DE2951922A1 - POLYMERES CONTAINING A PERFLUORALKYL GROUP IN ITS SIDE CHAIN, PROCESS FOR ITS PRODUCTION AND COATING MEASUREMENT OR CONTAINING IT -PREPARATION - Google Patents

Description

T 52 091

Applicant: Daikin Kogyo Co., Ltd.

No. 12-39, Umeda 1-chome, Kita-ku, Osaka _f Japan

Polymer that has a perfluoroal-

contains kylgruppe, process for its preparation

and coating composition or preparation containing it

The invention relates to a new polymer which contains a perfluoroalkyl group in its side chain, a process for its preparation and its use in a Coating compound or preparation and the coating compound or preparation obtained in the process.

Various types of coating compositions or preparations, such as paints, protective coating compositions and hair-styling compositions or preparations, are already known. in the generally, the coating composition mainly consists of a film-forming resin and a Solvent and it is applied to a base to form a film.

British Patent 1,290,367 discloses a film-forming resin for hair styling compositions or preparations described polymer used which contains a perfluoroalkyl group in its side chain. With the polymer it is a reaction product of a maleic anhydride / vinyl ether copolymer with a compound containing a perfluoroalkyl group. In the said British patent it is stated that the polymer is a

030030/061 5

improved balance of properties between the requirements for softness and curl retention and gives the hair a good hold at relatively high levels of moisture. The polymer however, it is remarkably poor in compatibility with film-forming resins and solvents. This polymer therefore does not give a satisfactory result in terms of smoothness Film surface when not used alone.

The aim of the present invention is to develop a new polymer which contains a perfluoroalkyl group in its side chain and which, when used in a mixture with a film-forming resin in a coating composition or preparation, has good compatibility (compatibility) with film-forming resins and solvents, so as to obtain a coating composition or -zubereitung with excellent leveling properties and excellent storage stability, and improves the smoothness of the surface of the film of the coating composition or -zubereitung by preventing that, when the film undesirable phenomena such as ". orange peel and whitening occur. Another object of the invention is to provide a method for making this new polymer. It is also an object of the invention to provide a coating composition containing the novel polymer in admixture with a film-forming resin.

These and other goals, features and advantages of the invention

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-y-

application can be found in the following description.

An object of the invention is a polymer in which it is an addition reaction product of a polymer of the general formula

pil pil

1 * 11 ^ \ s \ 1

² IR

CH - CH - j

I I

C = O C = O

¹ I 1

OH OR ¹

(D

where R is a phenyl or alkoxyl group with 1 to 12 carbon atoms, R is an alkyl group with 1 to 12 carbon atoms and η is an integer from 10 to 2000,

with an epoxy compound selected from group

(Ha) (Hb)

(lic)

R _f SO, NCH, CH

R ^{2 X (K} and R ^ OCH ₇ CH CH ₀

wherein R _{f is} a perfluoroalkyl group with 3 to 20 carbon

atoms and R is an alkyl group with 1 to 12 carbon atoms,

is, the addition reaction product per mole of the repeating unit of the polymer of the formula (I) 0.1 up to 50 mol.-X of the epoxy compound of the formulas (Ua) -

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to (lic) contains derived group.

The polymer according to the invention has good compatibility (compatibility) with those described below film-forming resins and solvents, which are generally used for coating compositions or coating preparations, and the result is a coating composition or preparation having excellent leveling properties and excellent storage stability, when it is incorporated into the coating material or preparation will. The film produced from such a mass or preparation has a significantly improved smoothness Film surface without unfavorable phenomena such as orange peel and whitening.

The polymer according to the invention differs clearly from the polymer described in the above-mentioned British patent specification 1,290,367 in that the polymer according to the invention together with the side chain containing a perfluoroalkyl group has a side chain Contains alkoxycarbonyl group which does not contain a fluorine atom (-COOR in the formula (I)), while the polymer according to the said British patent contains no such alkoxycarbonyl group as a side chain. The polymer of the present invention has much better compatibility (compatibility) with the above-mentioned film-forming resins and solvents than the polymer of the aforesaid British patent based on the above Structural difference between the two polymers. The consequence of this is that the polymer according to the invention is a film with a very smooth surface when it results

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is mixed with a film-forming resin than the polymer according to the aforementioned British patent.

