WO2016194560A1 - Film de protection contre les infrarouges - Google Patents

Film de protection contre les infrarouges Download PDF

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Publication number
WO2016194560A1
WO2016194560A1 PCT/JP2016/063906 JP2016063906W WO2016194560A1 WO 2016194560 A1 WO2016194560 A1 WO 2016194560A1 JP 2016063906 W JP2016063906 W JP 2016063906W WO 2016194560 A1 WO2016194560 A1 WO 2016194560A1
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Prior art keywords
layer
refractive index
heat ray
film
index layer
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PCT/JP2016/063906
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English (en)
Japanese (ja)
Inventor
友香子 高
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コニカミノルタ株式会社
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Publication of WO2016194560A1 publication Critical patent/WO2016194560A1/fr

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/26—Reflecting filters
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/28—Interference filters

Definitions

  • the multilayer film product described in Patent Document 1 has a problem that the infrared light absorbing nanoparticle layer containing metal oxide nanoparticles containing a large number of tin oxides has insufficient weather resistance such as discoloration. .
  • the infrared light absorbing nanoparticle layer absorbs heat, so the film curls due to thermal cracking and thermal expansion and contraction of the thermal barrier film (multilayer film product), and as a thermal barrier film on windows, etc.
  • the weather resistance was insufficient, such as peeling off the end.
  • the inventors of the present invention have developed a heat ray absorbing layer containing cesium-containing tungsten oxide that is particularly excellent in optical properties and weather resistance improvement effect among materials having heat ray absorbing ability.
  • Use the above-mentioned problem by adjusting the wavelength reflected by the heat ray reflective layer to the absorption wavelength of the tungsten oxide and further adjusting the film thickness of the heat ray absorbing layer so that the tungsten oxide is not broken by excessive heat ray absorption. It was learned that this could be solved and the present invention was completed.
  • a heat ray reflective layer comprising an alternating laminate of a high refractive index layer containing a polymer and a low refractive index layer containing a polymer, and a heat ray absorbing layer containing a cesium-containing tungsten oxide
  • an infrared shielding film characterized in that the average reflectance at a wavelength of 1300 to 1600 nm is 8% or more and the thickness of the heat ray absorbing layer is 10 ⁇ m or less.
  • tungsten oxide can be effectively prevented from collapsing due to excessive heat ray absorption, and further, discoloration of tungsten oxide can be prevented. Furthermore, by adjusting the wavelength reflected by the heat ray reflective layer (the above heat ray) and the film thickness of the heat ray absorbing layer, excessive heat ray absorption by tungsten oxide can be prevented and the heat ray absorbing layer can be prevented from becoming too hot. It can effectively prevent thermal cracking of the heat-absorbing layer, prevent curling of the film due to thermal expansion and contraction, and prevent it from peeling for a long time even when applied to windows etc. it can. As described above, it has been found that the structure of the present invention has good weather resistance and high heat shielding properties.
  • the heat ray reflective layer in order to increase the average reflectance of the wavelength of 1300 to 1600 nm reflected by the heat ray reflective layer, it is in a specific position in the alternate laminated structure of the high refractive index layer and the low refractive index layer constituting the heat ray reflective layer. It has been found that this can be realized by increasing the thickness of only the layer.
  • the number of heat ray reflective layers is the N layer that combines the high refractive index layer and the low refractive index layer, and one layer closest to the resin film (or heat ray absorbing layer) on which the heat ray reflective layer is laminated is one layer.
  • the infrared shielding film of the present invention has little film cracking and color tone change, excellent weather resistance, and high heat shielding properties. Therefore, the infrared shielding film of this invention can be used conveniently as an infrared shielding film installed in the window of a building, the member for vehicles, etc.
  • the number of heat ray reflective layers 3 is 13
  • the first layer from the resin film side is the low refractive index layer 3b
  • the sixth high refractive index layer is the lower of the fifth and seventh adjacent layers.
  • the high refractive index layer 3a ′ is made thicker than the thickness of the refractive index layer 3b and the fourth and eighth high refractive index layers 3a adjacent thereto.
  • the thicknesses of the low refractive index layers 3b are all the same, and the thicknesses of the high refractive index layers 3a other than the sixth layer are all the same.
  • the infrared shielding body 10 in FIG. 1B has a configuration in which the adhesive layer 2 of the infrared shielding film 1 in FIG. 1A is bonded (bonded) to the light-transmitting substrate 6.
  • the resin film 4 is not necessarily an essential component, but as shown in FIG. 1, the resin film is disposed on at least one surface of the heat ray absorbing layer 5. It is preferred that That is, the resin film 4 is preferably disposed between the heat ray reflective layer 3 and the heat ray absorbing layer 5.
  • the resin film 4 is less susceptible to external influences such as light and moisture, so that weather resistance can be improved and color tone change can be more effectively suppressed or prevented.
  • a hard coat layer (protective layer), a resin film (protective film), etc. are arranged on the surface opposite to the light incident side of the heat ray absorbing layer 5 as necessary. Also good. By adopting such a configuration, weather resistance can be improved more effectively because it is less susceptible to external influences such as scratches and moisture.
  • the heat ray reflective layer 3 designed so that the reflected wavelength matches the absorption wavelength of tungsten oxide is disposed on the side where sunlight enters, so that the wavelength 1300 to 1600 nm entering the heat ray absorbing layer 5 is disposed.
  • the amount of heat rays (infrared rays) can be reduced more effectively. For this reason, the amount of absorption of heat rays (infrared rays) such as tungsten oxide contained in the heat ray absorbing layer 5 is further reduced, and as a result, cracking (heat cracking) of the heat ray absorbing layer 5 can be more effectively suppressed or prevented.
  • a release layer (not shown) may be further provided on the adhesive layer, and the release layer may be peeled off when being attached to the substrate.
  • other layers for example, conductive layer, antistatic layer, gas barrier layer, easy-adhesion layer, antifouling layer, deodorant layer, drip layer, easy-slip layer, wear-resistant layer, antireflection layer, electromagnetic wave shield
  • conductive layer for example, conductive layer, antistatic layer, gas barrier layer, easy-adhesion layer, antifouling layer, deodorant layer, drip layer, easy-slip layer, wear-resistant layer, antireflection layer, electromagnetic wave shield
  • conductive layer for example, conductive layer, antistatic layer, gas barrier layer, easy-adhesion layer, antifouling layer, deodorant layer, drip layer, easy-slip layer, wear-resistant layer, antireflection layer, electromagnetic wave shield
  • ultraviolet absorbing layers for example, ultraviolet absorbing layers, infrared absorbing layers, printed layers, fluorescent light emitting layers, hologram layers
  • the average reflectance at a wavelength of 1300 to 1600 nm is 8% or more. This is achieved by adjusting the wavelength reflected by the heat ray reflective layer to the wavelength of 1300 to 1600 nm, which is the absorption wavelength of tungsten oxide used in the heat ray absorbing layer, so that the average reflectance in the wavelength region is within the range specified above. Was able to.
  • any one layer is preferably larger than the film thickness of the adjacent layer, and more preferably 1.2 times or more the film thickness of the adjacent layer.
  • the thickening layer is optimally a high refractive index layer.
  • the film thicknesses of the respective low refractive index layers are preferably the same film thickness (150 nm), and the film thicknesses of the respective high refractive index layers other than the layer to be similarly increased are preferably the same film thickness (120 nm).
  • the film thickness of each low refractive index layer may not be the same.
  • the thicknesses of the high refractive index layers other than the layer to be thickened may not be the same.
  • the infrared shielding film 1 has a heat ray reflective layer composed of an alternating laminate of a high refractive index layer containing a polymer and a low refractive index layer containing a polymer. That is, the heat-reflective layer is a multilayer reflector (laminated reflector) of layers having different refractive indexes, so that intrusion of heat rays (infrared rays) can be prevented, and the high-refractive index layer and the low-refractive index layer are alternately arranged. It is the laminated structure (laminated reflector).
  • the heat ray reflective layer (the high refractive index layer and the low refractive index layer constituting it) contains a polymer.
  • the flexibility of the layer is improved as compared with the heat ray reflective layer of the inorganic film formed only of the metal oxide material, so that film cracking can be effectively prevented.
  • the adhesiveness between each layer can be improved.
  • the heat ray reflective layer can be formed by coating or the like, uniform and large-area film formation is easy.
  • the heat ray reflective layer has at least one laminate (unit) in which a high refractive index layer containing a polymer and a low refractive index layer containing a polymer are laminated.
  • a more preferable form is demonstrated.
  • a set of portions where the high refractive index layer component is 50% by mass or more is defined as a high refractive index layer
  • a set of portions where the low refractive index layer component exceeds 50% by mass is defined as a low refractive index layer.
