JPS618350A - Vinylidene fluoride resin group multilayer film - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention provides a fluorinated resin which has excellent weather resistance, stain resistance, and solvent resistance, and has improved adhesiveness to plastics, im, and other base materials. It relates to a vinylidene resin composite film, and more specifically, it is composed of a vinylidene fluoride resin layer, a layer made of a mixture of vinylizo fluoride 7 resin WI and a methacrylic acid ester resin, and a methacrylic acid ester resin layer. The present invention relates to a polyvinylidene fluoride resin multilayer film.

(Prior Art) In recent years, polyvinyl chloride-based, polymethacrylate-based, polyfluorine-based films, and the like have been used together with various paints as surface protection films for interior and exterior members.

These protective films are used not only for interior purposes such as wallpaper and elevator cars, but also for roofing materials, wall materials, rain gutters, garage roofs, sunrooms, agricultural materials, signboards, signs, labels, etc.
It is used in a wide variety of applications, such as for window glass, due to its excellent weather resistance.

By the way, protective films based on the three types of materials mentioned above are used for various purposes depending on their price, characteristics, etc., but the former is the cheapest in terms of price, and the latter in terms of force characteristics. Excellent weather resistance. .

The target substrates for lamination of these protective films include plastic substrates such as polyvinyl chloride, polycarbonate, polymethyl methacrylate, acrylonitrile loose-tadiene-styrene copolymer, and FRP, as well as gPDMLCA.
A wide range of products include M and other im base materials, metals such as aluminum foil and steel plates, as well as plywood and glass.

(Problems to be Solved by the Invention) However, among these three types of film materials, polyfluorine film has far superior performance than the other two in terms of weather resistance, stain resistance, and strength. However, it has the disadvantage of poor adhesion to the base material.

Therefore, while polyvinyl chloride and polymethacrylic acid ester films use a thermal adhesive method depending on the application, all polyfluorine films use an adhesive method, which is also expensive. Therefore, the excellent weather resistance and stain resistance cannot be fully utilized, and there is currently a strong demand for improvement in imparting thermal adhesive properties.

The present invention improves the adhesion of a film made of vinylidene fluoride resin, and includes a vinylidene fluoride resin layer, a layer made of a mixture of vinylidene fluoride resin and methacrylic acid ester resin, and a layer made of a mixture of vinylidene fluoride resin and methacrylic acid ester resin. By using a multilayer film composed of a resin layer, a polyvinylidene fluoride resin-based multi-J-film is provided which has excellent weather resistance, stain resistance, and solvent resistance, and also has good adhesiveness to a substrate to be adhered. It is something.

(Means for Solving the Problem) The present invention provides an AI resin containing vinylidene fluoride resin as a component. #
and B containing 85 to 25 parts by weight of vinylidene fluoride resin and 15 to 75 parts by weight of methacrylic acid ester resin.
layer, and 0 containing methacrylic acid ester resin as a component.
This is a solute vinylidene resin multilayer film characterized by being composed of layers.

The vinylidene fluoride resin used in the present invention refers to a homopolymer of vinylidene fluoride or a copolymer of vinylidene fluoride and a copolymerizable monomer. Examples of copolymerizable monomers include vinyl fluoride, tetrafluoroethylene, and trifluorochloroethylene.

Next, the methacrylic acid ester resin refers to a copolymer of a homopolymer of methyl methacrylate and a monomer copolymerizable with methyl methacrylate.

Copolymerizable monomers include butyl methacrylate, ethyl methacrylate, and acrylic esters.

Next, the raw material used for layer B (hereinafter referred to as Bl-), which consists of a mixture of vinylidene fluoride resin and methacrylic ester resin, is prepared by mixing the vinylidene fluoride resin and methacrylic ester resin in a certain ratio. It is possible to use a product that has been melted into pellets using an extruder or the like, or a blend thereof.

The mixing ratio of vinylidene fluoride resin and methacrylic acid ester resin used for this B layer is 85 to 25 parts by weight/15 to 75 parts by weight, and p is when the vinylidene fluoride resin exceeds 85 parts by weight. , the adhesion with layer 0 (hereinafter referred to as C layer 5) composed of methacrylic acid ester resin was insufficient, and on the other hand, vinylidene fluoride resin
This is because if the amount is less than 1 part, the adhesion to layer A (hereinafter referred to as layer A) containing vinylidene fluoride resin will be insufficient.

