-3',5'-二第三戊基苯基)苯并***、2-(2'-羥基-4'-辛氧基苯基)苯并***、2-[2'-羥基-3'-(3",4",5",6"-四氫苯二醯亞胺甲基)-5'-甲基苯基]苯并***、2,2-亞甲基雙[4-(1,1,3,3-四甲基丁基)-6-(2H-苯并***-2-基)酚]、2-(2H-苯并***-2-基)-4,6-雙(1-甲基-1-苯基乙基)酚、及2-(2'-羥基-5'-甲基丙烯氧基乙基苯基)-2H-苯并***、2-(2'-羥基-5'-甲基丙烯氧基乙基-3-第三丁基苯基)-2H-苯并***、2-(2'-羥基-5'-甲基丙烯氧基丙基-3-第三丁基苯基)-5-氯-2H-苯并***、3-甲基丙烯醯基-2-羥基丙基-3-[3'-(2"-苯并***基)-4-羥基-5-第三丁基]苯基丙酸酯等聚合性苯并***系紫外線吸收劑或該等之(共)聚合物。The above benzotriazole-based ultraviolet absorber, specifically, for example, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5'-tributyl) Phenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-t-butylphenyl)benzotriazole, 2-(2-hydroxy-5-t-octylbenzene Benzotriazole, 2-(2-hydroxy-3,5-di-t-th-octylphenyl)benzotriazole, 2-[2'-hydroxy-3',5'-bis(α,α '-Dimethylbenzyl)phenyl]benzotriazole, methyl-3-[3-tert-butyl-5-(2H-benzotriazol-2-yl)-4-hydroxyphenyl] Condensate of propionate and polyethylene glycol (molecular weight 300), isooctyl-3-[3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl Propionate, 2-(3-dodecyl-5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'- Methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-third-pentylphenyl)benzotriazole, 2-(2'-hydroxy-4 '-Octyloxyphenyl)benzotriazole, 2-[2'-hydroxy-3'-(3",4",5",6"-tetrahydrobenzidine imine methyl)-5' -methylphenyl]benzotriazole, 2,2-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2- Phenol], 2-(2H-benzotriazol-2-yl)- 4,6-bis(1-methyl-1-phenylethyl)phenol, and 2-(2'-hydroxy-5'-methacryloxyethylphenyl)-2H-benzotriazole, 2-(2'-hydroxy-5'-methacryloxyethyl-3-tert-butylphenyl)-2H-benzotriazole, 2-(2'-hydroxy-5'-methacryl Oxypropyl-3-tert-butylphenyl)-5-chloro-2H-benzotriazole, 3-methylpropenyl-2-hydroxypropyl-3-[3'-(2"- A polymerizable benzotriazole-based ultraviolet absorber such as benzotriazolyl-4-hydroxy-5-tert-butyl]phenylpropionate or the like (co)polymer.

三嗪系紫外線吸收劑可適當地使用羥基苯基三嗪化合物。As the triazine-based ultraviolet absorber, a hydroxyphenyltriazine compound can be suitably used.

進一步含有受阻胺系及/或受阻酚系等光安定劑時，藉由與上述紫外線吸收劑之相乘效果，可更提高耐候性，故較佳。Further, when a light stabilizer such as a hindered amine-based or/or hindered phenol-based compound is contained, the weather resistance can be further improved by the effect of multiplying the ultraviolet ray absorbing agent, which is preferable.

受阻胺系光安定劑之具體例有雙(2,2,6,6-四甲基-4-哌啶基)丁二酸酯、雙(2,2,6,6-四甲基哌啶基)癸二酸酯、雙(1,2,2,6,6-五甲基-4-哌啶基)2-(3,5-二第三丁基-4-羥基苄基)-2-丁基丙二酸酯、1-[2-[3-(3,5-二第三丁基-4-羥基苯基)丙烯基氧基]乙基]-4-[3-(3,5-二第三丁基-4-羥基苯基)丙烯基氧基]-2,2,6,6-四甲基哌啶、雙(1,2,2,6,6-五甲基-4-哌啶基)癸二酸酯與甲基-1,2,2,6,6-五甲基-4-哌啶基-癸二酸酯之混合物、雙(1-辛氧基-2,2,6,6-四甲基-4-哌啶基)癸二酸酯、及1,2,2,6,6-五甲基-4-哌啶基甲基丙烯酸酯、1,2,2,6,6-五甲基-4-哌啶基丙烯酸酯、2,2,6,6-四甲基-4-哌啶基甲基丙烯酸酯、2,2,6,6-四甲基-4-哌啶基丙烯酸酯、1,2,2,6,6-五甲基-4-亞胺基哌啶基甲基丙烯酸酯、2,2,6,6-四甲基-4-亞胺基哌啶基甲基丙烯酸酯、4-氰基-2,2,6,6-四甲基-4-哌啶基甲基丙烯酸酯、4-氰基-1,2,2,6,6-五甲基-4-哌啶基甲基丙烯酸酯等聚合性之受阻胺系紫外線吸收劑或該等之(共)聚合物。Specific examples of hindered amine light stabilizers are bis(2,2,6,6-tetramethyl-4-piperidyl)succinate, bis(2,2,6,6-tetramethylpiperidine). Sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl)2-(3,5-di-t-butyl-4-hydroxybenzyl)-2 -butylmalonate, 1-[2-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propenyloxy]ethyl]-4-[3-(3, 5-di-t-butyl-4-hydroxyphenyl)propenyloxy]-2,2,6,6-tetramethylpiperidine, bis(1,2,2,6,6-pentamethyl- Mixture of 4-piperidinyl) sebacate with methyl-1,2,2,6,6-pentamethyl-4-piperidinyl-sebacate, bis(1-octyloxy-2) , 2,6,6-tetramethyl-4-piperidinyl) sebacate, and 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 1,2 , 2,6,6-pentamethyl-4-piperidyl acrylate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 2,2,6,6-tetra Methyl-4-piperidinyl acrylate, 1,2,2,6,6-pentamethyl-4-iminopiperidinyl methacrylate, 2,2,6,6-tetramethyl- 4-iminopiperidinyl methacrylate, 4-cyano-2,2,6,6-tetramethyl-4-piperidyl methacrylate, 4-cyano-1,2,2 , 6,6-pentamethyl-4-piperidyl methacrylate A hindered amine-based ultraviolet absorber or such (co)polymer.

另外，受阻酚系光安定劑之具體例可適當地使用雙(3,5-二第三丁基)-4-羥基甲苯。Further, as a specific example of the hindered phenol-based light stabilizer, bis(3,5-di-t-butyl)-4-hydroxytoluene can be suitably used.

依據本發明之較佳樣態時，中間層液為了改善其形成性，亦可含有造膜助劑。造膜助劑例如有乙酸異戊酯、乙酸氧代己酯、乙酸甲基甲氧基丁酯、丙酸乙基乙氧基酯、乙二醇單丁醚乙酸酯、二乙二醇單***乙酸酯、二乙二醇單丁醚乙酸酯、2,2,4-三甲基-1,3-戊二醇單異丁酸酯、2,2,4-三甲基-1,3-戊二醇二異丁酸酯、2,2,4-三甲基-1,3-戊二醇單2-乙基己酸酯、2,2,4-三甲基-1,3-戊二醇二2-乙基己酸酯等之酯系有機溶劑；苄醇、2,2,4-三甲基-1,3-戊二醇異丁酸酯(TEXANOL)、二乙二醇、異十三烷醇、1,3-辛二醇、甘油等醇系有機溶劑；乙二醇單己醚、乙二醇單2-乙基己醚、二乙二醇單***、二乙二醇二***、二乙二醇單丁醚、二乙二醇二丁醚、二乙二醇單2-乙基己醚、丙二醇單苯醚、三丙二醇甲醚等醚系有機溶劑等，可單獨或組合使用。In accordance with a preferred aspect of the invention, the intermediate layer fluid may also contain a film forming aid in order to improve its formability. The film-forming auxiliary agent is, for example, isoamyl acetate, oxoacetate acetate, methyl methoxybutyl acetate, ethyl ethoxy propionate, ethylene glycol monobutyl ether acetate, diethylene glycol single Ethyl acetate, diethylene glycol monobutyl ether acetate, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, 2,2,4-trimethyl-1 , 3-pentanediol diisobutyrate, 2,2,4-trimethyl-1,3-pentanediol mono-2-ethylhexanoate, 2,2,4-trimethyl-1, An ester-based organic solvent such as 3-pentanediol di-2-ethylhexanoate; benzyl alcohol, 2,2,4-trimethyl-1,3-pentanediol isobutyrate (TEXANOL), diethyl Alcohol-based organic solvent such as diol, isotridecyl alcohol, 1,3-octanediol or glycerin; ethylene glycol monohexyl ether, ethylene glycol mono-2-ethylhexyl ether, diethylene glycol monoethyl ether, two An ether-based organic solvent such as ethylene glycol diethyl ether, diethylene glycol monobutyl ether, diethylene glycol dibutyl ether, diethylene glycol mono 2-ethylhexyl ether, propylene glycol monophenyl ether or tripropylene glycol methyl ether. Can be used alone or in combination.

依據本發明之較佳樣態時，中間層可視需要併用矽氧成分與非矽氧成分中所含之官能基反應的硬化劑。In accordance with a preferred embodiment of the present invention, the intermediate layer may optionally be a hardener which reacts with a functional group contained in the non-oxygen component.

