WO2014050367A1 - Procédé pour produire une structure stratifiée à isolation thermique, structure stratifiée à isolation thermique et film stratifié transparent - Google Patents

Procédé pour produire une structure stratifiée à isolation thermique, structure stratifiée à isolation thermique et film stratifié transparent Download PDF

Info

Publication number
WO2014050367A1
WO2014050367A1 PCT/JP2013/072181 JP2013072181W WO2014050367A1 WO 2014050367 A1 WO2014050367 A1 WO 2014050367A1 JP 2013072181 W JP2013072181 W JP 2013072181W WO 2014050367 A1 WO2014050367 A1 WO 2014050367A1
Authority
WO
WIPO (PCT)
Prior art keywords
layer
laminated structure
film
polymer
transparent
Prior art date
Application number
PCT/JP2013/072181
Other languages
English (en)
Japanese (ja)
Inventor
健司 竹脇
後藤　修
徹司 楢▲崎▼
正隆 犬塚
翔一 池野
竹内　哲也
Original Assignee
東海ゴム工業株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 東海ゴム工業株式会社 filed Critical 東海ゴム工業株式会社
Publication of WO2014050367A1 publication Critical patent/WO2014050367A1/fr

Links

Images

Classifications

    • 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
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/06—Coating on the layer surface on metal layer
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/20—Inorganic coating
    • B32B2255/205—Metallic coating
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/304—Insulating
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent

Definitions

  • the present invention is suitable for a method for manufacturing a heat-insulating laminated structure, a heat-insulating laminated structure, and a heat-insulating laminated structure suitably used for window glass of buildings such as buildings and houses, and window glass of vehicles such as automobiles.
  • the present invention relates to a transparent laminated film.
  • Patent Document 1 discloses a so-called multilayer film type transparent laminated film in which metal oxide layers and metal layers are alternately laminated on one side of a transparent polymer film.
  • Patent Document 2 discloses a transparent laminate in which radio wave permeability is improved by forming a groove portion having a width of 30 ⁇ m or less in a laminated structure in which metal oxide layers and metal layers are alternately laminated on the surface of a transparent polymer film.
  • a film has been proposed.
  • the transparent polymer film is provided with an easy-adhesion layer on one side or both sides in advance in order to improve handling properties such as winding property.
  • the groove portion of the laminated structure is formed by forming a laminated structure on the easy adhesion layer of the transparent polymer film.
  • thermoplastic resin film having a conductive film formed on an uneven surface is disposed and sandwiched between two transparent substrates, and the transparent equipment and the thermoplastic resin film are bonded.
  • the resulting laminated structure is disclosed.
  • a window glass may be formed by sandwiching a heat ray cut film between two glass substrates for the purpose of shielding solar radiation.
  • the heat ray cut film is required to have visible light transmittance and solar shading as basic performance.
  • buildings such as buildings and houses may require high-frequency radio wave transmissivity of several hundred MHz or higher for the use of mobile phones and televisions.
  • radio wave transmission may be required so as not to interfere with radio wave reception of the ETC on-board unit.
  • the transparent laminated film described in Patent Document 1 has a poor radio wave transmission because the metal layer is continuous.
  • the transparent laminated film described in Patent Document 2 forms a groove portion in a laminated structure portion using an easy adhesion layer, and does not form a groove portion using an easy adhesion layer. Is different.
  • the laminated structure described in Patent Document 3 when the thermoplastic resin film is bonded to the transparent substrate, the uneven portions are deformed and flattened, and thus there is a possibility that desired radio wave transmission properties are difficult to obtain.
  • the problem to be solved by the present invention is to provide a method for manufacturing a heat-insulating laminated structure and a heat-insulating laminated structure that are excellent in solar radiation shielding properties and radio wave permeability. Moreover, it is providing the transparent laminated film which can be used suitably for such a laminated structure.
  • a method for manufacturing a heat-insulating laminated structure includes forming a polymer layer on the surface of a transparent polymer film, and forming a metal oxide layer and a metal layer on the surface of the polymer layer. Forming a laminated structure part to be laminated to obtain a transparent laminated film, and sandwiching the obtained transparent laminated film between two transparent substrates, and two transparent substrates under heating and pressure And in the film production process, the metal oxide layer of the laminated structure is formed by sol-gel curing of the metal oxide precursor, and the polymer of the polymer layer is combined with the polymer layer.
  • the gist is to form a groove part that divides the metal layer of the laminated structure part when the two transparent substrates are bonded together.
  • a polymer having a softening temperature of 40 to 130 ° C. as the polymer of the polymer layer.
  • the polymer layer is preferably formed to a thickness of 0.05 to 1.0 ⁇ m.
  • the groove for dividing the metal layer of the laminated structure is not formed in the film production process, or the width of the groove for dividing the metal layer of the laminated structure formed in the film production process is 0.6 ⁇ m or less. It is preferable to do.
  • a polymer having a softening temperature of 110 to 130 ° C. as the polymer of the polymer layer and to form the polymer layer with a thickness of 0.05 to 0.5 ⁇ m.
  • the gist of the heat-insulating laminated structure according to the present invention is obtained by the manufacturing method according to the present invention.
  • a polymer layer and a laminated structure in which a metal oxide layer and a metal layer are laminated are laminated in this order on the surface of the transparent polymer film.
  • a transparent laminated film and two transparent substrates to be bonded together, and the two transparent substrates are bonded to each other with the transparent laminated film sandwiched therebetween.
  • the gist of the present invention is that a groove part is formed to divide the line.
  • the softening temperature of the polymer in the polymer layer is preferably 40 to 130 ° C.
  • the thickness of the polymer layer is preferably 0.05 to 1.0 ⁇ m.
  • an acrylic resin, a phenoxy resin, and a butyral resin can be mentioned as a suitable thing.
  • the transparent laminated film according to the present invention has a laminated structure portion in which a metal oxide layer and a metal layer are laminated on the surface of the transparent polymer film, and is softened between the transparent polymer film and the laminated structure portion.
  • the gist is that a polymer layer having a temperature of 40 to 130 ° C. is disposed.
  • the thickness of the polymer layer is preferably 0.05 to 1.0 ⁇ m.
  • an acrylic resin, a phenoxy resin, and a butyral resin can be mentioned as a suitable thing.
  • a transparent laminated film having a laminated structure portion in which a metal oxide layer and a metal layer are laminated between two transparent substrates to be bonded is disposed. And since the groove part which divides
  • a polymer having a softening temperature of 40 to 130 ° C. is used as the polymer of the polymer layer, a groove for dividing the metal layer is easily formed in the laminated structure of the transparent laminated film.
  • the polymer layer is formed to a thickness of 0.05 to 1.0 ⁇ m, a groove part for dividing the metal layer is easily formed in the laminated structure part of the transparent laminated film.
  • the groove part that divides the metal layer of the laminated structure part is not formed in the film manufacturing process, it is possible to suppress the occurrence of a dent in the vicinity of the groove part of the metal layer during the aligning process. Thereby, the occurrence of irregular reflection of light near the groove is suppressed, and the appearance is also excellent.
  • the width of the groove part for dividing the metal layer of the laminated structure part formed in the film production process is 0.6 ⁇ m or less, the dent generated in the vicinity of the groove part of the metal layer during the aligning process can be reduced. Thereby, the influence of the irregular reflection of the light which arises in the vicinity of a groove part can be made small, and it is excellent in an external appearance.
  • the heat-insulating laminated structure according to the present invention comprising a transparent laminated film having a laminated structure part in which a metal oxide layer and a metal layer are laminated between two bonded transparent substrates, Since the groove part which divides
  • the transparent laminated film which concerns on this invention, it has a laminated structure part by which the metal oxide layer and the metal layer were laminated
  • the width of the groove portion for dividing the metal layer of the laminated structure portion formed at the time of the alignment process becomes narrower. It is possible to suppress the formation of a dent in the vicinity of the groove portion. Thereby, the occurrence of irregular reflection of light near the groove is suppressed, and the appearance is also excellent.
  • This production method includes a film production process for obtaining a transparent laminated film having heat shielding properties, and a combining process performed using the obtained transparent laminated film and two transparent substrates.
  • the film production process includes a first process of forming a polymer layer 18 on the surface of the transparent polymer film 12 as shown in FIG. 1 (a) and a polymer layer 18 as shown in FIG. 1 (b). And a second step of forming the laminated structure portion 16 in which the metal oxide layer 22 and the metal layer 24 are laminated on the surface.
  • the polymer layer 18 is provided for the purpose of forming the groove portion 20 in the laminated structure portion 16 in the combining step described later.
  • an easy-adhesion layer 14 may be formed on the surface of the transparent polymer film 12 in advance for the purpose of improving handling properties such as winding property.
  • 18 may be formed on the surface of the transparent polymer film 12 opposite to the surface on which the easy adhesion layer 14 is formed, or may be formed on the easy adhesion layer 14. May be.
  • the polymer layer 18 is formed by preparing a coating liquid containing a polymer material, coating the surface of the transparent polymer film 12, and then drying to form a coating film. it can.
  • a solvent for dissolving the polymer material can be used as necessary.
  • solvents include alcohols such as methanol, ethanol, propanol, butanol, heptanol and isopropyl alcohol, organic acid esters such as ethyl acetate, ketones such as acetonitrile, acetone and methyl ethyl ketone, and cycloethers such as tetrahydrofuran and dioxane.
