JPS6035921B2 - Method for producing oleophobic and hydrophobic fluorinated polymers - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for producing novel oleophobic and hydrophobic polymers based on fluorinated polymers.

Furthermore, the present invention relates to a method of rendering oleophobic and hydrophobic substrates such as textiles, paper, leather, metal surfaces, and generally any substrate that may be required to be rendered oleophobic and hydrophobic.
According to the present invention, one or more non-fluorinated alkyl acrylates or methacrylates, optionally together with other non-fluorinated monomers, are combined with the above-mentioned non-fluorinated alkyl acrylates or methacrylates and fluorinated acrylic or methacrylates. Provided is a method for producing an oleophobic and hydrophobic fluorinated polymer, characterized in that the polymerization is carried out in the presence of a Qinized acrylic or methacrylic resin with a cloud content of 20 to 8% based on the total weight of the system resin. be done.

Non-primed alkyl acrylates or methacrylates are those in which the alkyl group has up to 2 carbon atoms.

Other non-fluorinated monopolymers which may be used in minor proportions with such alkyl acrylates or methacrylates are preferably from hydroxyethyl or hydroxypropyl methacrylate or acrylate, glycidyl methacrylate or acrylate, acrylic acid, methacrylic acid, acrylamide and N-methylol acrylamide. To be elected.

The function of these other monomers is to facilitate the adhesion of the polymer according to the invention to the substrate and to improve the solidity of the resulting coating. These monomers may be present in amounts up to 2% by weight of all non-fluorinated monomers used. The fluorinated acrylic or methacrylic resins used for the production of the polymeric compounds according to the invention (hereinafter referred to as "compounds according to the invention") are homopolymers or monopolymers of acrylates or methacrylates of fluorinated alcohols. A copolymer based on acrylate and/or methacrylate of one or more fluorinated alcohols, which may further contain one or more non-fluorinated monomers.

Preferable fluorinated alcohol acrylate or methacrylate has the general formula: [wherein CnF2n+, n is 1 to
20 represents a straight or branched perfluoro chain, R
is a hydrogen atom, a hard alkyl group having 1 to 1 carbon atoms, and 5 carbon atoms.
~12 cycloalkyl groups, aryl groups optionally substituted with alkyl groups having 1 to 6 carbon atoms, or groups -
R'--OH (R' represents an alkylene group having 2 to 4 carbon atoms)] is a fluorinated alcohol methacrylic acid ester or acrylic ester.

The preparation of such fluorinated alcohols is described in our US Pat. No. 2,034,142.

In a preferred embodiment of the present invention, as the fluorinated resin,
Copolymers containing one or more fluorinated alcohol acrylates or methacrylates and one or more non-fluorinated monomers are used, where the non-fluorinated monomers are Preferably it is present in an amount up to 50% of the total weight of fluorinated and non-fluorinated monomers used in the preparation. Non-fluorinated monomers include alkyl acrylates and methacrylates, hydroxyethyl acrylates and methacrylates, hydroxypropyl acrylates and methacrylates, in which the alkyl group has preferably 2 carbon atoms,
Particularly selected from glycidyl acrylate and methacrylate, acrylic acid, methacrylic acid, acrylamide and N-methylol acrylamide. To prepare the compounds of the present invention, the polymerization of one or more non-fluorinated alkyl acrylates or methacrylates, optionally with small proportions of other non-fluorinated monomers, is carried out in solution in the presence of a fluorinated resin. , by a method of generating free radicals in an emulsion or suspension.

Solution polymerization in organic soot is the preferred method. In the case of solution polymerization processes in organic media, solvents or solvent mixtures which simultaneously dissolve the fluorinated resin and the non-fluorinated monomers used are in principle suitable as organic media.

