JPH02151428A - Foamed laminate coated with fluororesin film - Google Patents

Abstract

PURPOSE:To enhance weatherability, anti-staining properties and adhesion durability by laminating a multilayer film containing a vinylidene fluoride resin and a methacrylic ester resin as resin components or a laminate of the multilayer film and a metal foil to a resin foam body. CONSTITUTION:A composite film consisting of a film based on 100-50 pts.wt. of a vinylidene fluoride resin and 0-50 pts.wt. of a methacrylic ester resin and a film based on 50-0 pts.wt. of the vinylidene fluoride resin and 50-100 pts.wt. of the methacrylic ester resin is used in a surface layer and a resin foam body is used in a rear layer to form a laminate. Further, a metal foil may be provided to the intermediate layer of the composite film and resin foam body of said laminate. This laminate is excellent in anti-staining properties and adhesion durability and, since this laminate also has the excellent long-term weatherability possessed by the vinylidene fluoride resin and the adhesiveness of a base material is not lowered over a long period of time, said laminate can be effectively used as the interior and exterior materials of a building especially, as the exterior material liable to be severely affected by the direct rays.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention is a laminate made by laminating a fluororesin multilayer film and mainly a foam, which has excellent weather resistance, stain resistance, and adhesive durability. The present invention relates to a foamed laminate coated with a fluororesin film, which is used as a building material, a palace, an industrial product, etc.

(Prior Art) Generally, foam products are widely used indoors and outdoors as building materials, industrial products, vehicles, etc. because of their light weight and ease of processing. However, when foamed products are used outdoors, the resin deteriorates due to ultraviolet rays, making it impossible to use them outdoors for long periods as building materials. For this reason, it is necessary to protect the surface, and covering it with a weather-resistant film is being considered. For example, a vinyl heptadide resin film is considered,
This film has insufficient adhesive strength when bonded to foam or metal foil as a weather-resistant film.

(Problems to be Solved by the Invention) An object of the present invention is to provide a fluororesin film-coated foam laminate having excellent weather resistance, stain resistance, and adhesive durability.

In order to solve the above problems, the present inventors have conducted repeated research without being limited to conventionally used materials.The present inventors have developed a multilayer film whose resin components are vinylyrozoy fluoride resin and methacrylic acid ester resin. Alternatively, by laminating a laminate of a multilayer film with metal foil and a resin foam, a foam laminate with excellent weather resistance, stain resistance, and chemical resistance was discovered, and the present invention was achieved.

(Means for Solving the Problems) That is, the present invention has a surface layer made of vinylidene fluoride resin 1
00 to 50 parts by weight and 0 to 5 parts by weight of methacrylic acid ester resin
0 parts by weight of a film and a composite film of a film mainly composed of 50 to 0 parts by weight of a vinylidene fluoride resin and 50 to 100 parts by weight of a methacrylic acid ester resin, and the back layer is made from a resin foam. The present invention features a laminate comprising a laminate and a fluororesin film-covered foam laminate having a metal foil as an intermediate layer between the composite film and the resin foam of the laminate.

Vinylidene heptafluoride resin, which is the main component of the fluororesin film used in the surface layer of the present invention, is a homopolymer of vinylidene fluoride or a copolymer of vinylidene fluoride and a monomer copolymerizable with it. means. Examples of copolymerizable monomers include tetrafluoroethylene, 67fluoropropylene,
Examples include vinyl chloride fluoride and vinyl heptadide.

Next, methacrylic acid ester resin refers to a homopolymer of methyl methacrylate or a copolymer of methyl methacrylate and a monomer copolymerizable with it, such as a blend of polymethyl methacrylate and acrylic rubber. . Copolymerizable monomers include methacrylic esters having 2 to 4 carbon atoms, acrylic esters having 1 to 8 carbon atoms including decyl acrylate, styrene, α-methylstyrene,
7 Acrylonitrile, acrylic acid, and other ethylenically unsaturated monomers.

The film composition of the surface layer of the present invention is such that the film serving as the outermost layer of the laminate contains 100 to 50 parts by weight of vinylidene fluoride resin and 0 to 50 parts by weight of methacrylic acid ester resin, and 50 parts by weight of vinylidene fluoride resin. If the amount is less than 1 part by weight, weather resistance decreases. The inner layer film contains 0 to 50 parts by weight of vinylidene fluoride resin and 1 part by weight of methacrylate ester resin.
If the methacrylic acid ester resin is less than 50, the adhesive strength with other materials decreases. Further, the composite film may be either smooth or double-boss processed.

