JP6198624B2 - Light transmissive laminated film - Google Patents

Description

  The present invention relates to a light-transmitting laminated film, and more particularly to a light-transmitting laminated film that can be applied to members having excellent flexibility such as paper products and fabric products.

  A light-transmitting laminated film having a heat shielding property may be applied to a window glass of a building such as a building or a house or a window glass of a vehicle such as an automobile for the purpose of shielding solar radiation. Since this type of light-transmitting laminated film is applied to a hard window glass, the base film forming the heat-shielding functional film is required to have high light transmittance and mechanical strength, and is highly transparent and firm. A strong polyethylene terephthalate film (PET film) is often used as a substrate film.

  However, when trying to give a heat-shielding function to a member having excellent flexibility such as a paper product or a fabric product, if the stiffness of the base film of the light transmissive laminated film is strong, the light transmissive laminated film is applied. Since the original flexibility of the member excellent in flexibility is lost, it is difficult to apply the conventional light-transmitting laminated film applied to the window glass to the member excellent in flexibility as it is. That is, for example, a film that is weaker than a PET film needs to be used as a base material for forming a heat-shielding functional film.

  In this regard, there is no description that applies to a member having excellent flexibility, and it is described that it is applied to a hard member such as a window for a building or a vehicle, a transparent case for storing plants, a frozen or refrigerated showcase, and the like. However, Patent Document 1 includes an infrared reflection layer, a polycycloolefin layer that supports one main surface of the infrared reflection layer, and an adhesive layer formed on the other main surface of the infrared reflection layer. An infrared reflective film is provided.

JP 2012-189683 A

  When a metal thin film is formed on a polycycloolefin layer as in Patent Document 1, adhesion between the polycycloolefin layer and the metal thin film is poor, and peeling is likely to occur between these layers. Moreover, when comprising each layer like patent document 1, if an infrared reflective film is affixed on a window etc., a polycycloolefin layer will appear on the surface. The polycycloolefin layer that appears on the surface is easily scratched. And when forming a hard protective layer on the surface of a polycycloolefin layer, adhesion between a polycycloolefin layer and a protective layer becomes a problem.

  The problem to be solved by the present invention is to provide a light-transmitting laminated film that can be applied to members having excellent flexibility such as paper products and fabric products, and has good heat insulating properties, scratch resistance, and interlayer adhesion. is there.

  In order to solve the above problems, a light-transmitting laminated film according to the present invention comprises a metal-containing layer containing a metal or metal oxide (excluding a silver-containing layer), silver or a silver alloy on one surface of a polyolefin film. It has a silver-containing layer and an adhesive layer in this order, and has a hard coat layer made of an organic-inorganic hybrid material on the other surface of the polyolefin film, and the polyolefin film and the metal-containing layer ( The gist is that the adhesion strength measured according to JIS A5759 is 50 mN / 25 mm or more.

  In this case, the polyolefin film is preferably a biaxially stretched polypropylene film.

  Moreover, it is preferable that the mixture ratio of the raw material of the inorganic component which forms the said organic-inorganic hybrid material is 40-70 mass%.

  The organic component material forming the organic-inorganic hybrid material is preferably a curable resin, and the inorganic component material is preferably a metal compound. The curable resin is preferably at least one selected from acrylic resins, epoxy resins, and urethane resins, and the metal compound is preferably at least one selected from Si compounds, Ti compounds, and Zr compounds.

  And it is preferable that the metal oxide of the said metal containing layer (except a silver containing layer) exists in the surface by the side of the polyolefin film of the said metal containing layer (except a silver containing layer).

  The metal and metal oxide of the metal-containing layer (excluding the silver-containing layer) are preferably at least one metal selected from Si, Ti, and Zr and its oxide.

  Moreover, it is preferable that the atomic composition ratio of oxygen on the surface of the polyolefin film on the metal-containing layer (excluding the silver-containing layer) side is in the range of 1 to 30 atm%.

  The atomic composition ratio of oxygen on the hard coat layer side surface of the polyolefin film is preferably in the range of 1 to 30 atm%.

  According to the light-transmitting laminated film according to the present invention, a metal-containing layer containing a metal or a metal oxide (excluding a silver-containing layer) and a silver-containing silver or silver alloy-containing one surface of a polyolefin film. A layer and a pressure-sensitive adhesive layer in this order, a hard coat layer made of an organic-inorganic hybrid material on the other surface of the polyolefin film, a polyolefin film and a metal-containing layer (excluding a silver-containing layer), Adhesion strength measured in accordance with JIS A5759 is 50 mN / 25 mm or more, so it can be applied to flexible members such as paper products and fabric products, and has good heat insulation, scratch resistance, interlayer Adhesion. The reason why the interlayer adhesion between the polyolefin film and the hard coat layer is excellent is presumed that the curing shrinkage of the hard coat layer was suppressed by adding an inorganic component to the hard coat layer. Moreover, it is speculated that the interlayer adhesion between the polyolefin film and the metal-containing layer (excluding the silver-containing layer) is also affected by the suppression of curing shrinkage of the hard coat layer.

  And the interlayer adhesiveness of a polyolefin film and a hard-coat layer is especially favorable in the compounding ratio of the raw material of the inorganic component which forms organic-inorganic hybrid material being 40 mass% or more. Further, when the blending ratio of the raw materials of the inorganic components is 70% by mass or less, the coating solution is excellent in stability and the light transmittance of the hard coat layer is prevented from being lowered.

  When the organic component raw material forming the organic-inorganic hybrid material is a curable resin and the inorganic component raw material is a metal compound, the curing shrinkage of the hard coat layer is suppressed, and the interlayer adhesion between the polyolefin layer and the hard coat layer is suppressed. Will improve.

