JPH07299885A - Composite film material, housing structure and production of composite film material - Google Patents

Abstract

PURPOSE:To provide such a composite film material that the original characteristics thereof are not deteriorated, that the composite film material is vividly colored, that color fade is not thoroughly caused and that coloring properties are excellent by providing an optical interference film on at least one side of the composite film material formed of the composite body consisting of a glass fabric and a fluororesin. CONSTITUTION:When an optical interference film is formed of only a transparent layer film, a transparent layer 2 consisting of, for example, a transparent metallic compound film is provided on one side or both sides of a composite film 1 consisting of a glass fabric and a fluororesin through vapor deposition. In the composite film 1 in which the transparent layer 2 of this sort is laminated, coloring is caused by interference of reflected ray R1 on the surface of the transparent layer 2 and reflected ray R2 on the back thereof, namely the reflected ray on the boundary surface of the transparent layer 2 and the composite film 1 to which the transparent layer 2 is touched. The reflected rays R1, R2 are generated from incident light R on the surface. This coloring is variously changed in accordance with the material of the transparent layer 2, color of the composite film 1 itself and thickness of the transparent layer 2.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composite film material having excellent color developability and light interference properties, and more particularly to a film material for house structures and a method for producing the same.

[0002]

2. Description of the Related Art A film material composed of a composite of a glass fabric and a fluororesin is excellent in nonflammability, chemical resistance, antifouling property, water repellency, durability and translucency and has high strength. It has been used as a film material for house structures. Conventionally, a technique for producing a color film has been proposed in order to impart fashionability to a film material composed of a composite of a glass fabric and a fluororesin. For example, a method of adding a pigment to an aqueous dispersion of a fluororesin such as polytetrafluoroethylene used as an impregnating solution is known, as in JP-A-3-110146. However, the color was monochromatic, and there was room for improvement in terms of fashionability.

[0003]

DISCLOSURE OF THE INVENTION The object of the present invention was studied in order to improve the above-mentioned drawbacks, and the original characteristic of a membrane material composed of a composite of a glass fabric and a fluororesin, namely noncombustibility, Chemical resistance, antifouling property, water repellency, durability, translucency, high strength properties are not impaired, pigments are not mixed, and it produces vivid colors more than mono-hue color and two-hue color, and the viewing angle is It is intended to provide a film material having a deep and brilliant color forming property, which does not deteriorate the color brilliance even if it is changed and does not fade at all, and a manufacturing method thereof.

[0004]

The present invention adopts the following constitution in order to solve the above problems. That is,
The composite film material of the present invention is characterized in that an optical interference film is provided on at least one surface of a film material composed of a composite of a glass fabric and a fluororesin, and the house structure of the present invention. Is characterized in that the composite membrane material is used for a wall or a roof of a house structure, and the method for producing the composite membrane material is a membrane composed of a composite of a glass fabric and a fluororesin. The transparent metal film is vapor-deposited on at least one surface of the material, and further, the reflective metal film, the transparent metal film is formed on at least one surface of the film material composed of a composite of a glass fabric and a fluororesin. It is characterized in that at least one selected from a film and a semitransparent metal film is sequentially deposited.

[0005]

The film material of the present invention comprises a glass fabric, a fluororesin, a reflective metal film, a transparent metal compound film, and a metal layer such as a semitransparent metal film.

The composite of the glass fabric and the fluororesin is obtained by impregnating the glass fabric with an aqueous dispersion of the fluororesin and drying and firing to obtain a coating film on the surface, or by heating the sheet-like molding of the fluororesin. It can be obtained by sticking by fusion.

The glass fiber used in the present invention is not particularly limited in its type and diameter of the single fiber, but the diameter is 10
A value of μ or less is useful for obtaining high strength, and particularly when it is used as a film material, it is required to have high strength and bending resistance of 3-4.
The thing of about μ is used.

The design of the woven fabric used in the present invention is not particularly limited, but may be plain weave, basket weave, imitation weave, satin weave, or the like.

