EP0424765B1 - Dispersions of perfluoroalkyl groups containing copolymerizates - Google Patents

Description

Aqueous dispersions of copolymers and graft copolymers which are prepared with the use of perfluoroalkyl (meth) acrylates have been described many times in the literature (cf., for example, JP-A 83/59277, BE-A 677 859, DE-A 3 407 361, DE-A 3 407 362, DE-A 1 953 345 and DE-A 1 953 349) and are used as phobicizers on many substrates.

The use of alkyl (meth) acrylates as comonomers in the preparation of perfluoroalkyl copolymer dispersions and the use of these dispersions for textile treatment are also known (cf. for example US Pat. Nos. 2,803,615 and 3,062,765), often in addition to an oleophobic finish hydrophobization is also obtained.

With such perfluoroalkyl copolymers, however, a further improvement in the oleophobic / hydrophobic properties can only be achieved by increasing the fluorine-containing component in the copolymer dispersion.

However, these advantages are paid for with disadvantages such as hardening and sticking, which have a negative effect on the handle of the textiles finished with them.

In the post-published EP-A-0 368 338 (published on May 16, 1990) compositions for the hydrophobic / oleophobic finishing of textiles are described in which (co) polymers with fluoroalkyl groups are combined with glycerol-α-esters of C₁-C₆-carboxylic acids will. In addition to (meth) acrylates with fluoroalkyl groups, the copolymers can also contain fluorine-free comonomers from a large group of different types of compounds; however, the use of long-chain, fluorine-free (meth) acrylates is not apparent from this publication. The reworking of examples from this publication resulted in unsatisfactory oleophobic values.

The object was therefore to develop highly effective finishing agents which bring about the desired oleophobic / hydrophobic properties without increasing the fluorine-containing component and which therefore also cause the disadvantages not described above,

The present invention now relates to aqueous dispersions of copolymers and graft copolymers of ethylenically unsaturated perfluoroalkyl monomers with at least 6 carbon atoms in the perfluoro chain and perfluoroalkyl group-free ethylenically unsaturated monomers, characterized in that the dispersions additionally contain ester compounds which have at least 6 linearly linked carbon atoms have and either contain 1,2-substituted vinyl groups or are free of vinyl groups, and their use for the treatment of textiles, leather and paper.

The aqueous dispersions have solids contents of copolymers of about 10% by weight to 30% by weight and particle sizes of about 250 to 450 nm.

sowie

worin

R₁

C₁-C₄-Alkyl,

R₂

Wasserstoff oder Methyl,

m

1 bis 4 und

n

4 bis 12 bedeuten.

Suitable perfluoroalkyl monomers are those of the formulas

such as

wherein

R₁

C₁-C₄ alkyl,

R₂

Hydrogen or methyl,

m

1 to 4 and

n

4 to 12 mean.

R₁

C₁-C₂-Alkyl,

R₂

Wasserstoff oder Methyl

m

2 und

n

6 bis 8 bedeuten.

Monomers (I) in which

R₁

C₁-C₂ alkyl,

R₂

Hydrogen or methyl

m

2 and

n

6 to 8 mean.

worin

R₃

für Wasserstoff, Methyl oder Fluor und

R₄

für einen C₈-C₂₂-Alkylrest stehen.

Suitable perfluoroalkyl group-free monomers are, on the one hand, compounds of the general formula

wherein

R₃

for hydrogen, methyl or fluorine and

R₄

stand for a C₈-C₂₂-alkyl radical.

Such monomers (II) with R₃ = H or methyl and R₄ = C₁₂-C₂₂-alkyl are preferred.

