DE2307512A1 - Means for making fibrous material water-deviating and its use - Google Patents

Description

"Agent for making fibrous material water-repellent and its use ^M

Priority: February 17, 1972, Great Britain, No. 7430/72

The invention relates to a means for waterproofing hats of fiber goods, especially those containing cellulose! Material consisting of a water-repellent agent dispersed in a liquid medium Compound, which is characterized in that it is an aslactone with at least one long-acting contains aliphatic hydrocarbon radical.

The invention also relates to the use of the agent for Treatment of paper ", cotton or rayon containing Material.

The agent according to the invention preferably contains an azlactone

309834/1059

of the formulas (I to IV)

R_____ / - _____ r> —-——— V »—-—— y ^

Ns = C

c c:

II

4 I.

N == C

: _C c:

N C:

III

IV

1 2
in which R, R and R each represent a hydrogen atom or a

3 optionally substituted hydrocarbon radical, R is a two-

4 5 valent hydrocarbon radicals, R and R each a hydrogen atom or an optionally substituted hydrocarbon

4 5

rest or only R ^ or only R is a hydroxyl or ether group

mean.

The long-chain aliphatic hydrocarbon radical forms one the radicals R to R or is contained therein. This long-chain residue gives the azlactone hydrophobic properties. The measurement depends on the chain length of the residue, i.e. the longer the chain, the better the hydrophobic properties. Contains However, if the chain has more than 20 carbon atoms, then the.jf is correct Dependency no longer. Preferably the remainder contains at least 8, in particular 14 to 18 carbon atoms in the main chain. The main chain can be branched, with the substituents

309834/1059

e.g. short alkyl chains, cycloalkyl or aryl radicals. However, unbranched radicals are preferred. As a long chain Hydrocarbon radicals are suitable are alkyl radicals, e.g. n-octyl, n-decyl, n-undecyl, n-dodecyl, n-terdecyl, n-nonadecyl, n-eicosyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl and n-octadecyl radicals or olefinically unsaturated ones Radicals, e.g. the alkenyl radicals corresponding to the alkyl radicals »radicals with more than 20 carbon atoms in the main chain are less suitable for economic reasons.

Azlactones of the formula (III) in which one of the radicals R or R is a radical of the formula -SR, -NRR or -N ^ " ^is " at least partially under aqueous conditions, as are often used in coating or gluing processes, hydrolyte

-Speed eeps. Under these conditions the hydrolysis / the in

the inventive agents contained azlactones at least

p
dent determined in part by the remainder R.

It is important that the rate of hydrolysis does not increase

2 is big. The radical R is preferably an aliphatic rust, such as an alkyl or cycloalkyl radical, or a radical which is a or contains several carbon-carbon double bonds, e.g. an alkenyl or cycloalkenyl radical, or an aromatic rust, such as an aryl, arylalkyl, arylalkenyl or alkylaryl radical, e.g. a phenyl, benzyl or 2-phenylethenyl radical. Substituted with an alkyl radical, for example, are also suitable Cycloalkyl or cycloalkenyl radicals. The carbon-carbon

Double bond in the unsaturated R radical can be with the carbon nitrogen -Double bond in the azlactone ring be conjugated.

309834/1059

Preferred radicals are methyl, ethyl, n-propyl, isopropyl, η-butyl, isobutyl, tert-butyl, hexyl, cyclohexyl, Methylcyclohexyl, cyclohexenyl radicals or particularly long-chain aliphatic radicals.

Pur R and R is preferably the Y carbon atom or any radical,

2 12

which is suitable for R. The radicals R, R and R can be with one another be the same or different, e.g. R or R means

and the other radical _{1 is} a long-chain aliphatic Resi /, R or R is a water

substance atom and R is an alkyl radical, preferably a methyl or a second long-chain aliphatic radical. Examples of such azlactones are 2-methyl-4-hexadecylazlactone, 2-methyl-4-tetradecylazlactone, 2-methyl-4-decylazlactone, 2-heptadecyl-4-hexadecylazlactone, 2-terdecyl-4-tetradecylazlactone and 2-heptadecyl-4-decylazlactone.