  • Acid amides such as formamide and N, N-dimethylformamide, hydrocarbons such as hexane, aromatics such as toluene and xylene, and the like. These may be used alone or in combination.
  • the laminated structure portion 16 is formed by laminating a metal oxide layer 22 and a metal layer 24.
  • the metal oxide layer 22, the metal layer 24, the metal oxide layer 22... are alternately stacked on the surface of the polymer layer 18 in this order.
  • the lowermost metal oxide layer is represented by 22a
  • the uppermost metal oxide layer is represented by 22b
  • the metal oxide layer between them is the middle metal oxide layer. Call it.
  • the metal oxide layer 22 is formed by sol-gel curing of a metal oxide precursor.
  • a coating liquid (coating liquid) containing a metal oxide precursor is prepared, applied to the surface of the transparent polymer film 12 or the surface of the metal layer 24, and then dried to form a coating film.
  • sol-gel curing by a predetermined method.
  • the coating solution may contain water as necessary from the viewpoint that hydrolysis by the sol-gel method is promoted and a high refractive index is easily achieved.
  • the metal oxide precursor examples include organometallic compounds such as metal alkoxide, metal acylate, and metal chelate.
  • organometallic compounds such as metal alkoxide, metal acylate, and metal chelate.
  • the organic component derived from the organometallic compound can remain in the metal oxide layer 22.
  • flexibility of the transparent laminated film 10 increases because the metal oxide layer 22 contains an organic component with a metal oxide.
  • organometallic compounds metal chelates are preferable from the viewpoint of excellent stability in air.
  • sol-gel curing means examples include irradiation with light energy such as ultraviolet rays, electron beams, and X-rays, and heating.
  • light energy such as ultraviolet rays, electron beams, and X-rays
  • heating examples include irradiation with light energy such as ultraviolet rays, electron beams, and X-rays, and heating.
  • irradiation with light energy particularly irradiation with ultraviolet rays is preferable.
  • ultraviolet irradiation relatively simple equipment is sufficient.
  • the obtained transparent laminated film 10 is sandwiched between two transparent substrates 28 and 28, and the two transparent substrates 28 and 28 are heated and pressurized. Paste together. An adhesive can be used for bonding.
  • the transparent laminated film 10 is sandwiched between two transparent base materials 28 and 28 via an adhesive layer 26 made of an adhesive.
  • the transparent substrate 28 is not particularly limited as long as it is a plate-like transparent body that sufficiently transmits visible light, but preferred examples include a glass plate and a resin plate.
  • the glass include normal float glass, semi-tempered glass, and tempered glass.
  • the resin include an acrylic resin and a polycarbonate resin.
  • the thickness of the transparent substrate 28 may be determined as appropriate according to the application.
  • the main material of the adhesive examples include polyvinyl butyral (PVB), ethylene vinyl acetate (EVA), acrylic resin, silicone resin, and urethane resin.
  • the adhesive may be a liquid or a solid one.
  • the solid material examples include a film material.
  • the polymer of the polymer layer 18 a polymer having a softening temperature lower than the heating temperature in the combining step is used. If it does so, the softness
  • the softening temperature is a glass transition temperature (Tg) in the case of an amorphous polymer, and a melting point (Tm) in the case of a crystalline polymer, and can be measured by differential scanning calorimetry (DSC). .
  • the heating temperature in the mating step is set to a temperature at which the adhesive used is softened.
  • the heating temperature in the combining step is set to, for example, about 130 to 135 ° C. in consideration of the softening temperature. Therefore, in consideration of the softening temperature of the adhesive used, it is preferable to use a polymer having a softening temperature of 40 to 130 ° C. as the polymer of the polymer layer 18.
  • the softening temperature may be lower than the sol-gel curing temperature in the film manufacturing process.
  • the flexibility of the polymer layer 18 during sol-gel curing or the combining process changes, and the groove portion 20 is formed in the laminated structure portion 16.
  • the timing, the size of the width of the groove 20 to be formed, the divided shape of the laminated structure 16 and the like are changed. Therefore, the flexibility of the polymer layer 18 at the time of sol-gel curing or the combining process can be controlled by selecting the polymer of the polymer layer 18, the timing at which the groove 20 is formed in the laminated structure 16, and the groove to be formed It is possible to adjust the size of the width of 20, the divided shape of the laminated structure portion 16, and the like.
  • the groove portion 20 that divides the metal layer 24 of the laminated structure portion 16 can be formed before the alignment process.
  • the polymer of the polymer layer 18 is heated to the softening temperature or higher before the combining step, whereby the polymer layer It is also possible to soften the polymer 18 and release the stress generated in the metal oxide layer 22, thereby forming the groove 20 that divides the metal layer 24 of the laminated structure 16.
  • the timing at which the groove 20 is formed in the laminated structure 16 can be adjusted by the softening temperature of the polymer in the polymer layer 18. It can also be adjusted by the thickness of the polymer layer 18 and the temperature during sol-gel curing. As an example in the case of adjusting by the softening temperature, when the softening temperature of the polymer layer 18 is less than 40 ° C., the groove 20 (crack) is formed when the first metal oxide layer 22a of the laminated structure 16 is formed. Is done. When the softening temperature is not lower than 40 ° C. and lower than 60 ° C., the groove 20 (crack) is generated for the first time when the third metal oxide layer 22 of the laminated structure 16 is formed.
  • the groove 20 (crack) is formed when the uppermost metal oxide layer 22 is formed in the three-layer laminated structure, but the middle metal oxide layer 22 is formed in the five-layer laminated structure or the seven-layer laminated structure.
  • grooves 20 (cracks) are formed.
  • the softening temperature is not less than 60 ° C. and less than 70 ° C.
  • the groove 20 (crack) is generated for the first time when the fifth metal oxide layer 22 of the laminated structure 16 is formed.
  • the softening temperature is 70 ° C. or higher and 130 ° C. or lower, since the softening temperature is relatively high, the groove 20 (crack) is generated for the first time when the seventh metal oxide layer 22b of the laminated structure 16 is formed. In this case, even in the seven-layer stacked structure, the groove 20 (crack) can be formed when the uppermost metal oxide layer 22b is formed.
  • the thickness of the polymer layer 18 is preferably 1.0 ⁇ m or less. Further, from the viewpoint of suppressing the generation of the groove 20 before the alignment step, the thickness of the polymer layer 18 is preferably 0.5 ⁇ m or less.
  • the lower limit of the thickness is not particularly limited, but is preferably 0.05 ⁇ m or more from the viewpoint of manufacturing.
  • the flexibility of the polymer layer 18 is increased by the heat of the combining step, and the degree of freedom in the in-plane direction of the laminated structure portion 16 is increased.
  • the stacked structure portion 16 is further cracked starting from the groove portion 20 formed in advance, and the metal layer 24 divided by the groove portion 20 is further divided.
  • variety of the already formed groove part 20 may spread with progress of the fragmentation of the groove part 20.
  • the groove 20 is not formed in the transparent laminated film 10 itself before the alignment process, or the groove Even if 20 is formed, it is preferable that the groove 20 has a narrow width.
  • the width of the groove 20 is 0.6 ⁇ m or less from the viewpoint of suppressing the occurrence of irregular reflection of light. preferable. More preferably, it is 0.3 ⁇ m or less.
  • the width of the groove part 20 is an average value of the widths measured at three places (15 places in total) of the groove part 20 by photographing five surfaces of the laminated structure with an optical microscope.
  • the polymer layer 18 It is preferable to increase the softening temperature and reduce the thickness of the polymer layer 18.
  • the polymer softening temperature of the polymer layer 18 is 110 ° C. or more and the thickness of the polymer layer 18 is 0.5 ⁇ m or less. It is preferable to set to. Further, in order to make the width of the groove portion 20 0.6 ⁇ m or less, it is preferable to set the polymer softening temperature of the polymer layer 18 to 40 ° C. or more and the thickness of the polymer layer 18 to 0.5 ⁇ m or less. .
  • the material for the polymer layer 18 include acrylic resin, phenoxy resin, and butyral resin. Of these, acrylic resins and butyral resins are preferred from the viewpoints of excellent optical properties (transparency) and excellent coating properties.
  • the heat shielding laminated structure 30 has two transparent base materials 28 and 28 bonded together with the transparent laminated film 10 sandwiched therebetween, and the laminated structure portion 16 of the transparent laminated film 10 is attached. A groove 20 for dividing the metal layer 24 is formed.
  • the heat shielding laminated structure 30 includes the transparent laminated film 10, it is excellent in solar shading. Moreover, since the groove part 20 which divides