  • the low refractive index layer contains, for example, a first metal oxide as a low refractive index component
  • the high refractive index layer contains a second metal oxide as a high refractive index component
  • the metal oxide concentration profile in the film thickness direction in these laminated films is measured, and can be regarded as a high refractive index layer or a low refractive index layer depending on the composition.
  • the carbon concentration in the film thickness direction is measured to confirm that the mixed region exists, and the composition is further changed to EDX.
  • EDX Electrode X-ray spectroscopy; energy dispersive X-ray analysis
  • the heat ray reflective layer may have a configuration in which a high refractive index layer containing a polymer and a low refractive index layer containing a polymer are alternately laminated (multilayer laminate).
  • the number of layers is not particularly limited as long as the effects of the present invention are not impaired, and a range of 10 to 50 layers is preferable. If the number of layers is 10 or more, a desired infrared reflectance can be obtained and a high heat shielding effect can be obtained. If the number of layers is 50 or less, it is excellent in that sufficient heat resistance is obtained, for example, the heat ray reflective layer is difficult to break and edge peeling can be suppressed.
  • the heat ray reflective layer may have a structure (multilayer laminate) in which a high refractive index layer containing a polymer and a low refractive index layer containing a polymer are alternately laminated.
  • the lowermost layer and the outermost layer of the multilayer laminate constituting the heat ray reflective layer may be either a high refractive index layer or a low refractive index layer.
  • the adhesion to the lowermost adjacent layer for example, resin film, heat ray absorbing layer
  • the blowout resistance of the uppermost layer are excellent.
  • a layer configuration in which the lowermost layer and the outermost layer are low refractive index layers is preferable.
  • the high refractive index layer preferably has a higher refractive index.
  • the refractive index of the high refractive index layer is preferably 1.70 to 2.50, more preferably 1.80 to 2.20.
  • the low refractive index layer preferably has a lower refractive index.
  • the refractive index of the low refractive index layer is preferably 1.10 to 1.60, more preferably 1.30 to 1.55, and still more preferably 1.30 to 1.50.
  • the difference in refractive index between the adjacent high refractive index layer and low refractive index layer is preferably 0.1 or more, more preferably Is 0.2 or more, more preferably 0.25 or more.
  • the refractive index difference between the low refractive index layer and the high refractive index layer in all the units may be within the preferred range.
  • the outermost layer and the lowermost layer of the heat ray reflective layer, and the above-described thickened layer a configuration outside the above preferred range may be used.
  • the reflectance in a specific wavelength region is determined by the difference in refractive index between two adjacent layers (high refractive index layer and low refractive index layer) and the number of layers, and the larger the refractive index difference, the same reflectance can be obtained with fewer layers. .
  • the refractive index difference and the required number of layers can be calculated using commercially available optical design software. For example, in order to obtain an infrared reflectivity (infrared shielding rate) of 90% or more, if the difference in refractive index is smaller than 0.1, a laminate exceeding 100 layers is required, which not only reduces productivity. , Scattering at the laminated interface increases and transparency decreases. From the viewpoint of improving the reflectance and reducing the number of layers, there is no upper limit to the difference in refractive index, but it is substantially about 1.40.
  • the refractive index is obtained as a difference between the high refractive index layer and the low refractive index layer according to the following method. That is, each refractive index layer is formed as a single layer (using a substrate such as glass or a resin film if necessary), and this sample is cut into 10 cm ⁇ 10 cm, and then the refractive index is obtained according to the following method. Using a spectrophotometer (for example, U-4000 type; manufactured by Hitachi, Ltd.), the surface opposite to the measurement surface (back surface) of each sample is roughened and then light-absorbed with a black spray.
  • a spectrophotometer for example, U-4000 type; manufactured by Hitachi, Ltd.
  • the infrared region is particularly related to the indoor temperature rise, so shielding near-infrared light is particularly effective for suppressing the rise in indoor temperature.
  • the cumulative energy ratio from the shortest infrared wavelength (760 nm) to the longest wavelength 3200 nm based on the weight coefficient described in Japanese Industrial Standard JIS R3106: 1998 the infrared from the wavelength 760 nm to the longest wavelength 3200 nm
  • the cumulative energy from 760 nm to each wavelength when the total energy of the entire region is 100
  • the total energy from 760 to 1300 nm occupies about 75% of the entire infrared region. Therefore, shielding the wavelength region up to 1300 nm is efficient in energy saving effect by heat ray shielding.
  • the thickness of the layer to be thickened is a configuration outside the range of the thickness per layer (thickness after drying) of the low refractive index layer and high refractive index layer specified above It may be.
  • the thickness of the low refractive index layer and the high refractive index layer may be the same or different.
  • the thickness per layer of each refractive index layer can be adjusted by changing the width in the film thickness direction at the die extrusion port and / or by stretching conditions.
  • stretching a laminated reflector refsin film which laminated
  • the thickness per layer of each refractive index layer can be measured by the method described in the paragraph (Measurement of film thickness) of ⁇ Formation of heat ray reflective layer on resin film> in Example 1.
  • the film thickness of the heat ray reflective layer composed of the alternating laminate of the low refractive index layer and the high refractive index layer described above may be in a range that does not impair the effects of the invention, and is preferably 10 ⁇ m or less, more preferably 5.5 ⁇ m or less. The range is particularly preferably from 1.0 to 4.0 ⁇ m. When the film thickness of the heat ray reflective layer is 10 ⁇ m or less, particularly 5.5 ⁇ m or less, the workability at the time of construction on a window or the like can be improved.
  • the polymer contained in the high refractive index layer and the low refractive index layer is preferably a water-soluble polymer that functions as a binder.
  • a layer formation method that suppresses the use of an organic solvent can be adopted, so that environmental problems due to the organic solvent can be solved.
  • flexibility of a coating film can also be achieved, it is preferable.
  • each refractive index layer can be formed using a film forming method such as coating or spin coating.
  • the polymers contained in the high refractive index layer and the low refractive index layer may be the same component or different components, but are preferably different.
  • the water-soluble polymer include polyvinyl alcohol or a derivative thereof (polyvinyl alcohol-based resin), gelatin, or thickening polysaccharide. From the viewpoint of improving effects such as coating unevenness and film thickness uniformity (haze). Therefore, the refractive index layer preferably contains polyvinyl alcohol or a derivative thereof as a polymer.
  • a polymer may be used independently and may be used in combination of 2 or more type.
  • the polymer may be a synthetic product or a commercially available product.
  • the polymer is not particularly limited, and known polymers used for the high refractive index layer and the low refractive index layer, such as International Publication No. 2012/128109, JP2013-121567A, JP2013-148849A, and the like. Can be used in the same way.
  • the polyvinyl alcohol-based resin includes various modified polyvinyl alcohols in addition to ordinary polyvinyl alcohol obtained by hydrolyzing polyvinyl acetate.
  • the polyvinyl alcohol obtained by hydrolyzing vinyl acetate preferably has an average degree of polymerization of 1,000 or more, and particularly preferably an average degree of polymerization of 1,500 to 5,000.
  • the degree of saponification is preferably 70 to 100 mol%, particularly preferably 80 to 99.9 mol%.
  • polyvinyl alcohol for example, polyvinyl alcohol (trade name JP-45; degree of polymerization: 4500, degree of saponification: 88 mol%; manufactured by Nippon Acetate / Poval) can be used.
  • modified polyvinyl alcohol examples include cation-modified polyvinyl alcohol, anion-modified polyvinyl alcohol, nonion-modified polyvinyl alcohol, ethylene-modified polyvinyl alcohol, and vinyl alcohol polymers.
  • vinyl acetate resin for example, “Exeval” (registered trademark) manufactured by Kuraray Co., Ltd.
  • polyvinyl acetal resin obtained by reacting polyvinyl alcohol with aldehyde for example, “S REC” (registered trademark) manufactured by Sekisui Chemical Co., Ltd.)
  • Silanol-modified polyvinyl alcohol having a silanol group for example, “R-1130” manufactured by Kuraray Co., Ltd.
  • modified polyvinyl alcohol resin having an acetoacetyl group in the molecule for example, “GO” manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) Cefaimer (registered trademark) Z / WR series ”
  • Anion-modified polyvinyl alcohol is described in, for example, polyvinyl alcohol having an anionic group as described in JP-A-1-206088, JP-A-61-237681 and JP-A-63-307979.
  • examples thereof include a copolymer of vinyl alcohol and a vinyl compound having a water-soluble group, and modified polyvinyl alcohol having a water-soluble group as described in JP-A-7-285265.