4 5

Preferably R and R each represent a hydrogen atom or

OO · A

a residue that is also suitable for R. The residues R, R and

5
R can be the same or different, provided that only

4 5
one of the radicals R or R is a radical of the formula -OR.

4 5 One of the radicals R or R is preferably a long-chain one Alkyl radical or an optionally substituted aryl radical. An example of such an azlactone is 2-phenyl-4 - ("1-hydroxy-tetradecylidenj-azlactone.

Diradicals are attached to the azlactone residue by simple

■ 3 sigma bonds bound. Preferably R is a divalent one

aliphatic radical, such as a divalent alkyl or alkenyl radical, in particular a radical of the formula R J ^ CCf »der 5 or

309834/1059

Contains 6 carbon atoms in a ring / optionally one

2 substituents, e.g. a radical that is also suitable for R. According to formula (IV), the carbon-carbon double bonds are conjugated. PUr R are particularly suitable divalent Pentamethylene and pentenylene-2 radicals.

4 5
Particularly suitable for R and R is an aryl, alkenyl or cycloalkenyl radical which has two carbon-carbon double bonds conjugated according to formula (III).

To manufacture de. ic contained in the agents according to the invention Azlactone becomes a carboxylic acid of the formula RR'CH'COOH in the presence of phosphorus to a t * -bromocarboxylic acid of the formula RR CBrCOOH brominated. By implementing this bromocarboxylic acid with ammonia you get an o ^ _Aminocarboxylic acid, which with a

Acyl chloride of the formula R COCl to form an N-acyl-o ^ -aminocarbon-

1 2

acid of the formula RR C (NHCOR) COOH is converted. The ring closure is then carried out using acetic anhydride.

In a second process for the production of some azlactones one starts, for example, from diethyl acetamidomalonic acid, CIUCO-NHCH (COOCpHc) Ot ^a us, which is converted first with sodium ethylate and then with an organic halide to an acetamidoalkylmalonic acid diethyl ester, CH ^ CONHCR (COOC ₂ Hk) ₂ »is implemented. By treating this compound with potassium hydroxide and then with a mineral acid, the corresponding monocarboxylic acid is obtained, which is converted into the corresponding azlactou with acetic anhydride.

309834/1059

But you can also use the acetamidoalkylmalonic acid diethyl ester reflux with hydrochloric acid; an oc -aminocarboxylic acid is then obtained which, according to the first process, is converted into the corresponding azlactone is converted.

The agents according to the invention for rendering water repellent by dissolving the azlactone in an inert organic liquid or by emulsifying the azlactone with water or with an aqueous solution of a retention aid and / or an emulsifying agent prepared by conventional methods. The inert organic liquid does not contain any groups that react with the azlactone, i.e. no primary and secondary groups Amino and hydroxyl groups. Suitable organic liquids are hydrophobic liquids such as aromatic hydrocarbons, e.g. benzene. or toluene, or liquid halogenated hydrocarbons such as dichloromethane or carbon tetrachloride, or hydrophilic liquids such as ketones, e.g. acetone,

or aliphatic ethers. The liquid preferably has a boiling point below 150 ^° C., in particular below 100 ^° G.

The aqueous phase of the emulsion preferably contains a retention aid, such as a cationic organic polymer (e.g. those described in British Patent Specification No. 1,274,654) or polyacrylamides. Preferably the weight ratio of retention aid to azlactone is 2: 1 to 1 r 20.

The emulsion preferably contains an emulsifying agent such as a fatty acid sorbitan ester, in particular a polyoxyalkylene derivative

309834/1059

a fatty acid sorbitan ester, such as a polyoxyethylene or polyoxypropylene derivative of a monolauric acid, monopalmitic acid, Mono- or tristearic acid or mono- or trioleic acid eorbitan esters. Also glycerol esters of fatty acids, polyethylene glycol esters of fatty acids or mono- or dialkanolamide derivatives of fatty acids, such as lauric acid, palmitic acid, Stearic acid or oleic acid are suitable. The emulsifier can also be a polyalkylene oxide block copolymer, such as an ethylene oxide or propylene oxide condensate with aliphatic alcohols, more often alkylphenols, preferably with alcohols or phenols with 8 to 22 carbon atoms in the aliphatic chain, such as octylphenol, nonylphenol and palmityl, Stearyl or oleyl alcohol, or mixtures of these compounds, or an ethylene oxide or propylene oxide condensate with long-chain aliphatic amines, such as amines, which are preferred Contain 8 to 22 carbon atoms.