The film thicknesses of layer A, layer B, layer 0, and the entire layer are as follows:
Although not particularly specified, when used as a protective film, the A layer is preferably 6 to 100 μm, the B layer is 2 to 50 μm, and the 0 layer is 5 to 200 μm, and the total layer is preferably about 10 to 650 μm. However, in applications that require solvent resistance, this is not the case (Suryu can be used with just the thickness of the A layer.

On the other hand, it is also possible to use the A, B and 0 layers with a small amount (all of them) for the purpose of imparting light-shielding properties to improve the weather resistance of the base material. Fillers containing titanium, talc, calcium carbonate, carbon black, red iron and other formulated inorganic pigments,
This can be achieved by incorporating colorants.

In addition, the weather resistance of the base material is further improved in the form of a transparent film (
Especially for the purpose of blocking ultraviolet rays), layer A,
A method is adopted in which an ultraviolet absorber such as a pen-tria-toru type, a pen-tophenone type, or a salicylic acid derivative is kneaded into at least one of the B layer and the 0 layer. At this time, it is even more effective to use a radical scavenger or an antioxidant in combination.

Next, the manufacturing method will be described. The multilayer film according to the present invention is composed of three layers and is manufactured by melt extrusion.

For melt extrusion molding, a twin-screw extruder is used in addition to a general single-screw extruder, and the following methods are available for bonding a plurality of layers together.

First, the T-die coextrusion molding method, in which multiple extruders are used to bond resin in a molten state to form multiple layers, is called a multi-manifold die, and the resin layers are brought into a sheet state and then contacted. There are two methods: adhesion, and a method called feed block die, in which multiple resins are bonded and then spread into a sheet. Multilayer films can also be formed by a method called inflation molding that uses a master die.

Next, called the extrusion lamination method, one of the layers to be bonded together is formed into a film shape in advance.
It is also possible to use a method in which the other layers are extruded and bonded using heat or an adhesive (generally, an adhesive is applied in advance and the layers are bonded by pressure).

There is also a method of forming both layers into a film in advance and then integrating them using heat or adhesive, but this is disadvantageous in terms of process and cost compared to the previous method, and in the case of thin films, bonding is difficult. It's also difficult.

Next, in order to impart light-shielding properties to at least one of layer A, layer B, or layer 0, it is necessary to add about 2 to 30% by weight of pigment, and the resin and pigment are combined using an extruder or the like. A method of melting and kneading may also be used, but generally the pigment is not sufficiently dispersed, and a high-speed rotation and high shear wet wire machine, such as Kobe Steel's F
When used in a CM type mixer, the dispersion of the pigment becomes very good, and it is possible to provide a raw material for a light-shielding layer with an excellent surface condition.

(Example) From now on, vinylidene heptafluoride resin will be PVDF.

Methyl methacrylate resin will be abbreviated as PMMA.

The vinylidene fluoride resin is manufactured by Pennwalt Co., Ltd. under the trade name Kynar 740 (hereinafter abbreviated as -740), while the methacrylate ester resin is manufactured by Mitsubishi Rayon Co., Ltd. under the trade name Acryvet M D (hereinafter referred to as PMMA). MD) and HBE (methyl methacrylate resin containing an acrylic imme, hereinafter abbreviated as HBg) manufactured by the same company, product name Hypera) were used. Also, PVDF/P used for Bl'@
MMI6L constant ratio mixture product is a mixture of K-740 and MD or HBE at a constant ratio.
It was melted in a twin-screw extruder rotating in opposite directions and re-velletized for use.

Example 1 PVDF/PMMA obtained by MD with -740 as a raw material for A layer and -740 as a raw material for Bf@ = 80
/20 products, on the other hand, using HBE as the raw material for the C layer, "4
Six-layer coextrusion molding was carried out using six 0Hφ extruders, a feed block die, and a coat hanger tight die with a width of 450 mm and a slit width of 0.6 u. Note that the take-up roll closest to the T-die was water-cooled.

The thickness of the obtained 6-layer film was 24μ, and when calculated from the extrusion rate ratio of each extruder, the thickness of each layer was A.
The layer size was 10μ, the B layer was 116μ, and the 0 layer was 8μ. Further, as a result of evaluating the properties of this six-layer film, as shown in Table 1, it was found to be excellent in weather resistance, stain resistance, solvent resistance, and thermal adhesion.

