JPH0230528A - Fluororesin multilayer film - Google Patents

Abstract

PURPOSE:To enhance fastness, such as weatherability, resistances to stain, chemicals, and adhesion to various types of substrates by using a film of a resin composition mainly composed of a vinylidene fluoride resin and a methacrylate ester resin. CONSTITUTION:The title layer is formed by laminating a surface layer film of a resin composition mainly composed of 100-50 pts.wt. of vinylidene fluoride resin and 0-50 pts.wt. of methacrylate ester resin, an intermediate layer film of a resin composition mainly composed of 50-0 pts.wt. of vinylidene fluoride resin and 50-100 pts.wt. of methacrylate ester resin, and an adhesive layer in this order. As the adhesive for use, a thermoplastic adhesive or a rubber adhesive is used. It is preferable that an ultraviolet absorber is added to the layers including the adhesive layer, and particularly the addition to the surface layer or the intermediate layer is desired. The addition of the ultraviolet absorber by the amount of 0.1-15 pts.wt. per 100 pts.wt. of the resin composition can prevent the deteriorations of the adhesive itself as well as a substrate to be coated and protected.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention is applicable to plastics, rubber, metal plates, glass, wood plates,
It relates to a surface protection film that is permanently or semi-permanently attached to the surface of slate or other base materials for the purpose of surface protection, decoration, etc., and it is characterized by its fastness such as weather resistance, stain resistance, and resistance to goods, as well as various base materials. The present invention relates to a fluororesin-based multilayer film that has excellent adhesion to materials, and particularly excellent adhesive durability after being laminated to a base material.

(Prior art) Plastic plates, metal plates, and other various base materials conventionally used for the interior and exterior of buildings are coated with paint or durable film (printed) for the purpose of improving durability or decoration. (including those that have been processed) are fully laminated and used.

Substrates to be surface treated include polyvinyl chloride, polycarbonate, polymethyl methacrylate, acrylonitrile-butadiene-styrene co-M combination, plastic plastic substrates such as FRP, various rubber substrates, and metal substrates such as aluminum-stainless steel-zinc steel sheets. , Kono and other main boards, glass, slate, etc. are used for wallpaper and the interior of elevators and other vehicles, as well as roofing materials, wall materials, rain gutters, decking materials, garages, arcades, sunrooms, and tents. Our products cover a wide range of products, including land, agricultural materials, signboards, signs, soundproof walls, labels, window glass, furniture, and home appliances.

By the way, as a durable film, adhesive-coated fluororesin films have traditionally been used by laminating them on the various base materials mentioned above, but although this film has excellent weather resistance, it has poor adhesion strength with adhesives. Since the adhesive is weak and has excellent light transmittance, the adhesive itself may deteriorate, and the adhesive strength with the substrate to be protected may decrease, causing peeling.

(Problems to be Solved by the Invention) The present invention solves these drawbacks, and by using a film of a resin composition whose main components are vinylidene fluoride resin and methacrylic acid ester resin, weather resistance and We have completed the completion of a durable fluororesin multilayer film with excellent stain resistance, chemical resistance, etc., and excellent adhesion to various substrates.

(Means for solving the problem) That is, the present invention provides vinylidene fluoride resin 100 to 5
a surface layer film consisting of a resin composition whose main components are 0 parts by weight and 0 to 50 parts by weight of a methacrylic acid ester resin;
All features include an intermediate layer film made of a resin composition whose main components are 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 an adhesive layer laminated in this order. It is a fluororesin multilayer film.

Vinylidene fluoride resin (hereinafter referred to as PVD) used in the present invention
F) refers to a homopolymer of vinylidene fluoride or a copolymer of vinylidene fluoride and a copolymerizable monomer. Examples of copolymerizable monomers include tetrafluoroethylene, hexafluoropropylene, trifluorochloroethylene,
Examples include vinyl fluoride.

Next, methacrylic acid ester resin (hereinafter referred to as P1v1MA) is a homopolymer of methyl methacrylate or a copolymer of a monomer copolymerizable with methyl methacrylate,
For example, it refers to 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 such as butyl acrylate, styrene, α-methylstyrene, acrylonitrile, acrylic acid, and others. ethylenically unsaturated monomers, etc.

pvD as the main component of the resin composition that becomes the surface layer of the present invention.
0 to 50 parts by weight of Flo, 3 to 50 parts by weight of PMMA, preferably 90 to 60 parts of PVDF, PMMA
If the amount of PVDF is less than 50 parts by weight, the weather resistance will be poor, which is not preferable. The main component of the resin composition forming the intermediate layer is PMMA 100 to 50ffi.
Dobe, PVDF O~50 Parts by weight Te #ri, PVDF
If the amount exceeds 50 parts by weight, the adhesion between the surface layer and the adhesive will be poor, which is not preferable.