Preferably the weight ratio of emulsifier is to azlactone in the emulsion about 1: 2 to 1:50. increase in azlactone, emulsifier and retention agent concentration the viscosity of the emulsion increases. The azlactone concentration is preferably no more than about 3/4 percent by weight.

Presumably the azlactone reacts, at least partially, with the hydroxyl groups of the cellulose-containing material to form amidoesters and is thus chemically bound to the material. If the azlactone is applied from an aqueous emulsion, there is competition this reaction with the hydrolysis of the Azlactone through

309834/1059

Water.

However, the agent according to the invention can also be used for coating or use linen made from material that does not contain reactive groups. In this pail the azlactone is appropriately known Coating agents added, such as aliphatic alcohols or amines with a molecular weight of about 150 or above.

Cellulose or cellulose is suitable as a cellulose-containing material regenerated cellulose, such as cotton, linen or rayon, or their mixtures or preferably paper. The paper can in the form of an aqueous paper material that has been manufactured in a conventional manner, e.g. wood pulp, semi-pulp or cellulose, are present. The paper or pulp can be bleached, semi-bleached or non-bleached and fillers or pigments such as clay, e.g., kaolin, calcium carbonate, titanium dioxide or zinc oxide.

Contact is preferably made with the device according to the invention under approximately neutral or weakly alkaline conditions, e.g. at a pH of about 6 to 10, preferably of 7 to 9 · Under these conditions you can use calcium carbonate as a filler and also poor aging and Avoid resistance properties that can occur in paper under acidic conditions.

The best way to treat the cellulosic material is to shape it of dried webs or rolls by any conventional method for impregnating fibrous material. That is, the

309834/1059

dried webs or rolls of paper or other cellulosic » Material, such as textile fabrics, are made by a bath containing a solution of one or more azlactones in a suitable Contains organic solvent, passed through. The concentration of azlactone in the solution and that caused by the The amount of solution absorbed by paper determines the amount of azlactone present in the sized paper, as practically all of it Azlactone present in the solution reacts with the cellulose. On the other hand, the bath can be an aqueous emulsion of azlactone contain. The amount of agent according to the invention absorbed by the webs or rolls can be determined by conventional methods, such as the use of squeegee rollers, can be controlled. Other suitable impregnation methods are brushing on, spraying on or rolling.

After the agent according to the invention has come into contact with the cellulose-containing material, it is dried, for example by drying at room temperature or by heating. The drying temperature is chosen so that the material does not suffer any damage; generally it is above about 5O ⁰ G, such as paper is often dried at a temperature of about 100 to 12O ° C, tissue at a temperature of 100 to 150 ° G. The emulsion or solution containing the agent according to the invention is preferably used in such an amount and in such a concentration that, based on the dry paper, the dried and sized paper contains the lowest amount of azlactone required for good sizing. The quality of the paper sizing is measured by the Cobb test

309834/1059

Azlaotone weight in dry paper increases up to one the quality of the glue to a certain limit. Beyond this limit, however, an increase in the weight of azlactone results in dry conditions Paper no longer improves sizing. These

5 limit depends on the type of residues R to R and also on whether the paper has been treated with a solution or with an aqueous emulsion. Obviously, this limit is there

maximum
at / about 4 percent by weight azlactone, while its lower value at

about 0.05 weight percent.

Purely for storage and transport, it is desirable, though the azlactone is dispersed in the smallest amount of liquid medium. Although you can use solutions below 10 percent saturation solutions with more than 50 percent saturation, especially practically saturated solutions, are preferred. Because of the viscosity aqueous emulsions with an azlactone content of 1 to 10 percent by weight are preferred.