Since the polymer of the present invention is produced by the addition reaction of the carboxyl group of the polymer of Formula (I) and the epoxy group of the epoxy compound, the degree of polymerization of the polymer according to the invention is the same the degree of polymerization "n" of the polymer of the formula (I), and therefore it has a degree of polymerization of 10 to 2,000. The preferred degree of polymerization is within the range of 50 to 1,500. When the degree of polymerization is below the above range, it tends to be the polymer to plasticize the film-forming resins. If the degree of polymerization is above the above range, the polymer has poor compatibility with the film-forming resins on.

The polymer according to the invention contains 0.1 to 50 MoL-X _9, preferably 1 to 30 mol% of the group derived from the epoxy compound containing the perfluoroalkyl group per mol of the repeating unit of the polymer of the formula (I). If the content of the group derived from the epoxy compound is below the above range, the polymer has a poor effect in improving the smoothness of the film surface. If the content of the group derived from the epoxy compound is above the above range, the polymer has poor compatibility (compatibility) with and insolubility in the coating compositions or preparations (film-forming resins and / or solvents).

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ΛΑ.

teIn).

The polymer of the formula (I) used according to the invention contains, as side chains, an alkoxycarbonyl group which does not contain any Fluorine atom contains (-COOR), and a free carboxyl group (-COOH). Examples of such a polymer include Vinyl ether / maleic acid monoalkyles.ter copolymers, which are polymers of the formula (I) in which R represents an alkoxyl group having 1 to 12 carbon atoms, and styrene / maleic acid monoalkyl ester copolymers which are polymers of the formula (I) in which R is a phenyl group. Examples of the alkoxyl group represented by R in formula (I) are Methoxy, ethoxy, propoxy and butoxy. Examples of the alkyl group represented by R in formula (I) are methyl, ethyl, propyl and butyl.

The preferred polymer of the formula (I) is one in which R is an alkoxyl group with 1 to 4 carbon atoms, R is an alkyl group with 1 to 4 carbon atoms and η is an integer from 50 to 1,500.

The epoxy compounds used according to the invention are the compounds of the formulas (Ha), (lib) and (lic). _{Examples of the perfluoroalkyl group represented by R f} in formulas (Ha) to (lic) are perfluoropropyl, perfluorobutyl, perfluoropentyl, perfluorohexyl, perfluorooctyl, perfluomonyl and perfluorodecyl. The preferred perfluoroalkyl group contains 3 to 10

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Y-

Carbon atoms. Examples of the alkyl group included in the

2 Formula (lib) represented by R are methyl, ethyl, Propyl, butyl, hexyl, octyl and dodecyl. The preferred alkyl group contains 1 to 3 carbon atoms.

Typical examples of the epoxy compound are 3-perfluoropentyl-1,2-epoxypropane, 3-perfluorononyl-1,2-epoxypropane, 3-perfluorodecyl, 2-epoxypropane, 3- [N- (ethyl) -perfluorooctanesulfonamido] -l, 2-epoxypropane, 3- [N- (propyl) -perfluorooctanesulfonamido] -1, 2-epoxypropane, perfluoroisopropyl glycidyl ether and perfluoropentyl glycidyl ether.

The polymer of the invention is prepared by subjects the polymer of formula (I) to an addition reaction with the epoxy compound. In the addition reaction the carboxyl group contained in the polymer of the formula (I) reacts with that in the epoxy compound of the formulas (Ha) to (lic) containing epoxy group according to the following Reaction scheme:

(1) polymer (l) ♦ epoxy compound (Ha)

-au -

cn I

CH - CH

C = OC = O OR ¹

OCH, ClICH, R _r 2 j Zf

OH

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- γ.