前述硬化劑之具體例有具有矽烷醇基及/或水解性矽烷基之化合物、聚環氧化合物、聚噁唑啉化合物、聚異氰酸酯等。尤其，使用具有作為前述矽氧成分與非矽氧成分中所含之官能基為羧基或羧酸酯基者時，較佳為使用具有環氧基與矽烷醇基及/或水解性矽烷基之化合物、聚環氧化合物、聚噁唑啉化合物之組合。Specific examples of the curing agent include a compound having a stanol group and/or a hydrolyzable alkyl group, a polyepoxy compound, a polyoxazoline compound, a polyisocyanate, and the like. In particular, when the functional group contained in the above-mentioned oxygen-containing component and non-oxygenated component is a carboxyl group or a carboxylate group, it is preferred to use an epoxy group and a stanol group and/or a hydrolyzable alkyl group. A combination of a compound, a polyepoxide, and a polyoxazoline compound.

前述具有矽烷醇基及/或水解性矽烷基之化合物，可使用例如甲基三甲氧基矽烷、甲基三乙氧基矽烷、甲基三正丁氧基矽烷、乙基三甲氧基矽烷、正丙基三甲氧基矽烷、異丁基三甲氧基矽烷、環己基三甲氧基矽烷、苯基三甲氧基矽烷、苯基三乙氧基矽烷、乙烯基三甲氧基矽烷或3-(甲基)丙烯醯氧基丙基三甲氧基矽烷等有機三烷氧基矽烷；二甲基二甲氧基矽烷、二甲基二乙氧基矽烷、二甲基二正丁氧基矽烷、二乙基二甲氧基矽烷、二苯基二甲氧基矽烷、甲基環己基二甲氧基矽烷或甲基苯基二甲氧基矽烷等二有機二烷氧基矽烷類；甲基三氯矽烷、乙基三氯矽烷、苯基三氯矽烷、乙烯基三氯矽烷、3-(甲基)丙烯醯氧基丙基三氯矽烷、二甲基二氯矽烷、二乙基二氯矽烷或二苯基二氯矽烷等各種氯矽烷類，或該等之部分水解縮合物等，其中較佳為使用有機三烷氧基矽烷或二有機二烷氧基矽烷。該等矽烷化合物可單獨使用亦可併用兩種以上。其他例如有3-縮水甘油氧基丙基三甲氧基矽烷、3-縮水甘油氧基丙基甲基二甲氧矽烷、3-縮水甘油氧基丙基三乙氧基矽烷、3-縮水甘油氧基丙基甲基二乙氧基矽烷、β-(3,4-環氧基環己基)乙基三甲氧基矽烷、以及該等之水解縮合物等。As the compound having a stanol group and/or a hydrolyzable alkylene group, for example, methyltrimethoxydecane, methyltriethoxydecane, methyltri-n-butoxydecane, ethyltrimethoxydecane, or the like can be used. Propyltrimethoxydecane, isobutyltrimethoxydecane, cyclohexyltrimethoxydecane,phenyltrimethoxydecane,phenyltriethoxydecane,vinyltrimethoxydecane or 3-(methyl) An organic trialkoxy decane such as propylene methoxy propyl trimethoxy decane; dimethyl dimethoxy decane, dimethyl diethoxy decane, dimethyl di-n-butoxy decane, diethyl two a diorganodialkoxynonane such as methoxydecane, diphenyldimethoxydecane, methylcyclohexyldimethoxydecane or methylphenyldimethoxydecane; methyltrichlorodecane, B Trichlorodecane, phenyltrichlorodecane, vinyltrichlorodecane, 3-(methyl)propenyloxypropyltrichlorodecane, dimethyldichlorodecane, diethyldichlorodecane or diphenyl Various chlorodecanes such as dichlorodecane, or partially hydrolyzed condensates thereof, among which organoalkoxynes are preferably used. Silane organic dialkoxy or di-Silane. These decane compounds may be used singly or in combination of two or more. Other examples are 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, 3-glycidoxypropyltriethoxydecane, 3-glycidyloxygen Propylmethyldiethoxydecane, β-(3,4-epoxycyclohexyl)ethyltrimethoxynonane, and the like, and the like, and the like.

前述聚環氧化合物例如有具有源自乙二醇、己二醇、新戊二醇、三羥甲基丙烷、季戊四醇、山梨糖醇、氫化雙酚A等之脂肪族或脂環式多元醇構造之聚縮水甘油醚類；雙酚A、雙酚S、雙酚F等芳香族系二醇之聚縮水甘油醚類；聚乙二醇、聚丙二醇、聚丁二醇等聚醚多元醇之聚縮水甘油醚類；參(2-羥基乙基)異氰尿酸酯之聚縮水甘油醚類；己二酸、丁烷四羧酸、苯二甲酸、對苯二甲酸等之脂肪族或芳香族多羧酸之聚縮水甘油酯類；環辛二烯、乙烯基環己烯等烴系二烯類之雙環氧化物類；雙(3,4-環氧基環己基甲基)己二酸酯、3,4-環氧基環己基甲基-3,4-環氧基環己基羧酸酯等脂環式聚環氧化合物等。The polyepoxy compound may have, for example, an aliphatic or alicyclic polyol structure derived from ethylene glycol, hexanediol, neopentyl glycol, trimethylolpropane, pentaerythritol, sorbitol, hydrogenated bisphenol A or the like. Polyglycidyl ethers; polyglycidyl ethers of aromatic diols such as bisphenol A, bisphenol S, and bisphenol F; polyether polyols such as polyethylene glycol, polypropylene glycol, and polybutylene glycol Glycidyl ether; polyglycidyl ether of ginseng (2-hydroxyethyl) isocyanurate; aliphatic or aromatic of adipic acid, butane tetracarboxylic acid, phthalic acid, terephthalic acid, etc. Polyglycidyl esters of polycarboxylic acids; diepoxides of hydrocarbon-based dienes such as cyclooctadiene and vinylcyclohexene; bis(3,4-epoxycyclohexylmethyl)adipate An alicyclic polyepoxide such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate.

前述噁唑啉化合物可使用例如2,2'-對-伸苯基-雙(1,3-噁唑啉)、2,2'-伸丁基-雙(1,3-噁唑啉)、2,2'-伸辛基-雙(2-噁唑啉)、2-異丙烯基-1,3-噁唑啉、或該等之聚合物等。As the above oxazoline compound, for example, 2,2'-p-phenylene-bis(1,3-oxazoline), 2,2'-butylene-bis(1,3-oxazoline), 2,2'-Exenyl-bis(2-oxazoline), 2-isopropenyl-1,3-oxazoline, or such polymers.

前述聚異氰酸酯可使用例如甲苯二異氰酸酯、二苯基甲烷-4,4'-二異氰酸酯等芳香族二異氰酸酯類；間-二甲苯二異氰酸酯、α,α,α',α'-四甲基-間-二甲苯二異氰酸酯等芳烷基二異氰酸酯類；六亞甲基二異氰酸酯、離胺酸二異氰酸酯、1,3-雙異氰酸酯甲基環己烷、2-甲基-1,3-二異氰酸酯環己烷、2-甲基-1,5-二異氰酸酯環己烷、異佛爾酮二異氰酸酯等。As the polyisocyanate, for example, an aromatic diisocyanate such as toluene diisocyanate or diphenylmethane-4,4'-diisocyanate; m-xylene diisocyanate, α,α,α',α'-tetramethyl- can be used. Aralkyl diisocyanates such as m-xylene diisocyanate; hexamethylene diisocyanate, diazonic acid diisocyanate, 1,3-bisisocyanate methylcyclohexane, 2-methyl-1,3-diisocyanate Cyclohexane, 2-methyl-1,5-diisocyanate cyclohexane, isophorone diisocyanate, and the like.

另外，前述聚異氰酸酯可使用具有異氫酸酯基之各種預聚物、具有異氰尿酸酯環之預聚物、具有雙縮脲構造之聚異氰酸酯、含有異氰酸酯基之乙烯系單體。Further, as the polyisocyanate, various prepolymers having an isohydrocarbonate group, a prepolymer having an isocyanurate ring, a polyisocyanate having a biuret structure, and a vinyl monomer containing an isocyanate group can be used.

作為硬化劑之前述聚異氰酸酯所具有之異氰酸酯基，視需要可藉由甲醇等以往已知之封閉劑(Block agent)被封閉化。The isocyanate group of the polyisocyanate which is a curing agent can be blocked by a conventionally known blocking agent such as methanol, if necessary.

本發明之光觸媒塗佈物所具有之中間層可使用將上述成分分散於溶劑中的塗佈液，藉由乾燥或燒成而形成。The intermediate layer of the photocatalyst coating material of the present invention can be formed by drying or baking using a coating liquid in which the above components are dispersed in a solvent.

