WO2014162619A1 - Film de blindage contre les rayons calorifiques, matériau de base transparent stratifié de blindage contre les rayons calorifiques, automobile, et bâtiment - Google Patents

Film de blindage contre les rayons calorifiques, matériau de base transparent stratifié de blindage contre les rayons calorifiques, automobile, et bâtiment Download PDF

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Publication number
WO2014162619A1
WO2014162619A1 PCT/JP2013/071907 JP2013071907W WO2014162619A1 WO 2014162619 A1 WO2014162619 A1 WO 2014162619A1 JP 2013071907 W JP2013071907 W JP 2013071907W WO 2014162619 A1 WO2014162619 A1 WO 2014162619A1
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Prior art keywords
heat ray
ray shielding
compound
shielding film
tungsten oxide
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PCT/JP2013/071907
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English (en)
Japanese (ja)
Inventor
佳輔 町田
藤田　賢一
Original Assignee
住友金属鉱山株式会社
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Filing date
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Application filed by 住友金属鉱山株式会社 filed Critical 住友金属鉱山株式会社
Priority to JP2014070176A priority Critical patent/JP6098831B2/ja
Priority to US14/782,568 priority patent/US9868665B2/en
Priority to KR1020157031491A priority patent/KR102213882B1/ko
Priority to CN201480020194.XA priority patent/CN105307996B/zh
Priority to PCT/JP2014/059774 priority patent/WO2014163119A1/fr
Priority to EP15201250.6A priority patent/EP3034294B1/fr
Priority to EP14778759.2A priority patent/EP2982658B1/fr
Priority to TW103112764A priority patent/TWI602864B/zh
Publication of WO2014162619A1 publication Critical patent/WO2014162619A1/fr
Priority to US15/782,141 priority patent/US20180044228A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
    • C03C17/008—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character comprising a mixture of materials covered by two or more of the groups C03C17/02, C03C17/06, C03C17/22 and C03C17/28
    • C03C17/009—Mixtures of organic and inorganic materials, e.g. ormosils and ormocers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10614—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer comprising particles for purposes other than dyeing
    • B32B17/10633—Infrared radiation absorbing or reflecting agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10678—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer comprising UV absorbers or stabilizers, e.g. antioxidants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10688—Adjustment of the adherence to the glass layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10761—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing vinyl acetal
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/40—Coatings comprising at least one inhomogeneous layer
    • C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
    • C03C2217/44—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the composition of the continuous phase
    • C03C2217/445—Organic continuous phases
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/40—Coatings comprising at least one inhomogeneous layer
    • C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
    • C03C2217/46—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase
    • C03C2217/47—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase consisting of a specific material
    • C03C2217/475—Inorganic materials

Definitions

  • the present invention relates to a heat ray shielding film having good visible light transmittance and an excellent heat ray shielding function, a heat ray shielding laminated transparent base material, an automobile on which the heat ray shielding laminated transparent base material is mounted as a window material, and the heat ray.
  • the present invention relates to a building in which a shielding laminated transparent base material is used as a window material.
  • Patent Document 1 discloses a laminated glass in which a soft resin layer containing a heat ray shielding metal oxide made of tin oxide or indium oxide having a fine particle diameter of 0.1 ⁇ m or less is sandwiched between two opposing plate glasses. Is disclosed.
  • Patent Document 2 discloses that Sn, Ti, Si, Zn, Zr, Fe, Al, Cr, Co, Ce, In, Ni, Ag, Cu, Pt, Mn, at least between two opposing glass plates.
  • Metals such as Ta, W, V, and Mo, oxides of the metals, nitrides of the metals, sulfides of the metals, Sb and F dopants to the metals, and intermediate layers in which these composites are dispersed
  • a laminated glass sandwiching a glass is disclosed.
  • each of the conventional laminated glasses disclosed in Patent Documents 1 to 4 has a problem that the heat ray shielding function is not sufficient when high visible light transmittance is required.