(2) polymer (l) + epoxy compound (llb)

CH ₉ CH - CH — CH-

² III

R C = O C = O

OCH ₂ CHCH ₂ NO ₂ SR _£ OH R ²

(3) polymer (I) + epoxy compound (lic)

CH, - CiI - CII - CH

² III

R C = O C = O

OCH ₉ CHCH ₉ OR ,. OH

The addition reaction is preferably in the presence of a tertiary amine or a quaternary ammonium salt as Catalyst performed to increase the rate of conversion of the perfluoroalkyl group-containing Epoxy compound which is expensive to increase. Preferred examples of the tertiary amine are triethylamine, diazabicycloundecene and diazabicyclononane. Preferred examples of the quaternary ammonium salt are trimethylbenzylammonium chloride and trimethylhexadecylammonium chloride.

As a rule, the addition reaction is carried out in a solvent which is capable of the starting materials, namely the polymer of the formula (I) and the

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-f-

Epoxy compound, as well as to dissolve the polymer formed. Examples of suitable solvents are alcohols having a boiling point of 40 to 200 ⁰ C, such as methanol, ethanol, isopropanol and butanol, and ketones having a boiling point of 40 to 200 ° C, such as acetone, methyl ethyl ketone and methyl isobutyl ketone. As the solvent, the alcohols are preferred because the addition reaction proceeds smoothly. When a polymer having a high content of the group derived from the epoxy compound is desired, mixed solvents of the above alcohols or ketones and fluorine-containing solvents such as benzotrifluoride, hexafluoro-m-xylene, trichlorotrifluoroethane and tetrachlorodifluoroethane are preferably used. Higher temperatures are preferred as the reaction temperature, since the reaction is completed within a shorter period of time. Usually, however

Temperatures close to the reflux temperature of the

o the solvent used, such as 40 to 200 C, applied.

According to the present invention, the desired polymer containing a perfluoroalkyl group is satisfactorily obtained in the addition reaction in which the above-described reaction catalyst is used.

The polymer according to the invention, which in its side chain contains a perfluoroalkyl group, is particularly suitable as an additive for coating compositions or preparations. D. That is, when the polymer of the present invention is used in admixture with a film-forming resin to produce a film, the leveling properties of the film-forming resin are improved upon coating, resulting in

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ν-

improvements in the uniformity of thickness and smoothness of the film and also in terms of gloss and the homogeneity of the film leads.

The invention also relates to a coating composition or preparation which contains or consists of at least a polymer according to the invention as defined above which contains a perfluoroalkyl group in its side chain, and at least one film-forming resin. The coating composition or preparation according to the invention is produced in the usual way, for example by mixing the polymer according to the invention with the film-forming resin or by applying dissolve or swell the polymer according to the invention and the film-forming resin in a suitable solvent. The coating composition or preparation according to the invention is in various forms, for example in In the form of a solution, a powder or an aerosol, depending on the intended use.

Examples of film-forming resins which can be used in the present invention are epoxy resins such as the reaction products of epichlorohydrin and polyhydroxyphenols (such as bisphenol A), the contain at least two epoxy groups per molecule and are liquid or solid at normal temperature with a melting point of not more than 160 C; Acrylic resins such as homopolymers or copolymers of acrylic monomers (such as 2-hydroxyethyl methacrylate, N-butoxymethylacrylamide, glycidyl methacrylate, methyl methacrylate, butyl methacrylate, lauryl methacrylate, butyl acrylate, diacetone acrylic acid, acrylic acid and Methacrylic acid) and copolymers of the above acrylic

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monomeric and vinyl monomers (such as ethylene, vinyl acetate and vinyl chloride); Alkyd resins such as polycondensation products of polybasic acids (such as phthalic anhydride, isophthalic acid and maleic acid) and polyols (such as glycerin) and the Above mentioned polycondensation products, modified with drying oils, rosin (turpentine resin), phenolic resin, Silicone resin or a vinyl monomer (such as vinyl toluene); Polyamides such as polyamides represented by the following formula

- [- Nil— R ³ —CO-I-

3 wherein R is an alkylene group having 4 to 12 carbon atoms (such as pentamethylene), and polyamides of the following formula

