JPH10146927A - Fluororesin film laminate and manufacture thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To yield superior adhesiveness by using foundation material having a reaction group with silane, and a fluororesin being processed by corona- discharge at least in its one surface in a fluororesin film laminated body having a fluororesin film adhered onto a silane compound layer. SOLUTION: The fluororesin film laminated body is composed of a silane compound layer formed on a foundation material surface to further be laminated with a fluororesin film thereon, and also a foundation material adhered thereon with a silane compound formed on the surface of the fluororesin film. Such foundation material being laminated with a fluororesin film is preferably to have a reaction group with silane, e.g. there is used a glass plate and so on. Besides, the fluororesin film is given corona discharge and controlled in its surface tension in order to improve the adhesiveness to the foundation material. Then, silane compound solution is applied and then dried on the surface of the foundation material so as to form a silane compound layer to subsequently be heat melted with a fluororesin film.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fluororesin film laminate and a method for producing the same, and more particularly, to a fluororesin having excellent adhesion by laminating a fluororesin film after applying a silane compound solution to a substrate surface. The present invention relates to a film laminate, and particularly to a fluororesin film laminate excellent in transparency when a substrate is a glass plate.

[0002]

2. Description of the Related Art Fluororesin coatings are widely used as having excellent antifouling properties, water repellency and oil repellency.
Conventionally, a glass coated with a fluororesin is prepared by applying and drying an aminoalkyl trialkoxysilane as a coupling agent on the surface of the glass and then applying and firing a fluororesin paint (US Pat. No. 3,555,555). 3
No. 45). By pre-coating an aminoalkyl trialkoxysilane, it is possible to provide a fluororesin-coated glass having good fluororesin adhesion, but it is not possible to provide a fluororesin-coated glass having excellent transparency. It cannot be used for applications that require a property, for example, a microwave oven.

As a primer for applying a fluororesin paint to glass or a metal plate, a composition comprising a binder, a coagulant comprising a fluororesin, an alkali metal silicate and an amine salt of a polyamic acid, and a liquid carrier Has been developed (Japanese Patent Publication No. 60-35379), but the same primer cannot be used to adhere the fluororesin film to the substrate. Furthermore, a metal plate having a fluororesin film laminated using a primer obtained by dissolving or dispersing polyamideimide and / or polyimide, polyethersulfone, fluororesin, and metal powder in an organic solvent (Japanese Unexamined Patent Application Publication No. No. 264000)
Although the adhesion is good, when the same primer is used to laminate a fluororesin film on glass, not only the transparency is impaired because the primer layer is opaque, but also excellent adhesion cannot be obtained.

A primer for coating a glass with a fluororesin has also been developed, but when used for laminating a film, sufficient adhesion cannot be obtained and transparency is impaired. Further, as a laminated body using a film, tempered glass in which a film such as polyvinyl butyral is sandwiched between glass plates is known. However, a laminate in which a heat-resistant film such as a fluororesin film is sandwiched between glass plates has not been realized because of insufficient adhesion.

[0005]

SUMMARY OF THE INVENTION In order to solve the above-mentioned problems, the present invention provides a laminate of a fluororesin film having excellent adhesiveness and further having excellent transparency when the substrate is a glass plate. And a method for producing the same.

[0006]

According to the present invention, there is provided a fluororesin film having a substrate having a silane compound layer on the surface of the substrate and a fluororesin film adhered to the silane compound layer. A laminate, wherein the substrate is a substrate having a reactive group with silane, and the fluororesin film is a fluororesin film on which at least one surface is a corona discharge-treated fluororesin film About the body. In addition, other inventions,
A fluororesin having a fluororesin film bonded to a silane compound layer between a first substrate having a silane compound layer on the substrate surface and a second substrate having a silane compound layer on the substrate surface A film laminate, wherein the base material is a base material having a reactive group with silane, and the fluororesin film is a fluororesin film having both surfaces subjected to corona discharge treatment, or one surface is subjected to corona discharge treatment. 2
The present invention relates to a fluororesin film laminate, wherein the two fluororesin films are bonded together on a surface not subjected to corona discharge treatment.