  • the heat shielding laminated structure 30 can be set to a desired surface resistance value by adjusting the pressure and temperature conditions when the two transparent substrates 28 and 28 are bonded together.
  • the surface resistance value of the heat-insulating laminated structure 30 is preferably 100 ⁇ / ⁇ or more from the viewpoint of radio wave transmission.
  • the transparent laminated film 10 has a transparent polymer film 12, an easy adhesion layer 14, a laminated structure portion 16, and a polymer layer 18.
  • the easy adhesion layer 14 is provided on one surface of the transparent polymer film 12.
  • the laminated structure portion 16 is provided on a surface opposite to the surface on which the easy adhesion layer 14 of the transparent polymer film 12 is formed.
  • the polymer layer 18 is provided between the transparent polymer film 12 and the laminated structure portion 16.
  • the transparent polymer film 12 is a base material serving as a base for forming the laminated structure portion 16.
  • the material of the transparent polymer film 12 is not particularly limited as long as it has transparency in the visible light region and can form a thin film on the surface without hindrance.
  • the material of the transparent polymer film 12 include polyethylene terephthalate, polycarbonate, polymethyl methacrylate, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, polystyrene, polyimide, polyamide, polybutylene terephthalate, polyethylene naphthalate.
  • Polymer materials such as polysulfone, polyethersulfone, polyetheretherketone, polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, triacetyl cellulose, polyurethane, and cycloolefin polymer. These may be used alone or in combination of two or more.
  • polyethylene terephthalate, polycarbonate, polymethyl methacrylate, and cycloolefin polymer are more preferable materials from the viewpoint of excellent transparency, durability, and processability.
  • the easy-adhesion layer 14 is provided in advance on the transparent polymer film 12 in order to improve handling properties such as winding property of the transparent polymer film 12.
  • the easy adhesion layer 14 is often formed on the surface of the transparent polymer film 12 for optical applications. This is because it is difficult for the transparent polymer film 12 for optical applications to improve handling properties by blending silica particles or the like into the film.
  • the metal oxide layer 22, the metal layer 24, the metal oxide layer 22,... are alternately laminated in this order from the transparent polymer film 12 side. Further, it has a seven-layer laminated structure.
  • a metal oxide layer 22 is disposed on the innermost layer (22a) on the transparent polymer film 12 side and the outermost layer (22b) on the opposite side of the transparent polymer film 12.
  • the metal oxide layer 22 and the metal layer 24 are made of a thin film.
  • a barrier layer may be further formed on one surface or both surfaces of the metal layer 24.
  • the barrier layer is a thin film layer attached to the metal layer 24 and is counted as one layer together with the metal layer 24. The barrier layer suppresses diffusion of elements constituting the metal layer 24 into the metal oxide layer 22.
  • the metal oxide layer 22 exhibits functions such as enhancing transparency (excelling in the visible light region) by being laminated together with the metal layer 24, and can function mainly as a high refractive index layer. It is. High refractive index means a case where the refractive index for light of 633 nm is 1.7 or more.
  • the metal layer 24 can mainly function as a solar radiation shielding layer. Such a laminated structure 16 has good visible light transparency (transparency) and solar shading.
  • the number of layers of the laminated structure portion 16 may be appropriately set according to the optical characteristics such as visible light transparency (transparency) and solar shading, and the electrical characteristics such as the surface resistance of the entire film.
  • the number of layers can be other than seven.
  • the number of layers of the laminated structure portion 16 is preferably in the range of 2 to 10 layers in consideration of the material, film thickness, manufacturing cost, etc. of each thin film. In consideration of optical characteristics, odd-numbered layers are more preferable, and 3 layers, 5 layers, and 7 layers are particularly preferable.
  • the metal oxide layer 22, the metal layer 24, and the barrier layer of the laminated structure portion 16 will be described in detail.
  • Examples of the metal oxide of the metal oxide layer 22 of the multilayer structure portion 16 include titanium oxide, zinc oxide, indium oxide, tin oxide, indium and tin oxide, magnesium oxide, Examples thereof include aluminum oxide, zirconium oxide, niobium oxide, and cerium oxide. These may be contained alone or in combination of two or more. These metal oxides may be composite oxides in which two or more metal oxides are combined. Among these, titanium oxide, indium and tin oxide, zinc oxide, tin oxide, and the like are preferable from the viewpoint of relatively high refractive index with respect to visible light.
  • the lower limit of the content of the organic component contained in the metal oxide layer 22 is preferably 3% by mass or more, more preferably 5% by mass or more, and still more preferably, from the viewpoint of easily imparting flexibility. 7 mass% or more.
  • the upper limit of the content of the organic component contained in the metal oxide layer 22 is preferably 30% by mass or less from the viewpoint of easily ensuring a high refractive index and easily ensuring solvent resistance. More preferably, it is 25% by mass or less, and further preferably 20% by mass or less.
  • the organic content can be examined using X-ray photoelectron spectroscopy (XPS) or the like. Moreover, the kind of said organic content can be investigated using infrared spectroscopy (IR) (infrared absorption analysis) etc.
  • the metal oxide layer 22 is formed by sol-gel curing of a metal oxide precursor.
  • the organometallic compound is light-absorbing (for example, UV-absorbing). It is preferable to have a ligand that forms a chelate. By providing the light-absorbing chelate ligand, the metal oxide layer 22 can be formed at a relatively low temperature.
  • Such chelate ligands include ⁇ diketones, alkoxy alcohols, alkanolamines and the like.
  • ⁇ diketones include acetylacetone, benzoylacetone, ethyl acetoacetate, methyl acetoacetate, diethyl malonate, and the like.
  • alkoxy alcohols include 2-methoxyethanol, 2-ethoxyethanol, 2-methoxy-2-propanol and the like.
  • alkanolamines include monoethanolamine, diethanolamine, and triethanolamine. Of these, ⁇ diketones are preferred, and among them, acetylacetone can be most suitably used.
  • the content of the metal oxide precursor in the coating liquid is preferably 1 to 20% by mass, more preferably, from the viewpoint of the film thickness uniformity of the coating film and the film thickness that can be applied at one time. It is good that it is in the range of 3 to 15% by mass, more preferably 5 to 10% by mass.
  • the amount of the solvent is preferably from 5 to 100 times, more preferably from the viewpoint of the film thickness uniformity of the coating film and the film thickness that can be applied at one time with respect to the solid weight of the metal oxide precursor. 7 to 30 times, more preferably 10 to 20 times.
  • the amount of the solvent is more than 100 times, the film thickness that can be formed by one coating becomes thin, and a tendency to require many coatings to obtain a desired film thickness is observed.
  • the amount is less than 5 times, the film thickness becomes too thick and the hydrolysis / condensation reaction of the metal oxide precursor does not proceed sufficiently. Therefore, the amount of solvent should be selected in consideration of these.
  • the solvent for dissolving the metal oxide precursor include alcohols such as methanol, ethanol, propanol, butanol, heptanol, and isopropyl alcohol, organic acid esters such as ethyl acetate, acetonitrile, acetone, and methyl ethyl ketone.
  • the preparation of the coating liquid is performed by, for example, stirring the metal oxide precursor weighed so as to have a predetermined ratio, an appropriate amount of solvent, and other components added as necessary, with stirring means such as a stirrer. It can be prepared by a method such as stirring and mixing for a predetermined time. In this case, the components may be mixed at a time or may be mixed in a plurality of times.
  • the coating method of the coating liquid from the viewpoint of easy uniform coating, microgravure method, gravure method, reverse roll coating method, die coating method, knife coating method, dip coating method, spin coating method, bar coating Various wet coating methods such as the method can be exemplified as suitable ones. These may be appropriately selected and used, and one or more may be used in combination.
  • the applied coating liquid When the applied coating liquid is dried, it may be dried using a known drying device. Specific examples of the drying conditions include a temperature range of 80 ° C. to 120 ° C., Examples include a drying time of 0.5 minute to 5 minutes.
  • the sol-gel curing of the metal oxide precursor can be performed by irradiation with light energy such as ultraviolet rays, electron beams, X-rays or heating.
  • the amount of light energy to be irradiated can be variously adjusted in consideration of the type of metal oxide precursor, the thickness of the layer, and the like. However, if the amount of light energy to be irradiated is too small, it is difficult to increase the refractive index of the metal oxide layer 22. On the other hand, if the amount of light energy to be irradiated is excessively large, the transparent polymer film 12 may be deformed by the heat generated during the light energy irradiation. Therefore, these should be noted.