-P NH - R ⁴ - NIl - CO - R ⁵ - CO 4—

L. J Iu

4th wherein R is an alkylene group having 4 to 12 carbon atoms (such as hexamethylene) and R is an alkylene group of 4 to 12 Mean carbon atoms (such as tetramethylene); Cellulose derivatives such as nitrocellulose, cellulose acetate, benzyl cellulose and ethyl cellulose; Homopolymers of alkyl vinyl ethers (wherein the alkyl group has 1 to 4 carbon atoms), Copolymers of the above-mentioned alkyl vinyl ether and a maleic acid monoalkyl ester (in which the alkyl group is 1 to 4 Having carbon atoms) and copolymers of ethylene and the above-mentioned maleic acid monoalkyl ester; and copolymers of vinyl pyrrolidone and at least one compound from the group vinyl acetate, styrene, vinyl chloride, vinylidene chloride and ethylene. The polymer of the invention is usually in an amount of 0.05 to 2 parts by weight

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100 parts by weight of the film-forming resin used. If the amount of the polymer according to the invention is above the is in the above range, the resulting mass or preparation becomes cloudy in some cases. When the crowd of the polymer according to the invention is below the abovementioned range, the pronounced effects of the polymers according to the invention not on. Examples of suitable solvents are methanol, ethanol, isopropanol, Butanol, toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone and ethylene glycol ethyl ether and mixtures of that.

The composition or preparation according to the invention can also contain other additives, such as pigments, plasticizers, perfumes, dyes and surface-active agents, depending on their intended use. The mass or preparation according to the invention can be used for various purposes can be used, for example as paints, protective coating compositions or preparations and hair-styling compositions or preparations.

In addition to being used as an additive for the coating compositions or preparations described above, the Polymers can also be used with advantage for other interesting uses. For example, this is Polymers, modified with amines, used as sizing agents for papers, and the polymer in admixture with Proteins or synthetic surfactants is used as a foam flame extinguishing agent.

According to a preferred embodiment, the invention relates to

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a polymer that contains a perfluoroalkyl group in its side chain, which is an addition reaction product of a polymer of the general formula

- CH

2 ■

CII- -CH- -CH I. I. \ R. C = O C = O I.
OH OR ¹

(D

where R is a phenyl or alkoxyl group with 1 to 12 carbon atoms, R is an alkyl group with 1 to 12 carbon atoms and η is an integer from 10 to 2000,

with an epoxy compound selected from group

R, CH ₉ CH CH ,,

f 2 \ "/ 2»

RrSO ₉ NCH ₉ CH-CH ₉ £ 2.2 ^ / 2

(Ha) (Hb)

R, OCH ₉ CH CH ₉

f 2 \ _0/2

(lic)

wherein R- is a perfluoroalkyl group with 3 to 20 carbon

atoms and R is an alkyl group with 1 to 12 carbon atoms,

is, the addition reaction product per mole of the repeating unit of the polymer of the formula (I) 0.1

up to 50 mol% of the epoxy compound of the form In (I Ia) to (lic) originating group

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contains pe. The polymer has good compatibility with film-forming resins and solvents and improves the leveling properties of a coating composition or preparation when it is incorporated into them and the surface smoothness of the resulting mass or Preparation produced film.

The invention is illustrated in more detail by the following examples, without, however, being restricted thereto. The one in it Unless stated otherwise, the percentages given relate to weight.

example 1

20.2 g of an alternating methyl vinyl ether / monoethyl maleate copolymer with a molecular weight of about 2.1 10 (available under the trade name "Gantrez ES-225 "in the form of a 50% ethanol solution, manufactured by GAF Corporation). 5.26 g of 3-perfluorononyl-1,2-epoxypropane, 0.1 g of triethanolamine and 250 g of ethanol were added. The mixture was stirred for 16 hours under reflux (80 ⁰ C). After the completion of the reaction, ethanol was distilled off under reduced pressure with heating at 80 to 95 ° C to obtain a solid crude product. The product was extracted with three 500 g portions of hot trichlorotrifluoroethane (about 47 ° C.) in order to remove the unchanged epoxy compound. The purified polymer was dried in a vacuum desiccator for 24 hours at room temperature.