[0007] The base material is a glass plate.
The glass plate has a layer containing silicon dioxide, a porous layer containing silicon dioxide, or a layer containing tin dioxide formed on the surface thereof, and a silane compound layer formed on the layer. And a fluororesin film laminate comprising a glass plate and a fluororesin film adhered to the silane compound layer and having at least one surface subjected to corona discharge treatment. Further, the base material is a glass plate, and further,
The glass plate has a layer containing silicon dioxide, a porous layer containing silicon dioxide, or a layer containing tin dioxide formed on the surface thereof, and a silane compound layer formed on the layer. Having a first glass plate and a second glass plate, both surfaces of which are corona-discharge treated between the first glass plate and the second glass plate. A first glass plate and a second glass plate, either a treated fluororesin film or a film in which two fluororesin films, one surface of which has been subjected to corona discharge treatment, are bonded on a surface not subjected to corona discharge treatment. And a fluororesin film laminate having the silane compound layer in contact with the silane compound layer.

A method for producing the above-mentioned fluororesin film laminate, characterized by forming a silane compound layer by applying and drying a silane compound solution on the surface of a substrate, and then hot-melt bonding the fluororesin film. About. Further, a fluororesin film, both surfaces of which have been subjected to corona discharge treatment, is placed on the first substrate on which the silane compound layer is formed by applying and drying a silane compound solution on the surface of the substrate, Next, on the film, after placing the second substrate on which the silane compound layer is formed by applying and drying the silane compound solution on the substrate surface so that the silane compound layer and the film are in contact with each other, The present invention relates to a method for producing a fluororesin film laminate having a fluororesin film between substrates, wherein the fluororesin film is bonded by heat melting. Furthermore, a first fluororesin film, one surface of which is subjected to corona discharge treatment, is brought into contact with the first silane compound layer on which the silane compound layer is formed by applying and drying a silane compound solution on the surface of the substrate. Then, a second fluororesin film having one surface subjected to corona discharge treatment is placed on the first film, and the surface of the second film which has not been subjected to corona discharge treatment is brought into contact with the first film. The second substrate on which the silane compound layer was formed by further applying and drying the silane compound solution on the surface of the substrate was placed such that the silane compound layer and the second film were in contact with each other. Thereafter, the present invention relates to a method for producing a fluororesin film laminate having a fluororesin film between substrates, wherein the fluororesin film is bonded by heat melting.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The fluororesin film laminate of the present invention is obtained by forming a silane compound layer on the surface of a base material and further adhering a fluororesin film. The formed base material is bonded. The substrate on which the fluororesin film is laminated in the present invention may be any substrate having a reactive group with silane, and specifically, a glass plate, an aluminum oxide plate,
Examples include a ceramic plate, an aluminum plate, and a stainless steel plate. When a commercially available pre-cleaned glass plate is used as the base material, it can be used as it is, but when other glass plate, aluminum oxide plate, ceramic plate, aluminum plate, or stainless steel plate is used, 1 The surface is completely washed using a ceric oxide aqueous solution of 0.0% by weight until the surface is completely wetted.

The silane compound layer on the surface of the substrate is formed by applying and drying a silane compound solution. The silane compound may be any known silane compound, specifically, vinyl trichlorosilane, vinyl triethoxy silane, vinyl trimethoxy silane, vinyl tris (β-methoxyethoxy) silane, γ-methacryloxypropylmethyldimethoxy silane, γ- Vinylsilanes such as methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, and γ-methacryloxypropyltriethoxysilane, β (3,
4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ
Epoxy silanes such as glycidoxypropylmethyldiethoxysilane and γ-glycidoxypropyltriethoxysilane, mercaptosilanes such as γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, N-phenyl -Γ-aminopropyltrimethoxysilane, and γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, N-β- (amino ethyl)
-Γ-aminopropyltrimethoxysilane, N-β-
Examples include aminosilanes such as (aminoethyl) -γ-aminopropyltriethoxysilane, and γ-ureidopropyltriethoxysilane. The silane solution is prepared by dissolving a silane compound in pure water. The content of the silane compound based on the silane compound solution is 0.01 to 10.0% by weight, preferably 0.1 to 10.0% by weight.
1.0% by weight. The application of the silane compound solution may be performed by any known method such as a dipping method, a spray method, a spin coating method, and a brush coating method. Further, the film thickness is suitably about 1 nm to 100 nm. The method of drying is not particularly limited, but is usually at 50 to 200 ° C. for 10 minutes to
Perform by heating in an oven for 2 hours.