Examples include: acrylic and methacrylic acid esters of behenyl alcohol, stearyl alcohol, oleyl alcohol, nonyl or octyl alcohol or isomer mixtures of such alcohols.

worin

R₃

Wasserstoff, Methyl oder Fluor,

R₅

C₁- bis C₇-Alkyl,

R₆

C₁- bis C₇-Alkyl,

-CH₂-OH,
-CH₂-OCH₃ oder

R₇

H, CH₃, F oder Cl,

R₈

Cl, F, OR₁, Phenyl,

oder CN und

R₉

C₁-C₄-Alkyl

bedeuten.Suitable perfluoroalkyl group-free monomers are also compounds of the formulas (III):

wherein

R₃

Hydrogen, methyl or fluorine,

R₅

C₁ to C₇ alkyl,

R₆

C₁ to C₇ alkyl,

-CH₂-OH,
-CH₂-OCH₃ or

R₇

H, CH₃, F or Cl,

R₈

Cl, F, OR₁, phenyl,

or CN and

R₉

C₁-C₄ alkyl

mean.

Particularly preferred monomers (III) are vinyl esters such as vinyl acetate or vinyl propionate as well as acrylic and methacrylic acid esters of C₁-C₄ alcohols.

Preferred copolymers contain the individual types of comonomers in the quantitative ratios listed below;
Perfluoroalkyl monomers of the formulas (I) 15 to 70% by weight, preferably 25 to 60% by weight,
Comonomers of the formula (II) 5 to 35% by weight, preferably 10 to 25% by weight,
Comonomers of the formulas (III) 15 to 65% by weight, preferably 20 to 55% by weight.

In general, water-insoluble comonomers are preferred; to ensure some adhesion to the various substrates in the oleophobic / hydrophobic finish, water-soluble comonomers can also be used in proportions of up to 10% by weight, preferably up to 2% by weight.

• 1) Synthetische oder natürliche Ester und/oder Partialester von gesättigten, ungesättigten und/oder substituierten Fettsäuren der Kettenlänge C₆-C₂₂ mit Mono-, Di-, Tri- und Polyolen. Bevorzugte Fettsäuren sind Ölsäure, Stearinsäure, Arachinsäure, Behensäure, Palmitinsäure, Myristinsäure, Linolsäure, Linolensäure, Laurinsäure, Eleostearinsäure sowie Fettsäuren wie sie aus Naturprodukten gewonnen werden.
  Als Monohydroxykomponente zur Herstellung dieser Esterverbindungen werden bevorzugt Alkanole mit 1 bis 22 Kohlenstoffatomen, wie z.B. Methanol, Ethanol, Propanol, aber auch beispielsweise Stearyl- und Oleylalkohol eingesetzt.
  Fettsäureester von Diolen enthalten zweiwertige Alkohole mit 4 bis 12 Kohlenstoffatomen, beispielsweise 1,4-Butandiol, 1,5-Pentandiol, 1,6-Hexandiol, 1,12-Dodecandiol oder Neopentylglykol.
  Zu den Trihydroxyverbindungen als Alkoholkomponente der erfindungsgemäßen Esterverbindungen sind u.a. Glycerin, Trimethylolpropan und Cyclohexantriol zu zählen.
  Verwendbare Polyole sind beispielsweise Pentaerythrit, Sorbit und Mannit sowie Monosaccharide, wie Glucose und Fructose, und Oligosaccharide wie z.B. Saccharose, Maltose, Lactose und Raffinose.
  Geeignete natürliche Ester und Partialester sind Rindertalg, Walöl, Rinderklauenöl, Palmöl, Olivenöl, Erdnußöl, Maisöl, Leinöl, Rapsöl, Sojabohnenöl, Sonnenblumenöl, Kokusnußöl, Palmkernöl, Rizinusöl, Babussaöl.
• 2) Ester und/oder Partialester von Di-, Tri- und Tetracarbonsäuren mit gesättigten oder ungesättigten Fettalkoholen der Kettenlänge C₆-C₂₂.
  Als Carbonsäurekomponente seien beispielhaft Dicarbonsäuren mit 4 bis 10 Kohlenstoffatomen, wie z.B. Sebacinsäure, Phthalsäure, Isophthalsäure, Tricarbonsäuren, wie z.B. Zitronensäure, Trimellithsäure, sowie Pyromellithsäure als Tetracarbonsäure genannt.
• 3) Polyester auf Basis von mehrwertigen Alkoholen und mehrbasigen Carbonsäuren mit Molekulargewichten von etwa 1.000 bis 8.000.

