DE2012351A1 - Oil- and water-repellent emulsions and processes for their production and use - Google Patents

Description

Description: Oil and water repellent emulsions

as well as processes for their manufacture and use

The invention also relates containing a nitrogen emulsions with which textiles oil- and can be made water-repellent ", it relates to the individual emulsions of perfluoroalkyl-containing ^ oil- and water-repellent polymers in a mixture of water and a chlorinated fat hydrocarbon solvent _for said emulsion Contains emulsifier and optionally a certain class of aliphatic polyurethanes.

Around textiles, paper or leather objects oil «or water repellent To make it is known to use perfluoroalkyl-containing polymers, such as acrylic or methacrylic acid esters of the N-alkanol perfluoroalkanesulfonamides according to the USA " Patent 3,068,187 or acrylic and methacrylic acid esters of the perfluoroalkylalkylene alcohols according to the USA ^ Patentsehriftea 3,378,609, 3,462,296, 3,491,169,% 282o905, .3,102,103 or 3.642ο416. In these patents, polymer mixtures used in the form of aqueous dispersions that are applied to the fabrics and then usually hardened to the

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to achieve the desired oil or water repellent properties. The application to textile objects in the form of a Aqueous dispersion is currently considered a viable process both economically and qualitatively viewed.

In practice, however, there are serious disadvantages when the aqueous solutions are applied to the textile articles will. The sequence of the necessary work processes (namely padding, squeezing out by means of rollers, drying and hardening of the textiles) generally leads to damage to the finished material, in particular the "handle" of the material. The "handle" of the material is the degree of comfort one feels when touching the material; it depends on a number of properties, for example the friction between the fibers, the friction between the skin and the fiber, the modulus of elasticity of the fibers, the Surface electricity and the like. The "grip" of a textile determines its price and its economic value Success.

Another serious disadvantage is that many aqueous baths which contain the aqueous dispersions described above are cationic, which leads to a sensitivity to changes in the pH of the bath. Without ψ Correcting by adding acid, the oil and water repellent polymers often fall out of the dispersion in the form of non-dispersible lumps. In addition, the presence of electrolytes in the bath alone leads to such precipitations and, even if the pH of the bath is kept constant, the electrolyte and water-repellent polymer can flocculate out of the dispersion. Any ionic substance in the textile material to be treated can cause the polymer to precipitate. Furthermore, the aqueous dispersions are often incompatible with other textile treatment agents, such as agents which impart crease resistance, plasticizers, ultraviolet rays absorbing agents, and antistatic agents

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Agents, soil-loosening agents and the like, whereby not only a flocculation of these agents and / or the oil and water-repellent polymers is caused from the bath, but also the need to use such
Carry out means for textiles in separate, tent-consuming procedural steps * It is obvious that the above
Precipitation and flocculation described leads to the fact that the
UV- and water-repellent polymers on the textiles in
deposited in a coarse and uneven manner, rendering the treatment practically ineffective and useless.

Attempts have been made to eliminate the above-described deficiencies in the use of aqueous dispersions in textiles by
that the textiles with non-aqueous dispersions of the
Treated oil- and water-repellent polymers «Eb is difficult to use suitable non-aqueous solvents
find that form a dispersion with the aqueous dispersion of the oil- and water-repellent polymer. Attempts have therefore been made to isolate the polymer solids from their aqueous dispersion and to dissolve them in non-aqueous solvents. These attempts have generally proven unsuccessful because of the poor solubility of the polymers in such solvents. In addition, when such non-aqueous mixtures of the polymers were applied to textiles, the results were unsatisfactory because the polymers tend to separate during washing or "washing out" of the textiles during dry cleaning, and because the treated textiles are not abrasion-resistant.

It has now been found that those compositions of
present invention, which consists of an emulsion of the oil and
water-repellent polymer, water and a chlorinated fatty hydrocarbon emulsified with a certain nitrogen-containing emulsifier exist that eliminate the disadvantages described above, namely the bad "handle ¹¹ , the
Cation activity, incompatibility with ionizing
Means and with other means of treatment and to some extent

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Dimensions of the low durability. It has also been found that if a certain group of aliphatic polyurethanes is added to the emulsions described in the preceding sentence, the textiles treated with the emulsion retain their oil- and water-repellent properties after washing or dry cleaning do not lose and are resistant to abrasion.

The compositions of the present invention are therefore defined as emulsions containing a chlorinated fatty hydrocarbon solvent with 1-3 carbon atoms, in which is present in emulsified form:

I I. water;

II. An oil and water repellent containing perfluoroalkyl Polymer and

III. one of the following emulsifiers:

a) a mixture of a fatty ketone and a

methylated methylol melamine;

b) the condensation product of (i) a methylol compound of an aminotriazine or a urea ee, (ii) a primary alkyl amide or an aliphatic carboxylic acid and (iii) a primary or secondary amines;

c) a compound of the formula (RCONH) ₂ CH ₂ , in which

R is a fatty atoms hydrocarbon group with 16-30 carbon ψ; and either a urea formal

dehyde synthetic resin, a modified urea-formaldehyde synthetic resin, a melamine formaldehyde resin or a modified melamine formaldehyde resin;

d) a compound having the formula

RC

where each R is hydrogen or an alkyl of 1-3 carbon atoms and R _{2 is} an alkyl of 16-18

0098 ^ 1/1920

Is carbon atoms;
e). a compound having the formula

(CH ₂ OOOR) _x (CH ₂ OR ') ₆ _ _x

where R is an alkyl of 11-23 carbon atoms, χ is an integer of 2-3 and R ^{1 is} an alkyl of

Is 1-6 carbon atoms; f) stearamidomethylpyridinium chloride;

and optionally

IV. A substantially linear aliphatic ice polyurethane an aliphatic diisocyanate and a © ® polyalkylene glycol with a molecular weight between about 2000 and 5000 and with about $ 2 to 5 # free Isocyanate groups ",

It has been found that, in comparison with the aqueous dispersions used hitherto, when the emulsions according to the invention are used, the performance of the textile treatment process can be improved in that, in order to achieve a certain strength of the oil and water-repellent property _; smaller amount of oil- and water-repellent polymer is required. In other words, in order to achieve a certain strength of the water-repellent property of the treated aerials, less polymer is required in the emulsion according to the invention than in the previously used aqueous dispersion. The reason for this surprising result is not entirely clear, but it is assumed that the reason for this lies in the extremely fine distribution of the Si and water-repellent particles in the emulsion. The small, homogeneously distributed polyserizate particles are deposited more easily and more evenly on the textile material, so that not only a reinforcement of the 81- and water-repellent property, but also a better "grip" is achieved

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- b -

and, moreover, the polymer particles are less likely to precipitate or flocculate. It is further assumed that these results are partly due to the rapid evaporation of the cJilorierte Fatty hydrocarbon solvents are attributable, as the rapid evaporation a build-up of the polymer at the fiber crossing points of the textile material and consequently a prevents localized build-up of concentrated amounts of polymer. Compared to the previously used aqueous dispersions the emulsions according to the invention therefore provide better "coating" and penetration of the textile reached the polymer.

f A further advantage of the emulsions according to the invention is that they can be applied to the textiles without the usual "block" method, which were required in the aqueous dispersions. For example, many of the chlorinated hydrocarbon solvents are such that the emulsions can simply be sprayed onto the fabric. Furthermore, many of the solvents are known dry cleaning agents, so that conventional dry cleaning systems can be used to make the textiles oil and water repellent.