塗佈液亦可含有界面活性劑以改善其塗佈性。界面活性劑可使用磺酸聚氧伸乙基烷基苯基醚銨鹽、磺酸聚氧伸乙基烷基苯基醚鈉鹽、脂肪酸鈉皂、脂肪酸鉀皂、二辛基磺基丁二酸鈉、烷基硫酸鹽、烷基醚硫酸鹽、烷基硫酸鈉鹽、烷基醚硫酸鈉鹽、聚氧伸乙基烷基醚硫酸鹽、聚氧伸乙基烷基醚硫酸鈉鹽、烷基硫酸鹽TEA鹽、聚氧伸乙基烷基醚硫酸鹽TEA鹽、2-乙基己基烷基硫酸酯鈉、醯基甲基牛磺酸鈉、月桂醯基甲基牛磺酸鈉、十二烷基苯磺酸鈉、磺基丁二酸月桂基2鈉、聚氧伸乙基磺基丁二酸月桂基2鈉、聚羧酸、油醯基肌胺酸、醯胺醚硫酸酯、月桂醯基水楊酸鹽、磺基FA酯鈉鹽等陰離性界面活性劑；聚氧伸乙基月桂基醚、聚氧伸乙基十三烷基醚、聚氧伸乙基鯨蠟基醚、聚氧伸乙基硬脂基醚、聚氧伸乙基油基醚、聚氧伸乙基烷基醚、聚氧伸乙基烷基酯、聚氧伸乙基烷基酚醚、聚氧伸乙基壬基苯基醚、聚氧伸乙基辛基苯基醚、聚氧伸乙基月桂酸酯、聚氧伸乙基硬脂酸酯、聚氧伸乙基烷基苯基醚、聚氧伸乙基油酸酯、山梨糖醇酐烷酯、聚氧伸乙基山梨糖醇酐烷酯、聚醚改質之矽氧、聚酯改質之矽氧、山梨糖醇酐月桂酸酯、山梨糖醇酐硬脂酸酯、山梨糖醇酐棕櫚酸酯、山梨糖醇酐油酸酯、山梨糖醇酐倍半油酸酯、聚氧伸乙基山梨糖醇酐月桂酸酯、聚氧伸乙基山梨糖醇酐硬脂酸酯、聚氧伸乙基山梨糖醇酐棕櫚酸酯、聚氧伸乙基山梨糖醇酐油酸酯、甘油硬脂酸酯、聚甘油脂肪酸酯、烷基烷醇醯胺、月桂酸二乙醇醯胺、油酸二乙醇醯胺、氧基伸乙基十二烷基胺、聚氧伸乙基十二烷基胺、聚氧伸乙基烷基胺、聚氧伸乙基十八烷基胺、聚氧伸乙基烷基丙二胺、聚氧伸乙基氧伸丙基嵌段聚合物、聚氧伸乙基硬脂酸酯等非離子性界面活性劑；二甲基烷基甜菜鹼、烷基甘胺酸、醯胺甜菜鹼、咪唑啉等兩性界面活性劑，十八烷基二甲基苄基氯化銨、烷基二甲基苄基氯化銨、十四烷基甲基苄基氯化銨、二油基二甲基氯化銨、1-羥基乙基-2-烷基咪唑啉四級鹽、烷基異喹啉鎓溴鹽、高分子胺、十八烷基三甲基氯化銨、烷基三甲基氯化銨、十二烷基三甲基氯化銨、十六烷基三甲基氯化銨、山萮基三甲基氯化銨、烷基咪唑啉四級鹽、二烷基二甲基氯化銨、十八烷基胺乙酸鹽、十四烷基胺乙酸鹽、烷基丙二胺乙酸鹽、二癸基二甲基氯化銨等陽離子性界面活性劑。The coating liquid may also contain a surfactant to improve its coatability. As the surfactant, a sulfonic acid polyoxyethylidene ethyl phenyl ether salt, a sulfonic acid polyoxyethylene ethyl phenyl ether salt, a sodium fatty acid sodium soap, a fatty acid potassium soap, a dioctyl sulfobutyl group can be used. Sodium, alkyl sulfate, alkyl ether sulfate, sodium alkyl sulfate, alkyl ether sulfate, polyoxyethylene ethyl ether sulfate, polyoxyethylene ethyl ether sulfate, Alkyl sulfate TEA salt, polyoxyethylene ethyl ether sulfate TEA salt, sodium 2-ethylhexyl alkyl sulfate, sodium mercaptomethyl taurate, sodium lauryl methyl taurate, Sodium dodecylbenzene sulfonate, sodium lauryl sulfosuccinate, polyoxyethylene ethyl sulfosuccinate, sodium lauryl 2, polycarboxylic acid, oleic acid creatinine, indoleamine sulfate An anionic surfactant such as lauryl salicyl salicylate or sulfo-FA ester sodium salt; polyoxy-extension ethyl lauryl ether, polyoxy-extension ethyl tridecyl ether, polyoxy-extension ethyl cetyl wax Ether, polyoxyethylene ethyl stearyl ether, polyoxyethylene ethyl oleyl ether, polyoxyethylene ethyl ether, polyoxyethylene ethyl ester, polyoxyethylene ethyl phenol ether, Polyoxyethylene ethyl phenyl ether, Oxyethyl octyl phenyl ether, polyoxyethylene ethyl laurate, polyoxyethylene ethyl stearate, polyoxyethylene ethyl phenyl ether, polyoxyethylene ethyl oleate, sorbus Alcoholic anhydride alkyl esters, polyoxyethylene ethyl sorbitan alkyl esters, polyether modified oxime, polyester modified oxime, sorbitan laurate, sorbitan stearate , sorbitan palmitate, sorbitan oleate, sorbitan sesquioleate, polyoxyethyl sorbitan laurate, polyoxyethyl sorbitol Fatty acid ester, polyoxyethylene ethyl sorbitan palmitate, polyoxyethylene sorbitan oleate, glyceryl stearate, polyglycerol fatty acid ester, alkyl alkanolamine, laurel Acid diethanol decylamine, oleic acid diethanol decylamine, oxy extended ethyl dodecylamine, polyoxyethylene ethyl dodecylamine, polyoxyethylidene amine, polyoxyethyl ether Nonionic surfactants such as alkylamine, polyoxyethylene ethyl propylene diamine, polyoxyethylene ethyl propyl block polymer, polyoxyethylene ethyl stearate; dimethyl alkane Betaine, Amphoteric surfactants such as lysine, guanamine, imidazoline, octadecyldimethylbenzylammonium chloride, alkyldimethylbenzylammonium chloride, tetradecylmethylbenzyl Ammonium chloride, dioleyl dimethyl ammonium chloride, 1-hydroxyethyl-2-alkyl imidazoline quaternary salt, alkyl isoquinolinium bromide, polymeric amine, octadecyl trimethyl Ammonium chloride, alkyltrimethylammonium chloride, dodecyltrimethylammonium chloride, cetyltrimethylammonium chloride, behenyltrimethylammonium chloride, alkylimidazolinetetra Cationic interface such as grade salt, dialkyldimethylammonium chloride, octadecylamine acetate, tetradecylamine acetate, alkyl propylenediamine acetate, dimercaptodimethylammonium chloride Active agent.

本發明中，調製中間層用之塗佈液亦可適度含有黏度調整劑、消泡劑、pH調整劑等。In the present invention, the coating liquid for preparing the intermediate layer may appropriately contain a viscosity adjusting agent, an antifoaming agent, a pH adjusting agent, and the like.

基材Substrate

本發明所用的基材只要是可於其上形成光觸媒層的材料時，不論是無機材料、有機材料，各種材料均可，其形狀亦無限制。就材料之觀點而言，基材之較佳例有金屬、陶磁、玻璃、塑膠、橡膠、石材、水泥、混凝土、纖維、布帛、木材、紙、該等之組合、該等之層合體、該等之表面上具有至少一層被膜者。就因吸水造成膨脹變形所容許之觀點而言，更佳為水泥、混凝土，就因熱造成膨脹變形之觀點而言，更佳為金屬、樹脂。The substrate used in the present invention may be any material as long as it is a material on which a photocatalyst layer can be formed, and the shape thereof is not limited. From the viewpoint of materials, preferred examples of the substrate are metal, ceramic, glass, plastic, rubber, stone, cement, concrete, fiber, cloth, wood, paper, combinations of these, laminates thereof, The surface has at least one layer of film on the surface. From the viewpoint of allowing expansion deformation due to water absorption, it is more preferably a metal or a resin from the viewpoint of expansion deformation due to heat, and cement or concrete.

就用途之觀點而言，基材之較佳例有外牆、屋頂、隔音牆、護欄、橋樑。建材例如有外牆、屋頂。基材之形狀並無特別限制，並不限於平板狀，亦可使用於彎曲面狀者。對於此等基材之任一種，亦可與上述各構成適當組合。Preferred examples of the substrate include an exterior wall, a roof, a soundproof wall, a guardrail, and a bridge. Building materials include, for example, exterior walls and roofs. The shape of the substrate is not particularly limited, and is not limited to a flat shape, and may be used for a curved surface. Any of these substrates may be appropriately combined with each of the above structures.

特別是對於至少其表面以有機材料形成的基材，可適合使用本發明。此處，其表面以有機材料形成之基材亦包含基材全部以有機材料所構成者，以無機材料構成之基材表面被有機材料被覆者(例如化妝板)之任一種。In particular, the present invention can be suitably used for a substrate having at least a surface formed of an organic material. Here, the base material whose surface is formed of an organic material also includes any one of the base material composed of an organic material, and the surface of the base material made of an inorganic material is covered with an organic material (for example, a cosmetic board).

