JP2012037634A - Solar radiation control film and film-adhered glass using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a solar radiation control film which can achieve good stability and durability without reducing productivity and which can achieve good optical characteristic.SOLUTION: A solar radiation control film 1 includes a hard coat layer 3 on one of main surfaces of a polyester film 2, and a solar radiation reflecting laminate film 4 on the other of the main surfaces of the polyester film 2. The solar radiation reflecting laminate film 4 is formed by laminating a first zinc oxide layer 41, a first silver alloy layer 42, a second zinc oxide layer 43, a second silver alloy layer 44 and a third zinc oxide layer 45 in this order from the polyester film 2 side. The first to third zinc oxide layers 41, 43 and 45 are composed of oxides of zinc and metal element other than zinc, and among the zinc and the metal element other than zinc, the zinc becomes the main element composing the oxide. The first to second silver alloy layers 42 and 44 are composed of silver alloy including at least one metal selected from palladium and gold.

Description

  The present invention relates to a solar control film and a glass with a film using the same.

  Conventionally, a solar control film having a layered structure in which dielectric layers and metal layers are alternately laminated is known. A solar control film having such a layered structure transmits visible light and reflects light rays (heat rays) from the near-infrared part to the infrared part. It is used to block the solar energy to improve the cooling effect. Moreover, since such a solar control film has an electromagnetic shielding effect, the electromagnetic shielding film shields unnecessary external electromagnetic fields in order to suppress malfunctions of electronic devices, and further prevents information leakage due to internal wireless communication. It is also used to prevent. Furthermore, since it can suppress scattering when the window glass is broken, it is also used to improve safety.

  As a solar control film, for example, a dielectric layer made of indium oxide, a metal layer substantially made of silver, and a five-layer structure (for example, see Patent Document 1) is known. Further, for example, a dielectric layer made of titanium oxide, a metal layer substantially made of silver, and a five-layered structure is known (for example, see Patent Document 2). On the other hand, the dielectric layer is made of titanium oxide, tantalum oxide, zirconium oxide, tin oxide, silicon oxide, indium oxide, or zinc oxide, and the metal layer is made of gold, silver, copper, or aluminum to form a three-layer structure. Is known (see, for example, Patent Document 3).

JP-T-2002-523798 JP-T-2006-505811 JP 2001-310407 A

  However, in the case where the dielectric layer is made of titanium oxide, the metal layer is made of silver, and these layer structure portions are made of five layers, the compatibility between the dielectric layer and the metal layer is not necessarily good, and the metal layer made of silver Is not sufficiently stable and durable, it may cause cloudiness or whitening. For this reason, it has been studied to improve stability and durability by adopting a structure in which the layered structure portion is sandwiched between a pair of polyester films, etc., but a process of newly providing a polyester film etc. is required, and productivity is increased. From the viewpoint of the above, it is not necessarily preferable. On the other hand, when the dielectric layer is made of a material other than titanium oxide and the layered structure portion is made of three layers, it is not always possible to obtain a product having good optical characteristics, for example, a balance between visible light transmittance and solar reflectance. .

  The present invention has been made in order to solve the above-mentioned problems, and it is possible to obtain good stability and durability without reducing productivity, and to adjust solar radiation capable of obtaining good optical characteristics. It aims at providing a film and glass with a film using the same.

  The solar control film of the present invention has a hard coat layer on one main surface of a polyester film and a solar reflective laminated film on the other main surface, and the solar reflective laminated film is from the polyester film side. In this order, a first zinc oxide layer, a first silver alloy layer, a second zinc oxide layer, a second silver alloy layer, and a third zinc oxide layer are laminated. And the 1st-3rd zinc oxide layer consists of oxides of metal elements other than zinc and zinc, and zinc is the main oxide constituent element in these zinc and metal elements other than zinc, The first and second silver alloy layers are made of a silver alloy containing at least one metal selected from palladium and gold.

  Moreover, the glass with a film of the present invention is a glass with a film formed by sticking a film to a glass plate, and the film is the above-described solar control film of the present invention.

  According to the solar control film of the present invention, a hard coat layer is provided on one main surface of the polyester film, and a solar reflective multilayer film is provided on the other main surface, and the solar reflective multilayer film contains a zinc oxide layer and silver. By stacking the layers alternately and making the zinc oxide layer and the silver-containing layer as a whole into a five-layer structure, good stability and durability can be obtained without reducing productivity. And good optical characteristics can be obtained. Moreover, according to the glass with a film of the present invention, by having the above-mentioned solar control film, good stability and durability can be obtained, and good optical characteristics can be obtained.

Sectional drawing which shows an example of the solar radiation adjustment film of this invention. Sectional drawing which shows an example of the glass with a film of this invention.

Hereinafter, the solar radiation adjusting film of the present invention will be described with reference to the drawings.
FIG. 1 is a cross-sectional view showing an example of a solar control film.

  The solar radiation adjusting film 1 has a hard coat layer 3 on one main surface of a polyester film 2 and a solar reflective laminated film 4 on the other main surface. In the solar radiation adjusting film 1, a protective layer 5 and an adhesive layer 6 may be formed on the solar reflective laminated film 4 as shown in the figure.