Suitable ester compounds (IV) are:

• 1) Synthetic or natural esters and / or partial esters of saturated, unsaturated and / or substituted fatty acids of chain length C₆-C₂₂ with mono-, di-, tri- and polyols. Preferred fatty acids are oleic acid, stearic acid, arachic acid, behenic acid, palmitic acid, myristic acid, linoleic acid, linolenic acid, lauric acid, eleostearic acid and fatty acids as are obtained from natural products.
  Alkanols having 1 to 22 carbon atoms, such as, for example, methanol, ethanol, propanol, but also, for example, stearyl and oleyl alcohol are preferably used as the monohydroxy component for the preparation of these ester compounds.
  Fatty acid esters of diols contain dihydric alcohols with 4 to 12 carbon atoms, for example 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,12-dodecanediol or neopentyl glycol.
  The trihydroxy compounds as alcohol component of the ester compounds according to the invention include glycerol, trimethylolpropane and cyclohexanetriol.
  Usable polyols are, for example, pentaerythritol, sorbitol and mannitol as well as monosaccharides such as glucose and fructose and oligosaccharides such as sucrose, maltose, lactose and raffinose.
  Suitable natural esters and partial esters are beef tallow, whale oil, cattle claw oil, palm oil, olive oil, peanut oil, corn oil, linseed oil, rapeseed oil, soybean oil, sunflower oil, coconut oil, palm kernel oil, castor oil, babussa oil.
• 2) esters and / or partial esters of di-, tri- and tetracarboxylic acids with saturated or unsaturated fatty alcohols of chain length C₆-C₂₂.
  Examples of dicarboxylic acids with 4 to 10 carbon atoms, such as sebacic acid, phthalic acid, isophthalic acid, tricarboxylic acids, such as citric acid, trimellitic acid, and pyromellitic acid as tetracarboxylic acid may be mentioned as a carboxylic acid component.
• 3) Polyester based on polyhydric alcohols and polybasic carboxylic acids with molecular weights of about 1,000 to 8,000.

The esters (IV) contain at least 6 carbon atoms in the chain.

The esters (IV) described in items 1 to 3 can advantageously also be used as mixtures. The ester compounds used according to the invention are known. In the preparation of the copolymer according to the invention, the ester compounds can either be used directly, since the preparation is carried out by the emulsion polymerization process, but more advantageously in the form of their aqueous emulsions.

The aqueous emulsions contain the ester compounds mentioned in concentrations of 5 to 40% by weight, preferably 10 to 30% by weight. As emulsifiers for the preparation of the emulsions, it is possible to use both nonionic, anionic and cationic types and anionic / nonionic or cationic / nonionic combinations of the surface-active compounds in concentrations of 2 to 25, preferably 5 to 15% by weight, based on the one to be emulsified Use compound or mixtures thereof. The methods for emulsification are generally known.

The above-mentioned ester compounds are used to prepare the perfluoroalkyl copolymer dispersions according to the invention in amounts of 2 to 50, preferably 5 to 35,% by weight, based on the total amount of the monomers used for the copolymerization.

The aqueous dispersions according to the invention can contain further polymers, as described, for example, in DE-A 3 407 361 and 3 407 362, in particular hydrophobic vinyl polymers (V) and / or polycondensates (VI), as described, for example, in DE-A 956 990 are contained, optionally as a graft base, preferably in amounts of 8% by weight to 30% by weight, based on the copolymer of (I), (II) and (III).

Suitable vinyl polymers (V) are, for example, copolymers of (meth) acrylates, such as isobutyl methacrylate or butyl acrylate, which contain at least one comonomer with a hydrophobic alkyl radical, such as, for example, stearyl methacrylate. Suitable polycondensates (VI) are, for example, urea resins and melamine resins, such as those e.g. can be obtained by reacting hexamethylolmelamine pentamethyl ether with fatty acids and optionally with methyl dialkoanolamine, as described, for example, in EP-A 324 354.