Next, as the adhesive used for the adhesive layer of the present invention, (A)
A thermoplastic adhesive and (B) a rubber adhesive can be used.

(A) Thermoplastic adhesives include vinyl adhesives and adhesives containing polyamide, polyester, polyurethane, etc. These adhesives are made of non-crosslinked polymers, so they easily become a solution. Moreover, since it becomes molten by heating, it can be applied to the fluororesin film in the form of a solution, emulsion, or melt. Examples of resins used include polyvinyl acetate, methacrylic acid ester resin, vinyl chloride/vinyl acetate copolymer, polyvinylidene chloride, polyvinyl butyral, polyvinyl chloride, thermoplastic polyester, polycarbonate, polyacrylonitrile, polyamide, and ethylene acetic acid. Examples include vinyl copolymers, ABS resins, and polystyrene.

(B) Comb adhesives include polychloroprene, nitrile rubber, styrene-butadiene rubber, natural rubber, and the like.

When the above-mentioned adhesives (phantom and (B)) are used as a solution adhesive, the solvent may be any solvent as long as it is soluble in (A) and (B). For example, immediately after extrusion molding of a fluororesin film, the heated melts of (A) and (B, 1) are applied directly using a doctor knife, or after forming into a film, a roll coater method, a plush coating method, etc. Coater method, spray coater method, etc. can be used.

It is preferable to add an ultraviolet absorber to the fluorocarbon resin multilayer film of the present invention, including the adhesive layer, and particularly to the surface layer or the intermediate layer.

The amount of the ultraviolet absorber to be added is 1 to 15 parts by weight based on 100 parts by weight of the resin composition, so as to prevent deterioration of the adhesive itself and the substrate to be coated and protected. The UV absorber may be any UV absorber as long as it is compatible with the resin used, and in order to prevent volatilization, a high molecular weight UV absorber is preferred. Examples of the absorbent include benzotriazole type, oxidelic aracide type, benzophenone type,
Hindered amines and many other known types can be used.

Furthermore, a coloring agent, a dispersing agent, a coupling agent, etc. can be used in the fluororesin film of the present invention.

The coloring agent used for coloring the multilayer film is preferably an inorganic pigment type from the viewpoint of weather resistance, and for example, a complex oxide type inorganic pigment is preferable. The main complex oxide inorganic pigments include TiO
2-5b203 ・Titanium yellow type of rutile type or briplite type crystals mainly composed of BaO-NiO・Cr2O3k, zinc-iron type brown type of spinel type crystals mainly composed of ZnO-Fe2O3-Cr2O3, Coo -Al
2O3・0r203k Cobalt blue system with spinel type crystal as main component, TiO2・Coo・NiO-ZnO
Green type mainly composed of CuO, Cr2O3 and Cu
Spinel type black type with OHFe2O3HMn2O3f component, Coo -? There are violet types made of 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 method for producing the multilayer film of the present invention includes, for example, co-extruding films for the surface layer and the intermediate layer using two extruders to form a laminated film, and immediately after extrusion, on the same line,
There is a method in which the solution adhesive or molten adhesive is completely applied, or a method in which the extruded laminated film is completely wound up and the solution adhesive or molten adhesive is completely applied while being unwound by the required amount.

(Example) The present invention will be explained in detail below with reference to Examples.

Example 1 As a compound for the surface layer film, polyvinylidene fluoride trade name "SOLEF 1010J8" manufactured by Trubey Co., Ltd.
0 parts by weight, 20 parts by weight of a methacrylic acid ester resin manufactured by Mitsubishi Rayon Co., Ltd. under the trade name "Acrypera" MDj. After mixing, the mixture was kneaded using a twin-screw kneader to form a compound.

In addition, as a compound for the intermediate layer film, 1 part by weight of Solef 1010.20, 83 parts by weight of Acrivet MI) and 6 parts by weight of 2-hydroxy-4-n-octoxybenzophenone as an ultraviolet absorber were mixed, and then kneaded with 2111. The mixture was mixed in an extruder to form a compound. Next, two types of compounds were used as raw materials and extrusion molded using two 40 mm diameter extruders, a feed block die, and a coat hanger die with a slit width of 0.4 and a shoulder width of 450 mm. A laminated film was obtained.

Manufactured by Denki Kagaku Kogyo ■ as an adhesive layer on the resulting film,
An adhesive prepared by dissolving 1 kg of styrene resin (Denka Styrol GPJ) in 9 kg of toluene was applied using a roll coater.The applied laminated film was dried at 120°C for 5 minutes to obtain a 6-layer film coated with an 8 μm adhesive layer. The measurement results of physical properties are shown in the table.