The cellulose-containing material is preferably treated with the agents according to the invention in a two-step process. Curing in addition to conventional drying is not possible necessary.

The examples illustrate the invention.

309834/1059

Example 1 1. Preparation of 2-phenyl-4-n-hexadecylazlactone

50 g of stearic acid (C ₁₇ H ₅ ^ COOH) and 2.25 g of red phosphorus are thoroughly mixed together in a flask equipped with a dropping funnel and condenser, and 18 ml of bromine are added dropwise. The mixture is heated on the water bath for about 6 hours. The dark brown reaction product is then poured dropwise into cold water, whereupon 06-bromostearic acid precipitates out as a pale yellow precipitate. The precipitate is washed with water, dried and recrystallized from petroleum ether with a boiling range of 60 to 8O ⁰ C.

50 g of the oi-bromostearic acid are then mixed with a saturated ammonia solution in 150 ml of ethanol and heated ^{to about 135 to 140 ° C. in the autoclave for about 6 hours.} Ethanol and excess ammonia are then evaporated off under reduced pressure. The white crystalline residue (oc-amino stearic acid) is washed with water, hot petroleum ether and dilute sodium hydroxide solution and recrystallized from acetic acid.

5 g of the α-aminostearic acid are dissolved in 40 ml of 2N sodium hydroxide solution suspended and cooled in an ice bath. The suspension is shaken vigorously and alternately with low levels of cooling Amounts of benzoyl chloride and 2N sodium hydroxide solution are added, up to a total of 6 ml of benzoyl chloride and 30 ml of sodium hydroxide solution are used up. After 15 minutes the suspension is with concentrated hydrochloric acid adjusted to pH 4 bia 5 (Congo red).

309834/1059

The white pest is filtered off, washed with water and warm carbon tetrachloride and extracted from an ethanol / V / water mixture recrystallized. N-benzoyl-aminostearic acid is obtained.

4 g of this acid are added for 1 hour in the presence of 20 ml of acetic anhydride heated on the water bath. After the pest is completely dissolved, the excess acetic anhydride becomes evaporated under reduced pressure. The raw azlactone remains.

2. Preparation of 2-methyl-4-n-hexadecylazlactone

A solution of 2.3 g of sodium in 150 ml of absolute alcohol in a flask fitted with a stirrer, drying tube, condenser and dropping funnel is mixed with 21.7 g of diethyl acetamidomalonate and 0.2 g of potassium iodide. The solution is heated to reflux, then 30 g of n-hexadecyl bromide are added all at once and the mixture is refluxed for a further 50 hours with constant stirring. The ethanol is then evaporated off under reduced pressure, the residue is washed with water and ether. The aqueous phase is extracted with ether, the two ether fractions are combined and evaporated under reduced pressure. There remains raw Acetamidohexadecylmalonsäure acid diethyl ester, which is recrystallized from petroleum ether with a boiling range of 60 to 8O ⁰ C.

8.5 g of the Hexadecylmalonsäureesters are heated with a solution of 3 _f, 3 g of sodium hydroxide in 35 ml of water 1 1/2 hours weak reflux. The solution is cooled, with concentrated

309834/1059

trated hydrochloric acid adjusted to pH 4 and a further 1 1/2 hours heated to reflux. The 2-phase mixture is cooled in an ice bath and adjusted to pH 2. The precipitate that forms from crude 2-acetamidooctadecanoic acid is filtered off, dried and recrystallized from benzene.

The azlactone is cyclized as in Method # 1 made using acetic anhydride.

Hexadecylazlacton yl-4-n-3 Preparation of 2-n-heptadec _j

(K -bromostearic acid is produced according to process no. 1. 200 g of the acid are then continuously stirred for 8 hours at 60 ° C. in a mixture of 60 ml of aqueous ammonia (d-0.880) and 500 ml of methanol. The resulting α-amino stearic acid is filtered off, washed with hot methanol and recrystallized from glacial acetic acid.