The glass fabric used in the present invention has flexibility, and in order to improve the affinity with the fluororesin in the post-process, SF8417, SF8411, manufactured by Toray Dow Corning Silicone Co., Ltd. SF8413, BY-16-839, SH-8400
, BY-22-819, SM8701 and other softeners and γ- (2-aminoethyl) aminopropylmethyldimethoxysilane,
γ-glycidoxypropyltrimethoxysilane, γ-
A silicone-based coupling agent such as methacryloxypropyltrimethoxysilane, n- (trimethoxysilylpropyl) ethylenediamine, and tridecafluorooxyltriethoxysilane is applied. Usually, in the impregnation step, a continuous coating device including an impregnation tank, a squeezing roller or a knife roller for adjusting the amount of adhesion, and a heating zone is used. In the heating zone, the pretreatment agent for the softening agent and the coupling agent, the polytetrafluoroethylene is dried, and the polytetrafluoroethylene is baked.

The polytetrafluoroethylene layer coated on the above silicone layer is an aqueous dispersion of polytetrafluoroethylene, such as "Polyflon D-" manufactured by Daikin Industries, Ltd.
2 "," Teflon 30-J "manufactured by Mitsui DuPont Fluorochemicals Co., Ltd. can be formed.

The polytetrafluoroethylene aqueous dispersion contains methyl cellulose, in order to increase the coating thickness per application.
Thickeners such as sodium alginate, calcium fibrin glycolate, sodium fibrin glycolate, sodium polyacrylate, sodium starch phosphate, and sodium starch glycolate, micro glass balloons and micro to improve light diffusion. You may mix inorganic particles, such as glass beads and silica. After coating the polytetrafluoroethylene aqueous dispersion, drying for volatilizing water and firing for sintering are performed. Drying temperature is 90-200 ° C, firing temperature is 300-420 ° C.
The range of is desirable. If the temperature exceeds 420 ° C., the strength of the glass fiber is greatly reduced by heat treatment. The thickness of the polytetrafluoroethylene layer varies depending on the required performance such as required flexibility and mechanical properties, but is usually adjusted in the range of 20 to 500 μ.

The fluororesin sheet used in the present invention is
It is manufactured by extrusion molding to a required thickness with an extruder.

In the laminating of the fluororesin sheet used in the present invention and the above-mentioned pretreated glass fabric, the both are superposed and thermocompression bonded by a conventional press machine, calender roll or double belt press. Although the welding temperature depends on the pressure bonding time, a temperature of 5 to 70 ° C higher than the melting point of the fluororesin sheet is used as a reference.

The thickness of the fluororesin sheet of the present invention is selected according to the purpose and application, but 15 to 1000 μm imparts flexibility and strength of the film material, and further the film materials are joined by heat fusion. In this case, it is preferable from the viewpoint of maintaining a strong joint.

Applying the above-mentioned fluororesin dispersion having a good affinity for the fluororesin sheet as a pretreatment for heat-sealing the fluororesin sheet makes the heat-adhesion of the fluororesin sheet easier. It is also effective to enhance the affinity by subjecting the surface of the fluororesin sheet to plasma or corona discharge treatment. The film material having the interference color of the present invention is obtained by depositing a metal film such as a reflective metal film, a transparent metal compound film, or a semitransparent metal film on a composite film material of a glass fabric and a fluororesin obtained by the above method. be able to.

The metal film such as the reflective metal film, the transparent metal compound film, and the semitransparent metal film used in the present invention is a predetermined film for each film by the induction heating vacuum deposition method, the ion plating method, the sputtering method, and the electron beam method. The film thickness can be adjusted and vapor deposition can be performed.

After vapor deposition, the temperature is 130 ° C. or higher, more preferably 1
When heat-treated at 70 ° C. or higher, an oxide film is formed, the film strength is improved, and the interference color of the film material becomes more vivid, so that a metallic luster can be obtained.

The material of the reflective metal film used in the present invention is A
At least one selected from l, Cu, Ag, Mg, Ti, Ni, Co, Au, Cr, Pe and Rh is used.

The material of the transparent metal film used in the present invention is Si
O ₂ , SiO ₂ , In ₂ O ₃ , TiO ₂ , In ₂ O ₃ / SnO ₂ , Mg
At least one selected from F ₂ , Al ₂ O ₃ and Cr ₂ O ₃ is used.