  The polyester film 2 serves as a base material for the solar control film 1. The polyester film 2 is made of, for example, polyethylene terephthalate, polyethylene naphthalate, polymethacrylate, or the like.

  Among these, a film produced by a stretching method such as a polyethylene terephthalate film is preferable because it has a relatively high strength and can suppress the occurrence of defects such as breakage during production and processing. Although the thickness of the polyester film 2 is not necessarily limited, 5-200 micrometers is preferable. It is preferable for the thickness to be 5 μm or more because it is possible to suppress the occurrence of defects such as breakage during the production or processing of the polyester film 2. Moreover, since it can suppress the whole thickness of the solar radiation adjustment film 1 by setting it as 200 micrometers or less, it is preferable. 30-150 micrometers is preferable and, as for the thickness of the polyester film 2, 40-110 micrometers is more preferable.

  The hard coat layer 3 has a hardness higher than that of the polyester film 2 and suppresses the occurrence of fine scratches on the surface of the polyester film 2 when the solar radiation adjusting film 1 is attached to the glass. It is provided to suppress shrinkage.

  The hardness of the hard coat layer 3 is preferably H or more, more preferably H to 3H, in terms of pencil hardness. By setting the pencil hardness to H or higher, scratches or the like in the polyester film 2 can be effectively suppressed. On the other hand, if the pencil hardness is about 2H, scratches and the like can be sufficiently suppressed, and the occurrence of cracks and the like can be suppressed because the hard coat layer 3 becomes too hard. The pencil hardness of the hard coat layer 3 in the present invention is measured with a load of 100 g according to JIS K5400 (1990) for the hard coat layer 3 formed on the polyester film 2.

  The thickness of the hard coat layer 3 is preferably 0.5 to 20 μm, and more preferably 1 to 10 μm. By setting the thickness of the hard coat layer 3 to 0.5 μm or more, scratches, shrinkage, etc. in the polyester film 2 can be effectively suppressed. On the other hand, if the thickness of the hard coat layer 3 is about 20 μm, scratches and shrinkage in the polyester film 2 can be sufficiently suppressed, and cracks and the like may occur because the hard coat layer 3 becomes too hard. Can be suppressed.

  Such a hard coat layer 3 is made of, for example, a curable resin that is crosslinked and cured by the action of the resin itself or a curing agent. Specifically, urethane resin, aminoplast resin, silicone resin, epoxy resin, acrylic resin, etc., single-curing heat / ultraviolet ray / electron beam curable resin, polyester resin, acrylic resin, epoxy And thermosetting resins that are cured by a curing agent such as a resin. Among these, an acrylic resin is preferable because a good hard coat layer 3 can be easily formed.

  The solar reflective laminated film 4 is provided to reflect light rays (heat rays) from the near infrared part to the infrared part, and in order from the polyester film 2 side, the first zinc oxide layer 41 and the first silver alloy are provided. The layer 42, the second zinc oxide layer 43, the second silver alloy layer 44, and the third zinc oxide layer 45 are laminated.

  The first, second, and third zinc oxide layers 41, 43, and 45 (hereinafter sometimes collectively referred to as zinc oxide layers) are all made of zinc and oxides of metal elements other than zinc. It will be. Examples of such an oxide include an oxide containing zinc alone (zinc oxide) and a composite oxide of zinc and a metal element other than zinc. Such an oxide may further contain an oxide of a metal element other than zinc.

  Further, this oxide is a main oxide constituent element of zinc in zinc constituting the oxide and a metal element other than zinc. Specifically, the total amount of zinc and metal elements other than zinc is preferably 50 atomic% or more, more preferably 75 atomic% or more, and still more preferably 85% or more. The content of metal elements other than zinc is preferably 50 atomic% or less, more preferably 25 atomic% or less, and even more preferably 15% or less in the total amount of zinc and metal elements other than zinc. is there.

  According to such a zinc oxide layer, for example, the compatibility with the silver alloy layer is improved due to its crystallinity and the like, so that the stability and durability of the silver alloy layer can be improved. The first, second, and third zinc oxide layers 41, 43, and 45 can have different compositions, but it is usually preferable to have the same composition.

  On the other hand, the first and second silver alloy layers 42 and 44 (hereinafter, these may be collectively referred to as a silver alloy layer) are both silver alloys containing at least one metal selected from palladium and gold. It consists of According to such a silver alloy layer, good stability and durability can be obtained by containing at least one metal selected from palladium and gold. Note that the first and second silver alloy layers 42 and 44 can also have different compositions from each other, but usually have the same composition.

  According to the solar reflective multilayer film 4 composed of such a zinc oxide layer and a silver alloy layer, in addition to good stability and durability of the silver alloy layer itself, the zinc oxide layer and the silver alloy layer Therefore, the stability and durability of the silver alloy layer can be further improved. For this reason, it is not necessary to sandwich between a pair of polyester films to improve stability and durability as in the case of a conventional solar reflective laminated film, and it has good stability and durability while improving productivity. It can be.