  • the amount of light is preferably from 300 to 8000 mJ at a measurement wavelength of 300 to 390 nm from the viewpoint of the refractive index of the metal oxide layer 22 and damage to the transparent polymer film 12. / Cm 2 , more preferably in the range of 500 to 5000 mJ / cm 2 .
  • specific examples of the ultraviolet irradiator to be used include a mercury lamp, a xenon lamp, a deuterium lamp, an excimer lamp, a metal halide lamp, and the like. These may be used alone or in combination of two or more.
  • the film thickness of the metal oxide layer 22 can be adjusted in consideration of solar shading, visibility, reflection color, and the like.
  • the lower limit of the film thickness of the metal oxide layer 22 is preferably 10 nm or more, more preferably, from the viewpoints of easily suppressing red and yellow coloring of the reflected color, and easily obtaining high transparency. It is good that it is 15 nm or more, more preferably 20 nm or more.
  • the upper limit value of the film thickness of the metal oxide layer 22 is preferably 90 nm or less, more preferably, from the viewpoint of easily suppressing the green color of the reflected color and obtaining high transparency. 85 nm or less, more preferably 80 nm or less.
  • Examples of the metal of the metal layer 24 include metals such as silver, gold, platinum, copper, aluminum, chromium, titanium, zinc, tin, nickel, cobalt, niobium, tantalum, tungsten, zirconium, lead, palladium, and indium. And alloys thereof. These may be contained alone or in combination of two or more.
  • the metal of the metal layer 24 silver or a silver alloy is preferable from the viewpoint of being excellent in visible light transmittance, heat ray reflectivity, conductivity, and the like when laminated. More preferably, from the viewpoint of improving durability against environment such as heat, light, and water vapor, the main component is silver, and at least one metal element such as copper, bismuth, gold, palladium, platinum, and titanium is included. It should be a silver alloy. More preferably, a silver alloy containing copper (Ag—Cu alloy), a silver alloy containing bismuth (Ag—Bi alloy), a silver alloy containing titanium (Ag—Ti alloy), or the like is preferable. This is because there are advantages such as a large silver diffusion suppression effect and cost advantage.
  • the other elements include elements that can be dissolved in Ag such as Mg, Pd, Pt, Au, Zn, Al, Ga, In, Sn, Sb, Li, Cd, Hg, and As.
  • Ag-Cu alloys such as Be, Ru, Rh, Os, Ir, Bi, Ge, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Co, Ni, Si, Tl, Pb, etc.
  • Element which can be precipitated as a single phase in Y La, Ce, Nd, Sm, Gd, Tb, Dy, Ti, Zr, Hf, Na, Ca, Sr, Ba, Sc, Pr, Eu, Ho, Er, Tm
  • elements capable of precipitating intermetallic compounds with Ag such as Yb, Lu, S, Se, and Te. These may be contained alone or in combination of two or more.
  • the lower limit of the copper content is preferably 1 atomic% or more, more preferably 2 atomic% or more, and even more preferably 3 atomic% or more, from the viewpoint of obtaining the effect of addition. Good to be.
  • the upper limit of the copper content is preferably 20 atomic% or less, more preferably 10 atomic%, from the viewpoint of manufacturability such as easy to ensure high transparency and easy production of a sputtering target. Hereinafter, it is more preferable that it is 5 atomic% or less.
  • the other elements include elements that can be dissolved in Ag such as Mg, Pd, Pt, Au, Zn, Al, Ga, In, Sn, Sb, Li, Cd, Hg, and As. ; Be, Ru, Rh, Os, Ir, Cu, Ge, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Co, Ni, Si, Tl, Pb, etc.
  • the lower limit of the bismuth content is preferably 0.01 atomic% or more, more preferably 0.05 atomic% or more, and still more preferably, from the viewpoint of obtaining the effect of addition. It may be 0.1 atomic% or more.
  • the upper limit of the bismuth content is preferably 5 atomic% or less, more preferably 2 atomic% or less, and still more preferably 1 atomic% from the viewpoint of manufacturability such as easy production of a sputtering target. It is good to be below.
  • the other elements include elements that can be dissolved in Ag such as Mg, Pd, Pt, Au, Zn, Al, Ga, In, Sn, Sb, Li, Cd, Hg, and As. ; Be-Ru, Rh, Os, Ir, Cu, Ge, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Co, Ni, Si, Tl, Pb, Bi, etc., Ag-Ti system Elements that can be precipitated as a single phase in the alloy; Y, La, Ce, Nd, Sm, Gd, Tb, Dy, Zr, Hf, Na, Ca, Sr, Ba, Sc, Pr, Eu, Ho, Er, Tm Examples include elements capable of precipitating intermetallic compounds with Ag such as Yb, Lu, S, Se, and Te. These may be contained alone or in combination of two or more.
  • the lower limit value of the titanium content is preferably 0.01 atomic% or more, more preferably 0.05 atomic% or more, and still more preferably, from the viewpoint of obtaining an addition effect. It may be 0.1 atomic% or more.
  • the upper limit of the content of titanium is preferably 2 atomic% or less, more preferably 1.75 atomic% or less, and still more preferably, from the viewpoint that a complete solid solution is easily obtained when it is formed into a film. Is preferably 1.5 atomic% or less.
  • the ratio of subelements such as copper, bismuth and titanium can be measured using ICP analysis. Further, the metal (including alloy) constituting the metal layer 24 may be partially oxidized.
  • the lower limit of the film thickness of the metal layer 24 is preferably 3 nm or more, more preferably 5 nm or more, and even more preferably 7 nm or more from the viewpoints of stability, heat ray reflectivity, and the like.
  • the upper limit of the film thickness of the metal layer 24 is preferably 30 nm or less, more preferably 20 nm or less, and even more preferably 15 nm or less, from the viewpoints of transparency of visible light, economy, and the like.
  • a method of forming the metal layer 24 specifically, for example, a physical vapor deposition method (PVD) such as a vacuum deposition method, a sputtering method, an ion plating method, an MBE method, a laser ablation, a thermal method, etc.
  • PVD physical vapor deposition method
  • a vapor phase method such as a chemical vapor deposition method (CVD) such as a CVD method and a plasma CVD method.
  • CVD chemical vapor deposition method
  • the metal layer 24 may be formed using any one of these methods, or may be formed using two or more methods.
  • sputtering methods such as DC magnetron sputtering method and RF magnetron sputtering method can be preferably used from the viewpoint of obtaining a dense film quality and relatively easy film thickness control.
  • the metal layer 24 may be oxidized within a range that does not impair the function of the metal layer 24 by receiving post-oxidation or the like to be described later.
  • the barrier layer associated with the metal layer 24 mainly has a barrier function that suppresses the diffusion of elements constituting the metal layer 24 into the metal oxide layer 22. Further, by interposing between the metal oxide layer 22 and the metal layer 24, it is possible to contribute to improvement in adhesion between the two.
  • the barrier layer may have discontinuous portions such as floating islands as long as the diffusion can be suppressed.
  • the metal oxide constituting the barrier layer include, for example, titanium oxide, zinc oxide, indium oxide, tin oxide, indium and tin oxide, and magnesium oxide. And aluminum oxide, zirconium oxide, niobium oxide, cerium oxide, and the like. These may be contained alone or in combination of two or more. Further, these metal oxides may be double oxides in which two or more metal oxides are combined. Note that the barrier layer may contain inevitable impurities in addition to the metal oxide.
  • barrier layer it is mainly comprised from the oxide of the metal contained in the metal oxide layer 22 from a viewpoint of being excellent in the diffusion inhibitory effect of the metal which comprises the metal layer 24, and being excellent in adhesiveness. Good to be.
  • the barrier layer is a titanium oxide layer mainly composed of an oxide of Ti that is a metal contained in the TiO 2 layer. Good to be.
  • the barrier layer when the barrier layer is a titanium oxide layer, the barrier layer may be a thin film layer formed as titanium oxide from the beginning, or a thin film layer formed by post-oxidation of a metal Ti layer, Alternatively, it may be a thin film layer formed by post-oxidizing a partially oxidized titanium oxide layer.
  • the barrier layer is mainly composed of a metal oxide in the same manner as the metal oxide layer 22, but is set to be thinner than the metal oxide layer 22. This is because the diffusion of the metal constituting the metal layer 24 occurs at the atomic level, so that it is not necessary to increase the film thickness to a level necessary to ensure a sufficient refractive index. Moreover, by forming it thinly, the film-forming cost is reduced correspondingly, and it can contribute to the reduction of the manufacturing cost of the transparent laminated film 10.
  • the lower limit value of the film thickness of the barrier layer is preferably 1 nm or more, more preferably 1.5 nm or more, and further preferably 2 nm or more from the viewpoint of easily ensuring barrier properties.
  • the upper limit value of the thickness of the barrier layer is preferably 15 nm or less, more preferably 10 nm or less, and still more preferably 8 nm or less, from the viewpoint of economy and the like.
  • the lower limit value of the atomic molar ratio Ti / O of titanium to oxygen in the titanium oxide is 1.0 / 4.0 or more from the viewpoint of barrier properties and the like.