A special embodiment is the combination of such a melamine condensate with paraffin fractions or paraffin waxes.

The dispersions according to the invention are prepared in a manner known per se, for example the procedure for emulsion polymerization in water is employed.

It may be advantageous to use auxiliary solvents in the copolymerization, which are described, for example, in US Pat. No. 3,062,765. It is also possible to use auxiliary solvents which are immiscible with water, such as alkyl acetate, alkyl propionate or chlorofluorocarbons. The use of ethyl acetate or methyl propionate is particularly advantageous. The auxiliary solvent is removed by distillation after completion of the polymerization.

The emulsions are produced in stirring units, ultrasound apparatus or homogenizers.

The polymerization is triggered by radical formers. As radical formers e.g. aliphatic azo compounds such as azodiisobutyronitrile and organic or inorganic peroxides are suitable, which are used in conventional amounts. Organic peroxides which may be mentioned are: diacyl peroxides such as dibenzoyl peroxide, hydroperoxides such as tert-butyl hydroperoxide and percarbonates such as dicyclohexyl percarbonate. The alkaline salts of peroxidic sulfuric acid are particularly suitable as inorganic peroxides.

In general, the polymerization temperatures are up to 100 ° C., preferably 50 to 100 ° C., in particular 60 to 90 ° C.

It is also possible to carry out the copolymerization at temperatures of 40 ° C. and below by using redox systems. Suitable starter systems are e.g. Mixtures of peroxidisulfates and reducing sulfur compounds such as bisulfites or thiosulfates or combinations of diacyl peroxides with tert. Amines. The known chain transfer agents based on mercapto compounds or aliphatic aldehydes can be used to adjust the molecular weights or the molecular weight distributions.

Conventional anionic, cationic or nonionic emulsifiers and combinations of ionic and nonionic emulsifiers can be used to stabilize the dispersions according to the invention and also to prepare the monomer emulsions.

Examples of the cationic emulsifiers used are quaternary ammonium or pyridinium salts, e.g. Stearyldimethylbenzylammonium chloride or N, N, N-trimethyl-N-perfluorooctanesulfonamidopropylammonium chloride.

Examples of anionic emulsifiers are alkyl sulfonates, alkylarylsulfonates, fatty alcohol sulfates or sulfosuccinic acid esters, furthermore perfluoroalkyl group-containing emulsifiers such as ammonium or tetraethylammonium salts of perfluorooctanesulfonic acid or the potassium salt of N-ethyl-N-perfluorooctanesulfonylglycine.
The storage stability of the copolymer dispersions is particularly increased by non-ionic emulsifiers.

Examples of nonionic emulsifiers are polyglycol ethers, e.g. Ethylene oxide / propylene oxide copolymers, including those with a block structure, and alkoxylation products, in particular ethoxylation products of fatty alcohols, alkylphenols, fatty acids, fatty acid amides, sorbitol monooleate.

In a preferred embodiment, the polymerization of (I), (II) and (III) is carried out in the presence of (IV) and optionally (V) and / or (VI). (V) and (VI) are preferably used in the form of aqueous dispersions.

The dispersions according to the invention are outstandingly suitable for the treatment of natural and synthetic materials such as leather, paper, fibers, filaments, yarns, nonwovens, woven fabrics, knitted fabrics and knitted fabrics, in particular carpets, made in particular of cellulose and its derivatives, but also made of polyester, polyamide and polyacrylonitrile materials, wool or silk, to which the dispersions according to the invention impart oleophobic and hydrophobic properties.

The dispersions according to the invention can also be used in combination with other fluorine-containing or fluorine-free dispersions.

For finishing carpets, the copolymers and graft copolymers according to the invention are preferably in the form of aqueous dispersions containing the ester compounds used according to the invention, in combination with aqueous colloidal suspensions of organosiloxanes, as described, for example, in DE-A 3 307 420, and optionally in an additional combination with other fluorine-containing dispersions.

