JPH0319246B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a curable fluorine-containing copolymer composition, and more specifically to a curable fluorine-containing copolymer composition containing specific amounts of fluoroolefin, cyclohexyl vinyl ether, and glycidyl vinyl ether, each having improved curability. The present invention relates to a sexual composition. The applicant has discovered that the fluoroolefin-cyclohexyl vinyl ether copolymer has properties useful as a paint base, and also exhibits unique crosslinking properties, and can be heated in the presence of oxygen or short-term in a similar atmosphere. It is easily crosslinked by the action of wavelength ultraviolet rays, and furthermore, it is
As shown in Japanese Patent No. 25414, it has been found that the crosslinking property is improved by adding a specific amount of an oil-soluble manganese salt. As a result of further investigation into the curability of the above-mentioned copolymer mainly as a coating base, the present inventors found that when utilizing the inherent crosslinking properties of the above-mentioned copolymer, the degree of curing of the coating film should be adjusted to a practical level. In order to achieve this level, high temperature or long-term crosslinking treatment is required, and under mild conditions, the stain resistance of the coating film or its adhesion to the substrate may deteriorate in some cases. I learned that there are problems such as not having enough. Based on the recognition of the above-mentioned problems, the present inventors have conducted extensive research, and as a result, the present inventors have discovered that the fluoroolefin-cyclohexyl vinyl ether copolymer is further copolymerized with a specific amount of glycidyl vinyl ether as a curing site unit. - the curability of the cyclohexyl vinyl ether copolymer is significantly improved without impairing various useful properties as a paint base, and
It has been found that such an improved copolymer can be cured by using an amine compound containing two or more types of nitrogen atoms with different degrees of substitution in the same molecule as a curing agent to give a cured product with excellent physical properties. The present invention is characterized in that the content of units based on fluoroolefin, cyclohexyl vinyl ether, glycidyl vinyl ether and other comonomers is
40 to 60 mol%, 5 to 45 mol%, 3 to 45 mol% and 0 to 40 mol%, and the intrinsic viscosity measured in uncured state in tetrahydrofuran at 30°C is 0.1 to
An amine compound containing two or more types of nitrogen atoms with different degrees of substitution in the same molecule was added as a curing agent to 100 parts by weight of the fluorine-containing copolymer with a concentration of 1.5 dl/g.
The object of the present invention is to provide a novel fluorine-containing copolymer curable composition in which the fluorine-containing copolymer is blended in a proportion of 0.1 to 20 parts by weight. The copolymer in the present invention contains fluoroolefin, cyclohexyl vinyl ether, and glycidyl vinyl ether in proportions of 40 to 60 mol%, 5 to 45 mol%, and 3 to 45 mol%, respectively, preferably 45 to 55 mol%, respectively. ,
It is important that the content is between 10 and 30 mol% and between 5 and 20 mol%. Too low a fluoroolefin content is not only unfavorable from the viewpoint of weather resistance, but also causes problems in production. Also, those containing too high a fluoroolefin content are also difficult to manufacture. If the cyclohexyl vinyl ether content is too low, the hardness of the coating film will decrease, which is undesirable. Furthermore, if the glycidyl vinyl ether content is too low, the effect of improving curability will be lost, which is not preferable. Here, as the fluoroolefin, perhaloolefin, particularly chlorotrifluoroethylene or tetrafluoroethylene is preferably employed. The copolymer of the present invention may contain units based on comonomers other than the above three essential constituents in an amount not exceeding 40 mol%. Such comonomers include olefins such as ethylene, propylene, and isobutylene, haloolefins such as vinyl chloride and vinylidene chloride, unsaturated carboxylic acid esters such as methyl methacrylate, vinyl acetate, vinyl propionate, n- Various examples include vinyl carboxylates such as vinyl butyrate, vinyl ethers such as ethyl vinyl ether, isobutyl vinyl ether, n-butyl vinyl ether, etc., but alkyl vinyl ethers having an alkyl group having 2 to 8 carbon atoms are flexible. It can be preferably adopted from the viewpoint of provision. The copolymer in the present invention has an intrinsic viscosity measured at 30°C in tetrahydrofuran in an uncured state.