  • Nonionic modified polyvinyl alcohol includes, for example, a polyvinyl alcohol derivative in which a polyalkylene oxide group is added to a part of vinyl alcohol as described in JP-A-7-9758, and JP-A-8-25795.
  • Examples of the cation-modified polyvinyl alcohol include primary to tertiary amino groups and quaternary ammonium groups as described in JP-A No. 61-10383.
  • Examples of the ethylenically unsaturated monomer having a cationic group include trimethyl- (2-acrylamido-2,2-dimethylethyl) ammonium chloride and trimethyl- (3-acrylamido-3,3-dimethylpropyl) ammonium chloride.
  • the ratio of the cation-modified group-containing monomer of the cation-modified polyvinyl alcohol is preferably 0.1 to 10 mol%, more preferably 0.2 to 5 mol%, relative to vinyl acetate.
  • ethylene-modified polyvinyl alcohol for example, those described in JP-A-2009-107324, JP-A-2003-248123, JP-A-2003-342322, and International Publication No. 2015-0500171 can be used.
  • commercially available products such as EXEVAL (trade name: manufactured by Kuraray Co., Ltd.) may be used.
  • polyvinyl alcohol may be used alone or in combination of two or more.
  • Polyvinyl alcohol may be a synthetic product or a commercial product.
  • the weight average molecular weight of polyvinyl alcohol is preferably 1,000 to 200,000, and more preferably 3,000 to 60,000.
  • the value of “weight average molecular weight” is a static light scattering method, gel permeation chromatography (GPC), TOFMASS (Time-of-Flight mass spectrometer: time-of-flight (TOF) mass spectrometry. ) Etc. shall be adopted.
  • GPC gel permeation chromatography
  • TOFMASS Time-of-Flight mass spectrometer: time-of-flight (TOF) mass spectrometry.
  • the content of the water-soluble polymer in the refractive index layer is preferably 5 to 75% by mass, and more preferably 10 to 70% by mass with respect to the total solid content of the refractive index layer.
  • the content of the water-soluble polymer is 5% by mass or more, when the low refractive index layer is formed by a wet film forming method, the transparency of the film surface is disturbed when the coating film obtained by coating is dried. This is preferable because it is possible to prevent the deterioration.
  • the content of the water-soluble polymer is 75% by mass or less, the content is suitable when metal oxide particles are contained in the low refractive index layer, and the low refractive index layer and the high refractive index layer This is preferable because the refractive index difference can be increased.
  • content of water-soluble polymer is calculated
  • At least one of the low refractive index layer and the high refractive index layer in the infrared shielding film of this embodiment may contain a metal oxide (particle).
  • a metal oxide particle
  • the refractive index difference between the refractive index layers can be increased, and the reflection characteristics are improved.
  • both the low refractive index layer and the high refractive index layer contain metal oxide particles, the refractive index difference can be further increased.
  • the number of stacked layers can be reduced and a thin film can be obtained. By reducing the number of layers, productivity can be improved and a decrease in transparency due to scattering at the lamination interface can be suppressed.
  • the metal oxide particles are not particularly limited as long as they transmit visible light and reflect heat rays (infrared rays).
  • the metal constituting the metal oxide is Li, Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Rb, One selected from the group consisting of Sr, Y, Nb, Zr, Mo, Ag, Cd, In, Sn, Sb, Cs, Ba, La, Ta, Hf, W, Ir, Tl, Pb, Bi and rare earth metals
  • a metal oxide that is two or more kinds of metals can be used.
  • metal oxide particles used for the high refractive index layer include titanium dioxide (TiO 2 ), zirconium oxide (ZrO 2 ), zinc oxide, alumina, colloidal alumina, lead titanate, red lead, yellow lead, zinc yellow, Chrome oxide, ferric oxide, iron black, copper oxide, magnesium oxide, magnesium hydroxide, strontium titanate, yttrium oxide, hafnium oxide, niobium oxide, tantalum oxide (Ta 2 O 5 ), barium oxide, indium oxide, oxidation Europium, lanthanum oxide, zircon, tin oxide, lead oxide, and double oxides composed of these oxides such as lithium niobate, potassium niobate, lithium tantalate, aluminum / magnesium oxide (MgAl 2 O 4 ), etc. Is mentioned.
  • rare earth oxides can also be used as the metal oxide particles. Specifically, scandium oxide, yttrium oxide, lanthanum oxide, cerium oxide, praseodymium oxide, neodymium oxide, samarium oxide, europium oxide, gadolinium oxide, and oxidation. Examples also include terbium, dysprosium oxide, holmium oxide, erbium oxide, thulium oxide, ytterbium oxide, and lutetium oxide.
  • the metal oxide particles used in the high refractive index layer are preferably metal oxide particles having a refractive index of 1.90 or more, and examples thereof include zirconium oxide, cerium oxide, titanium oxide, and zinc oxide. Among these, titanium dioxide is preferable because it can form a transparent and higher refractive index layer having a higher refractive index, and rutile (tetragonal) titanium oxide particles are particularly preferable.
  • the metal oxide particles used for the high refractive index layer may be used singly or in combination of two or more.
  • titanium oxide is preferable as the metal oxide of the high refractive index layer.
  • the titanium oxide may be in the form of core-shell particles coated with a silicon-containing hydrated oxide.
  • the core-shell particles have a structure in which the surface of the titanium oxide particles is coated with a shell made of a silicon-containing hydrated oxide on a titanium oxide serving as a core.
  • the “coating” means a state in which a silicon-containing hydrated oxide is attached to at least a part of the surface of the titanium oxide particles. That is, the surface of the titanium oxide particles used as the metal oxide particles may be completely covered with a silicon-containing hydrated oxide, and a part of the surface of the titanium oxide particles is a silicon-containing hydrated oxide. It may be coated. From the viewpoint that the refractive index of the coated titanium oxide particles is controlled by the coating amount of the silicon-containing hydrated oxide, it is preferable that a part of the surface of the titanium oxide particles is coated with the silicon-containing hydrated oxide. .
  • such coated titanium oxide particles are also referred to as “silica-attached titanium dioxide sol”.
  • the titanium oxide particles As a method of coating the titanium oxide particles with a silicon-containing hydrated oxide, it can be produced by a conventionally known method.
  • JP-A-10-158015, JP-A-2000-204301, JP-A-2007 Reference can be made to the matters described in Japanese Patent No. 246351.
  • the volume average particle size of the metal oxide particles used in the high refractive index layer is preferably 100 nm or less, more preferably 50 nm or less, and 1 to 30 nm from the viewpoint of a low haze value and excellent visible light transmittance. It is more preferable that the thickness is 1 to 20 nm.
  • the volume average particle diameter means a method of observing the particle itself using a laser diffraction scattering method, a dynamic light scattering method, or an electron microscope, or a particle image appearing on the cross section or surface of the refractive index layer.
  • the content of the metal oxide particles in the high refractive index layer is 100% by mass of the solid content of the high refractive index layer, from the viewpoint of heat ray shielding and from the viewpoint of reducing color unevenness when a film is applied to curved glass. Therefore, it is preferably 20 to 80% by mass, more preferably 30 to 75% by mass, and further preferably 40 to 70% by mass.
  • the metal oxide particles used in the low refractive index layer silicon dioxide (SiO 2 ), magnesium fluoride (MgF 2 ) or the like is preferably used, and colloidal silica is particularly preferably used.
  • the metal oxide particles (preferably silicon dioxide) contained in the low refractive index layer preferably have an average particle size of 3 to 100 nm.
  • the average particle diameter of primary particles of silicon dioxide dispersed in a primary particle state is more preferably 3 to 50 nm, and further preferably 3 to 40 nm. It is particularly preferably 3 to 20 nm, and most preferably 4 to 10 nm.
  • grains it is preferable from a viewpoint with few hazes and excellent visible light transmittance
  • the average particle size of the metal oxide in the low refractive index layer is determined by observing the particles themselves or the cross section or surface of the refractive index layer with an electron microscope and measuring the particle size of 1,000 arbitrary particles. The simple average value (number average) is obtained.
  • the particle diameter of each particle is represented by a diameter assuming a circle equal to the projected area.
  • the content of the metal oxide particles in the low refractive index layer is preferably 5 to 70% by mass with respect to the solid content of the low refractive index layer, and preferably 10 to 50% by mass from the viewpoint of refractive index. More preferably.
  • Colloidal silica is obtained by heating and aging a silica sol obtained by metathesis of sodium silicate with an acid or the like or passing through an ion exchange resin layer.
  • a silica sol obtained by metathesis of sodium silicate with an acid or the like or passing through an ion exchange resin layer for example, JP-A-57-14091 and JP-A-60- No.
  • colloidal silica may be a synthetic product or a commercially available product.