Surprisingly, it has now been found that the dispersions according to the invention have significantly improved oleophobic and hydrophobic effects on the substrates equipped with them, such as textiles, leather and paper.

With the dispersions according to the invention, natural and synthetic materials such as leather, paper, fibers, filaments, yarns, nonwovens, fabrics, knitted fabrics and knitted fabrics, in particular carpets, made in particular of cellulose and its derivatives, but also made of polyester, polyamide and polyacrylonitrile materials, wool or silk can be successfully rendered oleophobic and hydrophobic.

When using the dispersions according to the invention which have been prepared with the addition of the abovementioned ester compounds, improved oleophobic and hydrophobic properties can be achieved without the proportion of the perfluoro-containing components which are decisive for these properties having to be increased in the dispersion.

Conventional oleophobic / hydrophobic finishing agents can only reach this application level with a significant increase in the proportion of perfluoro-containing component in the latex, but with disadvantages such as hardening and adhesions appear on the materials finished with them, which have a negative effect, for example, on properties such as the handle of textiles finished with them. When using the copolymer dispersions according to the invention, the disadvantages described can be avoided.

The finishing is carried out according to known methods, such as pull-out or padding methods, for example between room temperature and 40 ° C., but also by splashing, spraying or foam application with a subsequent temperature treatment at 80 to 180 ° C., preferably 120 to 150 ° C.

Examples Example A Emulsification of glycerol monooleate

240 parts by weight of glycerol monooleate (mixture of approx. 50% monoglyceride, approx. 38% di- and 12% triglyceride) together with 7.2 parts by weight of C₁₂-C₁₄-alkyldimethylbenzylammonium chloride (approx. 50% in water) are placed in a 2-liter flat-ground vessel with a flat-ground stirrer ) and 4.8 parts by weight of an oleyl alcohol-ethylene oxide adduct with about 56 EO units at 70 ° C. for 30 minutes, so that a homogeneous oil phase is present. The agitator is replaced by a ULTRA-TURRAX dispersing device and 1,008 parts by weight of deionized water (temperature: 60 to 70 ° C) are added dropwise within 45 to 60 minutes (speed of the dispersing device: 10,000 rpm). A stable, approximately 20% aqueous emulsion with particle sizes of 0.1 to 0.6 μm is obtained.

Example B Emulsification of glycerol trioleate

Glycerol trioleate is emulsified using the same procedure as described in Example A.

A stable, approximately 20% aqueous emulsion is obtained.

Example C Emulsification of sunflower oil

300 parts by weight of sunflower oil with 28.5 parts by weight of a C₁₂-C₁₃-alkyl alcohol-ethylene oxide adduct (approx. 4 mol EO) and 1.5 parts by weight of a reaction product of castor oil with approx. 30 mol ethylene oxide at 60 ° C stirred for 30 minutes so that a homogeneous oil phase is present.

1,200 parts by weight of deionized water at 60 ° C are mechanically agitated in a 2 liter flat ground vessel using a ULTRATURRAX dispersing device (10,000 rpm). The organic phase is metered into this template via a heatable dropping funnel (60 ° C.) within about 30 minutes. Finally, the dispersing device is left to run for a further 5 minutes.
The solids content in the finished emulsion is approximately 21.5%.

example 1

The following solution is prepared at room temperature and stirred for 15 minutes:

Then 540 parts by weight of deionized water are added and the solution is heated to 50 ° C. with stirring.

Solution 2 is prepared at 50 ° C, solution 3 at 30 ° C.

Solutions 1 and 2 are combined at 50 ° C. and emulsified in an emulsifying machine until the particle size is constant at 40 to 50 ° C. The emulsion obtained is placed in a reactor equipped with a stirrer, reflux condenser and internal thermometer and allowed to cool to 30 ° C. Solution 3 is then metered in at 30 ° C. and stirred at 30 to 40 ° C. for 15 minutes. The mixture is then heated to 60 ° C. within half an hour and stirred at 60 to 70 ° C. for one hour. Then allowed to react for three hours at 70 to 80 ° C and distilled off the ethyl acetate from an additional attached distillation apparatus. The mixture is stirred for a further two hours at 83 to 85 ° C and three hours at 85 to 90 ° C. Solids content: 14.4% Fluorine content in the solid: 20.1% Average particle size: (after light scattering) 367 nm

Example 2

Anschließend werden 540 Gewichtsteile entionisiertes Wasser zugegeben und die Lösung unter Rühren auf 50°C erhitzt.
Lösung 2 wird bei 50°C hergestellt, die Lösung 3 bei 30°C.