The extremely fine distribution of the polymer particles in the Emulsions according to the invention, i.e. the high emulsification " grad, is made by carefully monitoring the order and Speed of ingredient addition and other required conditions reached. In general, the Emulsifier mixed with a small amount of the solvent, usually in about an equimolar ratio of the solvent the active ingredient in the emulsifier. The agent is slowly stirred as either a finely divided solid or added in liquid form, for example in molten form or in dispersed aqueous or dissolved form, whereupon the aqueous dispersion of the polymer is mixed into the first mixture. What is important is the speed the addition of the liquids to the

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These limits remain, since the solvent is immiscible with the aqueous dispersions used.

Another but less preferred method of preparation of the compositions according to the invention consists in that the emulsifier is either in the form of finely divided pesticides or as a liquid (either as a molten solid, as an aqueous or solvent dispersion) slowly one aqueous dispersion of the polymer is added, whereupon the solvent is carefully mixed in. Before use you can use further solvents according to the description above to add.

While the mixture of the polymer with the emulsifier or of the emulsifiers and the solvent are not worth mentioning Difficulties are the conditions of the mixture of the chlorinated fatty hydrocarbon solvent with any aqueous dispersion is critical. The addition must be made in such a way that a sudden addition of the additive is avoided (because this would create lumps that would not be dispersed even with subsequent stirring); Rather, the addition must be made in such a way that the formation of diapergeable particles is favored, i.e. it must be prevented be that too large an amount is added at the beginning (what lead to a cluster of particles). After the initial mixing is done, it is preferable to set then an additional amount of the same or a different solvent to dilute the emulsion and to make them more stable.

All stirring operations described above should be carried out in such a way that promotes and sustains the formation of dispersible particles will. In other words, the stirring process should exert a strong shear effect, i.e. during the stirring process the diapergeable particles are cut up to make formation to avoid failing, separate phases. All of these operations are carried out at room temperatures, for example

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at 20-4-0 ° C, although also higher and lower Temperatures applicable bind.

Because the emulsions according to the invention form two phases after the addition of water, while they remain in a single phase after the addition of the solvent, one can use the Consider emulsions as water-in-oil emulsions in which the emulsified water particles contain the ultraviolet and water-repellent polymer in emulsified form. This theory takes into account the finely divided or highly dispersed nature the polymer particles to which - as described above - the advantages achieved with the emulsions are ascribed.

The initially obtained emulsions according to the invention contain about one part of water, about 0.05 to 0.5 parts of polymer solids, about 0.125 to one part of active emulsifier ingredients (discussed further below) and about 0.5 to five parts solvent. The solvent is added in two stages, with about 0.25 to 0.5 parts are added, while it is sufficient if the total amount of the solvent present in the second stage is brought to no more than about six parts. The emulsion initially present is a viscous fluid that can hold up to is stable for several months. The second stage of solvent addition serves to liquefy and improve the storage stability of the emulsion.

To increase the resistance of the treated textile material to abrasion, washing and dry cleaning, if the emulsions prepared by the processes described above are used before application to the textiles, im essential linear aliphatic polyurethane too. The addition is preferably carried out slowly with gentle stirring of the mixture at room temperature. It is believed that the polyurethane containing free isocyanate groups, the oil and water-repellent polymer binds to the textile fibers and thus good abrasion resistance and durability

0 0 9 R Λ 1/1920

is achieved. The polyurethane can either be added in solid pont, preferably finely ground, or dispersed in an additional solvent *

The emulsions according to the invention prepared by the processes described above can be used directly in the longitudinal textile treatment process, but the emulsions are preferably diluted with further solvent until they emulsify about 0.025 to 5% water, 0.005 to 1.0% polymer solids, 0.001 to Ki ° Substances and optionally 0.004 to 2.5 # polyurethane; the best consists of chlorinated fatty hydrocarbon solvents.

The emulsion produced in this way can be applied to the textiles by spraying, brushing, dipping, padding, coating with rollers or a combination of these processes. It is preferably eaten up. Typical textiles are not only webs and fabrics, but also threads, fibers, yarns and other articles made from natural, modified natural or synthetic polymeric fiber materials or mixtures of these fiber materials with other fibers. Paper ₉ Leather and other materials can be treated as well. Specific examples include cotton, silk, regenerated cellulose, nylon, fiber-forming linear polyester, polyacrylonitrile, cellulose nitrate or cellulose acetate, ethyl cellulose and the like.

In a preferred method, the textiles, iaafespecial knitwear, are prewashed with chlorinated fatty water stiff solvent. This Vorwaehnag usually done in such a way that the textiles are immersed in a quantity, the weight of two to swanzig eel 00 like. the weight of the textiles is that the similar solvents are then thrown out _f OQ25 dee emulsifier «and 0.01 to 4.8 Jt. of the polyurethane on the

00 9841/1920

Textile to be deposited. Drying and heat treatment usually uses temperatures of about 40 to 110 ° C for 10 seconds to 40 minutes, and then the temperature to about 80 to about 5 seconds to 20 minutes Increase 150 ° C.

Among those used in the emulsions according to the invention fluorine-containing, oil- and water-repellent polymers the polymers described in British Patent 1,011,612 or US Patent 3 * 378,609 are preferred. The fluorine-containing polymer can either be a homopolymer with units which have at least one polymerizable "Monomer with the formula

C _n P _{2n + 1} CH ₂ CH ₂ O ₂ CC (CH ₃ ) - CH ₂

Derived from Bind, in which η is an integer between 3 and 14 is. The units are preferably derived from a mixture of such monomers, where η is 6, 8 and 10 in the approximate weight eve jfhaltnie of 3: 2: 1, as well as 12 and 14 in general quantities vcfc less than 10 t

However, the fluorine-containing polymer is preferably a copolymer of the above-described monomers and one k polymerizable monovinyl compound that is free from non Tinylidated fluorine or a non-fluorinated conjugated diene. The applicable, τοη not tinylidated fluorine free polymerizable monovinyl compounds are alkyl acrylic acid esters and alkyl methacrylic acid esters, vinyl esters of fatty acids, Styrene and alkyl styrene, vinyl halides, vinylidene halides, Allyl Esters, Vinyl Alkyl Ketones and Acrylamides · The non-fluorinated conjugated dienes are preferably 1,3-butadienes. Typical compounds within the classes given above are methyl, propyl, butyl, 2-hydroxypropyl, 2-hydroxyethyl, 2-ethylethyl, octyl, decyl, lauryl, or cetyl Octadecyl acrylic acid ester or methacrylic acid ester; further Vinyl acetate, vinyl propionate, vinyl caprylate, vinyl laurate,

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Vinyl stearate, styrene, οί-methy1styrene, p-methylstyrene, vinyl fluoride, vinyl chloride, vinyl bromide, vinylidene fluoride, Vinylidene chloride, allylheptanyl, allyl acetate, allyl caprilate, Allyloaproate, vinyl methy! Ketone, vinyl ethyl ketone, 1,3-butadiene, 2-chloro-1,3-butadiene, 2,3-dichloro-1,3-butadiene, isoprene, I-methylol acrylamide, H-methylol methacrylamide, glycidyl acrylate and glycidyl methacrylate.

