+

WO2018181446A1 - Film de protection thermique et d'isolation thermique - Google Patents

Film de protection thermique et d'isolation thermique Download PDF

Info

Publication number
WO2018181446A1
WO2018181446A1 PCT/JP2018/012684 JP2018012684W WO2018181446A1 WO 2018181446 A1 WO2018181446 A1 WO 2018181446A1 JP 2018012684 W JP2018012684 W JP 2018012684W WO 2018181446 A1 WO2018181446 A1 WO 2018181446A1
Authority
WO
WIPO (PCT)
Prior art keywords
layer
heat
film
insulating
insulating film
Prior art date
Application number
PCT/JP2018/012684
Other languages
English (en)
Japanese (ja)
Inventor
聖彦 渡邊
雄太 島▲崎▼
大貴 加藤
友広 紺谷
Original Assignee
日東電工株式会社
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
Priority claimed from JP2018059376A external-priority patent/JP2018171914A/ja
Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Publication of WO2018181446A1 publication Critical patent/WO2018181446A1/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
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G02B1/113—Anti-reflection coatings using inorganic layer materials only
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/26—Reflecting filters

Definitions

  • the present invention relates to a heat insulating and heat insulating film.
  • the heat insulation and heat insulation film is a film having both a heat insulation function and a heat insulation function.
  • the infra-red reflection function allows the inflow of solar heat (near infrared) from the outside to the room and the heat from the room to the outside (far). Infrared) can be suppressed, and indoor comfort and energy saving effect can be improved throughout the year.
  • a heat insulating heat insulating film including a base material layer and an infrared reflecting layer has been proposed in recent years (Patent Documents 1 and 2).
  • the infrared reflecting layer has, for example, a configuration including a metal oxide layer on both sides of the metal layer, and can achieve both improved heat shielding by reflection of near infrared rays and improved heat insulation by reflection of far infrared rays.
  • thermal insulation and thermal insulation films are required to have high crack resistance that does not cause cracks when bent during handling or storage, and high adhesion that does not cause separation between layers. It is done.
  • An object of the present invention is to provide a heat insulating and heat insulating film excellent in crack resistance and adhesion.
  • the heat insulating and heat insulating film of the present invention is A heat insulating and heat insulating film including a base material layer and an infrared reflective layer, An antireflection layer is provided between the base material layer and the infrared reflective layer,
  • the antireflection layer comprises lead telluride (PbTe), nickel (Ni), rhodium (Rh), silicon mononitride (SiN), platinum (Pt), zinc monosulfide (ZnS), tantalum (Ta), titanium (Ti ), Silicon carbide (SiC), zinc selenide (ZnSe), iron (Fe), antimony trisulfide (Sb2S3), chromium (Cr), tungsten (W), molybdenum (Mo), germanium (Ge), silicon ( At least one selected from Si).
  • the infrared reflection layer and the antireflection layer are directly laminated.
  • the antireflection layer has a thickness of 30 nm or less.
  • the thermal insulation heat insulation film of this invention contains a base material layer and an infrared reflective layer, and is equipped with an antireflection layer between this base material layer and this infrared reflective layer.
  • FIG. 1 is a schematic cross-sectional view showing one embodiment of the heat-shielding and heat-insulating film of the present invention.
  • a heat insulating and heat insulating film 100 includes a base material layer 10, an antireflection layer 50, and an infrared reflection layer 20.
  • the heat-insulating and heat-insulating film of the present invention is provided on the side of the base material layer opposite to the infrared reflective layer, between the base material layer and the antireflection layer, between the antireflection layer and the infrared reflective layer, and antireflective layer of the infrared reflective layer.
  • Each of the opposite sides may be provided with any suitable other layers as required.
  • Such other layers may be one layer or two or more layers.
  • such other layers may be only 1 type, and may be 2 or more types.
  • FIG. 2 is a schematic cross-sectional view showing one embodiment of the heat-shielding and heat-insulating film of the present invention.
  • the heat insulating and heat insulating film 100 includes a base material layer 10, an undercoat layer 60, an antireflection layer 50, an infrared reflective layer 20, a protective topcoat layer 40, and a protective film 70.
  • the infrared reflective layer 20 is composed of three layers, a first metal oxide layer 22a, a metal layer 21, and a second metal oxide layer 22b.
  • the heat-insulating and heat-insulating film of the present invention may include an adhesive layer on the side of the base material layer opposite to the infrared reflective layer. Furthermore, a separator film may be provided on the surface of such an adhesive layer.
  • the heat insulating and heat insulating film of the present invention is preferably a transparent film.
  • the visible light transmittance of the heat-insulating and heat-insulating film of the present invention is preferably 30% to 85%, more preferably 45% to 80%, still more preferably 55% to 80%, and particularly preferably 55. % To 75%.
  • the visible light transmittance is measured according to JIS-A5759-2008 (film for architectural window glass).
  • the base material layer is preferably a transparent film, more preferably a flexible transparent film.
  • the visible light transmittance of the base material layer is preferably 80% or more, more preferably 85% or more, still more preferably 88% or more, and particularly preferably 90% or more.
  • the visible light transmittance is measured according to JIS-A5759-2008 (film for architectural window glass).
  • the thickness of the base material layer is preferably 5 ⁇ m to 500 ⁇ m, more preferably 10 ⁇ m to 300 ⁇ m, still more preferably 20 ⁇ m to 200 ⁇ m, and particularly preferably 30 ⁇ m to 100 ⁇ m.
  • Examples of the material constituting the base material layer include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyether ether ketone (PEEK), polycarbonate (PC), and the like from the viewpoint of excellent heat resistance.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • PEEK polyether ether ketone
  • PC polycarbonate
  • PET Polyethylene terephthalate
  • An undercoat layer may be provided on the surface of the base material layer on the side of the infrared reflecting layer.
  • the thickness of the undercoat layer is preferably 0.01 ⁇ m to 5 ⁇ m, more preferably 0.2 ⁇ m to 5 ⁇ m, still more preferably 0.2 ⁇ m to 3 ⁇ m, and particularly preferably 0.5 ⁇ m to 3 ⁇ m. Most preferably, it is 1 ⁇ m to 2 ⁇ m. If the thickness of the undercoat layer is within the above range, the mechanical strength of the heat-insulating and heat-insulating film of the present invention can be increased, and the scratch resistance of the heat-insulating and heat-insulating film of the present invention can be further improved.
