JP2004300864A - Exterior facing material and its munufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an exterior facing building material from which a fouling resulting from a sealing material does not scatter and to provide its antifouling method. <P>SOLUTION: The exterior facing material is provided with a building material and a silicone sealing material disposed in the periphery of the building material. An elution preventive layer is formed at the surface of the silicone sealing material. A photocatalyst layer is formed on the surface of the exterior facing material. Further, a surface layer including at least one selected from a group composed of aluminium oxide, zirconium oxide, silicon oxide and photocatalyst particles is formed in the vicinity of the silicone sealing material. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

【００３５】
【発明の効果】
本発明によれば、建材周辺部に配設されたシリコーンシーリング材とを具備してなる外装材であって、長期に亘り建材表面に雨筋汚れ等の汚れが付着しにくく、付着しても降雨や水洗により容易に除去可能な外装材を提供することが可能となる。
【図面の簡単な説明】
【図１】本発明の外装材の構造を示す断面図である。
【図２】本発明の外装材の構造を示す断面図である。
【図３】本発明の外装材の構造を示す平面図である。
【符号の説明】
１シリコーンシーリング材の近傍に、酸化アルミニウム、酸化ジルコニウム、酸化ケイ素からなる群から選ばれる少なくとも一つと光触媒粒子を含む表面層
２シーリング材
３建材
４光触媒層
５溶出防止層[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention is an exterior material comprising a building material, and a silicone sealing material disposed around the building material, and it is difficult for dirt such as rain streak to adhere to the surface of the building material. The present invention relates to an exterior material that can be easily removed by washing with water.
[0002]
[Prior art]
2. Description of the Related Art In recent years, attention has been paid to a technology utilizing photoexcitation hydrophilization of a photocatalyst.
By forming a photocatalytic semiconductor material that exhibits hydrophilicity in response to photoexcitation on the substrate surface, the contact angle with water becomes highly hydrophilic when exposed to the sun. It has been proposed that a contaminant mainly composed of is washed away and the surface is self-cleaned, and application to exterior building materials and building material glass has been proposed (for example, see Patent Document 1).
[0003]
On the other hand, as a prior example in which a photocatalytic thin film is formed on an exterior material including a building material and a silicone sealing material disposed around the building material, the sealing material itself is not decomposed or modified. It has been proposed to coat a photocatalyst on a surface in the vicinity thereof except for a portion in contact with the sealing material, thereby providing a building material that does not deteriorate the watertightness and airtightness of the sealing material (for example, Patent Document 2). reference).
[0004]
[Patent Document 1] Public information of WO 96/29375 [Patent Document 2] Public information of Japanese Patent Application Laid-Open No. 8-302856 [0005]
[Problems to be solved by the invention]
In an exterior material including a building material and a silicone sealing material disposed around the building material, dimethyl silicones in the silicone sealing material volatilize or elute during use. Therefore, in order to realize the proposal of Patent Document 1, when only the photocatalyst layer is formed on the surface of the building material, the dimethylsilicone gradually flows down or diffuses into the photocatalyst layer during use to form the dimethylsilicone and the photocatalyst. The resulting metal oxides such as titanium oxide combine to change to a water-repellent surface. Therefore, every time rainfall is received for a long period of time, pollutants mainly composed of hydrophobic substances in the atmosphere are washed away, and the function of self-cleaning the surface cannot be maintained.
[0006]
Further, even with the configuration of Patent Document 2, the amount of dimethyl silicones flowing down or diffusing into the photocatalyst layer per unit time could not be changed drastically.
[0007]
The present invention has been made in view of the above circumstances, and is an exterior material including a silicone sealing material disposed around a building material, and has a surface such as rain streak stains for a long period of time. It is an object of the present invention to provide an exterior material that is difficult to adhere to and can be easily removed by rainfall or water washing even if it adheres.