When a glass plate is used as the substrate, in order to further improve the adhesion of the fluororesin film, 1) apply a ceramic powder to the surface of the glass plate before applying the silane compound solution. It is preferable to blast by a method such as spraying, or 2) to form a layer containing silicon dioxide, a porous layer containing silicon dioxide, or a layer containing tin dioxide on the surface of the glass plate. From the viewpoint of excellent transparency, it is particularly preferable to form a layer containing silicon dioxide, a porous layer containing silicon dioxide, or a layer containing tin dioxide on the surface of the glass plate. Since the silane compound does not bind to sodium or calcium, which is a component of glass, providing a layer containing silicon dioxide or tin dioxide enhances the adhesion of the silane compound to silicon dioxide and tin dioxide effectively. Can be. When a porous layer containing silicon dioxide is provided, in addition to the chemical reaction between the silane compound and silicon dioxide, the contact surface area with the silane compound layer is further increased, so that the adhesion is further improved.

The layer containing silicon dioxide is formed by dispersing tetraethoxysilicate in a suitable solvent by a known method,
For example, it is formed by applying and baking by a method such as a dipping method, a spray method, and a spin coating method.
Particularly preferably, the polysilazane solution is applied so as to form a layer having a thickness of 1 nm to several microns, and 200 to 60 μm in air.
This is a method of firing at 0 ° C. for 10 to 100 minutes. The porous layer containing silicon dioxide may be formed by any known method. Specifically, a method of treating the surface of a glass plate with a supersaturated aqueous solution of hydrosilicofluoric acid (Japanese Patent Laid-open No. JP-A-166337), a method of coating and baking a solution in which two or more kinds of precursor sols having different average molecular weights of thousands and hundreds of thousands are mixed as a raw material solution of a silicon oxide (JP-A-5-147977), LPD (Liquid
(Phase Deposition) method and a method of forming a porous layer by firing a glass-organic polymer hybrid. Preferred methods are the LPD method and a method using a glass-organic polymer hybrid. The LPD method saturates silicon dioxide such as silica gel in an aqueous solution of hydrofluoric acid and then immerses the glass plate in an immersion liquid obtained by adding an aqueous solution of boric acid. This is a method of depositing a film. A method using a glass-organic polymer hybrid, a step of dissolving an organic polymer and a silicate compound in a solvent for a sol-gel reaction, and performing a sol-gel reaction with an acid catalyst to obtain a glass-organic polymer hybrid; A step of applying the glass-organic polymer hybrid obtained in this step to the surface of a glass plate and firing it at a temperature at which silicon dioxide does not melt to form a porous layer. A typical method for producing a glass-organic polymer hybrid by a sol-gel reaction is disclosed in
No. 509131. The pores of the porous layer formed on the glass surface are several tens to several thousand nm, preferably 10 to 100 nm. As the number of pores in this porous layer is larger, the silane compound is more effectively bonded,
The adhesion of the fluororesin film becomes good. The layer containing tin dioxide may be formed by any known method, specifically, a method of applying and baking using a sol-gel reaction, a method of directly spraying tin tetrachloride, and the like. Spray tin tetrachloride directly on the surface of the board,
A method of baking in air at 300 to 700 ° C. for 1 to 10 minutes is preferable.