  A metal-containing layer (excluding a silver-containing layer) having a metal oxide layer (excluding a silver-containing layer) on the surface of the polyolefin film side of the metal-containing layer (excluding a silver-containing layer) has a polyolefin film and a metal-containing layer (a silver-containing layer) The interlaminar adhesion is particularly good.

  When the metal and the metal oxide of the metal-containing layer (excluding the silver-containing layer) are at least one metal selected from Si, Ti, and Zr and the oxide thereof, the metal-containing layer (excluding the silver-containing layer) ) The metal oxide of the metal-containing layer (excluding the silver-containing layer) is likely to be present on the surface of the polyolefin film on the polyolefin film side, and the interlayer adhesion between the polyolefin film and the metal-containing layer (excluding the silver-containing layer) is easily improved. .

It is sectional drawing of the translucent laminated film which concerns on one Embodiment of this invention. It is sectional drawing of the light-transmitting laminated film which concerns on other embodiment of this invention.

  The light transmissive laminated film according to the present invention will be described in detail.

  The light-transmitting laminated film according to the present invention comprises a metal-containing layer containing a metal or metal oxide (excluding a silver-containing layer) and a silver-containing layer containing silver or a silver alloy on one surface of a polyolefin film. And an adhesive layer in this order, and a hard coat layer made of an organic-inorganic hybrid material on the other surface of the polyolefin film.

  FIG. 1 shows an embodiment of a light-transmitting laminated film according to the present invention. The light-transmitting laminated film 10 shown in FIG. 1A includes a metal-containing layer (excluding a silver-containing layer) 14, a silver-containing layer 16, and an adhesive layer 18 on one surface of a polyolefin film 12. In this order, a hard coat layer 20 made of an organic-inorganic hybrid material is provided on the other surface of the polyolefin film 12. The metal-containing layer (excluding the silver-containing layer) 14 is directly formed on one surface of the polyolefin film 12. The silver-containing layer 16 is directly formed on the surface of the metal-containing layer (excluding the silver-containing layer) 14. The pressure-sensitive adhesive layer 18 is directly formed on the surface of the silver-containing layer 16. The metal-containing layer (excluding the silver-containing layer) 14 is in contact with both the polyolefin film 12 and the silver-containing layer 16. The silver-containing layer 16 is in contact with both the metal-containing layer (excluding the silver-containing layer) 14 and the pressure-sensitive adhesive layer 18. The pressure-sensitive adhesive layer 18 is in contact with the silver-containing layer 16. The hard coat layer 20 is directly formed on the other surface of the polyolefin film 12 and is in contact with the polyolefin film 12. Therefore, the light-transmitting laminated film 10 includes the polyolefin film 12, the metal-containing layer (excluding the silver-containing layer) 14 in contact with one surface of the polyolefin film 12, and the silver in contact with the metal-containing layer (excluding the silver-containing layer) 14. It has the content layer 16 and the adhesive layer 18 in contact with the silver content layer 16 in this order, and further has a hard coat layer 20 in contact with the other surface of the polyolefin film 12.

  The polyolefin film 12 is a base material serving as a base for forming the metal-containing layer (excluding the silver-containing layer) 14 and the silver-containing layer 16. The base material needs to be excellent in flexibility, and is therefore a film. The film is a thin film, and generally has a thickness of 200 μm or less or 250 μm or less. What is necessary is just to have the softness | flexibility which can be wound in roll shape, and if it is such, it may be 200 micrometers or more or 250 micrometers or more thick. The film is generally delivered as a roll.

  The polyolefin film 12 has optical transparency. Light transmittance means that the transmittance value in the wavelength region of 360 to 830 nm is 50% or more. Examples of the polyolefin of the polyolefin film 12 include chain polyolefin and cyclic polyolefin. Examples of the chain polyolefin include polyethylene, polypropylene, and ethylene-α olefin copolymer. Examples of the cyclic polyolefin include cycloolefin polymers. As the polyolefin, polypropylene is preferable from the viewpoints of light transmittance, durability, workability, and the like. In particular, from the viewpoint of light transmittance and the like, biaxially oriented polypropylene (OPP) is preferable.

  The polyolefin film 12 is subjected to a surface treatment on one or both surfaces for the purpose of improving interlayer adhesion with a metal-containing layer 14 (excluding a silver-containing layer) 14 or a hard coat layer 20 in contact therewith. It may be. Further, for the purpose of improving interlayer adhesion, an easy adhesion layer may be provided on one or both surfaces thereof. Further, for the purpose of improving interlayer adhesion, a surface treatment may be performed on one surface, and an easy adhesion layer may be provided on the other surface. Examples of such surface treatment include corona treatment and plasma treatment. As a result, hydroxyl groups and oxygen groups are formed on the surface of the polyolefin film 12. Examples of the easy adhesion layer include a modified polyolefin layer having a polar group and an acrylic resin layer. Examples of the polar group include those having a heteroatom such as N, O, and S. Examples of the modified polyolefin include a polypropylene copolymer having a polar group, polyethylene having a polar group, polyisoprene having a polar group, polyisobutylene having a polar group, and the like.

  From the viewpoint of interlayer adhesion, the polyolefin film 12 is subjected to surface treatment on one or both surfaces thereof, an easy-adhesion layer is provided on one or both surfaces thereof, or on one surface thereof. It is preferable that surface treatment is performed and an easy-adhesion layer is provided on the other surface. In particular, it is preferable that one or both surfaces be subjected to surface treatment.

And by the surface treatment which improves interlayer adhesiveness, an easily bonding layer, etc., the atomic composition ratio of oxygen on the surface of the metal-containing layer (excluding the silver-containing layer) 14 of the polyolefin film 12 is within the range of 1 to 30 atm%. Preferably there is. More preferably, it is in the range of 1 to 15 atm%. The atomic composition ratio of oxygen on the surface of the polyolefin film 12 on the hard coat layer 20 side is preferably in the range of 1 to 30 atm%. More preferably, it is in the range of 1 to 15 atm%. When the atomic composition ratio of oxygen on the surface of the polyolefin film 12 is 1 atm% or more, the effect of improving interlayer adhesion is high. On the other hand, when the atomic composition ratio of oxygen on the surface of the polyolefin film 12 is 30 atm% or less, it is easy to prevent the raw film of the polyolefin film 12 wound into a roll from adhering between layers (blocking).