The material of the semitransparent metal film used in the present invention is
Al, Cu, Ag, Mg, Ti, Ni, Co, In, Cr, Si, Au, Au / Pt
At least one selected from is used.

The thickness of these metal films is expressed by the following formula (1),
It is preferable to satisfy the relationships of the expressions (2), (3) and (4).

450A ≦ d ₁ + d ₂ ≦ 7000A (1) 50A ≦ d ₁ ≦ 2000A (2) 400A ≦ d ₂ ≦ 5000A (3) d ₃ ≧ 500A (4) where d ₁ : half Film thickness of transparent metal film d ₂ : Film thickness of transparent metal compound film d ₃ : Film thickness of reflective metal film.

When the light interference film is a transparent layer film only, as shown in FIG. 1, a transparent layer 2 such as a transparent metal compound film is formed on one surface or both surfaces of the composite film 1 of glass fabric and fluororesin. It is provided by vapor deposition.

A composite film 1 in which such a transparent layer 2 is laminated
In (1), the light R incident from the front surface is reflected by the reflected light R1 on the front surface of the transparent layer 2 and the reflected light R2 on the rear surface thereof, that is, by the reflected light at the boundary surface between the transparent layer and the composite film in contact with the transparent layer.

This color development changes variously depending on the material of the transparent layer 2, the color of the composite film 1 itself, and the thickness of the transparent layer 2. In particular, the thickness of the transparent layer 2 is preferably 400 angstroms or more and 5000 angstroms or less in order to obtain a brilliant color.

Further, as shown in FIG. 2, the optical interference film is provided on one surface or both surfaces of the composite film 1 from the composite film side to the reflection layer. On one surface or both surfaces of the composite film 1 from the composite film 1 side to the reflection layer 2 and the transparent layer 3. May be formed by forming a two-layer structure in which The reflective layer 2 is made of, for example, a metal thin film having an average reflectance in the visible light region of 60% or more (preferably 90% or more), and the material of the reflective metal film is, for example, A
At least one selected from l, Cu, Ag, Mg, Ti, Ni, Co, Au, Cr, Pe and Rh is used. Such a reflective layer 2
Can also be provided by vapor deposition, and the thickness of the reflective metal film forming the reflective layer 2 is preferably 500 angstroms or more.

In the composite film 1 in which the reflective layer 2 and the transparent layer 3 are sequentially laminated, the light R incident from the front surface side is reflected light R1 on the surface of the transparent layer 3 and reflected light R on the back surface.
2 That is, the color is developed by the interference with the reflected light on the boundary surface between the transparent layer 3 and the reflective layer 2.

As shown in FIG. 3, the optical interference film is formed by sequentially laminating the reflective layer 2, the transparent layer 3 and the semitransparent layer 4 in this order on one surface or both surfaces of the composite film 1 from the composite film 1 side. It may be formed by forming a layered structure. Translucent layer 4
Is a semitransparent metal film having an average reflectance of 60 or less in the visible light region, and examples of the material of the semitransparent metal film include Al, Cu, Ag, Mg, Ti, Ni, Co, In, Cr and Si. , Au,
At least one selected from Au / Pt is used. Such a semitransparent layer 4 can also be provided by vapor deposition.

In the composite film 1 in which the reflective layer 2, the transparent layer 3 and the semi-transparent layer 4 are sequentially laminated, the light R incident from the front surface side, the surface of the semi-transparent layer 4, the surface of the transparent layer 2, The reflected light R1 on the front surface of the reflective layer 4 (the back surface of the transparent layer 3),
R2 and R3 are generated, and the reflected lights R1, R2 and R3 interfere with each other to develop an interference color.

The three-layer thin film may be applied to the entire surface of the film material, but it is not always necessary and may be applied partially. For example, a portion having an interference color is print dyed. You may adopt a pattern.

The minimum area of the surface part which causes interference coloring may be an area which allows humans to visually recognize the interference color.