Next, as the metal foil used in the intermediate layer of the present invention, aluminum, stainless steel, iron, copper, zinc steel plate, etc. are used, and aluminum is particularly preferable. The aluminum foil may be IIB fulminicum, an aluminum alloy, or a composite plate of these and other materials. The thickness of aluminum foil is within the range that can be bent, etc.
It is not something that specifically determines the corner.

Foams used in the back layer of the present invention include thermoplastic resin foams and Frethane foams, such as expanded polystyrene, foamed polyethylene, foamed polypropylene, and rigid and flexible Frethane foams. The foaming ratio is
There is no particular limit, but the thickness is preferably 5 to 70 times, and the thickness of the foam is 200" or less, preferably 1 to 100".
It is n.

In the present invention, there are two methods for adhering the fluororesin film and the foam, the fluororesin film and the metal foil, and the metal foil and the foam, including a method using thermal adhesion and a method using an adhesive.

As the adhesive, an epoxy resin-based adhesive, an acrylic resin-based adhesive, a urethane resin-based adhesive, or the like is used.

In addition, in the fluororesin film used for the surface layer of the present invention, inorganic pigments, ultraviolet absorbers, antioxidants, octopus-dispersed coupling agents, etc. may be used as necessary to improve weather resistance. You can also do it. As the pigment used for coloring the fluororesin film of the present invention, commercially available complex oxide-based inorganic pigments are used, such as TiO2.5b2
03 ・Titanium yellow type of rutile type or pre-prite type crystal whose main component is BaO-NiO・Cr203, zn
o -v・203・Cr203 as the main component, zinc-iron brown, Coo a Al2O3
” Cobalt del-based spinel-type crystals whose main components are Cr2C)3, green systems whose main components are TiO2, Coo, NiO, and ZnO, CuO, Cr2O3, and CuO
a Pe203 ' There are spinel-type black types containing Mn2O3 as a component, violet types consisting of C00 and Mn2O3, etc. In addition to these colored pigments, rutile titanium oxide, zinc white, calcium carbonate, barium sulfate, and other inorganic pigments can be used.

The amount of the colorant added is 0.61 to 50 parts by weight, preferably 10 to 40 parts by weight, based on 100 parts by weight of the entire resin used in the fluororesin film, and the compatibility with the inorganic pigment varies depending on the proportion of the resin used. Therefore, the amount added is not constant.

When the fluororesin film used for the surface layer of the present invention is bonded to other materials using an adhesive, it is preferable to use an ultraviolet absorber in order to prevent deterioration of the light resistance of the adhesive. Any UV absorber may be used as long as it is compatible with the resin used in the film, and a high molecular weight UV absorber is preferred in order to prevent volatilization.

Examples of the absorbent that can be used include benzotriazole-based, oxidelic aracide-based, benzophenone-based, hindered amine-based and many other types of known absorbents. More specifically, 2-(3,5-di(allophagimethylpencyl-2-hydroxyphenyl)benzotriazole, 2-(3゜5-cyt-butyl-2-
hydroxyphenyl)benzotriazole, 2-(3-
t-butyl-5-methyl-2-hydroxyphenyl)-
5-chlorobenzotriazole, 2-(3,5-cy7-phthyl-2-hydroxyphenyl)-5-/lolobenzotriazole, 2-(3,5-di-t-amyl-2-
Hydroxyphenyl)be/citriazole, 2-ethoxy-2ethyl oxide acid bisanilide, 2-ethoxy-5-tert-butyl-2'ethyl oxide acid bisanilide, 2-hydroxy-4-n-oct Oxybenzophenone, bis(1,2,2,6,6-pentymethyl-4-persol)sepacate, bis(1,2゜2.6.6-tetramethyl-4-perzyl)sepacate, dimethyl-2- (4-hydroxy-2゜2.6.6
-tetramethyl-1-piperisol)ethanol, 1-(
2-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy)-2,2,6,6-T-
Examples include nato-2-methylpiperidine.

The amount of the ultraviolet absorber added is 0.1 to 15 parts by weight, based on 100 parts by weight of the entire resin used in the fluororesin film. Since the capacity is low, the deterioration of the aluminum foil is accelerated. Further, even if the amount exceeds 15 parts, the ultraviolet light absorption ability effect remains almost the same and the cost increases.

In the production of the laminate of the present invention, a method of bonding without an adhesive or using an adhesive is usually used in the case of a laminate of a fluororesin film and a foam. In the case of a laminate, the common method is to laminate a fluororesin film onto a metal foil using an adhesive, and then laminate this and a foam using an adhesive, but the lamination order etc. can be changed arbitrarily. You can choose. In addition, when molding the fluororesin film-coated foam laminate of the present invention,
It can be molded using a vacuum or pressure molding machine.