Die Lösungen 1 und 2 werden bei 50°C zusammengegeben und bis zur Teilchengrößenkonstanz bei 40 bis 50°C in einer Emulgiermaschine emulgiert. Die erhaltene Emulsion gibt man in einen Reaktor, der mit Rührer, Rückflußkühler und Innenthermometer ausgestattet ist und läßt auf 30°C abkühlen. Lösung 3 wird dann bei 30°C zudosiert und eine halbe Stunde bei 30 bis 40°C gerührt. Anschließend wird innerhalb einer halben Stunde auf 60°C erhitzt und eineinhalb Stunden bei 60 bis 70°C gerührt. Danach läßt man drei Stunden bei 70 bis 80°C reagieren und destilliert dabei den Essigsäureethylester über eine zusätzlich angebrachte Destillationsapparatur ab. Es wird noch drei Stunden bei 85°C und eine Stunde bei 85 bis 90°C nachgerührt. Feststoffgehalt: 15,4 % Fluorgehalt im Feststoff: 17,9 % Mittlere Teilchengröße: (nach Lichtstreuung) 225 nm
b) Herstellung der Pfropfgrundlage
Als Pfropfgrundlage verwendbare Melaminkondensationsprodukte, wie sie z.B. in DE-A 3 800 845 bzw. in der US-P 2 398 569 beschrieben sind, können erhalten werden, indem man z.B. Methylolprodukte von Aminotriazinen oder deren Veretherungs- und Veresterungsprodukte mit z.B. aliphatischen Carbonsäuren und mit Aminen im Rahmen einer Polykondensation umsetzt. Man kann dazu zunächst die Carbonsäure mit dem Melaminderivat umsetzen und anschließend die Aminokomponente zur Reaktion bringen (siehe DE-A 956 990). Man stellt z.B. als Pfropfgrundlage her:

• b₁) eine Mischung aus 50 Gew.-% eines Kondensationsproduktes, hergestellt aus 1 Mol Hexamethylol-melamin-pentamethylether, 1,5 Mol Behensäure und 0,9 Mol N-Methyldiethanolamin bei 130°C während 3 Stunden und 50 Gew.-% Paraffin vom Schmelzpunkt 52°C;
• b₂) ein Polykondensat, das man dadurch erhält, daß man 3 Mol einer technischen Fettsäure, die zu ca. 50 % aus C₂₂-, ca. 40 % aus C₂₀-, ca. 5 % aus C₁₈- und zu ca. 5 % aus anderen Carbonsäuren besteht, bei 80°C aufschmilzt, mit 1 Mol Hexamethoxymethylmelamin versetzt und 24 Stunden bei 160 bis 190°C umsetzt.

a) The following solution is prepared at room temperature and stirred for half an hour.

Then 540 parts by weight of deionized water are added and the solution is heated to 50 ° C. with stirring.
Solution 2 is prepared at 50 ° C, solution 3 at 30 ° C.