[0008]
[Means for Solving the Problems]
As a result of intensive studies, the present inventors have found that water-repellent contamination caused by a silicone sealing material is concentrated and spread to nearby areas through water, and the discovery led to the present invention.
Details will be described below. Rain water accumulates at the bottom due to gravity, and water stays near the sealant for a long time. In particular, in the case of the photocatalyst layer, the dimethyl silicones oozing out of the sealing material migrate to the retained water, and further become hydrophilic, and the water wettability increases (surface energy increases). Dimethyl silicones, which are water-repellent components, continuously spread through water. As a result, the photocatalyst layer in a wide area becomes water-repellent.
In other words, if the flow of water is shut off so that water that connects the sealing material and the photocatalyst film is not retained, dirt such as rain streak dirt does not easily adhere to the surface of the building material for a long period of time. An exterior material that can be easily removed can be provided.
[0009]
In the present invention, in order to solve the above problems, an exterior material comprising a building material and a silicone sealing material provided around the building material, wherein an elution preventing layer is formed on the surface of the silicone sealing material. A photocatalyst layer containing a photocatalyst is formed on the surface of the exterior material, and at least one selected from the group consisting of aluminum oxide, zirconium oxide, and silicon oxide, and photocatalyst particles in the vicinity of the silicone sealing material. The present invention provides an exterior material provided with a surface layer containing:
[0010]
By forming the elution preventing layer covering the sealing material as described above, volatilization and elution of dimethyl silicone can be suppressed to less than half, if not completely.
Further, by providing a surface layer containing at least one selected from the group consisting of aluminum oxide, zirconium oxide, and silicon oxide and photocatalyst particles as described above, the dimethyl silicones suppressed by the elution prevention layer due to the trapping effect thereof. Blocking is realized almost completely, and diffusion of water-repellent contamination to the surface of the photocatalyst layer can be reduced. As a result, dirt such as rain streak dirt hardly adheres to the surface of the building material for a long period of time, and even if it adheres, it does not rain. It is possible to provide an exterior material that can be easily removed by washing with water or water.
[0011]
Further, in the present invention, a method for preventing contamination of an exterior material comprising a building material and a silicone sealing material provided around the building material, wherein a step of forming an elution preventing layer on the silicone sealing material is provided. Forming a photocatalyst layer containing a photocatalyst on the surface of the exterior material, and forming a surface layer containing photocatalyst particles and at least one selected from the group consisting of aluminum oxide, zirconium oxide, and silicon oxide in the vicinity of the silicone sealing material. And a method for preventing the exterior material from being stained.
[0012]
Further, in the present invention, a method for preventing contamination of an exterior material comprising a building material and a silicone sealing material provided around the building material, wherein a step of forming an elution preventing layer on the silicone sealing material is provided. Forming a photocatalyst layer containing a photocatalyst on the surface of the exterior material, and forming a surface layer containing photocatalyst particles and at least one selected from the group consisting of aluminum oxide, zirconium oxide, and silicon oxide in the vicinity of the silicone sealing material. And a method for preventing the exterior material from being stained.
[0013]
Further, in the present invention, a method for preventing contamination of an exterior material comprising a building material and a silicone sealing material disposed around the building material, and further including an elution preventing layer on the surface of the silicone sealing material, A step of forming a photocatalyst layer containing a photocatalyst on the surface of the exterior material, and forming a surface layer containing at least one selected from the group consisting of aluminum oxide, zirconium oxide and silicon oxide and photocatalyst particles in the vicinity of the silicone sealing material. And a method for preventing the exterior material from being stained.
