JPH01262133A - Fluoroplastic weather-resistant film - Google Patents

Abstract

PURPOSE:To prevent the ultraviolet degradation of a resin film existing in a lower layer by adding an ultraviolet absorber to the rear layer or intermediate layer of a multilayer weather-resistant film using a vinylidene fluoride resin and a methacrylic acid ester resin as resin components. CONSTITUTION:PVDF and PMMA are employed as the main component of a composition A as a surface layer, and each content of PVDE and PMMA is brought to 95-50pts.wt. and 5-50pts.wt. respectively. PVDF, PMMA and an ultraviolet absorber are used as the principal ingredients of a composition B as the surface layer and an intermediate layer, and the content of PMMA is brought to 95-5pts.wt. and PVDF to 5-95pts.wt. respectively. The content of the ultraviolet absorber is brought to 0.1-15pts.wt. based on the 100pts.wt. total quantity of PMMA and PVDF. A range of 10-100mum is preferable as the thickness of a weather-resistant film, and it is desirable that a film manufactured from the composition B occupies 20% or more in order to display performance as a protective film layer at the rate of the wall thickness of each film.

Description

[Detailed Description of the Invention] (Industrial Application Field) The present invention is applicable to Rusnak, Zam, metal plate, glass, wooden board,
This product relates to a surface preservation film that is permanently or semi-permanently attached to the surface of slate or other base materials for the purpose of surface preservation, decoration, etc., and is characterized by its fastness such as weather resistance, stain resistance, and chemical resistance. and 81 each relates to a fluororesin-based weather-resistant film that has excellent adhesion to the base material, and particularly excellent contact and collapse durability after lamination 7'c to the base material.

(Prior art) Plastic plates, metal plates, and other base materials conventionally used for the interior and exterior of buildings are coated on their surfaces for the purpose of improving durability and decoration. Films (including those that have been processed such as printing) are laminated and used for convenience.

Substrates to be surface treated include polyvinyl chloride, polycarbonate, polymethyl methacrylate, acrylonitrile-butadiene-styrene copolymer, plastic plastic substrates such as FRP, rubber-planted substrates, metal substrates such as aluminum-stainless steel-zinc steel plates, etc. Wood, glass, slate, etc. are used for wallpaper, interiors of elevator cars, etc., as well as roofing materials, wall materials, rain gutters, roofing materials, garages, arcades, etc. Sunrooms, tent areas, agricultural materials, signboards,
It covers a wide range of products including signs, soundproof walls, labels, window glass, furniture, and home appliances.

By the way, when using a durable film laminated to various base materials, the durability of the laminate is affected by the fastness of the durable film itself. In many cases, problems occur at the adhesive interface with the material, such as peeling, lifting, and blistering.

Durable films and various substrates are bonded together using adhesives or heat processing, but as mentioned above, light exposure is one of the major causes of problems such as peeling, lifting, and blistering at the adhesive interface. can be given. Whether using various plant adhesives or bonding by heat processing, organic substances such as polymeric materials are involved at least on one side of the bonding interface, especially in applications such as building exteriors. When exposed to sunlight, the photon energy of ultraviolet rays on the short wavelength side is also greater than the molecular bond energy of the organic material, which causes deterioration of the organic material, and the durability of the adhesive cannot be obtained. result.

Therefore, one possible way to prevent the deterioration of organic matter located at the adhesive interface is to provide the durable film itself with the ability to absorb ultraviolet rays, but if the durable film is thin, the physical Currently, it is technically difficult to manufacture films with excellent performance balance such as 1ldf, and the current situation is that they are used in thick films.
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[Problem to be solved by the invention]

An object of the present invention is to provide a durable surface purulent retention film that is excellent in fastness such as weather resistance, stain resistance, and chemical resistance, and in adhesion to each of the 41 substrates.

Another object of the present invention is to provide a surface protective film that has excellent adhesive durability after lamination with each i-substrate.

In order to solve the above problems, the present inventors have conducted research without being limited to conventionally used materials and films, and found that By adding an ultraviolet absorber to the back layer or intermediate layer of the multilayer weather-resistant film as a component, volatilization of the ultraviolet absorber can be prevented. The present inventors have discovered a multilayer film with excellent weather resistance that can prevent ultraviolet ray deterioration of resin films existing in the industry, and have completed the present invention.