  • the undercoat layer is preferably a cured film of a curable resin, and can be formed by, for example, a method in which a suitable cured film of an ultraviolet curable resin is provided on the base material layer.
  • curable resins include acrylic ultraviolet curable resins and silicone ultraviolet curable resins.
  • Surface modification treatment such as treatment by the above may be performed.
  • the heat insulation heat insulation film of this invention is equipped with a specific antireflection layer between a base material layer and an infrared reflective layer.
  • a specific antireflection layer By providing such a specific antireflection layer, the heat-insulating and heat-insulating film of the present invention is excellent in crack resistance and adhesion.
  • the antireflection layer is preferably laminated directly with the infrared reflection layer.
  • the heat-insulating and heat-insulating film of the present invention is more excellent in crack resistance and adhesion.
  • the antireflection layer is preferably laminated directly with a base material layer or an undercoat layer provided on the base material layer.
  • the heat-insulating and heat-insulating film of the present invention is more excellent in crack resistance and adhesion.
  • the thermal insulation heat insulation film of the present invention is superior in crack resistance and adhesion to the undercoat layer.
  • the thickness of the antireflection layer is preferably 30 nm or less, more preferably 1 nm to 25 nm, still more preferably 1 nm to 20 nm, still more preferably 1 nm to 15 nm, and particularly preferably 1 nm to 10 nm. Most preferably, it is 1 nm to 8 nm. If the thickness of the antireflection layer is within this range, the heat-insulating and heat-insulating film of the present invention is more excellent in crack resistance and adhesion.
  • the antireflection layer comprises lead telluride (PbTe), nickel (Ni), rhodium (Rh), silicon mononitride (SiN), platinum (Pt), zinc monosulfide (ZnS), tantalum (Ta), titanium (Ti) , Silicon carbide (SiC), zinc selenide (ZnSe), iron (Fe), antimony trisulfide (Sb2S3), chromium (Cr), tungsten (W), molybdenum (Mo), germanium (Ge), silicon (Si) ) At least one selected from.
  • the heat-insulating and heat-insulating film of the present invention is excellent in crack resistance and adhesion.
  • lead telluride PbTe
  • nickel Ni
  • rhodium Rh
  • silicon mononitride SiN
  • platinum Pt
  • zinc monosulfide ZnS
  • tantalum Ti
  • titanium Ti
  • Silicon carbide SiC
  • zinc selenide ZnSe
  • iron Fe
  • antimony trisulfide Sb2S3
  • chromium Cr
  • tungsten W
  • Mo molybdenum
  • Si The content ratio of at least one selected from Si) is preferably 50% by weight to 100% by weight, more preferably 70% by weight to 100% by weight, from the viewpoint that the effects of the present invention can be more manifested. More preferably, it is 90% to 100% by weight, particularly preferably 95% to 100% by weight, and most preferably substantially 100% by weight.
  • the antireflection layer is preferably at least one selected from zinc monosulfide (ZnS), silicon monocarbide (SiC), and silicon (Si) from the viewpoint that the effects of the present invention can be further exhibited.
  • any appropriate method can be adopted as a method for forming the antireflection layer.
  • a film forming method include a film forming method by a dry process such as a sputtering method, a vacuum evaporation method, a CVD method, and an electron beam evaporation method.
  • a film forming method of the antireflection layer a film forming method by a direct current sputtering method is preferable.
  • Infrared reflective layer any appropriate layer can be adopted as long as it is a layer that can achieve both a heat shield improvement by reflection of near infrared rays and a heat insulation improvement by reflection of far infrared rays.
  • the infrared reflective layer includes a first metal oxide layer, a metal layer, and a second metal oxide layer in this order, and the first metal oxide layer and the second metal oxide layer are directly laminated on the metal layer. Being done.
  • the infrared reflecting layer is preferably composed of three layers, a first metal oxide layer, a metal layer, and a second metal oxide layer, and the first metal oxide layer, the metal layer, and the second metal oxide layer. The material layers are provided in this order.
  • One embodiment of such an infrared reflecting layer can use, for example, embodiments described in JP-A-2016-93892 and JP-A-2016-94012.
  • the metal layer has a central role of infrared reflection.
  • the metal layer is preferably a silver alloy layer mainly composed of silver or a gold alloy layer mainly composed of gold. Since silver has a high free electron density, it is possible to realize a high reflectance of near infrared rays and far infrared rays. Therefore, even when the number of layers constituting the infrared reflection layer is small, it is possible to achieve both improvement in heat shielding by reflection of near infrared rays and improvement of heat insulation by reflection of far infrared rays.
  • the silver content in the metal layer is preferably 85% by weight to 99.9% by weight, more preferably 90% by weight to 99.8%. % By weight, more preferably 95% by weight to 99.7% by weight, and particularly preferably 97% by weight to 99.6% by weight.
  • the metal layer is preferably a silver alloy layer containing a metal other than silver for the purpose of enhancing durability. Specifically, as described above, the silver content in the metal layer is 99. It is preferable that it is 9 weight% or less.
  • the metal layer When the metal layer is a silver alloy layer containing silver as a main component, the metal layer preferably contains a metal other than silver for the purpose of enhancing durability as described above.
  • the content of the metal other than silver in the metal layer is preferably 0.1% by weight to 15% by weight, more preferably 0.2% by weight to 10% by weight, and further preferably 0.3% by weight. It is ⁇ 5% by weight, particularly preferably 0.4% by weight to 3% by weight.
  • metals other than silver include palladium (Pd), gold (Au), copper (Cu), bismuth (Bi), germanium (Ge), gallium (Ga), and the like, which can impart high durability. From the above, palladium (Pd) is preferable.
  • the metal oxide layer controls the amount of visible light reflection at the interface with the metal layer to achieve both high visible light transmittance and high infrared reflectance. It is provided for the purpose.
  • the metal oxide layer can also function as a protective layer for preventing deterioration of the metal layer. From the viewpoint of enhancing the wavelength selectivity of reflection and transmission in the infrared reflection layer, the refractive index of the metal oxide layer with respect to visible light is preferably 1.5 or more, more preferably 1.6 or more, and still more preferably. 1.7 or more.
  • the metal oxide layers are preferably oxides of metals such as Ti, Zr, Hf, Nb, Zn, Al, Ga, In, Tl, Sn, Alternatively, a composite oxide of these metals is included. More preferably, the metal oxide layer includes a composite metal oxide containing zinc oxide. The metal oxide layer is preferably amorphous. When the metal oxide layer is an amorphous layer containing zinc oxide, the durability of the metal oxide layer itself is enhanced and the function as a protective layer for the metal layer is increased, so that the deterioration of the metal layer is suppressed. Can be done.
