JP2008265092A - Infrared light and ultraviolet light barrier film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an infrared light and ultraviolet light barrier film which can intercept much more infrared light and ultraviolet light than visual light in the sun light by sticking it to a glass face. <P>SOLUTION: In a light barrier film for sticking on a transparent glass prepared by applying an anti-infrared light film and an ultraviolet light film on a film substrate, as a film substrate, a multi-layered film comprises at least twenty-layered ultrathin film layers having a substantially uniform thickness and made of a transparent thermoplastic resin. The thickness of each ultrathin film layer is within the wave length of visible light, and mutually adjoining ultrathin films are composed of two different thermoplastic resins. The anti-infrared light film is coated with a tin-doped antimony oxide, and the anti-ultraviolet light film is coated with benzotriazole, and either the anti-infrared light film or the anti-ultraviolet light film is provided with a thin film comprising lanthanum hexaboride. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an infrared ray and ultraviolet ray blocking film that blocks more infrared rays and ultraviolet rays in sunlight than visible rays by sticking to a glass surface.

Conventionally, in order to cut off the heat rays of sunlight, a film obtained by depositing a thin metal layer such as nickel, silver, aluminum, or chromium on a polyester base layer is attached to glass or the like. These have substantially the same blocking rate for visible light, infrared light, and ultraviolet light, and if the deposited film is thick, there is a risk of causing radio interference of communication equipment.
In order to avoid radio interference of communication equipment, there has been a method of kneading an organic material having an infrared blocking effect on the glass itself or sticking a film containing an organic material having an infrared blocking effect on the glass surface. . Organic materials gradually deteriorated by sunlight, their functions were lowered, and there was a problem with durability.

  Patent Document 1 discloses an antimony-doped tin oxide fine particle whose surface is coated with amorphous indium oxide on an interlayer film of laminated glass as a substance that blocks infrared rays, and antimony-doped tin oxide whose surface is coated with amorphous tin oxide. It is disclosed that fine particles are suitable for infrared shielding. Furthermore, ultraviolet absorbers such as benzotriazole, benzophenone, triazine, and benzoate are disclosed. However, this is only an interlayer film of laminated glass. In addition, the amount of infrared blocking agent and ultraviolet blocking agent used is large.

Furthermore, the multilayer film is disclosed in Patent Document 2 and Patent Document 3. Two types of layers having a refractive index different by at least 0.03 are alternately stacked, and the thickness of each layer is in the visible light wavelength range of about 380 to 780 nm. Such a multilayer film is a film having iridescent gloss depending on the number of layers and the film thickness.
JP 2006-21951 A Japanese Patent No. 2951890 Japanese Patent Publication No. 8-2618

  The present invention provides a film in which an anti-infrared film and an anti-ultraviolet film are provided on a film base, one surface is protected by an abrasion-resistant protective film, and the other surface can be attached to a ready-made glass. For this purpose, it is necessary to provide a film that has both an infrared ray shielding property and an ultraviolet ray shielding property and has a less visible light shielding degree.

The constitution of the present invention is a light-shielding film for application to transparent glass, which is obtained by applying an anti-infrared film and an anti-ultraviolet film to a film base material. It is a multilayer film made of transparent thermoplastic resin consisting of layers, the thickness of each ultra-thin film layer is in the visible light wavelength range, and the ultra-thin films adjacent to each other are composed of two different thermoplastic resins The anti-infrared film is coated with tin-doped antimony oxide, the anti-ultraviolet film is coated with benzotriazole, and either the anti-infrared film or the anti-ultraviolet film is a thin layer containing lanthanum hexaboride. Is provided.

  A multilayer film obtained by alternately stacking 20 to 300 layers of two or more synthetic resin materials having a thickness equivalent to the visible light wavelength range also has an infrared ray and ultraviolet ray blocking action. In addition, when an infrared shielding film is applied on the surface, a small amount of infrared and ultraviolet blocking substances are used to effectively block visible light and efficiently block infrared and ultraviolet rays. The present invention has been completed.