Particularly suitable are ketones, esters, chlorinated solvents, chlorinated fluorinated solvents or mixtures of these solvents. In solution, initiators selected from organic peroxides or azo compounds are used. The polymerization temperature varies depending on the initiator used, but
Generally it is 40-100q○. A particularly practical method of preparing the compounds according to the invention is to first prepare the compounds according to the invention on a base non-fluorinated resin in the same medium, under the same general conditions and in the same reaction vessel. Consisting of

When operating in this manner, the basic fluorinated resin is obtained in solution in the reaction vessel at the end of the first polymerization. Then, reactants (non-fluorinated monomer, initiator, solvent supplement) necessary to obtain the target compound are added to the reactor, and the newly used monomer is polymerized. However, although this method of preparation is particularly advantageous for the preparation of the compounds according to the invention, it is not the only method of preparation; the basic fluorinated resin is prepared separately under conditions totally different from those for the preparation of the target compound. It can also be manufactured without any difficulty. When producing the compound of the present invention, in addition to the above-mentioned reactants, a chain transfer agent that acts to change the molecular weight of the desired product can also be used.
The compounds of the invention are used to render textiles, leather, paper, metal surfaces or any other type of substrate oleophobic and hydrophobic.

Such compounds must be in the form of organic solutions or aqueous dispersions when applied to the substrate surface. When the polymer is prepared in a solvent soot according to a preferred embodiment of the invention, the compound can be first isolated by precipitation or drying and recovered in a suitable solvent medium, or more simply, left in the crude polymerization solution in a suitable solvent. It can also be used by diluting it with a solvent to a concentration suitable for coating.

The solvent is selected depending on its dissolving power for the compound of the invention, its volatility and the substrate to which the compound is to be applied. The solvents used are generally selected from esters, ketones, basic solvents and chlorinated fluorinated solvents. Diluents such as aliphatic or aromatic hydrocarbons may be added to the solvent or solvent mixture used. The active substance concentration of the coating solution is governed by the coating conditions, the amount of solution retained by the substrate and the amount of active substance to be deposited on the substrate, but the concentration may range from 1 to
It is about 2% by weight. Treatment of a substrate with a composition containing a compound of the invention, whether the composition is in the form of an organic solution or an aqueous dispersion, may be carried out by impregnation, milling or any other method.

After coating, the treated substrate is dried at a temperature below 100 pm.
This drying can conveniently be carried out at ambient temperature. Furthermore, heat treatment at higher temperatures may improve the solidity of the resulting coating, but may also serve to modify certain properties of the coating.
This is by no means mandatory. Furthermore, when heat treatment is performed, the temperature is selected depending on the type of substrate to be treated. For example, if the substrate is a textile, the temperature selected will generally be between 100 and 20,000. When treating metal surfaces, temperatures up to 250oC can be used without difficulty. Processing times vary depending on the temperature and the type of substrate being treated, and can reach several hours in some cases. In the case of textiles, it takes approximately a few minutes. The compounds of the present invention can impart oleophobic and hydrophobic properties to textiles, leather, paper and generally any porous substrate.

The compound also imparts stain resistance in conjunction with its oleophobic properties. When applied to smooth metal or other surfaces, the compounds of the present invention
In addition to imparting the aforementioned properties, they also make their surfaces anti-stick.

The compounds of the present invention can optionally be used in admixture with conventional compounds of heat for imparting properties other than those mentioned above to the substrate to which they are applied.

When applying the compounds of the present invention to textile fabrics, the degree of oleophobicity and hydrophobicity is evaluated by the AATCC method and the water repellent test, respectively.

AATCC oleophobicity test (Amencan ship socja
tjonofTextileChemistsandC
olorists, Test Method 118-1966) uses the following eight liquids in order of decreasing surface tension: No.
1 “Nujol Zoparaffin Oil M.21
65-35 Mixture of n-diol and n-hexadecane. 3 n-hexadecane 4 n-tetradecane M. 5n Dodecane M. 6 n-dekan shame. 7 n-octane No. 8 n-Heptane. Droplets of these different liquids are placed on the treated fabric and the lowest surface tension at which no wetting occurs, i.e. the highest No. Check number of fluids.