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The infrared spectrum of the polymer obtained was different from that of that used as the starting material Methyl vinyl ether / monoethyl maleate copolymers and instructed Maximum at 1260 cm on that of the perfluoroalkyl group originated. Elemental analysis of the polymer showed that it contained 21.05% fluorine, from which it was calculated that Polymers per mole of the repeating unit of the starting copolymer contained 18 mol% of the group derived from the epoxy compound.

Example 2

The same procedures were used as in Example 1, but this time 23.0 g of an alternating Methyl vinyl ether / monobutyl maleate copolymers with a molecular weight of about 2.5 10 (available under the Trade name "Gantrez ES-425" in the form of a 50% ethanol solution, manufactured by GAF Corporation) were used in place of the methyl vinyl ether / monoethyl maleate alternating copolymer, and the amount of 3-perfluorononyl-1,2-epoxypropane was changed to 2.63 g for the production of a polymer.

The infrared spectrum of the polymer obtained differed differed from that of the methyl vinyl ether / monobutyl maleate copolymer used as the starting material and it was pointed a maximum at 1260 cm "originating from the perfluoroalkyl group. Elemental analysis of the polymer showed that it contained 10.1% fluorine, from which it was calculated that the polymer per mole of the repeating unit of the starting copolymer is 7.5 mole percent of that of the epoxy compound

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derived group. Example 3

In a 500 ml four-necked flask equipped with a thermometer, a stirrer and a reflux condenser, 20.2 g of an alternating styrene / maleic anhydride copolymer with a molecular weight of about 1.0 10 (which was prepared according to the method described by Dr. H. Cherdron et al in ¹¹ Kobunshi Kagaku Jikkenho ", page 161 (Experiment No. 346), Asakura-Shoten, Tokyo, 1968) and 250 g of ethanol was introduced. The mixture was refluxed (80 ° C.) for 3 hours. At this stage, it was confirmed by infrared analysis that the starting copolymer was converted into a half ester, and 58.3 g of 3- [N- (ethyl) perfluorooctanesulfonamido] -l, 2-epoxypropane and 0.2 g of triethylamine were added to the mixture The resulting mixture was stirred under reflux for 16 hours, and after the reaction had ended, the ethanol was distilled off, followed by purification by extraction with hot trichlorotrifluoroethane and drying in the same manner as in Example 1 followed to obtain a polymer.

The infrared spectrum of the obtained polymer had a maximum at 1260 cm "which was derived from the perfluoroalkyl group. Elemental analysis of the polymer found that it contained 8.7% fluorine, from which it was calculated that the polymer was per mole of the repeating unit of the starting copolymer 8 , 0 mol% of the group derived from the epoxy compound.

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Example 4

To prepare a polymer, the same procedures as in Example 1 were repeated, this time using 13.6 g an alternating butyl vinyl ether / monobutyl maleate copolymer with a molecular weight of about 2.0 10 (prepared according to that in the above-mentioned literature reference described method) were used instead of the alternating ethyl vinyl ether / monoethyl maleate copolymers and the amount of 3-perfluorononyl-1,2-epoxypropane in 7.9g was changed.

The infrared spectrum of the polymer obtained had a maximum at 1260 cm ", that of the perfluoroalkyl group originated. The elemental analysis of the polymer showed that the polymer contained 24.1% fluorine, from which it was calculated that the polymer was per mole of repeating unit of the starting copolymer contained 28.0 mol% of the group derived from the epoxy compound.

Example 5 and Comparative Example 1

To 100 parts of a liquid epoxy resin (molecular weight about 380, epoxy equivalent 184-194, commercially available under the trade name "Epikote 828", manufactured by Shell Kagaku Kabushiki Kaisha), 10 parts of the obtained diethylene triamine as a curing agent and 0.2 parts of the Example 2 Polymers added for the production of a coating composition or preparation.