  • Patent Document 5 discloses that a metal oxide semiconductor, a near infrared absorber, and an ultraviolet absorber are mixed with a transparent synthetic resin and molded on a film. An ultraviolet and infrared shield is disclosed.
  • the optical properties of laminated glass for heat ray shielding in which hexaboride fine particles alone, or hexaboride fine particles and ITO fine particles and / or ATO fine particles are applied has a transmittance in the visible light region. In addition, it exhibits strong absorption in the near infrared region and has minimum transmittance.
  • the heat-shielding laminated glass is improved until the solar radiation transmittance when the visible light transmittance is 70% or more is in the 50% range. It was done.
  • Patent Document 7 As a heat ray shielding laminated glass in which a polyvinyl acetal resin is replaced with an ultraviolet curable resin and a heat ray shielding film in which a composite tungsten compound is contained in the ultraviolet curable resin is used as an intermediate layer. is doing.
  • the heat-shielding laminated glass has a solar radiation transmittance when the visible light transmittance is 70% or more as compared with the conventional laminated glass described in Patent Documents 1 to 4 and Patent Document 6. It was improved until the rate was around 35%.
  • the present inventors first conducted intensive research on a method for improving the heat ray shielding characteristics while maintaining high visible light transmittance.
  • the present inventors paid attention to the wavelength distribution of the weight coefficient used in the visible light transmittance calculation described in JIS R 3106. Specifically, the wavelength distribution of the weight coefficient used for calculating the visible light transmittance and the solar radiation energy in the short wavelength region were studied in detail. And the knowledge that it was possible to reduce only the solar radiation transmittance
  • ultraviolet light with a wavelength of 300 nm to 380 nm is used in spite of the common sense of using a conventional ultraviolet shielding agent that cuts the visible light region as much as possible.
  • a selective wavelength absorbing material having no absorption in the vicinity of wavelength 550 nm which is a region that greatly contributes to the calculation of visible light transmittance, coexists with the composite tungsten oxide fine particles. I came up with a composition.
  • the present inventors next applied the tint value calculated based on JIS Z 8701 from the spectral transmittance measurement of the laminated transparent base material, and the yellowness of the plastic calculated based on JIS K 7373 from the tint value (this Various investigations were made using “YI” in the invention as an index.
  • the present invention has been completed by conceiving a configuration in which a selective wavelength absorbing material having a large absorption in the vicinity of a wavelength of 420 nm coexists with the composite tungsten oxide fine particles.
  • the first invention for solving the above-described problem is Formula M y WO Z (where, M is, Cs, Rb, K, Tl , In, Ba, Li, Ca, Sr, 1 or more elements selected Fe, Sn, Al, from Cu, 0.1 ⁇ y ⁇ 0.5, 2.2 ⁇ z ⁇ 3.0) and a composite tungsten oxide fine particle having a hexagonal crystal structure, a selective wavelength absorbing material, a polyvinyl acetal resin, a plasticizer, A heat ray shielding film containing The selective wavelength absorbing material in the first period has a transmittance of light having a wavelength of 550 nm of 90% or more, and a transmittance of light having a wavelength of 420 nm when the transmittance of light having a wavelength of 460 nm is 90% or more.
  • the second invention is The composite tungsten oxide fine particle is at least one selected from Cs 0.33 WO 3 and Rb 0.33 WO 3.
  • the heat ray shielding film according to the first invention, The third invention is 2.
  • the heat ray shielding film according to the first or second invention, wherein the composite tungsten oxide fine particles are fine particles having a dispersed particle diameter of 40 nm or less.
  • the fourth invention is:
  • the selective wavelength absorbing material is at least one selected from a benzotriazole compound, a benzophenone compound, a hydroxyphenyltriazine compound, an indole compound, an azomethine compound, a benzotriazolyl compound, and a benzoyl compound. It is a heat ray shielding film in any one of 3rd invention.
  • the fifth invention is: 4. The heat ray shielding film according to any one of the first to third inventions, wherein the selective wavelength absorbing material is an indole compound.