The fluororesin film used in the present invention may be a film containing a perfluororesin, and specifically, a copolymer of tetrafluoroethylene-perfluoroalkylvinyl ether (PFA), tetrafluoroethylene-hexa A film consisting essentially of fluoropropylene copolymer (FEP), ethylene-tetrafluoroethylene copolymer (ETFE), and a blend of two or more thereof. Preferably, it is a film consisting essentially of PFA or FEP. The film is subjected to a corona discharge treatment in advance, and the surface tension is controlled to improve the adhesion of the film to the substrate. The surface tension of the film is not particularly limited.
The treatment is performed so as to be at least n / cm ² , preferably at least 36 dyn / cm ² . In the case of coating the film on the substrate, it may be subjected to a corona discharge treatment on one side of the film, but in the case of a laminate having the film between the substrate and the substrate, for example,
When a tempered glass is made by using a glass plate / film / glass plate, a film having both surfaces subjected to corona discharge treatment is used, or two films having one surface subjected to corona discharge treatment are subjected to corona discharge. It may be used by being superimposed on a surface that has not been treated. A film may be further interposed between the two films. Although the thickness of the film is not particularly limited, a film having a thickness of 10 to 250 μm is usually used. The method of bonding the film subjected to the corona discharge treatment is not particularly limited, but preferably the film is bonded to the substrate by hot-melt bonding. The conditions for the hot-melt bonding are appropriately selected, and the temperature at that time is not lower than the melting point of the fluororesin contained in the film. If so, 270 to 300C is preferable. Also,
The pressure at the time of hot-melt bonding is preferably 1 to 50 kg / cm ^2.
And is performed for 10 to 100 seconds.

[0014]

EXAMPLES The present invention will be described with reference to examples, but the present invention is not limited to these examples. (Example 1) A silane compound was dipped on a commercially available pre-cleaned glass plate (Precrine glass (trade name) manufactured by Matsunami Co.) using a 1.0% by weight aqueous solution of γ-aminopropyltriethoxysilane at a pulling rate of 100 mm / min. Coated.
The glass coated with the silane compound is placed in an oven for 1 hour.
Dry at 00 ° C. for 1 hour. Corona discharge treated PFA film (Dupont PFA500CL)
P, a surface tension of 38 dyn / cm ² , and a film thickness of 125 μm) were placed on a glass plate having a silane compound layer formed thereon, and the temperature was set at 320 ° C.
Under a pressure of 20 kg / cm ² for 40 seconds. It was left for about one day at room temperature to stabilize the adhesion. Thus, the peel strength of three test pieces of the glass plate on which the PFA film was laminated was measured. The peel strength was measured by holding the test piece between chucks and peeling the test piece so that the angle between the glass plate and the film was 180 °. Table 1 shows the average value of the measured peel strength values and the result of visual observation of the transparency. The surface roughness of the used glass plate was measured with an atomic force microscope, and the measured values are shown in Table 1.

(Example 2) The same glass plate as used in Example 1 was mechanically blasted by spraying a ceramic powder, and then an aqueous solution of γ-aminopropyltriethoxysilane was applied. A test piece was prepared in the same manner as in Example 1, the peel strength was measured, and the transparency was observed. Further, the surface roughness of the blasted glass plate was measured. The results are shown in Table 1. (Example 3) On the same glass plate used in Example 1,
Dip coating the polysilazane solution to form a layer of about 0.1 μm to form a silicon dioxide layer;
After firing in air at about 500 ° C. for about 30 minutes, γ
A test piece was prepared in the same manner as in Example 1 except that an aqueous solution of -aminopropyltriethoxysilane was applied, the peel strength was measured, and the transparency was observed. Further, the surface roughness of the glass plate on which the silicon dioxide layer was formed was measured. The results are shown in Table 1.
Shown in

Example 4 A commercially available glass plate (manufactured by Nippon Sheet Glass Avi Co., Ltd.) provided with a porous layer containing silicon dioxide by the LPD method was coated with an aqueous solution of γ-aminopropyltriethoxysilane. A test piece was prepared in the same manner as in Example 1, the peel strength was measured, and the transparency was observed. Further, the surface roughness of the glass plate on which the porous layer was formed was measured. The results are shown in Table 1. (Example 5) On the same glass plate used in Example 1,
An alcohol / hydrochloric acid aqueous solution mixture of tetraethoxysilicate and acrylic polymer having a weight ratio of silicon dioxide and acrylic polymer of 1: 1 is applied by dip coating,
A test piece was prepared in the same manner as in Example 1 except that after drying at room temperature overnight, the porous layer containing silicon dioxide was provided by baking at 500 ° C. for 30 minutes, and then an aqueous solution of γ-aminopropyltriethoxysilane was applied. Was prepared, the peel strength was measured, and the transparency was observed. Further, the surface roughness of the glass plate on which the porous layer was formed was measured. The results are shown in Table 1. (Example 6) A commercially available glass plate having a tin dioxide layer formed on tin soda lime glass using tin tetrachloride (manufactured by Asahi Glass Co., Ltd.)
, A test piece was prepared in the same manner as in Example 1 except that an aqueous solution of γ-aminopropyltriethoxysilane was applied thereto, the peel strength was measured, and the transparency was observed. Further, the surface roughness of the glass plate on which the tin dioxide layer was formed was measured. Result is,
It is shown in Table 1.