Example 2 Raw material for A layer is K-740, raw material for B layer is K-740
PvDF/PMMA = 50150 products obtained from and MD,
On the other hand, a three-layer film was coextruded in the same manner using the equipment of Example 1 using MD as the raw material for the C layer.

Table 1 shows the structure and properties of the three-layer film obtained.

Example 3 The raw material for the A layer is Ni-740, and the raw material for the B layer is Ni-740 and M
PVDF/PMIJiA obtained from D = 30/7
0 product was subjected to six-layer coextrusion molding in the same manner using the equipment of Example 1 using HBE as the raw material for the C layer.

The structure and properties of the obtained 6-layer film are shown in Table 1.

Example 4 The raw material for the A layer is NI-740, the raw material for the B layer is K-740 and PVDF/rubber-containing PMMA obtained from HBE = 60
Similarly, three layers were prepared using the equipment of Example 1, using light-shielding M and D prepared by melting and kneading 100 parts by weight of MD and 20 parts by weight of titanium oxide as raw materials for the C layer. Coextrusion molding was performed.

Table 1 shows the structure and properties of the three-layer film obtained.

Comparative Example 1 -740 and MD obtained pvI) F'/pMMA =
Using 50,150 products, 65 mm diameter extruder, width 3,301 m
, Surin) A single layer film was formed using a 0.5 mat T-die. The properties of the obtained film are shown in Table 2. PVDF/PMMA obtained by O Comparative Example 2 -740 and MD = 7
A single layer film was formed using the same equipment as in Comparative Example 1 using a 0/60 product. The properties of the film are shown in Table 2.

Comparative Examples 3 to 4 Characteristics of commercially available methacrylic acid ester resin films and commercially available fluororesin films were evaluated.

The results are shown in Table 2.

The characteristics measurements shown in Tables 1 and 2 were performed as follows.

(11 Film thickness: Measured using a peacock thickness meter with a scale of 1/1000 + 11 + IL. The thicknesses of the A, B and 0 layers among the three layers were calculated from the extrusion rate ratio of each extruder.

(2) Weather resistance (a) Accelerated weather resistance test JI8A-141
5 (-Yellowness measurement JrSK-7103 Yellowing index = Yellowness after exposure / Initial yellowness (3) Stain resistance (A layer side) 1. Test method 1 Mark each film with a marker about 1cIIL2 2 Drying Scrape off 30 times with gauze 3 Evaluate the remaining ink with the naked eye 2 Evaluation criteria 1: Completely removed 2 2 Removes but leaves a thin trace after rubbing 6: # 〃 Dark (Remaining 4 2 Partially removed but remains) 5: Does not come off at all (4) Solvent resistance (only the A layer side is immersed) 1. Test method: Visually immersed in each solvent for 2 days at room temperature It was evaluated by

(5) Thermal adhesion (B layer side) 1. Test method ■Base material: Soft PVC sheet for tablecloth 200μ ■Adhesive roll and conditions Mirror surface/Silico y-i” A I Q OφX 350 yml speed 1rn/min2, Evaluation method Strength measurement by peeling 25B@laminated sheet at 180 degrees at a rate of 2°/min (effect of the invention) The vinylidene fluoride resin layer of the present invention is made of a mixture of vinylidene fluoride resin and methacrylate ester resin. The vinylidene fluoride resin multilayer film, which is composed of a polyvinyl fluoride resin and a methacrylic acid ester resin, not only has high strength and elongation, but also has excellent long-term weather resistance, which is a characteristic of vinylidene fluoride resin. It has stain resistance and solvent resistance that allow it to be easily removed even if water-based or oil-based ink or dust adheres to it.On the other hand, the adhesive layer is made of methacrylic acid ester resin, so it cannot be used with adhesives. It goes without saying how to use it (it also has excellent adhesion using heat, so it can be applied to interiors of elevators, vehicles, etc., as well as roofing materials, wall materials, etc.).

Claims (1)

[Claims] A layer containing vinylidene fluoride resin as a component, a B layer containing 85 to 25 parts by weight of vinylidene fluoride resin, 15 to 75 parts by weight of methacrylic ester resin, and a methacrylic ester resin as components. A vinylidene fluoride resin multilayer film composed of a C layer.