  According to the present invention, it is possible to provide an insulating film that can block infrared rays and ultraviolet rays in preference to visible rays and has resistance to scratches and abrasion, that is, an impact-resistant heat insulating film. This film can be easily attached to the glass surface, and it has become possible to control the intrusion and release of heat rays from window glass or the like. Furthermore, ultraviolet rays have the effect of deteriorating indoors and indoor equipment, and the present invention can maintain the indoor temperature and prevent deterioration of the equipment.

  The infrared ray and ultraviolet ray blocking film of the present invention can be directly attached to the glass surface, mirror surface, etc. of buildings and vehicles to obtain light shielding properties. This film uses a multilayer film, which will be described later, as a base material layer, and an infrared blocking layer and an ultraviolet blocking layer are provided on both sides thereof. Then, a protective layer for reducing scratches and wear is provided on one of the surfaces. A pressure-sensitive adhesive is applied to a layer that is not provided with a protective layer that resists scratches and friction, and this surface is protected with a release paper. Or you may stick as it is.

  The multilayer film is a multilayer film obtained by alternately stacking 20 to 300 layers of films made of different resins disclosed in Patent Document 2 and Patent Document 3. The thickness of each layer is naturally thin and is in the range of the wavelength of visible light.

  In the method of the present invention, an acrylic resin is used for the first layer, and a polymer blend of polybutylene terephthalate, a polybutylene terephthalate elastic body and linear low density polyethylene is used for the second layer. Alternatively, as described in Patent Document 3, one is made of an elastomer, and the other is made of a material other than an elastomer or an elastomer containing a segment belonging to the same polymer system as one elastomer segment.

  The two polymers were fed with resin melts from each of the two extruders and combined with a feed block and a normal single manifold flat film die to arrange them in the desired layer pattern, Manufactured by chill roll casting method.

This feed block is used to form a two-component alternating layer. A very thin multi-layer flow of resin flows through a single manifold flat film die where each layer is simultaneously expanded to the die width and thinned to the final die exit thickness. The distribution of layer thickness can be changed by inserting different feedboard modules. The outermost layer is usually thick and is called the skin layer.
The thickness of each layer is the wavelength range of visible light, and is 20 to 300 layers, preferably 100 to 300 layers, more preferably 150 to 300 layers. Generally, when the number of layers exceeds 150, iridescent gloss decreases.

Assuming that the first thin-film-constituting resin is an acrylic resin, the second is polybutylene terephthalate (referred to as component A), a polybutylene terephthalate elastic body (referred to as B component), and linear low density polyethylene (referred to as C component). It is assumed that
The acrylic resin accounts for 30 to 50% by weight of the total components of the multilayer film. Specifically, this film is composed of an acrylic monomer polymer such as methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate or the like, or a monomer mainly composed of these monomers and other copolymerizable monomers. A copolymer is mentioned.

  The second thin film-constituting resin accounts for 50 to 70% by weight of the total components of the multilayer film, and is a copolymer of component A, component B and component C, preferably a block copolymer. The ratio of component A: component B: component C is 80 to 95: 3 to 15: 0.5 to 5 (% by weight), preferably 85 to 93: 5 to 10: 1 to 4 (% by weight).

  The component A is preferably a polycondensate obtained by catalytic polycondensation reaction with 1,4 butanediol and terephthalic acid or dimethyl terephthalate. As the B component polyethylene terephthalate elastic body, a copolymer of polyethylene terephthalate and polyethylene glycol, preferably a block copolymer is used. Commercially available products can be used as the C component linear low density polyethylene. In general, the specific gravity is 0.85 to 0.93, and the melt index (MI) is 1 to 50.

Further, the thermoplastic elastomer is a copolymer of a thermoplastic hard segment such as polybutyl terephthalate, polyethylene terephthalate, or polycarbonate and a soft elastomer segment such as polyether glycol or polyetherimide.
When the content of the soft elastomer segment is changed, elastomers having different refractive indexes can be obtained. In the method of Patent Document 3, 20 or more layers of two types of thermoplastic resins having different refractive indexes of 0.03 or more can be laminated.

The thermoplastic elastomer may also be a segmented thermoplastic copolyester containing repeats of long chain ester units derived from dicarboxylic acids and short chain ester units derived from dicarboxylic acids and low molecular weight diols. preferable.
Even if the multilayer film of Patent Document 3 is used, the infrared and ultraviolet blocking film of the present invention can be produced.