(Example 7) Instead of the PFA film used in Example 1, an FEP film subjected to corona discharge treatment (FEP500C manufactured by DuPont, surface tension 38 dyn / c)
(m ² , film thickness 125 μm), a test piece was prepared in the same manner as in Example 1 except that the temperature at the time of hot-melt bonding was 290 ° C., the peel strength was measured, and the transparency was observed.
The results are shown in Table 1. (Examples 8 and 9) Instead of the glass plate used in Example 1,
The surface roughness measured by a surface roughness measuring device is 0.20μ
A test piece was prepared in the same manner as in Example 1, except that an aluminum oxide plate of m (Example 8) and 0.66 μm (Example 9) was used, the peel strength was measured, and the transparency was observed. The results are shown in Table 1.

Comparative Example 1 The same PFA film as used in Example 1 was placed on the same glass plate as used in Example 1, and the same PFA film was used at 320 ° C. under a pressure of 20 kg / cm ² . Hot melt bonding was performed for 40 seconds. To stabilize the adhesion, leave it at room temperature for about 1 day, measure the peel strength,
Transparency was observed. The results are shown in Table 1. (Comparative Example 2) Instead of an aqueous solution of γ-aminopropyltriethoxysilane, a primer was spray-coated using a fluororesin primer for glass (458-500, manufactured by DuPont), and baked at 380 ° C for 15 minutes to form a film having a thickness of 8 µm. A test piece was prepared in the same manner as in Example 1 except that the primer layer was provided, the peel strength was measured, and the transparency was observed.

(Measurement of Tensile Strength of Film) The PFA films used in Examples and Comparative Examples were similarly hot-melted to a thickness of 105 μm, and then subjected to JIS Z0237,8,3.
When the tensile strength was measured in accordance with the section, 1.57 kg / cm
Met. This indicates that the film breaks when the peel strength is near this value. When the adhesion between the film and the substrate was strong and the film was broken before the film was separated from the substrate, "<" was described after the measured peel strength in Table 1.

[0020]

[Table 1]

When the peel strengths of Examples 1 to 6 and Comparative Example 1 are compared, it can be seen that all of them are significantly improved. In addition, Examples 1 and 3 to 6 are all transparent, but Comparative Example 2 shows that the peel strength is insufficient and the film becomes more opaque. Example 2
From this, it can be seen that mechanical blasting of the glass plate makes it slightly opaque. Comparing Example 1 with Example 2, Example 4 and Example 5, it can be seen that the rougher the glass surface, the higher the peel strength. Comparing Example 1 with Examples 3 and 6, it can be seen that even if the glass surface is not rough, the peel strength is increased by providing the layer containing silicon dioxide or tin dioxide. Furthermore, Example 7 shows that even when the FEP film is used, the peel strength and the transparency are excellent as in the case where the PFA film of Example 1 is used. Example 8
From FIGS. 9 and 10, it can be seen that the peel strength was excellent even when an aluminum oxide plate was used.

(Examples 10 to 20) γ used in Example 1
-Instead of an aqueous solution of aminopropyltriethoxysilane,
Using the other silane compound solutions shown in Table 2, test pieces were prepared in the same manner as in Example 1, and the peel strength was measured. Result is,
It is shown in Table 2. In addition, transparency was observed, and all the test pieces were transparent.

[0023]

[Table 2] Comparing the peel strengths of Examples 10 to 20 and Comparative Example 1, it can be seen that all of them are significantly improved. In particular, it can be seen that Examples 14 to 17 are excellent in adhesion.