塗裝體之使用Use of painted body

本發明之塗裝體即使於光觸媒被膜上產生龜裂，亦可確保基材與光觸媒層之密著性，且顯著抑制產生之龜裂朝表面側及基材側傳播或發展，同時對於氣體分解功能等之光觸媒功能也具有優異的性能。因此，本發明之塗裝體並不限於以下者，特別是適用於例如(1)橋樑等施加振動的情況，(2)基材為無釉之陶磁器、混凝土、水泥板、木材、石材等多孔質材料，且光觸媒塗裝體暴露於氣溫為0℃以下之氣氛的情形，(3)基材為金屬材料、橡膠、可撓性薄膜樹脂等具有可撓性的材料，光觸媒塗裝體係在形成光觸媒層後，經彎曲加工而形成的情況，(4)於一天之氣溫變化大為20℃以上之場所使用的情形，(5)基材為金屬、樹脂、橡膠、矽氧密封劑、墊圈等線膨脹率10-5 K-1 以上之熱膨脹率大之材料的情形，(6)氣溫之年溫差大為30℃以上之情形等之至少任一種情形，且光觸媒層之表面上被照射來自太陽光等可光激發光觸媒光之光源的光的情形。Even if the coating body of the present invention is cracked on the photocatalyst film, the adhesion between the substrate and the photocatalyst layer can be ensured, and the crack generated to the surface side and the substrate side can be remarkably suppressed from being propagated or developed, and at the same time, the gas is decomposed. Photocatalytic functions such as functions also have excellent performance. Therefore, the coated body of the present invention is not limited to the following, and is particularly suitable for, for example, (1) vibration application of a bridge or the like, and (2) substrate is an unglazed ceramic, concrete, cement board, wood, stone, etc. The material is used, and the photocatalyst coating body is exposed to an atmosphere having a temperature of 0 ° C or less. (3) The substrate is a flexible material such as a metal material, a rubber or a flexible film resin, and the photocatalyst coating system is formed. (4) When the photocatalyst layer is formed by bending, (4) When the temperature changes in a day is 20 ° C or more, (5) The substrate is made of metal, resin, rubber, silicone sealant, gasket, etc. At least one of the case where the coefficient of thermal expansion is 10 -5 K -1 or more, and (6) the temperature difference of the temperature is 30 ° C or more, and the surface of the photocatalyst layer is irradiated from the sun. A situation in which light such as light can excite light of a light source of photocatalyst light.

上述塗裝體於光觸媒層表面可能偶有下雨之環境下使用，也可發揮隨著降雨之自我清潔功能。再者，藉由使塗膜形成初期，換算與水之接觸角呈現未達20°，更佳為未達10°，更佳為未達5°之親水性，藉此可發揮實質上塗膜剛塗佈後優異之伴隨降雨所產生之自我清潔功能，同時可長時期維持其親水性。The above-mentioned coated body may be used in an environment where the surface of the photocatalyst layer may occasionally rain, and may also function as a self-cleaning function with rainfall. Further, by setting the initial stage of the coating film, the contact angle with water is less than 20°, more preferably less than 10°, more preferably less than 5°, whereby a substantially coating film can be exerted. It is excellent in self-cleaning function accompanying rainfall immediately after coating, and it can maintain its hydrophilicity for a long period of time.

[實施例][Examples]

光觸媒塗佈液之調製Photocatalyst coating liquid modulation

光觸媒塗佈液1Photocatalyst coating solution 1

將作為光觸媒之二氧化鈦水分散體(平均粒徑：30~60nm)、作為無機氧化物之水分散型膠體二氧化矽(平均粒徑：20~30nm)及水進行混合，得到固體成分濃度為5.5質量%、膠體二氧化矽含量在固體成分中為90質量%、光觸媒含量在固體成分中為10質量%的組成物。另外，相對於光觸媒塗佈劑100質量份，混合0.3質量份之非離子性界面活性劑，使塗佈光觸媒塗佈液時，獲得對基材之潤濕性，得到光觸媒塗佈液。A titanium dioxide aqueous dispersion (average particle diameter: 30 to 60 nm) as a photocatalyst, a water-dispersible colloidal ceria (average particle diameter: 20 to 30 nm) as an inorganic oxide, and water are mixed to obtain a solid concentration of 5.5. The mass% and the colloidal cerium oxide content were 90% by mass in the solid content, and the photocatalyst content was 10% by mass in the solid content. In addition, 0.3 parts by mass of the nonionic surfactant is mixed with 100 parts by mass of the photocatalyst coating agent, and when the photocatalyst coating liquid is applied, wettability to the substrate is obtained, and a photocatalyst coating liquid is obtained.

光觸媒塗佈液2Photocatalyst coating solution 2

將作為光觸媒之二氧化鈦水分散體(平均粒徑：30~60nm)、作為無機氧化物之水分散型膠體二氧化矽(平均粒徑：20~30nm)、四乙氧基矽烷及水進行混合，得到固體成分濃度為5.5質量%、膠體二氧化矽含量在固體成分中為66.2質量%、四乙氧基矽烷含量在固體成分中為26.5質量%、光觸媒含量在固體成分中為7.4質量%的組成物。另外，相對於光觸媒塗佈劑100質量份，混合0.3質量份之非離子性界面活性劑，使塗佈光觸媒塗佈液時，獲得對基材之潤濕性，得到光觸媒塗佈液。A titanium dioxide aqueous dispersion (average particle diameter: 30 to 60 nm) as a photocatalyst, a water-dispersible colloidal cerium oxide (average particle diameter: 20 to 30 nm) as an inorganic oxide, tetraethoxy decane, and water are mixed. The composition of the solid content was 5.5% by mass, the colloidal ceria content was 66.2% by mass in the solid content, the tetraethoxydecane content was 26.5% by mass in the solid content, and the photocatalyst content was 7.4% by mass in the solid content. Things. In addition, 0.3 parts by mass of the nonionic surfactant is mixed with 100 parts by mass of the photocatalyst coating agent, and when the photocatalyst coating liquid is applied, wettability to the substrate is obtained, and a photocatalyst coating liquid is obtained.

光觸媒塗佈液3Photocatalyst coating solution 3

將作為光觸媒之二氧化鈦水分散體(平均粒徑：30~60nm)、作為無機氧化物之水分散型膠體二氧化矽(平均粒徑：20~30nm)、四乙氧基矽烷及水進行混合，得到固體成分濃度為5.5質量%、膠體二氧化矽含量在固體成分中為31質量%、四乙氧基矽烷含量在固體成分中為62.1質量%、光觸媒含量在固體成分中為6.9質量%的組成物。另外，相對於光觸媒塗佈劑100質量份，混合0.3質量份之非離子性界面活性劑，使塗佈光觸媒塗佈液時，獲得對基材之潤濕性，得到光觸媒塗佈液。A titanium dioxide aqueous dispersion (average particle diameter: 30 to 60 nm) as a photocatalyst, a water-dispersible colloidal cerium oxide (average particle diameter: 20 to 30 nm) as an inorganic oxide, tetraethoxy decane, and water are mixed. A composition having a solid content concentration of 5.5% by mass, a colloidal cerium oxide content of 31% by mass in the solid content, a tetraethoxy decane content of 62.1% by mass in the solid content, and a photocatalyst content of 6.9% by mass in the solid content was obtained. Things. In addition, 0.3 parts by mass of the nonionic surfactant is mixed with 100 parts by mass of the photocatalyst coating agent, and when the photocatalyst coating liquid is applied, wettability to the substrate is obtained, and a photocatalyst coating liquid is obtained.

光觸媒塗佈液4Photocatalyst coating solution 4

將作為光觸媒之二氧化鈦水分散體(平均粒徑：30~60nm)、作為無機氧化物之水分散型膠體二氧化矽(平均粒徑：20~30nm)及烷氧基低聚物及水進行混合，得到固體成分濃度為5.5質量%、膠體二氧化矽含量在固體成分中為86.9質量%、烷氧基低聚物含量在固體成分中為3.5質量%、光觸媒含量在固體成分中為9.7質量%的組成物。另外，相對於光觸媒塗佈劑100質量份，混合0.3質量份之非離子性界面活性劑，使塗佈光觸媒塗佈液時，獲得對基材之潤濕性，得到光觸媒塗佈液。A titanium dioxide aqueous dispersion (average particle diameter: 30 to 60 nm) as a photocatalyst, a water-dispersible colloidal cerium oxide (average particle diameter: 20 to 30 nm) as an inorganic oxide, and an alkoxy oligomer and water are mixed. The solid content concentration was 5.5% by mass, the colloidal ceria content was 86.9 mass% in the solid content, the alkoxy oligomer content was 3.5% by mass in the solid content, and the photocatalyst content was 9.7% by mass in the solid content. Composition. In addition, 0.3 parts by mass of the nonionic surfactant is mixed with 100 parts by mass of the photocatalyst coating agent, and when the photocatalyst coating liquid is applied, wettability to the substrate is obtained, and a photocatalyst coating liquid is obtained.

光觸媒塗佈液5Photocatalyst coating solution 5

將作為光觸媒之二氧化鈦水分散體(平均粒徑：30~60nm)、作為無機氧化物之四乙氧基矽烷及水進行混合，得到固體成分濃度為5.5質量%、四乙氧基矽烷含量在固體成分中為78.3質量%、光觸媒含量在固體成分中為21.7質量%的組成物。另外，相對於光觸媒塗佈劑100質量份，混合0.3質量份之非離子性界面活性劑，使塗佈光觸媒塗佈液時，獲得對基材之潤濕性，得到光觸媒塗佈液。The titanium dioxide aqueous dispersion (average particle diameter: 30 to 60 nm) as a photocatalyst, tetraethoxy decane as an inorganic oxide, and water were mixed to obtain a solid concentration of 5.5% by mass and a tetraethoxy decane content in a solid. The composition was 78.3 mass% in the composition, and the photocatalyst content was 21.7% by mass in the solid content. In addition, 0.3 parts by mass of the nonionic surfactant is mixed with 100 parts by mass of the photocatalyst coating agent, and when the photocatalyst coating liquid is applied, wettability to the substrate is obtained, and a photocatalyst coating liquid is obtained.