  The silver-containing layer 16 is made of a metal that easily reflects far infrared rays (heat rays), and functions as a solar radiation shielding layer and a heat insulating layer. The silver-containing layer 16 is a layer containing silver or a silver alloy, but is preferably a layer containing a silver alloy from the viewpoint of improving durability against an environment such as heat, light, and water vapor. In addition, the silver containing layer 16 may be partially oxidized by the post-oxidation process etc. which are mentioned later within the range which does not impair the function of the silver containing layer 16.

  Examples of the silver alloy include alloys containing silver as a main component and containing at least one metal element such as copper, bismuth, gold, palladium, platinum, and titanium. The silver alloy is more preferably a silver alloy containing copper (Ag—Cu alloy), a silver alloy containing bismuth (Ag—Bi alloy), or a silver alloy containing titanium (Ag—Ti alloy). These alloys have advantages such as a large silver diffusion suppression effect and cost advantage. The proportion of subelements such as copper, bismuth, titanium, etc. in the silver-containing layer 16 can be measured using ICP analysis.

  When using a silver alloy containing copper, the content of copper is preferably 1 atomic% or more, more preferably 2 atomic% or more, and further preferably 3 atomic% or more from the viewpoint of obtaining an additive effect. On the other hand, from the viewpoint of manufacturability such as easy to ensure high transparency and easy production of a sputtering target, it is preferably 20 atomic% or less, more preferably 10 atomic% or less, and even more preferably 5 atomic% or less. .

  When using a silver alloy containing bismuth, the content of bismuth is preferably 0.01 atomic% or more, more preferably 0.05 atomic% or more, and even more preferably 0.1 atomic% or more, from the viewpoint of obtaining an additive effect. It is. On the other hand, from the viewpoint of manufacturability such as easy production of a sputtering target, it is preferably 5 atomic% or less, more preferably 2 atomic% or less, and even more preferably 1 atomic% or less.

  When using a silver alloy containing titanium, the content of titanium is preferably 0.01 atomic% or more, more preferably 0.05 atomic% or more, and still more preferably 0.1 atomic% or more, from the viewpoint of obtaining an additive effect. It is. On the other hand, when it is formed into a film, it is preferably 2 atomic% or less, more preferably 1.75 atomic% or less, and still more preferably 1.5 atomic% or less from the viewpoint that a complete solid solution is easily obtained.

  In the case of using a silver alloy containing copper, bismuth or titanium, in addition to silver, copper, bismuth and titanium, for example, other elements and inevitable impurities, as long as they do not adversely affect the aggregation / diffusion suppression effect of silver 1 type, or 2 or more types may be contained.

  Other elements include Mg, Pd, Pt, Au, Zn, Al, Ga, In, Sn, Sb, Li, Cd, Hg, As and other elements that can be dissolved in Ag; Be, Ru, Rh, Os , Ir, Bi, Ge, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Co, Ni, Si, Tl, Pb, and other elements that can be precipitated as a single phase in an Ag-Cu alloy Y, La, Ce, Nd, Sm, Gd, Tb, Dy, Ti, Zr, Hf, Na, Ca, Sr, Ba, Sc, Pr, Eu, Ho, Er, Tm, Yb, Lu, S, Se And elements that can precipitate an intermetallic compound with Ag such as Te.

  The film thickness of the silver-containing layer 16 is preferably 3 nm or more, more preferably 5 nm or more, and even more preferably 7 nm or more from the viewpoints of stability, heat ray reflectivity, and the like. On the other hand, it is preferably 30 nm or less, more preferably 20 nm or less, and still more preferably 15 nm or less, from the viewpoints of light transmittance and economy.

  The silver-containing layer 16 can be formed using a vapor phase method such as physical vapor deposition (PVD) or chemical vapor deposition (CVD). Examples of physical vapor deposition (PVD) include vacuum deposition, sputtering, ion plating, MBE, and laser ablation. Examples of chemical vapor deposition (CVD) include thermal CVD and plasma CVD. Among these, the sputtering method is particularly preferable from the viewpoints of obtaining a dense film and relatively easy film thickness control. Examples of the sputtering method include a DC magnetron sputtering method and an RF magnetron sputtering method.

  When the silver-containing layer 16 is directly formed on the surface of the polyolefin film 12, the adhesion with the polyolefin film 12 is poor. For this reason, a metal-containing layer (excluding the silver-containing layer) 14 is provided between the polyolefin film 12 and the silver-containing layer 16.

  The metal-containing layer (excluding the silver-containing layer) 14 is formed using a vapor phase method such as physical vapor deposition (PVD) or chemical vapor deposition (CVD), as with the silver-containing layer 16. Can do. Thereby, a thin film with a uniform thickness can be formed, which can form a dense film and has a thickness of several nm to several tens of nm. Examples of physical vapor deposition (PVD) include vacuum deposition, sputtering, ion plating, MBE, and laser ablation. Examples of chemical vapor deposition (CVD) include thermal CVD and plasma CVD. Among these, the sputtering method is particularly preferable from the viewpoints of obtaining a dense film and relatively easy film thickness control. Examples of the sputtering method include a DC magnetron sputtering method and an RF magnetron sputtering method.

