WO2012096304A1 - 遠赤外線反射積層体 - Google Patents
遠赤外線反射積層体 Download PDFInfo
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- WO2012096304A1 WO2012096304A1 PCT/JP2012/050372 JP2012050372W WO2012096304A1 WO 2012096304 A1 WO2012096304 A1 WO 2012096304A1 JP 2012050372 W JP2012050372 W JP 2012050372W WO 2012096304 A1 WO2012096304 A1 WO 2012096304A1
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
Definitions
- the present invention relates to a far-infrared reflective laminate.
- films see Patent Document 1 and Patent Document 2
- glass provided with an infrared reflective layer
- These infrared reflectors are provided with an infrared reflective layer having a structure in which a metal thin film layer made of gold, silver, copper, or the like is laminated with a metal oxide layer such as titanium oxide, ITO, or zinc oxide on a substrate that transmits visible light. It is possible to reflect near infrared rays while having visible light transmittance.
- These infrared reflectors are used for purposes such as improving the cooling effect by blocking the solar energy that enters from the windows of buildings and vehicles, and improving the cooling effect in a refrigerated showcase.
- Patent Document 1 and Patent Document 2 as means for physically protecting the infrared reflective layer, acrylic resins such as polymethyl methacrylate, silicon resins such as polymers obtained from ethyl silicate, polyester resins, melamine resins , Fluororesins and the like are described. It is also known to use a polyolefin-based resin as a protective layer.
- infrared reflectors When using infrared reflectors to obtain heat insulation or heat shielding effects, for those that have large energy in the near infrared region, such as sunlight, energy can be controlled by reflecting or absorbing near infrared rays. effective. However, it is important to reflect far-infrared rays in order to obtain effects such as suppressing the outflow of energy from the room in winter.
- the infrared reflector formed by the conventional technology absorbs far infrared rays because the hard coat layer and glass layer protecting the surface of the infrared reflecting layer absorb far infrared rays. It was not possible to avoid a significant drop.
- a polyolefin-based resin such as a biaxially stretched polypropylene film as a protective layer with little absorption of far-infrared rays, but the surface of the protective layer is inadequate because of the soft surface of the protective layer during construction and use. There was a problem that it was easily scratched and could not exhibit sufficient protection performance as a product used for windows.
- an object of the present invention is to provide a far-infrared reflective laminate having both a surface protection performance that prevents the surface from being scratched and a good far-infrared reflection performance.
- a far-infrared reflective laminate in which the following layers [A] to [C] are arranged in this order; [A] substrate; [B] A far-infrared reflective layer having the following structure [B1] or [B2]; [B1] a single layer structure of metal containing 95 to 100% by mass of silver (Ag); [B2] a multilayer structure comprising a metal layer containing 95 to 100% by mass of silver (Ag) and a layer containing a metal oxide and / or metal nitride and having a refractive index of 1.5 to 3; [C] A surface hard coat layer comprising a cross-linked resin having at least one polar group selected from the group consisting of a phosphoric acid group, a sulfonic acid group and an amide group, and having a thickness of 0.4 to 2.0 ⁇ m.
- Another embodiment of the present invention is a far-infrared reflective laminate in which a substrate, a metal layer, and a surface hard coat layer are arranged in this order, and the metal layer contains 95 to 100% by mass of silver,
- the thickness of the surface hard coat layer is 0.4 to 2.0 ⁇ m
- the far-infrared reflectance of the far-infrared reflective laminate is 60% or more
- the surface scratch resistance is 10/10 mm or less. It is a far-infrared reflective laminate.
- the present invention it is possible to provide a far-infrared reflective laminate having a surface that is hardly damaged and that has good far-infrared reflective performance.
- FIG. 6 is a schematic cross-sectional view of a far-infrared reflective laminate of Example 3.
- FIG. 6 is a schematic cross-sectional view of a far-infrared reflective laminate of Example 3.
- the substrate [A] used in the present invention is selected from resins, metals, metal oxides, and natural materials such as paper and wood according to the application to which the far-infrared reflective laminate is applied.
- the substrate [A] is preferably a transparent resin or transparent glass that transmits visible light.
- the substrate [A] is more preferably a transparent resin film having flexibility.
- resin film materials include aromatic polyesters represented by polyethylene terephthalate and polyethylene-2,6-naphthalate; aliphatic polyamides represented by nylon 6 and nylon 66; aromatic polyamides; represented by polyethylene and polypropylene.
- Examples thereof include polyolefins and polycarbonates.
- aromatic polyesters are preferable in terms of cost, ease of handling, and heat resistance against heat received during processing of the laminate, and polyethylene terephthalate or polyethylene-2,6-naphthalate is particularly preferable, particularly polyethylene.
- a terephthalate film is preferred.
- the biaxially stretched film which raised mechanical strength is preferable, and especially a biaxially stretched polyethylene terephthalate film is preferable.
- the thickness of the film is preferably in the range of 5 to 250 ⁇ m, and more preferably 15 to 150 ⁇ m.
- the far-infrared reflective layer [B] is a layer having the following [B1] or [B2] structure excellent in visible light transmission characteristics and far-infrared reflection characteristics.
- [B1] Single layer structure of metal containing 95 to 100% by mass of silver (Ag)
- [B2] Metal layer containing 95 to 100% by mass of silver (Ag) and metal oxide and / or metal nitride
- a multilayer structure comprising a layer having a refractive index of 1.5 to 3.
- a metal layer with excellent conductivity has the ability to reflect far-infrared rays, and in order to improve the far-infrared reflectivity, it is known that the metal layer may be used and its conductivity increased. ing.
- the metal layer is thickened to increase conductivity, visible light absorption and reflection by the metal layer increase, and the visible light transmission performance is lowered. Therefore, in order to obtain high far-infrared reflection performance and at the same time excellent visible light transmittance, as a metal layer that is commonly included in the structures of [B1] and [B2], conductivity and visible light transmittance are improved. It is preferable to use a metal layer containing 95 to 100% by mass of excellent Ag.
- the material of the metal layer containing 95 to 100% by mass of Ag As the material of the metal layer containing 95 to 100% by mass of Ag, Au, Pt, Pd, Cu, Bi, Ni, Nd, Mg, Zn, Al, Ti, Y, Eu, Pr, Ce, Sm, Ca, An alloy of at least one metal selected from Be, Si, Ge, Cr, Co, Ni and the like and Ag is preferable. By using an alloy with such a metal, it is possible to prevent Ag from deteriorating due to reaction with sulfur, oxygen, or the like, or to prevent occurrence of defects such as agglomeration when forming a metal layer. In order to improve the visible light transmission characteristics and the far-infrared reflection characteristics, the Ag content of the metal layer is preferably 95 to 100% by mass, and more preferably 98 to 100% by mass or more.
- the metal used as an alloy with Ag can be appropriately selected according to the required far-infrared reflection performance, visible light transmittance, chemical resistance, and environmental resistance.
- the alloy preferably contains 0.2 to 2% by mass of a metal selected from Au, Pd, Cu, Bi and Nd.
- a metal selected from Au, Pd, Cu, Bi and Nd a metal selected from Au, Pd, Cu, Bi and Nd.
- Ag alloys such as Ag-1 mass% Au, Ag-1 mass% Pd-1 mass% Cu, Ag-1 mass% Bi-1 mass% Au, Ag-0.2 mass% Nd-1 mass% Au, etc. Is preferred.
- the single-layer structure means that the far-infrared reflective layer [B] consists of a single metal layer containing 95 to 100% by mass of silver (Ag). It means to become.
- Such a single layer structure is advantageous in terms of stabilization of film quality and improvement of productivity because of its simple structure.
- the thickness of the [B] layer is preferably 5 to 20 nm, and more preferably 10 to 15 nm.
- Y, Ti, Zr, Nb, Ta, Cr, Mo, W, Ru, Ir, Pd, Pt, Cu so as to cover one side or both sides of the metal layer containing 95 to 100% by mass of Ag.
- a thin metal layer made of a metal selected from Au, Al, Ce, Nd, Sm, Tb, or a mixture thereof.
- the thickness of the metal thin layer is preferably 0.5 nm or more. In order to obtain good visible light transmission performance, the thickness of the metal thin layer is preferably 10 nm or less.
- the thickness of the metal thin layer is more preferably 1 nm or more and 5 nm or less.
- the metal thin layer is a protective layer provided to protect a metal layer containing 95 to 100% by weight of Ag from corrosion and has little influence on characteristics such as far-infrared reflection performance. Therefore, when considering the thickness of the [B] layer for characteristics such as far-infrared reflection performance, the metal thin layer is excluded.
- the surface resistance of the [B] layer is 3 to 30 ⁇ / ⁇ . Preferably, it is 5 to 10 ⁇ / ⁇ .
- the surface resistance of the [B] layer is preferably less than 3 ⁇ / ⁇ in order to improve the infrared reflection performance.
- the surface resistance is a value obtained by measurement by a 4-terminal 4-probe method constant current application method (hereinafter the same).
- the multilayer structure is a metal layer and metal oxide in which the far-infrared reflective layer [B] contains 95 to 100% by mass of silver (Ag). And / or a structure in which one or more layers each including a metal nitride and having a refractive index of 1.5 to 3 (hereinafter sometimes referred to as a high refractive index layer) are stacked.