The degree of oleophobicity of a textile fabric is characterized by this number.
For example, liquid snake. 1~earth. Liquid No. 6 doesn't get wet, but liquid No. 7 and earth. A fabric that wets by 8 has an oleophobicity of 6. An oleophobicity of 6 or higher is considered excellent.

Hydrophobicity measurements are made according to the ASTM-583-6 substandard.

The treated fabric, held in the stretched state by a mechanical device, is watered under specified conditions at a 45° angle. The fiber fabric still in the stretched state on the stretching device is then shaken off and the degree of hydrophobicity is judged according to the following criteria. Mark 100: No wetting and droplets do not scatter, Mark 90: Wetting may occur.
Droplets are scattered widely and irregularly, Mark 80: Wetting of the surface occurs at the water sprinkling point, Mark 70: The entire top surface is partially wetted, Mark 50: The entire top surface is wetted, Mark 0: Both sides are wetted. Get wet all over.

When applying the compounds of the invention to paper or other malleable porous substrates, the methods described above, as developed for textiles, can be applied as is or with minor modifications. .

Finally, when the compounds of the invention are applied to metal surfaces or other smooth or hard surfaces, the degree of oleophobicity is evaluated by placing a drop of "Nujol" paraffin oil on the surface.

The oleophobicity is good if the oil bran does not spread and the oil droplets flow without leaving any traces when the surface is tilted. The oleophobicity is zero if the oil droplet spreads out completely leaving a large wetted surface area on the inclined surface. If the oil droplets do not spread clearly and leave only a few traces of oil dripping when flowing on an inclined surface, the oleophobicity is fair. Evaluation of hydrophobicity is carried out in the same way by simply replacing oil with water. The compounds of the present invention give better performance for the same fluorine content than the simple random copolymers considered to be the base of common commercially available oleaginous compounds.

Oleophobic and hydrophobic compounds other than the compounds according to the invention are already known which exhibit better coating properties than simple random copolymers. Such compounds are disclosed in French Patent No. 21551.
It is stated in Specification No. 33. They contain one or more fluorinated monomers, optionally with a small proportion of one or more non-fluorinated monomers, and non-fluorinated acrylic resins (
This is obtained by polymerization in the presence of 20 to 8% by weight of the monomer/resin mixture. Preferred fluorinated monomers are the same as those that may be used in the present invention, and the resulting compounds may consist of the same constituents. These compounds can also impart oleophobic and hydrophobic properties to substrates (textiles or other types). However, the compounds of the invention give much better results for equal concentrations of fluorinated monomer, ie equal fluorine concentrations, as demonstrated in the comparative examples below. Next, the present invention will be specifically explained using examples.

In the examples, the abbreviations used refer to the following compounds.
AF6: The following fluorinated acrylate AF8: The following fluorinated acrylate Example 1 The compound of the present invention is used to prepare a fluorinated acrylic resin, and then a non-fluorinated monomer is polymerized in the presence of the resin. Obtained by.

a Reactant for producing the basic fluorinated acrylic resin: AF6 8 parts by weight stearyl
Methacrylate 2〃 1,1,1-trichloroethane 40〃 Lauroyl peroxide 0.1〃 The above reactants were placed in a reaction vessel, and after removing air by passing nitrogen, the reaction mixture was heated under a hawk at 74 qo for 3 heated for an hour.

Under these conditions, the polymerization of AF6 and stearyl methacrylate was almost complete. The polymer thus obtained was in the form of an approximately 20% solution in 1,1,1-trichloroethane. This solution was left in the reaction vessel. b
Preparation of Compounds According to the Invention The following reactants were added via an injection device to an open reactor containing the above solution: Stearyl methacrylate 9
Parts by weight Hydroxyethyl methacrylate 1 1,1,1-trichloroethane 40 Lauroyl peroxide 0.1 The thus obtained product contains the preformed fluorinated copolymer and the monomers and other reactants used. The resulting reaction mixture was heated under coagulation at 74 qo for 3 hours.

