JPS6126584B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a fluorine-containing polymer composition, and more particularly to a fluorine-containing polymer composition suitable as a coating material made by adding a perfluoropolymer to a specific fluorine-containing copolymer containing cyclohexyl vinyl ether. The present invention relates to a combined composition. The applicant has discovered that a new copolymer of fluoroolefin and cyclohexyl vinyl ether has high rigidity and can be cured by heating in the presence of oxygen or by exposure to specific radiation in a similar atmosphere. I discovered something and applied for a special patent application in 1972.
-9259 (Japanese Patent Publication No. 55-44083) and others. As a result of further research on the industrial use of such copolymers, the present inventors found that the copolymers have high surface hardness and are advantageous for forming coating films with excellent adhesion to substrates and weather resistance. Although it is extremely useful and can be applied to a wide range of applications such as coating materials, the coating film of this copolymer still has room for improvement in terms of antifouling properties, low friction properties, abrasion resistance, etc. I found out something. The present invention aims to provide a composition that solves the above-mentioned problems, and contains 30 to 70, 5 to 70, and 0 to 45 mol% of units based on fluoroolefin, cyclohexyl vinyl ether, and other comonomers, respectively. A perfluoropolymer is added to a fluoroolefin-cyclohexyl vinyl ether copolymer having an intrinsic viscosity of 0.1 to 2.0 g/dl as measured at 30°C in tetrahydrofuran.
The object of the present invention is to provide a new fluorine-containing polymer which is mixed in a proportion of 0.5 to 200 parts by weight per 100 parts by weight. In the present invention, the fluoroolefin-cyclohexyl vinyl ether copolymer is selected from fluoroolefin, cyclohexyl vinyl ether, and other copolymers from the viewpoint of weather resistance, crosslinking properties, mechanical properties, and workability when used as a paint base. 30 to 70 units based on quanta, respectively.
5 to 70, 0 to 45 mol%, and has an intrinsic viscosity of 0.1 to 2.0 g/
dl will be adopted. Those with a too low fluoroolefin content, too low a cyclohexyl vinyl ether content, and too low an intrinsic viscosity are disadvantageous because they reduce weather resistance, crosslinking properties, mechanical properties, etc., and those with an excessively high intrinsic viscosity are disadvantageous. When used as a solution-type paint, it is difficult to increase the concentration and the workability deteriorates, which is disadvantageous. Here, perhaloolefin, particularly tetrafluoroethylene or chlorotrifluoroethylene, is preferably employed as the fluoroolefin. Other comonomers include olefins such as ethylene, propylene, and isobutylene, haloolefins such as vinyl chloride and vinylidene chloride, unsaturated carboxylic acid esters of methyl methacrylate, vinyl acetate, vinyl n-butyrate, etc. Various examples include vinyl carboxylates, vinyl ethers such as ethyl vinyl ether, n-butyl vinyl ether, etc., but alkyl vinyl ethers having an alkyl group having 2 to 6 carbon atoms are preferred from the viewpoint of imparting flexibility. Adoptable. The fluoroolefin-cyclohexyl vinyl ether copolymer of the present invention is
As described in Publication No. 44083, a polymerization initiator such as a water-soluble initiator or an oil-soluble initiator or ionizing radiation is applied to a monomer mixture in a predetermined proportion in the presence or absence of a polymerization medium to initiate polymerization. It can be produced by causing a copolymerization reaction by causing a copolymerization reaction, and for the purpose of imparting a desired intrinsic viscosity,
If necessary, a chain transfer agent may be added. In the present invention, various types of perfluoropolymer can be used, including polytetrafluoroethylene, a copolymer of tetrafluoroethylene and hexafluoropropene, and a copolymer of tetrafluoroethylene and perfluoro(vinyl ether). Polytetrafluoroethylene, especially those whose molecular weight has been lowered by heat treatment or radiation irradiation, or chain transfer agents Low molecular weight polytetrafluoroethylene produced by polymerization in a polymerization medium such as an aqueous medium or a chlorofluorocarbon solvent in the presence of
Furthermore, polytetrafluoroethylene produced by emulsion polymerization method can be preferably used.
Such perfluoropolymer is used in an amount of 0.5 to 200 parts by weight, preferably 2 to 200 parts by weight, based on 100 parts by weight of the copolymer.
Used in a proportion of 50 parts by weight. In the present invention, the fluorine-containing copolymer and the perfluoropolymer can be mixed by various conventionally known or publicly known methods, but an organic solvent solution of the fluorine-containing copolymer is prepared in advance, This is mixed with a perfluoropolymer, or a fluorine-containing copolymer emulsion produced by an emulsion polymerization method is mixed with a perfluoropolymer emulsion produced by the same emulsion polymerization method to coagulate. method etc. can be preferably adopted from the viewpoint of uniformity. The composition of the present invention may contain appropriate pigments, stabilizers, fillers, and other appropriate additives, if desired. With such additives, it is possible to improve color tone, thermal stability, abrasion resistance, surface hardness, etc. The composition of the present invention provides a coating film with excellent weather resistance, corrosion resistance, and adhesion, high surface hardness, and excellent stain resistance, low friction, and abrasion resistance. It provides a highly glossy coating upon application and is extremely useful as a coating material. Next, the present invention will be explained in more detail with reference to Examples. In addition, the coating film test method adopted in the following examples is as follows. (1) Goban boiling test Draw 11 lines vertically and horizontally on the test piece at 1 mm intervals to create 100 dowels. Boil this in boiling water for 2 hours to remove the water, then stick cellophane adhesive tape on top of it and peel it off in one motion straight upwards. The gender was evaluated. For example, 100/100 shows no peeling at all, indicating good adhesion. (JIS-