89 g of <X -amino stearic acid are dissolved in 200 ml of dry methanol suspended. The suspension is saturated with hydrogen chloride and left to stand overnight. The excess methanol is evaporated in a drum evaporator, the residue, <? t -Ainostearic acid hydrochloride, is recrystallized from ethyl acetate.

114 g of methyl ester hydrochloride are dissolved in 1.5 liters of chloroform and refluxed for 30 minutes with 52 g of anhydrous sodium carbonate. The mixture v / ill be slowly within 20 minutes with 99 g of stearoyl chloride in 500 ml of chloroform comparable

309834/1059

sets and refluxed for a further 30 minutes. The chloroform is evaporated under reduced pressure, the residue, N-stearoyl-A-aminostearic acid methyl ester, is made from methanol recrystallized.

13.1 g of the ester are saponified by suspending in 58 ml of 1N sodium hydroxide solution and heated to the boil. Dioxane is added to the mixture until a clear solution is formed, and the mixture is refluxed for 1 hour. After adding 580 ml of cold water, the suspension is adjusted to pH 3 with hydrochloric acid. The reaction product, N-stearoyl-c * -amino stearic acid, is filtered off and recrystallized from ethyl acetate. Lütündiges by heating at 10O ⁰ C 3 of the amino acid with 25 ml of acetic anhydride g effected ring closure formation. The excess acetic anhydride and acetic acid are evaporated off as quickly as possible in the drum evaporator. The 2-n-heptadecyl-4-n-hexadecylazlaetone is obtained.

4. Preparation of 2-phenyl-4- (1-hydroxypalmit ylidene) -a zlact on

100 g of hippuric acid are stirred at 100 ⁰ C with 300 ml of acetic anhydride, and this until the Peststoff completely dissolved, the solvent is evaporated under reduced pressure at 100 ⁰ C in the drum evaporator.

40.3 g of 2-phenylazlactone are mixed with 250 ml of anhydrous ß-picoline, dried over calcium oxide, in a 1 liter capacity with a stirrer, dropper and protective tube (molecular sieve

309834/1059

with a mesh size of 4.76 mm) provided three-necked flask mixed. After the pesticide dissolves, it turns color the solution red.

The piston v / ill be immersed in a water bath at 25 to 3O ⁰ C.

The mixture is mixed with 68.5 g of palmitoyl chloride within 10 minutes and stirred for a further 20 minutes.

The dark red solution obtained is poured onto a rack of 250 ml of ice and 230 ml of concentrated hydrochloric acid and adjusted to pH 4 to 5 (Congo red) by adding more hydrochloric acid. The precipitate is extracted with 2 liters of chloroform. The solution is washed with water until neutral and dried over anhydrous sodium sulfate overnight. After decanting the sodium sulfate, the chloroform is evaporated in a drum evaporator. The remaining dark red oil is then dissolved in a small amount of hot hexane and left to stand overnight in an ice bath.

That's why 2-phenyl-4- (1-hydroxypalmitylidene) azlactone is used filtered off and recrystallized from hexane.

309834/1059

example

Solutions with the various percentages by weight of azlactone given in Table I are prepared from 2-methyl-4-n-hexadecylazlactone and benzene. By preeeing and drying bleached kraft pulp with a freeness of 32 according to Schopper-Riegler, hand-scooped paper webs treated with water glass are produced and glued at room temperature with an azlactone solution corresponding to their weight. The azlactone reacts with the cellulose essentially quantitatively, so that the paper has the weight fractions of azlactone given in Table I after drying. After 5 minutes of drying the paper at 105 ⁰ C the quality of the sizing is determined by the Cobb test. The values given in Table I relate to grams of water absorbed per square meter, measured after 1 minute. The lower the value, the better the glue.

Table I.

Weight percent azlactone based
dried on
paper Cobb - Value, in the solution 0.05 ß / m ² a 60 sec. O, 05 0.1 40 0, 1 0.2 16 O* 2 0.4 17th 4th 18th

309834/1069

Example 3

An aqueous emulsion is made from the following components:

Weight percent,

based on the emulsion

Azlactone ^v 1.1

Cationic starch 1.1 Nonionic emulsifier 0.2

Water 97.6

The azlactone used is 2-methyl-4-n-hexadeylazlactone.