In order to improve the durability of color development, it is also effective to coat the surface of the laminated three-layer thin film with a protective film having a high transparency which is close to the refractive index of the thin film substance. With such a protective film, not only the thin film can be protected, but also the surface reflected light from the surface of the film material can be reduced, and the interference color can be further darkened.

Further, as shown in FIG. 4, the optical interference film has a two-layer structure in which the transparent layer 2 and the semitransparent layer 3 are sequentially laminated on one side or both sides of the composite film 1 from the composite film 1 side. It may be formed by.

In such a composite film 1, a color is produced mainly by the interference of the reflected lights R1 and R2.

[0035]

EXAMPLES The present invention will be specifically described below with reference to examples.

Example 1 Pre-sized β yarn (single yarn diameter: 3.8μ)
Glass fabric consisting of ECB 150 4/2 (mass: 500g / m
² , weave structure: plain weave, weave density (vertical × horizontal): 24.5x19.5
3 / 25mm) to remove surface sizing agent
Heat treatment was performed under the conditions of 80 ° C. × 15 min. Next, as a softening agent, SF manufactured by Toray Dow Corning Silicone Co., Ltd.
It was impregnated with a 1.0% aqueous solution of 8413, squeezed with a mangle, and then heat-treated at 110 ° C. for 5 minutes to be dried. The same operation was performed by impregnating a 1.0% aqueous solution of the coupling agent γ- (2-aminoethyl) aminopropylmethyldimethoxysilane.

Next, a dispersion of polytetrafluoroethylene (D-2 manufactured by Daikin Industries, Ltd.) was impregnated, squeezed with a mangle, then heat-treated at 110 ° C. for 5 minutes to dry, and then sintered. In order to carry out, a heat treatment of 390 ° C. × 10 min was performed. In order to secure a required film thickness, impregnation heat treatment with polytetrafluoroethylene was carried out 5 times to obtain a film material in which a fluororesin was applied to a glass fabric. The thickness of the film material is 63
It was 6 μ. An optical interference film having a three-layer structure was deposited on one surface of the film material.

The reflective layer is made of Al and has a film thickness of 800 Å, and the transparent layer is made of SiO 2 and has a film thickness of 800 Å, 1000 Å, 1200 Å, 1500 Å, and is semitransparent. The layer was composed of Cr and had a film thickness of 50 Å. As for the film material having the obtained optical interference film deposited thereon, the transparent layer having a thickness of 800 Å produces a deep color mainly composed of blue, and the one having a thickness of 1000 Å obtains a deep color composed mainly of green. The color of 1200 angstrom was deep and the color was mainly yellow, and the color of 1500 angstrom was deep and was mainly red.

Example 2 The same glass fabric, softening agent, coupling agent and polytetrafluoroethylene dispersion as in Example 1 were applied and heat treated under the same drying conditions as in Example 1 to obtain polytetrafluoroethylene. The firing of was omitted. An unfired polytetrafluoroethylene film (100 μ) prepared in advance was overlaid on both sides of a glass woven fabric and pressure-bonded with a calender, followed by heat treatment at 390 ° C. × 10 min. Next, a tetrafluoroethylene-hexafluoropropylene copolymer was applied in order to facilitate the bondability of the film material and treated under the same conditions as in Comparative Example 1 to obtain a film material. The thickness of the film material was 650μ.

An optical interference film was formed under the same conditions as in Example 1 except that the upper semi-transparent film of Cr had a thickness of 70 Å. After metal deposition, heat treatment was performed at 170 ° C. for 2 minutes to increase the strength of the film. As a result, if the transparent layer has a thickness of 800 Å,
A deep color mainly consisting of blue is obtained, and a film thickness of 1000
For the angstrom, a deep color mainly composed of green is obtained, and for the 1200 angstrom, a deep color mainly composed of yellow is obtained.
In the case of 00 angstrom, a deep color mainly composed of red was obtained.