It is important that the amount is 0.1 to 1.5 dl/g, preferably 0.15 to 0.8 dl/g, and more preferably 0.2 to 0.5 dl/g. If the viscosity is too low, the mechanical strength will decrease, while if it is too high, when applied as a solution-type paint, the solution concentration will have to be lowered due to the viscosity, and the workability will be impaired. Both are undesirable. In the copolymer of the present invention as described above, a copolymerization reaction is carried out by applying a polymerization initiator or a polymerization initiation source such as ionizing radiation to a monomer mixture of a predetermined proportion in the presence or absence of a polymerization medium. It can be manufactured by tightening. Here, as the polymerization initiator, water-soluble or oil-soluble ones can be used as appropriate depending on the polymerization type or polymerization medium. Specifically, water-soluble initiators include redox initiators consisting of persulfates such as potassium persulfate, hydrogen peroxide, or combinations of these with reducing agents such as sodium bisulfite and sodium thiosulfate; An inorganic initiator such as a system in which a small amount of iron, ferrous salt, silver nitrate, etc. are present together, or dibasic acid peroxide such as disuccinic acid peroxide, siglutaric acid peroxide, monosuccinic acid peroxide,
Organic initiators such as azobisisobutyramidine dihydrochloride, and oil-soluble initiators such as peroxy ester type peroxides such as t-butyl peroxyisobutyrate and t-butyl peroxy acetate, diisopropyl Examples include dialkyl peroxydicarbonates such as peroxydicarbonate, penzoyl peroxide, and azobisisobutyronitrile. The amount of the polymerization initiator used can be changed as appropriate depending on the type, copolymerization reaction conditions, etc., but it is usually 0.005 to 5% by weight, especially 0.05 to 0.5% by weight, based on the total amount of monomers to be copolymerized.
Approximately % by weight is adopted. In the above copolymerization reaction, the reaction format is not particularly limited, and bulk polymerization, suspension polymerization, emulsion polymerization, solution polymerization, etc. can be adopted, but the stability of the polymerization reaction operation and the separation of the produced copolymer can be improved. For ease of use, emulsion polymerization in an aqueous medium or solution polymerization using a saturated halogenated hydrocarbon containing one or more fluorine atoms as a solvent is preferably employed. In addition, when carrying out a copolymerization reaction in an aqueous medium, it is preferable to add a basic buffer so that the PH value during polymerization does not fall below 4, preferably 6. Moreover, it goes without saying that the method of the present invention can be carried out by batch, semi-continuous, continuous, etc. operations. In such a copolymerization reaction, the copolymerization reaction temperature may be appropriately selected within the range of -30°C to +150°C depending on the polymerization initiation source, the type of polymerization medium, etc.; When carried out, a temperature of 0°C to +100°C, preferably about 10°C to 90°C may be employed. Further, the reaction pressure can be selected as appropriate, but is usually 1 to 100 Kg/cm ² , particularly 2 to 50 Kg/cm ²
It is desirable to adopt degrees. Furthermore, in order to suppress the intrinsic viscosity of the resulting copolymer within the above range, the copolymerization reaction may be carried out in the presence of an appropriate chain transfer agent. The copolymer in the present invention contains an epoxy ring based on glycidyl vinyl ether units as a curing site, and curing easily proceeds by heating in the presence of amines, carboxylic acids, phenols, alcohols, etc. When applied as a paint base, a cured coating film with excellent solvent resistance and stain resistance and excellent adhesion to materials can be obtained. In this case, by using a specific amount of an amine compound containing two or more types of nitrogen atoms with different degrees of substitution in the same molecule as a curing agent, rapid curing can be achieved under mild conditions, and the cured coating film can be cured quickly. It has the effect of suppressing yellowing. Therefore, the composition of the present invention uses an amine compound containing two or more types of nitrogen atoms with different degrees of substitution in the same molecule as a curing agent, based on 100 parts by weight of the specific fluorine-containing copolymer as described above. 0.1 to 20% by weight, preferably 1 to 10 parts by weight. In the composition of the present invention, it is important to use as a curing agent an amine compound containing nitrogen atoms with different degrees of substitution in the same molecule; for example, n
When using a curing agent such as a mixture of -hexylamine and tri-n-butylamine in which nitrogen atoms with different degrees of substitution are contained in separate molecules, problems such as insufficient curing accelerating effect occur. In the composition of the present invention, the amine compound containing two or more types of nitrogen atoms with different degrees of substitution in the same molecule is aminoethylpiperazine (