- a combination of a metal layer and a high refractive index layer is preferable for obtaining good visible light transmission characteristics while suppressing interface reflection.
- the metal layer containing 95 to 100% by mass of Ag has a low refractive index of, for example, 0.3 or less, and the visible light transmittance may be lowered due to the influence of reflection at the interface.
- the interface reflection of visible light can be reduced by using a multilayer structure in which a metal layer and a high refractive index layer having a refractive index of 1.5 to 3 are combined.
- the far-infrared reflective layer [B] has a structure in which a plurality of metal layers and a plurality of high refractive index layers are alternately stacked in order to obtain good visible light transmission characteristics while suppressing interface reflection. With such a multilayer structure, the absorption characteristics of visible light can be controlled, and the optical characteristics can be further improved.
- Examples of the material for the high refractive index layer include titanium oxide, zirconium oxide, yttrium oxide, niobium oxide, tantalum oxide, zinc oxide, tin-doped indium oxide (ITO), oxides such as tin oxide and bismuth oxide, and silicon nitride.
- ITO tin-doped indium oxide
- a nitride, a mixture thereof, or a metal-doped carbon such as aluminum or copper doped with carbon or the like can be appropriately selected and used according to the application.
- the refractive index and thickness of the high refractive index layer can be appropriately selected so as to suppress interface reflection in accordance with the refractive index and thickness of the metal layer and the layer configuration.
- the total thickness of the metal layer containing 95 to 100% by mass of Ag contained in the far-infrared reflective layer [B] is 5 to 20 nm. It is preferably 10 to 15 nm, and more preferably.
- the above-described metal thin layer covering the metal layer may be further provided. In this case, the thickness of the metal thin layer is considered excluding the thickness of the metal layer containing 95 to 100% by mass of Ag contained in the layer [B].
- the thickness per layer of the high refractive index layer is set to 2 in order to suppress the interface reflection between the respective layers and obtain a good visible light transmittance. It is preferably ⁇ 200 nm, more preferably 5 to 100 nm.
- the total surface resistance of the metal layer containing 95 to 100% by mass is preferably 3 to 30 ⁇ / ⁇ , and more preferably 5 to 10 ⁇ / ⁇ .
- the total surface resistance Pst of the metal layer is such that the far-infrared reflective layer [B] includes n metal layers containing 95 to 100% by mass of Ag, and the thickness of each layer is t1 to tn.
- the surface hard coat layer [C] in the present invention contains a crosslinked resin having one or more polar groups selected from the group consisting of a phosphoric acid group, a sulfonic acid group, and an amide group, and has a thickness of 0.4 to 2.
- the surface hard coat layer [C] protects the surface of the far-infrared reflective laminate of the present invention.
- the surface hard coat layer [C] may have a multilayer structure as well as a single layer structure. In the case of a multilayer structure, all the layers from the outside of the far-infrared reflective layer [B] to the outermost surface of the far-infrared reflective laminate are the surface hard coat layer [C].
- the surface hard coat layer is composed of (i) a single layer configuration of a layer containing a crosslinked resin having the polar group, (ii) a layer containing a crosslinked resin having the polar group and other crosslinked resins (having the polar group And (iii) a crosslinked resin having the polar group and another crosslinked resin (which may or may not have the polar group).
- the layer may be any of a tilted configuration in which the composition of both components continuously changes in the thickness direction.
- At least a layer in contact with the far-infrared reflective layer [B] (in the case of a multilayer configuration) or a region in contact with the far-infrared reflective layer [B] (inclined configuration) Case) contains a crosslinked resin having the polar group.
- polar groups such as phosphoric acid, amide and sulfonic acid are used.
- Acrylic acid derivative or methacrylic acid derivative is mixed with an acrylic hard coat agent that forms a crosslink by irradiating electromagnetic waves such as ultraviolet rays (hereinafter sometimes abbreviated as UV), and radiating electromagnetic waves such as ultraviolet rays.
- UV ultraviolet rays
- acrylic acid derivatives and methacrylic acid derivatives having polar groups such as phosphoric acid, amide, and sulfonic acid
- hydrogen phosphate bis [2- (methacryloyloxy) ethyl]
- those containing a phosphate group are preferable.
- the surface hard coat layer [C] has an appropriate range of polar groups. If the content of the polar group is too small or too large, the surface scratch resistance is lowered.
- the polar group is a phosphate group
- the signal intensity attributed to carbon is the intensity of the signal attributed to phosphorus obtained with a sector magnetic field type secondary ion mass spectrometer as an indicator of the phosphate group content. The normalized strength value calculated by dividing by is used. In the measurement using the sector magnetic field type secondary ion mass spectrometer, signal intensity profiles (P [31 (P)] profile, C [13 (C)] profile) attributed to phosphorus and carbon in the thickness direction are obtained. be able to.
- each signal intensity value at the position of interest is obtained from such data, and a normalized intensity value [P / C] at that position is obtained.
- the average of the normalized strength values [P / C] in the range of the center portion ⁇ 50 nm of the surface hard coat layer [C] is preferably in the range of 0.01-30. 0.1 to 10 is more preferable.
- a region in the range of 0 to 200 nm from the boundary with the far-infrared reflective layer [B] is defined as a region [C1], and a normalized intensity value in the region [C1] [
- the maximum value [P / C] (C1) of P / C] is preferably in the range of 0.01 to 30, and more preferably 0.1 to 10.
- the surface hard coat layer [C] adopts (ii) a multilayer structure or (iii) an inclined structure
- the surface hard coat layer [C] is 0 to 0 from the surface opposite to the far-infrared reflective layer [B] (the surface of the far-infrared reflective laminate).
- the region in the range of 200 nm is defined as region [C2], and the normalized intensity value [P / C] at a position of 100 nm from the surface of the far-infrared reflective laminate is defined as the normalized intensity value [P / C] in the region [C2] (C2 ) ,
- the normalized strength value [P / C] (C2) of the region [C2] is preferably 10% or less of the normalized strength value [P / C] (C1) of the region [C1]. That is, it is preferable that the phosphate group content in the region [C2] is very small compared to the phosphate group content in the region [C1].
- the region [C2] does not include a phosphate group.
- the polar group is a phosphoric acid group
- the polar group present in the region [C1] which is the boundary region with the far-infrared reflective layer [B]
- the polar group present in the region [C1] which is the boundary region with the far-infrared reflective layer [B]
- the polar group existing in other regions do not contribute to the improvement of affinity, and if they are present in excess, it may rather decrease the physical properties of the surface hard coat layer [C] itself. Infer.
- the region other than the region [C1] does not contain the polar group or the physical properties of the hard coat layer itself. It is preferable that the content does not decrease.
- the thickness of the region not including the polar group is preferably 20% or more of the thickness of the surface hard coat layer [C], more preferably 50% or more, and further preferably 80% or more.
- the material for the surface hard coat layer [C] can be appropriately selected according to the required surface scratch resistance, far-infrared reflection performance, visible light transmission performance, and the like.
- the photosensitive acrylic hard coat agent is preferably cured easily by irradiation with an electromagnetic wave such as ultraviolet rays to form a surface hard coat layer, so that the curing can be easily controlled.
- inorganic particles it is preferable to blend inorganic particles in order to modify the shrinkage and surface hardness of the surface hard coat layer.
- oxide particles containing at least one element of silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony and cerium are preferable.
- the shape of the inorganic particles includes a spherical shape, a hollow shape, a porous shape, a rod shape, a plate shape, a fiber shape, an indefinite shape, and the like, and can be appropriately selected according to necessary characteristics. Furthermore, by performing a surface treatment that introduces a functional group on the surface of the inorganic particles, the crosslinking reaction between the curable resin and the inorganic particles proceeds, and the hard coat characteristics can be further improved.
- the surface treatment for introducing a functional group for example, an organic compound containing a polymerizable unsaturated group can be bonded to inorganic particles.
- the polymerizable unsaturated group is not particularly limited, and examples thereof include acryloyl group, methacryloyl group, vinyl group, propenyl group, butadienyl group, styryl group, ethynyl group, cinnamoyl group, maleate group and acrylamide group. .
- the thickness of the surface hard coat layer can be appropriately selected according to the combination with the material of the hard coat in accordance with the required surface scratch resistance, far-infrared reflection performance, visible light transmission performance, and the like.
- the thickness is preferably 1.5 ⁇ m or less, more preferably 1.2 ⁇ m, in order not to significantly reduce far-infrared reflection performance. Or less, more preferably 0.9 ⁇ m or less.
- the thickness is preferably 0.4 ⁇ m or more, and more preferably 0.5 ⁇ m or more.
- the far-infrared reflective layer is made of a crosslinked resin between the substrate and the far-infrared reflective layer and has a thickness of 0. It is preferable to provide an internal hard coat layer [D] of 2 to 10.0 ⁇ m.
- the composition and the range of properties can be appropriately selected based on the same idea as the surface hard coat layer, but in terms of being located inside the far infrared reflective layer, the composition and A wider range of characteristics can be taken. That is, as the composition, the polar group is not essential, and a composition that increases absorption of far infrared rays may be employed.