Under such conditions, the polymerization of the added monomer becomes almost complete, and the compound of the present invention becomes about 2% in 1,1,1-trichloroethane.
Obtained in the form of a 0% solution. Considering only the monomers used in this second step, the compounds of the invention are stearyl
Presence of 5% by weight of a fluorinated acrylic resin formed from a 90:1 combination of methacrylate and hydroxyethyl methacrylate and 5% by weight of a fluorinated acrylic resin formed from an 80:2 combination of fluorinated acrylate and stearyl methacrylate. It was obtained by polymerizing the following.

The fluorinated acrylate used in the first stage constitutes about 4% by weight of the target compound according to the invention. Example 2 Similar to Example 1, but reducing the amount of monomer used in the preparation of the base fluorinated acrylic resin and adding non-fluorinated ions that are subsequently polymerized in the presence of the resin. ○Operations were carried out by increasing the amount of monomer.

The amounts used are as follows: - Preparation of fluorinated acrylic resin: AF6 6 parts by weight Stearyl methacrylate 1.5 - Preparation of the compound according to the invention: Stearyl methacrylate 11.25 Hydroxyethyl methacrylate 1. 25 Each step of the preparation was carried out under the same conditions as in Example 1 in the presence of lauroyl peroxide in 1,1,1-trichloroethane solution.

Similar to Example 1, the final compound was obtained in the form of an approximately 20% solution in 1,1,1-trichloroethane.

The target compound is thus a fluorinated acrylic compound formed from a 90:1 blend of stearyl methacrylate and hydroxyethyl methacrylate and an 80:2 blend of fluorinated acrylate and stearyl methacrylate. It was obtained by polymerizing in the presence of 37.5% by weight of resin.

The fluorinated acrylate used in the first stage constitutes about 3% by weight of the compound according to the invention. Example 3 A run similar to Examples 1 and 2 was carried out except that the amount of monomer used at each stage of the production was varied as described below.

- Production of fluorinated acrylic resin: AF6 4 parts by weight Stearyl methacrylate 1 - Production of compounds according to the invention: Stearyl methacrylate 13.5" 1.5 parts by weight of hydroxyethyl methacrylate The polymerization conditions were the same as in Example 1, and the final The compound is 1,1
, in the form of an approximately 20% solution in 1-trichloroethane.

Thus, the target compound is 75% by weight of a 90:1Q combination of stearyl methacrylate and hydroxyethyl methacrylate and 25% by weight of a fluorinated acrylic resin formed from an 80:2 combination of fluorinated acrylate and stearyl methacrylate. It was obtained by polymerizing in the presence of %.

The fluorinated acrylate used in the first stage constitutes about 2% by weight of the target compound according to the invention. Example 4 The operation was carried out as in Example 1, but using the following monomers at each stage of production.

-*Production of hydrogenated acrylic resin: AF6 8 parts by weight Stearyl methacrylate 1 part by weight Hydroxyethyl methacrylate 1 part by weight -Production of the compound according to the present invention: Stearyl methacrylate 1 part by weight The operating conditions were the same as in Example 1, and the final The compound was obtained in the form of an approximately 2% by weight solution in 1,1,1-trichloroethane.

Thus, the target compound is stearyl methacrylate 5
80% by weight of fluorinated acrylate, stearyl methacrylate and hydroxyethyl methacrylate.
:10:1 by polymerization in the presence of 5% by weight of a fluorinated acrylic resin formed from a 10:1 mixture.

The fluorinated acrylate used in the first stage constitutes about 4% by weight of the target compound according to the invention. Example 5 The operation was carried out as in Example 1, but using the following monomers at each stage of production.

- Production of fluorinated acrylic resin: 8 parts by weight of AF6 - Production of compound according to the invention: stearyl methacrylate
10.8 Hydroxyethyl methacrylate 1.2
〃 The operating conditions were the same as in Example 1, and the final compound was 1,1
, obtained in the form of an approximately 20% solution in 1-trichloroethane.