  • the metal oxide layer is particularly preferably a composite metal oxide containing zinc oxide.
  • the content of zinc oxide in the metal oxide layer is preferably 3 weights with respect to a total of 100 parts by weight of the metal oxide. Part or more, more preferably 5 parts by weight or more, and still more preferably 7 parts by weight or more. If the content ratio of zinc oxide is within the above range, the metal oxide layer tends to be an amorphous layer, and the durability tends to be improved. On the other hand, if the content ratio of zinc oxide is excessively large, the durability may be reduced, or the visible light transmittance may be reduced. Therefore, the content ratio of zinc oxide in the metal oxide layer is preferably 60 parts by weight or less, more preferably 50 parts by weight or less, and still more preferably 40 parts by weight with respect to the total 100 parts by weight of the metal oxide. Less than parts by weight.
  • indium-zinc composite oxide (IZO) and zinc-tin composite oxide (ZTO) are used from the viewpoint of satisfying all visible light transmittance, refractive index, and durability.
  • Indium-tin-zinc composite oxide (ITZO) is preferable.
  • These composite oxides may further contain metals such as Al and Ga, and oxides of these metals.
  • the thickness of the metal layer and the metal oxide layer is such that the infrared reflecting layer transmits the visible light and selectively reflects the near infrared light. It can be set appropriately considering the rate and the like.
  • the thickness of the metal layer is preferably 5 nm to 50 nm, more preferably 5 nm to 25 nm, and still more preferably 10 nm to 18 nm.
  • the thickness of the metal oxide layer (the thickness of each of the first metal oxide layer and the second metal oxide layer) is preferably 1 nm to 80 nm, more preferably 1 nm to 50 nm, and even more preferably 1 nm to 30 nm. It is particularly preferably 2 nm to 10 nm.
  • the thickness of the metal oxide layer (the thickness of each of the first metal oxide layer and the second metal oxide layer) can be made higher than the conventional product level. Can also be made thinner.
  • any appropriate method can be adopted as a method for forming the metal layer and the metal oxide layer.
  • a film forming method include a film forming method by a dry process such as a sputtering method, a vacuum evaporation method, a CVD method, and an electron beam evaporation method.
  • the method for forming the metal layer and the metal oxide layer is preferably a film forming method by a direct current sputtering method. In the case of adopting a film forming method by a direct current sputtering method, it is possible to form these plural layers in one pass by using a winding type sputtering apparatus provided with a plurality of film forming chambers.
  • a target to be DC sputtered may be added with a conductive impurity in order to impart conductivity, and a part thereof may be reducible.
  • the impurities may be mixed in the antireflection layer to be formed, or the composition of the layer may be different from the stoichiometric composition, but there is no problem as long as the effect of the present invention is exhibited.
  • an embodiment of a base material layer described in JP-A-2014-30910 can be used.
  • a topcoat layer may be provided on the surface of the infrared reflective layer opposite to the antireflection layer.
  • the heat-insulating and heat-insulating film of the present invention preferably has a high transparency by having a topcoat layer.
  • the heat-insulating and heat-insulating film of the present invention preferably has a high cotton scratch resistance by having a topcoat layer.
  • the topcoat layer is an oxide or nitride, oxynitride, or non-oxynitride mainly composed of one or more of Group 13 or Group 14 of the periodic table. Contains one or more ingredients.
  • the topcoat layer is preferably an oxide or nitride, oxynitride, non-nitride, or non-oxide mainly composed of one or more members of Group 14, and includes Group 3 or Group 4 of the periodic table. Contains one or more ingredients.
  • the topcoat layer is more preferably at least one selected from oxides or oxynitrides containing Si and Zr, oxides or oxynitrides containing Si and Y, and oxides or oxynitrides containing Si and Ti. including. More preferably, the topcoat layer contains at least one selected from an oxide containing Si and Zr, an oxide containing Si and Y, and an oxide containing Si and Ti.
  • the group 14 element is difficult to be an ion because it has four outermost electrons.
  • Group 13 elements are less likely to become anions due to three outermost electrons. Therefore, it is considered that the hardness of nitride, oxynitride, non-nitride, or non-oxide increases.
  • Addition of elements of Group 3 or Group 4 of the periodic table increases strength, improves corrosion resistance, and heat resistance by densifying the main component elements and densifying the molecular structure.
  • the amount of the Group 3 or Group 4 element added is preferably from 0.01 atm% to 49.9 atm%, more preferably from 0.05 atm% to the point where the effects of the present invention can be more manifested. It is 40.0 atm%, more preferably 0.1 atm% to 40.0 atm%, particularly preferably 0.5 atm% to 35.0 atm%.
  • the addition amount of the Group 3 or Group 4 element is small, the element is not uniformly inserted into the entire matrix, and thus the effects of the present invention may not be exhibited.
  • the amount of the Group 3 or Group 4 element added is too large, the compatibility with the main component is deteriorated and the effects of the present invention may not be exhibited. The compatibility can be confirmed by a phase diagram.
  • the thickness of the top coat layer is preferably 0.5 nm to 30 nm, more preferably 1 nm to 25 nm, still more preferably 2 nm to 20 nm, and particularly preferably 3 nm to 15 nm. If the thickness of the top coat layer is within the above range, the heat-insulating and heat-insulating film of the present invention can exhibit more excellent scratch resistance.
  • any appropriate method can be adopted as a method for forming the topcoat layer.
  • a film forming method include a film forming method by a dry process such as a sputtering method, a vacuum evaporation method, a CVD method, and an electron beam evaporation method.
  • the film formation method for the top coat layer is preferably a film formation method by direct current sputtering.
  • a film forming method by a direct current sputtering method it is possible to form these plural layers in one pass by using a winding type sputtering apparatus provided with a plurality of film forming chambers. For this reason, not only the productivity of the topcoat layer can be greatly improved, but also the productivity of the heat-insulating and heat-insulating film of the present invention can be greatly improved.
  • a protective topcoat layer may be provided on the side of the infrared reflective layer opposite to the antireflection layer.