  • the surface of the colloidal silica may be cation-modified, or may be treated with Al, Ca, Mg, Ba or the like.
  • colloidal silica may be a synthetic product or a commercially available product.
  • Snowtex (registered trademark) series sold by Nissan Chemical Industries, Ltd. Snowtex (registered trademark) OS, OXS, S, OS, 20, 30, 40, O, N, C, etc.) Is mentioned.
  • each refractive index layer includes, for example, ultraviolet absorbers described in JP-A-57-74193, JP-A-57-87988, and JP-A-62-261476, and JP-A-57-74192. JP-A-57-87989, JP-A-60-72785, JP-A-61465991, JP-A-1-95091 and JP-A-3-13376, etc. No.
  • optical brighteners sulfuric acid, phosphoric acid, acetic acid , PH adjusters such as citric acid, sodium hydroxide, potassium hydroxide, potassium carbonate, antifoaming agents, lubricants such as diethylene glycol, preservatives, antistatic agents,
  • Various known additives may be contained such Tsu bets agent. The content of these additives is preferably 0.1 to 10% by mass with respect to the solid content of the refractive index layer.
  • a curing agent can be used to cure the water-soluble polymer.
  • Curing agents include boric acid and its salts, ethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-diglycidylcyclohexane, N, N-diglycidyl-4-glycidyloxyaniline, sorbitol polyglycidyl Ether, glycerol polyglycidyl ether, etc.), aldehyde-based curing agents (formaldehyde, glyoxal, etc.), active halogen-based curing agents (2,4-dichloro-4-hydroxy-1,3,5, -s-triazine, etc.), active Examples thereof include vinyl compounds (1,3,5-trisacryloyl-hexahydro-s-triazine, bisvinylsulfonylmethyl ether, etc.
  • each refractive index layer may contain a surfactant for adjusting the surface tension at the time of application.
  • a surfactant for adjusting the surface tension at the time of application.
  • an anionic surfactant, a nonionic surfactant, an amphoteric surfactant, and the like can be used as the surfactant, and an anionic surfactant is more preferable.
  • Preferable compounds include those containing a hydrophobic group having 8 to 30 carbon atoms and a sulfonic acid group or a salt thereof in one molecule.
  • the content of the surfactant in each refractive index layer is preferably 0.01 to 5% by mass with respect to the solid content of the refractive index layer.
  • a surfactant for example, New Coal series (manufactured by Nippon Emulsifier Co., Ltd.) and the like can be used.
  • the infrared shielding film has a heat ray absorbing layer 5 containing cesium-containing tungsten oxide on a resin film (or heat ray reflective layer).
  • a configuration provided between a resin film (or heat ray reflective layer) and a surface protective film such as a hard coat layer is preferable. By adopting such a configuration, weather resistance is good and high heat shielding properties can be achieved, such as suppression or prevention of film cracking of an infrared shielding film (particularly, a heat ray absorbing layer and a heat ray reflecting layer).
  • the heat ray absorbing layer may be a single layer or a laminate of two or more layers.
  • the structure of each heat ray absorbing layer may be the same or different.
  • the heat ray absorbing layer contains cesium-containing tungsten oxide from the viewpoint of optical characteristics and weather resistance improvement effect as an infrared ray absorbing material among tungsten oxides and composite tungsten oxides having excellent heat ray absorbing ability as a near infrared ray absorbing material. .
  • the composition of the cesium-containing tungsten oxide which is one of the composite tungsten oxides, is not particularly limited, but is preferably an oxide represented by the general formula: Cs x W y O z from the viewpoint of stability.
  • Cs represents cesium.
  • W represents tungsten.
  • O represents oxygen.
  • x, y, and z are the composition of tungsten and cesium (the composition of cesium with respect to tungsten, x / y) satisfies the relationship of 0.001 ⁇ x / y ⁇ 1, and the composition of tungsten and oxygen (the ratio of oxygen to tungsten).
  • the composition, z / y) preferably satisfies the relationship of 2.2 ⁇ z / y ⁇ 3.
  • the shape of the cesium-containing tungsten oxide (hereinafter also simply referred to as tungsten oxide) is not particularly limited, and may be any structure such as a particulate shape, a spherical shape, a rod shape, a needle shape, a plate shape, a columnar shape, an irregular shape, a flake shape, and a spindle shape. However, it is preferably particulate or spherical.
  • the size of the cesium-containing tungsten oxide is not particularly limited, but when the cesium-containing tungsten oxide is particulate or spherical, the average particle diameter (average primary particle diameter, diameter) of the cesium-containing tungsten oxide particles is visible light.
  • the thickness is preferably from 5 to 200 nm, more preferably from 10 to 100 nm, because the heat ray absorption effect can be ensured while suppressing reflection of light, and haze deterioration due to scattering does not occur and transparency can be secured.
  • the average particle size is determined by observing particles themselves or particles appearing on the cross section or surface of the refractive index layer with an electron microscope, measuring the particle size of 1,000 arbitrary particles, and calculating the simple average value (number average). As required.
  • the particle diameter of each particle is represented by a diameter assuming a circle equal to the projected area.
  • the content of the cesium-containing tungsten oxide is preferably 10 to 80% by mass, more preferably 20 to 70% by mass with respect to the total solid content of the heat ray absorbing layer. If it is such quantity, since tungsten oxide etc. can absorb a heat ray enough, the heat insulation performance of an infrared shielding film can be improved.
  • the cesium-containing tungsten oxide as described above is, for example, a cesium-doped tungsten oxide dispersion (YMF-02A, total solid concentration 28% by mass (cesium-doped tungsten oxide concentration 18.5% by mass), composition: Cs 0. 33 WO 3 , average particle diameter 50 nm, manufactured by Sumitomo Metal Mining Co., Ltd.) or the like can be used.
  • YMF-02A cesium-doped tungsten oxide dispersion
  • total solid concentration 28% by mass cesium-doped tungsten oxide concentration 18.5% by mass
  • composition Cs 0. 33 WO 3 , average particle diameter 50 nm, manufactured by Sumitomo Metal Mining Co., Ltd.
  • the heat ray absorbing layer preferably contains antimony-doped tin oxide (ATO) or tin-doped indium oxide (ITO). These may be used singly or in combination (that is, ATO or ITO means ATO and / or ITO, and is also simply referred to as ATO / ITO).
  • ATO or ITO means ATO and / or ITO, and is also simply referred to as ATO / ITO.
  • the heat-absorbing layer is excellent in that it can provide a highly heat-shielding film by reflecting a part of far-infrared rays while enhancing the heat-shielding property. ing.
  • composition of antimony-doped tin oxide (ATO) or tin-doped indium oxide (ITO) is not particularly limited, and any commercially available one can be used sufficiently.
  • antimony-doped tin oxide (ATO) is a tin oxide containing a small amount of antimony oxide, and is a composite oxide of tin and antimony.
  • Tin-doped indium oxide (ITO) is indium oxide containing a small amount of tin oxide, and is a composite oxide of indium and tin.
  • the shape of ATO or ITO is not particularly limited, and may take any structure such as a particulate shape, a spherical shape, a rod shape, a needle shape, a plate shape, a columnar shape, an indeterminate shape, a flake shape, and a spindle shape. It is spherical.
  • the size of ATO or ITO is not particularly limited, but when ATO or ITO is particulate or spherical, the average particle diameter (average primary particle diameter, diameter) of ATO / ITO is 0.2 ⁇ m or less. It is preferable. This is because reflection of visible light becomes inconspicuous due to scattering and absorption by ATO and ITO particles.
  • the content of ATO / ITO is preferably in the range of 1/5 to 1/50 with respect to the content of cesium-containing tungsten oxide. This is because, if the content of ATO / ITO is within the above range, it is possible to obtain a highly heat-shielding film by reflecting a part of far-infrared rays while enhancing the heat-shielding property.
  • a synthetic product or a commercial product may be used for ATO and ITO as described above.
  • Examples of commercially available products include ATO particles (trade name: SR35M, manufactured by ANP), ATO dispersion (manufactured by Mitsubishi Materials Corporation), ITO dispersion (manufactured by Mitsubishi Materials Corporation), and the like.
  • the heat ray absorbing layer preferably further contains an active energy ray-curable resin such as an acrylate resin from the viewpoint of ease of molding.
  • the active energy ray-curable resin refers to a resin that is cured through a crosslinking reaction or the like by irradiation with active energy rays such as ultraviolet rays and electron beams.
  • the active energy ray-curable resin a component containing a monomer having an ethylenically unsaturated double bond is preferably used, and a resin that is cured by irradiation with active energy rays such as ultraviolet rays or electron beams is preferable.