  • the upper limit of the atomic molar ratio Ti / O of titanium to oxygen in the titanium oxide is preferably 1.0 / 0.5 or less, more preferably 1.0 / 0.7 or less, more preferably 1.0 / 1.0 or less, even more preferably 1.0 / 1.2 or less, most preferably 1 0.0 / 1.5 or less is preferable.
  • the Ti / O ratio can be calculated from the composition of the layer.
  • energy dispersive X-ray fluorescence analysis EDX
  • EDX energy dispersive X-ray fluorescence analysis
  • a test piece having a thickness of 100 nm or less in the cross-sectional direction of the laminated structure including the layer to be analyzed is prepared using an ultrathin section method (microtome) or the like.
  • the laminated structure and the position of the layer are confirmed by a transmission electron microscope (TEM) from the cross-sectional direction.
  • TEM transmission electron microscope
  • an electron beam is emitted from the electron gun of the EDX apparatus and is incident on the vicinity of the center of the film thickness of the layer to be analyzed.
  • Electrons incident from the surface of the test specimen enter to a certain depth and generate various electron beams and X-rays. By detecting and analyzing characteristic X-rays at this time, the constituent elements of the layer can be analyzed.
  • a vapor phase method can be suitably used from the viewpoint that a dense film can be formed and a thin film layer of about several nm to several tens of nm can be formed with a uniform film thickness.
  • the vapor phase method include physical vapor deposition methods (PVD) such as vacuum deposition, sputtering, ion plating, MBE, and laser ablation, thermal CVD, and plasma CVD. Examples thereof include chemical vapor deposition (CVD) and the like.
  • PVD physical vapor deposition methods
  • CVD chemical vapor deposition
  • a sputtering method such as a DC magnetron sputtering method or an RF magnetron sputtering method is preferable from the viewpoint of excellent adhesion at the film interface as compared with a vacuum deposition method and the like and easy control of the film thickness. Can be used.
  • Each barrier layer that can be included in the laminated structure may be formed using any one of these vapor phase methods, or formed using two or more methods. May be.
  • the barrier layer may be formed as the metal oxide layer 22 from the beginning using the above-described vapor phase method, or the metal layer 24 or the partially oxidized metal oxide layer 22 may be temporarily formed. It is also possible to form the film by oxidizing it after the film has been formed.
  • the partially oxidized metal oxide layer 22 refers to a metal oxide layer 22 that has room for further oxidation.
  • a gas containing oxygen as a reactive gas is mixed with an inert gas such as argon or neon as a sputtering gas, and the metal and oxygen are mixed.
  • a thin film may be formed while reacting with (reactive sputtering method).
  • the oxygen concentration in the atmosphere is the film thickness range described above. The optimum ratio may be appropriately selected in consideration of the above.
  • the metal layer 24 or the partially oxidized metal oxide layer 22 is formed and then post-oxidized later, specifically, the above-described laminated structure is formed on the transparent polymer film 12. Thereafter, the metal layer 24 or the partially oxidized metal oxide layer 22 in the laminated structure may be post-oxidized.
  • a sputtering method or the like may be used for forming the metal layer 24, and the reactive sputtering method or the like described above may be used for forming the partially oxidized metal oxide layer 22.
  • examples of the post-oxidation method include heat treatment, pressure treatment, chemical treatment, and natural oxidation. Of these post-oxidation techniques, heat treatment is preferable from the viewpoint of enabling post-oxidation relatively easily and reliably.
  • examples of the heat treatment include a method of causing the transparent polymer film 12 having the above-described laminated structure to exist in a heating atmosphere such as a heating furnace, a method of immersing in warm water, a method of microwave heating, A method of energizing and heating the metal layer 24, the partially oxidized metal oxide layer 22, and the like can be exemplified. These may be performed in combination of one or two or more.
  • the heating conditions at the time of the heat treatment are, for example, preferably 30 ° C. to 60 ° C., more preferably 32 ° C. to 57 ° C., and still more preferably 35 ° C. to 55 ° C.
  • the heating time is preferably selected from 5 days or longer, more preferably 10 days or longer, and even more preferably 15 days or longer. This is because the post-oxidation effect, the thermal deformation / fusion suppression of the transparent polymer film 12 and the like are good within the above heating condition range.
  • the heating atmosphere at the time of the heat treatment is preferably an atmosphere containing oxygen or moisture, such as the air, a high oxygen atmosphere, or a high humidity atmosphere. Particularly preferably, it is in the air from the viewpoint of manufacturability and cost reduction.
  • the moisture and oxygen contained in the metal oxide layer 22 are consumed during the post-oxidation.
  • the physical layer 22 becomes difficult to chemically react.
  • the metal oxide layer 22 is formed by a sol-gel method, moisture and oxygen contained in the metal oxide layer 22 are consumed at the time of post-oxidation.
  • the starting material (metal alkoxide or the like) by the sol-gel method remaining in the oxide layer 22 and moisture (adsorbed water or the like), oxygen, or the like hardly undergo a sol-gel curing reaction by sunlight. Therefore, it is possible to relieve internal stress caused by volume change such as curing shrinkage, and it is easy to suppress interfacial peeling of the laminated structure, and to improve durability against sunlight.
  • the transparent laminated film 10 is not limited to the configuration of the above embodiment, and may have a configuration in which the easy adhesion layer 14 is not provided in FIG. Moreover, the structure by which the easily bonding layer 14 is provided between the transparent polymer film 12 and the polymer body layer 18 in FIG.1 (b) may be sufficient.
  • the laminated structure portion 16 and the polymer layer 18 may be provided on both surfaces of the transparent polymer film 12, respectively. When the polymer layer 18 is formed on the easy-adhesion layer 14, adhesion to the transparent polymer film 12 is ensured via the easy-adhesion layer 14. There is an advantage that the range of selection of the resin is widened.
  • This coating liquid ⁇ 1> is opposite to the easy adhesive layer of a 50 ⁇ m thick polyethylene terephthalate film (manufactured by Toyobo Co., Ltd., “Cosmo Shine (registered trademark) A4100”) having an easy adhesive layer formed on one side.
  • the polymer layer (thickness 0.5 ⁇ m) made of an acrylic resin was formed by coating on the surface and drying at 100 ° C. for 2 minutes.
  • a three-layer laminated structure composed of metal oxide layer / metal layer / metal oxide layer was formed on the formed polymer layer.
  • the method for forming the three-layer laminated structure is as follows.
  • a TiO 2 layer was formed by a sol-gel method using ultraviolet energy during sol-gel curing (hereinafter sometimes abbreviated as “(sol-gel + UV)”).
  • ⁇ Coating solution for TiO 2 layer As titanium alkoxide, tetra-n-butoxytitanium tetramer (“B4” manufactured by Nippon Soda Co., Ltd.), acetylacetone as an additive that forms an ultraviolet-absorbing chelate, n-butanol and isopropyl alcohol The resulting mixture was mixed for 10 minutes using a stirrer to prepare a TiO 2 layer coating solution. At this time, the composition of tetra-n-butoxy titanium tetramer / acetylacetone / n-butanol / isopropyl alcohol was 6.75 mass% / 3.38 mass% / 59.87 mass% / 30.00 mass%, respectively. did.
  • each thin film constituting the second layer was formed on the formed first layer. That is, a lower metal Ti layer was formed by sputtering on the first TiO 2 layer using a DC magnetron sputtering apparatus. Next, an Ag—Cu alloy layer was formed on the lower metal Ti layer by sputtering. Next, an upper metal Ti layer was formed on this Ag—Cu alloy layer by sputtering. At this time, the film formation conditions of the upper and lower metal Ti layers were as follows: Ti target (purity 4N), vacuum ultimate pressure: 5 ⁇ 10 ⁇ 6 (Torr), inert gas: Ar, gas pressure: 2.5 ⁇ 10 ⁇ 3 (Torr), input power: 1.5 (kW), and film formation time: 1.1 seconds.
  • the film formation conditions of the Ag—Cu alloy thin film are as follows: Ag—Cu alloy target (Cu content: 4 atomic%), vacuum ultimate pressure: 5 ⁇ 10 ⁇ 6 (Torr), inert gas: Ar, gas pressure: 2.5 ⁇ 10 ⁇ 3 (Torr), input power: 1.5 (kW), and film formation time: 1.1 seconds.
  • a TiO 2 layer by (sol gel + UV) was formed as a third layer on the formed second layer.
  • the film forming procedure according to the first layer is performed twice to obtain a predetermined film thickness.
  • the film after the formation of the third layer is heat-treated in a heating furnace at 40 ° C. for 300 hours to thereby form the second layer (metal Ti layer / Ag—Cu alloy layer / metal Ti layer) of metal Ti.
  • the layer was post-oxidized.
  • the transparent laminated film of Example 1 which has a 3 layer laminated structure part was produced by the above.
  • 3 Transparent laminated films of Examples 2 to 4 having a layer laminated structure were produced.
  • the method for forming the seven-layer laminated structure is as follows. The same procedure as in Example 1 was performed until the formation of the third layer. The third layer had a predetermined thickness by performing the film formation procedure according to the first layer three times.
  • Each thin film constituting the fourth layer was formed on the formed third layer.