Example 2 A laminated film was obtained in the same manner as in Example 1, except that the compound for the surface layer film was the same as in Example 1, and the compound for the intermediate layer film was Acrivet MD alone and an ultraviolet absorber. Ta. Next, as an adhesive layer, a PVC/Vinyl acetate copolymer made by Denki Kagaku Kogyo ■, product name "
Denkabini Luna 1ooo” ikg total ethyl acetate 9kg
The procedure was carried out in the same manner as in Example 1 except that the solution was dissolved in 6
A layered film was obtained.

Example 6 Chloroprene rubber manufactured by Denki Kagaku Kogyo ■, trade name [Denka Chloroprene A-70Ji] was used as the adhesive layer.
The same operation as in Example 1 was performed to obtain a 6-layer film.

Example 4 Solef 10 was used as a compound for surface layer film.
10 65 parts by weight, Acryvet M D 35Xi parts and 2,5 Y which had been toned as a pigment mixture 8.
0/2.0 (Cream) A laminated film was obtained by carrying out all the operations similar to Example 1, except that a compound consisting of 10 parts by weight of Group D was used. Next, as an adhesive layer, a vinyl chloride resin manufactured by Denki Kagaku Kogyo ■, product name "Denka Vinyl 88" was used.
Example 1 except that the composition consisting of -i 10J I 00 parts by weight, DOP 53 parts by weight, and a stabilizer was mixed, heated and melted, and coated on the laminated film with a roll coater.
A 6-layer film was obtained in the same manner as above.

Example 5 As the adhesive layer, AB8 resin manufactured by Denki Kagaku Kogyo ■, trade name r
EXAMPLE 4 A complete 6-layer film was obtained by carrying out the same operation as in Example 4, except that a solution prepared by dissolving luene in 9 to 9 was used.

Example 6 A three-layer film was obtained in the same manner as in Example 4, except that a polyester adhesive manufactured by Denki Kagaku Kogyo ■ under the trade name "DENKANO-DROCK LC Mouth 90" was used as the adhesive layer.

Example 7 Using the laminated film obtained in Example 1, the adhesive layer was heated and melted at 150°C using styrene-butadiene block copolymer trade name 1Denka STR, Jk manufactured by Denki Kagaku Kogyo ■. A laminated film was coated with a roll coater to obtain a 6-no-film film.

Comparative Example 1 A 6-layer film was obtained by carrying out the same operations as in Example 1, except that the composition for the surface layer film was used in the combination of Solef 1010 25-layer part Acryvet MD75-layer lid part.

Comparative Example 2 A laminated film consisting of two layers, the surface layer and the intermediate layer of Example 1, was obtained.

Test method 1) Film thickness: %QQQ Measured using a peacock thickness gauge with n scale.

In addition, in the case of a two-layer configuration, the upper layer The thickness of the lower layer depends on the extrusion of each extruder. Calculated from the quantitative ratio.

2) Stain resistance: The degree of contamination was determined visually according to J.E.S.K-6902. However, excluding acetone grapes.

No change at all: ○ Slight change: △ 6) Chemical resistance = Dropped onto the top layer of the film at room temperature (23℃)
The appearance after 24 hours was visually judged.

Chemicals used = 10% HCI, 10% H2SO4, 10% CaC12, 10ThiaOH No change at all: ○ Minor change: △ 4) Weather resistance: Accelerated test using due cycle weather meter method Black panel 63℃, After 1000 hours of spraying, comparison was made with a blank sample, and the presence or absence of discoloration of the base material was determined visually.

5) Adhesive durability: After 100 hours of testing using the due cycle wetner meter method with cross-cuts placed on the side of the film adhered to the base material, cross-cuts and Cellotape peeling test: Those with no peeling at all: Those with all peeling: O/1o.

6) Adhesion to base material: Full use of roll laminate, warm summer 1
Thermal bonding was carried out at 40-170"C.

(Effects of the Invention As is clear from the above description, the multilayer film of the present invention has a laminate that has excellent stain resistance and chemical resistance, and also has the excellent long-term weather resistance of vinylidene fluoride resin. In addition, it has the characteristic that its adhesion 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)

[Claims] A surface layer film consisting of a resin composition whose main components are 100 to 50 parts by weight of vinylidene fluoride resin and 0 to 50 parts by weight of methacrylic acid ester resin, 50 to 0 parts by weight of vinylidene fluoride resin and methacrylic acid ester Resin 50
100 parts by weight of a resin composition as a main component, and an adhesive layer are laminated in this order.