  • the active energy ray curable resin examples include an ultraviolet curable resin and an electron beam curable resin, and an ultraviolet curable resin that is cured by irradiation with ultraviolet rays is preferable.
  • the active energy ray-curable resins can be used alone or in combination of two or more.
  • the content of the active energy ray curable resin is preferably 20 to 70% by mass, more preferably 30 to 60% by mass, based on the total solid content of the heat ray absorbing layer. . With such an amount, the film-forming property is good and the heat shielding property can be secured.
  • the ultraviolet curable resin examples include an ultraviolet curable urethane acrylate resin, an ultraviolet curable polyester acrylate resin, an ultraviolet curable epoxy acrylate resin, an ultraviolet curable polyol acrylate resin, an ultraviolet curable acrylic acrylate resin, and an ultraviolet curable epoxy resin. Etc. are preferably used.
  • the heat ray absorbing layer is an acrylate resin selected from an ultraviolet curable urethane acrylate resin, an ultraviolet curable polyester acrylate resin, an ultraviolet curable epoxy acrylate resin, an ultraviolet curable polyol acrylate resin, or an ultraviolet curable acrylic acrylate resin. It is more preferable to contain.
  • the UV curable urethane acrylate resin generally includes 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate (hereinafter referred to as methacrylate) in addition to a product obtained by reacting a polyester polyol with an isocyanate monomer or a prepolymer. It is easily obtained by reacting an acrylate monomer having a hydroxyl group such as 2-hydroxypropyl acrylate.
  • methacrylate 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate
  • methacrylate 2-hydroxyethyl methacrylate
  • An ultraviolet curable polyester acrylate resin can be easily obtained by reacting a monomer such as 2-hydroxyethyl acrylate, glycidyl acrylate or acrylic acid with a hydroxyl group or carboxyl group at the end of the polyester (see, for example, Japanese Patent Laid-Open No. 59). -151112).
  • the ultraviolet curable epoxy acrylate resin can be obtained by reacting a terminal hydroxyl group of an epoxy resin with a monomer such as acrylic acid, acrylic acid chloride, or glycidyl acrylate.
  • Examples of the ultraviolet curable polyol acrylate resin include ethylene glycol (meth) acrylate, polyethylene glycol di (meth) acrylate, glycerin tri (meth) acrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, and diester.
  • Pentaerythritol pentaacrylate A resin obtained by curing one or more monomers such as dipentaerythritol hexaacrylate.
  • benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether and their alkyl ethers; acetophenone, 2, 2 -Dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone (trade name: Irgacure (registered trademark) 184, manufactured by BASF Japan, or product name: Irgacure (registered trademark) 819, manufactured by BASF Japan) Acetophenones; anthraquinones such as methylanthraquinone, 2-ethylanthraquinone, 2-amylanthraquinone; thioxanthones such as thioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone
  • tertiary amines such as triethanolamine and methyldiethanolamine
  • photoinitiators such as benzoic acid derivatives such as 2-dimethylaminoethylbenzoic acid and ethyl 4-dimethylaminobenzoate
  • the use amount of these radical polymerization initiators is preferably 0.5 to 20 parts by mass, more preferably 1 to 15 parts by mass with respect to 100 parts by mass of the polymerizable component of the resin.
  • Unidic (registered trademark) series (manufactured by DIC Corporation) (for example, Unidic (registered trademark)) V-4018, Unidic (registered trademark) V-4025, Unidic (registered trademark) 17-806, Unidic (registered trademark) 17-824-9), Hitaroid (registered trademark) series (manufactured by Hitachi Chemical Co., Ltd.) , Purple light (registered trademark) series (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), beam set series (manufactured by Arakawa Chemical Industry Co., Ltd.) (for example, beam set (registered trademark) 575, beam set (registered trademark) 577), ETERMER 2382 ( ETERNAL manufactured by CHEMICAL), “EBECRYL (registered trademark) 350 (silicon diacryle) Theft,
  • the heat ray absorbing layer is formed by heat ray absorption including cesium-containing tungsten oxide, and optionally included active energy ray-curable resin, surfactant, infrared absorber, ultraviolet absorber and / or antioxidant.
  • a method of forming a film by applying a layer forming coating solution by wire bar coating, spin coating, dip coating or the like is employed.
  • coat and film-form using continuous coating apparatuses, such as a die coater, a gravure coater, and a comma coater.
  • the film forming conditions when the heat ray absorbing layer contains an active energy ray-curable resin change its reactivity depending on the irradiation wavelength, illuminance, and light quantity of the active energy ray, so the optimum conditions are appropriately selected depending on the resin used. It is preferable to do.
  • the illuminance is preferably 50 ⁇ 1500mW / cm 2
  • the amount of irradiation energy is preferably 50 ⁇ 1500mJ / cm 2.
  • the solvent used when forming the heat ray absorbing layer by a coating method is not particularly limited, and examples thereof include hydrocarbons (for example, toluene, xylene, cyclohexane, etc.), alcohols (for example, methanol, ethanol, isopropanol, butanol, cyclohexane).
  • hydrocarbons for example, toluene, xylene, cyclohexane, etc.
  • alcohols for example, methanol, ethanol, isopropanol, butanol, cyclohexane.
  • ketones eg, acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, etc.
  • ethers eg, tetrahydrofuran, etc.
  • glycol ethers For example, ethylene glycol monomethyl ether (methyl cellosolve), ethylene glycol monoethyl ether (ethyl cellosolve), ethylene glycol mono-n-butyl ether (butyl cellosolve), ethylene glycol Cole mono-tert-butyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, 3-methoxybutanol, 3-methoxy-3-methylbutanol, 3-methoxy-3-methylbutyl acetate, 1-methoxy-2- Propyl acetate, 1-
  • the coating solution for forming the heat ray absorbing layer may contain a surfactant.
  • a coating film When a coating film is formed with a coating solution for forming a heat-absorbing layer containing a surfactant, it becomes a highly leveled coating film, thus preventing the formation of parts with a high or low residual solvent amount.
  • adhesion with a resin film, a hard coat layer, or the like can be improved.
  • water repellency, slipperiness, etc. can be imparted to the hard coat layer or the like.
  • limiting in particular as a kind of surfactant A fluorine-type surfactant, an acrylic surfactant, a silicone-type surfactant, etc. can be used.
  • a fluorosurfactant is preferably used from the viewpoint of leveling properties, water repellency, and slipperiness of the coating solution.
  • the fluorosurfactant include, for example, Megafac (registered trademark) F series (F-430, F-477, F-552 to F-559, F-561, F-562, etc., manufactured by DIC Corporation.
  • acrylic surfactant examples include Polyflow Series (manufactured by Kyoeisha Chemical Co., Ltd.), New Coal Series (manufactured by Nippon Emulsifier Co., Ltd.), and BYK (registered trademark) -354 (manufactured by Big Chemie Japan Co., Ltd.).
  • silicone-based surfactant examples include BYK (registered trademark) -345, BYK (registered trademark) -347, BYK (registered trademark) -348, BYK (registered trademark) -349 (manufactured by BYK Japan).
  • Surfactants may be used alone or in admixture of two or more.
  • the coating solution for forming the heat ray absorbing layer may contain a metal salt.
  • the metal salt has a function of suppressing deterioration over time of the heat-shielding property, and this function is considered to be caused by the metal salt capturing moisture and radicals in the heat ray absorbing layer.
  • the metal constituting the metal salt is not particularly limited.
  • Zn, Mg, Ni, In, and Sn are preferable from the viewpoint of preventing discoloration, and Zn, Mg, and Ni are more preferable.
  • the metal salt may be an organic acid salt or an inorganic acid salt.
  • it may be a carboxylate, carbonyl complex, carbonate, phosphate, perchlorate, hypochlorite, chlorite, chlorate, or hydrochloride.
  • perchlorate for example, nickel perchlorate hexahydrate
  • carboxylate is more preferable, and carboxylate is more preferable.
  • the carboxylic acid constituting the more preferable carboxylate as the metal salt is not particularly limited, but for example, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, 2-ethylhexanoic acid, naphthenic acid, Enanthate, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, oleic acid, linoleic acid, linolenic acid, arachidonic acid, docosahexaenoic acid, eicosapentanoic acid, oxalic acid , Malonic acid, succinic acid, benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, gallic acid, mellitic acid, cinnamic acid, pyruvic acid, lactic acid,
  • Examples of the ⁇ -diketone constituting the carbonyl complex salt include acetylacetone, benzoylacetone, benzoyltrifluoroacetone, hexafluoroacetylacetone, 2-thenoyltrifluoroacetone and the like.
  • acetic acid, 2-ethylhexanoic acid, and stearic acid are preferable from the viewpoint of discoloration prevention effect.