The target compound is thus obtained by polymerizing 6% by weight of a 90:1 compound of stearyl methacrylate and hydroxyethyl methacrylate in the presence of 40% by weight of a fluorinated acrylic resin formed by polymerization of fluorinated acrylate alone. This is what was obtained by doing so.

The fluorinated acrylate used in the first stage constitutes about 4% by weight of the compound according to the invention. Example 6 The operation was carried out as in Example 1, but using the following monomers at each stage of production.

- Production of fluorinated acrylic resin: AF6 4 parts by weight - Production of compound according to the invention: Stearyl methacrylate 1
4.4″Hydroxyethyl methacrylate 1. Tablet weight parts The operating conditions were the same as in Example 1, and the final compound was 1.1
, in the form of an approximately 20% solution in 1-trichloroethane.

The target compound is thus prepared by polymerizing 8% by weight of a 90:1 mixture of stearyl methacrylate and hydroxyethyl methacrylate in the presence of 2% by weight of a fluorinated acrylic resin formed by polymerization alone with a fluorinated acrylate. It is obtained by polymerization.

The fluorinated acrylate used in the first stage constitutes about 2% by weight of the compound according to the invention. Example 7 Same as Example 1, except that stearyl methacrylate
The operation was carried out by replacing methacrylate with lauryl methacrylate.

The monomers used at each stage of the production are therefore as follows: - Preparation of the fluorinated acrylic resin: AF6 8 parts by weight Lauryl methacrylate 2 parts by weight - Preparation of the compound according to the invention: Lawalyl methacrylate 9 parts Hydroxyethyl methacrylate 1 The target compound was thus formed from 5% by weight of a 90:1 mixture of lauryl methacrylate and hydroxyethyl methacrylate and 5% by weight of an 80:2 mixture of fluorinated acrylate and lauryl methacrylate. It was obtained by polymerization in the presence of 5% by weight of a fluorinated acrylic resin.

The fluorinated acrylate used in the first stage constitutes about 4% by weight of the compound according to the invention. Example 8 The same machine as in Example 1 was run, but using heptyl methacrylate instead of stearyl methacrylate.

The monomers used at each stage of the production were therefore as follows: - Preparation of the fluorinated acrylic resin: AF6 8 parts by weight Heptyl methacrylate 2 - Preparation of the compound according to the invention: Heptyl methacrylate 9 〃 Hydroxyethyl methacrylate 1〃 Thus, the target compounds are heptyl methacrylate and hydride.

Polymerization of 5% by weight of a 90:1 combination of xyethyl methacrylate in the presence of 5% by weight of a fluorinated acrylic resin formed from an 80:2 combination of fluorinated acrylate and heptyl methacrylate. This can be achieved by doing so. The fluorinated acrylate used in the first stage constitutes about 4% by weight of the compound according to the invention. Example 9 The same operation as in Example 1 was carried out except that hydroxyethyl methacrylate was replaced with glycidyl methacrylate.

The monomers used in each step of the production were therefore: - Preparation of the fluorinated acrylic resin: AF6 8 parts by weight Stearyl methacrylate 2 - Preparation of the compound according to the invention: Stearyl methacrylate 9 Glycidyl methacrylate 1 The target compound is thus obtained by combining 5% by weight of a 90:10 mixture 5 of stearyl methacrylate and glycidyl methacrylate with fluorinated acrylic resin 5 formed from an 80:2 mixture of fluorinated acrylate and stearyl methacrylate. % by weight.

The fluorinated acrylate used in the first stage constitutes about 4% by weight of the compound according to the invention. Example 10 Example 1
The operation was carried out in the same manner as above, except that instead of the fluorinated acrylate AF6 having a perfluoro group at the C6 position, a fluorinated acrylate AF8 having a perfluoro group at the C8 position was used.