  There are various anti-infrared films, but in the present invention, ultrafine particles of tin-doped indium oxide, indium-doped tin oxide, tin-doped antimony oxide, antimony-doped tin oxide and the like having a particle size of 100 to 150 nm are preferable. For example, 0.4 to 1.0% by weight of an infrared shielding agent is added to a polycarbonate-based pressure-sensitive adhesive and sufficiently dispersed to obtain a paint. If it is less than 0.4% by weight, the effect of the anti-infrared film is not sufficiently exhibited, and if it exceeds 1.0% by weight, the transmittance of visible light is lowered.

  This paint is applied to one side of the multilayer film. The coating thickness is preferably 1 to 10 μm after drying. The diameter of the paint powder affects the infrared shielding effect of the product film from the sun and affects the appearance such as color, so the diameter of the ultrafine particles can be determined according to the actual usage. After coating, baking is performed at 55 to 75 ° C. to form a coating film.

  An anti-ultraviolet film is applied to the other surface of the multilayer film that has not been subjected to the anti-infrared treatment. A benzotriazole type, a benzophenone type, a triazine type, a benzoate type, etc. can be used for an ultraviolet absorber. Examples of the benzotriazole ultraviolet absorber include 2- (2′-hydroxy-5′methylphenyl) benzotriazole (manufactured by Ciba Geigy), 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl). ) Benzotriazole (manufactured by Ciba Geigy) and the like.

  If the ultraviolet absorber is dissolved and adhered in an acrylic adhesive or the like, it can be adhered to the glass to be adhered without particularly providing an adhesive layer. It can also be used by dissolving in a normal solvent such as polyacrylic acid. In any case, the concentration of the ultraviolet absorber is 0.3 to 0.7% by weight, and the applied thickness is preferably 1 to 5 μm after drying. If the amount is less than 0.3% by weight, the effect of the anti-ultraviolet agent is not expressed. If the amount exceeds 0.7% by weight, the anti-ultraviolet effect is not sufficiently improved, and the additive may be precipitated. After coating, it is baked at 50 to 70 ° C. and dried.

  A hard impact resistant layer having an anti-scratch and friction function is provided on either the anti-infrared layer or the anti-ultraviolet layer. The protective layer uses polyester as a solvent and dissolves and disperses 0.1 to 0.3% by weight of lanthanum hexaboride. It is preferable to solidify by heating after coating, and the thickness of the protective layer after solidification is 1 to 2 μm.

Production of multilayer film Polymethylmethacrylate (hereinafter referred to as PMMA), polybutylene terephthalate (hereinafter referred to as PBT), polybutylene terephthalate and polyethylene glycol copolymer elastomer (viscosity 1 Pa / s), and linear low density polyethylene (Density 0.92, MI = 2) was used as a raw material. In this example, PMMA was used as the first layer, and PBT, PBT elastic body and polyethylene were blended as the second layer. The blending ratio was 90% by weight of PBT, 7% by weight of PBT elastic body, and 3% by weight of polyethylene.

  These raw materials were stored in two dryers having temperatures different from 130 ° C. and 75 ° C., respectively. After the dew point of the raw material reached −40 ° C. td, the raw material was charged into two extruders having different extrusion amounts and temperatures. The working temperature of the first layer PMMA extruder was 235 ° C., and the extrusion rate was 47 kg / hour. The operating temperature of the extruder for the second layer resin mixture was 240 ° C., and the extrusion rate was 60 kg / hour.

The molten resin extruded from the extruder is sent to a feed block system, divided into 100 layers, and then passed through a single manifold flat film die, followed by roll casting at 30 to 40 ° C. to room temperature regular roll casting. Here, the thickness and width of the film are precisely controlled. Thereafter, the film having a uniform thickness was sent to a biaxial stretching machine at a working temperature of 120 ° C. and stretched 2.5 to 4.5 times in the longitudinal direction and 2.5 to 4.0 times in the transverse direction. The total thickness of the 100-layer multilayer film thus obtained was 25 μm and the width was 2 m.
This film was 65 wt% PBT and 35 wt% PMMA.