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- ¹ X;

For comparison, 100 parts of the same epoxy resin were used as above mixed with only 10 parts of diethylenetriamine to produce a coating composition or preparation.

Each composition or preparation was applied to a polypropylene film by means of a coating rod and dried at room temperature to produce a 0.1 mm thick film. The smoothness of the obtained film was judged with the naked eye. The results obtained are shown in Table 1 below.

Table I mass or preparation (parts). .

of the film

Epoxy resin diethylenetri-polymer

amine of example 2

Example 5 100 10 O ₁ 2 smooth See example l 100 10 0 waves

shaped

From Table I above, it can be seen that the conventional amine hardener type epoxy resin composition (Comparative Example 1) was repelled from the substrate because the Compound had a higher surface tension than the base and therefore no film with a smooth surface, but a film having a wavy surface was obtained. In contrast, the composition of the invention (Example 5) in which the polymer of the invention was incorporated into the conventional amine hardener type epoxy resin (Comparative Example 1) gave a film with a smooth surface.

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Examples 6 to 8

For each of the film-forming resins shown in Table II below, the polymer obtained in Example 1 was used in added in an amount of 0.1%. The mixture was dissolved in the solvent indicated in Table II to prepare a 5% solution.

The solution was placed on a 5 cm × 20 cm glass plate applied for thin layer chromatography and dried at room temperature. The transparency and the smoothness of the obtained film were evaluated. The results obtained are given in Table II below. the Compatibility (compatibility) of the polymer according to the invention with the film-forming resins was determined from the results.

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Table II

Ex. No.

film-forming resin

solvent

Movie

transparency

smoothness

soluble nylon ¹ )

CO O O CO O

7 8

Acrylic resin Ethy! Cellulose

Ethanol

Methyl ethyl ketone Ethanol

transparent transparent transparent

Well
Well

Well

manufactured by Toray Kabuhiki Kaisha

2}

manufactured by Daidou Kasei Kogyo Kabushiki Kaisha

CD

cn

CD

ro ro

From Table II above, it can be seen that the films made from the film-forming resins ^ blended with that of the invention Polymers, neither white nor cloudy, which showed that the polymer according to the invention had good compatibility (Compatibility) with the film-forming resins.

Examples 9 to 11 and Comparative Examples 2 to 4

To each of three kinds of commercially available hair styling agents shown in Table III, the polymer obtained in Example 1 was added in an amount of 0.1%. The mixture was dissolved in ethanol to make a 5 % solution.

1 g of the solution was precisely weighed out and placed on a laboratory dish with a diameter of 2.25 cm. The shell was allowed to stand at 19 C and a relative humidity of 60%. According to those given in Table III below The amount of solvent evaporated (amount of ethanol) was determined for periods of time.

For comparison, a 5% ethanol solution was used for each of the the same hair styling agents as were used above, without using the polymer according to the invention. With the ethanol solution, the amount of solvent evaporated was determined in the same manner as above. The one with it The results obtained are shown in Table III below.

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Table III

amount of solvent evaporated (g)

Hair styling agents according to the invention. —— - -

Polymer ₃₃

co Ex. 9 Plascize L-53P ^J added 0.22 0.35 0.67 ο

° ßfisp.2 " ^{not to} 8 ^e s ^e ben 0.22 0.39 0.85> V

7 ^

Example 10 MVE-MBM-Copoly- _Λ " _{Λ οο} "

meres neutralized added 0.22 0.33 0.57

with AMPD ² )

Y ₁ ] “not added 0.27 0.39 0.72 Ex. 3

Example 11 vinyl pyrrolidone ^ _2Ugege ben 0.23 0.36 0.59

Vinyl acetate co, ^{6 6} "* ro

polymer <^

See ι. not added 0.26 0.48 0.89 - »

Footnotes to Table III:

Trade name for a product made by neutralizing an acidic copolymer of acrylic acid, acrylates such as butyl acrylate and diacetone acrylic acid, and methacrylates such as methyl methacrylate, butyl methacrylate and Lauryl methacrylate, with 2-amino-2-methyl-1-propanol, manufactured by Goo Kagaku Kogyo Kabushiki Kaisha

Product made by neutralizing a methyl

vinyl ether / monobutyl maleate copolymers with 2-amino-2-methyl-1,3-propanediol up to a degree of 25%.