Accordingly, the monomers used at each stage of the production were as follows: - Production of fluorinated acrylic resin: AF8 8 parts by weight Stearyl methacrylate 2 - Production of the compound according to the invention: Stearyl methacrylate 9 - Hydroxy Ethyl methacrylate 1 Thus, the target compound contains 5% by weight of a 90:1 combination of stearyl methacrylate and hydroxyethyl methacrylate and 5% of the fluorine formed from an 80:2 combination of fluorinated acrylate and stearyl methacrylate. It was obtained by polymerizing in the presence of 5% by weight of acrylic resin.

The fluorinated acrylate used in the first stage constitutes about 4% by weight of the compound according to the invention. Example 11 Example 3
An operation was carried out in the same manner as above, but using fluorinated acrylate AF8 instead of fluorinated acrylate AF6.

The monomers used at each stage of the production were therefore as follows: - Preparation of the fluorinated acrylic resin: AF8 4 parts by weight Stearyl methacrylate 1 - Preparation of the compound according to the invention: Stearyl methacrylate 13.5 Hydroxyethyl methacrylate 1.5 The target compound is thus formed from a 90:IQ combination of stearyl methacrylate and hydroxyethyl methacrylate, 75% by weight, and an 80:2 combination of polyester acrylate and stearyl methacrylate. It was obtained by polymerization in the presence of 25% by weight of a fluorinated acrylic resin.

The fluorinated acrylate used in the first stage constitutes about 20% by weight of the compound according to the invention. The fluorine contents of the polymers of the present invention obtained in Examples 1 to 11 above are shown below. The fluorine content was determined according to known methods using Schönigel (
This was carried out by metallizing or flaring in a Schoni flask and then quantifying fluorine ions by an ionometric method using special electrodes.

Example 12 (Comparative example) AF6 produced from a random copolymer from the following monomers
8 parts by weight Stearyl methacrylate 11 Hydroxyethyl methacrylate 1 These monomers were polymerized in 1,1,1-trichloroethane in the same manner as in Example 1 in the presence of lauroyl peroxide.

However, in contrast to Example 1, in this comparative example all the monomers used in each step of the preparation of the compound according to the invention were polymerized together in one step (i.e. all the monomers were (into the mixture). The resulting random copolymer has the same overall composition as the inventive compound in Example 1, but was produced by a simple one-step copolymerization of all the monomers used, and is similar to the inventive compound in Example 1. not included within the scope.

Example 13 (Comparative Example) A simple random copolymer was prepared from the following monomers as in Example 12: AF6 6
parts by weight stearyl methacrylate 12.75 parts by weight hydroxyethyl methacrylate 1.25 parts by weight The random copolymer obtained has the same overall composition as the compound of Example 2, but does not constitute a compound according to the invention.

Example 14 (Comparative Example) A simple random copolymer was prepared from the following monomers as in Example 12: AF6
4 parts by weight stearyl methacrylate 14.5 hydroxyethyl methacrylate 1.5 The random copolymer obtained has the same overall composition as the compound of Example 3, but does not constitute a compound according to the invention.

Reference Example 1 (Example of coating on cotton poplin) A test was conducted in which the compound (indicated by Example No.) produced in the above examples (including comparative examples) was coated on cotton poplin at a weight of 140 g. Ta.

In the above example the compound was obtained in the form of an approximately 20% solution in 1,1,1-trichloroethane.

These solutions were diluted with the same solvent to a concentration of 1% and applied onto textile fabrics. The amount of dry matter deposited was 1.1-1.2% by weight, based on the fiber fabric. The resulting fabric samples were heat treated at 150°C for 5 minutes and then conditioned by standing in ambient air for at least 2 hours. The degree of oleophobicity and hydrophobicity of the coating was then determined by the methods described above. The obtained results are calculated as the amount (wt%) of the fluorinated acrylate (AF6 or AF8) used in the production of the test compound.
and are shown in the table below.

From the above results, it is recognized that the fiber fabrics treated with compounds 1 to 11 according to the present invention have good water resistance and oil resistance.