  The metal-containing layer (excluding the silver-containing layer) 14 is obtained by forming a metal thin film (excluding the silver thin film and the silver alloy thin film) on one surface of the polyolefin film 12 using the above-described vapor phase method. . The metal thin film is partially oxidized by oxygen in the atmosphere and hydroxyl groups or oxygen groups on the surface of the polyolefin film 12. The formed metal thin film may be oxidized into a metal oxide thin film by a post-oxidation process described later. In this sense, the metal-containing layer (excluding the silver-containing layer) 14 is a layer containing a metal or a metal oxide. The metal-containing layer (excluding the silver-containing layer) 14 may be any of a layer made of a metal, a layer made of a metal and a metal oxide, and a layer made of a metal oxide. The post-oxidation treatment can be performed, for example, by performing a heat treatment on the light transmissive laminated film 10 in an atmosphere in which oxygen or moisture exists, such as in the air, in a high oxygen atmosphere, or in a high humidity atmosphere.

  When the metal of the metal-containing layer (excluding the silver-containing layer) 14 reacts with the hydroxyl group or oxygen group on the surface of the polyolefin film 12, the surface of the metal-containing layer (excluding the silver-containing layer) 14 on the polyolefin film 12 side is The metal oxide of the containing layer (excluding the silver containing layer) 14 is formed, and the interlayer adhesion between the polyolefin film 12 and the metal containing layer (excluding the silver containing layer) 14 is further increased. From this viewpoint, it is preferable that a metal oxide of the metal-containing layer (excluding the silver-containing layer) 14 exists on the surface of the metal-containing layer (excluding the silver-containing layer) 14 on the polyolefin film 12 side.

  When the metal-containing layer (excluding the silver-containing layer) 14 is a layer containing a metal oxide, the atomic mole ratio (M / O) of the metal and oxygen is the polyolefin film 12 and the metal-containing layer (excluding the silver-containing layer). 14) From the viewpoints of interlayer adhesion, light transmittance and the like, preferably 1.0 / 4.0 or more, more preferably 1.0 / 3.8 or more, further preferably 1.0 / 3.5 or more, Even more preferably, it is 1.0 / 3.0 or more, and most preferably 1.0 / 2.8 or more. Further, from the viewpoint of visible light transmittance and the like, it is preferably 1.0 / 0.5 or less, more preferably 1.0 / 0.7 or less, still more preferably 1.0 / 1.0 or less, and even more preferably. 1.0 / 1.2 or less, most preferably 1.0 / 1.5 or less.

  The atomic molar ratio (M / O) of metal and oxygen in the metal-containing layer (excluding the silver-containing layer) 14 can be calculated from the composition of the thin film. As a method for analyzing the composition of the thin film, energy dispersive X-ray fluorescence analysis (EDX) can be suitably used from the viewpoint that the composition of an extremely thin film can be analyzed relatively accurately.

  The metal-containing layer (excluding the silver-containing layer) 14 improves the adhesion between the polyolefin film 12 and the silver-containing layer 16. Moreover, it suppresses that the metal of the silver containing layer 16 transfers to other layers, such as the polyolefin film 12 and the hard-coat layer 20. FIG. From the viewpoint of improving adhesion, the metal of the metal-containing layer (excluding the silver-containing layer) 14 is preferably a metal that easily reacts with a hydroxyl group or an oxygen group on the surface of the polyolefin film 12. Such a metal is a metal that forms a passive state, and specifically includes Si, Ti, Zr, Al, Cr, Ni, Fe, and the like. Among these, Si, Ti, and Zr are more preferable from the viewpoints of reactivity with hydroxyl groups and oxygen groups, film forming processability, and the like.

  The thickness of the metal-containing layer (excluding the silver-containing layer) 14 is preferably 1 nm or more, more preferably from the viewpoint of interlayer adhesion between the polyolefin film 12 and the metal-containing layer (excluding the silver-containing layer) 14, light transmittance, and the like. Is 1.5 nm or more, more preferably 2 nm or more. Further, from the viewpoints of visible light transmittance, economy, etc., it is preferably 15 nm or less, more preferably 10 nm or less, and even more preferably 8 nm or less.

  The pressure-sensitive adhesive layer 18 is for attaching the light transmissive laminated film 10 to an adherend such as a paper product or a cloth product. Before adhering to the adherend, the adhesive surface only needs to be covered with a cover film in order to protect the adhesive surface. In order to cope with reattachment of the light-transmitting laminated film 10, an adhesive is preferable. The pressure-sensitive adhesive is applied by applying pressure using the adhesiveness of the surface, and is distinguished from an adhesive that exhibits a peeling resistance force by solidification as a pressure-sensitive adhesive. Examples of the pressure-sensitive adhesive include acrylic pressure-sensitive adhesives, silicone pressure-sensitive adhesives, urethane pressure-sensitive adhesives, and rubber-based pressure-sensitive adhesives. The pressure-sensitive adhesive layer 18 can be formed by applying a pressure-sensitive adhesive composition.

  The thickness of the pressure-sensitive adhesive layer 18 is not particularly limited, but is preferably 100 μm or less from the viewpoint of easy attachment to an adherend. More preferably, it is 50 μm or less. Moreover, it is preferable that it is 1.5 micrometers or more from a viewpoint of being easy to apply to the member excellent in a softness | flexibility, and being excellent in the followable | trackability with respect to a deformation | transformation of a to-be-adhered body. More preferably, it is 5 μm or more.

  The hard coat layer 20 is a layer that appears on the surface when the light transmissive laminated film 10 is attached to an adherend such as a paper product or a cloth product, and the surface of the light transmissive laminated film 10 is damaged. suppress. In particular, since the polyolefin film 12 which is a base material is flexible and relatively soft, it is possible to prevent the film from being scratched.

  The hard coat layer 20 is composed of an organic-inorganic hybrid material. An organic-inorganic hybrid material is formed of an organic material (raw material of an organic component) and an inorganic material (raw material of an inorganic component), and the organic material and the inorganic material are combined at the nano level or the molecular level. Organic-inorganic hybrid materials are, for example, network-like cross-linked structures in which inorganic materials dispersed in organic materials and organic materials undergo a reaction such as a polymerization reaction, and inorganic components are highly dispersed in organic components through chemical bonds. It is what has.

