JP2013028167A - Film or sheet and method for producing the same, and exterior material, glass and exterior execution method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a film or sheet which has excellent weather resistance and is capable of restraining a rise in temperature or thermal deterioration in the sunshine and to provide a method for producing the film or sheet, and an exterior material and glass which use the film or sheet, and an exterior execution method.SOLUTION: The film or sheet has a layer in which a compound metal oxide pigment including oxides of Bi (bismuth) and/or Y (yttrium) and an oxide of Mn (manganese), and/or a hollow particle are kneaded in a resin. The film or sheet restrains the rise in temperature or the thermal deterioration in the sunshine and has excellent weather resistance. Consequently, the film or sheet having the layer where the compound metal oxide pigment and/or the hollow particle are kneaded in the resin is useful as a film or sheet for the exterior material or the glass and also useful when the exterior is executed.

Description

  The present invention relates to a film or sheet, a method for producing the same, and an exterior material, glass, and an exterior construction method using the film or sheet.

  Fluororesin, especially tetrafluoroethylene copolymer, has good properties such as weather resistance, transparency and stain resistance, and is suitable for roofing materials and wall materials as materials whose properties are maintained outdoors for over 15 years. It is used as a fluororesin film. In recent years, in order to reduce the cooling load, there has been a demand for the development of building materials that reflect so-called infrared rays, in which the temperature of these materials does not increase.

  Patent Document 1 proposes a structure in which a heat ray blocking film such as a polyethylene terephthalate film having a metal oxide laminated on its surface is attached to a transparent glass. Patent Document 2 proposes a film coated with a composition in which tin oxide fine particles having heat-absorbing ability or tin oxide fine particles doped with antimony are dispersed in an ultraviolet curable acrylic resin.

  However, since any film is blocked by infrared absorption, a large temperature rise of the film is observed due to the heat rays, and the weather resistance of the film itself is impaired.

  In particular, in the case of the invention described in Patent Document 2, since the composition is coated on the film, there is a problem that the coating film and the film are peeled off during long-term outdoor use. In particular, in the case of an exterior material, if the daily temperature difference is large, a large difference occurs in the thermal expansion between the film and the coating film, so that the coating film and the film tend to peel off.

  Further, Patent Document 3 proposes a film in which a composition in which tin difluoride naphthalocyanine that absorbs infrared rays is dispersed in polyester, polyethylene, or polyvinyl chloride is formed as a thin layer on a substrate. However, the weather resistance of tin difluoride naphthalocyanine is not sufficient, and it is difficult to use it outdoors for a long time.

Japanese Patent Application Laid-Open No. 10-139489 JP-A-9-151203 JP 11-246570 A

  The present invention has been made in view of the above problems, and is a film or sheet excellent in weather resistance and capable of suppressing temperature rise and thermal degradation due to solar radiation, a method for producing the same, and the film or sheet. An object is to provide an exterior material, glass, and an exterior construction method.

  As a result of intensive studies in order to solve the above problems, the present inventors have a film base resin layer, and the film base resin contains an oxide of Bi and / or Y and an oxide of Mn. In the film or sheet in which the composite metal oxide pigment is kneaded, the composite metal oxide pigment does not have a photocatalytic action on the resin, and by having the layer, the temperature of the film or sheet is increased by solar radiation. It discovered that it could suppress and heat deterioration. Moreover, since the above-mentioned film and sheet | seat can maintain an optical characteristic over a long period of time, it turned out that it is excellent in a weather resistance. Thus, the present inventors have completed the present invention.

The film or sheet according to the present invention has a film base resin layer and a laminate resin layer formed on the surface of the film base resin layer , and the film base resin and / or the laminate resin includes Bi. and / or have complex metal oxide Pigments are kneaded comprising an oxide of oxides and Mn of Y, the laminate resin is a fluorine resin, and the film base resin layer and the laminate resin layer extruded while merging to mold, or characterized by Rukoto are integrated extruded to the said film base resin layer and the laminate resin layer into a sheet. The film or sheet according to the present invention may further have a photocatalyst layer containing a photocatalyst on the laminate resin layer.

The fluororesin is, for example, an ethylene-tetrafluoroethylene copolymer, a hexafluoropropylene-tetrafluoroethylene copolymer, a perfluoro (alkyl vinyl ether) -tetrafluoroethylene copolymer, or a tetrafluoroethylene-hexafluoro. propylene - vinylidene fluoride copolymer, and is any one selected from the group consisting of polyvinylidene fluoride.