Often the above-described fluorine-containing oil and water-repellent homopolymers and copolymers with non-fluorine-containing polymers, the so-called blend or filler polymers, mixed, and the term "polymer solids" in this description denotes the total amount of those present in the emulsions according to the invention Polymers. These filler polymers are polymers of the polymerizable monoviny! compounds that are free of non vinylidated fluorine or non-fluorinated conjugated bees. In other words, these filler polymers exist from units which are derived from the same monomers that can be used to produce τοη copolymers, which units of the fluorine-containing

^C n ^P 2n + 1 ^CH 2 ^CH 2 ° 2 ^{CC (C} V " ^CH 2

Monomers included. The above details of the classes and special compounds of such monomers also apply to these Filler polymers and therefore do not need to be repeated here to become.

Preferred monomers for use as τοη non-vinylidated fluorine-free monovinyl compounds both in units of the Copolymers of the fluorine-containing monomer as well as in the Püller polymers are

RCH (OH) CH ₂ O ₂ GC (R ¹ ) * CH ₂

where R and R ^{1 are} each a hydrogen or a methyl (ie, 2-hydroxyethyl or 2-hydroxypropyl acrylic acid ester or methacrylic acid ester); furthermore alkyl acrylic acid esters or methacrylic acid esters, in particular n-lauryl methacrylic acid esters or 2-ethylhexyl methacrylic acid esters. Advantageously

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All of these polymers contain a small amount of units derived from Jf-methylolacrylamide or H-methylolmethacrylamide and glycidyl methacrylic acid ester or glyidyl methacrylic acid ester in order to improve the resistance of the polymer solids to washing and dry cleaning. A preferred filler polymer contains units derived from an alkyl methacrylic acid ester, e.g. one which contains 98 wt .- ^ units, which of 2-ethylhexyl methacrylic acid ester and 2 wt .- # ■ contains units which are derived from N-methylol acrylamide.

In the fluorine-containing copolymer, the units derived from the fluorine-W- containing monomer can account for 3 to 95% of the total weight. If the fluorine-containing copolymer is mixed with a filler polymer, then the polymer should contain about 3 to 60% of the weight of the polymer solids in units derived from the fluorine-containing monomer.

Useful in the compositions of the present invention, special fluorine-containing copolymers are:

a) 55-70 wt -.%

C _n P _{2n + 1} CH ₂ CH ₂ O ₂ CC (CH ₃ ) - CH ₂

^ 29-45 parts by weight of lauryl methacrylic acid ester

* (an alkyl methacrylic acid ester with predominantly

12 alkyl carbons)

0.1-0.5% by weight 2-Hydroxyäthylakryläureeeter or Methacrylic acid ester (preferably methacrylic acid ester) 0-0.5 wt .- C 9 methylol acrylamide or methacrylamide

(preferably acrylamide).

This fluorinated copolymer can be used alone in the emulsions according to the invention, or it can be mixed with one of the filler polymers described above, although if these Mixing is made, the weight of the dated

009841 / 192Q

- 13 - ■ .. "■ '.'

H ₃ ) = CH ₂

derived units from $ 3 to $ 60 by weight of polymer solids must make out.

b) 70-95 wt .- ^

^C n ^F 2n ₊ 1 ^CH 2 ^CH 2 ° 2 ^C ^ ^CH 3 ⁾ =, ^CH 2 5-30 wt. -I *

2-Ethylhexyl methacrylic acid ester 0.1 - 1 $> Hydroxyäthylakryläureester or

Methacrylic acid esters (preferably methacrylic

acid ester)

0 - 0.5 $> N-methylol acrylamide.

This fluorinated copolymer can be used alone in the emulsions of the present invention or it can be with one of the above-described filler polymers be mixed, provided that in the case of this mixture the weight of the

C _n F _{2n + 1} CH ₂ CH ₂ O ₂ CC (CH ₅ ) = CH ₂

derived units from $ 3 to $ 60 by weight of polymer solids matters.

In addition, these polymer solids can be found to be about 1.5% of the total solids weight of a compound with the following structure

(CH ₂ CH ₂ O) _x H.

^C 18 ^H 37 ^N <T

combine, where χ and y are at least 1. These compounds are described in U.S. Patent 3,348,925.

Also as the fluorinated polymer are any of the above

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-H-

Polymers described useful in which the fluorinated Monomer derived. Units are derived from the following monomer:

^C n ^P 2n ₊ 1 ^CH 2 ⁰ 2 ^CCH " ^CH ₂ ·

The polymers containing the polymer solids used in the emulsions can be obtained by separate polymerizations generally by emulsion polymerization processes. The "milk" of the fluorine-containing polymer and that of the non-fluorine-containing polymer are then mixed in the proportions you want. In general, the polymers can be prepared using any of the known methods

Prepare P for emulsion polymerization of vinyl compounds. The process can be carried out in a reaction vessel, which is provided with a stirrer and with external means either for heating or for cooling the filling. The monomer or the monomers to be polymerized together is in an aqueous solution of a surface-active agent up to a certain concentration of, for example, $ 5-50 dispersed. Usually the temperature is raised to 40-70 ° C to allow polymerization in the presence of an added Catalyst, such as sodium peroxide or 2,2'-azodiisobutyronitrile or another catalyst to initiate the polymerization of an ethylene-unsaturated compound

^ effect.

Other preferred fluorine-containing polymers for use in the compositions of the present invention are the polymeric fluorocarbon acrylate or methacrylate esters, as described in U.S. Patent 2,803 * 615. These homopolymers and copolymers with ethylene-unsaturated polymerizable monomers contain polyaerizable units, that of an acrylic acid ester with the formula

R _f so ₂ N <- ο γ

R-CH ₂ -OCC * CH ₂

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are derived in which R _{f is} a perfluoroalkyl group with 4 to 12 carbon atoms, R is an alkylene group with 1 to 12 carbon atoms, R ^{1 is} an alkyl group with 1 to 6 carbon atoms and R ^{M is} a hydrogen or methyl group. Propyl, N-ethanol perfluorooctanesulphonamide is typical »In the case of the copolymer, the second monomer is selected from ethylene-unsaturated polymerizable monomers, such as maleic anhydride, acrylonitrile, vinyl acetate, vinyl chloride, styrene, methyl acrylate, methyl methacrylate, ethylene, isoprene, butadiene or 2-chlorobutadiene.

For the preparation of the aqueous dispersion of the polymer fuels, i.e. the fluorine-containing polymer and the Filler polymers, the polymers are prepared separately, usually by aqueous emulsion processes, and then put together.

The chlorinated fatty hydrocarbon solvents useful in the emulsions of the present invention include chlorinated alkane solvents and preferably have 1 to 2 Carbon atoms. These are trichlorethylene, tetrachlorethylene, ethylene chloride, tetrachloroethane, Dichloroethane, monochloroethane, dichloromethane, trichloromethane and ethylidene chloride and the like. Preferred solvents are trichlorethylene and tetrachlorethylene.