- the upper limit of the thickness can be 10.0 ⁇ m. It is also preferable to blend inorganic particles in order to modify the shrinkage and surface hardness of the hard coat layer.
- the material can be selected in the same way as the surface hard coat layer.
- the thickness of the internal hard coat layer matches the required surface abrasion resistance and visible light transmission performance. Depending on the combination with the material of the hard coat, it can be selected as appropriate. For example, in an internal hard coat layer using a photosensitive acrylic hard coat agent, in order to obtain good surface scratch resistance, a thicker hard coat layer is preferable.
- the thickness is preferably 0.5 ⁇ m to 10 ⁇ m, more preferably 0.5 ⁇ m to 5 ⁇ m, because it is disadvantageous in terms of stress on the substrate interface due to film shrinkage during coating formation.
- the thickness of the surface hard coat layer and the internal hard coat layer can be determined from the SEM observation image.
- the far-infrared reflective laminate of the present invention comprises a substrate, a far-infrared reflective layer, a surface hard coat layer, and, if necessary, an internal hard coat layer and other constituent layers, components, film quality, film thickness, resistance value, etc. By adjusting the characteristics, it is possible to design the far-infrared reflectance suitable for the application.
- the far-infrared reflectance of the far-infrared reflective laminate is preferably 60% or more, more preferably 70% or more, and further preferably 80% or more.
- the far-infrared reflectivity is measured in accordance with JIS R 3106 (1998), and the reflectivity for thermal radiation of 283K is obtained from the spectral reflectivity with a wavelength of 5 to 25 ⁇ m as the far-infrared reflectivity (%). To do.
- the far-infrared reflective laminate of the present invention adjusts the components, film quality and film thickness of the substrate, far-infrared reflective layer, surface hard coat layer, and internal hard coat layer and other constituent layers as necessary.
- the visible light transmittance can be designed according to the application.
- the visible light transmittance of the far-infrared reflective laminate is preferably 40% or more, more preferably 50% or more, and further preferably 60% or more.
- the measurement of the visible light transmittance is performed according to JIS R 3106 (1998), and the value obtained from the spectral transmittance at a wavelength of 380 to 780 nm is defined as the visible light transmittance (%).
- the far-infrared reflective layer may have a structure in which a metal layer having a thickness of 9 to 15 nm containing 95 to 100% by mass of Ag and a tin-doped indium oxide (ITO) layer having a thickness of 40 to 60 nm are stacked.
- ITO indium oxide
- the surface hard coat layer [C] contains the cross-linked resin having the polar group, so that the surface hard coat layer [C] has a thickness of 0.4 to 2.0 ⁇ m. Even when it is relatively thin, it can have high surface scratch resistance.
- Surface abrasion resistance is measured by fixing a far-infrared reflective laminate to a glass plate, and using a rubbing device (for example, RT-200 manufactured by Daiei Kagaku Seisakusho Co., Ltd.) A 500 g load is applied to the fixed 30 mm (width direction) ⁇ 10 mm (friction direction) friction element, and after 100 reciprocations, the surface can be visually observed. Details will be described later.
- the surface scratch resistance of the far-infrared reflective laminate of the present invention is such that there are no visual scratches of 2 mm width or more and the visual scratches are 10/10 mm or less when the visual scratches at the time of 100 reciprocations are evaluated. It is preferable that the visual scratch is 5 pieces / 10 mm or less. When the number of rubbing cycles is 100, the surface scratch resistance is low and it is not preferable. Further, when the number of rubbing cycles is 100, the visual scratch having a width of 2 mm or more is not preferable because the surface scratch resistance is extremely low.
- the far-infrared reflective laminate of the present invention takes advantage of the properties excellent in far-infrared reflective performance and surface scratch resistance, improves the heating and cooling effect by blocking heat energy flowing in and out of windows of buildings and vehicles, and for plant growth It can be used for applications such as improving the thermal environment retention in cases and houses, improving the cooling effect in freezing and refrigerated showcases, and reducing heat radiation flowing in and out of the monitoring window during high and low temperature operations.
- the far-infrared reflective laminate of the present invention on the surface of interior materials such as walls and ceilings, furniture, and home appliances, it can be used to reduce the thermal energy that flows out of the space due to the radiation of far-infrared rays. can do.
- the far-infrared reflective laminate of the present invention Since the far-infrared reflective laminate of the present invention has an electromagnetic shielding performance, it also has an effect as an electromagnetic shielding material.
- the far-infrared reflective laminate using a resin film substrate is used by sticking it to a glass plate with an adhesive, etc., to prevent scattering when the glass plate is damaged and to protect the glass plate. This also has the effect of reducing breakage.
- an ultraviolet absorber to the resin film substrate surface or an adhesive layer such as an adhesive.
- the spectral reflectance of a light beam having a wavelength of 5 to 25 ⁇ m was measured according to JIS R 3106 (1998) by entering light from the laminate surface side (surface hard coat layer side) with the following apparatus and measurement conditions.
- the reflectance for thermal radiation of 283K was determined based on the above.
- the measurement position is gradually changed in one evaluation sample piece. It was measured by moving, and the largest value was taken as the far-infrared reflectance (%) of the evaluation sample piece.
- Measurement device IR Prestige-21 manufactured by Shimadzu Corporation ⁇ Specular reflection measurement unit: SRM-8000A -Wave number range: 400-2000cm -1 -Measurement mode:% Transmittance ⁇ Abodoid coefficient: Happ-Genzel ⁇ Number of integration: 10 Decomposition: 4.0 N number of measurements: use the average value of 3 samples excluding the maximum and minimum values of 5 evaluation samples.
- the visible light transmittance (%) was determined in accordance with JIS R 3106 (1998).
- ⁇ Measurement device UV-3150 manufactured by Shimadzu Corporation ⁇ Wavelength range: 380-780nm ⁇ Slit width: (20) ⁇ Scanning speed: High speed ⁇ Sampling: 1 nm ⁇ Grating: 720nm N number of measurements: use the average value of 3 samples excluding the maximum and minimum values of 5 evaluation samples.
- the surface resistance ( ⁇ / ⁇ ) of the far-infrared reflective layer was measured using a Loresta (registered trademark) EP MCP-T360 type (4-terminal 4-probe method constant current application method) manufactured by Mitsubishi Chemical Analytech Co., Ltd.
- [P / C] (C1) and [P / C] (C2) were determined as follows.
- [P / C] (C1) The maximum value of the normalized intensity value [P / C] in the region of 0 to 200 nm from the boundary with the far-infrared reflective layer [B] was defined as [P / C] (C1) .
- [P / C] (C2) The normalized intensity value [P / C] at a position of 100 nm from the surface opposite to the far-infrared reflective layer [B] (the surface of the far-infrared reflective laminate) [P / C] (C2) . 2.
- Apparatus Sector magnetic field type secondary ion mass spectrometer 3. Measurement conditions: Cs + ions accelerated at an acceleration voltage of 14.5 kV were used as primary ions. -At the time of analysis, E-gun was used for charge compensation of the sample, and the sample stage offset potential was set to 0V. -EM (Electron Multiplier) was used for detection of secondary ions, and m / z 31 (P) and 13 (C) were detected with negative ions. The mass resolution should be 2000 or more (31 (SiH) and 31 (P), 13 (CH) and 13 (C) can be sufficiently separated). ⁇ The accumulated time of C and P is the same. -Number of measurement n: 1.
- Example criteria About the sample obtained by the Example and the comparative example, the far-infrared reflectance, the surface abrasion resistance, and the visible light transmittance were measured as mentioned above, and the performance was determined according to the following criteria.
- Example 1 A PET film (Toughtop (registered trademark) C0T0 (100 ⁇ m thickness) manufactured by Toray Film Processing Co., Ltd.) having an acrylic hard coat (film thickness 3.3 ⁇ m) in advance as an internal hard coat layer on the substrate was used.
- Toughtop registered trademark
- C0T0 100 ⁇ m thickness
- acrylic hard coat film thickness 3.3 ⁇ m
- a surface hard coat layer made of a crosslinked resin containing a phosphate group was formed as follows.
- Acrylic hard coat agent (OPSR (registered trademark) Z7535 manufactured by JSR Corporation) that forms a crosslink by irradiation with ultraviolet rays is added to a methacrylic acid derivative containing a phosphate group (Light Ester P-2M manufactured by Kyoeisha Chemical Co., Ltd.). ) was mixed to a solid content of 2% by mass, and diluted to a solid content concentration of 7.5% by mass using methyl ethyl ketone as a diluent solvent to obtain a coating solution.
- OPSR registered trademark
- methacrylic acid derivative containing a phosphate group Light Ester P-2M manufactured by Kyoeisha Chemical Co., Ltd.
- the obtained coating liquid was applied onto the far-infrared reflective layer using a bar coater (counter No. 10), dried at 80 ° C. for 3 minutes, and then UV (using a mercury lamp, 1200 mJ / cm 2 ). Irradiated to crosslink the coating to form a surface hard coat layer.
- the surface resistance of the far-infrared reflective layer was measured at the stage where the far-infrared reflective layer was formed, it was 1 ⁇ / ⁇ .
- the film thickness of the surface hard coat layer was 0.8 ⁇ m.