  Further, the solar reflective laminated film 4 has a five-layer structure of a zinc oxide layer and a silver alloy layer, that is, two silver alloy layers, so that good optical characteristics such as visible light transmittance and solar reflectance are obtained. And can be balanced. That is, in the case of a three-layer structure of a zinc oxide layer and a silver alloy layer, that is, a layer having one silver alloy layer, it is not always possible to obtain a material having a balance between visible light transmittance and solar reflectance. In addition, even a seven-layer structure, that is, a layer having three silver alloy layers, cannot always obtain a balanced light transmittance and solar reflectance, and is not excellent in productivity.

  According to what has the solar reflective laminated film 4 of the 5-layer structure of a zinc oxide layer and a silver alloy layer, for example, when pasted on a glass plate, the visible light transmittance measured according to JIS A5759 is 70%. As described above, the solar reflectance can be set to 30% or more, and the visible light transmittance and the solar reflectance can be balanced.

  The first, second, and third zinc oxide layers 41, 43, and 45 preferably have a refractive index of 1.7 to 2.3, more preferably 1.8 to 2.2, More preferably, it is 1.9 to 2.1. By setting it as such a refractive index, both visible light transmittance and solar reflectance can be made high by the interference effect with the 1st, 2nd silver alloy layers 42 and 44. The refractive index means the refractive index at a wavelength of 555 nm.

  Examples of the metal element other than zinc in the first, second, and third zinc oxide layers 41, 43, and 45 include tin, aluminum, chromium, titanium, magnesium, and gallium. Only one species or two or more species can be used. Among these, in particular, by using aluminum, titanium, or gallium, for example, compatibility with the silver alloy layer can be improved, and internal stress can be effectively reduced to improve adhesion with the silver alloy layer. As a result, stability and durability can be improved.

  When the metal element other than zinc is aluminum or gallium, the content of the aluminum element or gallium element in the oxide is preferably 1 to 15 atomic% in the total amount of the zinc element and the aluminum element or gallium element. By setting the content of aluminum element or gallium element to 1 atomic% or more, for example, the internal stress of the zinc oxide layer is effectively reduced, and the adhesiveness with the silver alloy layer is enhanced to improve the stability and durability. It can be. On the other hand, by setting it to 10 atomic% or less, for example, the crystallinity can be maintained and compatibility with the silver alloy layer can be maintained, and as a result, moisture resistance and the like can be improved. The content of aluminum element or gallium element is preferably 1.5 to 10 atomic%, more preferably 1.5 to 8.0 atomic%, in the total amount of zinc element and aluminum element or gallium element.

  On the other hand, when the element other than zinc is titanium, the content of the titanium element is preferably 2 to 20 atomic% in the total amount of the zinc element and the titanium element. By setting the content of titanium element to 2 atomic% or more, for example, the internal stress of the zinc oxide layer is effectively reduced, and the adhesion with the silver alloy layer is enhanced to improve the stability and durability. Can do. On the other hand, by setting it to 20 atomic% or less, for example, the crystallinity can be maintained and compatibility with the silver alloy layer can be maintained, and as a result, moisture resistance and the like can be improved. The content of titanium element is preferably 3 to 15 atomic% in the total amount of zinc element and titanium element.

  The thicknesses of the first and third zinc oxide layers 41 and 45 (physical film thickness, the same applies hereinafter) are each preferably 25 to 45 nm, and the thickness of the second zinc oxide layer 43 is preferably 60 to 90 nm. . The first zinc oxide layer 41 is more preferably 35 to 45 nm, and the thickness of the third zinc oxide layer 45 is more preferably 30 to 40 nm. The thickness of the second zinc oxide layer 43 is more preferably 70 to 90 nm.

  The first and second silver alloy layers 42 and 44 are both made of a silver alloy containing at least one metal selected from palladium and gold. The total content of palladium and gold is preferably 0.2 to 3% by mass and more preferably 0.2 to 1.5% by mass in the total amount of silver, palladium and gold. By setting the content of palladium and gold within such a range, for example, diffusion of silver can be suppressed, and thereby moisture resistance can be increased, and the specific resistance of the silver alloy layer can be reduced to 10 μΩcm or less. it can.

  The thicknesses of the first and second silver alloy layers 42 and 44 are preferably 5 to 25 nm, more preferably 5 to 20 nm, and still more preferably 5 to 15 nm. The second silver alloy layer 44 is preferably thicker than the first silver alloy layer 42, and the second silver alloy layer 44 is preferably 1 to 8 nm thicker than the first silver alloy layer 42. It is more preferably ˜6 nm thick, and further preferably 1-5 nm thick.

  Such a solar reflective multilayer film 4 preferably has a surface resistance value of 2 to 4 Ω / sq. According to what has such a surface resistance value, the electromagnetic wave shielding effect becomes favorable and it can suppress malfunction of an electronic device effectively as an electromagnetic wave shielding film.

  The protective layer 5 is provided in order to improve the adhesion with the adhesive layer 6 and also plays a role of protecting the solar reflective laminated film 4 from moisture and the like. The protective layer 5 is provided on the solar reflective laminated film 4 as necessary, and is mainly composed of a metal oxide or nitride layer such as tin, indium, titanium, silicon, gallium, or hydrogenated carbon. Examples include layers. The protective layer 5 is particularly preferably an oxide layer of indium, tin, and gallium, or a layer containing hydrogenated carbon as a main component.