  • 2-ethylhexanoic acid is more preferable from the viewpoint of particularly good compatibility with the heat ray absorbing layer and excellent haze suppression effect.
  • Specific metal salts are not particularly limited, and examples thereof include Ni perchlorate, Mg stearate, Zn acetate, and bis (2-ethylhexanoic acid) Zn.
  • the content of the metal salt is not particularly limited, but is preferably 0.005 to 10% by mass with respect to the total mass of the components excluding the solvent of the coating solution for the heat ray absorbing layer.
  • the content of the metal salt is 0.005% by mass or more, the discoloration preventing effect of the heat ray absorbing layer is further increased.
  • the reason for this is considered to be that the metal salt has a good effect of capturing moisture and radicals in the heat ray absorbing layer.
  • the adhesive improvement effect of a heat ray absorption layer increases more as content of a metal salt is 10 mass% or less.
  • the content of the metal salt is more preferably 0.01 to 1.0% by mass, and still more preferably 0.05 to 1.0% by mass.
  • the thickness of the heat ray absorbing layer is 10 ⁇ m or less.
  • the film thickness of the heat ray absorbing layer exceeds 10 ⁇ m, the difference in shrinkage between the adjacent resin film or the heat ray reflective layer increases, the heat ray absorbing layer is easily broken, and the adhesion with the adjacent resin film or the heat ray reflective layer is deteriorated.
  • the thickness of the heat ray absorbing layer is preferably in the range of 1 to 7 ⁇ m, which is preferable in terms of a good balance between durability and weather resistance.
  • the heat ray absorbing layer of the present invention preferably has a hard coat property.
  • the film thickness is 1 ⁇ m or more, the heat ray can be sufficiently absorbed, and a sufficient hardness can be obtained. It is excellent in that the effect of the invention can be effectively expressed without providing a hard coat layer on the heat ray absorbing layer. That is, it can be said that the heat ray absorbing layer is used as a hard coat layer in this embodiment.
  • the film thickness of a heat ray absorption layer is in the said range, it does not exclude providing a hard-coat layer, but it is excellent in the penetration
  • the hard coat layer may contain inorganic fine particles other than the infrared absorber.
  • Preferable inorganic fine particles include fine particles of an inorganic compound containing a metal such as titanium, silica, zirconium, aluminum, magnesium, antimony, zinc or tin.
  • the average particle size of the inorganic fine particles is preferably 1000 nm or less, and more preferably in the range of 10 to 500 nm, from the viewpoint of ensuring visible light transmittance.
  • inorganic fine particles have a higher bonding strength with the curable resin forming the hard coat layer, they can be prevented from falling out of the hard coat layer, so that a photopolymerization reactivity such as monofunctional or polyfunctional acrylate is present. Those having a functional group introduced on the surface are preferred.
  • the hue can be adjusted by adding dyes or pigments to the hard coat layer (heat ray absorbing layer).
  • dyes or pigments for example, cadmium red, molybdenum red, chromium permillion, chromium oxide, viridian, titanium cobalt green, cobalt green, cobalt chrome green, Victoria green, ultramarine blue, ultramarine blue, bitumen, Berlin blue, miloli blue, cobalt blue, cerulean blue,
  • Colored inorganic pigments such as cobalt silica blue, cobalt zinc blue, manganese violet, mineral violet, and cobalt violet, organic pigments such as phthalocyanine pigments, and anthraquinone dyes are preferably used.
  • Examples of the method for forming the hard coat layer include a method in which a coating solution for hard coat layer is applied on the heat ray absorbing layer by wire bar coating, spin coating, dip coating, etc., and film formation is performed. It can also be formed by a dry film forming method such as Moreover, it is possible to apply and form a film using a continuous coating apparatus such as a die coater, a gravure coater, or a comma coater. For example, in the case of a polysiloxane-based hard coat material, after application, after drying the solvent, a heat treatment is performed in a temperature range of 50 to 150 ° C.
  • the treatment is carried out in the range of 40 to 80 ° C. for 2 days or more.
  • the reactivity varies depending on the irradiation wavelength, the illuminance, and the light amount of the active energy ray, and therefore it is necessary to select optimum conditions depending on the resin to be used.
  • the illuminance is preferably 50 to 1500 mW / cm 2 and the irradiation energy amount is preferably 50 to 1500 mJ / cm 2 .
  • the solvent used when the hard coat layer (heat ray absorbing layer) is formed by a coating method is not particularly limited.
  • solvents can be used alone or in combination.
  • the coating liquid for forming the hard coat layer may contain a surfactant.
  • a coating film When a coating film is formed with a coating liquid for forming a hard coat layer containing a surfactant, it becomes a highly leveled coating film, thus preventing the formation of parts with a high or low residual solvent amount. And it can be expected to improve the adhesion of the hard coat layer.
  • water repellency, slipperiness, etc. can be provided to the hard coat layer.
  • a fluorosurfactant is preferably used from the viewpoint of leveling properties, water repellency, and slipperiness of the coating solution.
  • these surfactants those described above for the heat-absorbing layer can be used.
  • the amount of the surfactant in the hard coat layer can be adjusted by changing the blending amount of the surfactant in the hard coat coating solution, and the mass of the surfactant per dry mass of the hard coat layer can be adjusted.
  • the content is preferably 0.01 to 5% by mass.
  • a resin film may be disposed on at least one surface of the heat ray absorbing layer.
  • a heat ray reflective layer 3 composed of an alternating laminate of a high refractive index layer and a low refractive index layer containing a polymer from the light incident side, a resin film 4, and a heat ray containing cesium-containing tungsten oxide.
  • the absorption layer 5 is configured to be laminated in this order.
  • the applicable resin film is preferably a film support, and the film support may be transparent or opaque, and various resin films can be used.
  • polyester films polyethylene, polypropylene, etc.
  • polyester films polyethylene terephthalate, polyethylene naphthalate, etc.
  • polyvinyl chloride polyvinyl chloride
  • cellulose triacetate etc.
  • polyester films are preferred.
  • polyester film it does not specifically limit as a polyester film (henceforth polyester)
  • polyester it is preferable that it is polyester which has the film formation property which has a dicarboxylic acid component and a diol component as main structural components.
  • the thickness of the resin film used in this embodiment is preferably 10 to 300 ⁇ m, particularly 20 to 150 ⁇ m.
  • Two or more resin films may be stacked, and in this case, each resin film may be the same or different.
  • each resin film may be the same or different.
  • the infrared shielding film 1 of this form may have an adhesive layer on the heat ray reflective layer opposite to the layer on which the heat ray absorbing layer is formed.
  • the so-called water pasting method is repositioned and positioned. It is preferably used from the viewpoint of correction. For this reason, a pressure-sensitive adhesive having a low adhesive strength in the presence of water is preferable.
  • the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer is not particularly limited, and known pressure-sensitive adhesives can be used in the same manner. Specific examples include acrylic adhesives, silicon adhesives, urethane adhesives, polyvinyl butyral adhesives, ethylene-vinyl acetate adhesives, and the like. Among these, acrylic pressure-sensitive adhesives are preferable from the viewpoints of durability, transparency, and ease of adjustment of adhesive properties.
  • the acrylic pressure-sensitive adhesive uses an acrylic polymer that is mainly composed of alkyl acrylate and copolymerized with a polar monomer component.
  • the alkyl acrylate ester is an alkyl ester of acrylic acid or methacrylic acid and is not particularly limited.
  • Commercially available products may be used as the pressure-sensitive adhesive. Specifically, BPS5978 manufactured by Toyo Ink Co., Ltd., Coponil (registered trademark) manufactured by Nippon Synthetic Chemical Industry Co., Ltd. (for example, N-2147, 5697, 5698). , 5705L) can be used.
  • an acrylic adhesive curing agent can be used.
  • the curing agent for the acrylic pressure-sensitive adhesive is not particularly limited, and for example, an isocyanate-based, epoxy-based, or alidiline-based curing agent can be used.
  • an aromatic type such as tonoleylene diisocyanate (TDI) can be preferably used in order to obtain a stable adhesive force even after long-term storage and to form a harder adhesive layer.
  • TDI tonoleylene diisocyanate
  • BXX5134 manufactured by Toyo Ink Co., Ltd. can be used.
  • the addition amount of the curing agent (in terms of solid content) is preferably 2 to 9% by mass, more preferably 3 to 7% by mass with respect to the pressure-sensitive adhesive. If it is such a range, an adhesive will not remain easily and sufficient adhesive force can also be ensured.
  • the adhesive layer may contain an additive in addition to the adhesive.
  • the additive is not particularly limited.
  • Coloring agents, adhesion regulators and the like it is preferable that an adhesion layer contains a ultraviolet absorber.