Solutions 1 and 2 are combined at 50 ° C. and emulsified in an emulsifying machine until the particle size is constant at 40 to 50 ° C. The emulsion obtained is placed in a reactor equipped with a stirrer, reflux condenser and internal thermometer and allowed to cool to 30 ° C. Solution 3 is then metered in at 30 ° C. and stirred at 30 to 40 ° C. for half an hour. The mixture is then heated to 60 ° C. within half an hour and stirred at 60 to 70 ° C for one and a half hours. Then allowed to react for three hours at 70 to 80 ° C and distilled off the ethyl acetate from an additional attached distillation apparatus. The mixture is stirred for a further three hours at 85 ° C. and one hour at 85 to 90 ° C. Solids content: 15.4% Fluorine content in the solid: 17.9% Average particle size: (after light scattering) 225 nm
b) Preparation of the graft base
Melamine condensation products which can be used as the graft base, as described, for example, in DE-A 3 800 845 or in US Pat. No. 2,398,569, can be obtained by, for example, methylol products of aminotriazines or their etherification and esterification products with, for example, aliphatic carboxylic acids and with Reacts amines in the context of a polycondensation. To this end, the carboxylic acid can first be reacted with the melamine derivative and then the amino component can be reacted (see DE-A 956 990). One produces, for example, as a graft base:

• b₁) a mixture of 50 wt .-% of a condensation product, made from 1 mol of hexamethylol-melamine-pentamethyl ether, 1.5 mol of behenic acid and 0.9 mol of N-methyldiethanolamine 130 ° C for 3 hours and 50% by weight paraffin with a melting point of 52 ° C;
• b₂) a polycondensate which is obtained by adding 3 moles of a technical fatty acid, which is about 50% from C₂₂-, about 40% from C₂₀-, about 5% from C₁₈- and about 5% other carboxylic acids, melted at 80 ° C, mixed with 1 mol of hexamethoxymethylmelamine and reacted at 160 to 190 ° C for 24 hours.

Example 3

The preparation is carried out as described in Example 2a) with the solutions mentioned there with the only difference that solution 2 contains 7.32 parts by weight of a condensation product b₂) instead of the graft base 2b₁). Solids content: 16.8% Fluorine content in the solid: 18.9%

Example 4

The copolymer dispersion is prepared as described in Example 2a), with the only difference that the emulsion of glycerol monooleate prepared according to Example A is not added to solution 1, but only after polymerization and Distillation of the finished copolymer dispersion is added in the same proportions as described in Example 2a). Solids content: 15.3% Fluorine content in the solid: 17.9%

Example 5 (comparison)

The preparation is carried out as in Example 2a) with the solutions mentioned there, with the only difference that Solution 1 does not contain an aqueous emulsion of an ester compound to be used according to the invention prepared according to Example A. Solids content: 14.4% Fluorine content in the solid: 22.8% Average particle size: (after light scattering) 471 nm

Example 6

The preparation is carried out as in Example 2a) with the solutions mentioned there with the only difference that solution 1 contains the same amount of an emulsion prepared according to Example B instead of an aqueous emulsion of an ester compound prepared according to Example A. Solids content: 15.5% Fluorine content in the solid: 17.9% Average particle size: (after light scattering) 295 nm

Example 7

The preparation is carried out as in Example 2a) with the solutions mentioned there, with the only difference that solution 1 contains the same amount of an emulsion prepared according to Example C instead of an aqueous emulsion of an ester compound prepared according to Example A. Solids content: 16.5% Fluorine content in the solid: 17.9%

Example 8

The preparation is carried out as in Example 2a) with the solutions mentioned there with the only difference that solution 1 contains 28.7 g of linseed oil instead of the aqueous emulsion of an ester compound prepared according to Example A. Solids content: 18.2% Fluorine content in the solid: 17.5%

Example 9 (Use)

An aqueous dispersion according to Example 1 is produced. 40 parts by weight of this dispersion are mixed with 60 parts by weight of an aqueous colloidal suspension of organosiloxanes, as described in DE-A-3 307 420.

A 2.5% aqueous dilution of this mixture is applied to a polyamide carpet (tufted fabric with 30% residual moisture, pile weight: 500 g / m²) (spray application) in such a way that a coating of 1% by weight of the above mixture ( based on the pile weight) remains on the carpet.

It is then dried and condensed at 125 to 150 ° C for 5 to 15 minutes, air-conditioned for 24 hours at 23 ° C and 65% relative humidity, and then the application tests are carried out.

Analogously, dispersions prepared according to Examples 2 to 8 are used for finishing polyamide carpets.

