JP2574017B2 - Fluororesin-based film-coated foam laminate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a laminate obtained by laminating a fluorine-based resin multilayer film and mainly a foam, and having excellent weather resistance, stain resistance and adhesion durability. In addition, the present invention relates to a fluororesin-based film-coated foam laminate used as a building material, a vehicle, an industrial product, or the like.

(Prior Art) In general, foam products are widely used indoors and outdoors for building materials, industrial products, vehicles, and the like, because of their lightness and ease of processing. However, when foam products are used outdoors,
The resin is deteriorated by ultraviolet rays, and cannot be used outdoors for a long time as a building material. For this reason, it is necessary to protect the surface, and it has been studied to coat the film with a weather-resistant film.For example, a fluorinated vinyl resin film can be considered, but when this film is bonded to a foam or a metal foil as a weather-resistant film. Adhesion is insufficient.

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

In order to solve the above problems, the present inventors have conducted research without being limited to conventionally used materials.As a result, a multilayer film or a multilayer film containing a vinylidene fluoride resin and a methacrylic ester resin as resin components. By laminating the laminate with the metal foil and the resin foam, a foam laminate excellent in weather resistance, stain resistance and chemical resistance was found, and the present invention was reached.

(Means for Solving the Problems) That is, according to the present invention, the surface layer is a vinylidene fluoride resin.
50 to 0 parts by weight of a film and vinylidene fluoride resin containing 100 to 50 parts by weight and 0 to 50 parts by weight of a methacrylate resin, and 50 to 50 parts by weight of a methacrylate resin.
A composite film of a film containing 100 parts by weight as a main component and a laminate in which the back layer is made of a resin foam, and a fluororesin-based film in which a metal foil is provided in an intermediate layer between the composite film and the resin foam of the laminate. It features a coated foam laminate.

The vinylidene fluoride resin which is a main component of the fluorine resin film used in the surface layer of the present invention is a homopolymer of vinylidene fluoride, or a copolymer of a monomer copolymerizable with vinylidene fluoride. Say. Examples of copolymerizable monomers include ethylene tetrafluoride, propylene hexafluoride,
There are trifluorinated ethylene chloride and vinyl fluoride.

Next, the methacrylate resin is a homopolymer of methyl methacrylate or a copolymer of a monomer copolymerizable with methyl methacrylate, such as a blend of polymethyl methacrylate and an acrylic rubber. . Examples of the copolymerizable monomer include methacrylic acid esters having 2 to 4 carbon atoms and 1 to 8 carbon atoms including butyl acrylate.
Acrylate, styrene, α-methylstyrene, acrylonitrile, acrylic acid, and other ethylenically unsaturated monomers.

The film composition of the surface layer of the present invention is such that the film as the outermost layer of the laminate is 100 to 50 parts by weight of a vinylidene fluoride resin and 0 to 50 parts by weight of a methacrylate resin, and the vinylidene fluoride resin is 50 parts by weight. If the amount is less than the weight part, the weather resistance is reduced. The inner layer film is composed of 0 to 50 parts by weight of vinylidene fluoride resin and 100 to 50 parts by weight of methacrylate ester resin. If the amount of the methacrylate ester resin is less than 50, the adhesive strength to other materials is reduced. The composite film may be smooth or embossed.

Next, as the metal foil used in the intermediate layer of the present invention, aluminum, stainless steel, iron, copper, zinc steel plate or the like is used, and aluminum is particularly preferable. The aluminum foil may be pure aluminum, an aluminum alloy, or a composite plate of these and other materials. The thickness of the aluminum foil is not particularly limited as long as it can be bent or the like.

Foams used in the back layer of the present invention include thermoplastic resin foams and urethane foams, such as foamed polystyrene, foamed polyethylene, foamed polypropylene, and hard / soft urethane foam. The expansion ratio is not particularly limited, but is preferably 5 to 70 times, and the thickness of the foam is 200 mm or less, preferably 1 to 100 mm.