The cationic starch contains quaternary ammonium groups and is commercially available under the name Q-TAC (Corn Products Limited).

The nonionic emulsifier is / condensation product of polyoxyethylene with an oleic acid monosorbitan ester, known under the name TWEEN 80 (Honeywill & Atlas Chemicals Ltd.).

First, the strength with V / ater mixed to form a slurry, which is then diluted and 10 minutes is heated with gentle stirring to 90 ⁰ C. Then, the molten azlactone (melting point about 55 ⁰ C) is added within 5 minutes under vigorous stirring (etv / a 8500 rpm), the temperature being maintained at about 9O ⁰ C. An aqueous suspension of bleached kraft pulp with a freeness of 32 according to Schopper-Riegler is mixed with the emulsion in such a way that, based on the dried paper, 0.45 to 2.3 percent by weight of azlactone in the paper

309834/1059

are included. The standard procedure is then followed on the Paper machine made hand-scooped paper webs. These are dried as in Example 2. The quality of the sizing is determined using the Cobb test. The results are in Table II summarized.

Table II

Weight percent azlactone,
based on dried paper Cobb
g / m ² - Value,
ä 60 sec. 0.45 49 0.9 39 1.4 21 2.3 18th

Example 4

Example 2 is repeated, but the azlactone is the 2-phenyl-4-n-hexadecylazlactone used. The results of the Cobb tests are summarized in Table III.

309834/1059

- 19 Table III

Weight percent azlactone,
based on dried paper Cobb value,
g / m - 60 sec. 0.23
0.4
1.0 27.6
21.6
18th

Example5

According to example 2, hand-treated with water glass: scooped paper webs glued with 2-n-heptadecyl-4-n-hexadecylazlactone. However, dichloromethane is used as a solvent. The drying time on the drum dryer is 2.5 minutes * The results of the Cobb tea are summarized in Table IV,

Table IV ί

Weight percent azlactone, Gobb - Value, based on dried paper g / m ² 4 60 sec. 0.01 54 0.015 48 0.02 36 0.025 20th 0.05 1B 0.075 16 0.10 15th

3098U / 10S9

Example 6

An aqueous emulsion is produced from the following components :

. . Weight percent,

based on the emulsion

Distearyl azlactone 1.1

Emulsifier 0.11

cationic starch. 1.1

Water ad 100

The emulsifier (ETHYLAN D 257 from Lankro Chemicals Ltd.) is an ethoxylated primary alcohol. The starch solution is prepared as in Example 3 and cooled to room temperature.

The azlactone and the emulsifier are dissolved in 15 ml of acetone and in a laboratory emulsifier while stirring vigorously with the Starch solution mixed up.

Hand-scooped paper webs are then produced using standard methods, with the azlactone emulsion being added in the shredder. The paper webs are at 105 ⁰ C for 2.5 minutes on the V / alzen tumble dried. The Cobb values obtained are summarized in Table V.

309834/1059

Table V

Weight percent azlactone,
based on dried paper Cobb value,
g / md 60 sec. 0.2
0.28
0.36
0.53 53
43
25th
18th

Example 7

Example 6 is repeated, but 0.11 percent by weight of an ethylene oxide-fatty acid amine condensation product (ETHYLAN TC from Lankro Chemicals Ltd.) is used as an emulsifying agent. In addition, the emulsion contains only 0.55 percent by weight cationic starch.

The handmade paper webs are at a pH of glued.

The results of the Cobb test are summarized in Table VI.

309834/1059

Table VI

23Ü7512

Weight percent azlactone,
based on dried paper Cobb
ß / m - Value,
ä 60 sec. 0.2 47 0.27 23 0.3 20th 0.33 18th

example

Hand-made paper webs treated with Y / ater glass are made with 2-phenyl-4- (1 ~ hydroxypalmitylidene) azlactone according to the example 5 glued. The Cobb values are summarized in Table VE.