On the other hand, compounds 12, 13 and 14, which are simple random copolymers containing the same components as compounds 1, 2 and 3 of the present invention, respectively, but which are outside the scope of the present invention, have much lower (sometimes even 0) Shows wisteria oil property and hydrophobicity. This difference in performance is particularly noticeable for compounds containing approximately 30% and 20% fluorinated acrylate. Reference Example 2 (Example of Coating on Polyester-Cotton Poplin) The various compounds described in Examples 1 to 14 were coated on polyester-cotton poplin having a weight of 12 female/bottom and a composition ratio of 65:35.

The coating conditions and firing of the treated fiber cloth were the same as in Reference Example 1.

The amount of dry substance deposited is of the order of 1% by weight, based on the fiber fabric. The results obtained are shown below.

From the above table, it can be seen that compounds 1 to 11 according to the invention show overall high values for oleophobicity and hydrophobicity, and these values are close to the values obtained for cotton poplin in Reference Example 1. .

The three compounds (12, 13 and 14) as simple random copolymers which are outside the scope of the invention are compounds of the invention containing the same amount of fluorinated acrylate, in particular compounds of the invention each consisting of the same constituents. Compared to compounds 1, 2 and 3, it exhibits much lower lipophobicity.

This difference is especially true for fluorinated acrylate contents of 20% and 30%.
This is noticeable in the compounds of Reference Example 3 (Example of coating on paper) Compounds 1, 2, 7, 8 and 9 were tested in coating on unsized light coated paper weighing 73 g.

The test compounds were used in the form of 1% solutions in 1,1,1-trichloroethane, and paper samples were soaked in these solutions, drained, and dried.

The amount of dry matter deposited was of the order of 1.1% by weight, based on the paper. The test results are shown below.

It should be noted that the unsized paper used in the test has a high absorbency for oil and water due to its nature.

It is therefore observed that the oleophobic and hydrophobic efficiency of the compounds according to the invention is particularly remarkable. Reference example 4 (Example of application on leather goods) Compounds 1, 2 and 3 in the form of a 1% solution in 1,1,1-trichloroethane are used in the manufacture of footwear, clothing and decorative leather goods. It was applied to smooth and flexible leather by powdering.

The leather treated in this way was not wetted by either water or paraffin oil. Reference Example 5 (Example of application to metal surface) Compounds 1, 2 and 3 in the form of a 1% solution in 1,1,1-trichloroethane were brushed onto an aluminum specimen, mattified and completely coated. Degreased.

The specimen before application of the fluorinated compound was wet with water and oil;
No water or oil wetting occurred after treatment. Water and paraffin oil droplets placed on treated metal paper strips did not spread and flowed without leaving a trace when the coupon was tilted. Reference Example 5 Comparison of the compound according to the present invention and the compound described in French Patent No. 2155133 Compound A (compound according to the French patent) A non-fluorinated acrylic resin was first produced by polymerization of the following monomers: stearyl Methacrylate 9 Parts by weight Hydroxyethyl Methacrylate 1'' The following monomer mixture was then polymerized in the presence of this copolymer: AF6 8 Parts by weight Stearyl Methacrylate 2 The polymerization operations at each stage were the same as in Example 1 above. 1,1,1-triclo in the presence of lauroyl peroxide under conditions.

It was carried out in ethane solvent. It will be appreciated that Compound A thus obtained was produced from the same raw materials as the compound of Example 1 (Compound 1).

Furthermore, the operating conditions were chosen similarly. The only significant difference is that the monomers used to prepare the base acrylic resin and the monomers subsequently polymerized in the presence of this resin are reversed as in Example 1. be. Compound B (compound according to the French patent) A non-fluorinated acrylic resin was first prepared by polymerization of the following monomers: 11.25 parts by weight of stearyl methacrylate 1.25 parts by weight of hydroxyethyl methacrylate, then in the presence of this copolymer. The following monomeric polymer was polymerized: AF6 6 parts by weight stearyl methacrylate 1.5'' The run was carried out under the same conditions as above.