The emulsifiers that can be used in the context of the present invention include the emulsifiers described in US Pat. No. 3 * 180.750, which consist of a mixture of

(a) a larger amount of a petroleum ketone with the formula RCOR *, where R and R * have 1 - 30 carbon atoms, provided that at least one of them or both have at least 12 carbon atoms (R and R ¹ are either an alkyl, an alkenyl, an aryl, a cycloalkyl or an alkaryl. R and R * are preferably an alkyl.); and

(b) a methylated methylol melamine. The fatty ketone is preferably a stearone, which is one of about 75 ^ stearic acid,

■ 00 98.41 / 1920 ■

about 22% pelmitic acid and about 3% oleic acid derived ketone high molecular weight 1st; Meanwhile, the melamine is one TrI (methoxymethyl) melamine. The preferred composition can be obtained as an aqueous dispersion containing about 45% contains active ingredients.

Another useful class of emulsifiers is in the United States patent 2,783,231, which is the condensation product of

(A) a methylol compound of an aminotriazine or a Urea,

(b) w acid and a primary alkyl amide or an aliphatic carboxylic

(c) a primary or secondary amine. Examples of the Substances specified under (a) are the reaction product of formaldehyde with 2, 4, 6-triamino-1,3,5-triazine (melamine) or methylated methylol melamine. Examples of the substances given under (b) are the amides of methylamine, ethylamine or Octadecylamine or carboxylic acids such as acetic, butter, stearic, behenic or oleic acid. Examples of the substances given under (c) are aliphatic amines, such as methylamine, ethylamine, propanolamine, triethanolamine and the like. Preference is given to using hexamethylolmelamine for the substance indicated under (a), and for the sub-

^ punch stearic acid and for the substance specified under (c) ™ triethanolamine. To make the preferred product about one mole of hexamethylolmelamine is condensed with about 3 moles of stearic acid and about 1 mole of triethanolamine, as described in Example 1 of this patent. The preferred product is commercially available as a composition of about 1 part paraffin wax with about 3 parts active ingredients.

A third class of emulsifiers is in U.S. Patent 3,067,159 described. These emulsifiers consist of an aqueous dispersion of a compound with the formula

0G9841 / 1920

where R is an aliphatic. Is a hydrocarbon group with 16-30 carbon atoms, and either a urea-formaldehyde resin, a modified urea-formaldehyde resin,
a helamine formaldehyde resin or a modified melamine formaldehyde resin. You connection with the formal

(RCONH) ₂ CH ₂

is for example a methylenedistearamide, a methylenedioleylamide, a methylenedimontanamide. Preferably it is to a methylenedistearamide, according to Example II of this USA patent is established; the second component is preferably a modified urea-formaldehyde resin, the production of which is described in the same example.

A fourth class of in the compositions of the invention useful emulsifiers is described in U.S. Patent 3,236,672. These emulsifiers are ethylene or propylene imine derivatives with the formula

RCH

RCH.

where R is hydrogen or an alkyl having 1 to 3 carbon atoms and Rp is an alkyl having 16 to 18 carbon atoms. Typical of these agents are octadecylethylene urea,
Octadecylpropylene urea, stearamidethyleneimine, lauramidethyleneimine, stearamidpropyleneimine and lauramidopropyleneimine. Either octadecylethylene urea or octadecyl propylene urea is preferred.

Another class of emulsifiers is in U.S. Patent 3 · 480,579 described. These have the formula

00 984 1/1920

(CH ₂ OOCR) ₁ (CH ₂ ORM _6-1

where R is an alkyl having 11 to 28 carbon atoms and χ is a of the integers is 2 or 3. Preferably this compound is tri (methoxymethyl) tri (behenoyloxymethyl) melamine. Man is usually mixed with paraffin wax. This means are usually by reaction τοπ hexamethylolmelamine with a lower allyl alcohol, resulting in a Reaction with a long-chain aliphatic carboxylic acid follows.

Another useful emulsifier is stearamidomethyl pyridine chloride. It is usually obtained as an aqueous dispersion of about 30 % methylenedistearamide, about 18% stearamidomethylpyridine chloride, about 5% melamine-formaldehyde resin, the balance being isopropyl alcohol.

Most of the above emulsifiers contain wax, such as paraffin wax. The wax does not have any emulsifying agents Properties and is therefore not one of the "active" ingredients of the emulsifier ». The wax therefore does not form a necessary one Part of the emulsions of the invention. The wax deteriorates or adversely affects the emulsions according to the invention not and, since many commercially available preparations of the emulsifiers described above contain wax, it is used off not to remove the emulsifiers.

The emulsifiers preferred for use in the context of the invention are (a) a mixture of pellet ketone and methylated Methylolmelamine (a substance of this type is available under the trademark "Argus" DWR, the 45 * active ingredient aqueous dispersion of stearon and a melamine formaldehyde resin), and (b) the condensation product of a

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Methylol compound of an aminotriazine or a Harnetoffee, a primary «alkylamide or an aliphatic carbonic acid and a primary · ■ or secondaryβ amine (a substance of this kind iet available under the trademark "Phobotex" f / t / c which is a preferred product of the class described above). Most preferred is an under (b) indicated emulsifier, i.e. a condensation product.

The essentially linear aliphatic polyurethane is obtained by polymerizing an aliphatic diisocyanate, Mostly, an alkylene diisocyanate having 2 to 8 carbon atoms, with a polyalkylene glycol using known ones Procedure. The polyurethane is preferably obtained from polypropylene glycol and 1, e-hexamethylene diisocyanate, with it being a average molecular weight of about 3000 to 4000 (usually about 3300) and contains about 3 to 4% free isocyanate groups (usually about 3.3 ^). Such a product is im Commercially available under the trademark "Synthappret" LKF.

The following examples serve to further explain the Emulsions and processes according to the invention. The parts are given in parts by weight, unless something is expressly stated something else is being announced.

In the examples, the strength of the water-repellent property of the treated with the emulsions according to the invention Tissue according to the method and with the devices American Association of Textile Chemists and Colorists Test Method 22-1967 determined. In this method, each examined sample receives a graduation between 50 and 100. A graduation tone 100 means that there are no traces of moisture on the surface of the sample are present, i.e. that they are essentially perfect Water repellency is given; on the other hand, the graduation 50 corresponds to an essentially completely wet surface. In the tests used in the examples for the oil-repellent property, drops of liquid hydrocarbons of different surface tension were on the surface

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- 20 -

of the treated samples and the degree of penetration or degree of dispersion of the drop into the sample is determined. This degree of penetration then becomes the following standard scale related:

Hydrocarbon value the oil repellency n-heptane 9 n-octane 8th n-decane 7th n-dodecane 6th n-tetradecane VJl 50/50 mixture of mineral oil and n-hexadecane 4th 75/25 mixture of mineral oil and n-hexadecane 3 mineral oil 2

The standard washing tests used in the examples were carried out in a horizontal washing device with a washing drum τοη 50 cm in diameter and the same length. Samples measuring 20 × 25 cm were cut, to which square pieces with an edge length of 20 cm and torn sides of cotton poplin, satin or bark were added, so that the total weight of the dry material was 1.5 kg. These fabrics (without the samples to be examined) were placed in the washing machine and soft water was let in until the water level in the washing drum was 15 cm high. After heating to 50 ° C, neutral soap (a non-alkaline, mild fatty acid soap) was added up to a concentration of 0.1? T based on the total weight of the water in the washing machine. The samples to be examined were then inserted and the washing machine switched on for 40 minutes with the heater closed. The samples were then removed and hand rinsed in soft water at 45 ° C, wringing them out between rinses to remove the soap. The samples were then dried, ironed and stored at 21 ° C + 1 ° C to 65% ± 2 $ relative

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Moisture conditioned for at least 4 hours prior to use water-repellent and oil-repellent property was determined.