Formation of anti-infrared layer An anti-infrared layer was formed on the first surface of the multilayer film. Tin-doped indium oxide having an average particle diameter of 110 μm was mixed with polycarbonate to produce a polycarbonate containing a coating solution containing 0.5% by weight of tin-doped indium oxide. This coating solution was applied to one surface of the multilayer film at a speed of 50 m / min using a coating machine. When baked at 65 ° C. and solidified, an anti-infrared layer having a thickness of 5 μm was formed on one surface of the multilayer film.

Formation of protective layer In this example, a protective layer was provided on the anti-infrared layer. Lanthanum hexaboride was mixed with polyester. This mixture contains 0.4% by weight of lanthanum hexaboride. The mixture was applied onto the anti-infrared layer at a speed of 50 m / min by the same application machine as that used to form the anti-infrared layer. After the coating, it was solidified by baking at 60 ° C. to form a protective layer having a thickness of 1.5 μm on the surface of the anti-infrared layer.

Formation of anti-ultraviolet layer An anti-ultraviolet layer was formed on the second surface of the multilayer film. As polybenzoic acid, 2- (2′-hydroxy-5′methylphenyl) benzotriazole (manufactured by Ciba Geigy) was blended as benzotriazole to obtain a coating solution of 0.5% by weight of benzotriazole blended polyacrylic acid. . This coating solution was applied onto the second layer of the multilayer film at a coating speed of 50 m / min using a roll type coater. Subsequently, it was solidified by baking at 60 ° C. to form an anti-ultraviolet layer having a thickness of 3 μm.

The obtained infrared and ultraviolet blocking films were tested with Experiment No. It was set to 1 and it used for the following test.
In actual use, a pressure-sensitive adhesive layer can be provided on the anti-ultraviolet layer, and the pressure-sensitive adhesive surface can be protected with a release paper and provided on the market.

  The obtained experiment No. The infrared and ultraviolet blocking films of No. 1 were measured for their infrared blocking rate and ultraviolet blocking rate using a 2-beam UV / VIS / NIR spectrometer (Jasco V-570). Impact resistance was measured according to ANSI Z97.1 measurement standard. Further, the visible light transmittance was measured, and these results are shown in Table 1.

Experiment No. 2 except that the number of layers of the multilayer film was increased to 200. In the same manner as in Example 1, an infrared ray and ultraviolet ray blocking film was produced. Due to the increase in the number of layers, the thickness of the multilayer film was 35 μm.
Experiment No. 3 except that the number of layers of the multilayer film was 300 and the thickness of the multilayer film was 42 μm. In the same manner as in Example 1, an infrared ray and ultraviolet ray blocking film was produced. Experiment No. No. 4 except that the number of layers of the multilayer film was 20 and the thickness of the multilayer film was 18 μm. In the same manner as in Example 1, an infrared ray and ultraviolet ray blocking film was produced. Experiment No. 2 to Experiment No. 4 with respect to Experiment No. In the same manner as in Example 1, the infrared ray blocking rate, the ultraviolet ray blocking rate, the impact resistance, and the visible light transmittance were measured and listed in Table 1.

Experiment No. No. 5 except that the concentration of the infrared blocking substance in the coating solution for forming the anti-infrared layer was 0.7% by weight. In the same manner as in Example 1, an infrared ray and ultraviolet ray blocking film was produced.
Experiment No. No. 6 except that the concentration of the infrared absorbing substance in the coating solution for forming the anti-infrared layer was 1.0% by weight. In the same manner as in Example 1, an infrared ray and ultraviolet ray blocking film was produced.
Experiment No. For Experiments 5 and 6, Experiment No. In the same manner as in Example 1, the infrared ray blocking rate, the ultraviolet ray blocking rate, the impact resistance, and the visible light transmittance were measured and listed in Table 1.

Experiment No. 7 except that the number of layers of the multilayer film was 10 and the thickness of the multilayer film was 15 μm. In the same manner as in Example 1, an infrared ray and ultraviolet ray blocking film was produced.
Experiment No. 8 except that the number of layers of the multilayer film was 400 and the thickness of the multilayer film was 50 μm. In the same manner as in Example 1, an infrared ray and ultraviolet ray blocking film was produced. Experiment No. No. 9 except that the concentration of the infrared absorbing material in the coating solution for forming the anti-infrared layer was 0.3. In the same manner as in Example 1, an infrared ray and ultraviolet ray blocking film was produced.