[0014]
Further, in the present invention, a building material, comprising a silicone sealing material disposed around the building material, further comprising an elution prevention layer on the surface of the silicone sealing material, a photocatalyst layer containing a photocatalyst on the building material surface. A method for preventing contamination of an exterior material provided, comprising a step of forming a surface layer containing photocatalyst particles and at least one selected from the group consisting of aluminum oxide, zirconium oxide, and silicon oxide, in the vicinity of the silicone sealing material. Provided is a method for preventing contamination of an exterior material, which is characterized in that:
[0015]
BEST MODE FOR CARRYING OUT THE INVENTION
The exterior material of the present invention can be used in any structure as long as the exterior material is used outdoors exposed to rain and the sealing material is used together with the building material, and rainwater transmitted on the surface of the exterior material is used as the sealing material. This is suitable for a structure arranged so as to touch the surface. Cases for waterproofing devices such as camera cases and sensor covers, such as panels and glass constituting walls and roofs of buildings, and the like.
[0016]
1 and 2 are cross-sectional views of an exterior material showing an embodiment of the present invention, and FIG. 3 is a plan view thereof. A coated photocatalyst layer 4 is formed on the surface of the building material 3, and a sealing material 2 is formed between the sash 7 and the building material 3 or between the building material 3 and the building material 3 to waterproof the building material 3. A dissolution preventing layer 5 is formed on the surface, and a surface layer 1 containing photocatalyst particles and at least one selected from the group consisting of aluminum oxide, zirconium oxide, and silicon oxide is formed near the silicone sealing material 2. . The surface layer 1 may be provided on the photocatalyst layer 4 (FIG. 1) or directly on the building material 3 (FIG. 2).
The surface layer 1 containing at least one selected from the group consisting of aluminum oxide, zirconium oxide, and silicon oxide and photocatalyst particles blocks dimethyl silicones leaking from the elution preventing layer 5 and diffuses water-repellent contamination to the photocatalyst layer surface. As a result, it is possible to provide an exterior material in which dirt such as rain streak does not easily adhere to the surface of the building material for a long period of time, and even if it adheres, the exterior material can be easily removed by rainfall or washing with water. .
[0017]
The sealing material of the present invention contains silicone polymer as a main component, has appropriate flexibility and strength, and is a silicone-based sealing material which has conventionally been a problem of contamination. There are various types of silicone sealants, including a one-component type that cures with moisture and a two-component type that reacts with a catalyst. Depending on the curing mechanism, there are oxime type, aminoxy type, alcohol type, acetic acid type and the like.
[0018]
Further, the elution preventing layer formed on the sealing material of the present invention is a layer for preventing bleeding of dimethyl silicones which cause water-repellent contamination. The cost may be selected in consideration of the cost. For example, a fluorine-based, silicone-based, modified silicone-based, or polysulfide-based resin coating film is used, and examples thereof include a stain preventive agent X33-089 for silicone sealing materials manufactured by Shin-Etsu Chemical and Hamatite VY-52 manufactured by Yokohama Rubber Co., Ltd. In order to also serve as the water-repellent layer, a material having a small surface energy is preferable, and a material having a surface energy of 20 dyne / cm or less, for example, a fluorine-based coating agent such as Defencer TR230K and TR310 manufactured by Dainippon Ink and Megafac A perfluoroalkyl group-containing oligomer such as F178K is preferred.
[0019]
As the photocatalyst, any semiconductor can be used as long as it has a photocatalytic action, and examples thereof include TiO ₂ , SrTiO ₃ , ZnO, CdS, and SnO ₂ . Further, the form such as a particulate form or a form obtained by crystallizing a precursor can be selected according to the use conditions.
In addition, the coating of the photocatalytic film can be performed by coating the exterior member outdoors at a construction site or the like, or can be brought to a construction site or an installation site after being processed in a factory in advance. Regarding the method of forming the photocatalyst layer, a person mixed with a photocatalyst, a binder, and a solvent is spray-coated, dip-coated, flow-coated, spin-coated, roll-coated, brushed, sponged, etc. on the surface of the exterior material. Can be used.