  • the sixth invention is:
  • the selective wavelength absorbing material is an indole compound represented by (Chemical Formula 1), wherein R is an alkyl group having 1 to 10 carbon atoms or an aralkyl group having 7 to 10 carbon atoms.
  • the seventh invention 4.
  • the heat ray shielding according to any one of the first to third inventions, wherein the selective wavelength absorbing material is a compound in which R in the formula is a methyl group among the indole compounds represented by (Chemical Formula 1) It is a membrane.
  • the eighth invention The heat ray shielding film according to any one of the first to seventh inventions, wherein the heat ray shielding film further contains an ultraviolet absorber.
  • a heat ray shielding film according to any one of the first to tenth inventions wherein The twelfth invention is The heat ray shielding film according to any one of the first to eleventh aspects, wherein the heat ray shielding film further contains an infrared absorbing organic compound.
  • the thirteenth invention is The infrared absorbing organic compound is a phthalocyanine compound, naphthalocyanine compound, imonium compound, diimonium compound, polymethine compound, diphenylmethane compound, triphenylmethane compound, quinone compound, azo compound, pentadiene compound, azomethine compound, squarylium compound, organometallic complex
  • the fourteenth invention is The infrared ray absorbing organic compound is at least one selected from a phthalocyanine compound and a diimonium compound.
  • the heat ray shielding film according to the twelfth aspect of the invention The fifteenth invention
  • the sixteenth invention is A heat ray shielding laminated transparent substrate, wherein the heat ray shielding film according to any one of the first to fifteenth inventions is present between a plurality of transparent substrates.
  • the seventeenth invention The heat ray-shielding laminated transparent base material according to the sixteenth aspect, wherein the yellowness (YI) calculated by JIS K 7373 is -20.0 or more and 10.0 or less.
  • the eighteenth invention The heat ray shielding laminated transparent base material according to the sixteenth aspect, wherein the yellowness (YI) calculated in accordance with JIS K 7373 is from -20.0 to 5.0.
  • the nineteenth invention Any of the sixteenth to eighteenth inventions, wherein an infrared reflective film having a visible light transmittance of 88% or more and a solar reflectance of 21% or more is present between the plurality of transparent substrates. It is a heat ray shielding laminated transparent base material as described above.
  • the twentieth invention is The heat ray shielding laminated transparent base material according to any one of the sixteenth to nineteenth aspects, wherein at least one of the transparent base materials is glass.
  • the twenty-first invention The visible light transmittance calculated by JIS R 3106 is 70% or more, and the solar radiation transmittance when the visible light transmittance is 70% is 32.5% or less.
  • the twenty-second invention relates to A heat ray shielding laminated transparent base material according to any one of the sixteenth to twenty-first aspects of the present invention is mounted on a window material.
  • the twenty-third invention A heat ray shielding laminated transparent base material according to any of the sixteenth to twenty-first aspects is a building characterized in that it is used as a window material.
  • a composite tungsten oxide fine particle and a selective wavelength absorbing material are used in combination with a polyvinyl acetal resin as a main component, thereby exhibiting excellent optical characteristics and high weather resistance, and a natural color tone. It was possible to obtain a heat ray shielding film having And the heat ray shielding laminated transparent base material which exhibits the outstanding optical characteristic, high weather resistance, and the outstanding mechanical characteristic was able to be obtained by using the said heat ray shielding film. Furthermore, by mounting the heat ray shielding laminated transparent base material on a car as a window material, it has become possible to suppress a rise in the temperature inside the car in summer. Moreover, the said heat ray shielding matching transparent base material was used for the opening part of a building as a window material, and the building which can suppress the temperature rise in the building in summer was implement
  • the heat ray shielding film according to the present invention is composed of composite tungsten oxide fine particles, a dispersant, a selective wavelength absorbing material, an infrared absorbing organic compound if necessary, a polyvinyl acetal resin, a plasticizer, an adhesive strength adjusting agent if desired, and other additions if desired. It contains things.