  The Mn content in the composite metal oxide pigment is preferably 5 to 65% by mass with respect to the total mass.

  The film or sheet according to the present invention may further have an adhesive layer.

  The exterior material and glass which concern on this invention have either the film or sheet mentioned above.

The manufacturing method according to the present invention is a method for manufacturing a film or sheet having a film base resin layer and a laminate resin layer, wherein Bi and / or Y is added to the film base resin and / or the laminate resin. look including the step of kneading the composite metal oxide Pigment comprising an oxide of oxides and Mn of the laminate resin, a fluorine resin, the laminate resin layer on the surface of the film base resin layer Forming and joining the film base resin layer and the laminate resin layer while extruding, or forming the film base resin layer and the laminate resin layer into a sheet and integrating them And

  The exterior construction method according to the present invention is characterized by using the above-described film or sheet or the above-described exterior material.

  ADVANTAGE OF THE INVENTION According to this invention, it is excellent in weather resistance, the film or sheet | seat which can suppress the temperature rise and thermal deterioration by solar radiation, its manufacturing method, and the exterior material, glass, and exterior construction using the said film or sheet | seat A method can be provided.

In one Example of this invention, it is a figure which shows the result of having measured the light transmittance in 200-2500 nm of the film of samples 1 and 2, the comparative example 1, and a control sample. In one Example of this invention, it is a figure which shows the result of having measured the light reflectivity in 200-2500 nm of the film of samples 1 and 2, the comparative example 1, and a control sample.

  Hereinafter, the form for implementing this invention is demonstrated in detail, giving an Example.

== Exterior film or sheet according to the present invention ==
As shown in Examples, a composite metal oxide pigment (hereinafter referred to as “composite pigment”) containing an oxide of Bi and / or Y and an oxide of Mn is kneaded into a resin (for example, melt-kneaded). ) Film produced by extrusion molding is JIS R3106 “Transparency / Reflectivity / Emissivity / Solar heat acquisition rate of plate glass compared to film produced by kneading carbon black into resin and extrusion molding. It was revealed that the solar transmittance defined in “Test method” is low, the solar reflectance is excellent, and the solar heat acquisition rate is low.

  In addition, it has been clarified that the film containing the above-described composite pigment has little temperature increase due to the addition of the composite pigment. Furthermore, the weather resistance test using an open frame carbon arc lamp in accordance with JIS K7350-4 reveals that optical characteristics (such as solar transmittance, solar reflectance, and solar heat acquisition rate) can be maintained over a long period of time. It was found to be excellent in performance.

  Furthermore, since the film containing the above composite pigment does not contain chromium, it is excellent in environmental properties.

  As described above, a film or sheet having a film base resin layer in which a composite pigment is kneaded into a resin is excellent in environmental properties and weather resistance, and can suppress temperature rise and thermal deterioration due to solar radiation. Not only is the durability of the sheet improved, but it can also suppress the increase in the temperature of the base material to which the film or sheet is applied and the adhesive layer for application, and the decrease in adhesive force due to thermal history (hot cooling repetition) It is possible to prevent thermal deterioration and improve the durability of the base material and the adhesive layer, and to alleviate the heat island phenomenon.

  Therefore, in the above-described film or sheet having a film base resin layer in which a composite pigment is kneaded into a resin, a film or sheet in which a part or all of the composite pigment is replaced with hollow particles known as a heat shielding material is also included. The effect as described above can be obtained by blocking heat from sunlight.

  A film or sheet having a film base resin layer and a laminate resin layer, wherein the film base resin layer and / or the laminate resin layer is a layer in which a composite pigment and / or hollow particles are kneaded is also described above. Such effects can be obtained.

  From the above, the film or sheet according to the present invention is useful as an exterior (construction) film or sheet for exterior finishing, repair, repair, etc., and is useful as a protective material against solar radiation of the exterior substrate. The film or sheet according to the present invention is also useful, for example, as a film or sheet for glass for crime prevention, blindfolding, design improvement and the like. The exterior base material is not particularly limited as long as it is a base material used for an exterior part irradiated with heat rays such as sunlight (for example, a roof or an outer wall of a structure). Brick, stone, concrete, aluminum curtain wall panel, weather-resistant steel plate panel, etc. can be mentioned.