- the far-infrared reflectance was 93%
- the surface abrasion resistance was 3/10 mm
- the visible light transmittance was 1%
- the overall judgment 1 was A
- the overall judgment 2 was C.
- Example 2 A sample was obtained in the same manner as in Example 1 except that the conveyance speed at the time of forming the far-infrared reflective layer having a single layer structure of metal containing 95 to 100% by mass of Ag was 0.8 m / min. The results are shown in Tables 1 and 3.
- the surface resistance of the far-infrared reflective layer was measured and found to be 7 ⁇ / ⁇ . Further, when the film thickness was analyzed using a high-speed spectroscopic ellipsometer at this stage, the film thickness of the internal hard coat layer laminated on Toughtop (registered trademark) C0T0 manufactured by Toray Film Processing Co., Ltd. was 3.3 ⁇ m, far infrared rays. The thickness of the reflective layer was 12.1 nm. The film thickness of the surface hard coat layer was 0.8 ⁇ m. The far-infrared reflectance was 88%, the surface abrasion resistance was 3/10 mm, the visible light transmittance was 54%, the overall judgment 1 was A, and the overall judgment 2 was B.
- Example 3 A far-infrared reflective layer having a multilayer structure comprising a metal layer containing 95 to 100% by mass of Ag as a far-infrared reflective layer and a high-refractive index layer containing a metal oxide and having a refractive index of 1.5 to 3 A sample was obtained in the same manner as in Example 1 except that was formed as follows.
- the surface resistance was measured and found to be 9 ⁇ / ⁇ .
- the normalized intensity obtained by reversing the P profile observed at the surface magnetic coat layer with a sector magnetic field type secondary ion mass spectrometer at each point of the C profile is within a range of depth of 400 nm ⁇ 50 nm from the surface hard coat layer surface.
- the average value P / C was 1.3.
- the far-infrared reflectance was 86%
- the surface abrasion resistance was 2/10 mm
- the visible light transmittance was 67%.
- the overall judgment 1 was A
- the overall judgment 2 was also A.
- Example 4 In the process of forming the surface hard coat layer, the same procedure as in Example 3 was conducted, except that a methacrylic acid derivative containing a phosphoric acid group (light ester P-2M manufactured by Kyoeisha Chemical Co., Ltd.) was mixed to a solid content of 5% by mass. Sample. The results are shown in Tables 1 and 3. The far-infrared reflectance was 88%, the surface abrasion resistance was 5/10 mm, the visible light transmittance was 66%, the overall judgment 1 was A, and the overall judgment 2 was also A.
- Example 5 In the process of forming the surface hard coat layer, the same procedure as in Example 3 was conducted, except that a methacrylic acid derivative containing a phosphoric acid group (light ester P-2M manufactured by Kyoeisha Chemical Co., Ltd.) was mixed to a solid content of 10% by mass. Sample. The results are shown in Tables 1 and 3.
- the normalized intensity obtained by reversing the P profile observed at the surface magnetic coat layer with a sector magnetic field type secondary ion mass spectrometer at each point of the C profile is within a range of depth of 400 nm ⁇ 50 nm from the surface hard coat layer surface.
- the average value P / C was 6.2.
- the far-infrared reflectance was 86%
- the surface abrasion resistance was 7/10 mm
- the visible light transmittance was 67%
- the overall judgment 1 was B
- the overall judgment 2 was B.
- Example 6 In the step of forming the surface hard coat layer, a methacrylic acid derivative containing a phosphoric acid group (light ester P-2M manufactured by Kyoeisha Chemical Co., Ltd.) is mixed so as to be 2% by mass in the solid content, and methyl ethyl ketone is used as a dilution solvent.
- the coating liquid was obtained by diluting to a solid content concentration of 0.75% by mass.
- the obtained coating liquid was applied onto the far-infrared reflective layer using a bar coater (counter No. 10), and dried at 80 ° C. for 3 minutes.
- an acrylic hard coat agent (Opster (registered trademark) Z7535, manufactured by JSR Corporation) was added as a dilution solvent without adding a methacrylic acid derivative containing a phosphoric acid group (light ester P-2M manufactured by Kyoeisha Chemical Co., Ltd.).
- a methacrylic acid derivative containing a phosphoric acid group (light ester P-2M manufactured by Kyoeisha Chemical Co., Ltd.).
- the obtained coating liquid was applied onto the coating film using a bar coater (counter No. 10) and dried at 80 ° C. for 3 minutes.
- UV using a mercury lamp, 1200 mJ / cm 2
- Example 3 A sample was obtained in the same manner as in Example 3 except that the formation of the surface hard coat layer was as described above. The results are shown in Tables 1 and 3. The far-infrared reflectance was 85%, the surface abrasion resistance was 2/10 mm, and the visible light transmittance was 67%. The overall judgment 1 was A, and the overall judgment 2 was also A.
- Example 7 In the step of forming the surface hard coat layer, a methacrylic acid derivative containing a phosphoric acid group (Light Ester P-2M manufactured by Kyoeisha Chemical Co., Ltd.) was mixed in the solid content so as to be 10% by mass instead of 2% by mass. A sample was obtained in the same manner as in Example 6. The results are shown in Tables 1 and 3. The far-infrared reflectance was 85%, the surface abrasion resistance was 1/10 mm, and the visible light transmittance was 68%. The overall judgment 1 was A, and the overall judgment 2 was also A.
- Example 8 In the step of forming the surface hard coat layer, a methacrylic acid derivative containing a phosphoric acid group (light ester P-2M manufactured by Kyoeisha Chemical Co., Ltd.) was mixed in the solid content so that it was 20% by mass instead of 2% by mass. A sample was obtained in the same manner as in Example 6. The results are shown in Tables 1 and 3. The far-infrared reflectance was 85%, the surface abrasion resistance was 4/10 mm, and the visible light transmittance was 68%. The overall judgment 1 was A, and the overall judgment 2 was also A.
- Example 9 A far-infrared reflective layer having a multilayer structure composed of a metal layer containing 95 to 100% by mass of Ag and a high-refractive index layer containing a metal oxide and having a refractive index of 1.5 to 3 is used as the far-infrared reflective layer.
- a sample was obtained in the same manner as in Example 1 except that it was formed as described above.
- First layer ultimate pressure: 2E-3 Pa or less, Ti target (127 mm ⁇ 386 mm ⁇ 1 sheet), transport speed: 0.2 m / min, sputtering gas: Ar-35% by volume O 2 , sputtering pressure: 0.3 Pa, Input power: A TiO 2 layer was formed by sputtering at a DC pulse (50 kHz) of 9.5 kw.
- Second layer Ultimate pressure: 2E-3 Pa or less, Ag alloy target (76 mm ⁇ 330 mm ⁇ 2 sheets: Ag-0.2 mass% Nd-1 mass% Au), transport speed: 3.5 m / min, sputtering gas: A metal layer was formed by sputtering with Ar, sputtering pressure: 9.5E-2 Pa, input power: LF power supply (40 kHz) 1.0 kW.
- Third layer ultimate pressure: 2E-3 Pa or less, Ti target (127 mm ⁇ 386 mm ⁇ 1 sheet), transport speed: 5.0 m / min, sputtering gas: Ar, sputtering pressure: 0.2 Pa, input power: DC pulse ( (50 kHz) A Ti layer was formed by sputtering at 4.3 kw.
- Fourth layer ultimate pressure: 2E-3 Pa or less, Ti target (127 mm ⁇ 386 mm ⁇ 1 sheet), transport speed: 0.2 m / min, sputtering gas: Ar-35% by volume O 2 , sputtering pressure: 0.3 Pa, Input power: A TiO 2 layer was formed by sputtering at a DC pulse (50 kHz) of 9.5 kw.
- a far-infrared reflective layer having a multilayer structure composed of a metal layer containing 95 to 100% by mass of Ag as a far-infrared reflective layer and a high refractive index layer containing a metal oxide and having a refractive index of 1.5 to 3 is as follows. A sample was obtained in the same manner as in Example 1 except that it was formed as described above.
- First layer ultimate pressure: 2E-3 Pa or less, Ti target (127 mm ⁇ 386 mm ⁇ 1 sheet), transport speed: 0.2 m / min, sputtering gas: Ar-35% by volume O 2 , sputtering pressure: 0.3 Pa, Input power: A TiO 2 layer was formed by sputtering at a DC pulse (50 kHz) of 9.5 kw.
- Second layer Ultimate pressure: 2E-3 Pa or less, Ag alloy target (76 mm ⁇ 330 mm ⁇ 2 sheets: Ag-0.2 mass% Nd-1 mass% Au), transport speed: 3.5 m / min, sputtering gas: A metal layer was formed by sputtering with Ar, sputtering pressure: 9.5E-2 Pa, input power: LF power supply (40 kHz) 1.0 kW.
- Third layer ultimate pressure: 2E-3 Pa or less, Ti target (127 mm ⁇ 386 mm ⁇ 1 sheet), transport speed: 5.0 m / min, sputtering gas: Ar, sputtering pressure: 0.2 Pa, input power: DC pulse ( (50 kHz) A Ti layer was formed by sputtering at 1.7 kw.