  2-30 nm is preferable, as for the film thickness of the protective layer 5, 3-20 nm is more preferable, and 3-10 nm is further more preferable. By setting the thickness of the protective layer 5 to 2 nm or more, the adhesion with the adhesive layer 6 can be improved, and the solar reflective multilayer film 4 can be effectively protected from moisture and the like. In addition, by setting the thickness of the protective layer 5 to 30 nm or less, the entire thickness of the solar control film 1 can be suppressed while the solar reflective multilayer film 4 is effectively protected from moisture and the like.

  The adhesive layer 6 is used for adhering the solar radiation adjusting film 1 to a window glass of a building or a vehicle, and is provided as necessary. Examples of the pressure-sensitive adhesive layer 6 include those composed only of a pressure-sensitive adhesive or those in which an ultraviolet absorber is contained in the pressure-sensitive adhesive. Among these, those containing an ultraviolet absorber, when the solar radiation adjusting film 1 is attached to a window glass of a building or a vehicle, suppresses sunburn in the indoor human body and articles due to ultraviolet rays, and has an adverse effect on the human body. It is preferable because it can be suppressed.

  As the ultraviolet absorber, for example, a triazine ultraviolet absorber is preferably used. As UV absorbers, benzophenone and benzotriazole UV absorbers are also known, but these UV absorbers may cause insufficient cross-linking of the pressure-sensitive adhesive and reduce retention or yellowing. is there. For this reason, it is preferable to use a triazine ultraviolet absorber as the ultraviolet absorber.

  Examples of the pressure-sensitive adhesive include acrylic pressure-sensitive adhesives, silicone-based pressure-sensitive adhesives, urethane-based pressure-sensitive adhesives, and butadiene-based pressure-sensitive adhesives. Among these, acrylic pressure-sensitive adhesives are preferably used. An acrylic adhesive is a polymer containing an acrylic monomer unit as a main component. The acrylic monomer includes (meth) acrylic acid, itaconic acid, (anhydrous) maleic acid, and (anhydrous) fumaric acid. Examples include acids, crotonic acid, and alkyl esters thereof. Here, (meth) acrylic acid is used as a general term for acrylic acid and methacrylic acid.

  According to the adhesive layer 6 having such an adhesive layer 6 containing an ultraviolet absorber, for example, when adhered to a glass plate, the ultraviolet transmittance measured according to JIS A5759 is 1% or less. It is possible to effectively suppress sunburn in the indoor human body and articles caused by ultraviolet rays, and to effectively suppress adverse effects on the human body.

  Such a solar radiation adjusting film 1 can be used as glass with a film by sticking to a glass plate using the adhesive layer 6, for example. FIG. 2 is a cross-sectional view showing an example of glass with a film.

  The glass with film 11 has a glass plate 12, and the solar radiation adjusting film 1 is attached to the glass plate 12 using the adhesive layer 6. Typical examples of the glass plate 12 include window glass for buildings and vehicles, but the glass plate 12 is not necessarily limited thereto, and may be a glass plate such as a refrigerated / frozen showcase. Absent.

  By providing the solar control film 1 on a window glass of a building or vehicle, the incident solar energy can be cut off and the cooling effect can be improved. Moreover, since this solar radiation adjustment film 1 has an electromagnetic wave shielding effect, it can also suppress the malfunction of an electronic device as an electromagnetic wave shielding film, and can also prevent the leakage of an electromagnetic wave. Furthermore, since the scattering when the window glass is broken can be suppressed, safety can also be improved.

  The glass with film 11 preferably has a visible light transmittance of, for example, 70% or more and a solar reflectance of 30% or more measured according to JIS A5759. The visible light transmittance is more preferably 72% or more. The solar reflectance is more preferably 32% or more. By having such visible light transmittance, solar reflectance, and the like, for example, both visibility from the inside to the outside and the cooling effect by blocking solar energy can be achieved. In addition, such visible light transmittance and solar reflectance are such that the solar reflective laminated film 4 in the solar radiation adjusting film 1 is mainly composed of a zinc oxide layer and a silver alloy layer as described above, and the number of laminated layers is This can be achieved by using five layers, that is, two silver alloy layers.

  Moreover, it is preferable that the glass-with-film 11 is 1% or less of the ultraviolet-ray transmittance measured, for example according to JIS A5759. By setting it as such an ultraviolet-ray transmittance, the sunburn in the indoor human body and goods by an ultraviolet-ray can be suppressed, and the bad influence to a human body can be suppressed effectively. Such ultraviolet transmittance can also be achieved by providing the solar control film 1 with the adhesive layer 6 containing the ultraviolet absorber as described above.

Next, the manufacturing method of the solar radiation adjustment film 1 is demonstrated.
The solar control film 1 is formed by applying and curing a thermosetting resin or the like on one main surface of the polyester film 2 to form a hard coat layer 3, and on the other main surface, a sputtering method, a vacuum deposition method, or an ion plating method. The solar reflective multilayer film 4 is formed by a method, a chemical vapor deposition method, or the like, and the protective layer 5 and the adhesive layer 6 are formed on the solar reflective multilayer film 4 as necessary.