[0020]
As the binder, for example, a substance having a siloxane bond can be suitably used. Silanol groups with high affinity for water are present on the surface of the compound having a siloxane bond, which has the effect of imparting or strengthening the function of maintaining hydrophilicity in a dark place, and is self-cleaning by rainfall. Improve the effect. As the substance having a siloxane bond, an alkali silicate such as water glass, colloidal silica, or an aluminosilicate compound can also be used.
[0021]
Further, as the silane compound, a partial hydrolyzate and a dehydration polymer of the following compounds can be suitably used: methyltrichlorosilane, methyltribromosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriethoxysilane. Isopropoxysilane, methyltri-t-butoxysilane; ethyltrichlorosilane, ethyltribromosilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltri-t-butoxysilane; n-propyltrichlorosilane, n-propyl Tribromosilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltriisopropoxysilane, n-propyltri-t-butoxysilane; n-hexyltrichlorosilane, n-hexyl Ribromosilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, n-hexyltriisopropoxysilane, n-hexyltri-t-butoxysilane; n-decyltrichlorosilane, n-decyltribromosilane, n-decyltrimethoxy Silane, n-decyltriethoxysilane, n-decyltriisopropoxysilane, n-decyltri-t-butoxysilane; n-octadecyltrichlorosilane, n-octadecyltribromosilane, n-octadecyltrimethoxysilane, n-octadecyltriethoxy Silane, n-octadecyltriisopropoxysilane, n-octadecyltri-t-butoxysilane; phenyltrichlorosilane, phenyltribromosilane, phenyltrimethoxysilane, phenyltriethoxysilane Phenyltriisopropoxysilane, phenyltri-t-butoxysilane; tetrachlorosilane, tetrabromosilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, dimethoxydiethoxysilane; dimethyldichlorosilane, dimethyldibromosilane, Dimethyldimethoxysilane, dimethyldiethoxysilane; diphenyldichlorosilane, diphenyldibromosilane, diphenyldimethoxysilane, diphenyldiethoxysilane; phenylmethyldichlorosilane, phenylmethyldibromosilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane ; Trichlorohydrosilane, tribromohydrosilane, trimethoxyhydrosilane, triethoxyhydrosilane, triisopropoxyhydrosilane , Tri-t-butoxyhydrosilane; vinyltrichlorosilane, vinyltribromosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltri-t-butoxysilane; trifluoropropyltrichlorosilane, trifluoropropyltribromosilane Trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, trifluoropropyltriisopropoxysilane, trifluoropropyltri-t-butoxysilane; γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldi Ethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltriisopropoxysila Γ-glycidoxypropyltri-t-butoxysilane; γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxy Propyltriethoxysilane, γ-methacryloxypropyltriisopropoxysilane, γ-methacryloxypropyltri-t-butoxysilane; γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropyltri Methoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropyltri-t-butoxysilane; γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyl Diethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropyltriisopropoxysilane, γ-mercaptopropyltri-t-butoxysilane; β- (3,4-epoxycyclohexyl) ethyl Trimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane.
[0022]
Further, as a binder when used as the coating material, a silicone emulsion or a fluororesin emulsion can be used. A coating film containing a silicone emulsion or a fluororesin emulsion has high chemical stability and high weather resistance.
[0023]
The aluminum oxide, zirconium oxide, and silicon oxide used in the present invention may be used alone or in combination. The morphology can be selected according to the use conditions, such as a particulate morphology or a crystallization of a precursor. The mixing ratio of the photocatalyst to aluminum oxide, zirconium oxide, and silicon oxide can be appropriately selected depending on the usage conditions and shape of the exterior material.
[0024]
Further, the width of the surface layer containing any of the aluminum oxide, zirconium oxide, and silicon oxide of the present invention and the photocatalyst particles is extremely small, because water-repellent contamination due to the silicone sealing material cannot be reduced. It is necessary to make it 1 mm or more. Depending on the shape and inclination of the silicone sealing material used, the width and shape may be appropriately selected.Also, the thickness of the surface layer containing any of aluminum oxide, zirconium oxide and silicon oxide and photocatalyst particles may be increased. May be. Even when the thickness of the photocatalyst layer cannot be increased in terms of transparency and durability, the thickness in the vicinity of the sealing material is preferably set to 40 nm or more and 200 nm or less.