[Formula]) (hereinafter abbreviated as AEP) containing three types of nitrogen atoms, primary, secondary and tertiary, in the same molecule, aminomethylpiperidine (

Examples include those containing two types of nitrogen atoms, primary and tertiary, such as [Formula] (hereinafter referred to as AMP), or analogs thereof. In order to accelerate curing, it is preferable that the composition of the present invention further contains a polyhydroxy compound in an amount of 0.1 to 10 parts by weight per 100 parts by weight of the fluorine-containing copolymer as a curing aid. As such a polyhydroxy compound, a non-aromatic diol can be preferably employed from the viewpoint of preventing yellowing of the cured product, and when a fluorine-containing linear diol is used, the effect of significantly accelerating curing is is also demonstrated. The compositions of the invention include pigments, stabilizers, lubricants,
It is also possible to contain fillers, flame retardants and other additives as appropriate. These additives can improve color tone, thermal stability, abrasion resistance, non-stick properties, surface hardness,
It is possible to improve flame resistance and other properties. When the composition of the present invention is used as a paint base, it can provide a coating film with excellent surface hardness, gloss, solvent resistance, stain resistance, and weather resistance under mild conditions. For applications such as glass coating, glass fiber reinforced polyester resin coating, plastic coating such as PVC, nylon, acrylic, polyester, aluminum sash, swimming pools, cement roofing, sizing, roof coating, pre-coated metal, etc. Extremely useful. Hereinafter, the present invention will be explained in more detail with reference to Examples. Synthesis Example 1 In a stainless steel autoclave with an internal volume of 200 c.c., add 120 g of deoxygenated water, 0.6 g of ammonium perfluorononanoate, 12 g of trifluorotrichloroethane, 2.16 g of disodium phosphate dodecahydrate, and 0.06 g of ammonium persulfate. After charging, cyclohexyl vinyl ether (C-HyVE) 10.8
g, 10.3 g of ethyl vinyl ether (EVE) and 5.72 g of glycidyl vinyl ether (GVE). After repeating the freezing, degassing, and thawing operations using liquid nitrogen in the autoclave twice, 33.2 g of chlorotrifluoroethylene (CTFE) was introduced. Gradually warm the autoclave to 30°C while stirring.
Hold at this temperature when reached. pressure 3.3
Kg/cm ² G, and a decrease in pressure is observed after 2 hours. After 7.5 hours, the pressure reaches approximately 1 Kg/cm ² G, and almost no pressure drop is observed. Eight hours after the start of the reaction, the reaction vessel was cooled with ice water and the monomer was purged. The latex obtained in the reactor (concentration 2.75
%) was destroyed by adding a large amount of ethanol, and 45.4 g of white powder was obtained by filtration, washing and drying. The monomer reaction rate was 83% and the average polymerization rate was 47 g/h. From the analysis of the obtained copolymer by ¹³ CNMR,
The copolymers include CTFE, crHyVE, EVE and
51, 14, 26 and 9 units based on GVE respectively
% by mole, and it was found that there was substantially no chain of vinyl ether units. In addition, the intrinsic viscosity (hereinafter abbreviated as [η]) of the copolymer in tetrahydrofuran at 30°C is 0.34 dl/g.
It was hot. Synthesis Example 2 The same polymerization as in Synthesis Example 1 was carried out using 0.8 g of carbon tetrachloride instead of trifluorotrichloroethane.
The experiment was carried out using 3.6 g of sodium lauryl sulfate instead of ammonium perfluorononanoate. The initial pressure of 4.3 Kg/cm ² G was reduced to 2.3 Kg/cm ² G after 8 hours, yielding 48.5 g of polymer. copolymer
¹³ CNMR analysis shows that the copolymer is CTFE50, c-
It was shown to contain HxVE15, EVE25, and GVE10 mol%. Moreover, [η] was 0.32 dl/g. Synthesis Example 3 Polymerization was carried out under the same conditions as in Synthesis Example 1. However, in this case, 12 g of t-butanol was added. After 7 hours, the reaction was stopped and the latex was collected. Almost no polymers in the latex were observed in the reactor, resulting in a high latex selectivity.
51 g of polymer was recovered at 99% (30% latex concentration). The composition of the polymer is CTFE51%, c-
At HxVE16%, EVE25%, GVE9 mol%, [η] is
It was 0.29 dl/g. Synthesis Examples 4 to 6 Polymerizations similar to those in Synthesis Example 1 were carried out by changing the monomer composition charged. The polymerization rate, composition and intrinsic viscosity of the produced copolymer in each case are summarized in Table 1.