  The film or sheet according to the present invention may be composed of one layer, but may be composed of two or more layers. Examples of the film or sheet composed of two or more layers include a film base resin layer and one or two or more laminate resin layers formed on the film base resin layer.

  The above-mentioned resin is not particularly limited as long as it is an existing resin used for the production of films and sheets. For example, fluororesin, polyester resin, styrene resin, polyetherimide resin, polyethylene terephthalate resin, A plastic such as an epoxy resin or an aramid resin can be used, but it is preferable to use a weather resistant resin such as a fluororesin in order to improve the weather resistance of the film or sheet.

  The film base resin is not particularly limited as long as it is an existing resin used as a film base. For example, polyethylene resin, polypropylene resin, vinyl chloride resin, acrylic resin, polycarbonate resin, polyethylene terephthalate resin, Plastics such as polyester resin, fluorine resin, and polyimide resin can be used.

  The laminating resin is not particularly limited as long as it is an existing resin used for laminating a film base resin layer. For example, a fluororesin, a polyethylene resin, a vinyl chloride resin, a polyethylene terephthalate resin, etc. Although plastic can be used, it is preferable to use a weather resistant resin such as a fluororesin in order to improve the weather resistance of the film or sheet. When two or more laminate resin layers are present, it is preferable to use a weather resistant resin such as a fluororesin as the resin of the laminate resin layer closest to the surface in order to improve the weather resistance of the film or sheet. .

  In the present invention, specific examples of the fluororesin include an ethylene-tetrafluoroethylene copolymer (hereinafter referred to as ETFE), a hexafluoropropylene-tetrafluoroethylene copolymer (hereinafter referred to as FEP), and perfluoro. (Alkyl vinyl ether) -tetrafluoroethylene copolymer (hereinafter referred to as PFA), tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer (hereinafter referred to as THV), polyvinylidene fluoride (hereinafter referred to as PVDF) And vinylidene fluoride-hexafluoropropylene copolymer, polyvinyl fluoride, and the like. Of these, ETFE, PVDF, THV and the like are preferable, and ETFE and PVDF are particularly preferable.

In the present invention, ETFE is preferably a copolymer of tetrafluoroethylene (hereinafter referred to as TFE) and ethylene (hereinafter referred to as E) and a copolymer of TFE, E and other monomers. Other monomers include fluoroolefins such as chlorotrifluoroethylene, hexafluoropropylene, perfluoro (alkyl vinyl ether), vinylidene fluoride, CH ₂ ═CHRf (where Rf is a polyfluoroalkyl group having 1 to 8 carbon atoms) And the same applies to the following) and polyfluoroalkylethylenes such as CH ₂ = CFRf, and polyfluoroalkyltrifluorovinyl ethers such as CF ₂ = CFOCH ₂ Rf. These may be used alone or in combination of two kinds. You may use the above together. Preferably _CH 2 = CHRf as other monomers, Rf is more preferably _CH 2 = CHRf a perfluoroalkyl group having 3 to 6 carbon _atoms, CH 2 = _CHC 4 _{F 9} is most preferable.

  As the composition of ETFE, the molar ratio of the repeating unit based on TFE / the repeating unit based on E is preferably 70/30 to 30/70, more preferably 65/35 to 40/60, 60 Most preferred is / 40 to 45/55. When the repeating unit based on another comonomer is contained, the content is preferably 0.01 to 30 mol% with respect to the total number of moles of the repeating unit based on TFE and the repeating unit based on ethylene. More preferably, it is 05-15 mol%, and most preferably 0.1-10 mol%.

  In the present invention, the fluororesin may contain fluororubber in order to impart flexibility. Examples of the fluororubber include tetrafluoroethylene-propylene-based elastic copolymers, tetrafluoroethylene-vinylidene fluoride-propylene-based elastic copolymers, vinylidene fluoride-hexafluoropropylene-based elastic copolymers, tetrafluoroethylene- A vinylidene fluoride-hexafluoropropylene-based elastic copolymer, a tetrafluoroethylene-perfluoro (alkyl vinyl ether) -based elastic copolymer, etc. can be used. These may be used alone or in combination of two or more. May be.

  The content of the fluororubber is preferably 40 parts by mass or less, particularly preferably 20 parts by mass or less, with respect to 100 parts by mass of the fluororesin.