The width of the surface layer containing either the above-mentioned aluminum oxide or zirconium oxide and the photocatalyst particles may be set according to the amount of dimethyl silicone eluted from the sealing material, and the width may be reduced by increasing the film thickness. In the case where years have passed since the sealing material was cast, the width can be made narrower than in the case of new construction. The width is desirably from 5 mm to 200 mm, more desirably from 5 mm to 50 mm, and desirably from 5 mm to 15 mm.
[0025]
【Example】
Hereinafter, the effects of the present invention will be described more specifically with reference to Examples, Comparative Examples, and Test Examples, but the present invention is not limited to the following Examples.
[0026]
Preparation of test piece Wash the float glass of thickness 2 mm and 10 cm square, fix it with aluminum tape with a gap of 5 mm on a 20 cm square polycarbonate plate with the side facing the tin bath at the time of float, and masking tape. Then, a silicone sealing material (Tosseal sp10 manufactured by Toshiba GE, New Gray, deaminoxy type) was cast into the gap of 5 mm, and a test piece was prepared in which the sealing material was finished smoothly and the sealing material was cured. Next, the masking tape of the test piece was peeled off, the glass surface was polished and cleaned using cerium oxide for cleaning glass until the water wettability was improved, and the test piece was subjected to the test.
[0027]
Comparative Test of Actual Exposure The test piece was fixed by inclining at an angle of 45 ° to the south, and natural exposure was performed. Every three days, water was sprayed on the test piece surface, and it was determined that the portion to which water droplets had adhered at that time was a portion that was subjected to water-repellent contamination due to the sealing material. Further, the distance from the end of the sealing material was measured, and the length (hydrophobic portion) was compared one week and one month later, and it was determined that the shorter the length, the less the contamination of the sealing material was.
In addition, the water contact angle of the surface of the test piece was measured, and a portion exceeding 50 ° was judged to be contaminated with the silicone sealing material, and the contact angle at a distance of 1 cm from the edge of the sealing material exceeded 50 °. The elapsed days were determined and used as an index for maintaining hydrophilicity.
[0028]
Preparation of Coating Agent As the photocatalyst, a TiO2 sol having an anatase fine particle having an X-ray crystallite diameter of 7 nm and a particle diameter of about 10 nm was used, and a hydrolyzate of an alkyl silicate was used as a binder. They were synthesized so that the weight ratio of titania and silicate in terms of SiO2 was 65 parts by weight and 35 parts by weight. After that, a photocatalyst coating agent A was prepared by diluting with a mixed solvent of normal propyl alcohol, propylene glycol monomethyl ether, and dipropylene glycol propyl ether such that the solid content concentration became 0.2%.
[0029]
Preparation of a coating composition for a surface layer containing any of aluminum oxide, zirconium oxide, and silicon oxide and photocatalyst particles For the photocatalyst, a TiO2 sol having an anatase fine particle having an X-ray crystallite diameter of 7 nm and a particle diameter of about 10 nm was used. Aluminum oxide having a particle diameter of 2 nm was used for the metal oxide, and a hydrolyzate of alkyl silicate was used for the binder. They were adjusted so that the weight ratio of titania, alumina and silicate in terms of SiO2 was 64 parts by weight, 2 parts by weight, and 34 parts by weight. Then, the coating agent B was diluted with normal propyl alcohol so that the solid concentration became 0.24%.
[0030]
(Comparative Example 1) Only the photocatalyst layer was placed horizontally on the glass panel, the roller was impregnated with the photocatalyst coating agent A, and moved several times vertically and horizontally so that the roller did not rotate, and applied to the glass surface. did.