[Table] Synthesis Example 7 Polymerization was carried out under the same conditions as Synthesis Example 1 except that 28.3 g of tetrafluoroethylene (TFE) was used instead of CTFE. The reaction was stopped after 6 hours, and the polymer contained in the latex was recovered. 35g of white powder polymer contains 50 mol% TFE, 14% c-HxVE,
Including EVE25% and GVE11% [η] is 0.33dl/g
It was hot. Examples 1 to 7 Using each of the copolymers obtained in Synthesis Examples 1 to 7, solution-type paints having the following formulations were prepared. Copolymer 33 parts by weight AEP 1.65 〃 Titanium oxide 14 〃 Methyl isobutyl ketone 40 〃 Xylene 13 〃 The viscosity of each paint is Ford cup #4.
It took 60-80 seconds. The paint thus obtained was applied to a chromate-treated aluminum plate (thickness 0.5 mm; 180 mm x 120 mm) using a film applicator (JISK 5400B type, gap
100μ) and air-dried for 10 minutes at room temperature, then 210μ
A coated aluminum plate was obtained by heating for 5 minutes in an electric furnace maintained at .degree. Each coating film passed the Xylol Rub Test 100 times or more, showed no yellowing, and passed the Magic Ink Test. The pencil hardness of each coating film is summarized in Table 2. The magic ink test is a test in which a line is drawn on the paint film using red and black magic ink, and after being left for 24 hours, the magic ink is wiped off with gauze moistened with xylene and the presence or absence of traces is observed.

[Table] Examples 8 and 9 Using the copolymer obtained in Synthesis Example 1, the curing agent components were AEP 8 phr + bentanediol 4 phr.
(Example 8) AEP8 phr + 1,1,6,6-tetrahydroperfluorohexanediol 2 phr
(Example 9) A coated aluminum plate was obtained in the same manner as in Example 1 except that the baking conditions were 210° C. for 3 minutes. The xylene rub test, presence of yellowing, magic ink test, and pencil hardness test results for each coating film were all as good as in Example 1. Example 10 Using the copolymer obtained in Synthesis Example 1, a coated aluminum plate was obtained in the same manner as in Example 1 except that the curing component was AMP5phr. The results of the xylol rub test, presence of yellowing, magic ink test, and pencil hardness of this coating film were all as good as in Example 1. Comparative Example 1 The charging ratio of each monomer was changed to CTFE/c-HyVE/
The same copolymerization reaction as in Example 1 was carried out except that EVE/GVE=50/15/35/2, and CTFE/c
−HyVE/EVE/GVE=52/15/31/2; [η]
A copolymer of =0.28 dl/g was obtained at a rate of 50 g/hr. A coated aluminum plate was obtained in the same manner as in Example 1 using the thus obtained copolymer, but
The base of the coating film was exposed in the xylene rub test five times, clear traces were observed in the magic ink test, and the pencil hardness was only H to 2H. Comparative Example 2 The charging ratio of each monomer was changed to CTFE/c-HyVE/
The same copolymerization reaction as in Synthesis Example 1 was carried out except that EVE/GVE=51/0/34/15, and CTFE/c
−HyVE/EVE/GVE=50/0/35/14;
[η] = 0.32dl/g copolymer at 57g/・hr
obtained at a rate of A coated aluminum plate was obtained in the same manner as in Example 1 using the thus obtained copolymer. The coating film has been tested over 100 times in the xylol rub test.
Although it passed the magic ink test, the pencil hardness was only F. Comparative Examples 3 to 7 A coated aluminum plate was obtained in the same manner as in Example 1 except that the copolymer obtained under the same conditions as in Synthesis Example 1 was used, and the curing agent and curing aid were changed.
The physical properties of the coating film were tested. The results are summarized in Table 3.

【table】

【table】

Claims (1)

[Claims] 1. The content of units based on fluoroolefin, cyclohexyl vinyl ether, glycidyl vinyl ether and other comonomers is 40 to 60 mol%, 5 to 45 mol%, 3 to 45 mol%, and 0 to 45 mol%, respectively. 40
mol% and has an intrinsic viscosity of 0.1 to 1.5 dl/g measured in uncured state in tetrahydrofuran at 30°C.
0.1 to 20 parts by weight of an amine compound containing two or more types of nitrogen atoms with different degrees of substitution in the same molecule as a curing agent to 100 parts by weight of the fluorine-containing copolymer. Fluorine-containing copolymer curable composition. 2 Fluorine-containing copolymer 100 as a curing aid
2. A composition according to claim 1, containing from 0.1 to 10 parts by weight of polyhydroxy compound. 3. The composition according to claim 2, wherein the polyhydroxy compound is a non-aromatic diol. 4 The amine compound is aminoethylpiperazine,
The composition according to claim 1, which is at least one selected from aminomethylpiperidine and their analogs.