  • the heat ray shielding film according to the present invention was obtained by dispersing the composite tungsten oxide fine particles and the dispersant in a part of the plasticizer added to the polyvinyl acetal resin to obtain a composite tungsten oxide fine particle dispersion. It can be manufactured by kneading the dispersion, the selective wavelength absorbing material, the polyvinyl acetal resin, and the plasticizer, and then molding the film by a known method such as an extrusion molding method or a calendar molding method.
  • the heat ray shielding film according to the present invention obtains a dispersion liquid in which the composite tungsten oxide fine particles and the dispersing agent are dispersed in a general organic solvent, and then removes the organic solvent into the solid dispersing agent.
  • a composite tungsten oxide fine particle dispersion in which composite tungsten oxide fine particles are dispersed is obtained, and the obtained dispersion, a selective wavelength absorbing material, a polyvinyl acetal resin, and a plasticizer are kneaded and then extrusion molded. It can also be produced by molding into a film by a known method such as a method or a calender molding method.
  • examples of preferable composite tungsten oxide fine particles include Cs 0.33 WO 3 and Rb 0.33 WO 3 .
  • the addition amount of the additive element M is preferably 0.1 or more and 0.5 or less, and more preferably around 0.33. This is because the value theoretically calculated from the hexagonal crystal structure is 0.33, and preferable optical characteristics can be obtained with the addition amount before and after this.
  • the particle diameter of the composite tungsten oxide fine particles can be appropriately selected depending on the purpose of use of the heat ray shielding film.
  • the volume average diameter measured by dynamic light scattering light of the composite tungsten oxide fine particles (hereinafter referred to as a dispersed particle diameter or a dispersed average particle diameter). ) Is preferably 40 nm or less. If the composite tungsten oxide fine particles have a dispersed particle size smaller than 40 nm, light is not completely blocked by scattering, and visibility in the visible light region is maintained, and at the same time, transparency is efficiently maintained. Because you can.
  • the dispersed tungsten oxide fine particles have a small dispersed particle diameter.
  • the dispersed particle diameter of the composite tungsten oxide fine particles is 1 nm or more, industrial production is possible.
  • the amount of the composite tungsten particles contained in the heat-ray shielding film, per unit area 0.2g / m 2 ⁇ 2.5g / m 2 is desirable.
  • the dispersant is preferably a dispersant having an amine-containing group, a hydroxyl group, a carboxyl group, or an epoxy group as a functional group.
  • These functional groups are adsorbed on the surface of the composite tungsten oxide fine particles, prevent aggregation of the composite tungsten oxide fine particles, and have an effect of uniformly dispersing the fine particles even in the heat ray shielding film.
  • Specific examples include acrylic-styrene copolymer dispersants having a carboxyl group as a functional group and acrylic dispersants having an amine-containing group as a functional group.
  • the dispersant having an amine-containing group as a functional group preferably has a molecular weight Mw of 2000 to 200,000 and an amine value of 5 to 100 mgKOH / g.
  • the dispersant having a carboxyl group preferably has a molecular weight of Mw 2000 to 200000 and an acid value of 1 to 50 mgKOH / g.
  • the selective wavelength absorbing material itself excluding the absorption of the medium and the substrate has a light transmittance of 90% or more and a light transmittance of 460 nm.
  • the transmittance of light having a wavelength of 420 nm is preferably 40% or less.
  • the transmittance of light having a wavelength of 550 nm is 90% or more and the transmittance of light having a wavelength of 460 nm is 90% or more, the transmittance of light having a wavelength of 420 nm is more preferably 15% or less.
  • the indole compounds represented by (Chemical Formula 1) a compound in which R is a methyl group is particularly preferable as the selective wavelength absorption material according to the present invention.
  • the indole compound represented by (Chemical Formula 1) even if it is not the indole compound represented by (Chemical Formula 1), it has an indole skeleton, the indole compound itself excluding the absorption of the medium and the substrate has a light transmittance of 90% or more at a wavelength of 550 nm and a wavelength of 460 nm.