The dry cleaning tests used in the examples were, with an American Association of Textile Chemieta and Colorists Standard Launder-Qmeter. A sample of 20 χ 25 cm is placed in a 500 ml bottle with 150 ml perchlorethylene, 2.25 g "Street's Detergent 886" (a sodium fatty alkyl sulfonate detergent) and 0.15g water brought. The bottle is then placed in the holders of the Launder-Ometers are used and this device is then used for 20 minutes switched on for a long time at room temperature. The sample was then taken out, wrung out, dried, and so on the washing test conditioned with water before the leats to Determination of the water-repellent and © '! Repellent properties were carried out.

Examples 1 to 4 descriptive preparations of polymer dispersions for use in the emulsions according to the invention.

Example 1 : Preparation of an aqueous fluoropolymer

dispersion.
The polymers were prepared according to the following recipes:

A. Fluorinated polymer le-ile

Water 2,200

Fluorinated monomer 1,000

n-butyl acrylate 20

N-Methylolaerylamide as a 60 # aqueous solution 5 Dimethyloctadecylamine 30

Glacial acetic acid. 18.3

Acetone 791

Azodiisobutyramidine dihydrochloride 0.4

The monomer was CH ₂ «C (CH ₅ ) CO ₂ CH ₂ CH ₂ (CFg) _n F with η = 6, 8 and 10 in the relative proportions 3: 2: 1, as well as small amounts

0 0 9841/1920

with η = 12 and H.

The mixture was heated to 60 ° C. for hours. B. Non-fluorinated monomer parts

Water 2,200

2-ethylhexyl methacrylate 1,000

N-methylolacrylamide as a 60% aqueous solution 18 Dimethylοctadecylaain 20 Glacial acetic acid 12.2 Sodium chloride 0.7

Acetone 237

Azodiisobutyramidine dihydrochloride 0.222 The mixture was heated to 70 ° C. for animal hours.

Aqueous dispersions A and B were mixed such that 4-½ solids of the polymerized fluorinated monomer were mixed with 6 ½ l solids of the polymerized non-fluorinated monomer, and then the mixture was diluted with water until it was H.33 Active solid parts contained. This fluoropolymeric aqueous dispersion can be used to prepare the emulsions according to the invention.

Example 2; Preparation of an aqueous fluoropolymer

^ Dispersion.

"A. The polymerization was six at 60 ° C

Carried out for hours with the following recipe (addition in the order given) χ

Parts

Water 2,200

Dimethyl octadecylamine 30 Glacial acetic acid 18.3 Fluorinated monomer of Example 1 1,000

n-butyl acrylate 20

N-methylol acrylamide 5

Acetone 1,000

Azodiisobutyramidine dihydrochloride 0.4

009841/1920

B. Here the production becomes a · typical crosslinked Vinylpolymerisatee shown.

The polymerization was carried out at 70 ° C for four hours with the following recipe (addition in the order given) carried out:

file

Water 2,200

Dimethyloctadecylamine 20 Acetic acid 12.2

2-ethylhexyl methacrylate 950

N-methylol acrylamide 18

ethylene dimethaorylate (55t) 50

Acetone 237

Sodium chloride 0.7 Azobiisobutyramidine dihydrochloride 0.222

The two aqueous dispersions were mixed and diluted, among other things to form a single aqueous dispersion, the whole 11.65c contains active pesticide ingredients, namely 5,856 of each of the two dispersions.

Example 3t Preparation of an Aqueous Polymeric Dispersion. A. Fluorinated polymer

The polymerization was carried out at 60 ° C in six hours with the following recipe (addition in the specified order) performed 1 '

Parts

Water * . ". 2,200

Dirnethyloctadecylamine 30.0 Acetic acid 18.3 Fluorinated monomer of Example 1 750.0

2-ethylhexyl methacrylate 250.0

H-methylolacrylamide .2.5

2-hydroxyethyl methacrylate. ■ 2.5

Acetone 1,000.0

Azodiisobutyramidine dihydrochloride 0.4

00 9 8 L 1/1 9 2 0

B. Wicht fluorinated vinylidene polymer -

networked.

The polymerization took place in animal hours at 70 ° C with the following recipe (addition in the specified order):

Parts

Water 2,200.0

Whore thyloctadeeylamine 20.0 Glacial acetic acid 12.2

2-ethylhexyl methacrylate 950.0

H-methylolaerylamide 18.0 Ethylene diethacrylate 5.0

Acetone 237.0

Sodium chloride, 0.7 Azobisisobutyramidine dihydrochloride 0.222

C. The polymerization of the aqueous solution of this Example took place at 70 ° C. in animal hours with the following Recipe (addition in the order given):

Parts

Demineralized water 2,200.0 Octadedyldimethylamine 20.0 Acetic acid 12.2

2-ethylhexyl methacrylate 1,000.0

Acetone 237.0

Sodium chloride 0.7

60 * H-methylol acrylamide 18.0

A * o Bi (isobutyramidine) dihydrochloride 0.222

An approximately 30% dispersion of a polymer resulted with 98 * 2-ethylhexyl methacrylate and 2 * H-methylolacrylamide.

The aqueous dispersion A can either with the aqueous Dispersion B or C can be mixed and diluted to make a to produce aqueous dispersion that is used for the production of the Emulsion according to the invention is suitable. In one example a mixture is used that contains a total of 14.3 * active solid components, namely 8.28 * of A and 6.03 * of C.

00 9 8 Λ 1/1920

Example 4; Production of an aqueous polymer dispersion. A. A fluoropolymer membrane was made as follows:

(A) Dimethyl Di (hydrogenated tallow) ammonium chloride (Aliquat H 226 - General Hills) (6.25 g, Q, 45 # based on the Monomer weighted * OWM) was dissolved in 2.37 g of water with stirring. Then 1003.4 g (66.5 * OWM)

CH ₂ = C (CH ₃ ) CO ₂ OH ₂ CH ₂ (CPg) _n P

with η a 6, 8 and 10 in the weight ratio 3: 2s1, the less as 10 £ η - 12 and contains H, and 497.9 g (33, O # OWM) one commercially available lauryl methacrylate (60 ^ n-dodecyl, 27 ^ n-Tetradedyl, 7 # lower esters, 6 # higher esters, molecular weight 262) and homogenized with the aqueous solution. Water (1 * 650 g) in a separate container was with Nitrogen and boil degassed and then the above monomer dispersion added. Dodecylmereaptane (2.25 g> 0.15 $ OWM), 6.28 g (A25 ^ OWM) of a 60 # aqueous solution of N-methylolacrylamide and 3.77 g (0.25 # OWM) of a 2-hydroxyethyl methyl acrylate were added and the mixture was heated to 60 ° C with stirring and 1.1 g (0.07 £ OWM) Azobi- (isobutyramidine dihydrochloride) added. The polymerization was initiated and heating continued at 60-70 ° C to completion (4 to 5 hours). Which resulting aqueous dispersion contained about 28% solids.

