JPH0228239A - Fluororesin-based outdoor film or sheet having low gloss and production thereof - Google Patents

Abstract

PURPOSE:To obtain the title film or sheet having low surface gloss, excellent weather resistance, stain resistance and chemical resistance comprising vinylidene fluoride resin and methacrylic acid ester-based resin. CONSTITUTION:A resin composition consisting essentially of (A) 50-95 pts.wt. vinylidene fluoride resin and (B) 5-50 pts.wt. methacrylic acid ester-based resin is extruded by an extruder and passed through embossing rolls to give the aimed film or sheet having <=25% surface gloss by JIS Z-8741.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a low-gloss fluororesin outdoor film or sheet that has a low surface gloss and excellent weather resistance, stain resistance, and chemical resistance. This relates to a manufacturing method.

(Prior art) At present, vinylidene fluoride resin films or sheets have excellent weather resistance, stain resistance, chemical resistance, etc.
It is widely used as a surface protection film that can be attached semi-permanently or permanently for the purpose of protecting or decorating the surface of other substrates. In recent years, there has been a strong trend toward higher quality, higher functionality, and specialization of these films or sheets, and as a result, the need for low-gloss films or sheets has increased. The method is die embossing with an embossing roll,
There may be a method of chemically or physically roughening the surface of the film by the action of chemicals or by spraying solid particles, but with vinylidene fluoride resin alone, the range from the melting point to the temperature at which crystallization starts is narrow. However, because of the high crystallization initiation temperature and rapid crystallization, it has been difficult to uniformly embossing the surface of a film or sheet to reduce gloss.

(Problems to be Solved by the Invention) The present invention solves these drawbacks, and by using a resin composition made of a vinylidene fluoride resin and a resin with excellent compatibility, low gloss and weather resistance can be achieved. We have now completed a film or sheet with excellent stain resistance and chemical resistance, and a method for producing the same.
A film or sheet consisting of a resin composition whose main components are 1 part by weight and 5 to 50 parts by weight of a methacrylic acid ester resin, the surface gloss of the film or sheet being JI
The present invention provides a fluororesin outdoor film or sheet and a method for producing the same, characterized in that the glossiness is 25 inches or less as measured by SZ-8741.

Vinylidene fluoride resin C or less used in the present invention PVD
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, 67fluorochloroethylene,
Examples include vinyl fluoride.

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 decyl acrylate, styrene, α-methylstyrene, acrylonitrile, acrylic acid, and other ethylenically unsaturated monomers.

Further, the resin composition may appropriately contain colorants, ultraviolet absorbers, antioxidants, fillers, and the like as additives. The colorant is preferably a complex oxide-based inorganic pigment with excellent weather resistance, and the main complex oxide-based inorganic pigment includes TiO2
・5b203- Titanium yellow type of rutile type or pre-prite type crystal whose main component is BaO・N10Cr 20 , zinc-iron type brown type of spinel type crystal whose main component is ZnO・Fe2O3@Cr201, Coo a
Cobalt blue system of spinel type crystals mainly composed of Al2O3C'r203, TiO2・Coo・NiO・
Green type mainly composed of ZnO, CuO・Cr2O3
, CuO* Fe2O3a, spinel type black type containing Mn2O3 as a component, violet type consisting of Coo 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 to be added is not particularly specified since it varies depending on the color tone (pigment composition), but is generally 5 to 60 parts by weight per 100 parts by weight of the resin composition consisting of PVDF and PMMA.

Next, the resin composition used for the film or sheet of the present invention should not contain 95 to 50 parts by weight of PVDF and 5 to 50 parts by weight of PMMA. If PMMI6k is less than 5 parts by weight, it is difficult to obtain low gloss properties, and If it exceeds 50 parts by weight, weather resistance;
It is not possible to fully demonstrate the fastness such as stain resistance and chemical resistance.

The surface gloss of the film or sheet of the present invention is JISz-
It has a gloss level of 25% or less as measured by 8741, and can be produced by passing a film or sheet immediately after melt extrusion using an extruder through an embossing roll to form irregularities. Another manufacturing method may be to cool the extruded film or sheet, then reheat it and pass it through an embossing roll to reduce the gloss.

In addition, there is a method in which a resin composition highly filled with a filler is used to form a film or sheet, and the film or sheet is passed through an erasing roll. The film or sheet of the present invention can be used alone or in combination with other thermoplastic resins, such as methacrylic ester resins, compositions of methacrylic ester resins and vinylidene fluoride resins, and vinyl chloride. Multi-JWi with film or sheet of resin, styrene resin, ABS resin, polyester, polycarbonate, polyamide, etc.
It can also be used as a

(Example) The present invention will be explained in more detail with reference to the following Examples.
10J80 parts by weight, Mitsubishi 21570 Co., Ltd. methacrylic acid ester resin trade name [acryvet MDJ20 double part and pigment mixture toned 2,5Y 8.
0/2.0 (Cream) After mixing 20 parts of heavy acid pigment, the mixture was kneaded using a twin-screw kneading extruder to form a compound. Next, use the prepared compound as a raw material and make a 40uφ
The extruder was equipped with a coatless die with a slit of 0.4 ml and a width of 450 mm, and the die temperature was 260°.
Melt extrusion was carried out using an embossing roll coated with a compound containing 100 parts by weight of silicone rubber and 50 parts by weight of a filler on one of a pair of cooling rolls, and a 60 μm thick Okiichi low The results for obtaining a glossy film are shown in the table.