Table VII

Weight percent azlactone, Cobb-V / ort, based on dried paper g / m ² ä 60 fei :. 0.1 61 0.15 16 0.2 16 0.4 16

309834/1059

example

An aqueous emulsion is produced from the following components :

Weight percent,

based on the emulsion

Azlactone
Emulsifier

Palmitic acid mono sorbitane st he

Condensation product of polyoxyethylene and oleic acid monosorbitan ester

cationic starch
water

0.02

0.04

1.1 to 100

This emulsion is worked up as in Example 6. The azlactone used is 2-phenyl-4- (1-hydroxypalmitylidene) azlactone.

The Cobb values are summarized in Table VIII,

Table VIII

Weight percent azlactone, Cobb - Value, based on dried paper g / m ² a 60 sec. 0.5 49 1.0 38 1.5 31 2.5 20th 3.0 17th 3.5 17th

309834/1059

example

10

Hand-scooped paper webs treated with water glass are glued with the azlactone and according to the method of Example 2 However, carbon tetrachloride is used as the solvent. The results of the Cobb test are summarized in Table IX.

Table IX

Weight percent azlactone,
based on dried paper Cobb value,
g / ra ² - 60 sec. 0.02
0.12
0.24
0.5.
1.0 53
25th
20th
17th
16
*

309834/1059

Claims (16)

Claims 1. Means for making fiber material, in particular cellulose-containing, water-repellent! Material consisting of one in one liquid medium dispersed water-repellent compound, characterized in that that it contains an azlactone with at least one long-chain aliphatic hydrocarbon radical. 2. Means according to claim 1, characterized in that it contains an azlactone of the formulas (I to IV) R ^A C C N == C O O C- O O II C- N ' O O ■ c: C: .O. III IV 1 2
in which R, R and R each represent a hydrogen atom or an optionally substituted hydrocarbon radical, "5 4 5 R is a divalent hydrocarbon _{radical r} R and R are each a V / aseerstoffatom or an optionally substituted 4 5th hydrocarbon radical or only R or only R one Mean hydroxyl or ether group. 309834/1059 3 »Means according to claim 1 and 2, characterized in that the long-chain aliphatic hydrocarbon radical has 8 to 20, preferably H to 18, carbon atoms. 4. Composition according to claim 1 to 3, characterized in that the long-chain aliphatic hydrocarbon radical is a Is alkyl or alkenyl. 5 »Means according to claim 1 and 2, characterized in that "2 1 · R and either R or R each represent a long-chain aliphatic radical. 6. Composition according to claim 1 and 2, characterized in that the divalent radical R with the carbon atom on which it is bonded to form a 6-membered carbocyclic ring 7 · Means according to claim 1 and 2, characterized in that R or R ^ is a long-chain aliphatic radical or a optionally substituted aryl radical. 8. Means according to claim 1 and 2, characterized in that daes azlaoton in an inert organic liquid, preferably a hydrocarbon, halogenated hydrocarbon, Ketone or aliphatic ether is dissolved. 9 · Agent according to claim 1 to 7, characterized in that the azlactone with water, an emulsifying agent and optionally is emulsified with a retention aid. 309834/1059 23U7512 10. Means according to claim 9 »characterized in that the Emulsifier a fatty acid ester or a fatty acid dialkanolamide derivative, like a sorbitan glycerol or polyethylene glycol ester which is lauric, palmitic, stearic or oleic acid. 11. Composition according to claim 9, characterized in that the emulsifying agent is a condensation product of ethylene oxide or propylene oxide with an aliphatic alcohol or amine or an alkyl phenol. 12. Composition according to claim 9 »characterized in that the weight ratio of emulsifier to azlactone is 1: 2 to 1s 50. 13. Means according to claim 91, characterized in that the Retention agent a cationic organic polymer, preferably a cationic starch or polyacrylamide, is. 14. Means according to claim 91, characterized in that the The weight ratio of retention aid to azlactone is 2: 1 to 1:20. 15. Use of the agent according to claim 1 to 14 for treatment of material containing paper, cotton or rayon. 16. Embodiment according to claim 15, characterized in that an aqueous paper material containing calcium as a filler 309834/1059 contains carbonate, is treated. 309834/1059