  • the protective topcoat layer can cause the heat-insulating and heat-insulating film of the present invention to exhibit better scratch resistance.
  • the protective topcoat layer preferably has a high visible light transmittance.
  • the protective top coat layer preferably has little absorption of far infrared rays. If the far-infrared absorption in the protective topcoat layer is small, the far-infrared rays in the room are reflected into the room by the infrared-reflecting layer, so that the heat insulation effect can be enhanced. Examples of a method for reducing the far-infrared absorption amount by the protective topcoat layer include a method using a material having a low far-infrared absorptivity as a material for the protective topcoat layer, a method for reducing the thickness of the protective topcoat layer, and the like.
  • the far-infrared absorption in the protective topcoat layer is large, the far-infrared rays in the room are absorbed by the protective topcoat layer, and are not reflected by the infrared reflective layer, but are radiated to the outside by heat conduction. May decrease.
  • the far-infrared absorption can be kept small even when the thickness of the protective topcoat layer is large, and the protective effect on the infrared reflective layer is enhanced. Can do.
  • a material for the protective topcoat layer having a small far-infrared absorption a compound having a small content such as a C ⁇ C bond, a C ⁇ O bond, a C—O bond or an aromatic ring is preferably used. Examples of such compounds include polyolefins such as polyethylene and polypropylene, alicyclic polymers such as cycloolefin polymers, and rubber polymers.
  • the thickness of the protective topcoat layer is preferably 500 nm or less, more preferably 300 nm or less, still more preferably 200 nm or less, and even more preferably 150 nm or less, from the viewpoint of reducing far-infrared absorption. Particularly preferably, it is 120 nm or less, and most preferably 100 nm or less.
  • the optical film thickness (product of refractive index and physical film thickness) of the protective topcoat layer overlaps the visible light wavelength range, the surface of the heat-insulating and heat-insulating film of the present invention is rainbow-patterned due to multiple reflection interference at the interface. "Iris phenomenon" may appear. Since the refractive index of a general resin is about 1.5, the thickness of the protective topcoat layer is more preferably 200 nm or less from the viewpoint of suppressing the iris phenomenon.
  • the thickness of the protective topcoat layer is preferably 5 nm or more, more preferably 15 nm or more from the viewpoint of imparting mechanical strength and chemical strength to the protective topcoat layer and enhancing the durability of the heat-insulating and heat-insulating film of the present invention. More preferably, it is 30 nm or more, and particularly preferably 50 nm or more.
  • the thickness of the protective topcoat layer is within the above range, the reflectance of visible light is reduced due to multiple reflection interference between the reflected light on the surface side of the protective topcoat layer and the reflected light on the infrared reflective layer side interface. be able to. Therefore, in addition to the reflectance lowering effect due to the light absorption of the infrared reflecting layer, the antireflection effect by the protective topcoat layer can be obtained, and the visibility of the heat insulating and heat insulating film of the present invention can be further enhanced.
  • a material for the protective top coat layer a material having high visible light transmittance and excellent mechanical strength and chemical strength is preferable.
  • actinic ray curable or thermosetting organic resins such as fluorine resin, acrylic resin, urethane resin, ester resin, epoxy resin, silicone resin, silicon oxide, silicon nitride, silicon oxynitride,
  • Inorganic materials such as aluminum oxide, titanium oxide, zirconium oxide, sialon (SiAlON), or organic / inorganic hybrid materials in which an organic component and an inorganic component are chemically bonded are preferably used.
  • a crosslinked structure be introduced.
  • the mechanical strength and chemical strength of the protective topcoat layer are increased, and the protective function for the infrared reflective layer is increased.
  • a crosslinked structure derived from an ester compound having an acidic group and a polymerizable functional group in the same molecule is preferably introduced.
  • ester compounds having an acidic group and a polymerizable functional group in the same molecule include polyvalent acids such as phosphoric acid, sulfuric acid, oxalic acid, succinic acid, phthalic acid, fumaric acid, and maleic acid; And an ester of a compound having a polymerizable functional group such as a group, silanol group or epoxy group and a hydroxyl group in the molecule.
  • the ester compound may be a polyester such as a diester or triester, but it is preferable that at least one acidic group of the polyvalent acid is not esterified.
  • the protective topcoat layer has a crosslinked structure derived from the ester compound
  • the mechanical strength and chemical strength of the protective topcoat layer are increased, and the adhesion between the protective topcoat layer and the infrared reflective layer is increased.
  • the durability of the infrared reflective layer can be increased.
  • an ester compound (phosphate ester compound) of phosphoric acid and an organic acid having a polymerizable functional group is particularly preferable because of excellent adhesion to the infrared reflective layer.
  • the ester compound preferably contains a (meth) acryloyl group as a polymerizable functional group.
  • the ester compound may have a plurality of polymerizable functional groups in the molecule.
  • a phosphoric acid monoester compound or a phosphoric acid diester compound represented by the general formula (1) is preferable.
  • phosphoric acid monoester and phosphoric acid diester can also be used together.
  • X represents a hydrogen atom or a methyl group
  • (Y) represents an —OCO (CH 2 ) 5 — group
  • n is 0 or 1
  • p is 1 or 2.
  • the content ratio of the structure derived from the ester compound in the protective topcoat layer is preferably 1% by weight to 20% by weight, more preferably 1.5% by weight to 17.5% by weight, and still more preferably It is 2 to 15% by weight, particularly preferably 2.5 to 12.5% by weight.
  • the content ratio of the structure derived from the ester compound in the protective topcoat layer can be set to a desired range by adjusting the content ratio of the ester compound when forming the protective topcoat layer.
  • the adhesion between the topcoat layer and the protective topcoat layer can be further enhanced.
  • the improvement in the adhesion between the topcoat layer and the protective topcoat layer is considered to be derived from the fact that the acidic group in the ester compound shows high affinity with the metal oxide in the topcoat layer. Since the hydroxy phosphate group in the compound is excellent in affinity with the metal oxide, it is considered that the adhesion is further improved.
  • any appropriate forming method can be adopted as long as the effects of the present invention are not impaired.