[0031]
(Comparative Example 2) An S coat 58 manufactured by Shin-Etsu Chemical Co., Ltd. was applied to the surface of the sealing material of the test piece prepared as described above using a brush.
[0032]
Example 1 A surface layer containing a dissolution inhibitor + aluminum oxide, zirconium oxide, or silicon oxide and photocatalyst particles was coated in the same manner as in Comparative Example 1, and then coating agent B was applied to the vicinity of the silicone sealing material. Was applied with a width of 30 mm. An S coat 58 manufactured by Shin-Etsu Chemical Co., Ltd. was applied to the surface of the sealing material using a brush.
[0033]
The test pieces of Comparative Examples 1 and 2 and Example 1 were simultaneously subjected to the actual exposure test described above. As shown in Table 1, the length of the hydrophobic part in Example 1 was shorter than that in the comparative example, and it was confirmed that contamination was reduced.
[0034]
[Table 1]

[0035]
【The invention's effect】
According to the present invention, there is provided an exterior material including a silicone sealing material disposed around a building material, and it is difficult for dirt such as rain streak to adhere to the surface of the building material over a long period of time. An exterior material that can be easily removed by rainfall or water washing can be provided.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view showing a structure of an exterior material of the present invention.
FIG. 2 is a cross-sectional view showing a structure of an exterior material of the present invention.
FIG. 3 is a plan view showing the structure of the exterior material of the present invention.
[Explanation of symbols]
1 Surface layer containing photocatalyst particles and at least one selected from the group consisting of aluminum oxide, zirconium oxide and silicon oxide in the vicinity of a silicone sealing material 2 Sealing material 3 Building material 4 Photocatalyst layer 5 Elution preventing layer

Claims (5)

A building material, and an exterior material including a silicone sealing material disposed around the building material,
An elution preventing layer is formed on the surface of the silicone sealing material,
A photocatalyst layer containing a photocatalyst is formed on the surface of the exterior material,
An exterior material, wherein a surface layer including at least one selected from the group consisting of aluminum oxide, zirconium oxide, and silicon oxide and photocatalyst particles is provided near the silicone sealing material. A method for preventing soiling of exterior materials comprising a building material and a silicone sealing material disposed around the building material,
Forming a dissolution preventing layer on the silicone sealing material,
Forming a photocatalyst layer containing a photocatalyst on the exterior material surface,
Forming a surface layer containing at least one selected from the group consisting of aluminum oxide, zirconium oxide and silicon oxide and photocatalyst particles in the vicinity of the silicone sealing material; How to prevent dirt. A building material, comprising a silicone sealing material disposed around the building material, a method for preventing contamination of an exterior material having an elution preventing layer on the surface of the silicone sealing material,
Forming a photocatalyst layer containing a photocatalyst on the exterior material surface,
Forming a surface layer containing at least one selected from the group consisting of aluminum oxide, zirconium oxide and silicon oxide and photocatalyst particles in the vicinity of the silicone sealing material; How to prevent dirt. A building material, comprising a silicone sealing material disposed around the building material, a method for preventing contamination of an exterior material having a photocatalyst layer containing a photocatalyst on the surface of the building material,
Forming a dissolution preventing layer on the surface of the silicone sealing material disposed around the exterior material,
Forming a surface layer containing at least one selected from the group consisting of aluminum oxide, zirconium oxide and silicon oxide and photocatalyst particles in the vicinity of the silicone sealing material; How to prevent dirt. Contamination of exterior material comprising a building material and a silicone sealing material disposed around the building material, further comprising an elution preventing layer on the surface of the silicone sealing material, and a photocatalyst layer containing a photocatalyst on the surface of the building material. Prevention method,
Forming a surface layer containing at least one selected from the group consisting of aluminum oxide, zirconium oxide and silicon oxide and photocatalyst particles in the vicinity of the silicone sealing material; How to prevent dirt.

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