- Fourth layer ultimate pressure: 2E-3 Pa or less, Ti target (127 mm ⁇ 386 mm ⁇ 1 sheet), transport speed: 0.2 m / min, sputtering gas: Ar-35% by volume O 2 , sputtering pressure: 0.3 Pa, Input power: A TiO 2 layer was formed by sputtering at a DC pulse (50 kHz) of 9.5 kw.
- a far-infrared reflective layer having a multilayer structure composed of a metal layer containing 95 to 100% by mass of Ag as a far-infrared reflective layer and a high refractive index layer containing a metal oxide and having a refractive index of 1.5 to 3 is as follows. A sample was obtained in the same manner as in Example 1 except that it was formed as described above.
- First layer ultimate pressure: 2E-3 Pa or less, Nb target (127 mm ⁇ 386 mm ⁇ 1 sheet), transport speed: 0.3 m / min, sputtering gas: Ar-30 vol% O 2 , sputtering pressure: 0.3 Pa, Input power: An Nb 2 O 5 layer was formed by sputtering at a DC pulse (50 kHz) of 5 kw.
- Second layer Ultimate pressure: 2E-3 Pa or less, Ag alloy target (76 mm ⁇ 330 mm ⁇ 2 sheets: Ag-0.2 mass% Nd-1 mass% Au), transport speed: 3.5 m / min, sputtering gas: A metal layer was formed by sputtering with Ar, sputtering pressure: 9.5E-2 Pa, input power: LF power supply (40 kHz) 1.0 kW.
- Third layer ultimate pressure: 2E-3 Pa or less, Nb target (127 mm ⁇ 386 mm ⁇ 1 sheet), transport speed: 5.0 m / min, sputtering gas: Ar, sputtering pressure: 0.1 Pa, input power: DC pulse ( (50 kHz) An Nb layer was formed by sputtering at 2.3 kW.
- Nb target (127 mm ⁇ 386 mm ⁇ 1 sheet), transport speed: 0.3 m / min, sputtering gas: Ar-30 vol% O 2 , sputtering pressure: 0.3 Pa, Input power: An Nb 2 O 5 layer was formed by sputtering at a DC pulse (50 kHz) of 5 kw.
- a far-infrared reflective layer having a multilayer structure composed of a metal layer containing 95 to 100% by mass of Ag as a far-infrared reflective layer and a high refractive index layer containing a metal oxide and having a refractive index of 1.5 to 3 is as follows. A sample was obtained in the same manner as in Example 1 except that it was formed as described above.
- First layer ultimate pressure: 2E-3 Pa or less, Nb target (127 mm ⁇ 386 mm ⁇ 1 sheet), transport speed: 0.3 m / min, sputtering gas: Ar-30 vol% O 2 , sputtering pressure: 0.3 Pa, Input power: An Nb 2 O 5 layer was formed by sputtering at a DC pulse (50 kHz) of 5 kw.
- Second layer Ultimate pressure: 2E-3 Pa or less, Ag alloy target (76 mm ⁇ 330 mm ⁇ 2 sheets: Ag-0.2 mass% Nd-1 mass% Au), transport speed: 3.5 m / min, sputtering gas: A metal layer was formed by sputtering with Ar, sputtering pressure: 9.5E-2 Pa, input power: LF power supply (40 kHz) 1.0 kW.
- Third layer ultimate pressure: 2E-3 Pa or less, Nb target (127 mm ⁇ 386 mm ⁇ 1 sheet), transport speed: 5.0 m / min, sputtering gas: Ar, sputtering pressure: 0.1 Pa, input power: DC pulse ( The Nb layer was formed by sputtering at 50 kHz) 0.9 kW.
- Nb target (127 mm ⁇ 386 mm ⁇ 1 sheet), transport speed: 0.3 m / min, sputtering gas: Ar-30 vol% O 2 , sputtering pressure: 0.3 Pa, Input power: An Nb 2 O 5 layer was formed by sputtering at a DC pulse (50 kHz) of 5 kw.
- Comparative Example 1 Leftel (registered trademark) ZC05G (substrate (PET film) / metal layer and dielectric layer (titanium oxide) made of Teijin DuPont Films Co., Ltd.) having a polyolefin-based resin on the surface layer was used as a sample of Comparative Example 1.
- the results are shown in Table 2 and Table 3.
- the far-infrared reflectance was 81%, and the surface scratch resistance was innumerable scratches of 11/10 mm or more, the visible light transmittance was 66%, the overall judgment 1 was C, and the overall judgment 2 was D. .
- Example 2 A sample was obtained in the same manner as in Example 1 except that in the step of forming the surface hard coat layer, a methacrylic acid derivative containing phosphoric acid groups (light ester P-2M manufactured by Kyoeisha Chemical Co., Ltd.) was not added. The results are shown in Table 2 and Table 3.
- the film thickness of the surface hard coat layer of Comparative Example 2 was 0.8 ⁇ m.
- the far-infrared reflectance was 87%, and scratches with a width of 2 mm or more were observed with respect to the surface scratch resistance, the visible light transmittance was 53%, the overall judgment 1 was C, and the overall judgment 2 was E.
- the film thickness of the surface hard coat layer of Comparative Example 3 was 3 ⁇ m.
- the far-infrared reflectance was 54%
- the surface abrasion resistance was 0/10 mm
- the visible light transmittance was 54%
- the overall judgment 1 was C
- the overall judgment 2 was E.
- Example 4 A sample was obtained in the same manner as in Example 3 except that in the step of forming the surface hard coat layer, a methacrylic acid derivative containing phosphoric acid groups (light ester P-2M manufactured by Kyoeisha Chemical Co., Ltd.) was not added. The results are shown in Table 2 and Table 3.
- the normalized intensity obtained by reversing the P profile observed at the surface magnetic coat layer with a sector magnetic field type secondary ion mass spectrometer at each point of the C profile is within a range of depth of 400 nm ⁇ 50 nm from the surface hard coat layer surface.
- the average value P / C was 6 ⁇ 10 ⁇ 4 .
- the far-infrared reflectivity was 87%, and scratches with a width of 2 mm or more were observed with respect to the surface scratch resistance, the visible light transmittance was 67%, the overall judgment 1 was C, and the overall judgment 2 was D.
- the film thickness of the surface hard coat layer of Comparative Example 5 was 0.2 ⁇ m.
- the far-infrared reflectance was 89%, and scratches with a width of 2 mm or more were observed with respect to the surface abrasion resistance, the visible light transmittance was 64%, the overall judgment 1 was C, and the overall judgment 2 was D.
- the far-infrared reflective laminate of the present invention has a high far-infrared reflectance and good scratch resistance to the surface, it is preferably used for applications that maintain a thermal environment by shielding thermal energy flowing in and out from windows and the like. Can do. In particular, it can be suitably used for applications that suppress the outflow of energy from the room in winter.