  The formation of the solar reflective laminated film 4 is particularly preferably performed by a sputtering method because the quality and stability of characteristics are good. Examples of the sputtering method include a DC sputtering method, an AC sputtering method, and a high frequency sputtering method. The solar reflective multilayer film 4 can be formed by sputtering as follows, for example.

  First, while introducing an argon gas mixed with an oxygen gas, DC sputtering is performed on the surface of the polyester film 2 using a mixed target made of an oxide of zinc and titanium to form a first zinc oxide layer 41. Further, while introducing argon gas, DC sputtering is performed using a silver alloy target to form the first silver alloy layer 42. By repeating such an operation, the second zinc oxide layer 43, the second silver alloy layer 44, and the third zinc oxide layer 45 are sequentially formed on the first silver alloy layer 42. The solar reflective laminated film 4 can be formed.

  The thicknesses of the zinc oxide layer and the silver alloy layer can be adjusted by the power density and the sputtering time when performing DC sputtering. The above-mentioned mixed target can be produced by mixing high-purity (usually 99.9%) powders of oxides of individual metals, forming and sintering using a cold isostatic press or the like.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. In addition, the film thickness in an Example is the value calculated | required from the optical characteristic or the sputtering film-forming rate, and the sputtering time, and is not the film thickness actually measured. Each characteristic in the examples was measured as follows.

(Measurement of visible light transmittance (Tv), solar transmittance (Te), solar reflectance (Re))
The solar control film was cut into a size of 50 mm × 50 mm, and was uniformly attached to a soda lime glass plate having a thickness of 50 mm × 50 mm and a thickness of 3 mm through the adhesive layer so that glass with a film was produced. This glass with film was measured with a UV-3150 spectrophotometer manufactured by Shimadzu Corporation in accordance with JIS A5759. The light source was incident from the glass side.

(Measurement of shielding coefficient and heat flow rate)
The solar control film was cut into a size of 50 mm × 50 mm, and was uniformly attached to a soda lime glass plate having a thickness of 50 mm × 50 mm and a thickness of 3 mm through the adhesive layer so that glass with a film was produced. About this glass with a film, vertical emissivity was measured with the FT / IR-420 Fourier-transform infrared spectrophotometer by JASCO Corporation based on JISR3106, and it calculated | required by calculation based on JISA5759.

(Wear resistance test)
The solar control film was cut into a size of 70 mm × 150 mm, and was uniformly attached to a soda lime glass plate having a thickness of 70 mm × 150 mm and a thickness of 2 mm through the adhesive layer so that glass with a film was produced. About this glass with a film, a weather resistance test for 1,000 hours and 2,000 hours was conducted using a sunshine carbon arc lamp type weather resistance tester in accordance with JIS A5759, Visible light transmittance, solar transmittance, and solar reflectance were measured.

(Measurement of sheet resistance)
The solar control film was cut into a size of 100 mm × 100 mm, and the sheet resistance value (surface resistance value) was measured using an eddy current type resistance measuring instrument (trade name: SRM12) manufactured by Nagy.

[Sample 1]
A solar control film was produced as follows using a roll coater.
First, dry cleaning using an ion beam is performed for the purpose of cleaning the surface of the PET film (PET film thickness: 100 μm) on which the hard coat layer is formed, on which the hard coat layer is not formed (formation surface of the solar reflective laminated film). went. This dry cleaning was performed by applying a power of 100 W while introducing a mixed gas obtained by mixing about 30% oxygen into argon gas and irradiating argon ions and oxygen ions ionized by an ion beam source.

  Next, 10 vol% oxygen gas is mixed with argon gas using a target (zinc oxide: titanium oxide = 90: 10 (mass ratio)) obtained by mixing and baking zinc oxide and titanium oxide on the formation surface. AC magnetron sputtering is performed at a pressure of 0.1 Pa, the power density and sputtering time are adjusted, and a 39 nm thick zinc and titanium oxide film (refractive index 2.02, first zinc oxidation) Material layer, composition abbreviation: TZO).

  On the first zinc oxide layer, while introducing argon gas using a silver alloy target doped with 1.0% by mass of palladium, DC magnetron sputtering with a frequency of 100 kHz and an inversion pulse width of 5 μsec was performed at a pressure of 0.3 Pa. Then, the metal film (first silver alloy layer) having a thickness of 10 nm was formed by adjusting the power density and the sputtering time.

  Using a target (zinc oxide: titanium oxide = 90: 10 (mass ratio)) obtained by mixing and baking zinc oxide and titanium oxide on the first silver alloy layer, 10% by volume of oxygen gas in argon gas The mixture was introduced, AC magnetron sputtering was performed at a pressure of 0.1 Pa, the power density and the sputtering time were adjusted, and a 78 nm thick zinc and titanium oxide film (refractive index 2.02; 2 zinc oxide layer, composition abbreviation: TZO).