Example 2 The same procedure as in Example 1 was performed except that 60 heavy acid parts of Solef 1010 and 40 heavy acid parts of Acrybet MD were used in Example 1. The results are shown in the table.

Comparative Example 1 The same procedure as in Example 1 was conducted except that Solef 1010 was used alone. The results are shown in the table.

Comparative Example 2 The same procedure as in Example 1 was carried out except that 60 parts by weight of Solef 1010 and 70 parts by weight of Acrybet MD were used. The results are shown in the table.

Example 6 [Compound for Surface Layer] Example I A compound was prepared in the same manner as in Example 1, except that in VC, Solef 101,065 parts by weight and Acrybet M035 parts by weight were used.

[Compound for back layer]

Tsurupei polyvinylidene fluoride product name “Soref 10”
After mixing 20 parts by weight of 10J, 80 parts by weight of methacrylic acid ester resin (trade name: "Acrivet MD"), and 6 parts of 2-hydroxy 4-n-octoxybenzophenone as an ultraviolet absorber. ,2
The mixture was kneaded using an axial kneading extruder to form a compound.

Next, use the prepared 2-pound compound as raw material and 40#I
Using a device equipped with two Iφ extruders, a feed block die, a coat hanger die with a slit width of 0.41 and a width of 450 m, melt extrusion was carried out at a die temperature of 260°C, and the same as in Example 1 was applied to the surface layer side. Press the second roll fully,
Embossed. The results are shown in the table.

Example 4 Solef 10 in the surface layer compound of Example N6
10. Using 90 parts by weight of Acrybet MD1Q,
The same procedure as in Example 3 was carried out except that Mitsubishi Gas Chemical Co., Ltd.'s polycarbonate product Corbilon 7030A was used as the compound for the back layer.

Example 5 [Surface layer compound] The composition used in Example 1 was used.

[Middle layer compound]

Product name of polyvinylidene fluoride manufactured by Nrupay Co., Ltd. [SOLEF 10]
After mixing 20 parts by weight of 10J, 80 parts by weight of methacrylic acid ester resin "Acrivet MD" manufactured by Mitsubishi Rayon Co., Ltd., and 6 parts by weight of 2-hydroxy-4-n-octoxybenzophenone as an ultraviolet absorber,
The mixture was kneaded using an axial kneading extruder to form a compound.

[Compound for protection]

San-Ai Gas Chemical Co., Ltd. Polycarbonate trade name [Nipilon 7030AJ was used.

Next, six types of compounds with a resistance to 4#l were used as raw materials and 65
The same procedure as in Example 6 was carried out except that one φ extruder and two 40 φ extruders were used. The results are shown in the table.

Example 1 @ I6 In Example 6, a rubber roll was used instead of the second roll to produce a glossy film, and then, in a separate step, the film was heated to 150°C, and then an embossing roll similar to Example 1 was used. I pressed it and embossed it. The results are shown in the table.

(Note 1) Surface thickness: The overall thickness was measured using a peacock thickness gauge with a 1/1000i scale, and in the case of multiple layers, the thickness was calculated based on the extrusion rate ratio of each extruder.

Using 6C3 specular gloss, a part of the film to be measured was measured in accordance with JIS Z8741-1962 method 6. The smaller the value, the lower the gloss.

(Note 2) Glossiness: (Effect of the invention) What is the above? By using a specific resin composition, the present invention has excellent weather resistance, stain resistance, and chemical resistance, and has the characteristics of reducing surface gloss.ヮPatent Applicant: Electrochemistry Industrial Co., Ltd.

Claims (1)

[Scope of Claims] 1. A film or sheet comprising a resin composition containing 95 to 50 parts by weight of a vinylidene fluoride resin and 5 to 50 parts by weight of a methacrylic acid ester resin, the film or The surface gloss of the sheet is JISZ-8741
A fluororesin outdoor film or sheet having a glossiness of 25% or less as measured by . 2. After extruding a film or sheet using an extruder from a resin composition containing 95 to 50 parts by weight of vinylidene fluoride resin and 5 to 50 parts by weight of methacrylic acid ester resin as main components, the film or sheet is passed through an embossing roll. A method for producing a low-gloss fluororesin-based outdoor film or sheet, characterized in that the surface gloss of the film or sheet is 25% or less as measured by JIS Z-8741. 3. The method for producing a film or sheet according to claim 2, wherein the embossing of the film or sheet is performed immediately after extrusion. 4. The method for producing a film or sheet according to claim 2, wherein the embossing of the film or sheet is performed by reheating after extrusion and cooling.