Furthermore, the 7-strand resin film-coated foam laminate of the present invention can be used as it is for building materials, industrial products, vehicles, etc., and can also be used with other base materials by applying an adhesive or pressure-sensitive adhesive to the foam surface. It can also be used in a stacked manner.

(Example) The present invention will be explained in detail below.

Example 1 [Preparation of raw material composition for surface layer upper layer film] Polyvinylidene fluoride trade name (Solef ID10J, manufactured by Nor44 Co., Ltd. 70 parts by weight, Mitsubishi Rayon Co., Ltd.'s methacrylic acid ester resin trade name "Acrypera" MDJ, 30 parts by weight), and a pigment mixture. 2,5 Y 3.0/1.0 toned as
After mixing 25 parts by weight of (brown) pigment, the mixture was kneaded using a twin-screw kneading extruder to form a compound.

[Preparation of raw material composition for surface layer lower layer film] Polyvinylidene fluoride (trade name) manufactured by Tsurubay Co., Ltd. (30 parts by weight of Solef 1010J), 70 parts by weight of methacrylic acid ester resin (trade name) "Acrypet MD" manufactured by Mitsubishi Rayon Co., Ltd., and toned as a pigment mixture 2,5 Y 3.1/1.
After mixing 25 parts by weight of 0 (brown) pigment, the mixture was kneaded using a twin-screw kneading extruder to form a compound.

[Creation of film]

Using the two types of compounds obtained by the above method as raw materials, 4
Extrusion molding was carried out using an apparatus equipped with two 0111φ extruders, a feed block die, a slit 00-4yr, and a coat hanger die with a width of 450 mm to obtain a two-layer film with a thickness of 4 Q Am.

[Creation of laminate]

A polystyrene foam sheet with a thickness of 5 times (expansion ratio 15 times) manufactured by Tsukisui Kaseihin Kogyo Co., Ltd. was coated with 3 times the product name "Hard Rock E!-510-07" manufactured by Denki Kagaku Kogyo (Tan) as an adhesive.
The film was coated to a thickness of 0 μm, the lower layer of the film was placed on the adhesive surface, and the adhesive was pressed and bonded at a pressure of 101 QF/cm'' to obtain a foamed laminate.

The evaluation results are shown in the table.

Example 2 2-Hydroxy-4 as a UV absorber in the lower film
A foamed laminate was obtained by carrying out the same operation as in Example 1 except for using the -n-octoxybenzophenone triple layer.

The evaluation results are shown in the table.

Example 3 [Preparation of raw material composition for surface layer upper layer film] 90 parts by weight of polyvinylidene heptadide manufactured by Tsurubay Co., Ltd. [Soref 1010J], 10 parts by weight of methacrylate ester resin manufactured by Mitsubishi Rayon Co., Ltd. and pigment. 2,5 Y 8.0/2 toned as a mixture
．． After mixing 25 parts by weight of the 0 (cream) pigment, the mixture was kneaded using a twin-screw kneading extruder to form a compound.

[Adjustment of surface layer lower layer film raw material composition] Nor41 Co., Ltd. polyvinylidene fluoride trade name [Sole; l 010J 2
After mixing 0 parts by weight of Mitsubishi Rayon (Tosha methacrylic dispersion resin trade name "Acrypera") MDJ8Q and 3 parts by weight of 2-hydroxy-4-n-octoxybenzophenone as an ultraviolet absorber, the mixture was mixed using a twin-screw extruder. The mixture was kneaded to form a compound.

The following film was prepared in the same manner as in Example 1 to a thickness of 45 mm.
A film having a μm two-layer structure was obtained.

[Creation of laminate]

To Nagazumi, Denki Kagaku Kogyo Co., Ltd. (Ten)Raku, product name "Hard Rock E- 510-07J to a thickness of 3 Q μm,
Lay the lower layer of the film on the adhesive surface and apply a pressure of 10 kl?
/cIn2 was applied and bonded to obtain a foamed product. The evaluation results are shown in the table.

Example 4 [Preparation of raw material composition for surface layer upper layer film] 0 parts by weight of polyvinylidene heptadide manufactured by Nor44 Co., Ltd. "Noref 1010J", 30 parts by weight of methacrylate ester resin manufactured by Mitsubishi Rayon (a) Co., Ltd. After mixing, the mixture was kneaded using a twin-screw kneading extruder to form a compound.