  On the second zinc oxide layer, DC magnetron sputtering with a frequency of 100 kHz and a reverse pulse width of 5 μsec was performed at a pressure of 0.3 Pa while introducing argon gas using a silver alloy target doped with 1.0% by mass of palladium. The power density and the sputtering time were adjusted to form a 13 nm thick metal film (second silver alloy layer).

  Using a target (zinc oxide: titanium oxide = 90: 10 (mass ratio)) obtained by mixing and baking zinc oxide and titanium oxide on the second silver alloy layer, 10% by volume of oxygen gas in argon gas The mixture was introduced, AC magnetron sputtering was performed at a pressure of 0.1 Pa, the power density and sputtering time were adjusted, and a 34 nm thick zinc and titanium oxide film (refractive index 2.02; 3 zinc oxide layer, composition abbreviation: TZO).

  Furthermore, on this solar reflective multilayer film (third zinc oxide layer), 7% by volume in argon gas using an oxide target of gallium, indium and tin (manufactured by AGC Ceramics, trade name: GIT target). While introducing a mixed gas of oxygen gas, DC magnetron sputtering with a pressure of 0.1 Pa and a frequency of 100 kHz and an inversion pulse width of 1 μsec is performed, and the power density and sputtering time are adjusted to form a protective layer (refracting) Rate 2.08). Furthermore, an adhesive film (trade name: PU-V, manufactured by Lintec Co., Ltd.) containing an ultraviolet absorber was bonded onto the protective layer to form an adhesive layer, which was used as a solar control film.

[Sample 2]
A solar control film was prepared in the same manner as Sample 1 except that the thickness of the PET film was changed to 75 μm.

[Sample 3]
A solar control film was prepared in the same manner as Sample 1 except that the thickness of the PET film was changed to 50 μm.

[Sample 4]
In substantially the same manner as Sample 1, a first zinc oxide layer (thickness 39 nm), a first silver alloy layer (thickness 10 nm), and a second zinc oxide are formed on a PET film on which a hard coat layer is formed. Three layers of physical layers (thickness 34 nm) were formed in order to form a solar reflective laminated film. Thereafter, in the same manner as in Sample 1, a protective layer and an adhesive layer were formed in this order on the solar reflective laminated film to obtain a solar control film. In addition, this sample 4 is a thing of a solar radiation reflection laminated film 3 layers (one silver alloy layer), and becomes a comparative example of this invention.

[Sample 5]
In substantially the same manner as Sample 1, a first zinc oxide layer (thickness 36 nm), a first silver alloy layer (thickness 10 nm), and a second zinc oxide are formed on a PET film on which a hard coat layer is formed. Physical layer (thickness 72 nm), second silver alloy layer (thickness 11 nm), third zinc oxide layer (thickness 72 nm), third silver alloy layer (thickness 10 nm), fourth zinc oxide Seven layers of physical layers (thickness 31 nm) were formed in order to form a solar reflective laminated film. Thereafter, in the same manner as in Sample 1, a protective layer and an adhesive layer were formed in this order on the solar reflective laminated film to obtain a solar control film. In addition, this sample 5 is a thing of 7 layers (3 silver alloy layers) of a solar reflective laminated film, and becomes a comparative example of this invention.

[Sample 6]
A solar control film was prepared as follows using a batch type sputtering apparatus.
First, a target obtained by mixing and baking zinc oxide and titanium oxide on the surface of a PET film having a hard coat layer that has been cleaned in the same manner as in sample 1 (formation surface of the solar reflective laminated film) (zinc oxide: 6 vol% oxygen gas was mixed with argon gas using titanium oxide = 90: 10 (mass ratio), and DC magnetron sputtering with a frequency of 50 kHz and an inversion pulse width of 2 μsec was performed at a pressure of 0.2 Pa. The power density and the sputtering time were adjusted to form a 39 nm thick zinc and titanium oxide film (refractive index 2.02, first zinc oxide layer, composition abbreviation: TZO).

  On the first zinc oxide layer, while introducing argon gas using a silver alloy target doped with 1.0% by mass of palladium, DC magnetron sputtering with a frequency of 50 kHz and an inversion pulse width of 10 μsec was performed at a pressure of 1.0 Pa. Then, the metal film (first silver alloy layer) having a thickness of 10 nm was formed by adjusting the power density and the sputtering time.

  Using a target (zinc oxide: titanium oxide = 90: 10 (mass ratio)) obtained by mixing and baking zinc oxide and titanium oxide on the first silver alloy layer, 6 vol% oxygen gas is added to argon gas. Was mixed, and DC magnetron sputtering with a frequency of 50 kHz and a reversal pulse width of 2 μsec was performed at a pressure of 0.2 Pa, and the power density and sputtering time were adjusted to form a 78 nm thick zinc and titanium oxide film (refractive Ratio 2.02, second zinc oxide layer, composition abbreviation: TZO).

  On the second zinc oxide layer, while introducing argon gas using a silver alloy target doped with 1.0% by mass of palladium, DC magnetron sputtering with a frequency of 50 kHz and an inversion pulse width of 10 μsec was performed at a pressure of 1.0 Pa. Then, the metal film (second silver alloy layer) having a thickness of 12 nm was formed by adjusting the power density and the sputtering time.