  • a forming method for example, an organic resin or a curable monomer or oligomer of an organic resin and the above ester compound are dissolved in a solvent to prepare a solution, the solution is applied on the infrared reflective layer, and the solvent is dried. After curing, there is a method of curing by irradiating with ultraviolet rays or electron beams or applying thermal energy.
  • coupling agents such as silane coupling agents and titanium coupling agents, leveling agents, ultraviolet absorbers, antioxidants, and heat stability
  • Additives such as agents, lubricants, plasticizers, anti-coloring agents, flame retardants and antistatic agents may be included.
  • content of these additives arbitrary appropriate content can be employ
  • a protective film may be provided on the side of the protective topcoat layer opposite to the infrared reflective layer.
  • the thickness of the protective film is preferably 25 ⁇ m to 100 ⁇ m, more preferably 30 ⁇ m to 75 ⁇ m, still more preferably 35 ⁇ m to 65 ⁇ m, and particularly preferably 35 ⁇ m to 50 ⁇ m.
  • An adhesive layer may be provided on the side of the base material layer opposite to the infrared reflective layer.
  • An adhesive bond layer can be used for bonding with a window glass etc., for example.
  • the adhesive layer preferably has a high visible light transmittance and a small refractive index difference from the base material layer.
  • a material for the adhesive layer any appropriate material can be adopted as long as the effects of the present invention are not impaired.
  • An example of such a material is an acrylic pressure-sensitive adhesive (acrylic pressure-sensitive adhesive).
  • Acrylic pressure-sensitive adhesive (acrylic pressure-sensitive adhesive) has excellent optical transparency, moderate wettability, cohesiveness and adhesion, and excellent weather resistance and heat resistance. It is suitable as.
  • the adhesive layer preferably has a high visible light transmittance and a low ultraviolet transmittance.
  • the adhesive layer By reducing the ultraviolet transmittance of the adhesive layer, it is possible to suppress deterioration of the infrared reflective layer due to ultraviolet rays such as sunlight.
  • the adhesive layer preferably contains an ultraviolet absorber.
  • degradation of the infrared reflective layer resulting from the ultraviolet rays from the outdoors can also be suppressed by using a base material layer containing an ultraviolet absorber.
  • the exposed surface of the adhesive layer is preferably covered with a separator temporarily for the purpose of preventing contamination of the exposed surface until the thermal barrier heat insulating film of the present invention is put to practical use.
  • a separator can prevent contamination due to contact with the outside of the exposed surface of the adhesive layer in a usual handling state.
  • the heat-insulating and heat-insulating film of the present invention can be used for windows such as buildings and vehicles, transparent cases for storing plants, frozen or refrigerated showcases, etc., and has the effect of improving the heating / cooling effect and preventing sudden temperature changes. Can do.
  • FIG. 3 is a cross-sectional view schematically showing an example of a usage pattern of the heat-insulating and heat-insulating film of the present invention.
  • the heat-insulating and heat-insulating film 100 of the present invention is disposed by bonding the base material layer 10 side to the indoor side of a window 1000 of a building or an automobile via any appropriate adhesive layer 80.
  • the heat-insulating and heat-insulating film 100 of the present invention transmits visible light (VIS) from the outside and introduces it into the room, and transmits near-infrared (NIR) from the outside to the infrared reflecting layer. Reflected at 20.
  • VIS visible light
  • NIR near-infrared
  • the near-infrared reflection suppresses the inflow of heat from the outside into the room due to sunlight or the like (a heat shielding effect is exhibited), so that, for example, the cooling efficiency in summer can be increased. Furthermore, since the infrared reflective layer 20 reflects indoor far infrared rays (FIR) radiated from the heating appliance 90, a heat insulating effect is exhibited, and heating efficiency in winter can be enhanced. Moreover, since the thermal insulation heat insulation film 100 of this invention is provided with the infrared rays reflection layer 20, the reflectance of visible light is reduced, When used for a showcase, a show window, etc., visibility of goods etc. falls. Without making it possible, it is possible to impart heat insulation and heat insulation.
  • FIR far infrared rays
  • the heat-insulating and heat-insulating film of the present invention can be used by being fitted into a frame or the like as disclosed in, for example, Japanese Patent Application Laid-Open No. 2013-61370.
  • a material having a low content of functional groups such as C ⁇ C bond, C ⁇ O bond, C—O bond, and aromatic ring (for example, cyclic polyolefin) is used as the base layer.
  • Far infrared rays from the material layer side can be reflected by the infrared reflection layer, and heat insulation can be imparted to both sides of the heat-insulating and heat-insulating film of the present invention.
  • Such a configuration is particularly useful, for example, in a refrigerated showcase or a frozen showcase.
  • test and evaluation method in an Example etc. are as follows. Note that “parts” means “parts by weight” unless otherwise noted, and “%” means “% by weight” unless otherwise noted.
  • the film thickness of the metal oxide layer, metal layer, and antireflection layer is processed by the focused ion beam (FIB) method using a focused ion beam processing observation device (product name “FB-2100”, manufactured by Hitachi, Ltd.).
  • the cross section was obtained by observing with a field emission transmission electron microscope (product name “HF-2000”, manufactured by Hitachi, Ltd.).
  • the film thickness of the protective topcoat layer and undercoat layer is an interference pattern of the reflectance of visible light when light is incident from the measurement target side using an instantaneous multi-photometry system (product name “MCPD3000” manufactured by Otsuka Electronics). From the above, it was calculated.
  • ⁇ Base layer side reflectance is less than 20%.
  • X Base layer side reflectance is 20% or more.
  • ⁇ Mandrel test (2mm ⁇ , 3mm ⁇ )> A bending test (JIS K 5600-5-1) was performed on the heat insulating heat insulating film using a mandrel with the protective top coat layer side of the heat insulating heat insulating film facing outside. The case where cracks did not occur at a diameter of 2 mm or 3 mm was marked as ⁇ , and the case where cracks occurred was marked as x.
  • ⁇ Cross-cut peel test> The adhesion of the heat-insulating and heat-insulating film was evaluated by a cross-cut peel test in accordance with JIS K5600-5-6: 1999. More specifically, the surface of the protective top coat layer of the heat-insulating and heat-insulating film is cut into 10 grids at intervals of 1 mm to create 100 grids, and the cellophane adhesive tape is completely adhered thereon, Evaluation was made according to the following classifications 0 to 5 according to the number of grids from which one end of the tape was momentarily separated and the coating film in the grid was peeled off.