光觸媒塗佈液6Photocatalyst coating liquid 6

將作為光觸媒之二氧化鈦水分散體(平均粒徑：30~60nm)、作為無機氧化物之烷氧基低聚物及水進行混合，得到固體成分濃度為5.5質量%、烷氧基低聚物含量在固體成分中為26.5質量%、光觸媒含量在固體成分中為73.5質量%的組成物。另外，相對於光觸媒塗佈劑100質量份，混合0.3質量份之非離子性界面活性劑，使塗佈光觸媒塗佈液時，獲得對基材之潤濕性，得到光觸媒塗佈液。The titanium dioxide aqueous dispersion (average particle diameter: 30 to 60 nm) as a photocatalyst, an alkoxy oligomer as an inorganic oxide, and water are mixed to obtain a solid content concentration of 5.5% by mass and an alkoxy oligomer content. The composition was 26.5% by mass in the solid content, and the photocatalyst content was 73.5% by mass in the solid content. In addition, 0.3 parts by mass of the nonionic surfactant is mixed with 100 parts by mass of the photocatalyst coating agent, and when the photocatalyst coating liquid is applied, wettability to the substrate is obtained, and a photocatalyst coating liquid is obtained.

中間層塗佈液之調製Modulation of the intermediate layer coating solution

以下實施例中使用之水系丙烯酸矽氧樹脂分散液之固體成分濃度為35%，水系胺基甲酸酯聚醚樹脂分散液之固體成分濃度為30%。The aqueous acrylic oxime resin dispersion used in the following examples had a solid content concentration of 35%, and the aqueous urethane polyether resin dispersion had a solid concentration of 30%.

又，以下係如下測定塗膜在25℃之損失正切。換言之，將中間層塗佈液以棒塗佈機#20塗佈於Teflon(註冊商標)薄片上並經乾燥。接著，於所得之塗膜上以棒塗佈機#20重複塗佈中間塗佈液並經乾燥。重複此操作直到乾燥膜厚成為約20μm為止。將所得之塗膜裁切成5mm×50mm之短條狀，並自Teflon(註冊商標)薄片上剝離，設置於固體黏彈性測定裝置上，以拉伸模式以頻率1Hz測定。Further, the following is a measurement of the loss tangent of the coating film at 25 °C. In other words, the intermediate layer coating liquid was applied onto a Teflon (registered trademark) sheet by a bar coater #20 and dried. Next, the intermediate coating liquid was repeatedly applied to the obtained coating film by a bar coater #20 and dried. This operation was repeated until the dry film thickness became about 20 μm. The obtained coating film was cut into a strip shape of 5 mm × 50 mm, and peeled off from a Teflon (registered trademark) sheet, and placed on a solid viscoelasticity measuring apparatus, and measured in a tensile mode at a frequency of 1 Hz.

中間層塗佈液1Intermediate layer coating solution 1

於矽氧含有率以SiO2 換算為75質量%之水系丙烯酸矽氧樹脂分散液100質量份中，依序添加202質量份之水系胺基甲酸酯聚醚樹脂分散液、14質量份之造膜助劑、5.4質量份之硬化劑、82質量份之水。所得混合液以攪拌機攪拌30分鐘，獲得固體成分濃度為25質量%之中間層塗佈液1。此中間層塗佈液1之聚矽氧烷比率為30質量%。20 parts by mass of an aqueous urethane polyether resin dispersion and 14 parts by mass of a water-based urethane resin polyether dispersion in an amount of 75% by mass in terms of SiO 2 . A film auxiliary agent, 5.4 parts by mass of a hardener, and 82 parts by mass of water. The resulting mixture was stirred with a stirrer for 30 minutes to obtain an intermediate layer coating liquid 1 having a solid concentration of 25% by mass. The ratio of the polyoxymethane of this intermediate layer coating liquid 1 was 30% by mass.

又，此處使用之水系胺基甲酸酯聚醚樹脂分散液之藉由依據JIS K7244-4之固體黏彈性測定裝置測定之損失彈性率的溫度變化曲線如圖1所示。如圖所示，光譜波峰係-30℃。又，所得之塗膜在25℃之損失正切為0.28。Further, the temperature change curve of the loss elastic modulus measured by the solid viscoelasticity measuring apparatus according to JIS K7244-4 is shown in Fig. 1 of the aqueous urethane polyether resin dispersion used herein. As shown, the spectral peak is -30 °C. Further, the loss of the obtained coating film at 25 ° C was 0.28.

中間層塗佈液2Intermediate layer coating solution 2

於矽氧含有率為75%之水系丙烯酸矽氧樹脂分散液100份中，依序添加875份之水系胺基甲酸酯聚醚樹脂分散液、45份之造膜助劑、5.4份之硬化劑、187份之水。所得混合液以攪拌機攪拌30分鐘，藉此獲得固體成分濃度為25%之中間層塗佈液2。該中間層塗佈液2之聚矽氧烷比率為10%。又，此處使用之水系胺基甲酸酯聚醚樹脂分散液之藉由依據JIS K7244-4之固體黏彈性測定裝置測定之損失彈性率的溫度變化曲線之光譜波峰係-30℃。又，自中間層塗佈液2所得之塗膜在25℃之損失正切為0.48。875 parts of water-based urethane polyether resin dispersion, 45 parts of film-forming auxiliary agent, and 5.4 parts of hardening were added to 100 parts of water-based acrylic oxime resin dispersion containing 75% oxygen content. Agent, 187 parts of water. The resulting mixture was stirred with a stirrer for 30 minutes, whereby an intermediate layer coating liquid 2 having a solid concentration of 25% was obtained. The intermediate layer coating liquid 2 had a polyoxane ratio of 10%. Further, the aqueous urethane polyether resin dispersion used herein has a spectral peak of -30 ° C which is a temperature change curve of the loss elastic modulus measured by a solid viscoelasticity measuring apparatus according to JIS K7244-4. Further, the loss tangent of the coating film obtained from the intermediate layer coating liquid 2 at 25 ° C was 0.48.

中間層塗佈液3Intermediate layer coating solution 3

於矽氧含有率為75%之水系丙烯酸矽氧樹脂分散液100份中，依序添加1885份之水系胺基甲酸酯聚醚樹脂分散液、90份之造膜助劑、5.4份之硬化劑、343份之水。所得混合液以攪拌機攪拌30分鐘，藉此獲得固體成分濃度為25%之中間層塗佈液3。該中間層塗佈液3之聚矽氧烷比率為5%。此處使用之水系胺基甲酸酯聚醚樹脂分散液之藉由依據JIS K7244-4之固體黏彈性測定裝置測定之損失彈性率的溫度變化曲線之光譜波峰之一為-30℃。又，自中間層塗佈液3所得之塗膜在25℃之損失正切為0.52。Adding 1885 parts of aqueous urethane polyether resin dispersion, 90 parts of film-forming auxiliary agent, and 5.4 parts of hardening to 100 parts of water-based acrylic oxime resin dispersion containing 75% oxygen content. Agent, 343 parts of water. The resulting mixture was stirred with a stirrer for 30 minutes, whereby an intermediate layer coating liquid 3 having a solid concentration of 25% was obtained. The ratio of the polyoxymethane of the intermediate layer coating liquid 3 was 5%. One of the spectral peaks of the temperature change curve of the loss elastic modulus measured by the solid viscoelasticity measuring apparatus according to JIS K7244-4 is -30 ° C, for the water-based urethane polyether resin dispersion used herein. Further, the coating film obtained from the intermediate layer coating liquid 3 had a loss tangent of 0.52 at 25 °C.

中間層塗佈液4Intermediate layer coating solution 4

於矽氧含有率為75%之水系丙烯酸矽氧樹脂分散液100份(固體成分濃度35%)中，依序添加10300份之水系丙烯酸酯系樹脂乳液、779份之造膜助劑、5.4份之硬化劑、9578份之水。所得混合液以攪拌機攪拌30分鐘，藉此獲得固成分濃度為25%之中間層塗佈液4。該中間層塗佈液4之聚矽氧烷比率為0.5%。又，此處使用之水系丙烯酸酯系樹脂乳液之藉由依據JIS K7244-4之固體黏彈性測定裝置測定之損失彈性率的溫度變化曲線之光譜波峰之一係2℃。又，自中間層塗佈液4所得之塗膜在25℃之損失正切為0.60。10 parts of water-based acrylate-based resin emulsion, 779 parts of film-forming auxiliary agent, and 5.4 parts were added to 100 parts of water-based acrylic acid-oxygen resin dispersion (solid content: 35%) having a nitrogen content of 75%. Hardener, 9576 parts of water. The resulting mixture was stirred with a stirrer for 30 minutes, whereby an intermediate layer coating liquid 4 having a solid concentration of 25% was obtained. The ratio of the polyoxymethane of the intermediate layer coating liquid 4 was 0.5%. In addition, one of the spectral peaks of the temperature change curve of the loss elastic modulus measured by the solid viscoelasticity measuring apparatus according to JIS K7244-4 is 2 ° C. Further, the coating film obtained from the intermediate layer coating liquid 4 had a loss tangent of 0.60 at 25 °C.

中間層塗佈液5Intermediate layer coating solution 5

於矽氧含有率為75%之水系丙烯酸矽氧樹脂分散液(固體成分濃度35%)100份中，依序添加11444份之水系丙烯酸酯系樹脂乳液、779份之造膜助劑、5.4份之硬化劑、8433份之水。所得混合液以攪拌機攪拌30分鐘，藉此獲得固體成分濃度為25%之中間層塗佈液5。此中間層塗佈液5之聚矽氧烷比率為0.5%。又，此處使用之水系丙烯酸酯系樹脂乳液之藉由依據JIS K7244-4之固體黏彈性測定裝置測定之損失彈性率的溫度變化曲線之光譜波峰之一係-35℃。又，自中間層塗佈液5所得之塗膜在25℃之損失正切為0.48。In 100 parts of a water-based acrylic oxime resin dispersion (solid content: 35%) having a nitrogen content of 75%, 11444 parts of a water-based acrylate-based resin emulsion, 779 parts of a film-forming auxiliary agent, and 5.4 parts were sequentially added. Hardener, 8433 parts of water. The resulting mixture was stirred with a stirrer for 30 minutes, whereby an intermediate layer coating liquid 5 having a solid concentration of 25% was obtained. The ratio of the polyoxymethane of this intermediate layer coating liquid 5 was 0.5%. In addition, one of the spectral peaks of the temperature change curve of the loss elastic modulus measured by the solid viscoelasticity measuring apparatus according to JIS K7244-4 is -35 ° C. Moreover, the loss tangent of the coating film obtained from the intermediate layer coating liquid 5 at 25 ° C was 0.48.