Abstract
Description
以下の[A]~[C]の層が、この順で配されてなる遠赤外線反射積層体;
[A]基板;
[B]次の[B1]または[B2]の構造を有する遠赤外線反射層;
[B1]銀(Ag)を95~100質量%含有する金属の単層構造;
[B2]銀(Ag)を95~100質量%含有する金属層と金属酸化物および/または金属窒化物を含み、屈折率が1.5~3である層とからなる多層構造;
[C]リン酸基、スルホン酸基およびアミド基からなる群より選ばれる1種以上の極性基を有する架橋樹脂を含み、かつ、厚みが0.4~2.0μmである表面ハードコート層。
本発明に用いる基板[A]は、遠赤外線反射積層体を適用する用途に合わせて樹脂、金属、金属酸化物および紙や木材などの天然素材から選択される。外光を取り入れたり内部を観察する窓に使用する用途に適用する遠赤外線反射積層体の場合、基板[A]が可視光線を透過する透明樹脂や透明ガラスであることが好ましい。取り扱いを容易とするためには、基板[A]が可撓性を有する透明な樹脂フィルムであることがより好ましい。樹脂フィルムの材料としては、例えば、ポリエチレンテレフタレートやポリエチレン-2,6-ナフタレートに代表される芳香族ポリエステル;ナイロン6やナイロン66に代表される脂肪族ポリアミド;芳香族ポリアミド;ポリエチレンやポリプロピレンに代表されるポリオレフィン;ポリカーボネート等が例示される。これらの中で、コストや取り扱いの容易さ、積層体を加工する際に受ける熱に対する耐熱性といった面で、芳香族ポリエステルが好ましく、中でもポリエチレンテレフタレートまたはポリエチレン-2,6-ナフタレートが好ましく、特にポリエチレンテレフタレートフィルムが好ましい。また、機械強度を高めた二軸延伸フィルムが好ましく、特に二軸延伸ポリエチレンテレフタレートフィルムが好ましい。取り扱いの容易さや、加工単位の長尺化による生産性向上といった点からは、フィルムの厚みは5~250μmの範囲が好ましく、15~150μmであることがさらに好ましい。
遠赤外線反射層[B]は、可視光透過特性や遠赤外線反射特性に優れた次の[B1]または[B2]の構造を有する層である。
[B1]銀(Ag)を95~100質量%含有する金属の単層構造
[B2]銀(Ag)を95~100質量%含有する金属の層と金属酸化物および/または金属窒化物を含み、屈折率が1.5~3である層とからなる多層構造。
1/Pst=1/Ps1+1/Ps2+1/Ps3+・・・・1/Psn
の式で計算することができる。
本発明における表面ハードコート層[C]は、リン酸基、スルホン酸基およびアミド基からなる群より選ばれる1種以上の極性基を有する架橋樹脂を含み、かつ、厚みが0.4~2.0μmである層である。厚み0.4μm未満ではハードコート性能が乏しくなり表面保護性能が低くなる。一方、厚みが2.0μmを超えると、ハードコート層による遠赤外線の吸収が過大となり、遠赤外線反射層の性能を著しく妨げる。
本発明の遠赤外線反射積層体において、各層の内部や層間の界面に応力が集中して破壊されることを防ぐために、基板と遠赤外線反射層との間に架橋樹脂からなり、厚みが0.2~10.0μmである内部ハードコート層[D]を設けることが好ましい。
内部ハードコート層の厚みは、必要とする耐表面擦過性能と可視光透過性能などに合わせて、ハードコートの材料との組み合わせにより適宜選ぶことができる。例えば、感光性のアクリル系ハードコート剤を用いた内部ハードコート層においては、良好な耐表面擦過性を得るためにはハードコート層の膜厚は厚い方が好ましいが、膜厚が厚くなるとハードコート形成時の膜収縮による基板界面への応力などの点で不利となるため、厚みは、0.5μm~10μmが好ましく、0.5μm~5μmがさらに好ましい。表面ハードコート層および内部ハードコート層の厚みは、SEM観察画像より求めることができる。
本発明の遠赤外線反射積層体は、基材、遠赤外線反射層、表面ハードコート層、および、必要に応じて内部ハードコート層や他の構成層について、成分、膜質、膜厚および抵抗値などの特性を調整することで、用途に合わせた遠赤外線反射率を設計することができる。遠赤外線反射積層体の遠赤外線反射率は、60%以上であることが好ましく、70%以上がより好ましく、80%以上がさらに好ましい。
本発明の遠赤外線反射積層体は、基材、遠赤外線反射層、表面ハードコート層、および、必要に応じて内部ハードコート層や他の構成層について、成分、膜質および膜厚を調整することで、用途に合わせた可視光透過率を設計することができる。遠赤外線反射積層体の可視光透過率は40%以上が好ましく、50%以上がより好ましく、60%以上がさらに好ましい。
本発明の遠赤外線反射積層体は、表面ハードコート層[C]に、前記の極性基を有する架橋樹脂を含むことにより、表面ハードコート層[C]の厚みが0.4~2.0μmと、比較的薄い場合であっても、高い耐表面擦過性を有することができる。
本発明の遠赤外線反射積層体は、遠赤外線反射性能と耐表面擦過性に優れた特性を生かし、建築物や乗り物などの窓から流出入する熱エネルギー遮断による冷暖房効果の向上、植物育成用のケースやハウスにおける熱環境保持性の向上、冷凍冷蔵ショーケースにおける保冷効果向上、および、高低温作業時に監視窓から流出入する熱輻射の低減などの用途に利用できる。また、本発明の遠赤外線反射積層体を壁や天井などの内装材や家具、家電製品などの表面に使用することで、遠赤外線の放射によって空間内から流出する熱エネルギーを低減することに利用することができる。本発明の遠赤外線反射積層体は、電磁波遮蔽性能を有することから、電磁波シールド材としての効果も有する。また、樹脂フィルム基板を用いた遠赤外線反射積層体は、粘着剤などを用いてガラス板などに貼り合わせて使用することで、ガラス板などが破損した場合の飛散防止やガラス板などを保護して破損を低減する効果も有する。樹脂フィルム基板が紫外線により劣化するのを防ぐためには、樹脂フィルム基板表面や粘着剤などの接着層に紫外線吸収剤を付与しておくことが好ましい。
(遠赤外線反射率)
50mm角の遠赤外線反射積層体サンプルの片端部を、7.5mm幅×50mm長にカットした両面テープ((株)ニトムズ製PROSELF(登録商標)No.539R)を用いて、50mm角の3mm厚ガラス板に、シワや弛みが発生しないように固定して評価サンプル片を作成した。評価サンプル片について、下記の装置および測定条件により、積層体表面側(表面ハードコート層側)から入光して、波長5~25μmの光線の分光反射率を測定し、JIS R 3106(1998)に準拠して283Kの熱放射に対する反射率を求めた。なお、評価サンプル片表面の遠赤外線反射積層体が部分的にたるんでいたりして正確な面が出ていない位置では測定値が低く出るので、1つの評価サンプル片の中で測定位置を少しずつ動かして測定し、最も大きな値をその評価サンプル片の遠赤外線反射率(%)とした。
・測定装置:(株)島津製作所製 IRPrestige-21
・正反射測定ユニット:SRM-8000A
・波数範囲:400~2000cm-1
・測定モード:%Transmittance
・アボダイズ係数:Happ-Genzel
・積算回数:10
・分解:4.0
・測定n数:評価サンプル5個のうち最大値と最小値のものを除いた3個の平均値を使用。
50mm角の遠赤外線反射積層体サンプルの片端部を、7.5mm幅×50mm長にカットした両面テープ((株)ニトムズ製PROSELF(登録商標)No.539R)を用いて、50mm角の3mm厚ガラス板に、シワや弛みが発生しないように固定して評価サンプル片を作成した。評価サンプル片中央部について、下記の装置および測定条件により、ガラス側(積層体表面側(表面ハードコート層側)の逆面)から入光して、波長380~780nmの分光透過率を測定し、JIS R 3106(1998)に準拠して可視光透過率(%)を求めた。
・測定装置:(株)島津製作所製 UV-3150
・波長範囲:380~780nm
・スリット幅:(20)
・スキャンスピード:高速
・サンプリング:1nm
・グレーティング:720nm
・測定n数:評価サンプル5個のうち最大値と最小値のものを除いた3個の平均値を使用。
50mm角の遠赤外線反射積層体サンプルを、7.5mm幅×50mm長にカットした両面テープ((株)ニトムズ製PROSELF(登録商標) No.539R)を用いて、50mm角の3mm厚ガラス板に、遠赤外線反射積層体サンプル表面にシワや弛みが発生しないように擦過方向と平行な両端部を固定して表面擦過試験用評価サンプル片とした。以下の装置および条件でスチールウールを固定した摩擦子を用いて積層体表面側(ハードコート層1側)を擦過した後、サンプル中央部20mm角部分の表面を目視観察した。
・擦過装置:(株)大栄科学精器製作所製 RT-200
・擦過速度:10
・擦過回数:100往復
・荷重:500g
・摩擦子:30mm(幅方向)×10mm(摩擦方向)
・スチールウール:日本スチールウール(株)製 ボンスター(登録商標) No.0000
・測定n数:評価サンプル5個のうち最大値と最小値のものを除いた3個の平均値を使用。
三菱化学アナリテック(株)製 ロレスタ(登録商標)EP MCP-T360型(4端子4探針法定電流印加方式)を用いて、遠赤外線反射層の表面抵抗(Ω/□)を測定した。
以下の方法で、遠赤外線反射積層体のサンプルを調製し、SEM観察を行い、サンプルのハードコート層厚みを算出した。
1.サンプル調製
(i)断面面出し
・日本ミクロトーム研究所製「ロータリミクロトーム RMS」で切削
・切削刃 スチール製レザー刃(フェザー製片刃)
・スチール製レザー刃切削角度 3度
・切削量 30μm
(ii)スパッタ処理
(株)エイコー・エンジニアリング社製「イオンコーターIB-3型」でスパッタ処理を行った。
・スパッタ金属 Pt 85質量%+Pd 15質量%
・スパッタ条件 2mA 5分間
・スパッタ膜厚 約10nm
2.SEM観察
(株)トプコン社製 走査型電子顕微鏡「ABT-32」を使用した。