  Using a target (zinc oxide: titanium oxide = 90: 10 (mass ratio)) obtained by mixing and baking zinc oxide and titanium oxide on the second silver alloy layer, 6 vol% oxygen gas was added to the argon gas. Was mixed, and DC magnetron sputtering with a frequency of 50 kHz and a reversal pulse width of 2 μsec was performed at a pressure of 0.2 Pa, and the power density and sputtering time were adjusted to make a 34 nm thick zinc and titanium oxide film (refractive A rate of 2.02, a third zinc oxide layer, composition abbreviation: TZO) was formed to form a solar reflective laminated film.

  Furthermore, on this solar reflective multilayer film (third zinc oxide layer), 7% by volume in argon gas using an oxide target of gallium, indium and tin (manufactured by AGC Ceramics, trade name: GIT target). While introducing a mixed gas of oxygen gas, DC magnetron sputtering with a pressure of 0.1 Pa and a frequency of 50 kHz and an inversion pulse width of 2 μsec is performed, and the power density and the sputtering time are adjusted to form a protective layer (refracting) Rate 2.08). Furthermore, the adhesive film containing a ultraviolet absorber was bonded together on the protective layer, and it was set as the adhesive layer, and it was set as the solar radiation adjustment film.

[Sample 7]
Instead of the silver alloy target doped with 1.0% by mass of palladium, a silver alloy target doped with 1.0% by mass of gold was used, and the first silver alloy layer was 8 nm and the second silver alloy layer was 10 nm. Except for the above, a solar control film was prepared in the same manner as Sample 6.

[Sample 8]
Instead of a target obtained by mixing and baking zinc oxide and titanium oxide, a target obtained by mixing and baking zinc oxide and aluminum oxide (zinc oxide: aluminum oxide = 97: 3 (mass ratio)) was used. A solar control film was prepared in the same manner as Sample 6, except that an oxide film of zinc and aluminum (refractive index: 1.95, zinc oxide layer, composition abbreviation: AZO) was formed.

[Sample 9]
A solar control film was prepared using the same batch type sputtering apparatus as Sample 6.
First, a titanium oxide target (manufactured by AGC Ceramics Co., Ltd., trade name: TXO target) is applied to the surface of a PET film having a hard coat layer that has been cleaned in the same manner as Sample 1 (formation surface of a solar reflective laminated film). Using argon gas mixed with 6% by volume of oxygen gas, DC magnetron sputtering with a frequency of 50 kHz and an inversion pulse width of 2 μsec is performed at a pressure of 0.2 Pa, and the thickness is adjusted by adjusting the power density and sputtering time. A 25 nm titanium oxide film (refractive index 2.4, first titanium oxide layer, composition abbreviation: TiOx) was formed.

  On the first titanium oxide layer, DC magnetron sputtering with a frequency of 50 kHz and an inversion pulse width of 10 μsec was performed at a pressure of 1.0 Pa while introducing argon gas using a silver alloy target doped with 1.0 mass% of palladium. The metal layer (first silver alloy layer) having a thickness of 10 nm was formed by adjusting the power density and the sputtering time.

  Argon gas was introduced onto the first silver alloy layer using a titanium oxide target (manufactured by AGC Ceramics, trade name: TXO target), with a pressure of 0.2 Pa, a frequency of 50 kHz, and an inversion pulse width of 2 μsec. DC magnetron sputtering was performed to adjust the power density and sputtering time to form a first barrier film having a thickness of 3 nm.

  On the first barrier film, a titanium oxide target (manufactured by AGC Ceramics Co., Ltd., trade name: TXO target) was used, and 6 vol% oxygen gas was mixed with argon gas and introduced at a pressure of 0.2 Pa. DC magnetron sputtering with a frequency of 50 kHz and an inversion pulse width of 2 μsec, and adjusting the power density and sputtering time to a thickness of 47 nm titanium oxide film (refractive index 2.4, second titanium oxide layer, composition abbreviation: TiOx) Formed.

  On the second titanium oxide layer, DC magnetron sputtering with a frequency of 50 kHz and an inversion pulse width of 10 μsec was performed at a pressure of 1.0 Pa while introducing argon gas using a silver alloy target doped with 1.0 mass% of palladium. The metal layer (second silver alloy layer) having a thickness of 12 nm was formed by adjusting the power density and the sputtering time.

  Argon gas was introduced onto the second silver alloy layer using a titanium oxide target (manufactured by AGC Ceramics, trade name: TXO target), with a pressure of 0.2 Pa, a frequency of 50 kHz, and an inversion pulse width of 2 μsec. DC magnetron sputtering was performed to adjust the power density and sputtering time to form a second barrier film having a thickness of 3 nm.

  On the second barrier film, a titanium oxide target (manufactured by AGC Ceramics Co., Ltd., trade name: TXO target) was used to mix and introduce 6 vol% oxygen gas into argon gas at a pressure of 0.2 Pa. DC magnetron sputtering with a frequency of 50 kHz and an inversion pulse width of 2 μsec, and a power density and a sputtering time are adjusted to form a titanium oxide film having a thickness of 22 nm (refractive index 2.4, third titanium oxide layer, composition abbreviation: TiOx). To form a solar reflective laminated film.