中間層塗佈液6Intermediate layer coating solution 6

於矽氧含有率為75%之水系丙烯酸矽氧樹脂分散液100份中，依序添加10300份之水系丙烯酸酯系樹脂乳液、779份之造膜助劑、5.4份之硬化劑、9578份之水。所得混合液以攪拌機攪拌30分鐘，藉此獲得固體成分濃度為25%之中間層塗佈液6。此中間層塗佈液6之聚矽氧烷比率為0.5%。又，此處使用之水系丙烯酸酯系樹脂乳液之藉由依據JIS K7244-4之固體黏彈性測定裝置測定之損失彈性率的溫度變化曲線之光譜波峰之一係24℃。又，自中間層塗佈液6所得之塗膜在25℃之損失正切為1.00。10 parts of water-based acrylate-based resin emulsion, 779 parts of film-forming auxiliary agent, 5.4 parts of hardening agent, and 9778 parts were added to 100 parts of water-based acrylic oxime resin dispersion containing 75% oxygen content. water. The resulting mixture was stirred with a stirrer for 30 minutes, whereby an intermediate layer coating liquid 6 having a solid concentration of 25% was obtained. The ratio of the polyoxymethane of this intermediate layer coating liquid 6 was 0.5%. In addition, one of the spectral peaks of the temperature change curve of the loss elastic modulus measured by the solid viscoelasticity measuring apparatus according to JIS K7244-4 is 24 ° C. Further, the coating film obtained from the intermediate layer coating liquid 6 had a loss tangent at 25 ° C of 1.00.

中間層塗佈液7Intermediate layer coating solution 7

於矽氧含有率為75%之水系丙烯酸矽氧樹脂分散液100份中，依序添加9346份之水系丙烯酸酯系樹脂乳液、776份之造膜助劑、5.4份之硬化劑、10495份之水。所得混合液以攪拌機攪拌30分鐘，藉此獲得固體成分濃度為25%之中間層塗佈液7。此中間層塗佈液7之聚矽氧烷比率為0.6%。又，此處使用之水系丙烯酸酯系樹脂乳液之藉由依據JIS K7244-4之固體黏彈性測定裝置測定之損失彈性率的溫度變化曲線之光譜波峰之一係24℃。又，自中間層塗佈液7所得之塗膜在25℃之損失正切為0.49。In 100 parts of a water-based acrylic oxime resin dispersion having a 矽oxygen content of 75%, 9346 parts of a water-based acrylate-based resin emulsion, 776 parts of a film-forming auxiliary agent, 5.4 parts of a hardening agent, and 10,495 parts were sequentially added. water. The resulting mixture was stirred with a stirrer for 30 minutes, whereby an intermediate layer coating liquid 7 having a solid concentration of 25% was obtained. The ratio of the polyoxymethane of this intermediate layer coating liquid 7 was 0.6%. In addition, one of the spectral peaks of the temperature change curve of the loss elastic modulus measured by the solid viscoelasticity measuring apparatus according to JIS K7244-4 is 24 ° C. Further, the loss tangent of the coating film obtained from the intermediate layer coating liquid 7 at 25 ° C was 0.49.

中間層塗佈液8Intermediate layer coating solution 8

於矽氧含有率為30%之水系丙烯酸矽氧樹脂分散液100份中，依序添加159份之水系胺基甲酸酯聚醚樹脂分散液、14份之造膜助劑、7.7份之硬化劑、100份之水。以攪拌機攪拌所得混合液30分鐘，藉此獲得固體成分濃度為25%之中間層塗佈液8。此中間層塗佈液8之聚矽氧烷比率為15%。此處使用之水系胺基甲酸酯聚醚樹脂乳液之藉由依據JIS K7244-4之固體黏彈性測定裝置測定之損失彈性率的溫度變化曲線之光譜波峰之一係-30℃。又，自中間層塗佈液8所得之塗膜在25℃之損失正切為0.48。In 100 parts of water-based acrylic oxime resin dispersion containing 30% oxygen content, 159 parts of aqueous urethane polyether resin dispersion, 14 parts of film-forming auxiliary agent, and 7.7 parts of hardening were sequentially added. Agent, 100 parts of water. The resulting mixture was stirred with a stirrer for 30 minutes, whereby an intermediate layer coating liquid 8 having a solid concentration of 25% was obtained. The ratio of the polyoxymethane of this intermediate layer coating liquid 8 was 15%. One of the spectral peaks of the temperature change curve of the loss elastic modulus measured by the solid viscoelasticity measuring apparatus according to JIS K7244-4 is -30 ° C. Further, the loss tangent of the coating film obtained from the intermediate layer coating liquid 8 at 25 ° C was 0.48.

中間層塗佈液9(比較例)Intermediate layer coating liquid 9 (comparative example)

於矽氧含有率為75%之水系丙烯酸矽氧樹脂分散液100份中，依序添加67份之水系胺基甲酸酯聚醚樹脂分散液、8.3份之造膜助劑、5.4份之硬化劑、61份之水。所得混合液以攪拌機攪拌30分鐘，藉此獲得固體成分濃度為25%之中間層塗佈液9。此中間層塗佈液9之聚矽氧烷比率為50%。又，此處使用之水系胺基甲酸酯聚醚樹脂乳液之藉由依據JIS K7244-4之固體黏彈性測定裝置測定之損失彈性率的溫度變化曲線之光譜波峰之一係-30℃。又，自中間層塗佈液9所得之塗膜在25℃之損失正切為0.13。In 100 parts of water-based acrylic oxime resin dispersion containing 75% oxygen content, 67 parts of water-based urethane polyether resin dispersion, 8.3 parts of film-forming auxiliary agent, and 5.4 parts of hardening were sequentially added. Agent, 61 parts of water. The resulting mixture was stirred with a stirrer for 30 minutes, whereby an intermediate layer coating liquid 9 having a solid concentration of 25% was obtained. The intermediate layer coating liquid 9 had a polyoxane ratio of 50%. Further, one of the spectral peaks of the temperature change curve of the loss elastic modulus measured by the solid viscoelasticity measuring apparatus according to JIS K7244-4 is -30 ° C. Further, the coating film obtained from the intermediate layer coating liquid 9 had a loss tangent at 25 ° C of 0.13.

中間層塗佈液10(比較例)Intermediate layer coating liquid 10 (comparative example)

於矽氧含有率為75%之水系丙烯酸矽氧樹脂分散液100份中，依序添加34份之水系胺基甲酸酯聚醚樹脂分散液、6.8份之造膜助劑、5.4份之硬化劑、56份之水。所得混合液以攪拌機攪拌30分鐘，藉此獲得固體成分濃度為25%之中間層塗佈液10。此中間層塗佈液10之聚矽氧烷比率為60%。又，自中間層塗佈液10所得之塗膜在25℃之損失正切為0.09。In 100 parts of water-based acrylic oxime resin dispersion containing 75% oxygen content, 34 parts of water-based urethane polyether resin dispersion, 6.8 parts of film-forming auxiliary agent, and 5.4 parts of hardening were sequentially added. Agent, 56 parts of water. The resulting mixture was stirred with a stirrer for 30 minutes, whereby an intermediate layer coating liquid 10 having a solid concentration of 25% was obtained. The intermediate layer coating liquid 10 had a polyoxane ratio of 60%. Further, the loss tangent of the coating film obtained from the intermediate layer coating liquid 10 at 25 ° C was 0.09.

中間層塗佈液11(比較例)Intermediate layer coating liquid 11 (comparative example)

於矽氧含有率為30%之水系丙烯酸矽氧樹脂分散液100份中，依序添加7.2份之造膜助劑、7.9份之硬化劑、76.5份之水。所得混合液以攪拌機攪拌30分鐘，藉此獲得固體成分濃度為25%之中間層塗佈液11。此中間層塗佈液11之聚矽氧烷比率為30%。又，此處使用之水系胺基甲酸酯聚醚樹脂乳液之藉由依據JIS K7244-4之固體黏彈性測定裝置測定之損失彈性率的溫度變化曲線之光譜波峰之一係60℃。又，自中間層塗佈液11所得之塗膜在25℃之損失正切為0.10。In 100 parts of the water-based acrylic oxime resin dispersion having a cerium oxygen content of 30%, 7.2 parts of a film-forming auxiliary agent, 7.9 parts of a curing agent, and 76.5 parts of water were sequentially added. The resulting mixture was stirred with a stirrer for 30 minutes, whereby an intermediate layer coating liquid 11 having a solid concentration of 25% was obtained. The intermediate layer coating liquid 11 had a polyoxane ratio of 30%. Further, one of the spectral peaks of the temperature change curve of the loss elastic modulus measured by the solid viscoelasticity measuring apparatus according to JIS K7244-4 is 60 ° C. Further, the coating film obtained from the intermediate layer coating liquid 11 had a loss tangent at 25 ° C of 0.10.