(i)使用観察条件
・加速電圧 15KV
・スポットサイズレベル 6
・ワーキングディスタンス 20mm
・観察角度 0度(対断面90度)
・観察倍率 20000倍。
(ii)厚み算出
・SEM像上で測定した厚みと観察倍率から計算した。
・なお、計算に当たっては、標準資料としてGratingSpace 500×500mμ(Oken製)を測定した結果を用いて誤差補正を行った。
1.測定法
下記の装置および測定条件により、測定サンプルからの反射光の偏光状態の変化を測定し、光学定数を計算により求めた。計算は、試料で測定されたΔ(位相差)とψ(振幅反射率)のスペクトルを計算モデルから算出された(Δ、ψ)と比較し、測定値(Δ、ψ)に近づくように誘電関数を変化させてフィッティングしていく。ここで示されたフィッティング結果は、測定値と理論値がベストフィット(平均二乗誤差が最小に収束)した結果である。
2.装置
・高速分光エリプソメーター
・M-2000(J.A.Woollam 社製)
・回転補償子型(RCE: Rotating Compensator Ellipsometer)
・300mm R-Theta ステージ
3.測定条件
・入射角:65 度、70 度、75 度
・測定波長: 195nm~1680nm
・解析ソフト:WVASE32
・ビーム径:1×2mm 程度
・測定n数:1。
1.測定法
下記の装置および測定条件により、遠赤外線反射積層体サンプルの表面ハードコート層を測定し、厚み方向のP[31(P)]プロファイルおよびC[13(C)]プロファイルを取得し、厚み方向の各点にて、31(P)の強度値を13(C)の強度値で除して規格化強度[P/C]を求めた。
(i)単層構成の場合、ハードコート層[C]の中心部±50nmの範囲における規格化強度値[P/C]の平均値を求めた。
(ii)多層構成または(iii)傾斜構成の場合、[P/C](C1)および、[P/C](C2)は、以下のように求めた。
[P/C](C1):遠赤外線反射層[B]との境界から0~200nmの領域における規格化強度値[P/C]の最大値を[P/C](C1)とした。
[P/C](C2):遠赤外線反射層[B]の反対側の面(遠赤外線反射積層体の表面)から100nmの位置における規格化強度値[P/C]を[P/C](C2)とした。
2.装置
セクター磁場型二次イオン質量分析装置
3.測定条件
・一次イオンには14.5kVの加速電圧で加速したCs+イオンを使用した。
・分析時には、試料の帯電補償のためE-gunを使用し、試料台オフセット電位は0Vとした。
・二次イオンの検出にはEM(Electron Multiplier)を使用し、負イオンにてm/z=31(P), 13(C)を検出した。
・質量分解能には2000以上(31(SiH)と31(P)、13(CH)と13(C)が十分分離可能であること)が必要である。
・CとPの積算時間は同一とする。
・測定n数:1。
実施例および比較例で得られたサンプルについて、上記のとおりにして遠赤外線反射率、耐表面擦過性および可視光透過率を測定し、以下の判定基準により、性能を判定した。
・遠赤外線反射率
A:80%以上
B:60%以上80%未満
C:60%未満
・耐表面擦過性
A:擦過回数100往復時に2mm幅以上の目視キズがなく、目視キズ0~5本/10mm
B:擦過回数100往復時に2mm幅以上の目視キズがなく、目視キズ6~10本/10mm
C:擦過回数100往復時に2mm幅以上の目視キズがあるか、または、目視キズ11本/10mm以上
・可視光透過率
A:60%以上
B:40%以上60%未満
C:40%未満
・総合判定1
遠赤外線反射率および耐表面擦過性の判定において以下の基準で判定した。
A:すべての判定がA
B:判定にBを1つ含み、残りはA
C:判定にBを2つ以上含む、もしくはCを含む
・総合判定2
総合判定1および可視光透過率の判定において以下の基準で判定し、A~Cを合格とした。
A:すべての判定がA
B:判定にBを1つ含み、残りは全てA
C:総合判定1がB以上であり、判定にBを2つ以上含む、もしくはCを含む。
D:総合判定1がCであり、可視光透過率の判定がAである。
E:総合判定1がCであり、可視光透過率の判定がB以下である。
基板上に内部ハードコート層として予めアクリル系ハードコート(膜厚3.3μm)を有するPETフィルム(東レフィルム加工(株)製タフトップ(登録商標)C0T0(100μm厚))を使用した。
Agを95~100質量%含有する金属の単層構造の遠赤外線反射層を形成する際の搬送速度を0.8m/minとした以外は実施例1と同様にしてサンプルを得た。結果を表1および表3に示す。
遠赤外線反射層として、Agを95~100質量%含有する金属の層、および、金属酸化物を含み屈折率が1.5~3である高屈折率層とからなる多層構造の遠赤外線反射層を以下のように形成した他は実施例1と同様にしてサンプルを得た。
到達圧力:2E-3Pa、Ag合金ターゲット(76mm×330mm×2枚:Ag-0.2質量%Nd-1質量%Au)、搬送速度:3.5m/min、スパッタガス:Ar、スパッタ圧力:9.5E-2Pa、投入電力:LF電源(40kHz)1.0kwにて金属層をスパッタ加工にて形成した後、到達圧力:2E-3Pa以下、ITOターゲット(127mm×386mm×1枚:90質量%In2O3-10質量%SnO2)、搬送速度:0.9m/min、スパッタガス:Ar-3体積%O2、スパッタ圧力:9.5E-2Pa、投入電力:DCパルス(50kHz)2.5kwにてITO層をスパッタ加工にて形成した。結果を表1および表3に示す。
表面ハードコート層の形成工程において、リン酸基を含むメタクリル酸誘導体(共栄社化学(株)製ライトエステルP-2M)を固形分中5質量%となるよう混合した以外は実施例3と同様にしてサンプルを得た。結果を表1および表3に示す。遠赤外線反射率が88%、耐表面擦過性では5本/10mm、可視光透過率が66%であり、総合判定1はA、総合判定2もAであった。
表面ハードコート層の形成工程において、リン酸基を含むメタクリル酸誘導体(共栄社化学(株)製ライトエステルP-2M)を固形分中10質量%となるよう混合した以外は実施例3と同様にしてサンプルを得た。結果を表1および表3に示す。
表面ハードコート層の形成工程において、リン酸基を含むメタクリル酸誘導体(共栄社化学(株)製ライトエステルP-2M)を固形分中2質量%となるよう混合し、希釈溶媒としてメチルエチルケトンを用いて固形分濃度0.75質量%に希釈して塗液を得た。得られた塗液を、バーコーター(番手No.10)を用いて、遠赤外線反射層上に塗布し、80℃で3分乾燥した。次に、リン酸基を含むメタクリル酸誘導体(共栄社化学(株)製ライトエステルP-2M)を添加せずにアクリル系ハードコート剤(JSR(株)製オプスター(登録商標)Z7535)を希釈溶媒としてメチルエチルケトンを用いて固形分濃度6.75質量%に希釈して塗液を得た。得られた塗液を、バーコーター(番手No.10)を用いて、前記塗膜上に塗布し、80℃で3分乾燥した。続いて、UV(水銀ランプ使用、1200mJ/cm2)を照射し、塗膜を架橋させて、積層構造からなる表面ハードコート層を形成させた。表面ハードコート層の形成を以上のようにした以外は実施例3と同様にしてサンプルを得た。結果を表1および表3に示す。遠赤外線反射率が85%、耐表面擦過性では2本/10mm、可視光透過率が67%であり、総合判定1はA、総合判定2もAであった。
表面ハードコート層の形成工程において、リン酸基を含むメタクリル酸誘導体(共栄社化学(株)製ライトエステルP-2M)を固形分中、2質量%ではなく10質量%となるよう混合した以外は実施例6と同様にしてサンプルを得た。結果を表1および表3に示す。遠赤外線反射率が85%、耐表面擦過性では1本/10mm、可視光透過率が68%であり、総合判定1はA、総合判定2もAであった。
表面ハードコート層の形成工程において、リン酸基を含むメタクリル酸誘導体(共栄社化学(株)製ライトエステルP-2M)を固形分中、2質量%ではなく20質量%となるよう混合した以外は実施例6と同様にしてサンプルを得た。結果を表1および表3に示す。遠赤外線反射率が85%、耐表面擦過性では4本/10mm、可視光透過率が68%であり、総合判定1はA、総合判定2もAであった。
[実施例9]
遠赤外線反射層として、Agを95~100質量%含有する金属の層と金属酸化物を含み屈折率が1.5~3である高屈折率層とからなる多層構造の遠赤外線反射層を以下のように形成した他は実施例1と同様にしてサンプルを得た。
第1層:到達圧力:2E-3Pa以下、Tiターゲット(127mm×386mm×1枚)、搬送速度:0.2m/min、スパッタガス:Ar-35体積% O2、スパッタ圧力:0.3Pa、投入電力:DCパルス(50kHz)9.5kwにてTiO2層をスパッタ加工にて形成した。
第2層:到達圧力:2E-3Pa以下、Ag合金ターゲット(76mm×330mm×2枚:Ag-0.2質量%Nd-1質量%Au)、搬送速度:3.5m/min、スパッタガス:Ar、スパッタ圧力:9.5E-2Pa、投入電力:LF電源(40kHz)1.0kwにて金属層をスパッタ加工にて形成した。
第3層:到達圧力:2E-3Pa以下、Tiターゲット(127mm×386mm×1枚)、搬送速度:5.0m/min、スパッタガス:Ar、スパッタ圧力:0.2Pa、投入電力:DCパルス(50kHz)4.3 kwにてTi層をスパッタ加工にて形成した。
第4層:到達圧力:2E-3Pa以下、Tiターゲット(127mm×386mm×1枚)、搬送速度:0.2m/min、スパッタガス:Ar-35体積% O2、スパッタ圧力:0.3Pa、投入電力:DCパルス(50kHz)9.5kwにてTiO2層をスパッタ加工にて形成した。
[実施例10]
遠赤外線反射層としてAgを95~100質量%含有する金属の層と金属酸化物を含み屈折率が1.5~3である高屈折率層とからなる多層構造の遠赤外線反射層を以下のように形成した他は実施例1と同様にしてサンプルを得た。