  The thickness of the film or sheet according to the present invention is not particularly limited, but is usually 6 to 500 μm, preferably 10 to 200 μm.

In the present invention, one side of the fluororesin film is subjected to surface treatment such as corona discharge treatment, and a silica-based hydrophilic coating agent or the like is applied, or a photocatalyst coating layer typified by anatase titanium oxide is provided. Thus, the stain resistance may be further improved.
The composite pigment used in the present invention contains Bi and / or Y oxide and Mn oxide. This composite pigment is dispersed in the resin as fine particles having a specific average particle diameter, and absorbs and blocks visible light to near infrared rays of 300 to 1000 nm, but reflects near infrared rays to middle infrared rays of 1000 to 2500 nm. It has a shielding property.

  The reason for this is not clear, but these fine particles have a large amount of free electrons, and the absorption energy of indirect interband transition due to free electrons inside and on the surface of the particles is in the vicinity of visible light to near infrared, It is thought that it reflects near-infrared to mid-infrared. In particular, the composite pigment has a maximum reflection wavelength in the vicinity of 1000 to 1100 nm, which is considered to be the strongest in the near infrared rays generated from sunlight.

  The average particle size of the fine particles of the composite pigment is preferably 0.005 to 0.40 μm, more preferably 0.05 to 0.2 μm. When the average particle size is in this range, the smoothness of the film containing the composite pigment is maintained, the specific surface area is reduced, and the reaction with a small amount of hydrofluoric acid (HF) generated in the fluororesin becomes difficult.

  The composite pigment contains an oxide of Bi and / or Y and an oxide of Mn. The content of manganese in the composite pigment is preferably 5 to 65% by mass, and more preferably 10 to 50% by mass. If the manganese content is low, the heat ray reflection effect may not be sufficiently obtained.

  The mass ratio of Mn: Bi and Mn: Y is preferably 10:90 to 99: 1.

  It is preferable to use a composite pigment obtained by firing a mixture of Bi and / or Y and Mn at a firing temperature of 700 ° C. or higher.

  This ratio can be arbitrarily changed, and the color changes from green to black as the Mn content increases. In this example, since the purpose is to produce a black infrared reflective film, the mass ratio of Mn: Bi and Mn: Y is preferably a composition having a high Mn content of 20:80 to 90:10.

  The average particle size of the composite pigment M is preferably 0.1 μm to 30 μm. If the average particle size is larger than 30 μm, the gloss may be lowered. Examples of commercially available products that satisfy these preferable conditions include Asahi Kasei Kogyo Co., Ltd. Black 6303, Black 6301, and the like.

  In the present invention, the content of the composite pigment is not particularly limited, but is preferably 0.02 to 4 parts by mass, and preferably 0.2 to 2 parts by mass with respect to 100 parts by mass of the resin to be kneaded. It is more preferable that When it exists in this range, it can avoid impairing the design property of the exterior base material and glass which affix a film and a seal | sticker.

  In addition to the composite pigment, the layer in the film or sheet in the present invention may be one obtained by further kneading a color pigment into the above-described resin in order to adjust the solar reflectance or color tone. Coloring pigments include white titanium oxide, yellow titanium yellow, and other inorganic pigments such as brown, ocher, calcium carbonate, aluminum silicate, white carbon, fine silicate, phthalocyanine blue, phthalocyanine green, quinacridone, isoindo Organic pigments such as linone, benzimidazolone and dioxazine can be used. With these compositions, the solar reflectance can be controlled to 10% to 50%. Moreover, you may contain inorganic pigments, such as an iron oxide and a cobalt oxide, and control visible light transmittance | permeability. Further, in addition to the composite pigment, cerium oxide and / or zinc oxide may be contained in a total amount of 1 to 10 parts by mass with respect to 1 part by mass of the composite pigment, for example, and ultraviolet transmission of 360 nm or less may be blocked.

  The hollow particles used in the present invention are not particularly limited as long as they can block heat rays. For example, inorganic balloons or resin balloons having a vacuum or hollow inside can be used. Specific examples include ceramic balloons, glass balloons, shirasu balloons, alumina balloons, zirconia balloons, aluminosilicate balloons, and the like.