  • a film forming procedure according to the second layer was performed.
  • the above-mentioned film formation conditions are as follows: Ag—Cu alloy target (Cu content: 4 atom%), vacuum ultimate pressure: 5 ⁇ 10 ⁇ 6 (Torr), inert gas
  • the film thickness was changed by changing: Ar, gas pressure: 2.5 ⁇ 10 ⁇ 3 (Torr), input power: 1.8 (kW), and film formation time: 1.1 seconds.
  • a TiO 2 layer having the same configuration as that of the third layer (sol gel + UV) was formed as a fifth layer on the formed fourth layer.
  • each thin film having the same configuration as the second layer was formed as the sixth layer on the formed fifth layer.
  • a TiO 2 layer by (sol gel + UV) was formed as a seventh layer on the formed sixth layer.
  • a predetermined film thickness is obtained by performing the film formation procedure according to the first layer once.
  • the film after forming the seventh layer is heat-treated in a heating furnace at 40 ° C. for 300 hours, whereby the second, fourth, and sixth layers (metal Ti layer / Ag—Cu alloy layer / metal Ti layer).
  • the metal Ti layer was post-oxidized.
  • a transparent laminated film of Example 5 having a 7-layer laminated structure was produced.
  • Example 8 A transparent laminated film of Example 8 having a 7-layer laminated structure was produced in the same manner as in Example 5 except that the polyethylene terephthalate film having a thickness of 50 ⁇ m was changed to a polyethylene terephthalate film having a thickness of 125 ⁇ m.
  • Comparative Example 2 The 7-layer laminated structure was formed in the same manner as in Example 5 except that the 7-layer laminated structure was formed directly on the easy-adhesive layer of the polyethylene terephthalate film and the polymer layer corresponding to Example 1 was not formed. A transparent laminated film of Comparative Example 2 was prepared.
  • Table 1 shows the detailed layer structure of the transparent laminated films of Examples 1 to 4 and Comparative Example 1 (transparent laminated film having a three-layer laminated structure).
  • Table 2 shows the detailed layer structure of the transparent laminated films of Examples 5 to 8 and Comparative Example 2 (transparent laminated film having a 7-layer laminated structure).
  • unit was measured using the eddy current meter (made by DELCOM company), and the groove width was measured. Furthermore, optical characteristics, radio wave permeability, and appearance were evaluated by the evaluation methods shown below.
  • a 22 ⁇ m thick acrylic adhesive sheet (“N-CLE”, manufactured by Toyo Packaging Co., Ltd.) was attached to the thin film laminated surface of the transparent laminated film, and the adhesive layer of this adhesive sheet was What was affixed on the single side
  • FIG. 3 (e): Example 6 Comparative Example 2
  • the thin film layer forming surface side of the transparent laminated film was attached with water using a window glass. It was confirmed whether a groove part was visually recognized from the position 30 cm away. The appearance was good when the groove was not visually recognized, and the appearance was poor when the groove was visible.
  • the refractive index of the TiO 2 layer was measured by FilmTek 3000 (manufactured by Scientific Computing International). Moreover, content of the organic component contained in the TiO 2 layer was measured by X-ray photoelectron spectroscopy (XPS).
  • EDX analysis was performed on the titanium oxide thin film formed by post-oxidizing the metal Ti layer, and the Ti / O ratio was determined as follows. That is, a transparent laminated film is cut out with a microtome (“Lultrome V2088” manufactured by LKB Co., Ltd.), and a test piece having a thickness in a cross-sectional direction of a laminated structure portion including a titanium oxide layer (barrier layer) to be analyzed is 100 nm or less. Was made. The cross section of the produced test piece was confirmed with a field emission electron microscope (HRTEM) (manufactured by JEOL Ltd., “JEM2001F”).
  • HRTEM field emission electron microscope
  • an electron beam is emitted from the electron gun of this device, and a titanium oxide layer (barrier layer) to be analyzed
  • the elemental component of the titanium oxide layer (barrier layer) was analyzed by making it incident near the center of the film thickness and detecting and analyzing the generated characteristic X-rays.
  • the content of the sub-element Cu in the alloy layer was determined as follows. That is, under each film forming condition, a test piece in which an Ag—Cu alloy layer was separately formed on a glass substrate was prepared, and this test piece was immersed in a 6% HNO 3 solution and eluted with ultrasonic waves for 20 minutes. Then, it measured by the concentration method of ICP analysis method using the obtained sample solution.
  • the film thickness of each layer was measured from the cross-sectional observation of the test piece by the field emission electron microscope (HRTEM) (manufactured by JEOL Ltd., “JEM2001F”). Further, the width of the groove formed in the metal layer was measured from the surface observation of the test piece by the field emission electron microscope (HRTEM) (manufactured by JEOL Ltd., “JEM2001F”).
  • HRTEM field emission electron microscope
  • the polymer softening temperature of the polymer layer is less than 40 ° C.
  • a crack was generated in the laminated structure portion when the first layer of sol-gel was cured, and a groove portion was formed. Since the formed groove was visually recognized, the appearance was poor.
  • the 7-layer laminated structure is formed directly on the easy-adhesion layer without providing a polymer layer.
  • no crack was formed in the laminated structure portion and no groove portion was formed even when the seventh layer of sol-gel was cured. For this reason, the radio wave permeability was inferior.
  • the softening temperature of the polymer in the polymer layer is within a desired range.
  • Examples 1 to 5 and 7 to 8 cracks were formed in the laminated structure portion when the metal oxide layer was formed. The manner in which cracks are formed in the laminated structure is shown in FIGS. 3B to 3D as an example. The groove width was 0.3 to 0.6 ⁇ m.
  • Example 6 no crack was generated in the laminated structure portion and no groove portion was formed even when the seventh layer of sol-gel was cured. This situation is shown in FIG.
  • the surface resistance of the film alone was high (100 ⁇ / ⁇ or more), and it was confirmed that the film alone was excellent in radio wave transmission.
  • Example 6 the surface resistance of the film alone was slightly low (less than 100 ⁇ / ⁇ ). And in all of the Examples, the solar shading was excellent and the appearance was also good.
  • the softening temperature of the polymer in the polymer layer is 70 ° C. or higher, and cracks are formed in the laminated structure for the first time when the seventh layer of sol-gel is cured to form a groove. It was.
  • the softening temperature of the polymer in the polymer layer was less than 60 ° C., and cracks were formed in the laminated structure for the first time when the third layer of sol-gel was cured to form a groove. From these results, it was shown that by adjusting the softening temperature of the polymer in the polymer layer, it is possible to control the timing of generating cracks in the laminated structure.
  • laminated glass was made using each of the produced transparent laminated films, and the obtained laminated glass was evaluated.
  • Comparative Example 1 the appearance of the film alone was poor, the width of the groove was further expanded by vitrification, and the appearance of the laminated glass was also poor.
  • Comparative Example 2 no crack was formed in the laminated structure portion in the film alone, but no crack was formed in the laminated structure portion even by vitrification. For this reason, the laminated glass was inferior in radio wave transmission.
  • Example 1 to 5 and 7 to 8 in which the groove portion was formed in the laminated structure portion by a single film the laminated structure portion (metal layer) was divided due to the laminated glass.
  • An example of the progress of the segmentation of the laminated structure portion (metal layer) is shown in FIGS. 4B to 4D.
  • Example 6 in which the groove portion was not formed in the laminated structure portion with a single film cracks (groove portions) were formed in the laminated structure portion (metal layer) due to the laminated glass. This is shown in FIG.
  • Example 6 the surface resistance value of the film alone was less than 100 ⁇ / ⁇ , but the surface resistance value greatly increased as a result of the laminated glass, and the laminated glass was 100 ⁇ / ⁇ or more, and was excellent in radio wave transmission. Was confirmed. In all of the examples, the solar shading was excellent and the appearance was also good.
  • Example 6 since the groove portion was not formed in the laminated structure portion in the film alone, no dent was formed in the vicinity of the groove portion formed at the time of forming the laminated glass, and the occurrence of irregular reflection of light near the groove portion was suppressed. It can be seen that it has the best appearance as a laminated glass.
  • Examples 1 to 5 and 7 to 8 since a groove was formed in the laminated structure portion of the film alone, it was found that a recess was formed in the vicinity of the groove portion when the laminated glass was formed. However, the smaller the width of the groove is, the smaller the recess is formed, and the less the influence on the appearance is.
  • the width of the groove was 0.3 to 0.6 ⁇ m, the influence on the appearance was small, and the appearance was good.
  • the groove widths of 0.6 ⁇ m or less those having a groove width of 0.3 ⁇ m or less were particularly good in appearance.