第1層:到達圧力:2E-3Pa以下、Tiターゲット(127mm×386mm×1枚)、搬送速度:0.2m/min、スパッタガス:Ar-35体積% O2、スパッタ圧力:0.3Pa、投入電力:DCパルス(50kHz)9.5kwにてTiO2層をスパッタ加工にて形成した。
第2層:到達圧力:2E-3Pa以下、Ag合金ターゲット(76mm×330mm×2枚:Ag-0.2質量%Nd-1質量%Au)、搬送速度:3.5m/min、スパッタガス:Ar、スパッタ圧力:9.5E-2Pa、投入電力:LF電源(40kHz)1.0kwにて金属層をスパッタ加工にて形成した。
第3層:到達圧力:2E-3Pa以下、Tiターゲット(127mm×386mm×1枚)、搬送速度:5.0m/min、スパッタガス:Ar、スパッタ圧力:0.2Pa、投入電力:DCパルス(50kHz)1.7 kwにてTi層をスパッタ加工にて形成した。
第4層:到達圧力:2E-3Pa以下、Tiターゲット(127mm×386mm×1枚)、搬送速度:0.2m/min、スパッタガス:Ar-35体積% O2、スパッタ圧力:0.3Pa、投入電力:DCパルス(50kHz)9.5kwにてTiO2層をスパッタ加工にて形成した。
[実施例11]
遠赤外線反射層としてAgを95~100質量%含有する金属の層と金属酸化物を含み屈折率が1.5~3である高屈折率層とからなる多層構造の遠赤外線反射層を以下のように形成した他は実施例1と同様にしてサンプルを得た。
第1層:到達圧力:2E-3Pa以下、Nbターゲット(127mm×386mm×1枚)、搬送速度:0.3m/min、スパッタガス:Ar-30体積% O2、スパッタ圧力:0.3Pa、投入電力:DCパルス(50kHz)5kwにてNb2O5層をスパッタ加工にて形成した。
第2層:到達圧力:2E-3Pa以下、Ag合金ターゲット(76mm×330mm×2枚:Ag-0.2質量%Nd-1質量%Au)、搬送速度:3.5m/min、スパッタガス:Ar、スパッタ圧力:9.5E-2Pa、投入電力:LF電源(40kHz)1.0kwにて金属層をスパッタ加工にて形成した。
第3層:到達圧力:2E-3Pa以下、Nbターゲット(127mm×386mm×1枚)、搬送速度:5.0m/min、スパッタガス:Ar、スパッタ圧力:0.1Pa、投入電力:DCパルス(50kHz)2.3kwにてNb層をスパッタ加工にて形成した。
第4層:到達圧力:2E-3Pa以下、Nbターゲット(127mm×386mm×1枚)、搬送速度:0.3m/min、スパッタガス:Ar-30体積% O2、スパッタ圧力:0.3Pa、投入電力:DCパルス(50kHz)5kwにてNb2O5層をスパッタ加工にて形成した。
[実施例12]
遠赤外線反射層としてAgを95~100質量%含有する金属の層と金属酸化物を含み屈折率が1.5~3である高屈折率層とからなる多層構造の遠赤外線反射層を以下のように形成した他は実施例1と同様にしてサンプルを得た。
第1層:到達圧力:2E-3Pa以下、Nbターゲット(127mm×386mm×1枚)、搬送速度:0.3m/min、スパッタガス:Ar-30体積% O2、スパッタ圧力:0.3Pa、投入電力:DCパルス(50kHz)5kwにてNb2O5層をスパッタ加工にて形成した。
第2層:到達圧力:2E-3Pa以下、Ag合金ターゲット(76mm×330mm×2枚:Ag-0.2質量%Nd-1質量%Au)、搬送速度:3.5m/min、スパッタガス:Ar、スパッタ圧力:9.5E-2Pa、投入電力:LF電源(40kHz)1.0kwにて金属層をスパッタ加工にて形成した。
第3層:到達圧力:2E-3Pa以下、Nbターゲット(127mm×386mm×1枚)、搬送速度:5.0m/min、スパッタガス:Ar、スパッタ圧力:0.1Pa、投入電力:DCパルス(50kHz)0.9kwにてNb層をスパッタ加工にて形成した。
第4層:到達圧力:2E-3Pa以下、Nbターゲット(127mm×386mm×1枚)、搬送速度:0.3m/min、スパッタガス:Ar-30体積% O2、スパッタ圧力:0.3Pa、投入電力:DCパルス(50kHz)5kwにてNb2O5層をスパッタ加工にて形成した。
ポリオレフィン系樹脂を表層に有している帝人デュポンフィルム(株)製レフテル(登録商標)ZC05G(基板(PETフィルム)/金属層と誘電体層(酸化チタン)からなる遠赤外線反射層/OPPフィルム)を比較例1のサンプルとした。結果を表2および表3に示す。遠赤外線反射率が81%、耐表面擦過性では11本/10mm以上の無数のキズが観察され、可視光透過率が66%であり、総合判定1はC、総合判定2はDであった。
表面ハードコート層の形成工程において、リン酸基を含むメタクリル酸誘導体(共栄社化学(株)製ライトエステルP-2M)を添加しない他は実施例1と同様にしてサンプルを得た。結果を表2および表3に示す。
表面ハードコート層の形成工程において、アクリル系ハードコート剤としてJSR(株)製オプスターZ7535を用い、希釈溶媒としてメチルエチルケトンを用いて固形分濃度20質量%に希釈したものを塗液とし、該塗液をバーコーター(番手No.12)を用いて塗布する他は実施例1と同様にしてサンプルを得た。結果を表2および表3に示す。
表面ハードコート層の形成工程において、リン酸基を含むメタクリル酸誘導体(共栄社化学(株)製ライトエステルP-2M)を添加しない他は実施例3と同様にしてサンプルを得た。結果を表2および表3に示す。
表面ハードコート層の形成工程において、アクリル系ハードコート剤としてJSR(株)製オプスターZ7535に、リン酸基を含むメタクリル酸誘導体(共栄社化学(株)製ライトエステルP-2M)を固形分中2質量%となるよう混合し、希釈溶媒としてメチルエチルケトンを用いて固形分濃度1.9質量%に希釈して塗液を得た。得られた塗液を、バーコーター(番手No.10)を用いて塗布する他は実施例3と同様にしてサンプルを得た。結果を表2および表3に示す。
2:遠赤外線反射層[B]
3:内部ハードコート層[D]
4:基板[A]
Claims (6)
- 以下の[A]~[C]の層が、この順で配された遠赤外線反射積層体;
[A]基板;
[B]次の[B1]または[B2]の構造を有する遠赤外線反射層;
[B1]銀を95~100質量%含有する金属の単層構造;
[B2]銀を95~100質量%含有する金属の層と金属酸化物および/または金属窒化物を含み、屈折率が1.5~3である層とからなる多層構造;
[C]リン酸基、スルホン酸基およびアミド基からなる群より選ばれる1種以上の極性基を有する架橋樹脂を含み、かつ、厚みが0.4~2.0μmである表面ハードコート層。 - 基板、金属層および表面ハードコート層が、この順で配された遠赤外線反射積層体であって、該金属層が銀を95~100質量%含有し、該表面ハードコート層の厚みが0.4~2.0μmであり、かつ、該遠赤外線反射積層体の遠赤外線反射率が60%以上、かつ、耐表面擦過性が10本/10mm以下である遠赤外線反射積層体。
- 前記[C]層において、前記極性基がリン酸基を含む請求項1または2に記載の遠赤外線反射積層体。
- 前記[A]層と、前記[B]層との間に以下の[D]層が配されている請求項1~3のいずれかに記載の遠赤外線反射積層体;
[D]架橋樹脂からなり、厚みが0.2~10.0μmである内部ハードコート層。 - 前記[C]層が、多層構成または組成が厚み方向に連続的に変化する傾斜構成であり、
前記[C]層において、前記[C]層と前記[B]層との境界から0~200nmの範囲の領域[C1]におけるセクター磁場型二次イオン質量分析装置にて得た規格化強度値[P/C](C1)が0.01~30である請求項1~4のいずれかに記載の遠赤外線反射積層体。 - 前記[C]層において、前記[B]層とは反対側の表面から0~200nmの範囲の領域[C2]におけるセクター磁場型二次イオン質量分析装置にて得た規格化強度値[P/C](C2)が、前記規格化強度値[P/C](C1)の10%以下である請求項5に記載の遠赤外線反射積層体。
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CN201280005387.9A CN103313850B (zh) | 2011-01-13 | 2012-01-11 | 远红外线反射层合体 |
JP2012503142A JP5729376B2 (ja) | 2011-01-13 | 2012-01-11 | 遠赤外線反射積層体 |
US13/978,241 US20130279000A1 (en) | 2011-01-13 | 2012-01-11 | Far infrared reflecting laminate |
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Publication number | Publication date |
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US20130279000A1 (en) | 2013-10-24 |
CN103313850A (zh) | 2013-09-18 |
EP2666628A1 (en) | 2013-11-27 |
JP5729376B2 (ja) | 2015-06-03 |
JPWO2012096304A1 (ja) | 2014-06-09 |
TW201236863A (en) | 2012-09-16 |
CN103313850B (zh) | 2015-01-28 |
TWI517971B (zh) | 2016-01-21 |
EP2666628A4 (en) | 2016-05-25 |
KR20140005225A (ko) | 2014-01-14 |
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