  In the film or sheet according to the present invention, when a film base resin layer made of a resin in which a composite pigment and / or hollow particles are kneaded is arranged on the surface layer, a photocatalyst may be contained in the resin, or the hollow particles Alternatively, hollow particles carrying a photocatalyst may be kneaded. As the photocatalyst, there can be used, for example, an existing one such as titanium oxide or a content thereof (for example, one containing titanium oxide and a metal or metal oxide other than titanium or silica gel). Thus, by kneading the photocatalyst with the composite pigment and / or hollow particles into the resin, the hydrophilicity of the film base resin layer can be improved, and the stain can be prevented by the self-cleaning effect, thereby improving the design. And maintenance of aesthetics, and prevention of deterioration of heat ray reflection performance (heat shielding performance) by the composite pigment.

  The film or sheet according to the present invention may be provided with a photocatalyst layer containing a photocatalyst on a film base resin layer made of a resin kneaded with a composite pigment and / or hollow particles, or on a laminate resin layer. Good. By providing the photocatalyst layer in this way, the same effects as those obtained when the photocatalyst is kneaded into the resin or the laminate resin as described above can be obtained.

  In addition, as a method of forming the photocatalyst layer on the layer, for example, a photocatalyst paint is applied on a film base resin layer made of a resin kneaded with a composite pigment and / or hollow particles, or on a laminate resin layer. A method of laminating and integrating a film obtained by extruding a resin composition containing a photocatalyst via an adhesive or heat fusing and integrating It may be.

  The photocatalyst paint is not particularly limited as long as it contains an existing resin used for paint such as fluororesin, acrylic resin, urethane resin, and silicone resin and the above-mentioned photocatalyst. It is preferable to use a photocatalyst clear paint containing a resin, an acrylic resin, or a urethane resin and a photocatalyst from the viewpoint of design.

  In addition, the film or sheet according to the present invention can be applied to a surface to be attached to an exterior substrate or glass, for example, a silicone-based adhesive, an acrylic-based adhesive, a rubber-based adhesive, an emulsion-based adhesive, an epoxy-based adhesive, a polyimide You may have the contact bonding layer formed by apply | coating existing adhesive agents, such as a system adhesive and a polyurethane-type adhesive.

== Production Method of Film or Sheet According to the Present Invention ==
The film or sheet according to the present invention can be produced, for example, by kneading a composite pigment and / or hollow particles into a resin (for example, melt-kneading) and extruding. When the film or sheet according to the present invention is composed of two or more layers, for example, the composite pigment and / or hollow particles are kneaded into all or part of the resin constituting each layer, and then merged while extruding each layer. It is possible to manufacture by forming two or more layers of films or sheets. Further, after kneading the composite pigment and / or hollow particles into all or part of the resin constituting each layer, each layer is extruded into a sheet shape, and the surface in contact with each layer is subjected to oxygen functional groups by surface treatment such as corona discharge. May be manufactured by laminating and integrating each layer through an adhesive, or by fusing each layer together by heat fusion, but it is limited to these methods. It is not something. When the film or sheet according to the present invention has a film base resin layer and a laminate resin layer, for example, a composite pigment and / or hollow particles are kneaded into the film base resin and / or the laminate resin. Then, you may manufacture by making each layer join, extrusion, and shape | molding. In addition, each layer is extruded into a sheet shape, and the surface in contact with each layer is formed with an oxygen functional group by surface treatment such as corona discharge, and then each layer is laminated and integrated with an adhesive, or each layer is integrated. You may manufacture by heat-seal | fusing and integrating.

  In addition, since what is called a commercially available PVDF film is normally made from the mixed resin which mixed PVDF resin and acrylic resin at about 95: 5-70: 30, taking advantage of the adhesiveness of the acrylic resin, vinyl chloride and They may be integrated with acrylic or polycarbonate resin by heat fusion.

  The composite pigment is a black-colored pigment, and can be dispersed by kneading into each of the above-mentioned resins. In order to prevent aggregation of the particles of the composite pigment particles during the above-mentioned kneading. Furthermore, it is preferable that the surface of the composite pigment particles is subjected to a hydrophobic treatment with a surface treatment agent. As the surface treatment agent, it is preferable to use a material that has high reactivity with the surface of the composite pigment particle and can impart hydrophobicity to the surface of the composite pigment particle in a small amount. For example, a silane coupling agent, an organosilicone compound, etc. Can be mentioned.