  • the heat insulating and heat insulating films included in the categories 0 to 1 were evaluated as good (indicated by ⁇ ), and the heat insulating and heat insulating films included in the categories 2 to 5 were evaluated as defective (indicated by “ ⁇ ”).
  • Classification 0 The edge of the incision is completely smooth, and the coating film in any grid is not peeled off.
  • Classification 1 There is a small peeling of the coating film at the intersection of the cuts. It is clearly not more than 5% that the cut is affected.
  • Classification 2 The coating film is peeled along the edge of the cut and / or at the intersection. It is clearly over 5% but not more than 15% that is affected by the cut.
  • Classification 3 The coating film is partially or completely peeled along the edge of the cut, and / or various portions of the grid are partially or completely peeled off. It is clearly over 15% that the cut is affected, but not more than 35%.
  • Classification 4 The coating film is largely or partially peeled along the edge of the cut, and / or some grids are partially or completely peeled off. It is clearly not more than 35% that the cut is affected.
  • Category 5 The case where the degree of peeling exceeds Category 4.
  • Example 1 (Formation of undercoat layer on substrate layer) An acrylic UV curable hard coat layer (JSR, Z7540) is 2 ⁇ m thick on one side of a 50 ⁇ m thick polyethylene terephthalate film substrate (trade name “Lumirror U48”, visible light transmittance 93%, manufactured by Toray Industries, Inc.) Formed with. Specifically, the hard coat layer solution is applied with a gravure coater, dried at 80 ° C., then irradiated with ultraviolet light with an integrated light amount of 300 mJ / cm 2 with an ultrahigh pressure mercury lamp, cured, and undercoated onto the base material layer. A coat layer was formed.
  • a 6-nm thick SiC layer and a 10-nm-thick zinc-tin composite oxide (ZTO) are formed on the undercoat layer formed on the base material layer by direct current magnetron sputtering.
  • a 15 nm thick Ag—Pd alloy layer and a 10 nm thick zinc-tin composite oxide (ZTO) layer are sequentially formed, and an antireflection layer and a first metal oxide layer are formed on the undercoat layer.
  • the metal layer and the second metal oxide layer were formed in this order.
  • a silicon carbide target manufactured by Mitsubishi Materials
  • sputtering was performed at a power density of 2.67 W / cm 2 and a process pressure of 0.4 Pa.
  • Sputtering was performed at a process pressure of 0.4 Pa.
  • the amount of gas introduced into the sputtering film forming chamber was adjusted so that Ar: O 2 was 98: 2 (volume ratio).
  • the Ag—Pd alloy layer For the formation of the Ag—Pd alloy layer, a metal target containing silver: palladium in a weight ratio of 96.4: 3.6 was used. The power density was 1.33 W / cm 2 and the process pressure was 0.4 Pa. Sputtering was performed. (Formation of protective topcoat layer) On the said 2nd metal oxide layer, the transparent protective layer which consists of a fluorine-type ultraviolet curable resin which has the crosslinked structure derived from a phosphate ester compound was formed with a film thickness of 60 nm.
  • 5 phosphoric acid ester compounds (trade name “KAYAMER PM-21”, manufactured by Nippon Kayaku Co., Ltd.) are added to 100 parts by weight of the solid content of the fluorine-based hard coat resin solution (trade name “JUA204”, manufactured by JSR).
  • the solution added with parts by weight was applied using an applicator, dried at 60 ° C. for 1 minute, and then cured by irradiating with an ultra-high pressure mercury lamp with a UV light with an integrated light amount of 400 mJ / cm 2 in a nitrogen atmosphere.
  • a heat insulating and heat insulating film (1) having a configuration of metal oxide layer (thickness 10 nm) / protective topcoat layer (thickness 60 nm) was obtained. The results are shown in Table 1.
  • Example 2 Except having changed the film thickness of the SiC layer into 10 nm, it carried out similarly to Example 1 and obtained the heat insulation heat insulation film (2). The results are shown in Table 1.
  • Example 3 Except having changed the film thickness of the SiC layer into 20 nm, it carried out similarly to Example 1 and obtained the heat insulation heat insulation film (3). The results are shown in Table 1.
  • Example 4 Except having changed into the SiC layer and forming the Si layer, it carried out similarly to Example 1 and obtained the heat insulation heat insulation film (4).
  • the Si layer was sputtered at a power density of 0.50 kW / cm 2 and a process pressure of 0.4 Pa using a silicon target.
  • the thickness was 6 nm. The results are shown in Table 1.
  • Example 5 Except having changed the film thickness of Si layer into 10 nm, it carried out similarly to Example 4 and obtained the heat insulation heat insulation film (5). The results are shown in Table 1.
  • Example 6 Except having changed the film thickness of Si layer into 20 nm, it carried out similarly to Example 4 and obtained the heat insulation heat insulation film (6). The results are shown in Table 1.
  • Example 7 Except having formed the ZnS layer instead of the SiC layer, it carried out similarly to Example 1 and obtained the heat insulation heat insulation film (7).
  • the ZnS layer was sputtered using a ZnS target at a power density of 2.67 kW / cm 2 and a process pressure of 0.4 Pa.
  • the thickness was 6 nm. The results are shown in Table 1.
  • Example 8 Except having changed the film thickness of the ZnS layer into 10 nm, it carried out similarly to Example 7 and obtained the heat insulation heat insulation film (8). The results are shown in Table 1.
  • Example 9 Except having changed the film thickness of the ZnS layer into 20 nm, it carried out similarly to Example 7 and obtained the heat insulation heat insulation film (9). The results are shown in Table 1.
  • Example 4 Except for forming the Nb 2 O 5 layer in place of the SiC layer were performed in the same manner as in Example 1 to obtain a thermal barrier insulation film (C4).
  • the Nb 2 O 5 layer was sputtered using an Nb target at a power density of 2.3 kW / cm 2 and a process pressure of 0.4 Pa.
  • the thickness was 6 nm. The results are shown in Table 1.
  • Example 7 Except having formed the ZTO layer instead of the SiC layer, it carried out similarly to Example 1 and obtained the heat insulation heat insulation film (C7).
  • a target obtained by sintering zinc oxide, tin oxide and metal zinc powder at a weight ratio of 8.5: 83: 8.5 was used, and power density: 2.67 W / cm. 2.
  • Sputtering was performed under the conditions of process pressure: 0.4 Pa and substrate temperature of 80 ° C. At this time, the amount of gas introduced into the sputtering film forming chamber was adjusted so that Ar: O 2 was 98: 2 (volume ratio). The results are shown in Table 1.
  • the heat-insulating and heat-insulating film of the present invention can be used, for example, in windows for buildings and vehicles, transparent cases for storing plants, frozen or refrigerated showcases, and the like.