光觸媒塗裝體之製造及其評價Fabrication and evaluation of photocatalyst coating body

將水性丙烯酸樹脂塗料以乾燥膜厚成為約20μm之方式噴霧塗佈於可撓性板上，且以80℃乾燥30分鐘。接著，以使乾燥膜厚成為約200μm之方式噴霧塗佈水性丙烯酸胺基甲酸酯樹脂塗料，以80℃乾燥30分鐘，得到密著試驗用底塗塗裝基材。The aqueous acrylic resin coating was spray-coated on a flexible sheet so that the dried film thickness became about 20 μm, and dried at 80 ° C for 30 minutes. Then, the aqueous urethane acrylate resin coating material was spray-coated so that the dry film thickness became about 200 μm, and dried at 80 ° C for 30 minutes to obtain a primer coating substrate for adhesion test.

接著，以使乾燥膜厚成為10μm之方式將中間層塗佈液1~11噴霧塗佈於預先加熱至約50℃之密著試驗用底塗塗裝基材上，以90℃乾燥2分鐘。接著以乾燥膜厚成為0.3~0.7μm之方式噴霧塗佈光觸媒塗佈液1~6，得到光觸媒塗裝體。中間層塗佈液與光觸媒塗佈液之組合係如後表所示。Then, the intermediate layer coating liquids 1 to 11 were spray-coated on the primer substrate for adhesion test which was previously heated to about 50 ° C so that the dry film thickness was 10 μm, and dried at 90 ° C for 2 minutes. Then, the photocatalyst coating liquids 1 to 6 were spray-coated so that the dried film thickness was 0.3 to 0.7 μm to obtain a photocatalyst-coated body. The combination of the intermediate layer coating liquid and the photocatalyst coating liquid is as shown in the following table.

密著性能評價Adhesion performance evaluation

針對如此獲得之光觸媒塗裝體，如下述進行密著性能評價。首先，將光觸媒塗裝體投入於以JIS B7753所規定之日光耐候試驗機(SUGA試驗機製造，S-300C)中，100小時後取出。接著，在60℃水中浸漬10小時，接著以100℃乾燥1小時，接著在殺菌燈(東芝Litech製造)下(波長254nm)，以試驗體表面之照度成為10W/m2 之方式設置12小時之步驟，合計重複8次，總計試驗時間184小時。以接觸角計(協和界面科學製造之CA-X150型)測定所得之塗裝體與水之接觸角。接著，以掃描電子顯微鏡(日立製造，S800)100倍觀察所得之塗裝體表面，以目視評價光觸媒層之大約的殘存率。With respect to the photocatalyst-coated body thus obtained, adhesion performance evaluation was performed as follows. First, the photocatalyst-coated body was placed in a solar weathering tester (manufactured by SUGA Test Machine, S-300C) prescribed in JIS B7753, and taken out 100 hours later. Subsequently, it was immersed in water at 60 ° C for 10 hours, and then dried at 100 ° C for 1 hour, and then placed under a germicidal lamp (manufactured by Toshiba Litech) (wavelength: 254 nm), and the illuminance of the surface of the test piece was set to 10 W/m 2 for 12 hours. The procedure was repeated 8 times in total, and the total test time was 184 hours. The contact angle of the obtained coated body with water was measured by a contact angle meter (Model CA-X150 manufactured by Kyowa Interface Science Co., Ltd.). Next, the surface of the obtained coated body was observed 100 times by a scanning electron microscope (manufactured by Hitachi, S800), and the approximate residual ratio of the photocatalyst layer was visually evaluated.

耐熱冷試驗Heat resistant cold test

如下實施耐熱冷試驗。首先，將光觸媒塗裝體投入於以JIS B7753所規定之日光耐候試驗機(SUGA試驗機製造，S-300C)中，100小時後取出。接著以100℃加熱1小時，接著以-20℃冷卻1小時之步驟，合計重複10次，總計試驗時間20小時。再將所得之塗裝體投入於以JIS B7753所規定之日光耐候試驗機(SUGA試驗機製造，S-300C)中，100小時後取出，以接觸角計(協和界面科學製造之CA-X150型)測定與水之接觸角。The heat-resistant cold test was carried out as follows. First, the photocatalyst-coated body was placed in a solar weathering tester (manufactured by SUGA Test Machine, S-300C) prescribed in JIS B7753, and taken out 100 hours later. Subsequently, the mixture was heated at 100 ° C for 1 hour, and then cooled at -20 ° C for 1 hour, and the mixture was repeated 10 times in total for a total test time of 20 hours. The obtained coated body was placed in a solar weathering tester (manufactured by SUGA Test Machine, S-300C) prescribed in JIS B7753, and taken out 100 hours later. The contact angle meter (CA-X150 type manufactured by Kyowa Interface Science Co., Ltd.) was used. ) Determine the contact angle with water.

耐彎曲試驗Bending resistance test

如下述實施耐彎曲試驗。首先，將光觸媒塗裝體投入於以JIS B7753所規定之日光耐候試驗機(SUGA試驗機製造，S-300C)中，100小時後取出。接著將所得之塗裝體以10Φ 彎曲180°後，以目視觀察彎曲部有無龜裂。再以接觸角計(協和界面科學製造之CA-X150型)測定彎曲部與水之接觸角。The bending resistance test was carried out as follows. First, the photocatalyst-coated body was placed in a solar weathering tester (manufactured by SUGA Test Machine, S-300C) prescribed in JIS B7753, and taken out 100 hours later. Next, the obtained coated body was bent at 180 Φ by 10 Φ , and then the crack was observed by visual observation. Then, the contact angle of the bent portion with water was measured by a contact angle meter (Model CA-X150 manufactured by Kyowa Interface Science Co., Ltd.).

耐振動試驗Vibration resistance test

如下述實施耐振動試驗。首先，將光觸媒塗裝體投入於以JIS B7753所規定之日光耐候試驗機(SUGA試驗機製造，S-300C)中，100小時後取出。將所得之塗裝體固定於振動試驗機上，以振動數5Hz、振動加速度1G之條件施加10分鐘之振動。以接觸角計(協和界面科學製造之CA-X150型)測定施加振動後之塗裝體與水之接觸角。The vibration resistance test was carried out as follows. First, the photocatalyst-coated body was placed in a solar weathering tester (manufactured by SUGA Test Machine, S-300C) prescribed in JIS B7753, and taken out 100 hours later. The obtained coated body was fixed to a vibration tester, and vibration was applied for 10 minutes under the conditions of a vibration number of 5 Hz and a vibration acceleration of 1 G. The contact angle of the coated body with water after vibration application was measured by a contact angle meter (Model CA-X150 manufactured by Kyowa Interface Science Co., Ltd.).

以上的結果如下表所示。The above results are shown in the table below.

又，密著評價試驗後之塗膜之電子顯微鏡照片如圖2所示。圖2中，照片1~5係分別為實施例1~3及比較例1及2之塗膜之電子顯微鏡照片。Further, an electron micrograph of the coating film after the adhesion evaluation test is shown in Fig. 2 . In Fig. 2, photographs 1 to 5 are electron micrographs of the coating films of Examples 1 to 3 and Comparative Examples 1 and 2, respectively.

[圖1]係表示例1中使用的水系胺基甲酸酯聚醚樹脂分散之藉由依據JIS K7244-4之固體黏彈性測定裝置所測定的損失彈性率之溫度變化曲線圖。Fig. 1 is a graph showing the temperature change of the loss elastic modulus measured by the solid viscoelasticity measuring apparatus according to JIS K7244-4, in which the aqueous urethane polyether resin used in Example 1 is dispersed.

[圖2]照片1~5係各自例1~3、7及8之密著評價試驗後之塗膜的電子顯微鏡觀察照片。[Fig. 2] Photographs 1 to 5 are electron microscopic observation photographs of coating films after adhesion evaluation tests of Examples 1 to 3, 7 and 8 of the respective Examples.

Claims (29)