(Example 21) A commercially available pre-cleaned glass plate (Preclin glass (trade name) manufactured by Matsunami Co., Ltd.) was set to 1.0.
A silane compound was dip-coated with a 100% by weight aqueous solution of γ-aminopropyltriethoxysilane at a pulling rate of 100 mm / min. The glass coated with the silane compound was dried in an oven at 100 ° C. for 1 hour. Two glasses on which the silane compound layer was formed were prepared. Two PFA films (PFA500CLP manufactured by DuPont, surface tension: 38 dyn / cm ² , film thickness: 125 μm) having one surface subjected to corona discharge treatment are prepared, and superposed so that the surface subjected to corona discharge treatment is in contact with the silane compound layer. ,
Place on the first glass plate on which the silane compound layer is formed,
Further, a second glass plate on which a silane compound layer was formed was placed on the film. Then, at 320 ° C., 20 kg
Under a pressure of / cm ² for 40 seconds. It was left for about one day at room temperature to stabilize the adhesion. The laminate obtained in this way was transparent and adhered so strongly that it was difficult to peel off the glass by hand. Even when the silane compound was applied to the glass plate by brushing, a transparent laminate having excellent adhesion was similarly obtained.

[0025]

As described above, the fluororesin film laminate of the present invention has excellent adhesion and can be used in various applications. The present invention can provide a fluororesin film laminate having not only excellent adhesion but also excellent transparency when the base material is glass.

Claims (8)

[Claims] 1. A fluororesin film laminate comprising a substrate having a silane compound layer on the surface of the substrate and a fluororesin film adhered to the silane compound layer, wherein the substrate has a reactive group with silane. Wherein the fluororesin film is a fluororesin film on which at least one surface is subjected to a corona discharge treatment. 2. A first material having a silane compound layer on a substrate surface.
The base material, between the second base material having a silane compound layer on the base material surface, a fluororesin film laminate having a fluororesin film adhered to the silane compound layer,
A fluororesin film laminate, wherein the substrate is a substrate having a reactive group with silane, and the fluororesin film is a fluororesin film having both surfaces subjected to corona discharge treatment. 3. A first material having a silane compound layer on a substrate surface.
The base material, between the second base material having a silane compound layer on the base material surface, a fluororesin film laminate having a fluororesin film adhered to the silane compound layer,
The base material is a base material having a reactive group with silane, and the fluororesin film is a film in which two fluororesin films having one surface subjected to corona discharge treatment are adhered on a surface not subjected to corona discharge treatment. A fluororesin film laminate, characterized in that: 4. The fluororesin film laminate according to claim 1, wherein the substrate is a glass plate. 5. The glass plate according to claim 1, wherein the glass plate has a layer containing silicon dioxide, a porous layer containing silicon dioxide, or a layer containing tin dioxide formed on the surface thereof. The fluororesin film laminate according to claim 4. 6. The fluororesin film according to claim 1, wherein the silane compound layer is formed by applying and drying the silane compound solution on the surface of the base material, and then the fluororesin film is bonded by hot-melt. A method for manufacturing a laminate. 7. A fluororesin film, both surfaces of which have been subjected to a corona discharge treatment, are placed on the first substrate having a silane compound layer formed by applying and drying a silane compound solution on the surface of the substrate. Then, a second substrate on which a silane compound layer is formed by applying a silane compound solution on the surface of the substrate and drying is placed on the film so that the silane compound layer and the film are in contact with each other. The method for producing a fluororesin film laminate according to claim 2, wherein the fluororesin film is bonded by hot-melt after the step. 8. A first fluororesin film, one surface of which is subjected to corona discharge treatment, is coated on a first substrate having a silane compound layer formed by applying and drying a silane compound solution on the surface of the substrate. Then, a second fluororesin film, one surface of which is subjected to corona discharge treatment, is placed on the first film on the first film, the surface of the second film which has not been subjected to corona discharge treatment. The second substrate on which the silane compound layer is formed by applying and drying the silane compound solution on the substrate surface is further placed so that the silane compound layer and the second film are in contact with each other. The method for producing a fluororesin film laminate according to claim 3, wherein the fluororesin film is heat-melted and bonded after being placed.