As can be seen from the above Table III, in the case of the compositions or preparations in which the polymer according to the invention was used in a mixture with the conventional hair styling agent (Examples 9 to 11), the solvent contained therein hardly, compared with the compositions or preparations in which the inventive Polymers was not included (Comparative Examples 2 to 4) · The consequence of this is that when making a film from the mass or preparation according to the invention the leveling of the mass or preparation in a suitable manner is controlled (controlled).

Example 12 and Comparative Examples 5 to 7

The above-mentioned commercial hair styling agent Plascize L-53P was the polymer obtained in Example 4 in added in an amount of 0.05%. The mixture was dissolved in ethanol to make a 5% solution.

For comparison, Plascize L-53P was used with polyoxyethylene (10) -

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■ / -

cetyl ether (the number in brackets indicates the average number of moles of ethylene oxide added per mole Alcohol an) as a surfactant was mixed in an amount of 5% and the mixture was dissolved in ethanol for the preparation of a 5% solution (comparative example 5). Plascize L-53P was made with polyoxyethylene (20) sorbitol monolaurate as a surfactant in an amount of 10% and the mixture was dissolved in ethanol to prepare a 5% solution (Comparative Example 6). Plascize L-53P was dissolved in ethanol to produce a 5% solution (Comparative Example 7).

Each of the solutions and a propellant mixture of dichlorodifluoromethane and trichloromonofluoromethane (weight ratio 70:30) were placed in a container for an aerosol in a ratio of solution to propellant of 40:60 (based on weight) introduced for production of a hairspray for styling hair.

Using the hairspray obtained, the hair styling preparation was sprayed onto a 5 cm × 20 cm glass plate for thin layer chromatography for two seconds and dried for 24 hours at room temperature. The smoothness of the surface of the film obtained was determined and the hardness of the film was measured at 21 C and a relative humidity of 54% using the Sward Rocker hardness tests b "rs% IMMT _t at which the curing of a polished glass plate, and a polymethyl methacrylate with 50 and 20 are specified. The results obtained are given in Table IV below.

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Table IV

Component mixed with Plascize L-53P

Art

Lot (%)

Example 12 polymer according to Example 4

0.05

See Example 5 polyoxyethylene (10) -cetyl ether

See Example 6 polyoxyethylene (20) sorbitol monolaurate

See example 7

5 10 film

smoothness

smooth

hardness

24

waves
shaped 21 waves
shaped 17th waves
shaped 23

CO

cn

—Λ

CD K)

■ ο, ή.

From Table IV it can be seen that the film produced from the preparation in which the polymer according to the invention is in Combination with the commercially available hair styling agent (Example 12) had a significantly better smoothness and had beauty without whitening and undulating surface and suitable hardness as compared with the films from the preparation in which only the customary hair styling agent was used (Comparative Example 7) and the preparations in which the hair styling agent and an additive other than that according to the invention Polymers used (Comparative Examples 5 and 6) were prepared.

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Claims (6)