  • the light transmittance is 90% or more
  • any indole compound having a light transmittance of 40% or less at a wavelength of 420 nm can be suitably used as the selective wavelength absorbing material according to the present invention.
  • the mixing ratio of the addition amount of the selective wavelength absorbing material is 100/800 or less, the absorption in the visible light short wavelength region, which has a great influence on YI, is not increased, and the heat ray shielding film does not increase significantly without increasing YI. This is because the color tone is maintained.
  • the selective wavelength absorbing material is uniformly dispersed in the heat ray shielding film, and any method that does not impair the transparency of the obtained heat ray shielding film is preferably used.
  • the heat ray shielding laminated transparent base material according to the present invention is mounted.
  • the second reason is that by adding an ultraviolet absorber, the photodegradation of the selective wavelength absorbing material due to sunlight or the like can be suppressed.
  • an ultraviolet absorber is further added to the heat ray shielding film according to the present invention. By doing so, it is possible to suppress light degradation of the selected wavelength absorbing material due to sunlight or the like.
  • the ultraviolet shielding agent examples include organic ultraviolet absorbers such as benzophenone compounds, salicylic acid compounds, HALS compounds, benzotriazole compounds, triazine compounds, benzotriazolyl compounds, and benzoyl compounds, and inorganic substances such as zinc oxide, titanium oxide, and cerium oxide.
  • organic ultraviolet absorbers such as benzophenone compounds, salicylic acid compounds, HALS compounds, benzotriazole compounds, triazine compounds, benzotriazolyl compounds, and benzoyl compounds, and inorganic substances such as zinc oxide, titanium oxide, and cerium oxide.
  • examples include ultraviolet absorbers, and among them, benzotriazole compounds and benzophenone compounds are particularly preferable. This is because the benzotriazole compound and the benzophenone compound have very high visible light transmittance and high durability against long-term exposure to strong ultraviolet rays even when a concentration sufficient to absorb ultraviolet rays is added.
  • the content of the ultraviolet absorber in the heat ray shielding film is preferably 0.1% by weight or more and 5.0% by weight or less. If the content is 0.1% by weight or more, it is possible to sufficiently absorb ultraviolet light that cannot be absorbed by the selective wavelength absorbing material, and to sufficiently prevent photodegradation of the selective wavelength absorbing material. Because. In addition, when the content is 5.0% by weight or less, the ultraviolet absorber does not precipitate in the heat ray shielding film, and does not significantly affect the strength, adhesive force, and penetration resistance of the film.
  • compounds such as benzotriazole compounds, benzophenone compounds, triazine compounds, benzotriazolyl compounds, and benzoyl compounds have a light absorption coefficient at a wavelength of 420 nm, although they are lower than indole compounds and azomethine compounds. Therefore, by adding a considerable amount of these compounds to the heat ray shielding film, when the transmittance of light having a wavelength of 550 nm is 90% or more and the transmittance of light having a wavelength of 460 nm is 90% or more, a wavelength of 420 nm The effect that the light transmittance is 40% or less can also be exhibited. According to the said structure, these compounds will serve as the effect of a selective wavelength absorption material and a ultraviolet absorber.
  • an infrared-absorbing organic compound having strong absorption in the near-infrared region may be further added to the heat ray shielding film as desired.
  • infrared absorbing organic compounds used for this purpose include phthalocyanine compounds, naphthalocyanine compounds, imonium compounds, diimonium compounds, polymethine compounds, diphenylmethane compounds, triphenylmethane compounds, quinone compounds, azo compounds, pentadiene compounds, azomethine compounds, squarylium. Compounds, organometallic complexes, cyanine compounds and the like can be used.
  • the infrared absorbing organic compound it is preferable to select one that dissolves in the plasticizer constituting the heat ray shielding film described above, because the transparency of the obtained heat ray shielding film is not impaired.