(Determined Means for Solving the Problems) That is, the present invention provides a composition (Al't - As a surface layer, methacrylic acid ester based tree 195~5 weight louse vinylidene fluoride based tree @5~95
A fluororesin-based weather-resistant film having a back layer consisting of a composition fBlk containing 0.1 to 15 parts by weight of an ultraviolet absorber as a main component.

2. Composition mainly composed of 95 to 50 parts by weight of vinylidene fluoride resin and 5 to 50 parts by weight of methacrylic ester resin<gt--surface layer and back layer, 95 to 5 parts by weight of methacrylic ester resin , a composition containing 5 to 95 parts by weight of a vinyl heptadide resin and 0.1 to 15 parts by weight of an ultraviolet absorber as main components (B) A fluororesin-based weather resistant material having a t-intermediate layer. It's a film.

The t-nylidene fluoride resin (hereinafter referred to as PVDF) used in the compositions (A) and (B) of the present invention is a homopolymer of nylidene fluoride or a copolymer with vinylidene fluoride. Refers to copolymers with possible monomers. Examples of copolymerizable monomers include tetrafluoroethylene, hexafluoropropylene, hexafluoroethylene vinyl fluoride, and the like.

Next, methacrylic acid ester resin (hereinafter referred to as PMMA) is a homopolymer of methyl methacrylate or a copolymer of a monomer copolymerizable with methyl methacrylate, such as a polymer of polymethyl methacrylate and acrylic rubber. Refers to blends, etc. The copolymerizable monomer has 2 carbon atoms.
-4 methacrylic esters, acrylic esters having 1 to 8 carbon atoms including butyl acrylate, styrene, α-methylstyrene, acrylonitrile, acrylic acid, and other ethylenically unsaturated monomers.

As the ultraviolet absorber used in the composition (B) of the present invention,
The composition (as long as it is compatible with the resin used for the odor), and a high molecular weight ultraviolet absorber is preferable to prevent volatilization. Examples of the absorbent include Medium derrick acid type, benzophenone type, hindered amine type and many other types of known types can be conveniently used.

More specifically, 2-[6,5-cy(allophagimethylpenzyl-2-hydrocyphenylcopenzotriazole), 2-C5,5-di-t-butyl-2-hydroxyphenyl)benzotriazole , 2-1-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-C5,5-not-butyl-2-and-diphenyl)-5-chlorobenzotriazole , 2-C6,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, C2 in 2-eth
-Ethyl-ethylated bisanilide, 2-ethoxy-5-tert-butyl-2ethylated bisanilide, 2-hydrogine-4-n-octoxypenzophenol, bis(1,2, 2,6,6-benchimethyl-4-piperidyl) sebacate, bis(1,2,2,6
, 6-tetramethyl-4-piperidyl) sebacate, dimethyl-2-(4-hydroxy-2,2,6°6-tetramethyl-1-peridyl)ethanol, 1-C2-5
-C6,5-C-detyl-4- and di-diphenyl)propionyloxy)-2゜2.6.6-T-tetramethylpiperidine and the like.

The composition that becomes the surface layer and back layer of the present invention (PVDF and PMMA are used as the main components of Al, and the content of each is 95-50 parts by weight of pvnE and 5-50 parts by weight of PMMA.
Parts by weight. If the PVDF content exceeds 95 parts by weight, the adhesion to other layers will decrease, which is not preferable. If it is less than 50 parts by weight, the weather resistance will be lowered and the effect as a scratch-preserving film layer will be lowered, which is not preferable.

Next, PvDF, PMMA and an ultraviolet absorber are used as the main components of the composition (B) which becomes the back layer and intermediate layer of the present invention, and PMMA is 95 to 5 parts by weight, preferably 9 parts by weight.
5 to 50 parts by weight, and 5 to 95 parts by weight of PVDF, preferably 5 to 50 parts by weight. pm content PMMA
and ffDF 0.1 to 100 parts by weight of total amount
15 parts by weight2. Preferably it is rzo, s~5 parts by weight.

If the amount added is less than 0.1, the amount of ultraviolet absorption is small, so the performance as a peritoneal membrane layer is insufficient.Even if it exceeds 15 parts by weight, the effect remains the same and the cost increases.

The composition (N) and composition (B) of the present invention can also contain antioxidants, pigments, dispersants, coupling agents, etc.