  Since the hard coat layer 20 is made of an organic-inorganic hybrid material, the interlayer adhesion between the polyolefin film 12 and the hard coat layer 20 is improved. This is presumably because curing shrinkage of the hard coat layer 20 was suppressed by adding an inorganic component to the material forming the hard coat layer 20. That is, it is inferred that the curing shrinkage of the hard coat layer 20 is suppressed, so that the distortion of the laminate (light-transmitting laminated film 10) is reduced and the stress to be peeled between the polyolefin film 12 and the hard coat layer 20 is reduced. Is done.

  Moreover, since the curing shrinkage of the hard coat layer 20 affects the distortion of the laminate (light-transmitting laminated film 10), the curing shrinkage of the hard coat layer 20 is included in the laminate (light-transmitting laminated film 10). This also affects the interlayer adhesion between the polyolefin film 12 and the metal-containing layer 14 (excluding the silver-containing layer). That is, by suppressing the curing shrinkage of the hard coat layer 20, the distortion of the laminate (light transmissive laminate film 10) is reduced, and as a result, the interlayer between the polyolefin film 12 and the metal-containing layer (excluding the silver-containing layer) 14 is reduced. The stress to be peeled becomes smaller. Therefore, the hard coat layer 20 made of an organic-inorganic hybrid material suppresses deterioration in interlayer adhesion between the polyolefin film 12 and the metal-containing layer (excluding the silver-containing layer) 14, and improves the condition.

  Examples of the raw material of the organic component forming the organic-inorganic hybrid material include curable resins. Examples of the curable resin include acrylic resin, epoxy resin, and urethane resin. These may be used alone or in combination of two or more. Moreover, a metal compound etc. are mentioned as a raw material of an inorganic component. Examples of the metal compound include a Si compound, a Ti compound, and a Zr compound. These may be used alone or in combination of two or more. The metal compound is a compound containing an inorganic component such as Si, Ti, or Zr, and can be compounded by causing a reaction such as a polymerization reaction with a raw material of the organic component. More specifically, examples of the metal compound include organometallic compounds. Examples of organometallic compounds include silane coupling agents, metal alkoxides, metal acylates, metal chelates, and silazanes.

  As for the compounding ratio of the raw material of the inorganic component which forms organic-inorganic hybrid material, 10 mass% or more is preferable. More preferably, it is 40 mass% or more. When the blending ratio of the inorganic component raw material is 10% by mass or more, the interlayer adhesion between the polyolefin film 12 and the hard coat layer 20 is remarkably improved. Further, when the blending ratio of the raw materials of the inorganic components is 40% by mass or more, the interlayer adhesion between the polyolefin film 12 and the hard coat layer 20 is particularly good. Interlayer adhesion between the polyolefin film 12 and the hard coat layer 20 can be evaluated by a cross-cut test based on JIS K5600-5-6.

  Further, the blending ratio of the raw materials of the inorganic components forming the organic-inorganic hybrid material is preferably 70% by mass or less. More preferably, it is 60 mass% or less. When the blending ratio of the raw materials of the inorganic components is 70% by mass or less, the coating liquid is excellent in stability and the light transmittance of the hard coat layer 20 is prevented from being lowered. When the blending ratio of the inorganic component raw material is 60% by mass or less, the effect is further improved.

  Furthermore, the content ratio of the metal component contained in the hard coat layer 20 made of an organic-inorganic hybrid material is preferably 5.9% by mass or more. More preferably, it is 23.7 mass% or more. When the content ratio of the metal component is 5.9% by mass or more, the interlayer adhesion between the polyolefin film 12 and the hard coat layer 20 is remarkably improved. Further, the content ratio of the metal component contained in the hard coat layer 20 made of an organic-inorganic hybrid material is preferably 41.4% by mass or less. More preferably, it is 35.5 mass% or less. When the content ratio of the metal component is 41.4% by mass or less, the stability of the coating liquid is excellent, and a decrease in light transmittance of the hard coat layer 20 is suppressed.

  The content of the metal component contained in the hard coat layer made of an organic-inorganic hybrid material can be examined using a heating residue analysis, X-ray photoelectron spectroscopy (XPS), or the like.

  The thickness of the hard coat layer 20 is preferably 2.0 μm or less from the viewpoint of excellent heat insulation (suppressing the heat transmissivity low). More preferably, it is 1.6 micrometers or less, More preferably, it is 1.0 micrometers or less. Moreover, it is preferable that it is 0.4 micrometer or more from a viewpoint of being excellent in abrasion resistance. More preferably, it is 0.6 micrometer or more, More preferably, it is 0.8 micrometer or more.

  In the light-transmitting laminated film 10, the adhesion between the polyolefin film 12 and the metal-containing layer (excluding the silver-containing layer) 14 is 50 mN / 25 mm or more. This interlayer adhesion is an adhesion measured according to JIS A5759. Thereby, the adhesive force between the polyolefin film 12 and the metal-containing layer (excluding the silver-containing layer) 14 is good.