  As the silane coupling agent, those having no reactive functional group such as an epoxy group or amino group or a hydrophilic group are preferred, and an organosilicon compound having a hydrophobic organic group is particularly preferred. As the organic group having hydrophobicity, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, a fluoroalkyl group, a fluoroaryl group or the like is preferably used, and an alkyl group having 2 to 20 carbon atoms or a carbon having a fluorine atom is used. It is particularly preferable to use a fluoroalkyl group having a number of 2 to 20, a phenyl group, a phenyl group substituted with an alkyl group or a fluoroalkyl group, or the like.

  Examples of the hydrolyzable group in the organosilicon compound include an alkoxy group, an acyloxy group, an amino group, an isocyanate group, and a chlorine atom, and an alkoxy group having 4 or less carbon atoms is preferable. It is preferable that 1-4 hydrolyzable groups are bonded to the silicon atom, particularly 2-3 bonds.

  As the organosilicone compound, an organosilicone in which an organic group and a hydroxyl group or a hydrolyzable group are directly bonded to a silicon atom is preferable. As the organic group, an alkyl group having 4 or less carbon atoms or a phenyl group is preferable. As the organosilicone, silicone oil is preferable.

  Specific examples of the organosilicon compound that is a surface treatment agent include the following compounds. Tetraalkoxysilanes such as tetraethoxysilane, tetramethoxysilane, trialkoxysilanes such as isobutyltrimethoxysilane, hexyltrimethoxysilane, (3,3,3-trifluoropropyl) trimethoxysilane, ethyltriethoxysilane, Silicone oils such as dimethyl silicone oil, methyl hydrogen silicone oil, and phenylmethyl silicone oil. Of these, isobutyltrimethoxysilane, hexyltrimethoxysilane, ethyltriethoxysilane, dimethylsilicone oil, and phenylmethylsilicone are preferable.

  The amount of the surface treatment agent used is preferably appropriately selected depending on the specific surface area of the composite pigment particles, the reactivity between the composite pigment particles and the surface treatment agent, and the like. In this invention, it is preferable that it is 1-50 mass parts with respect to 100 mass parts of composite pigment fine particles, and, as for the usage-amount of a surface treating agent, it is more preferable that it is 3-20 mass parts, and 5-10 masses. Most preferably. When it is in this range, aggregates of the composite pigment fine particles are hardly generated, and the film appearance does not deteriorate.

  The treatment method with the surface treatment agent is not particularly limited, but a method of drying after dispersing the composite pigment particles in a solution of water, alcohol, acetone, n-hexane, toluene or the like in which the surface treatment agent is dissolved is preferable. . In addition, in the case of adding particles of cerium oxide and / or zinc oxide in addition to the composite pigment as described above, it may be kneaded into the resin after being hydrophobized using a surface treatment agent in the same manner as described above. preferable.

  The film or sheet of the present invention thus produced is attached to a support such as a metal, plastic, or exterior base material via an adhesive layer such as a pressure-sensitive adhesive or adhesive, and is used as an exterior material such as a wall. Used for exterior (construction) such as finishing, repair, and renovation, or as a so-called decorative film or sheet, for exterior (construction) exterior or construction, such as exterior finish, repair, or renovation, for crime prevention, blindfolding, design improvement, etc. Not only can it be used as a film or sheet for glass, but it can also be used as a film or sheet in a tent warehouse or barn without having a support outdoors.

  In addition, the exterior material which concerns on this invention can be manufactured by affixing the above-mentioned film or sheet to an exterior base material through an adhesive agent. Since the exterior material obtained in this way can perform the process of constructing an exterior with an exterior base material and the process of attaching a film or a sheet on the exterior base material in one process, the cost is low. Rapid construction is possible.

  Moreover, the glass which concerns on this invention can be manufactured by affixing the above-mentioned film or sheet on the surface of glass through an adhesive agent. The glass thus obtained is useful as a crime prevention glass, a blindfold (privacy) glass, and a design improvement glass.

== Exterior construction method according to the present invention ==
The exterior construction method according to the present invention is not particularly limited as long as it is a method of finishing the exterior using the above-described film or sheet, or exterior material, or performing repair / renovation of the exterior, for example, After pasting the exterior base material using an adhesive (eg, mortar, adhesive, etc.) or after fixing the exterior base material with a fixture (eg, nail, wire, etc.), adhere to the exterior base material Examples thereof include a method of attaching a film or sheet via an agent, a method of attaching an exterior material using an adhesive, and a method of fixing the exterior material with a fixture.