A single polymer dispersion having a total of 15 polymer solids was prepared to contain 5.5% of the solids of Dispersion A above, 4.14% of the solids of Dispersion A of Example 5, and 6% of the solids of Dispersion B of Example 3. This combined dispersion can be used to prepare the emulsions according to the invention. -

Examples 5 to 13 describe the preparation of emulsions according to the invention and its application to textiles.

009841/1920

Example 5 ;

In a suitable container were mixed with vigorous stirring *

(1) 1000 g of a dispersion available under the trade name "Scotchgard OF-208" as an oil and water repellent Application in textiles is distributed. The product contained 28% of a polymer with perfluorinated chains in an aqueous mixture containing some ethylene glycol. £ s is an aqueous dispersion of a polymer believed to be derived from the following monomers

I ^lat:

O ₃ H ₇ 0

50% C ₈ F ₁₇ SO ₂ H-CH ₂ CH ₂ OC-CH - CH ₂

01 50% CH ₂ * C-CH - CH ₂

Its preparation is described in U.S. Patent 3,068,187, Example 8, Part B;

(2) 1000 g of an aqueous dispersion of an emulsifier which is sold under the trade name "Phobotex f / t / c", a Composition from one part paraffin wax to three parts reaction product of a hexamethoxymethyl melamine + 3 MeI Stearic acid + 1 mol triethanolamine + acetic acid according to the

Spelling in Example 1 of US Pat. No. 2,783,231. This commercially available product may also contain stabilizers depending on the intended use.

The stirred mixture were then

(3) 500 g of a 1,1,1-trichloroethane were added at a rate of 12 ml per second. The temperature was 31 ° C and a gravity stirrer such as a "Waring" mixer was used. The slightly thickened emulsion was stirred an additional 15 minutes and then 3ooo g Trichlorätb * B were each added at a rate of 30 ml second addition, the ^t: ■ yielding · emulsion was at least five days oh "© jegliohe phase separation stable.

009841/1920 '

ORIGINAL

It was then further diluted with solvent to obtain used for the treatment of made-up textile product niases to become.

Beiapiel 6t

Its aqueous fluoropolymer dispersion was used for the preparation a cooperation according to the invention with that of the company Union Chimique Beige used under the trade name "Argue" DWR sold and noted above emulsifier.

The combined aqueous diaperion formed in the case of 3 *, inter alia, the diaperions A and C, with a total content of meat of 14.35t was to be given a composition according to the present invention. .

In a suitable container, 500 g of the above-mentioned combined, aqueous Diaperaion were placed and 1000 g of the above-mentioned Emulsifier "Argus' ¹ DWR with 45 * active" ingredients and 100 g of the condensation catalyst prescribed for "Argue" DWR were added 300 g of triohloroethylene were added to the resulting aqueous suapenaion at a rate of 10 ml per second at 30 ° C. During the addition of the solvent, the mixture was stirred relatively vigorously the resulting emulsion was stored for seven days without any phase separation.

Beiapiel 7t

The emulsified composition of Example 6 was shown in FIG Stirring diluted with trichlorethylene so that the concentration of the fluoropolymer emulsion is 1.2 pounds (0.162? T) of solid active ingredients (and the concentration of the surface modification agent "Argus" PWR 2.4 * -1.08 * solids) fraud. The diluted composition was injected with nozzles

.009841 / 1920-

a wool fabric with a weight of 0.4 kg per meter would have. The spray was applied evenly on both sides of the piece of fabric at 100 ^ moisture absorption based on the fabric weight. After about 6 seconds of allowing the composition to penetrate the fabric and completely cover it, the frobe was in a chamber with an inlet temperature of 85 ° C and an initial temperature of 130 ° C. The total heating time was 36 seconds. When the treated fabric was examined in the manner already described above, an oil repellency value was found that was initially around 7 and after one and three washes was 6. The degree of water removal according to the “spray rating” test described above was approximately 100 at the beginning and 90 after one and three washes. The "handle" was almost the same as that of an untreated one Material.

Example 8?

The Hf 35 * solids-containing dispersion from the combination of dispersions A and C in Example 3 was used to prepare a combined emulsion with "Phobotex" f / t / c and "Synthappret" LKF, which is an 80 # solution is in ethylacetate of a polymer prepared from an aliphatic isocyanate and propylene glycol with a molecular weight of about 3500 Jk and 3% to 4% free isocyanate groups.

1000 g of the above-mentioned fluoropolymer dispersion were placed in a suitable container and this became 300 g "Phobotex" added f / t / c. A solution of 400 g of "Synthappret" LKF in 400 g of trichlorethylene was prepared and this solution was added to the combined emulsion with vigorous stirring at a rate of 30 ml per second. After stirring for an additional 15 minutes, an additional 3000 g of trichlorethylene was added at a rate of 50 ml added per second. This stable emulsion was up to a concentration of 0.5 # in the fluoropolymer product,

0098-1 / 1920

0.15% "Phobotex" f / t / c and 0.2% in "Synthappret" LKP diluted · The diluted emulsion has been diluted to different Jersey knitwear samples were sprayed on, the garments taking up 118% of their dry weight in emulsion. Samples were previously soaked in Triehloräthylen and then the excess solvent was removed in a centrifuge been. The samples were dried at 95 ° C for 20 minutes and then cured at 125 ° Ö for 15 minutes. The results The examination of these samples for their oil- and water-repellent properties are shown in the following table I put together.

textile
composition Oil repellency
Water repellency y
At the start After three
Washes After three
Dry
cleaning. Table I. polyester
fiber yarn η oil repellency
Water repellency 6th
100 6 - 7
90 6th
70-80 polyester
wool, 55/45 Oil repellency
Water repellency 6th
80 6-7
80-90 6th
70 nylon Oil repellency
Water repellency 5-6
100 5
70-80 .4
70 acetate
fiber 6th
90-100 4th
80-90 6th
70-80 Example 9:

To prepare an emulsion, a "Waring" mixer 100 ml of the dispersion according to Example 4 and 30 g "Phobotex" f / t / c combined. 90 ml of triohlorethylene were added to this emulsion poured slowly in. The mixture was stirred at high speed for 15 minutes and then an additional 60 al

0098417 1920

Trichlorethylene added in the same way. The emulsion prepared was diluted to give three dilute emulsion treatment baths. For bath a) 9.2 g of the emulsion were diluted with trichlorethylene to a total bath amount of 1000 g. For bath b) 6.3 g of the emulsion were diluted to a total of 1000 g and for bath c) 19.0 g of the emulsion were diluted to a total of 1000 g.

A piece of fabric made of pure wool was immersed in bath a), taken out of this again and ao deeply wringed out that the piece of fabric had absorbed 48% of its weight in emulsion. A f 100> from Acrylfaaern existing tissue piece was w b in daa bath) immersed herauagenommen and · to auagewrungen to an emulsion Low 33O ^ a piece of fabric of polyester / cotton in Yerhältnia 65/35 was in daa Bad c) immersed herauagenommen and bia to an emulaiona recording of 160 ^ auagewrungen.