  In order to set the interlayer adhesion to a specific value or more, for example, the surface of the polyolefin film 12 on which the metal-containing layer (excluding the silver-containing layer) 14 is formed is subjected to surface treatment or an easy-adhesion layer. A functional group such as a hydroxyl group or an oxygen group is formed on the surface, and a metal thin film of the metal-containing layer (excluding the silver-containing layer) 14 is formed on the surface having the functional group by sputtering or the like. The metal of the metal thin film to be formed is preferably a metal that easily reacts with a functional group such as a hydroxyl group or an oxygen group to easily become a metal oxide (for example, a metal that forms a passive state, Si, Ti, Zr, etc.). The atomic composition ratio of oxygen on the surface of the polyolefin film 12 forming the metal thin film is preferably 1 atm% or more. By having such a structure, a functional group such as a hydroxyl group or an oxygen group on the surface of the polyolefin film 12 and a metal of the metal thin film form a bond at the contact interface, and the polyolefin film 12 and the metal-containing layer (silver-containing layer Excluding) 14 interlayer adhesion becomes good. Interlayer adhesion between the polyolefin film 12 and the metal-containing layer (excluding the silver-containing layer) 14 can be evaluated by a cross-cut test based on JIS K5600-5-6.

  And by forming the silver-containing layer 16 on the surface of the metal-containing layer (excluding the silver-containing layer) 14 by sputtering or the like, the interlayer adhesion between the metal-containing layer (excluding the silver-containing layer) 14 and the silver-containing layer 16 is The interlaminar adhesion becomes better than when the silver-containing layer 16 is directly formed on the surface of the polyolefin film 12.

  The light transmissive laminated film 10 can be manufactured as follows, for example. A metal-containing layer (excluding a silver-containing layer) 14 and a silver-containing layer 16 are sequentially stacked and formed on one surface of the polyolefin film 12 by a predetermined thin film forming method. Thereafter, heat treatment such as post-oxidation is performed as necessary. Thereafter, the pressure-sensitive adhesive composition is applied to the surface of the silver-containing layer 16 to form the pressure-sensitive adhesive layer 18. Then, on the other surface of the polyolefin film 12, a raw material for forming the organic-inorganic hybrid material is applied to form a coating film, and the formed coating film is cured, and the organic-inorganic hybrid material is used. A hard coat layer 20 is formed. Thus, the light transmissive laminated film 10 can be obtained.

  According to the light-transmitting laminated film 10 having the above-described configuration, the substrate film can be applied to a member having excellent flexibility, such as a paper product or a cloth product, by ensuring the flexibility of the base film. The silver-containing layer 16 can exhibit good heat insulation, and the hard coat layer 20 made of an organic-inorganic hybrid material can satisfy the scratch resistance. Excellent.

  The light transmissive laminated film 10 having such characteristics can be applied to a member having excellent flexibility such as a paper product or a cloth product. Examples of the member having excellent flexibility include wallpaper, a roll screen, and a curtain. Further, it can be applied to window glass of buildings such as buildings and houses, and window glass of vehicles such as automobiles.

  In the light transmissive laminated film 10, the hard coat layer 20 is provided in contact with the polyolefin film 12, but if adhesion is secured, a layer is provided between the polyolefin film 12 and the hard coat layer 20. One or more layers may be provided. Examples of such a layer include the above-described easy adhesion layer, an adhesive layer, and a metal-containing layer.

  In addition, the light transmissive laminated film 10 has a metal-containing layer (excluding a silver-containing layer) 14, a silver-containing layer 16, and an adhesive layer 18 in this order on one surface of the polyolefin film 12. In the present invention, another metal-containing layer (excluding the silver-containing layer) may be formed between the silver-containing layer 16 and the pressure-sensitive adhesive layer 18.

  FIG. 2 shows a light transmissive laminated film 30 according to another embodiment. As shown in FIG. 2, the light transmissive laminated film 30 has a metal-containing layer (excluding a silver-containing layer) 14, a silver-containing layer 16, and another metal-containing layer (silver) on one surface of a polyolefin film 12. 22) and the pressure-sensitive adhesive layer 18 are provided in this order, and the hard coat layer 20 made of an organic-inorganic hybrid material is provided on the other surface of the polyolefin film 12. The other metal-containing layer (excluding the silver-containing layer) 22 may have the same configuration as the metal-containing layer (excluding the silver-containing layer) 14. The other metal-containing layer (excluding the silver-containing layer) 22 can suppress the metal of the silver-containing layer 16 from moving to the pressure-sensitive adhesive layer 18 or the like.

  Hereinafter, the present invention will be described in detail using Examples and Comparative Examples.

Example 1
An OPP film (P2111, film thickness 20 μm, double-sided corona treatment) manufactured by Toyobo Co., Ltd. was used as the polyolefin film. A metal Ti thin film was formed on one surface of the polyolefin film by sputtering using a DC magnetron sputtering apparatus. Next, an Ag—Cu alloy thin film was formed on the metal Ti thin film by sputtering. Further, a UV curable organic-inorganic hybrid material (TG series manufactured by Dainichi Seika Kogyo Co., Ltd.) was applied on the other surface of the polyolefin film, and UV cured to form a hard coat layer. Thus, the light transmissive laminated film of Example 1 was produced.

(Example 2)
Furthermore, a light-transmitting laminated film of Example 2 was produced in the same manner as in Example 1 except that a metal Ti thin film was formed on the Ag—Cu alloy thin film by sputtering.

(Examples 3 to 7)
Light transmissive laminated films of Examples 3 to 7 were produced in the same manner as in Example 2 except that the inorganic material ratio of the UV curable organic-inorganic hybrid material was changed. In the light transmissive laminated films of Examples 3 to 7, as in Example 2, a metal Ti thin film was formed on an Ag—Cu alloy thin film by sputtering.

(Example 8)
An OPP film (EM-201, film thickness 50 μm, single-sided corona treatment) manufactured by Oji F-Tex was used in place of the OPP film (P2111, 20 μm, double-sided corona treatment) manufactured by Toyobo. The surface that was previously corona treated was the other surface on which the hard coat layer was formed, and the surface that was not corona treated was the one surface on which the metal Ti thin film was formed. And before forming a metal Ti thin film, the corona treatment was given to the one surface, and after setting it as the predetermined oxygen ratio, the metal Ti thin film was formed in the corona treatment surface. A light transmissive laminated film of Example 8 was produced in the same manner as Example 2 except for the above.