  Hereinafter, the present invention will be specifically described by way of examples. In addition, these Examples illustrate the weather resistance of the film or sheet according to the present invention, the effect of suppressing the temperature rise due to solar radiation, and the like, and do not limit the scope of the present invention.

  The sheet produced in this example was evaluated as a film for a black wall material. The required performance is “temperature does not rise and weather resistance is good”. As a measure for measuring that the temperature of the film does not rise, generally the solar heat gain rate is used. Therefore, the solar radiation transmittance and solar reflectance are calculated from the optical characteristics, and the solar heat acquisition rate is assumed that 34% of the heat absorbed by the film is stored and 66% is released to the outside by the wind. Calculated.

That is,
Solar heat acquisition rate = solar radiation transmittance + solar radiation absorption rate x 0.34
However, solar absorptivity = 1- (solar radiation transmittance)-(solar radiation reflectance)
It is.

(Measurement of solar transmittance and solar reflectance)
In accordance with JIS R3106 “Testing method for transmittance, reflectance, emissivity, and solar heat gain of plate glass”, solar transmittance and solar reflectance were measured.

(Measurement of film temperature under outdoor sunlight)
The film produced in this example was left in the direct sunlight (weather: fine weather) from 9 am to 2 pm, and the maximum temperature during that time was measured. Moreover, the maximum temperature was similarly measured about the 100 micrometer ETFE film as a control sample, and the temperature rise degree of the film manufactured in the present Example was evaluated.

(Weather resistance evaluation)
Using an open frame carbon arc lamp in accordance with JIS K7350-4, a weather resistance test is performed for 5000 hours, and optical characteristics before and after the test are measured to examine the degree of change in the initial solar reflectance and solar absorption rate. It was.

(Sample 1)
40 g of Mn—Bi oxide fine particles (black 6301: (Bi, Mn) 203, manufactured by Asahi Kasei Kogyo; Mn, Bi composite oxide pigment) having an average particle size of 0.1 μm were placed in a 5% toluene solution of phenylmethylsilicone. Dispersed. Next, toluene was removed by evaporation at 140 ° C. to obtain 42 g of Mn—Bi oxide fine particles hydrophobized with phenylmethylsilicone.

  20 g of hydrophobized Mn-Bi oxide fine particles and 4 kg of ETFE (Fullon ETFE88AX manufactured by Asahi Glass) were dry-mixed with a V mixer. This mixture was pelletized at 320 ° C. by a twin screw extruder. Using this pellet, a 100 μm film (sample 1) was formed at 320 ° C. by a T-die method.

  Thereafter, the optical characteristics of Sample 1 were measured with a Shimadzu UV-VIS-IR spectrometer UV3100. As a result of measuring the spectral characteristics by a method based on JIS R3106, it was found that the solar radiation transmittance was 1.58% and the solar reflectance was 23.4%. Further, the solar heat gain rate was found to be 27.1% according to the above formula.

  Next, sample 1 was exposed outdoors from 9:00 to 14:00 on a sunny day, and the surface temperature of sample 1 was measured. As a result, it was found that the temperature rose to 55 ° C. The control sample rose to 44 ° C., and the difference was + 11 ° C.

  The transmitted light chart of the film before the test of Sample 1 is shown in FIG. 1, and the reflected light chart is shown in FIG. A transmitted light chart of the 100 μm ETFE film of the control sample is shown in FIG. 1, and a reflected light chart is shown in FIG.

  In addition, the solar radiation transmittance of the control sample of 100 μm ETFE was 92.3%, and the solar reflectance was 6.3%.

  Moreover, when the above-mentioned weather resistance evaluation was performed on the film of Sample 1, the solar radiation transmittance was 1.58%, the solar reflectance was 23.4%, and the solar heat acquisition rate was 27.1%. It became clear that there was no.

(Sample 2)
Mn-Y oxide fine particles (black 6303: (Y, Mn) 204, manufactured by Asahi Kasei Kogyo; Mn, Y composite oxide pigment) having an average particle diameter of 0.1 μm were used in the same manner as in Sample 1. Sample 2 was manufactured and the same measurement as sample 1 was performed. As a result, it was found that the solar transmittance was 5.48%, the solar reflectance was 23.1%, and the solar heat acquisition rate was 29.8%.