一種光觸媒塗裝體，其係具備：基材；含有光觸媒所成之光觸媒層；介於前述基材及前述光觸媒層之間，且被設定為與前述光觸媒層下方接觸的中間層所成的光觸媒塗裝體，其特徵係前述中間層為含有樹脂成分所成，前述樹脂成分為含有矽氧成分與柔軟之非矽氧成分所成，且前述中間層之25℃下藉由依據JIS K7244-4之固體黏彈性測定裝置所測定的損失正切超過0.2，未達1.5，前述中間層之藉由依據JIS K7244-4之固體黏彈性測定裝置所測定之損失彈性率之溫度變化曲線中之光譜波峰之至少1個超過-80度，且30度以下。 A photocatalyst coated body comprising: a substrate; a photocatalyst layer comprising a photocatalyst; a photocatalyst formed between the substrate and the photocatalyst layer and disposed in an intermediate layer in contact with the photocatalyst layer The coated body is characterized in that the intermediate layer is made of a resin component, and the resin component is made of a non-oxygen component and a soft non-oxygen component, and the intermediate layer is formed at 25 ° C according to JIS K7244-4. The loss tangent measured by the solid viscoelasticity measuring apparatus exceeds 0.2, which is less than 1.5, and the spectral peak of the intermediate layer by the temperature change curve of the loss elastic modulus measured by the solid viscoelasticity measuring apparatus of JIS K7244-4 At least one of more than -80 degrees and less than 30 degrees. 如申請專利範圍第1項之光觸媒塗裝體，其中前述損失正切為超過0.2，且未達1.0。 For example, in the photocatalyst coating body of claim 1, wherein the aforementioned loss tangent is more than 0.2 and less than 1.0. 如申請專利範圍第1項之光觸媒塗裝體，其中前述柔軟的非矽氧成分為柔軟的非矽氧樹脂或柔軟的非矽氧片段。 The photocatalyst coated body of claim 1, wherein the soft non-oxygenated component is a soft non-oxygenated resin or a soft non-oxygenated fragment. 如申請專利範圍第1~3項中任一項之光觸媒塗裝體，其中前述藉由依據JIS K7244-4之固體黏彈性測定裝置所測定之損失彈性率之溫度變化曲線中之光譜波峰為-40度以上30度以下。 The photocatalyst coated body according to any one of claims 1 to 3, wherein the spectral peak in the temperature change curve of the loss elastic modulus measured by the solid viscoelasticity measuring apparatus according to JIS K7244-4 is - 40 degrees or more and 30 degrees or less. 如申請專利範圍第1項之光觸媒塗裝體，其中前述光觸媒層為含有作為粒子成分之光觸媒粒子與無機氧化物粒子所成，且前述粒子成分含有70質量%以上所成。 The photocatalyst coating body according to the first aspect of the invention, wherein the photocatalyst layer is formed by containing photocatalyst particles and inorganic oxide particles as a particle component, and the particle component is contained in an amount of 70% by mass or more. 如申請專利範圍第1項之光觸媒塗裝體，其中前述光觸媒層之表面接受前述光觸媒之光激發，呈現親水性。 The photocatalyst coated body according to claim 1, wherein the surface of the photocatalyst layer is excited by light of the photocatalyst to exhibit hydrophilicity. 如申請專利範圍第6項之光觸媒塗裝體，其中前述光觸媒層之表面接受前述光觸媒之光激發，呈現換算成與水之接觸角為未達20°的親水性。 The photocatalyst coated body according to claim 6, wherein the surface of the photocatalyst layer is excited by light of the photocatalyst, and exhibits hydrophilicity in a contact angle with water of less than 20°. 如申請專利範圍第1或5項之光觸媒塗裝體，其中前述光觸媒層中之光觸媒之比例為1質量%以上，未達20質量%。 The photocatalyst coated body according to claim 1 or 5, wherein a ratio of the photocatalyst in the photocatalyst layer is 1% by mass or more and less than 20% by mass. 如申請專利範圍第5項之光觸媒塗裝體，其中前述光觸媒粒子之平均粒徑為10nm以上，未達1000nm。 The photocatalyst coated body according to claim 5, wherein the photocatalyst particles have an average particle diameter of 10 nm or more and less than 1000 nm. 如申請專利範圍第5項之光觸媒塗裝體，其中前述光觸媒粒子之平均粒徑為10nm以上，未達100nm。 The photocatalyst coated body according to claim 5, wherein the photocatalyst particles have an average particle diameter of 10 nm or more and less than 100 nm. 如申請專利範圍第1項之光觸媒塗裝體，其中前述光觸媒為結晶性氧化鈦。 The photocatalyst coated body according to claim 1, wherein the photocatalyst is crystalline titanium oxide. 如申請專利範圍第5項之光觸媒塗裝體，其中前述無機氧化物粒子之平均粒徑為5nm以上，未達100nm。 The photocatalyst coated body according to claim 5, wherein the inorganic oxide particles have an average particle diameter of 5 nm or more and less than 100 nm. 如申請專利範圍第5項之光觸媒塗裝體，其中前述無機氧化物粒子為氧化矽粒子。 The photocatalyst coated body according to claim 5, wherein the inorganic oxide particles are cerium oxide particles. 如申請專利範圍第1項之光觸媒塗裝體，其中前述光觸媒層之膜厚為3μm以下。 The photocatalyst coated body according to claim 1, wherein the photocatalyst layer has a film thickness of 3 μm or less. 如申請專利範圍第5項之光觸媒塗裝體，其中前述光觸媒層具有粒子間隙，該粒子間隙相對於前述光觸媒層，為20體積%以上，35體積%以下。 The photocatalyst coated body according to claim 5, wherein the photocatalyst layer has a particle gap, and the particle gap is 20% by volume or more and 35% by volume or less based on the photocatalyst layer. 如申請專利範圍第1項之光觸媒塗裝體，其中前述 樹脂成分中之矽氧成分的比例，以SiO2 換算為0.5質量%以上30質量%以下。The photocatalyst-coated body of the first aspect of the invention, wherein the proportion of the oxygen component in the resin component is 0.5% by mass or more and 30% by mass or less in terms of SiO 2 . 如申請專利範圍第1項之光觸媒塗裝體，其中前述柔軟之非矽氧成分的量係相對於前述矽氧成分中之Si的量，為20質量%以上100000質量%以下。 The photocatalyst-coated body according to the first aspect of the invention, wherein the amount of the soft non-oxygen component is from 20% by mass to 100,000% by mass based on the amount of Si in the oxygen-containing component. 如申請專利範圍第1項之光觸媒塗裝體，其中前述柔軟的非矽氧成分係選自由聚胺基甲酸酯聚醚、聚胺基甲酸酯聚酯、聚胺基甲酸酯聚碳酸酯、聚醚、聚酯、聚丙烯酸酯、聚甲基丙烯酸酯、聚丙烯酸、聚甲基丙烯酸、聚乙烯基群之至少一種的成分。 The photocatalyst coating body of claim 1, wherein the soft non-oxygenated component is selected from the group consisting of polyurethane polyethers, polyurethane polyesters, and polyurethane polyurethanes. A component of at least one of an ester, a polyether, a polyester, a polyacrylate, a polymethacrylate, a polyacrylic acid, a polymethacrylic acid, and a polyvinyl group. 如申請專利範圍第1項之光觸媒塗裝體，其中前述柔軟的非矽氧成分係選自由聚胺基甲酸酯聚醚、聚胺基甲酸酯聚酯、聚醚、聚丙烯酸酯群之至少一種的成分。 The photocatalyst coated body according to claim 1, wherein the soft non-oxygenated component is selected from the group consisting of polyurethane polyethers, polyurethane polyesters, polyethers, and polyacrylate groups. At least one ingredient. 一種如申請專利範圍第1~19項中任一項之光觸媒塗裝體之使用，其係對前述塗裝體施加振動，且前述光觸媒層之表面被照射太陽光之環境下使用。 A photocatalyst coated body according to any one of claims 1 to 19, which is used in an environment in which vibration is applied to the coated body and the surface of the photocatalyst layer is irradiated with sunlight. 一種如申請專利範圍第1~19項中任一項之光觸媒塗裝體之使用，其中前述基材為多孔質基材，前述光觸媒塗裝體被配設於氣溫為0℃以下之氣氛中，且前述光觸媒層之表面被照射太陽光之環境下使用。 The photocatalyst coated body according to any one of claims 1 to 19, wherein the substrate is a porous substrate, and the photocatalyst coated body is disposed in an atmosphere having a temperature of 0 ° C or less. And the surface of the photocatalyst layer is used in an environment where sunlight is irradiated. 一種如申請專利範圍第1~19項中任一項之光觸媒塗裝體之使用，其中前述基材為具有可撓性的基材，前述光觸媒塗裝體在形成前述光觸媒層後，被進行彎曲加工而成，且前述光觸媒層之表面被照射太陽光之環境下使用。 The photocatalyst coated body according to any one of claims 1 to 19, wherein the substrate is a flexible substrate, and the photocatalyst coated body is bent after forming the photocatalyst layer It is processed and used in the environment where the surface of the photocatalyst layer is exposed to sunlight. 一種如申請專利範圍第1~19項中任一項之光觸媒塗裝體之使用，其中前述光觸媒塗裝體被配設於一日之氣溫變化為20℃以上的場所，且前述光觸媒層之表面被照射太陽光之環境下使用。 The use of a photocatalyst coated body according to any one of claims 1 to 19, wherein the photocatalyst coated body is disposed in a place where the temperature of the day changes to 20 ° C or more, and the surface of the photocatalyst layer Used in an environment exposed to sunlight. 一種如申請專利範圍第1~19項中任一項之光觸媒塗裝體之使用，其中前述基材為線膨脹率10-5 K-1 以上的材料，且前述光觸媒層之表面被照射太陽光之環境下使用。The use of a photocatalyst coated body according to any one of claims 1 to 19, wherein the substrate is a material having a linear expansion coefficient of 10 -5 K -1 or more, and the surface of the photocatalyst layer is irradiated with sunlight. Used in the environment. 一種如申請專利範圍第1~19項中任一項之光觸媒塗裝體之使用，其中前述光觸媒塗裝體被配設於氣溫之年溫差為30℃以上的場所，且前述光觸媒層之表面被照射太陽光之環境下使用。 The photocatalyst coated body according to any one of claims 1 to 19, wherein the photocatalyst coated body is disposed at a temperature difference of 30 ° C or more, and the surface of the photocatalyst layer is Use in an environment exposed to sunlight. 如申請專利範圍第20項之光觸媒塗裝體之使用，其中前述基材為橋梁。 The use of a photocatalyst coating body according to claim 20, wherein the substrate is a bridge. 如申請專利範圍第21項之光觸媒塗裝體之使用，其中前述基材為無釉的陶磁器、混凝土、水泥板、木材、石材。 For example, the use of the photocatalyst coating body in the scope of claim 21, wherein the substrate is an unglazed ceramic, concrete, cement board, wood, stone. 如申請專利範圍第22項之光觸媒塗裝體之使用，其中前述基材為金屬材料、橡膠、可撓性薄膜樹脂之至少一種。 The photocatalyst coated body according to claim 22, wherein the substrate is at least one of a metal material, a rubber, and a flexible film resin. 如申請專利範圍第23項之光觸媒塗裝體之使用，其中前述基材為金屬、樹脂、橡膠、矽氧密封膠、密封塗層之至少一種。 The photocatalyst coated body according to claim 23, wherein the substrate is at least one of a metal, a resin, a rubber, a silicone sealant, and a seal coat.
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