Compound B thus obtained was produced from the same raw material components as the compound of Example 2 (Compound 2), but the presence of this resin was similar to that of the monomer used to produce the basic acrylic resin. The monomers polymerized below are the opposite of those in Example 2.

Compound C (compound according to the French patent) Under the same conditions as above, first the following monomer: stearyl
A non-fluorinated acrylic resin is prepared by polymerizing 13.5 parts by weight of methacrylate 1.5 parts by weight of hydroxyethyl methacrylate, and then in the presence of this copolymer the following monostar mixture: AF6
4 parts by weight of stearyl methacrylate 1 was polymerized.

Compound C thus obtained was produced from the same raw material components as the compound of Example 3 (Compound 3), but the presence of this resin was similar to that of the monomer used to produce the basic acrylic resin. The monomers polymerized below are the opposite of those in Example 3.

Comparison of compounds A, B, C according to the French patent with compounds 1, 2, 3 according to the invention These compounds were applied to cotton poplin under the conditions described in Reference Example 1.

The results obtained are shown in the table below along with the amount (% by weight) of fluorinated acrylate (AF6) used in the production of the test compound. Compounds 1, 2, and 3 exhibit better coating properties than compounds A, B, and C for equal amounts of acrylate used.

Claims (1)

[Scope of Claims] 1. One or more non-fluorinated alkyl acrylates or methacrylates (where the alkyl group has 1 to 2 carbon atoms)
0) in the presence of 20 to 80% by weight of a fluorinated acrylic or methacrylic resin based on the total weight of the non-fluorinated alkyl acrylate or methacrylate and the fluorinated acrylic or methacrylic resin. 1. A method for producing an oleophobic and hydrophobic fluorinated polymer, the method comprising polymerizing an oleophobic and hydrophobic fluorinated polymer. 2. The method according to claim 1, wherein the fluorinated acrylic or methacrylic resin used is a homopolymer of fluorinated acrylic ester or methacrylic ester. 3. The method according to claim 1, wherein the fluorinated resin used is a copolymer based on one or more fluorinated acrylic esters or methacrylic esters. 4
Claims in which the copolymer further comprises one or more non-fluorinated monomers which may account for up to 50% by weight of all fluorinated and non-fluorinated monomers used in its preparation. The method described in Section 3. 5 Homopolymers of fluorinated acrylic esters or methacrylic esters have the general formula: ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, C_nF_2_n_+_1 is a straight or branched perfluoro chain in which n is 1 to 20. represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, an aryl group optionally substituted with an alkyl group having 1 to 6 carbon atoms, or a group -R'-O
H (R' is an alkylene group having 2 to 4 carbon atoms)] is produced from a monomer selected from acrylic esters or methacrylic esters of fluorinated alcohols. The method described in Section 2. 6 A copolymer based on one or more fluorinated acrylic esters or methacrylic esters has the general formula: ▲
There are mathematical formulas, chemical formulas, tables, etc. A cycloalkyl group having 5 to 12 carbon atoms, an aryl group optionally substituted with an alkyl group having 1 to 6 carbon atoms, or a group -R'-O
H (R' is an alkylene group having 2 to 4 carbon atoms)] manufactured from one or more monomers selected from acrylic esters or methacrylic esters of fluorinated alcohols. The third claim is
The method described in section. 7. The fluorinated component of a copolymer based on one or more fluorinated acrylic esters or methacrylic esters and containing one or more non-fluorinated monomers is defined in claim 6. The method according to claim 4, which is produced from one or more monomers selected from the acrylic esters or methacrylic esters of the fluorinated alcohols described. 8 The non-fluorinated monomers constituting part of the copolymer include alkyl acrylates and methacrylates, hydroxyethyl acrylates and methacrylates, hydroxypropyl acrylates and methacrylates, glycidyl acrylates and 8. A method according to claim 4 or claim 7, wherein the material is selected from methacrylate, acrylic acid, methacrylic acid, acrylamide and N-methylolacrylamide.