  • the infrared-absorbing organic compound is more preferably a material that strongly absorbs light in the range from the visible long wavelength region to the near infrared region having a wavelength of 650 nm to 1000 nm. This is because there is a large synergistic effect when the infrared absorbing organic compound having the optical characteristics and the composite tungsten oxide fine particles having strong absorption in the wavelength region of 800 nm or more are used in combination. This is because a higher heat shielding performance can be obtained as compared with the case of using in the above. From this viewpoint, as the infrared absorbing organic compound used in the present invention, a diimonium compound and a phthalocyanine compound are particularly preferable.
  • the mixing ratio of the addition amount of the infrared absorbing organic compound is 100/100 or less in the above-mentioned weight ratio, the wavelength region near 550 nm, which is a wavelength region that greatly contributes to the visible light transmittance calculation by the infrared absorbing organic compound. Therefore, it is possible to avoid a decrease in visible light transmittance. For this reason, even if the visible light transmittance is combined, the heat shielding property is secured, which is preferable.
  • Polyvinyl acetal resin As the polyvinyl acetal resin used for the heat ray shielding film according to the present invention, a polyvinyl butyral resin is preferable. Further, in consideration of the physical properties of the heat ray shielding film, a plurality of types of polyvinyl acetal resins having different degrees of acetalization may be used in combination. Furthermore, a copolyvinyl acetal resin obtained by reacting a plurality of types of aldehydes in combination during acetalization can also be preferably used. From this viewpoint, the preferable lower limit of the degree of acetalization of the polyvinyl acetal resin is 60%, and the upper limit is 75%.
  • the polyvinyl acetal resin can be prepared by acetalizing polyvinyl alcohol with an aldehyde.
  • the polyvinyl alcohol is usually obtained by saponifying polyvinyl acetate. Generally, polyvinyl alcohol having a saponification degree of 80 to 99.8 mol% is used.
  • the preferable minimum of the polymerization degree of the said polyvinyl alcohol is 200, and an upper limit is 3000.
  • the degree of polymerization is 200 or more, resistance to penetration of the manufactured heat ray shielding laminated transparent base material is maintained, and safety is maintained.
  • it is 3000 or less the moldability of the resin film is maintained, the rigidity of the resin film is also maintained in a preferable range, and the workability is maintained.
  • the aldehyde is not particularly limited, and in general, aldehydes having 1 to 10 carbon atoms such as n-butyraldehyde, isobutyraldehyde, 2-ethylbutyraldehyde, n-hexylaldehyde, n-octylaldehyde, acetaldehyde and the like are used. It is done. Of these, n-butyraldehyde, n-hexylaldehyde, and n-valeraldehyde are preferable, and butyraldehyde having 4 carbon atoms is more preferable.
  • Plasticizer used for the heat ray shielding film mainly composed of the polyvinyl acetal resin according to the present invention includes a plasticizer that is a compound of a monohydric alcohol and an organic acid ester, and a polyhydric alcohol organic acid ester.
  • a plasticizer that is a compound of a monohydric alcohol and an organic acid ester
  • a polyhydric alcohol organic acid ester examples include ester plasticizers such as compounds, and phosphoric acid plasticizers such as organic phosphate plasticizers.
  • Any plasticizer is preferably liquid at room temperature.
  • a plasticizer that is an ester compound synthesized from a polyhydric alcohol and a fatty acid is preferred.
  • the ester compound synthesized from the polyhydric alcohol and fatty acid is not particularly limited.
  • glycol such as triethylene glycol, tetraethylene glycol, tripropylene glycol, butyric acid, isobutyric acid, caproic acid, 2-ethylbutyric acid, heptyl
  • glycol ester compounds obtained by reaction with monobasic organic acids such as acids, n-octylic acid, 2-ethylhexylic acid, pelargonic acid (n-nonyl acid), and decyl acid.
  • ester compounds of tetraethylene glycol, tripropylene glycol, and the above-mentioned monobasic organic are also included.
  • triethylene glycol di-2-ethylhexanate, triethylene glycol di-2-ethylbutyrate, and tetraethylene glycol di-2-ethylhexanate are preferable.
  • a carboxylic acid magnesium salt having 2 to 16 carbon atoms and a potassium carboxylate salt having 2 to 16 carbon atoms are preferable.