The results of the application tests are shown in Table 1. Table 1 Oleophobia ¹⁾ Hydrophobicity ²⁾ example 1 3-4 60 / 40-50 / 50 Example 2 5 20/80 Example 3 4-5 30 / 70-20 / 80 Example 4 5 20/80 Example 5 2nd 60/40 Example 6 5 20/80 Example 7 2-3 30 / 70-20 / 80 Example 8 3-4 40 / 60-30 / 70 ¹⁾ According to AATCC test method 118 (5 better than 4) ²⁾ Resistance to aqueous isopropanol solutions (water / isopropanol = 60/40 better than 70/30)

Compared to a copolymer dispersion which was prepared without the ester compounds used according to the invention (Example 5), the copolymer dispersions according to the invention show a marked improvement in both the oleophobic and the hydrophobic effect. The soiling behavior of the carpets finished with these copolymer dispersions is also improved and corresponds to increased requirements.

Claims (10)

1. Aqueous dispersions of copolymers and graft copolymers of ethylenically unsaturated perfluoroalkyl monomers having at least 6 C atoms in the perfluorinated chain and ethylenically unsaturated monomers containing no perfluoroalkyl groups, characterized in that the dispersions additionally contain ester compounds which contain at least 6 C atoms linked linearly to one another and either contain 1,2-substituted vinylic groups or are free from vinylic groups.
2. Aqueous dispersions of copolymers and graft copolymers according to Claim 1, characterized in that they contain as ester compounds

   a) synthetic or naturally occurring esters and/or partial esters of saturated, unsaturated and/or substituted fatty acids of chain length C₆-C₂₂ with mono-, di-, tri- and polyols,

   b) esters and/or partial esters of di-, tri- and tetracarboxylic acids with saturated or unsaturated fatty alcohols of chain length C₆-C₂₂,

   c) polyesters based on polyhydric alcohols and polybasic carboxylic acids having molecular weights of about 1,000 to 8,000.
3. Aqueous dispersions according to Claim 1, characterized in that the perfluoroalkyl (meth)acrylates correspond to the formulae

   

   and

   

   and

   

   wherein

   R₁   denotes C₁-C₄-alkyl,

   R₂   denotes hydrogen or methyl,

   m   denotes 1 to 4 and

   n   denotes 6 to 12.
4. Aqueous dispersions according to Claim 1, characterized in that the monomers containing no perfluoroalkyl groups correspond to the formulae

   

   and

   

   or

   

   or

   

   wherein

   R₃   denotes hydrogen, methyl or fluorine and

   R₄   represents a C₈-C₂₂-alkyl radical,

   R₅   denotes C₁- to C₇-alkyl,

   R₆   denotes C₁- to C₇-alkyl,

   

   -CH₂-OH,
   -CH₂-OCH₃ or

   

   R₇   denotes H, CH₃, F or Cl, and

   R₈   denotes Cl, F, OR₁, phenyl,

   

   or CN and

   R₉   denotes C₁-C₄-alkyl.
5. Aqueous dispersions according to Claim 1 or 4, characterized in that the comonomers containing no perfluoroalkyl groups are vinyl esters or acrylic and methacrylic eaters of C₁-C₄-alkanols and acrylic and methacrylic eaters of C₁₂-C₂₂-alkanols.
6. Aqueous dispersions according to Claim 1, characterized in that hydrophobic vinyl polymers and/or polycondensates are employed as the graft base.
7. Aqueous dispersions according to Claim 1, characterized in that the content of non-copolymerized ester compounds having at least 6 C atoms additionally contained in the dispersions is 2 to 50% by weight, preferably 5 to 35% by weight, based on the monomers employed.
8. Process for finishing textiles, carpets, leather and paper, characterized in that aqueous dispersions of Claim 1 are used.
9. Process according to Claim 8, characterized in that combinations of the dispersions according to Claim 1 with other fluorine-containing polymer dispersions are used.
10. Process according to Claim 8, characterized in that combinations of the dispersions according to Claim 1 with polysiloxane dispersions are used.