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne un film de protection thermique et d'isolation thermique ayant une excellente résistance à la fissuration et une excellente adhérence. Le film de protection thermique et d'isolation thermique de la présente invention qui comprend un film de substrat et un film réfléchissant les infrarouges est pourvu d'un film empêchant la réflexion entre le film de substrat et le film réfléchissant les infrarouges, le film empêchant la réflexion comprenant au moins un parmi les éléments suivants: le tellurure de plomb (PbTe), le nickel (Ni), le rhodium (Rh), le mononitrure de silicium (SiN), le platine (Pt), le sulfure de zinc (ZnS), le tantale (Ta), le titane (Ti), le carbure de silicium (SiC), le séléniure de zinc (ZnSe), le fer (Fe), le trisulfure d'antimoine (Sb2S3), le chrome (Cr), le tungstène (W), le molybdène (Mo), le germanium (Ge) et le silicium (Si).
PCT/JP2018/012684 2017-03-30 2018-03-28 Film de protection thermique et d'isolation thermique WO2018181446A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2017066620 2017-03-30
JP2017-066620 2017-03-30
JP2018-059376 2018-03-27
JP2018059376A JP2018171914A (ja) 2017-03-30 2018-03-27 遮熱断熱フィルム

Publications (1)

Publication Number Publication Date
WO2018181446A1 true WO2018181446A1 (fr) 2018-10-04