  • the amount of sunlight (particularly infrared light) entering the heat ray absorbing layer (the sun of the heat ray absorbing layer) by providing an adhesive layer containing an ultraviolet absorber on the sunlight incident side (light incident side) with respect to the heat ray absorbing layer (Light absorption) is further reduced.
  • the ultraviolet absorber is not particularly limited, and a known ultraviolet absorber can be used.
  • benzophenone ultraviolet absorbers such as 2,4-dihydroxy-benzophenone and 2-hydroxy-4-methoxy-benzophenone; 2- (2′-hydroxy-5-methylphenyl) benzotriazole, 2- (2′-hydroxy Benzotriazole UV absorbers such as -3 ', 5'-di-t-butylphenyl) benzotriazole; phenyl salicylate, 2-4-di-t-butylphenyl-3,5-di-t-butyl Phenyl salicylate UV absorbers such as -4-hydroxybenzoate; hindered amine UV absorbers such as bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate; 2,4-diphenyl-6- ( 2-hydroxy-4-methoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2 Triazine-based UV
  • the ultraviolet absorber includes a compound having a function of converting the energy held by ultraviolet rays into vibrational energy in the molecule and releasing the vibrational energy as thermal energy.
  • an ultraviolet absorber individually or in mixture of 2 or more types.
  • a synthetic product or a commercially available product may be used. Examples of commercially available products include, for example, Tinuvin (registered trademark) 320, Tinuvin (registered trademark) 328, Tinuvin (registered trademark) 234, Tinuvin (registered trademark) 477, Tinuvin (registered trademark) 1577, and Tinuvin (registered trademark) 622.
  • ADK STAB registered trademark LA-31 (above, manufactured by ADEKA CORPORATION)
  • SEESORB registered trademark 102
  • SESORB registered trademark
  • SEESORB registered trademark
  • the addition amount of the ultraviolet absorber (in terms of solid content) is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass with respect to the pressure-sensitive adhesive. If it is such a range, the sunlight absorption amount of a heat ray absorption layer can be reduced more effectively.
  • the thickness of the adhesive layer is preferably 1 to 100 ⁇ m, more preferably 3 to 50 ⁇ m. If it is 1 micrometer or more, there exists a tendency for adhesiveness to improve and sufficient adhesive force is acquired. On the other hand, if the thickness is 100 ⁇ m or less, not only the transparency of the infrared shielding film is improved, but also after the infrared shielding film is attached to the window glass, when it is peeled off, cohesive failure does not occur between the adhesive layers. There is a tendency for the remaining adhesive to disappear.
  • the coating liquid for adhesion layers is apply
  • a method of bonding the adhesive layer and the heat ray reflective layer after forming the adhesive layer is preferable.
  • Examples of the separator used at this time include a silicone-coated release PET film (separator SP-PET (brand: PET-O2-BU; manufactured by Mitsui Chemicals, Inc.)), a silicone-coated PE film, and the like.
  • the method of applying the coating solution for the adhesive layer on the separator is not particularly limited, and examples thereof include a method of applying the coating solution by wire bar coating, spin coating, dip coating, etc., and forming a film. It is possible to apply and form a film using a continuous coating apparatus such as a coater or a comma coater.
  • adhesive strength is calculated
  • the infrared shielding film provided by this form can be applied to a wide field.
  • it can be used as a window pasting film (infrared shielding film) that is bonded to facilities exposed to sunlight for a long period of time, such as an outdoor window of a building or an automobile window, and imparts an infrared shielding effect.
  • an infrared shielding body using the above-described infrared shielding film is provided.
  • an infrared shielding body in which the above-described infrared shielding film is attached to a light-transmitting substrate is also provided.
  • the infrared shielding body has a structure in which an infrared shielding film is bonded (bonded) to a light-transmitting substrate by an adhesive layer provided on the outermost layer.
  • the light transmissive substrate include, for example, glass, polycarbonate resin, polysulfone resin, acrylic resin, polyolefin resin, polyether resin, polyester resin, polyamide resin, polysulfide resin, unsaturated polyester resin, epoxy resin, Examples include melamine resin, phenol resin, diallyl phthalate resin, polyimide resin, urethane resin, polyvinyl acetate resin, polyvinyl alcohol resin, styrene resin, and vinyl chloride resin. Further, the light-transmitting substrate may have total light transmittance or may have light transmittance for a partial wavelength region.
  • “Curved surface” means a surface having a radius of curvature of 3 m or less. The reason why the radius of curvature is 3 m or less is that when the radius of curvature exceeds 3 m, there is no difference from a planar light-transmitting substrate.
  • colloidal silica aqueous solution solid content: 10% by mass
  • OXS average particle size of primary
  • ⁇ Preparation of coating solution for high refractive index layer> (Preparation of silica-attached titanium dioxide sol) After adding 2 parts by mass of pure water to 0.5 parts by mass of titanium oxide sol having a solid content of 15.0% by mass (SRD-W, volume average particle size: 5 nm, rutile titanium dioxide particles, manufactured by Sakai Chemical Co., Ltd.), 90 Heated to ° C. Next, 0.5 parts by mass of an aqueous silicic acid solution (sodium silicate 4 (manufactured by Nippon Chemical Industry Co., Ltd.) diluted with pure water so that the SiO 2 concentration becomes 0.5 mass%) was gradually added. Then, heat treatment was performed at 175 ° C.
  • an aqueous silicic acid solution sodium silicate 4 (manufactured by Nippon Chemical Industry Co., Ltd.) diluted with pure water so that the SiO 2 concentration becomes 0.5 mass
  • TiO 2 titanium dioxide sol
  • Silica-attached titanium dioxide sol (volume average particle size: 9 nm) was obtained.
  • the lowermost layer and the uppermost layer were low refractive index layers, and other than that, the low refractive index layers and the high refractive index layers were alternately laminated.
  • the low refractive index layer immediately above the resin film was the first layer.
  • Low refractive index layer 1, 3, 5, 7, 9, 11, 13, 15, 17, 19, 21st layer; 150 nm
  • High refractive index layer 2, 4, 6, 8, 12, 14, 16, 18, 20th layer; 110 nm, 10th layer (thickened layer); 230 nm (total 2870 nm).
  • An adhesive layer coating solution was prepared according to the following formulation.
  • the above adhesive layer coating solution was dried with a comma coater on the silicon surface of separator SP-PET (brand: PET-O2-BU) (Mitsui Chemicals Tosero Co., Ltd.), which is a release film (release layer). Is applied at a temperature of 10 ⁇ m, dried at 80 ° C. for 1 minute, fed from the second sheet with a resin film on which the heat ray reflective layer is formed, laminated with the heat ray reflective layer, and adhered onto the heat ray reflective layer. A layer was formed.
  • separator SP-PET brand: PET-O2-BU
  • release film release layer
  • Example 2 In ⁇ Formation of Heat Ray Reflective Layer on Resin Film> in Example 1, 15 layers were simultaneously applied (total film thickness of heat ray reflective layer; 2.3 ⁇ m).
  • the infrared shielding film sample 2 was produced like Example 1 except having changed so that it might become.
  • Low refractive index layers 1, 3, 5, 7, 9, 11, 13, 15th layer; 170 nm
  • High refractive index layer 2, 4, 8, 10, 12, 14th layer; 120 nm, 6th layer (thickened layer); 250 nm (2330 nm in total).
  • Example 3 In ⁇ Formation of Heat Ray Reflective Layer on Resin Film> in Example 1, 11 layers were simultaneously applied (total film thickness of heat ray reflective layer: 1.9 ⁇ m), and the coating amount was changed and the film thickness upon drying was as follows: The infrared shielding film sample 3 was produced like Example 1 except having changed so that it might become.
  • Low refractive index layer 1, 3, 5, 7, 9, 11th layer; 180 nm
  • High refractive index layer 2, 6, 8, 10th layer; 130 nm, 4th layer (thickened layer); 300 nm (total 1900 nm).
  • Example 4 In ⁇ Formation of heat ray reflective layer on resin film> in Example 1, 41 layers are simultaneously applied (total thickness of heat ray reflective layer: 5.8 ⁇ m), and the coating amount is changed and the film thickness upon drying is as follows.
  • the infrared shielding film sample 4 was produced like Example 1 except having changed so that it might become.
  • Example 5 In Example 1 (Preparation of coating solution for heat ray absorbing layer), antimony-doped tin oxide (ATO) particles (trade name: SR35M, manufactured by ANP) were used as cesium-containing tungsten oxide particles. An infrared shielding film sample 5 was produced in the same manner as in Example 1 except that an amount of 1/5 (mass ratio) of the content was added.