  • the carboxylic acid magnesium salt or potassium salt of the organic acid having 2 to 16 carbon atoms is not particularly limited, and examples thereof include magnesium acetate, potassium acetate, magnesium propionate, potassium propionate, magnesium 2-ethylbutanoate, and 2-ethylbutane. Potassium acid, magnesium 2-ethylhexanoate, potassium 2-ethylhexanoate and the like are preferably used.
  • the produced composite tungsten oxide fine particle plasticizer dispersion, or the produced composite tungsten oxide fine particle dispersion, the selective wavelength absorbing material, the polyvinyl acetal resin, the plasticizer, and preferably the ultraviolet absorber can be produced by, for example, forming into a film by a known method such as an extrusion molding method or a calender molding method after mixing and kneading other additives and an adhesive strength adjusting agent. Further, if an infrared absorbing organic compound is added to the heat ray shielding film as desired, higher heat ray shielding characteristics can be obtained.
  • an organic solvent having a boiling point of 120 ° C. or lower may be added as desired.
  • the organic solvent those having a boiling point of 120 ° C. or less are preferably used. If the boiling point is 120 ° C. or lower, it is easy to remove by a drying step, which is a subsequent step, particularly by drying under reduced pressure. As a result, removal in the reduced-pressure drying step proceeds rapidly, contributing to the productivity of the composite tungsten oxide fine particle-containing composition. Furthermore, since the vacuum drying process proceeds easily and sufficiently, it can be avoided that an excess organic solvent remains in the composite tungsten oxide fine particle-containing composition according to the present invention.
  • the method of uniformly dispersing the composite tungsten oxide fine particles in the organic solvent can be arbitrarily selected from general methods. As specific examples, methods such as a bead mill, a ball mill, a sand mill, and ultrasonic dispersion can be used.
  • the removal efficiency of the solvent is improved, and the composite tungsten oxide fine particle-containing composition is not exposed to high temperature for a long time, so that aggregation of dispersed fine particles does not occur. preferable. Furthermore, productivity is increased, and it is easy to collect the evaporated organic solvent, which is preferable from the environmental consideration.
  • the plasticizer dispersion liquid of the composite tungsten oxide fine particles described above, or the composite tungsten oxide fine particles, the dispersant, and the plasticizer have a boiling point of 120 ° C. or less.
  • a composite tungsten oxide fine particle dispersion in which the concentration of the composite tungsten oxide fine particles is 50% by mass or less is produced using a general dispersion method.
  • the concentration of the composite tungsten oxide fine particles in the plasticizer is preferably 50% by mass or less. If the concentration of the composite tungsten oxide fine particles in the plasticizer is 50% by mass or less, the fine particles are hardly aggregated, easily dispersed, a sudden increase in viscosity can be avoided, and handling is easy.
  • a method of uniformly dispersing the composite tungsten oxide fine particles in the plasticizer can be arbitrarily selected from general methods. As a specific example, after obtaining a dispersion containing composite tungsten oxide fine particles, the organic solvent is removed by a known method, so that the composite tungsten oxide fine particles are dispersed in a solid dispersant. A dispersion can also be obtained.
  • the organic solvent for dissolving the selected wavelength absorbing material one kind arbitrarily selected from toluene, methyl isobutyl ketone, and N-methyl-2-pyrrolidinone according to the solvent solubility of the selected wavelength absorbing material was used.
  • the visible light transmittance and solar radiation transmittance of the transparent substrate with heat ray shielding were similarly measured using a spectrophotometer U-4000.