The weather-resistant film of the present invention has at least two layers, a surface layer and an 1S surface layer, and is a multilayer film in which a composition containing an ultraviolet absorber (a) and a composition not containing an ultraviolet absorber (Al) are alternately provided. The weather-resistant film of the present invention has a total thickness of 150 μm or less, preferably 10 to 10 μm.
It is in the range of 0 μm. Furthermore, in order to maximize the performance as a protective film layer, the proportion of the thickness of each film should be determined by the film made from Composition (B) 1 containing an ultraviolet absorber accounting for 20% or more. desirable.

Furthermore, it goes without saying that the weather-resistant film of the present invention can be conveniently used for various purposes after printing on the surface layer. Nine, general adhesives such as Evo resin, acrylic resin, and urethane resin can be used to bond the weather-resistant film and various base materials in the present invention, and natural rubber, acrylic resin, etc. The pressure-sensitive adhesive used can be applied in advance to the adhesive surface of the weather-resistant film for convenient use, and depending on the type of substrate, it can also be bonded only by heat processing.

Next, the fluororesin-based weather-resistant film of the present invention can be extruded using a coextrusion molding method that usually combines a plurality of layers together.

The T-die method and co-extrusion molding method uses multiple extrusion molding machines to bond resin in a molten state to form multiple layers. There are two methods: one method is to make them contact each other and adhere to each other, and the other method is to spread them out into a foot shape after all the resins are adhered. A multilayer film can also be formed by a method called the inflation stain/forming method, which uses a round die f:2.

A method of mixing additives such as inorganic pigments and ultraviolet absorbers into a layer of PVDF and PMMA that serves as the bottom resin layer is as follows:
Alternatively, the resin and additives may be mixed in advance and then melt-kneaded using a commonly used single-screw extruder.
Generally, the additives are not sufficiently dispersed in the resin, and a high kneading type twin-screw extruder can provide raw materials with excellent surface conditions.

As a method to further improve dispersibility, PVDF and/or
Alternatively, it is preferable to use a part or all of PMMA as a powdered raw material.

(Example) The present invention will be explained in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

Example 1 [Preparation of surface layer film raw material composition (A)] Polyvinylidene fluoride trade name (SOLEF 1010j, Fu 0 parts by weight, manufactured by Tsurubay Co., Ltd., methacrylic acid ester resin trade name [Acrypera) MDj 15, manufactured by Mitsubishi Rayon Co., Ltd.] Parts by weight, Asahi Kasei Industries, Ltd. methacrylate ester resin product name
Delpet 5R-6500415 parts by weight was kneaded in a twin-screw kneading extruder after mixing with Mikikungure to obtain Co/Paun P.

[Back layer film raw material composition (adjustment of Bl) Polynylidene fluoride manufactured by Tsurupei Co., Ltd. Product name [Solef 1010J30]
Parts by weight, Mitsubishi Rayon Co., Ltd.'s methacrylic acid ester resin product name "Acribella" MDJ 55 parts by weight, Asahi Kasei Corporation's methacrylic acid ester resin product name (Delpera) SR-6500J 35 parts by weight, and as an ultraviolet absorber After mixing 6 M parts of 2-hydroxy-4-n-octoxybenzophenone, the mixture was kneaded using a twin-screw kneading extruder to form a compound.

Next, adjust and use 92 types of compounds as raw materials and 40mφ
2 extruders, feed block die, slit width 0-4
Co-extrusion molding was carried out using a co-extrusion device equipped with a coat hanger die having a width of 450 m to obtain the two-layered film shown in the table.The test results of the obtained film are shown in the table.

Example 2 Ultraviolet absorber t2 of film raw material composition β) of Example 1
Proceed in the same manner except that -C5,5-di-tert-butyl-2-hydro (7phenyl)-5-chlorobenzotriazole was used. The results are shown in the table.

Example 6 The ultraviolet absorber of the film raw material composition (B) of Example 1 was carried out in the same manner as bis-(2,2,6,6-tetramethyl-4-biperdyl)separate. Shown in the table.