In the present invention, the fluororesin film and the foam, the fluororesin film and the metal foil, and the metal foil and the foam may be bonded to each other by a method of thermal bonding or a method of using an adhesive. As the adhesive, an epoxy resin-based, acrylic resin-based, urethane resin-based adhesive, or the like is used.

Further, the fluororesin film used for the surface layer of the present invention may use an inorganic pigment, an ultraviolet absorber, an antioxidant, a pigment dispersant, a coupling agent, and the like as needed for improving weather resistance. it can. The pigments used for coloring fluorine resin film of the present invention, the composite oxide inorganic pigments are used which are commercially available, for _{example, TiO 2 · Sb 2 O 3} · B
aO ・ NiO ・ Cr ₂ O ₃ as a main component, rutile-type or briderite type crystal of titanium yellow type, ZnO ・ Fe ₂ O ₃・ Cr ₂ O ₃ as a main component of spinel type crystal zinc-iron type brown, CoO ・ A
l ₂ O ₃ · Cr ₂ O ₃ as a main component, spinel type crystal cobalt blue type, TiO ₂ · CoO · NiO · ZnO as a main component, CuO · Cr ₂ O ₃ or CuO · Fe ₂ O _There are a spinel-type black system containing ₃ · Mn ₂ O ₃ as a component, a biolet system composed of CoO and Mn ₂ O _3, and the like. Rutile-type titanium oxide, zinc white, calcium carbonate, barium sulfate and other inorganic pigments can be used together with these colored pigments.

The addition amount of the coloring agent is 0.1 to 50 parts by weight, preferably 100 parts by weight of the entire resin used for the fluororesin-based film, preferably
The content is 10 to 40 parts by weight, and the compatibility with the inorganic pigment varies depending on the proportion of the resin used.

The fluororesin film used for the surface layer of the present invention is:
When an adhesive is used for bonding with another material, it is preferable to use an ultraviolet absorber in order to prevent deterioration of the tip resistance of the adhesive, and the ultraviolet absorber to be used is compatible with the resin used for the film. It is only necessary to use a soluble one, and in order to prevent volatilization, a high molecular weight ultraviolet absorber is preferable. Examples of the absorbent include benzotriazoles,
Oxalixacids, benzophenones, hindered amines, and many other known types can be used. More specifically, 2- [3,5-di- (allopha-
Dimethylbenzyl-2-hydroxyphenyl] benzotriazole, 2- (3,5-di-tert-butyl-2-hydroxyphenyl) benzotriazole, 2- (3-tert-butyl-5-methyl-2-hydroxy) Phenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-amyl-2) -Hydroxyphenyl) benzotriazole, 2-ethoxy-2'-ethyloxascidbisanilide, 2-ethoxy-
5-tert-butyl-2'-ethyloxacidobisanilide, 2-hydroxy-4-n-octoxybenzophenone, bis (1,2,2,6,6-pentimethyl-4-piperdyl) sebacate, Bis (1,2,2,6,6-tetramethyl-4-piperdyl) sebacate, dimethyl-2- (4-
Hydroxy-2,2,6,6-tetramethyl-1-piperidyl) ethanol, 1- [2-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy]-
2,2,6,6-T-tetramethylpiperidine and the like.

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 for the fluororesin-based film.
Since the ultraviolet ray absorbing ability is small, the deterioration of the aluminum foil is promoted. Even if the amount exceeds 15 parts by weight, the effect of the ultraviolet ray absorbing ability hardly changes and the cost increases.

In the production of the laminate of the present invention, a method of bonding with or without an adhesive is generally used in the case of a laminate of a fluororesin film and a foam, and a fluororesin film,
In the case of a laminate of a metal foil and a foam, a method of laminating a fluorine-based resin film on the metal foil using an adhesive and laminating this and the foam using an adhesive is generally used. The stacking order and the like can be arbitrarily selected. When the fluororesin film-coated foam laminate of the present invention is molded, it can be molded by a vacuum or air pressure molding machine.