  • the said solar transmittance is an parameter

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Biochemistry (AREA)
  • Joining Of Glass To Other Materials (AREA)
  • Laminated Bodies (AREA)
  • Optical Filters (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention fournit : un film de blindage contre les rayons calorifiques qui tout en ayant pour composant principal une résine d'acétal polyvinylique, se révèle excellent en termes de caractéristiques de barrière thermique ; un matériau de base transparent stratifié de blindage contre les rayons calorifiques mettant en œuvre ledit film de blindage contre les rayons calorifiques ; une automobile dans laquelle ce matériau de base transparent stratifié de blindage contre les rayons calorifiques, est monté en tant que matériaux de vitre ; et un bâtiment dans lequel ce matériau de base transparent stratifié de blindage contre les rayons calorifiques, est mis en œuvre en tant que matériaux de vitre. Le film de blindage contre les rayons calorifiques de l'invention comprend des microparticules composites d'oxyde de tungstène représentées par la formule générale MyWOz, et présentant une strucuture cristalline à cristaux hexagonaux, une matière d'absorption de longueur d'onde sélective, la résine d'acétal polyvinylique, et un plastifiant. Ladite matière d'absorption de longueur d'onde sélective possède un profil de transmittance tel que lorsque la transmittance d'une lumière de longueur d'onde de 550nm et de 460nm, est supérieure ou égale à 90%, alors la transmittance d'une lumière de longueur d'onde de 420nm, est inférieure ou égale à 40%. Le rapport massique entre lesdites microparticules composites d'oxyde de tungstène et ladite matière d'absorption de longueur d'onde sélective, est compris dans une plage telle que (microparticules composites d'oxyde de tungstène / matière d'absorption de longueur d'onde sélective) = 100/2 à 100/800. Ainsi, l'invention fournit un film de blindage contre les rayons calorifiques, et un matériau de base transparent stratifié de blindage contre les rayons calorifiques mettant en œuvre celui-ci.
PCT/JP2013/071907 2013-04-03 2013-08-14 Film de blindage contre les rayons calorifiques, matériau de base transparent stratifié de blindage contre les rayons calorifiques, automobile, et bâtiment WO2014162619A1 (fr)

Priority Applications (9)

Application Number Priority Date Filing Date Title
JP2014070176A JP6098831B2 (ja) 2013-04-03 2014-03-28 熱線遮蔽膜、熱線遮蔽合わせ透明基材、自動車および建造物
US14/782,568 US9868665B2 (en) 2013-04-03 2014-04-02 Heat ray-shielding film, heat ray-shielding laminated transparent base material, heat ray-shielding resin sheet material, automobile and building
KR1020157031491A KR102213882B1 (ko) 2013-04-03 2014-04-02 열선 차폐막, 열선 차폐 적층 투명기재, 열선 차폐 수지 시트재, 자동차 및 건조물
CN201480020194.XA CN105307996B (zh) 2013-04-03 2014-04-02 热线屏蔽膜、热线屏蔽夹层透明基材、热线屏蔽树脂片材、汽车及建筑物
PCT/JP2014/059774 WO2014163119A1 (fr) 2013-04-03 2014-04-02 Film de blindage contre les rayons calorifiques, matériau de base transparent stratifié de blindage contre les rayons calorifiques, matériau de feuille de résine de blindage contre les rayons calorifiques, automobile, et bâtiment
EP15201250.6A EP3034294B1 (fr) 2013-04-03 2014-04-02 Matériau de feuille de résine de blindage contre les rayons calorifiques, automobile, et bâtiment
EP14778759.2A EP2982658B1 (fr) 2013-04-03 2014-04-02 Film de blindage contre les rayons calorifiques, matériau de base transparent stratifié de blindage contre les rayons calorifiques, matériau de feuille de résine de blindage contre les rayons calorifiques, automobile, et bâtiment
TW103112764A TWI602864B (zh) 2013-04-03 2014-04-03 熱射線遮蔽膜，熱射線遮蔽疊層透明基材，熱射線遮蔽樹脂片材，汽車及建造物
US15/782,141 US20180044228A1 (en) 2013-04-03 2017-10-12 Heat ray-shielding film, heat ray-shielding laminated transparent base material, heat ray-shielding resin sheet material, automobile and building

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2013-077829 2013-04-03
JP2013077829 2013-04-03

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WO2014162619A1 true WO2014162619A1 (fr) 2014-10-09

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JP (1) JP6098831B2 (fr)
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