All three treated fabrics were dried in a "Ciaael" rotary drum dryer at 60 ° C for two to three minutes and then held at 120 ° C for two minutes. The pieces were cooled and examined for their oil- and water-repellent properties. The treated wool showed in the "spray test" a water repellency value of 90 and an oil repellency * value of 6. The acrylic fiber had a water repellency value of 90 and an oil repellency value of 5. Cotton fabric showed a Waaaerabweiaunga value of 80 and an oil repellency value of 2.

Example 10;

To produce an emulsion, 1000 g of the combined Pluorpolymeriaatdiaperaion dea Beiapiela 3A and C were first made with 300 g of "Phobotex" f / t / e with vigorous stirring. Then 500 g of trichlorethylene were i® al vigorous stirring with a Geachwindlgkeit of about 15? * Ku £ ·. $% ^ I gageben. Laughing was another 10 minutes long gertfb fc hollows, were more

009841/1920

BATH

100 g of trichlorethylene were added per second at a rate of τοη 30 al, a thick, stable emulsion being formed. To prepare a treatment bath, 10 g of the emulsion were thinned with 2500 g of trichlorethylene. Samples of wool, 100 % polyeater knitwear and cotton knitwear were dipped in trichlorethylene and wrung out or thrown out to such an extent that 30% of solvents were retained; the samples were then immersed in the treatment bath and allowed to take up 400 to 500 pounds of liquid, so that 1.6 to 2.0 centimeters of the undiluted, stable emulsion were taken up based on the weight of the fabric. The samples were then drum dried for two to three minutes at 60 ° C and then heated at 120 ° C for three minutes. In the "spray test", all fabrics showed a water repellency value of 90-100 and also had an oil repellency value of 6 to 7 The concentration corresponds to 0.5 to 0.6 tons of the fluoropolymer emulsion based on the weight of the fabric.

Example 11 »

43 g of "Phobotex" f / t / c and 3H g of trichlorethylene were placed in a "Waring" mixer and the mixture was stirred at high speed for five minutes to form a solution. Bann were 143 g of the dispersion of Parts A and C of Example 3 14 ₉ 31 * solids content slowly poured, was further stirred with a high speed. After the whole aqueous dispersion was poured out; the mixture was stirred for five minutes and then a further 314 β trichlorethylene was added with stirring. 20 g of the stable emulsion were thinned to a total of 3000 g with trichlorethylene and then used for treating τοη fabric samples made of pure wool, polyester knitted fabric and cotton knitted fabric. The fabric samples were immersed in trichlorethylene and wrung out or spun out so far that 30% of the solvent remained. They were then immersed in the thinned emulsion of the treatment bath β, removed and wrung out so far.

- .... 0098-1 / 1920

gen or centrifuged so that about 450% moisture absorption remained (about 1.8% of the concentrated emulsion based on the fiber weight). The treated pieces of fabric were dried in a "diesel" dryer with circulation at 60 ° C. for two to three minutes and then heated to 120 ° C. for three minutes. In the "Spray Rating" test, the water repellency value was 90-100 and the oil repellency value was 6-7 for all three types of fabric.

Example 12:

An aqueous emulsion with about 28% of a perfluorinated one Polymer composition with the formula

R ^ OgNiRMRCHgOCOCH = CHg

as described above, was mixed with stirring with part of an emulsifier «which is produced by the reaction of a Moles of Hezamethylolmelamin with 3 moles of stearic acid and 1 mole of triethanolamine and neutralized with acetic acid The resulting product had a waxy consistency and contained essentially 100% active ingredients. to the aqueous dispersion mixture was then half a part 1,1,1-trichiorethane slowly and evenly while stirring gently fc added. The viscosity increases with the addition of the solvent until the mixture finally becomes a thick, viscous paste is. After mixing for about 13 minutes, an additional three parts of the same solvent were added fairly quickly with gentle stirring. This suspension is stable and shows no separation after five days of standing. The stable suspension contains about 5.8% of the fluoropolymer composition (1.62% fluoropolymer). After further dilution with solvent, which increases the concentration of Fluoropolymer composition is brought to about 0.1%, the composition can be applied to textiles.

0098/11/1 920

Example 13:

Eight emulsions according to the invention were prepared according to the method described in Se Example 8 and, for use diluted to the ingredient proportions indicated in # in the following table. With each of the compositions, the Treated textiles specified in the table and there were Then the oil and water repellency values of the samples given in the following table were determined

00 984 17 1920

Textile composition

Emilia ion (diluted)

Moisture Rejection Rejection after Dry rice 4th recording at the start Washes inclinations
1 5 70 (based on d. 1 3 Fiber-oriented) 4th ) 108 * oil - 5 6 5 Water 90/100 80/90

100 * wool

0.50 * "Zepel" B (example 3)

0.15 * "Phobotex" PTC

(Ex. 5) 0.20 * "Synthappret" LKF

50 * wool 0.80 * "Zepel" B 50 * polyester 0.24 * "Phobotex" FTC

0.20 * "Synthappret" LKF

cc 100 * polyester 0.50 * "Zepel" B

ο 0.15 * "PhQbotex" ITC

0.20 * "Synthappret" LKF 113 * oil - 5

Water 90/100 Fabric hardened for 5 min

Fabric 5 back hardened at 120 C _/ after soaking in solvent

5 5 4 4 90/100 70

12O ⁰ Cy without soaking

6 6 6 5 90/100 70/80

soaked in solvent

118 *

oil - 6 Water 100

75 * polyester 1.50 * "Zepel" B

25 * polyamide 0.45 * "Phobetex- FIC

0.30 * "Synthappret" LKF 137 *

oil - 6/7 6 Water 90/100

6 6 6 90/100 90/100 without soaking

Textile etching

Emulsion (diluted) resistance to skin resistance

recording at the beginning (based on d. Pasergewicht) rejection after. Wiping dry

approvals 13 1 3

100 * polyamide 0.50 * »Zepel« B

0.1556 "Phobot ei ¹¹ PTC 0.20 * " Synthappret "LKP

118 *

(£>
OO IOO54 acrylic fiber 0.80 * "Zepel" B . i 0.24 * ■ Phobotex ¹ · PTC ¹ ^
"J 0.20 * "Synthappret ¹ · LKP <£> N> O viscose 1.50 * "Zepel" B Rayon 0.45 * "Phobotex" PTC 0.30 * " Synthappret" LKP cotton 2.00 * "Zepel" B 0.60 * "Phobotex" PTC 0.40 * ^w Synthappret ¹¹ LKP

92.5 * oil - 5/6
Water 100

6-5 5 4 70/80 70 soaked in solvent

Oil - 7 5-654 water 100 70/80 70 fabric 5 min. Hardened at 100 ⁰ C, soaked in

solvent

103 * oil - 6
Water 90-

4th
50

6 80

Fabric 5 back hardened at 130 C, without soaking

107 * oil. - 6 3 2- 4 4 water 100 50 80

Fabric cured for 5 minutes at 130 ° C without soaking

The above representative examples can be taken as a whole of the invention on the basis of the skill in the art «may of course be modified to essentially include the achieve the same results.

Of course, the above description only serves to explain and better understand, but not to delimit the invention.