T 52 091 Applicant: Daikin Kogyo Co., Ltd. No. 12-39, Umeda 1-chome, Kita-ku, Osaka. Japan Claims Ii polymer which contains a perfluoroalkyl group in its side chain, characterized in that it is an addition reaction product of a polymer of the general formula -CIl. -CH- I
R. -CII CII - I I C = O C = O ι ι ι on oir (D where R is a phenyl or alkoxyl group with 1 to 12 carbon atoms, R is an alkyl group with 1 to 12 carbon atoms and η is an integer from 10 to 2000, with an epoxy compound which is selected from the group RfCH ₂ CTh- ^ CH ₂ , (Ha) and RrSO ₇ NCH ₉ CII CH ₀ f 2, 2 X _0/2 RrOCH ₉ GI CH ₉ t 2 V _0/2 (Hb) (lic) wherein R is a perfluoroalkyl group of 3 to 20 carbon 030030/0615 ORIGINAL INSPECTED atoms and R is an alkyl group with 1 to 12 carbon atoms, is, the addition reaction product per mole of the repeating unit of the polymer of the formula (I) 0.1 to 50 mol% of the group derived from the epoxy compound. 2. Polymer according to claim 1, characterized in that the polymer of formula (i) is one in which R is an alkoxyl group having 1 to 4 carbon atoms, R is an alkyl group having 1 to 4 carbon atoms and η is an integer from 50 to 1,500 , and that the epoxy compound is one which is selected from the group of the compounds of the formulas (Ha), (lib) and (lic), in which R _f a perfluoroalkyl group having 3 to 10 carbon atoms and R represents an alkyl group having 1 to 3 carbon atoms, the addition reaction product being per mole of the repeating unit of the polymer of the formula (I) 1 to 30 mol% of the group derived from the epoxy compound contains. 3. Process for the preparation of a polymer which contains a perfluoroalkyl group in its side chain, in particular One such according to claim 1 or 2, characterized in that a polymer of the general formula ClI -CH- CJI- CJI- I I I R c = o c = o, I], ^ω Oil OH ¹ 030030/061 5 where R is a phenyl or alkoxyl group with 1 to 12 carbon atoms, R is an alkyl group with 1 to 12 carbon atoms and η is an integer from 10 to 2000, with an epoxy compound selected from the group R ₄ -SO ₉ NCH ₉ CH CH ₉ (Hb) f 2, 2 x _0/2 and R ^ OCH ₉ CIl CH ₉ f 2 _No / 2 wherein R _{f is} a perfluoroalkyl group with 3 to 20 carbon atoms and R is an alkyl group with 1 to 12 carbon atoms, in the presence of a tertiary amine or a quaternary Reacts ammonium salt, so that the reaction product obtained per mole of the repeating unit of the polymer Formula (I) contains 0.1 to 50 mol% of the group derived from the epoxy compound. 4. Coating composition or preparation, characterized in that it contains or consists of at least one film-forming resin and at least an effective amount of a polymer containing a perfluoroalkyl group in its side chain, which is an addition reaction product of a polymer of the general formula 03C0 3 0/061 ¹ p CH, —CH CH CH- -CH- I. I. I. R. C = O C = O I.
Oil OR ¹ (D wherein R is a phenyl or alkoxyl group with 1 to 12 carbon atoms, R is an alkyl group with 1 to 12 carbon atoms and η is an integer from 10 to 2000, with an epoxy compound selected from the group "" .. ", m, (Ha) RfSO ₂ NCIl ₂ Ql-CH ₂ and RfOCH ₂ Ql-CH ₂ (Hb) (lic) wherein R _{f is} a perfluoroalkyl group of 3 to 20 carbon · ^r 2 atoms and R is an alkyl group with 1 to 12 carbon atoms, is, the addition reaction product per mole of the repeating unit of the polymer of the formula (I) 0.1 to 50 mol% of the group derived from the epoxy compound. 5. Coating compound or preparation according to claim 4, 03C030 / 0615 characterized in that the polymer containing a perfluoroalkyl group is an addition reaction product of the polymer of formula (I) wherein R is Alkoxyl group with 1 to 4 carbon atoms, R an alkyl group with 1 to 4 carbon atoms and η a whole Number from 50 to 1500 mean, with the epoxy compound which is selected from the group of the compounds of Formulas (Ha), (lib) and (lic), in which R _{f is} a perfluoro ^r 2 alkyl group with 3 to 10 carbon atoms and R is an alkyl group with 1 to 3 carbon atoms, wherein the addition reaction product per mole of the repeating unit of the polymer of the formula (I) is 1 to 30 mol% the group derived from the epoxy compound. 6. Coating wet or coating preparation according to claim 4 or 5, characterized in that the polymer containing a perfluoroalkyl group in an amount of 0.05 to 2 parts by weight per 100 parts by weight of the film-forming resin is used. 030030/0615