Further, the fluororesin film-coated foam laminate of the present invention can be used as it is for building materials, industrial products, vehicles and the like, and can be laminated with another base material by applying an adhesive or pressure-sensitive adhesive to the foam surface. It can also be used.

(Examples) Hereinafter, the present invention will be described in detail.

Example 1 [Preparation of Raw Material Composition for Upper Layer Film on Surface Layer] Solef 10 (trade name of polyvinylidene fluoride polyvinylidene fluoride)
10 "70 parts by weight, Mitsubishi Rayon Co., Ltd. methacrylate resin trade name" Acrypet MD "30 parts by weight and 2.5Y3.0 / 1.0 (brown) pigment 25 toned as a pigment mixture
After mixing the parts by weight, the mixture is kneaded with a twin-screw kneading extruder,
Compound.

(Adjustment of surface layer lower layer film raw material composition)

Solvay polyvinylidene fluoride
10 ”30 parts by weight, 70 parts by weight of“ Acrypet MD ”, a methacrylic acid ester-based resin trade name of Mitsubishi Rayon Co., Ltd., and 2.5Y3.1 / 1.0 (brown) pigment 25 toned as a pigment mixture
After mixing the parts by weight, the mixture is kneaded with a twin-screw kneading extruder,
Compound.

[Creating a film]

Using the two types of compounds obtained by the above method as raw materials,
Two 40mmφ extruders, feed block dies, slits 0.
Extrusion was performed using an apparatus equipped with a coat hanger die having a width of 4 mm and a width of 450 mm to obtain a two-layer film having a thickness of 40 μm.

(Creation of laminate)

Adhesive to 5mm thick polystyrene foam sheet (expansion ratio 15 times) manufactured by Sekisui Plastics Co., Ltd.
The product name “Hard Lock E-510-07” is applied to a thickness of 30 μm, and the lower surface of the film is laminated on the adhesive surface,
It was pressurized and bonded at a pressure of 10 kg / cm ² to obtain a foamed laminate.

 The evaluation results are shown in the table.

Example 2 2-hydroxy- as an ultraviolet absorber for the lower film
A foamed laminate was obtained in the same manner as in Example 1, except that 3 parts by weight of 4-n-octoxybenzophenone was used.
The evaluation results are shown in the table.

Example 3 [Preparation of Raw Material Composition for Upper Layer Film on Surface Layer] Solef 10 (vinylidene fluoride trade name, Solef 10)
10 "90 parts by weight, 10 parts by weight of methacrylic acid ester-based resin" Acrypet MD "manufactured by Mitsubishi Rayon Co., Ltd. and 2.5Y8.0 / 2.0 (cream) toned as a pigment mixture
After mixing 25 parts by weight of the pigment, the mixture was kneaded with a twin-screw kneading extruder to obtain a compound.

(Adjustment of surface layer lower layer film raw material composition)

Solvay polyvinylidene fluoride
10 ", 20 parts by weight, 80 parts by weight of" Acrypet MD ", a methacrylic acid ester-based resin trade name of Mitsubishi Rayon Co., Ltd., and 3 parts by weight of 2-hydroxy-4-n-octoxybenzophenone as an ultraviolet absorber were mixed. Thereafter, the mixture was kneaded with a twin screw extruder to obtain a compound.

Thereafter, the film was prepared in the same manner as in Example 1 and had a thickness of 45 mm.
A film having a μm two-layer structure was obtained.

(Creation of laminate)

Sekisui Chemical Co., Ltd. 5mm-thick high-expansion polyethylene foam sheet trade name "Softlon" (expansion ratio 30 times) "Adhesive" manufactured by Denki Kagaku Kogyo Co., Ltd., trade name "Hard Rock E-510-07" The film was applied to a thickness of 30 μm, the lower surface of the film was superposed on the adhesive surface, and the film was pressed at a pressure of 10 kg / cm ² and adhered to obtain a foamed laminate. The evaluation results are shown in the table.