  Moreover, as a result of exposing Sample 2 outdoors from 9:00 to 14:00 on a sunny day and measuring the surface temperature of Sample 2, it was found that the temperature rose to 57 ° C. and the difference from the control sample was + 13 ° C. . Moreover, when the weather resistance evaluation was performed on the film of sample 2, the solar radiation transmittance was 5.85%, the solar reflectance was 23.2%, and the solar heat acquisition rate was 30.01%, which was almost unchanged. It became clear not to show. In addition, the transmitted light chart of the film before the test of Sample 2 is shown in FIG. 1, and the reflected light chart is shown in FIG.

(Comparative Example 1)
4 g of carbon black having an average particle size of 0.1 μm and 4 kg of ETFE (Fullon ETFE88AX manufactured by Asahi Glass) were dry-mixed with a V mixer. The mixture was pelletized at 320 ° C. with a twin screw extruder. Using this pellet, a 100 μm film (Comparative Example 1) was formed at 320 ° C. by a T-die method. The same measurement as in Sample 1 was performed on the film of Comparative Example 1. As a result, it was found that the solar radiation transmittance was 0.0%, the solar reflectance was 3.6%, and the solar heat acquisition rate was 32.8%.

  Moreover, as a result of exposing the film of Comparative Example 1 outdoors from 9:00 to 14:00 on a sunny day and measuring the surface temperature of the film of Comparative Example 1, the film rose to 67 ° C., and the difference from the control sample was + 23 ° C. I found out that Moreover, when the weather resistance evaluation was performed on the film of Comparative Example 1, the solar transmittance was 0.0%, the solar reflectance was 3.6%, and the solar heat acquisition rate was 32.8%, which was almost the same. It became clear not to show. The transmitted light chart of the film of Comparative Example 1 is shown in FIG. 1, and the reflected light chart is shown in FIG.

  From the above, in a film or sheet having a layer in which a composite pigment is kneaded into a resin, the composite pigment does not have a photocatalytic action on the resin. It was found that thermal degradation can be suppressed by suppressing the rise. Moreover, since the said film and sheet | seat can maintain an optical characteristic for a long term, it turned out that it is excellent in a weather resistance.

Claims (9)

Having a film base resin layer and a laminate resin layer formed on the surface of the film base resin layer ;
A composite metal oxide pigment containing an oxide of Bi and / or Y and an oxide of Mn is kneaded into the film base resin and / or the laminate resin,
The laminate resin, Ri fluororesin der,
Forming the said film base resin layer and the laminate resin layer is combined with extrusion, or, characterized Rukoto are integrated extruded to the said film base resin layer and the laminate resin layer into a sheet Film or sheet. The film or sheet according to claim 1 , further comprising a photocatalyst layer containing a photocatalyst on the laminate resin layer. The fluororesin is an ethylene-tetrafluoroethylene copolymer, a hexafluoropropylene-tetrafluoroethylene copolymer, a perfluoro (alkyl vinyl ether) -tetrafluoroethylene copolymer, or a tetrafluoroethylene-hexafluoropropylene- The film or sheet according to claim 1 or 2 , wherein the film or sheet is selected from the group consisting of a vinylidene fluoride copolymer and polyvinylidene fluoride. The film or sheet according to any one of claims 1 to 3 , wherein a content of Mn in the composite metal oxide pigment is 5 to 65 mass% with respect to a total mass. The film or sheet according to any one of claims 1 to 4 , further comprising an adhesive layer. The exterior material which has a film or sheet in any one of Claims 1-5 . The glass which has a film or sheet in any one of Claims 1-5 . A method for producing a film or sheet having a film base resin layer and a laminate resin layer,
A step of kneading a composite metal oxide pigment containing an oxide of Bi and / or Y and an oxide of Mn into the film base resin and / or the laminate resin;
The laminate resin, Ri fluororesin der,
The laminate resin layer is formed on the surface of the film base resin layer,
Forming the said film base resin layer and the laminate resin layer is combined with extrusion, or, characterized Rukoto are integrated extruded to the said film base resin layer and the laminate resin layer into a sheet Production method. Film or sheet according to any one of claims 1 to 5 or, exterior construction method, which comprises using an exterior material according to claim 6.

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