0Q9fUi / 1920

Claims (1)

EXPECTATIONS II. An oil and water repellent containing perfluoroalkyl Polymer and - III. one * of the following emulsifiers: a) a mixture of a fatty ketone and a methylated methylol melamine; b) the condensation product of (i) a methylol compound an aminotriazine or a urea, (ii) a primary alkyl amide or a aliphatic carboxylic acid and (iii) a primary or secondary amine j c) a compound having the formula (RCOIiH) ₂ CH ₂ , in which R is a fatty hydrocarbon group having 16-30 carbon atoms; and either a urea-formaldehyde resin, a modified urea-formaldehyde resin, a melami-formaldehyde resin. or a modified melamine formaldehyde resin; 00 98 41/1920 d) its compound with the formula HCH HCH -CO-NHR, where each R is hydrogen or an alkyl of 1-3 carbon atoms and R _{2 is} an alkyl of 16-18 carbon atoms; e) a compound having the formula (CH ₂ OOCE) _x (CH ₂ ORM _6-1 where R is an alkyl of 11-23 carbon atoms, ζ is an integer from 2-3 and R ^{1 is} an alkyl of Is 1-6 carbon atoms; f) stearamidomethylpyridinium chloride; and optionally IV. An essentially linear aliphatic polyurethane of an aliphatic diisocyanate and a polyalkylene glycol with a molecular weight between about 2000 and 5000 and with about 2f> to 5 # free isocyanate groups. 2 · Emulsion according to claim 1 with a chlorinated one Fatty hydrocarbon solvents with 1-3 carbon atoms, which contains in emulsified form: I. water; . > II. A perfluoroalkyl-containing oil- and water-repellent polymer which either has a polymer which contains units which are derived from C _n F _{2n + 1} CH ₂ CH ₂ O ₂ CC (CH ₃ ) 0098-1 / 1920 - ... - 39 - ■■■■■. '■■ are derived, where η. an integer between 3 and 14, or a polymer, the units contains «the from ^R ' R-CH ₂ O ₂ CCE "= CF ₂ are derived, where R _{f is} a perfluoroalkyl group with 4-12 carbon atoms, R is an alkylene group with 1-1-2 carbon atoms, R 'is an alkyl group with 1-6 carbon atoms and R "is a hydrogen or a methyl; and
III. an emulsifier according to claim 1. 3 · Emulsion according to claim 1 with a chlorinated one Fatty hydrocarbon solvents with 1-3 carbon atoms ₈ which are contained in emulsified form? • I. Water; II. An oil and water repellent containing perfluoroalkyl Polymer which either has a polymer which contains units from ^{= CH} 2 are derived, where η is an integer between 3 and Hist, or a polymer containing units ent keeps that of R-CH ₂ O ₂ CCR "« CF ₂ are derived, where R ~ is a perfluoroalkyl group with 4-12 carbon atoms, R is an alkylene group with 1-12 carbon atoms, R ^{1 is} an alkyl group with 1-6 carbon atoms and R "is hydrogen or methyl; 0098A1 / 1920 III. an emulsifier according to claim 1 and IV. A polyurethane according to claim 1. 4- emulsion according to claim 2, characterized in that that the perfluoroalkyl containing oil and water repellent Polymer a polymer with at least one compound of the formula C _n P _{2n + 1} CH ₂ CH ₂ O ₂ CC (CH ₃ ) = CH ₂ where η is an integer between 3 and 14 and at least _k is a polymerizable monovinyl compound which is free from non-vinylidated fluorine. 5. Emulsion according to claim 4 »characterized in that that the emulsifier either: a) a mixture of a larger amount of a fatty ketone with the formula RCOR ¹ , where R and R »are alkyls with 1-30 carbon atoms and at least one of these
both has at least 12 carbon atoms, and
a smaller amount of a methylated methylolmelamine, or b) the condensation product of a methylolmelamine, a Is carbonic acid and an aliphatic amine. 6. Emulsion according to claim 5, characterized in that the emulsion contains an oil- and water-repellent Composition of a mixture of (a) a copolymer with at least one compound of the formula C _n F _{2n + 1} CH ₂ CH ₂ O ₂ CC (GH ₃ ) * CH ₂ where η is an integer between 3 and 14, further from (b) one or more monomers having the formula RCH (OH) CH ₂ O ₂ CC (R ¹ ) »CH ₂ 0 09RZ _{1 1/1920} \ t where R and R ^{1 are} each hydrogen or methyl, furthermore (c) from an alkyl acrylate or methacrylate and (d) from an N-methylolacrylamide or methacrylamide, and a copolymer which contains units derived from an alkyl methacrylate. · 7. Emulsion according to claim 6, characterized in that the emulsifier is the condensation product of Hexamethylolmelamine, stearic acid and triethanolamine and that solvent is trichlorethylene or tetrachlorethylene. 8. Emulsion according to claim 4, characterized in that the perfluoroalkyl-containing oil and water repellent Polymer is a copolymer of at least one compound with the formula where η is an integer between 3 and H and at least one polymerizable monoviny! compound which is free from vinylidated fluorine '- 9 * Emulsion according to claim 8, characterized indicates that the emulsifier either: a) a mixture of a major amount of fatty ketone of the formula RCOR ', wherein R and R' is an alkyl having 1-30 coal ₄ are lenstoffatomen and at least one of them at least 12 carbon atoms, and a minor amount of a methylated methylolmelamine or b) is the condensation product of a methylol melamine, a carboxylic acid and an aliphatic amine. 10. Emulsion according to claim 9 »characterized in that it contains: an oil and water repellent composition, consisting of a mixture of a copolymer of (a) at least one compound with the formula 0098A1 / 1920 - 42 -C _n P _{2n + 1} CH ₂ CH ₂ O ₂ CC (CH ₃ ) - CH ₂ where η «is an integer between 3 and 14, and (b) one or more monomers with the formula RCH (OH) CH ₂ O ₂ CC (R ¹ ) = CH ₂ where R and R 'are each hydrogen or methyl, furthermore (c) an alkyl acrylate or methacrylate and (d) N-methylolacrylamide or methacrylamide, and a copolymer containing units derived from an alkyl methacrylate contains, and finally a polyurethane of an alkylene P diieocyanat with 2-8 carbon atoms and a polyalkylene glycol. 11. Emulsion according to claim 10, characterized in that the emulsifier is the condensation product of Hexamethylolmelamine, stearic acid and friäthanolamin and the solvent is trichlorethylene or tetrachlorethylene and that the polyurethane from 1,6-Hezamethylene diisocyanate and Polypropylene glycol with a molecular weight between about 3000 and 4000 and with about 3-4% free isocyanate groups. t 12. Method for preparing an emulsion according to Claim 2, characterized in that the chlorinated fatty hydrocarbon solvent is mixed with gentle stirring slowly in an aqueous mixture of the perfluoro-containing oil and water-repellent polymer and emulsifier. 13 * Method for making the emulsion according to Claim 3 _f, characterized in that the emulsifier is the condensation product of hexamethylolmelamine, stearic acid and triethanolamine and the solvent is trichlorethylene or tetrachlorethylene, into which the polyurethane is then slowly added with gentle stirring. 0098A1 / 1920 14 · Process for treating textiles with The Eauleion according to Claims 1 to 11, characterized in that the emulsion is applied by spraying or dipping, and the Teitilie is then dried and, if necessary, hardened. OfäPfiA 1 / TQTfI