Example 3 A glass fabric was treated under the same conditions as in Example 1 to obtain a membrane material in which the glass fabric was coated with a fluororesin. The thickness of the film material is 64
It was 2 μ. A two-layer optical interference film was vapor-deposited on one surface of the film material. The reflective metal film is made of Al and has a film thickness of 800 angstroms, and the transparent layer film is made of SiO ₂ and has film thicknesses of 1000 angstroms, 1500 angstroms and 2000 angstroms, respectively. A deep color mainly composed of green for angstrom and yellow for 2,000 angstrom was obtained.

Example 4 A glass fabric was treated under the same conditions as in Example 1 to obtain a membrane material in which the glass fabric was coated with a fluororesin. The thickness of the film material is 63
It was 7 μ. A one-layer optical interference film was vapor-deposited on one surface of the film material. The transparent metal film was made of SiO ₂ and had film thicknesses of 1500 angstrom, 2000 angstrom, and 2500 angstrom, respectively, and the color was a deep yellow to deep yellow color.

[0043]

According to the present invention, the characteristics of nonflammability, chemical resistance, antifouling property, water repellency, durability, translucency, and high strength are not impaired, a pigment is not mixed, and a monochromatic color, and It is possible to provide a film material and a house structure that are more vivid than two-hue colors, do not deteriorate the brightness of the color even when the viewing angle is changed, and do not fade, and have a deep color developability. it can.

[Brief description of drawings]

FIG. 1 is a cross-sectional view showing an example of a composite film material of the present invention and also shows how light is reflected.

FIG. 2 is a cross-sectional view showing another example of the composite film material of the present invention, and also shows how light is reflected.

FIG. 3 is a cross-sectional view showing another example of the composite film material of the present invention, and also shows how light is reflected.

FIG. 4 is a cross-sectional view showing another example of the composite film material of the present invention and also shows how light is reflected.

[Explanation of symbols]

 1: Composite film 2: Reflective thin film 3: Transparent thin film 4: Semi-transparent thin film R1, R2, R3: Reflected light

Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display location C23C 14/08 A 8414-4K D 8414-4K E 8414-4K 14/14 D 8414-4K B 8414-4K

Claims (9)

[Claims] 1. A composite film material, wherein an optical interference film is provided on at least one surface of a film material composed of a composite of a glass fabric and a fluororesin. 2. The fluororesin is selected from tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-ethylene copolymer and tetrafluoroethylene-perfluoroalkylvinylether copolymer. The composite membrane material according to claim 1, which is composed of at least one of the following: 3. The optical interference film comprises SiO ₂ , SiO ₂ , In ₂ O ₃ and Ti.
O ₂ , In ₂ O ₃ / SnO ₂ , MgF ₂ , Al ₂ O ₃ and Cr ₂ O
_The composite film material having an interference color according to claim 1, which is a transparent metal film made of at least one selected from ₃ . 4. The light interference film has an average reflectance of 60% or more in the visible light region of Al, Cu, Ag, Mg, Ti, Ni, Co,
The composite film material according to claim 1, which is a two-layer laminated film in which a reflective metal film made of at least one selected from Au, Cr, Pe, and Rh and the transparent metal film according to claim 3 are sequentially laminated. . 5. The light interference film, the reflective metal film according to claim 4, the transparent metal film according to claim 3, and Al, Cu, Ag, Mg having an average reflectance of less than 60% in a visible light region. Ti, Ni,
At least 1 selected from Co, In, Cr, Si, Au, Au / Pt
The composite film material according to claim 1, which is a three-layer laminated film including a semi-transparent metal film including a seed. 6. The composite film material according to claim 1, wherein the light interference film is a two-layer laminated film obtained by sequentially laminating the transparent metal film according to claim 3 and the semitransparent metal film according to claim 4. 7. A composite film material having a light interference film provided on at least one surface of a film material composed of a composite of a glass fabric and a fluororesin is used for a wall or a roof of a house structure. House structure. 8. A method for producing a composite film material, comprising depositing the transparent metal film on at least one surface of a composite film material comprising a glass woven fabric and a fluororesin. 9. A reflective metal film according to claim 4, a transparent metal film according to claim 3, and a translucent metal according to claim 5, on at least one surface of a film material composed of a composite of a glass fabric and a fluororesin. A method for producing a composite film material, which comprises sequentially depositing at least one selected from films.