(Examples 9 to 10)
An OPP film (Y562, film thickness 50 μm, single-sided corona treatment) manufactured by Toray Industries, Inc. was used in place of the Toyobo OPP film (P2111, 20 μm, double-sided corona treatment). As in Example 8, the surface that had been previously corona treated was the other surface on which the hard coat layer was formed, and the surface that was not corona treated was the one surface on which the metal Ti thin film was formed. Then, before forming the metal Ti thin film, plasma treatment was performed on one surface thereof to obtain a predetermined oxygen ratio, and then a metal Ti thin film was formed on the plasma treatment surface. Except this, it carried out similarly to Example 2, and produced the light transmissive laminated | multilayer film of Examples 9-10.

(Example 11)
A film with a multilayer thin film obtained by sequentially laminating a metal Ti thin film / Ag—Cu alloy thin film / metal Ti thin film on one surface of a polyolefin film is heated in an atmosphere at 40 ° C. for 300 hours. Thus, the metal Ti thin film was thermally oxidized to obtain a titanium oxide thin film. Except this, a light-transmitting laminated film of Example 11 was produced in the same manner as Example 2.

(Comparative Example 1)
Instead of the UV curable organic / inorganic hybrid material, a hard coat layer was formed using a UV curable acrylic resin (manufactured by DIC Corporation, “UVT Clear-TEF046”). A light-transmitting laminated film according to Comparative Example 1 was produced.

(Comparative Example 2)
An OPP film (EM-201, film thickness 50 μm, single-sided corona treatment) manufactured by Oji F-Tex was used in place of the OPP film (P2111, 20 μm, double-sided corona treatment) manufactured by Toyobo. The surface that was previously corona treated was the other surface on which the hard coat layer was formed, and the surface that was not corona treated was the one surface on which the metal Ti thin film was formed. And before forming a metal Ti thin film, the corona treatment was given to the one surface, and after setting it as the predetermined oxygen ratio, the metal Ti thin film was formed in the corona treatment surface. A light-transmitting laminated film of Comparative Example 2 was produced in the same manner as in Example 8 except that the oxygen ratio was changed.

(Measurement of atomic composition ratio of oxygen on polyolefin film surface)
The measurement was performed using an XPS measuring instrument ("PHI5000 VersaProbeII" manufactured by ULVAC-PHI).

(Measurement of Ti / O ratio)
The titanium oxide thin film formed by thermally oxidizing the metal Ti thin film was subjected to EDX analysis, and the Ti / O ratio was determined as follows. That is, the film with a thin film layer was cut out by a microtome (manufactured by LKB Co., Ltd., “Ultrome V2088”), and a test piece having a thickness in the cross-sectional direction of the thin film layer containing the titanium oxide thin film to be analyzed was 100 nm or less. The cross section of the produced test piece was confirmed with a field emission electron microscope (HRTEM) (manufactured by JEOL Ltd., “JEM2001F”). Then, using an EDX apparatus (resolution of 133 eV or less) (manufactured by JEOL Ltd., “JED-2300T”), an electron beam is emitted from the electron gun of this apparatus, and the film thickness center of the titanium oxide thin film to be analyzed The component element of the titanium oxide thin film was analyzed by detecting the incident characteristic X-ray and analyzing it.

(Measurement of Cu content)
The subelement (Cu) content in the Ag-Cu alloy thin film was determined as follows. That is, under each film forming condition, a test piece in which an Ag—Cu alloy thin film was formed on a glass substrate was separately prepared, and this test piece was immersed in a 6% HNO ₃ solution and eluted with ultrasonic waves for 20 minutes. Then, it measured by the concentration method of ICP analysis method using the obtained sample solution.

(Measurement of film thickness)
The film thickness of each thin film was measured from the cross-sectional observation of the test piece by the field emission electron microscope (HRTEM) (manufactured by JEOL Ltd., “JEM2001F”).

  The characteristics of each of the produced light transmissive laminated films were evaluated. Specifically, adhesion between the polyolefin film and the metal Ti thin film (peel strength), scratch resistance, adhesion between the polyolefin film and the metal Ti thin film, adhesion between the polyolefin film and the hard coat layer, and heat insulation (heat flow through) Rate) and visible light transmittance.

(Adhesion between polyolefin film and metal Ti thin film)
A test piece in which a metal Ti thin film was formed on one surface of a polyolefin film and a hard coat layer was formed on the other surface was used. The adhesive surface of the protective film (“PT # 25 (M)” manufactured by Toyo Wrapping Materials)) is bonded to the surface of the metal Ti thin film, and the protective film is adhered using a desktop tensile tester (“AGS-1kNG” manufactured by Minebeva). A 180 ° peel test (based on JIS A5759, tensile speed 300 mm / min) was performed at the interface between the surface and the metal Ti thin film, the peel force was measured, and this was defined as the adhesion between the layers.

(Abrasion resistance)
Steel wool (“Bon Star No. 0000” manufactured by Nippon Steel Co., Ltd.) was used, and steel wool was rubbed back and forth 10 times while applying a constant load (20 g / cm ² ) to the surface of the hard coat layer of the light-transmitting laminated film. At this time, the case where no scratches were observed by visual inspection was judged as “good”, and the case where scratches were observed was judged as “poor”.

(Adhesion between polyolefin film and metal Ti thin film)
It measured based on JIS K5600-5-6. Apply the blade so that it is perpendicular to the surface of the OPP film on which the metal Ti thin film is formed, make 6 cuts at intervals of 2 mm, then change the direction by 90 degrees and make 6 cuts perpendicular to the previous cut Were put at intervals of 2 mm to produce 25 squares. Thereafter, a tape was applied to the cut portion of the film lattice, and the tape was rubbed. Thereafter, the tape was peeled off at an angle close to 60 degrees, and the number of remaining cells was visually confirmed. Adhesion is good when the number of remaining masses is 20 or more, “○”, especially when the number of remaining masses is 25, “◎”, adhesion when the number of remaining masses is less than 20 The property was judged as “x”.