  • ATO antimony-doped tin oxide particles
  • Example 1 formation of heat ray absorbing layer; preparation of infrared shielding film sample 1
  • the heat ray absorbing layer was formed under the condition that the dry film thickness was 11.0 ⁇ m.
  • an infrared shielding film sample 6 was produced.
  • Example 2 In ⁇ Formation of Heat Ray Reflective Layer on Resin Film> in Example 1, 19 layers are simultaneously applied (total film thickness of heat ray reflective layer: 3.2 ⁇ m), and the coating amount is changed and the film thickness upon drying is as follows.
  • the infrared shielding film sample 7 was produced like Example 1 except having changed so that it might become.
  • Low refractive index layer 3, 5, 7, 9, 11, 13, 15, 17th layer; 150 nm, 1st layer (thickened layer); 800 nm, 19th layer; 100 nm High refractive index layers: 2, 4, 6, 8, 10, 12, 14, 16, 18th layer; 120 nm (total 3180 nm).
  • (PMMA (152 nm) / PEN (137 nm)) 64 means that 64 units each having a PMMA having a thickness of 152 nm and a PEN having a thickness of 137 nm stacked in this order are stacked. It is.
  • HC layer tungsten oxide-containing layer
  • Beam set 577 (Arakawa Chemical Industries, Ltd.) was used as an ultraviolet curable resin, and methyl ethyl ketone was added as a solvent.
  • a fluorine-based surfactant (trade name: Footage (registered trademark) 650A, manufactured by Neos Co., Ltd.), 20% by mass of the same cesium-doped tungsten oxide dispersion as in Example 1,
  • a hard coating layer coating solution was prepared by adjusting the total solid content to 40 parts by mass.
  • the hard coat layer coating solution prepared above is applied to the outermost layer opposite to the layer on which the adhesive layer has been formed with a gravure coater under the condition that the dry layer thickness is 5.0 ⁇ m, and at 90 ° C. for 1 minute. Dried.
  • an ultraviolet ray lamp is used to cure the coating film by irradiating ultraviolet rays under the conditions of an illuminance of 100 mW / cm 2 and an irradiation amount of 0.5 J / cm 2 to form a hard coat layer, and an infrared shielding film sample 8 was produced.
  • This infrared shielding film sample 8 has a layer structure in which an adhesive layer, a reflective layer, and a hard coat layer are laminated in this order from the light incident side.
  • infrared shielding film samples 1 to 8 For the infrared shielding film samples 1 to 8 produced in the above examples and comparative examples, infrared reflectance / visible light transmittance, weather resistance (discoloration ( ⁇ E), cracking of heat ray absorbing layer, edge portion) are as follows. (Peeling) was evaluated. The results are shown in Table 1 below.
  • the separator SP-PET peeleling film
  • the adhesive layer of the infrared shielding film sample is attached to 6 cm ⁇ 12 cm glass, and the glass side is arranged to be the light incident side.
  • Xenon weather meter temperature: BPT63 ° C, humidity: 50% RH, SX-75 manufactured by Suga Test Instruments Co., Ltd.
  • radiation intensity 60W / m 2 irradiation + rainfall 18 minutes / irradiation 120 minutes cycle conditions
  • the L * value, a * value, and b * value were calculated from the transmitted light before and after irradiation, and the color difference ( ⁇ E) was calculated from the difference.
  • a smaller value of ⁇ E means that the degree of coloring due to exposure to xenon light is smaller.
  • the transmitted light before and after irradiation was measured using a spectrophotometer (U-4000 type) (using an integrating sphere, manufactured by Hitachi, Ltd.).
  • the film thickness of the heat ray absorbing layer of Comparative Example 3 in Table 1 indicates the film thickness of the hard coat layer (HC layer).
  • the average reflectance at a wavelength of 800 to 1300 nm is 30% or more, and the infrared shielding films of Examples 1, 4, and 5 (having a wavelength of 1300 to 1600 nm).
  • the average reflectance is also high, and it is not clear which action and effect), but at least as compared with the infrared shielding films of Examples 3 and 4, the heat ray absorbing layer is effectively prevented from cracking. I found out that I could do it.
  • the infrared shielding films of Examples 1 to 5 are used. It was found that the edge peeling of the infrared shielding film can be effectively prevented as compared with the film.
  • the heat ray absorbing layer and further Example 5 containing antimony-doped tin oxide (ATO) are compared with the infrared shielding films of Examples 1 to 4.
  • discoloration ( ⁇ E) which is an evaluation item of weather resistance, cracking of the heat ray absorbing layer, and peeling off of the end portions are enhanced in a balanced manner, and in particular, the occurrence of discoloration ( ⁇ E) can be effectively prevented (evaluation ⁇ ). )I understood it.
  • Infrared shielding film 1 ... Infrared shielding film, 2 ... Adhesive layer, 3 ... heat ray reflective layer, 3a ... high refractive index layer, 3a '... thickened layer (high refractive index layer), 3b ... low refractive index layer, 4 ... Resin film, 5 ... heat ray absorbing layer, 6 ... Light transmissive substrate, 10: Infrared shield.

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Abstract

La présente invention vise à fournir un film de protection contre les infrarouges ayant une bonne résistance aux intempéries et des caractéristiques de protection thermique élevées. À cet effet, l'invention concerne un film de protection contre les infrarouges obtenu par stratification, depuis le côté d'incidence de lumière, d'une couche réfléchissant la chaleur composée de corps stratifiés alternés d'une couche à indice de réfraction élevé et d'une couche à indice de réfraction faible contenant un polymère, et d'une couche absorbant la chaleur contenant un oxyde de tungstène contenant du césium, le film étant caractérisé en ce que la réflectance moyenne dans la plage de longueur d'onde de 1300 à 1600 nm est de 8 % ou plus, et l'épaisseur de la couche absorbant la chaleur est de 10 µm ou moins.
PCT/JP2016/063906 2015-05-29 2016-05-10 Film de protection contre les infrarouges WO2016194560A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018124449A (ja) * 2017-02-01 2018-08-09 Tdk株式会社 調光体用の積層体、及び調光体
JP2021524610A (ja) * 2018-07-10 2021-09-13 ディーエスエム アドバンスド ソーラー ビー．ブイ． Ｎｉｒ反射性多層材料シート
JP2022036065A (ja) * 2020-08-21 2022-03-04 イノックス アドバンスド マテリアルズ カンパニーリミテッド ディスプレイ用接着フィルム
WO2022165886A1 (fr) * 2021-02-04 2022-08-11 宁波瑞凌新能源科技有限公司 Film de refroidissement par rayonnement et produit le comprenant

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020132452A (ja) * 2019-02-15 2020-08-31 日本化薬株式会社 熱線遮蔽構造体、熱線遮蔽シート、熱線遮蔽中間膜、及び合わせガラス

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013179902A1 (fr) * 2012-05-31 2013-12-05 コニカミノルタ株式会社 Objet de protection contre les infrarouges
WO2014010532A1 (fr) * 2012-07-10 2014-01-16 コニカミノルタ株式会社 Film de protection contre les infrarouges ayant une structure de film multicouche diélectrique
WO2014185518A1 (fr) * 2013-05-16 2014-11-20 日本化薬株式会社 Feuille de protection contre les infrarouges, son procédé de fabrication et son application

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013179902A1 (fr) * 2012-05-31 2013-12-05 コニカミノルタ株式会社 Objet de protection contre les infrarouges
WO2014010532A1 (fr) * 2012-07-10 2014-01-16 コニカミノルタ株式会社 Film de protection contre les infrarouges ayant une structure de film multicouche diélectrique
WO2014185518A1 (fr) * 2013-05-16 2014-11-20 日本化薬株式会社 Feuille de protection contre les infrarouges, son procédé de fabrication et son application

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018124449A (ja) * 2017-02-01 2018-08-09 Tdk株式会社 調光体用の積層体、及び調光体
JP2021524610A (ja) * 2018-07-10 2021-09-13 ディーエスエム アドバンスド ソーラー ビー．ブイ． Ｎｉｒ反射性多層材料シート
JP7505412B2 (ja) 2018-07-10 2024-06-25 エンデュランス ソーラー ソリューションズ ビー．ブイ． Ｎｉｒ反射性多層材料シート
JP2022036065A (ja) * 2020-08-21 2022-03-04 イノックス アドバンスド マテリアルズ カンパニーリミテッド ディスプレイ用接着フィルム
WO2022165886A1 (fr) * 2021-02-04 2022-08-11 宁波瑞凌新能源科技有限公司 Film de refroidissement par rayonnement et produit le comprenant
US11867434B1 (en) 2021-02-04 2024-01-09 Ningbo Radi-Cool Advanced Energy Technologies Co., Ltd. Radiative cooling film and product thereof

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