Example 4 [Preparation of Raw Material Composition for Upper Layer Film on Surface Layer] Solef 10 (vinylidene fluoride trade name, Solef 10)
After mixing 70 parts by weight of "10" and 30 parts by weight of "Acrypet MD" (trade name of methacrylate resin based on Mitsubishi Rayon Co., Ltd.), the mixture was kneaded with a twin-screw kneading extruder to obtain a compound.

(Adjustment of surface layer lower layer film raw material composition)

Solvay polyvinylidene fluoride
10 ", 30 parts by weight, 70 parts by weight of a methacrylic acid ester-based resin" Acrypet MD "manufactured by Mitsubishi Rayon Co., Ltd., and 3 parts by weight of 2-hydroxy-4-n-octoxybenzophenone as an ultraviolet absorbent were mixed. Thereafter, the mixture was kneaded with a twin screw extruder to obtain a compound.

Thereafter, the film was prepared in the same manner as in Example 1, and the thickness was 50
A film having a μm two-layer structure was obtained.

(Creation of laminate)

Adhesive on Sekisui Chemical's 5mm thick polypropylene foam sheet (expansion ratio: 50x) as an adhesive
Co., Ltd., product name “Hard Lock E-510-07” is applied to a thickness of 30 μm, the lower surface of the film is overlaid on the adhesive surface, and pressurized and bonded at a pressure of 10 kg / cm ² to obtain a foam laminate. Was. The evaluation results are shown in the table.

Example 5 Sony Chemical SC-427 was applied as an adhesive to both surfaces of a commercially available 100 μm aluminum foil and heated at 120 ° C. for 2 minutes to remove the solvent. The application amount of the adhesive was 7 g / m ² on one side.

Next, the film of Example 1 was coated on the surface coated with the aluminum adhesive, heated in a 140 ° C. oven for 5 minutes, quickly taken out, and laminated by a laminating roll heated to 140 ° C.

Further, 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 performed except that a copper foil was used instead of the aluminum foil of Example 5, and a polyurethane foam (expansion ratio: 50 times) manufactured by Sekisui Chemical Co., Ltd. was used instead of the polystyrene sheet. A foam laminate was obtained. The evaluation results are shown in the table.

Comparative Example 1 A foamed laminate was obtained in the same manner as in Example 1, except that a film made of a methacrylic acid ester resin was used instead of the surface layer upper and lower fluororesin films of Example 1. The evaluation results are shown in the table.

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

Test method 1) Weather resistance: Accelerated test by Du-cycle weather meter method Black panel 63 ° C, with spray Color difference (△ Eab) and gloss retention (GR) after 1000 hours
The color difference meter (Nippon Denshoku Industries Co., Ltd., side color, color difference meter ND-101)
Measured in D).

2) Stain resistance: Performed according to JIS K-6902, and the degree of contamination was visually determined. However, acetone is excluded.

No change at all: ○ Minor change: △ 3) Adhesion durability: Inserting a groove on the film side adhered to the base material and testing with the Du-cycle weather meter method After 1000 hours, the peeling test on the sticker and cellophane tape None: 100/100 Completely peeled: 0/100 (Effect of the Invention) As is clear from the above description, the fluororesin-based film-coated foamed laminate obtained according to the present invention is resistant to contamination. It has excellent properties and adhesion durability, and has the excellent long-term weather resistance of the vinylidene fluoride resin, and also has the feature that the adhesion to the substrate does not decrease for a long time. Therefore, it can be effectively used for interior and exterior of buildings, especially exterior applications where the influence of direct sunlight is severe.

Claims (2)

(57) [Claims] (1) The surface layer has a vinylidene fluoride resin of 100 to 50.
Film and vinylidene fluoride resin 50 parts by weight as a main component and 0 to 50 parts by weight of a methacrylate resin
A composite film of a film mainly containing 0 to 0 parts by weight and 50 to 100 parts by weight of a methacrylic acid ester resin, and a fluororesin film-coated foam laminate having a back layer made of a resin foam. 2. A fluorine resin-based film-coated foam laminate comprising a metal foil on an intermediate layer between the front layer and the back layer according to claim 1.