Family

ID=63676299

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2018/012684 WO2018181446A1 (fr) 2017-03-30 2018-03-28 Film de protection thermique et d'isolation thermique

Country Status (1)

Country Link
WO (1) WO2018181446A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7532834B2 (ja) 2020-03-23 2024-08-14 住友金属鉱山株式会社 熱線遮蔽合わせ透明基材

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56169056A (en) * 1980-06-02 1981-12-25 Teijin Ltd Laminate
JPS6389792A (ja) * 1986-09-29 1988-04-20 株式会社　麗光 熱線遮蔽性透明フイルム
JPH09314745A (ja) * 1996-02-09 1997-12-09 Saint Gobain Vitrage 赤外線特性を有する薄膜積重体を備えた透明基材
JP2009122416A (ja) * 2007-11-15 2009-06-04 Toppan Printing Co Ltd 光学薄膜フィルム
WO2015133370A1 (fr) * 2014-03-03 2015-09-11 日東電工株式会社 Substrat réfléchissant les infrarouges et procédé pour sa production
WO2016103128A1 (fr) * 2014-12-23 2016-06-30 Basf Se Film réfléchissant ir

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56169056A (en) * 1980-06-02 1981-12-25 Teijin Ltd Laminate
JPS6389792A (ja) * 1986-09-29 1988-04-20 株式会社　麗光 熱線遮蔽性透明フイルム
JPH09314745A (ja) * 1996-02-09 1997-12-09 Saint Gobain Vitrage 赤外線特性を有する薄膜積重体を備えた透明基材
JP2009122416A (ja) * 2007-11-15 2009-06-04 Toppan Printing Co Ltd 光学薄膜フィルム
WO2015133370A1 (fr) * 2014-03-03 2015-09-11 日東電工株式会社 Substrat réfléchissant les infrarouges et procédé pour sa production
WO2016103128A1 (fr) * 2014-12-23 2016-06-30 Basf Se Film réfléchissant ir

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7532834B2 (ja) 2020-03-23 2024-08-14 住友金属鉱山株式会社 熱線遮蔽合わせ透明基材

Similar Documents

Publication Publication Date Title
WO2016021532A1 (fr) Substrat réfléchissant les infrarouges
JP6000991B2 (ja) 赤外線反射フィルム
JP6282142B2 (ja) 赤外線反射基板およびその製造方法
JP6423198B2 (ja) 赤外線反射フィルム
US10007037B2 (en) Infrared-ray reflective film
WO2014119683A1 (fr) Procédé de fabrication d'un film réfléchissant le rayonnement infrarouge
WO2014119668A1 (fr) Procédé de production d'un film réfléchissant le rayonnement infrarouge
JP6370347B2 (ja) 赤外線反射フィルム
WO2018181424A1 (fr) Substrat de protection thermique et d'isolation thermique
WO2018181446A1 (fr) Film de protection thermique et d'isolation thermique
JP2018171914A (ja) 遮熱断熱フィルム
JP7145629B2 (ja) 遮熱断熱基板
JP6761625B2 (ja) 赤外線反射フィルム
WO2018181444A1 (fr) Substrat isolant thermique formant bouclier thermique
JP2018173166A (ja) 遮熱断熱基板
JP2016036929A (ja) 赤外線反射基板

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: 18775353

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: 18775353

Country of ref document: EP

Kind code of ref document: A1

点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载