  Furthermore, an adhesive film containing an ultraviolet absorber was laminated on the solar reflective laminated film (third titanium oxide layer) to form an adhesive layer, thereby obtaining a solar control film. In Sample 9, the solar reflective laminated film is composed of a titanium oxide layer and a silver alloy layer, which is a comparative example of the present invention.

[Sample 10]
A solar control film was prepared in the same manner as Sample 9, except that the first silver alloy layer was 12 nm and the second silver alloy layer was 15 nm. In this sample 10 as well, the solar reflective laminated film is composed of a titanium oxide layer and a silver alloy layer, which is a comparative example of the present invention.

[Sample 11]
The first silver alloy layer was 12 nm, the second silver alloy layer was 14 nm, and the target used for forming the first and second silver alloy layers was a silver alloy target doped with 5.0% by mass of palladium. In addition, a solar control film was prepared in the same manner as Sample 1 except that the protective layer was not formed.

[Sample 12]
The first silver alloy layer was 13 nm, the second silver alloy layer was 16 nm, and the target used to form the first and second silver alloys was a silver alloy target doped with 5.0% by mass of tin. Except for the above, a solar control film was produced in the same manner as Sample 11. The sample 12 is a comparative example of the present invention because the silver alloy does not contain one or more metals selected from palladium and gold.

[Sample 13]
A silver alloy in which the first silver alloy layer is 10 nm, the second silver alloy layer is 12 nm, and the target used for forming the first and second silver alloys is doped with 2% by mass of palladium and 3% by mass of gold. A solar control film was prepared in the same manner as Sample 11 except that the target was used.

  The solar control film thus obtained was measured by the above method. Table 4 shows the results of the electrical characteristics and optical characteristics, Table 5 shows the results of the shielding coefficient and the thermal conductivity, and Table 6 shows the results of the weather resistance test.

  As is apparent from Table 4, all of the solar control films having a solar reflective laminated film having a five-layer structure composed of a zinc oxide layer and a silver-containing layer have a visible light transmittance (Tv) of 70% or more, and solar reflectivity. The rate (Re) was found to be 30% or more. Further, as apparent from Table 6, it was recognized that the solar control film having the solar reflective laminated film composed of the zinc oxide layer and the silver-containing layer also has good durability.

1 ... Solar control film 1
DESCRIPTION OF SYMBOLS 2 ... Polyester film 3 ... Hard-coat layer 4 ... Solar-reflection reflection film 41 ... 1st zinc oxide layer 42 ... 1st silver alloy layer 43 ... 2nd zinc oxide layer 44 ... 2nd silver alloy layer 45 3rd zinc oxide layer 5 ... protective layer 6 ... adhesive layer 11 ... glass with film 12 ... glass plate

Claims (10)

A film having a hard coat layer on one main surface of the polyester film and a solar reflective laminated film on the other main surface,
The solar reflective laminated film is in order from the polyester film side,
A first zinc oxide layer comprising zinc and an oxide of a metal element other than zinc, wherein the zinc is a main oxide constituent element in the zinc and the metal element other than zinc;
A first silver alloy layer comprising a silver alloy containing at least one metal selected from palladium and gold;
A second zinc oxide layer comprising zinc and an oxide of a metal element other than zinc, wherein the zinc is a main oxide constituent element in the zinc and the metal element other than zinc,
A second silver alloy layer comprising a silver alloy containing at least one metal selected from palladium and gold, and an oxide of a metal element other than zinc and zinc, wherein the zinc and the metal element other than zinc are A solar control film, comprising: a third zinc oxide layer in which zinc is a main oxide constituent element.   2. The solar control film according to claim 1, further comprising a protective layer mainly composed of tin oxide on the solar reflective laminated film.   3. The solar control film according to claim 2, further comprising an adhesive layer containing an ultraviolet absorber on the protective layer. The first zinc oxide layer and the third zinc oxide layer have a thickness of 25 to 45 nm,
The solar control film according to any one of claims 1 to 3, wherein the second zinc oxide layer has a thickness of 60 to 90 nm. The first silver alloy layer and the second silver alloy layer have a thickness of 10 to 25 nm,
The solar radiation adjusting film according to any one of claims 1 to 4, wherein the second silver alloy layer is thicker than the first silver alloy layer.   The solar radiation adjusting film according to claim 1, wherein the metal element other than zinc is aluminum, titanium, or gallium.   The solar radiation adjusting film according to any one of claims 1 to 6, wherein a surface resistance value of the solar reflective laminated film is 2 to 4 Ω / sq. It is glass with a film formed by sticking a film to a glass plate,
Glass with a film that the film is a solar control film according to any one of claims 1 to 7.   The glass with a film according to claim 8, wherein the visible light transmittance measured in accordance with JIS A5759 is 70% or more and the solar reflectance is 30% or more.   The glass with a film according to claim 8 or 9, wherein the ultraviolet transmittance measured according to JIS A5759 is 1% or less.

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