Landscapes

  • Laminated Bodies (AREA)

Abstract

L'invention porte sur un procédé pour produire une structure stratifiée à isolation thermique, qui présente à la fois une excellente performance de protection solaire et une excellente capacité de transmission d'onde radioélectrique. Ce procédé comprend : une étape de fabrication de film servant à fabriquer un film stratifié transparent en formant une couche polymère (18) sur la surface d'un film polymère transparent (12), puis en formant une partie de structure stratifiée qui comprend une couche d'oxyde métallique et une couche métallique sur la surface de la couche polymère (18) ; et une étape de stratification servant à stratifier, par chauffage et pression, deux substrats transparents (28, 28), avec le film stratifié transparent placé entre eux. Dans l'étape de fabrication de film, la couche d'oxyde métallique de la partie de structure stratifiée est formée par le durcissement sol-gel d'un précurseur d'oxyde métallique, tandis qu'un polymère qui a un point de ramollissement inférieur à la température de chauffage pendant l'étape de stratification est utilisé comme polymère constituant la couche polymère (18). Dans la stratification des deux substrats transparents (28, 28), on forme une rainure de façon à diviser la couche métallique de la partie de structure stratifiée.
PCT/JP2013/072181 2012-09-25 2013-08-20 Procédé pour produire une structure stratifiée à isolation thermique, structure stratifiée à isolation thermique et film stratifié transparent WO2014050367A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2012211126 2012-09-25
JP2012-211126 2012-09-25

Publications (1)

Publication Number Publication Date
WO2014050367A1 true WO2014050367A1 (fr) 2014-04-03

Family

ID=50387777

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2013/072181 WO2014050367A1 (fr) 2012-09-25 2013-08-20 Procédé pour produire une structure stratifiée à isolation thermique, structure stratifiée à isolation thermique et film stratifié transparent

Country Status (1)

Country Link
WO (1) WO2014050367A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014126135A1 (fr) * 2013-02-13 2014-08-21 東洋紡株式会社 Stratifié transparent émettant des ondes radio et reflétant des rayons calorifiques
JP2015205795A (ja) * 2014-04-21 2015-11-19 王子ホールディングス株式会社 熱線遮蔽合わせガラス

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003005659A (ja) * 2001-04-17 2003-01-08 Tokai Rubber Ind Ltd プラズマディスプレイ用透明電磁波シールドフィルムおよびそれを用いたプラズマディスプレイパネル用前面フィルターならびにプラズマディスプレイ
JP2006327177A (ja) * 2005-04-26 2006-12-07 Tokai Rubber Ind Ltd 透明積層フィルム、透明積層体およびプラズマディスプレイ
JP2010149347A (ja) * 2008-12-25 2010-07-08 Tokai Rubber Ind Ltd 透明積層フィルム
WO2011024756A1 (fr) * 2009-08-26 2011-03-03 東海ゴム工業株式会社 Film stratifié transparent et procédé pour la production de celui-ci
WO2012111367A1 (fr) * 2011-02-14 2012-08-23 東海ゴム工業株式会社 Procédé pour la production d'une structure de feuille calorifuge, structure de feuille calorifuge et film stratifié transparent pour structure de feuille

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003005659A (ja) * 2001-04-17 2003-01-08 Tokai Rubber Ind Ltd プラズマディスプレイ用透明電磁波シールドフィルムおよびそれを用いたプラズマディスプレイパネル用前面フィルターならびにプラズマディスプレイ
JP2006327177A (ja) * 2005-04-26 2006-12-07 Tokai Rubber Ind Ltd 透明積層フィルム、透明積層体およびプラズマディスプレイ
JP2010149347A (ja) * 2008-12-25 2010-07-08 Tokai Rubber Ind Ltd 透明積層フィルム
WO2011024756A1 (fr) * 2009-08-26 2011-03-03 東海ゴム工業株式会社 Film stratifié transparent et procédé pour la production de celui-ci
WO2012111367A1 (fr) * 2011-02-14 2012-08-23 東海ゴム工業株式会社 Procédé pour la production d'une structure de feuille calorifuge, structure de feuille calorifuge et film stratifié transparent pour structure de feuille

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014126135A1 (fr) * 2013-02-13 2014-08-21 東洋紡株式会社 Stratifié transparent émettant des ondes radio et reflétant des rayons calorifiques
JP2015205795A (ja) * 2014-04-21 2015-11-19 王子ホールディングス株式会社 熱線遮蔽合わせガラス

Similar Documents

Publication Publication Date Title
JP5197850B2 (ja) 透明積層フィルムおよびその製造方法
JP5662824B2 (ja) 遮熱性合わせ構造体の製造方法、遮熱性合わせ構造体、合わせ構造体用透明積層フィルム
JP5363508B2 (ja) 透明積層フィルムおよびその製造方法
WO2014049891A1 (fr) Film stratifié transparent
JP2012207445A (ja) 透明ロールスクリーン
JP5806836B2 (ja) 透明積層フィルムおよびこれを用いた透明積層体ならびに透明積層フィルムの使用方法
JP2014231199A (ja) 透明積層フィルム
JP2013209230A (ja) 遮熱性合わせ構造体、遮熱性合わせ構造体の製造方法、合わせ構造体用透明積層フィルム
JP2012135888A (ja) 透明積層フィルムおよび透明積層フィルムの使用方法
WO2014050237A1 (fr) Film stratifié transparent et procédé de fabrication de film stratifié transparent
JP4982149B2 (ja) 透明積層フィルムおよび透明積層体
WO2014050367A1 (fr) Procédé pour produire une structure stratifiée à isolation thermique, structure stratifiée à isolation thermique et film stratifié transparent
JP5926092B2 (ja) 透明積層フィルム
JP2009241581A (ja) 透明積層フィルム
JP2011133721A (ja) 透明積層フィルム
JP5143717B2 (ja) 透明積層フィルム
JP5314536B2 (ja) 透明積層フィルム
JP2012207444A (ja) 網入り窓ガラスの日射調整方法
JP2012161925A (ja) 透明積層フィルムおよび複層ガラス
JP5421505B1 (ja) 透明積層フィルム
JP6134223B2 (ja) 光透過性積層体
WO2015029706A1 (fr) Corps à couches transmettant la lumière

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13841890

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 13841890

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: JP