(Adhesion between polyolefin film and hard coat layer)
It measured based on JIS K5600-5-6. Apply the blade so as to be perpendicular to the surface of the OPP film on which the hard coat layer is formed, make 6 cuts at intervals of 2 mm, and then change the direction by 90 degrees and make 6 cuts perpendicular to the previous cut. Were put at intervals of 2 mm to produce 25 squares. Thereafter, a tape was applied to the cut portion of the film lattice, and the tape was rubbed. Thereafter, the tape was peeled off at an angle close to 60 degrees, and the number of remaining cells was visually confirmed. Adhesion is good when the number of remaining masses is 20 or more, “○”, especially when the number of remaining masses is 25, “◎”, adhesion when the number of remaining masses is less than 20 The property was judged as “x”.

(Heat flow rate)
An acrylic pressure-sensitive adhesive sheet (“5402” manufactured by Sekisui Chemical Co., Ltd.) having a thickness of 25 μm is pasted on the surface of the Ag—Cu alloy thin film or the metal Ti thin film on the light-transmitting laminated film thus produced. The surface was affixed to one side of the plate glass. Measurement light was incident from the hard coat layer side, the vertical emissivity of the glass surface and the film surface was determined in accordance with JIS R3106, and the thermal conductivity (W / m ² K) was determined in accordance with JIS A5759.

(Visible light transmittance)
In accordance with JIS R3212, a transmission spectrum with a wavelength of 300 to 1000 nm was measured using a spectrophotometer (manufactured by Shimadzu Corporation, “SolidSpec-3700”), and the visible light transmittance was calculated. . The greater the visible light transmittance, the better the transparency.

  Tables 1 and 2 show the layer configuration and evaluation results of each light-transmitting laminated film.

  In Comparative Example 1, since the material of the hard coat layer is a UV curable acrylic resin having a large cure shrinkage, the adhesion between the polyolefin film and the hard coat layer is poor. Also, the adhesion between the polyolefin film and the metal Ti thin film is poor. This is presumed to be an effect of the hard coat layer. In Comparative Example 2, the adhesion between the polyolefin film and the metal Ti thin film is less than 50 mN / 25 mm, so the adhesion between the polyolefin film and the metal Ti thin film is poor.

  On the other hand, in an Example, it has a metal content layer (except for a silver content layer) and a silver content layer in this order on one side of a polyolefin film, and an organic inorganic layer on the other side of a polyolefin film. It has a hard coat layer made of a hybrid material, and the adhesion between the polyolefin film and the metal-containing layer (excluding the silver-containing layer) is 50 mN / 25 mm or more, so it has good heat insulation, scratch resistance, interlayer It turns out that it has adhesiveness.

  Moreover, it turns out that the adhesiveness between a polyolefin film and a hard-coat layer is especially excellent when an inorganic material ratio exists in the range of 40-70 mass% from an Example. Further, from the examples, when the metal-containing layer (excluding the silver-containing layer) is a metal oxide layer, the adhesion and light transmission between the polyolefin film and the metal-containing layer (excluding the silver-containing layer) are improved. I understand that

  Although the embodiments and examples of the present invention have been described above, the present invention is not limited to the above-described embodiments and examples, and various modifications can be made without departing from the spirit of the present invention. .

10 Light-transmissive laminated film 12 Polyolefin film 14 Metal-containing layer (excluding silver-containing layer)
16 Silver-containing layer 18 Adhesive layer 20 Hard coat layer 22 Metal-containing layer (excluding silver-containing layer)

Claims (10)

  On one side of the polyolefin film, a metal-containing layer containing a metal or metal oxide (excluding a silver-containing layer), a silver-containing layer containing silver or a silver alloy, and an adhesive layer are provided in this order. And having a hard coat layer made of an organic-inorganic hybrid material on the other surface of the polyolefin film, measured according to JIS A5759 between the polyolefin film and the metal-containing layer (excluding the silver-containing layer). The light-transmitting laminated film is characterized in that the adhesive force is 50 mN / 25 mm or more.   The light-transmitting laminated film according to claim 1, wherein the polyolefin film is a biaxially stretched polypropylene film.   3. The light-transmitting laminated film according to claim 1, wherein a blending ratio of raw materials of the inorganic components forming the organic-inorganic hybrid material is 40 to 70% by mass.   4. The light transmissive laminated film according to any one of 1 to 3, wherein the organic component raw material forming the organic-inorganic hybrid material is made of a curable resin, and the inorganic component raw material is made of a metal compound. .   The light transmissive laminated film according to claim 4, wherein the curable resin is at least one selected from an acrylic resin, an epoxy resin, and a urethane resin.   The light-transmitting laminated film according to claim 4 or 5, wherein the metal compound as a raw material of the inorganic component is a metal compound composed of at least one metal selected from Si, Ti, and Zr.   The metal-containing layer (excluding the silver-containing layer) on the surface of the polyolefin film side has a metal oxide of the metal-containing layer (excluding the silver-containing layer). The light-transmitting laminated film according to any one of the above.   The metal and metal oxide of the metal-containing layer (excluding the silver-containing layer) are at least one metal selected from Si, Ti, and Zr and an oxide thereof. The light-transmitting laminated film according to any one of the above.   9. The atomic composition ratio of oxygen on the surface of the polyolefin film on the metal-containing layer (excluding the silver-containing layer) side is in the range of 1 to 30 atm%, according to claim 1. Light transmissive laminated film.   10. The light transmissive laminated film according to claim 1, wherein an atomic composition ratio of oxygen on a surface of the polyolefin film on a hard coat layer side is in a range of 1 to 30 atm%.

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