(according to the method using K5400) (2) Drawing Erichsen test 20 helices with a diameter of 10 mm and a phase difference of 2.5 mm per rotation are drawn on the test piece at a constant speed of 1 rotation per revolution using a drawing tester. Then, using an Erichsen tester, the test piece was extruded to a height of 5 mm with the drawn portion facing outward, and damage to the paint film, peeling, etc. was visually determined. (3) Weather resistance After a certain period of irradiation test using Sunshine Weather Ometer device manufactured by Suga Test Instruments Co., Ltd., JISK-5400
The 60 degree specular gloss specified in the above was measured, and the gloss retention rate was calculated relative to the pre-test gloss rate. This gloss retention rate and appearance observation were used as evaluation criteria. (4) Salt water spray test A painted board test piece (with a cross cut that reaches the substrate) was placed at an angle of 15 to 30 degrees from the vertical in a salt water spray tester maintained at 35 ± 1°C.
Spray saline at a rate of 1 to 2 ml/80 cm ³・hn,
After 1000 hours, rusting and other abnormalities on the painted surface were visually determined. (According to JIS-Z2371) Example 1 A binary compound in which the molar ratio of chlorotrifluoroethylene and cyclohexyl vinyl ether is 50/50 and the intrinsic viscosity measured at 30°C in tetrahydrofuran is 0.62 g/dl. Polymist F-5 (low molecular weight polytetrafluoroethylene: Asahi Glass Co., Ltd. A mixed solution was prepared by mixing 20 parts by weight and 45 parts by weight of titanium oxide with respect to 100 parts by weight of the copolymer. The above mixed solution was subjected to chromate treatment in advance.
It was applied to a 0.8 mm thick aluminum plate using a film applicator (JIS K5400B type; gap 100 μ), air-dried for 10 minutes at room temperature, and then heated for 30 minutes in an electric furnace (atmosphere: air) maintained at 210°C. A white coated aluminum plate with an excellent gloss of about 20μ was obtained. As a result of applying various coating film test methods to the coated aluminum plate obtained above, no abnormalities were observed in the boiling test and drawing Erichsen test, and no abnormalities were observed after 1000 hours in the salt spray test. Furthermore, in an accelerated weathering test using a sunshine weather meter, there was no change in the coating surface even after 1000 hours, and the gloss retention rate was over 90%. Further, the coated plate was preheated to 70°C and drawn with a drafting pencil having a hardness of 2H, but no damage was caused to the coated film surface. Furthermore, the above coated plate was subjected to Taber abrasion test (ASTM D1044-56: wear wheel CS-17, load 500).
When g) was carried out, the amount of wear after 200 revolutions was 6 mg. Also, the advancing contact angle of the coating film with water is
It was 102 degrees. Furthermore, when lines were drawn on the coating film with black quick-drying marking ink and wiped with acetone-impregnated gauze after drying, the lines could be erased without leaving traces. On the other hand, the coating film formed in the same manner as above except without adding Polymist F-5 has excellent coating film properties, but the Taber abrasion amount measured in the same manner as above was 17 mg, and the advancing contact angle with respect to water was It was 81 degrees. Further, the lines drawn with black marking ink on the coating film left traces even if wiped off in the same manner as above. Examples 2 to 4 White coated aluminum plates were obtained in the same manner as in Example 1, except that the type or amount of perfluoropolymer to be mixed was changed. Table 1 summarizes the Taber wear amount and the advancing contact angle with water of the coating film thus obtained.

[Table] The fluorine-containing copolymer and the perfluoropolymer were mixed in the same manner as in Example 1 in Example 2, and in the emulsion state after emulsion polymerization in Example 3. In addition, in Example 4, a mixture of an organic solvent solution and an organic dispersion was used. Examples 5 to 9 A white coating film was formed on an aluminum plate in the same manner as in Example 1 except that copolymers having different copolymer compositions and intrinsic viscosities were used, and the Taber wear amount and the advancing contact angle with respect to water were determined. was measured and the results shown in Table 2 were obtained.

【table】

Claims (1)

[Claims] 1 Contains 30 to 70, 5 to 70, and 0 to 45 mol% of units based on fluoroolefin, cyclohexyl vinyl ether, and other comonomers, respectively, and has an intrinsic viscosity measured at 30 °C in tetrahydrofuran.
A perfluoropolymer is added to a fluoroolefin-cyclohexyl vinyl ether copolymer with a concentration of 0.1 to 2.0 g/dl per 100 parts by weight of the copolymer.
A fluorine-containing polymer composition mixed in a proportion of 0.5 to 200 parts by weight.