Experiment No. No. 10 except that the amount of tin-doped antimony oxide used in the anti-infrared layer was 1.1% by weight. In the same manner as in Example 1, an infrared ray and ultraviolet ray blocking film was produced.
Experiment No. 7 to Experiment No. No. 10, experiment no. In the same manner as in Example 1, the infrared ray blocking rate, the ultraviolet ray blocking rate, the impact resistance, and the visible light transmittance were measured and listed in Table 1.

Experiment No. 11 was used as a 20 μm thick polyester film (trade name, o-PET, CH289, manufactured by Nanya Plastics Co., Ltd.) as a heat insulating film.
Experiment No. No. 12, experiment no. A multilayer film having 100 layers and a thickness of 20 μm produced by the method 1 was used. Experiment No. 11 and 12, neither the anti-infrared layer, the anti-ultraviolet layer, nor the impact-resistant layer was provided. The same test as 1 was conducted. The results are shown in Table 1.

Experiment No. No. 13, Experiment No. No. 11 except that a film identical to the polyester film used in No. 11 and having a thickness different from 25 μm was used. In the same manner as in Example 1, an infrared ray and ultraviolet ray blocking film was produced.
The above film was subjected to Experiment No. In the same manner as in Example 1, an infrared ray and ultraviolet ray blocking film was produced. For each of the obtained films, the infrared blocking rate, the ultraviolet blocking rate, the impact resistance and the visible light transmittance were measured and listed in Table 2.

  Experiment No. Infrared and ultraviolet blocking films were produced in the same manner as in Example 1 except that the blending amount of benzotriazole blended with polyacrylic acid was changed from 0.1 to 0.9. For each of the obtained films, the experiment No. The blocking rate of infrared rays, ultraviolet rays and visible light was measured in the same manner as in Table 1 and shown in Table 2. Experiment No. In No. 17, not only the anti-ultraviolet characteristics were not improved, but also an additive was deposited.

  According to Tables 1 and 2, the concentration of the drug blended in the infrared blocking film is preferably 0.4 to 1.0% by weight, and the concentration of the drug blended in the UV blocking film is preferably 0.2 to 0.7% by weight. .

Claims (7)

In a light shielding film for attaching a transparent glass, wherein a film substrate is provided with an anti-infrared film and an anti-ultraviolet film, the film substrate is a transparent film comprising at least 20 ultra-thin layers having a substantially uniform thickness. A multilayer film made of a thermoplastic resin, wherein the thickness of each ultra-thin film layer is in the visible light wavelength range, and the ultra-thin films adjacent to each other are composed of two different thermoplastic resins. Infrared, UV blocking film. One resin constituting the ultrathin film layer is an acrylic resin, and the other resin is a polybutylene terephthalate, a copolymer of polybutylene terephthalate and polyethylene glycol, and a multilayer film that is a polymer blend of linear low density polyethylene. The infrared ray and ultraviolet ray blocking film according to claim 1. The infrared and ultraviolet blocking film according to claim 2, wherein the multilayer film has 100 to 300 layers. A tin-doped antimony oxide or an indium-doped tin oxide is dispersed as an anti-infrared film in an amount of 0.4 to 1.0% by weight in an adhesive and applied to a thickness of 1 to 10 µm. Item 4. The infrared and ultraviolet blocking film described in item 3. The infrared and ultraviolet blocking film according to claim 1, wherein a thermoplastic solution of 0.3 to 0.7% of benzotriazole is applied as an anti-ultraviolet film to a thickness of 1 to 5 μm. The infrared ray according to any one of claims 1 to 5, wherein a protective layer made of polyester containing 0.1 to 0.3% by weight of lanthanum hexaboride is provided directly or indirectly on the film substrate. UV blocking film. An infrared ray shielding layer and an ultraviolet ray shielding layer are provided on both surfaces of the multilayer film, respectively, a protective layer is provided on one surface, and an adhesive layer for bonding to the glass surface is provided on the other surface. Infrared and ultraviolet blocking films described in 1 to 6.