Example 4 [Preparation of surface layer and back layer film raw material composition +A)]
Polyvinylidene fluoride product name “Noref 10” manufactured by Tsurubay Co., Ltd.
10'' 80 parts by weight, Mitsubishi Rayon Co., Ltd. methacrylate ester resin trade name [Acrypera] MDJiQ weight part, Asahi Kasei Corporation methacrylate ester resin trade name [Delpet 5R-6500J 10 parts by weight were mixed. After that, it is kneaded using a twin-screw kneading extruder to form a compound. [Adjustment of intermediate layer film raw material composition IBI] Polyfluorinated polyfluoride made by Tsurubay Co., Ltd. Nyriden product name "So L/71010"
” 50 parts by weight, Mitsubishi Rayon Co., Ltd. methacrylate ester resin trade name [Acrypera] MDJ 25 parts by weight, Asahi Kasei Kogyo Co., Ltd. methacrylate ester resin trade name “
Delpera) SR-6500'' 25 parts by weight and 6 parts by weight of 2-hydroxy-4-n-octoxybenzophenone as an ultraviolet absorber were mixed in a single mold in a single mold, and then kneaded in a twin-screw extruder to form a compound.

Next, six 40 mm φ extruders and feed Zoroku die,
Furthermore, 6j coextrusion molding was performed using a coat hanger type coat hanger with a width of 450 mm and a slit width of 0.6 nm. The coat hanger type take-up roll was water-cooled. The results are shown in the table.

Comparative Example 1 The film raw material composition IAI of Example 1 was used as the surface layer,
The same operations as in Example 1 were performed except that the film raw material composition of Example 1 (Bl', which did not contain any ultraviolet absorber) was used as the back layer. The results are shown in the table.

Comparative Example 2 Film raw material composition of Example 4 as surface layer and back layer cA)t: Film raw material composition of Example 4 containing no ultraviolet absorber as intermediate layer (Same as Example 4 except that Bl was used) A similar operation was performed and the results are shown in the table.

Application Examples The weather-resistant films of Examples 1 to 4 and Comparative Examples 1 to 2 were used to form a back layer of the weather-resistant film and a vinyl chloride resin plate (hereinafter referred to as PVC).
(hereinafter referred to as Ag3 plate) and a styrene-butadiene-acrylonitrile copolymer resin plate (hereinafter referred to as Ag3 plate), and all physical properties were measured. The results are shown in the table.

Test method 1) Film thickness: Measured using a Peacock thickness gauge with '/1ooo wx scale. In addition, in the case of a two-layer structure, the thickness of the upper layer and lower layer is calculated from the extrusion volume ratio of each extruder.

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

No change at all 20 Slight change: Δ 3) Chemical resistance: Dropped onto the top layer of the film at room temperature (26℃)
Visually judge the appearance after 24 hours. Chemicals used = 10% HC1,10% H2SO410%Ca (42,10chiN1) 0H No change at all: ○ Minor change: Δ 4) Weather resistance: Accelerated test using due cycle weather meter method Black panel 63°C1 After 1,000 hours of spraying, compare with the blank sample and visually judge whether the base material has changed color or not. 5) Adhesive durability: In contact with the base material, put a goblin on the 7'C film side and use a ducycle sea urchin. After 10,001 yen of test using the B-meter method, there was no peeling at all in the cellophane peel test.''/100 All peeled off: oAoo 6) Adhesion to the base material: Using a roll laminator at a temperature of 1
It was thermally bonded with adhesive at 40'O.

(Effects of the Invention) As is clear from the above explanation, the fluororesin weather-resistant film obtained by the present invention 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. Together, they 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 (2)

[Claims] (1) The surface layer is a composition (A) containing 95 to 50 parts by weight of a vinylidene fluoride resin and 5 to 50 parts by weight of a methacrylic ester resin, and 95 to 5 parts by weight of a methacrylic ester resin; Vinylidene fluoride resin 5-95
1. A fluororesin-based weather-resistant film characterized in that the back layer is a composition (B) containing 0.1 to 15 parts by weight of an ultraviolet absorber and a UV absorber. (2) Composition (A) containing 95 to 50 parts by weight of vinylidene fluoride resin and 5 to 50 parts by weight of methacrylic ester resin as the surface layer and back layer; 1. A fluororesin-based weather-resistant film characterized in that the intermediate layer is a composition (B) whose main components are 5 to 95 parts by weight of a vinylidene fluoride resin and 0.1 to 15 parts by weight of an ultraviolet absorber.