[Preparation of raw material composition for surface layer lower layer film] 30 parts by weight of polyvinylidene fluoride manufactured by Tsurupei Co., Ltd. (trade name: R Solef 1010J), 70 parts by weight of methacrylic acid ester resin (trade name: "Acrypera", manufactured by Mitsubishi Rayon Co., Ltd.) and MDJ as an ultraviolet absorber. After mixing 3 parts by weight of 2-hydroxy-4-n-octoxybenzophenone, the mixture was kneaded using a twin-screw extruder to form a compound.

The following film was prepared in the same manner as in Example 1 to a thickness of 50 mm.
A film having a μm two-layer structure was obtained.

[Creation of laminate]

Made by Denki Kagaku Kogyo Co., Ltd., product name [Hard Rock -510-0] was used as an adhesive on a polypropylene foam sheet with a thickness of 5III1 (foaming ratio: 50 times) made by Okisui Kagaku Kogyo Co., Ltd.
7J was applied to a thickness of 60 μm, the lower layer surface of the film was placed on the adhesive surface, and the adhesive was pressed and bonded at a pressure of 10 Y/I to obtain a foamed laminate. The evaluation results are shown in the table.

Example 5 Sony Chemical's 5C-427 was applied as an adhesive to both sides of a commercially available 100 μm aluminum foil, and the adhesive was heated at 120° C. for 2 minutes to remove the solvent. Adhesive coverage was 7 g/71'' per side.

Next, the film of Example 1 was coated on the surface coated with aluminum adhesive, and the film was placed in an open oven at 140°C and heated for 5 minutes.

After heating, it was quickly taken out, heated to 140°C, and laminated with a laminating roll.

Furthermore, the polystyrene/foam sheet used in Example 1 was adhered to the aluminum foil surface of the fluororesin film/aluminum foil lamination product to obtain a foam laminate. The evaluation results are shown in the table.

Example 6 The same operation as in Example 5 was carried out, except that steel foil was used instead of the aluminum foil in Example 5, and polyurethane foam (expansion ratio: 50 times) manufactured by Miki Kaseihin Kogyo Co., Ltd. was used instead of the polystyrene sheet. A foamed laminate was obtained. The evaluation results are shown in the table.

Comparative Example 1 A foamed laminate was obtained by carrying out the same operations as in Example 1 except for using films made of methacrylic acid ester resin instead of the upper and lower surface layer fluororesin films of Example 1. The evaluation results are shown in the table.

Comparative Example 2 A foamed laminate was obtained in the same manner as in Example 4, except that a film made of a methacrylic acid ester resin was used instead of the upper and lower surface layer fluororesin films of Example 4. The evaluation results are shown in the table.

Table Test Method 1) Weather resistance: Accelerated test using the Ducycle Uniday Meter method The color difference (Δl1ab) and gloss retention rate (GR) after 1000 hours of black panel at 63°C with spraying were measured using a color difference meter (Nippon Denshoku Kogyo Co., Ltd.) Co., Ltd., Colorimeter, Color Difference Meter ND-101D).

2) Contamination Resistance The degree of contamination was determined visually according to 2J Engineering S K-6902. However, acetone is excluded.

No change at all 20 Slight change: Δ 3) Adhesive durability 2 Depan marks were placed on the side of the film bonded to the base material, and after 1000 hours of testing using the due cycle quedemeter method, the marks were removed, and the cellophane tape peeling test showed no peeling. Totally absent: I DO/100 Totally peeled: 0/100 (Effect of the invention) As is clear from the above explanation, the fluororesin film-coated foam laminate obtained by the present invention has excellent stain resistance and It has excellent adhesive durability, has the excellent long-term weather resistance that vinylidene fluoride resin has, and also has the characteristic that the adhesiveness to the base material does not deteriorate over a long period of time. Therefore, it can be effectively used for the interior and exterior of buildings, especially for exterior applications that are severely affected by direct sunlight.

Patent applicant Denki Kagaku Kogyo Co., Ltd.

Claims (1)

[Scope of Claims] 1. A film whose surface layer is mainly composed of 100 to 50 parts by weight of a vinylidene fluoride resin and 0 to 50 parts by weight of a methacrylic acid ester resin, and a vinylidene fluoride resin 50
~0 parts by weight and 50-100 parts of methacrylic acid ester resin
A fluororesin-based film-coated foam laminate comprising a composite film of a film whose main components are: 2. A foamed laminate coated with a fluororesin film, characterized in that an intermediate layer between the surface layer and the back layer according to claim 1 is provided with a metal foil.