DE1419504C - Aqueous dispersion for making textile fabrics water-repellent - Google Patents

Description

1 2

The invention relates to an aqueous dispersion for averaging, however, wash fastness becomes very rare

Making textile fabrics water-repellent. achieved.

The purpose of the invention is to create new means in synthetic textile fibers such as polyamide That will make water repellent in the form of stable fibers, polyester fibers or acrylic fibers aqueous concentrates are placed on the market 5 problem is made even more difficult by the fact that they can are easily hydrophobic without flocculation or otherwise and the treatment agent is im practical difficulties on aqueous treatment generally from an aqueous treatment bath Allow baths to dilute and apply to non-absorbent. The hydrophobic nature a large number of different textile fibers; however, all of these fibers are not strong enough to withstand the especially for the treatment of polyamide, polyester, io fibers for practical purposes sufficient water-polyacrylic, Cellulose ester or similar to make synthetic repellent, so that they are z. B. immediately to see textile fibers, which are treated with rainproof clothing Means for making water repellent so far could be special. The hydrophobic nature of these fibers This was difficult because it was so pronounced that the Treatment baths are applied, do not stain any affinic fibers from aqueous baths with difficulty or with did show. Let the soak in the other aqueous textile treatment agents according to the invention. Agents containing dispersions have the unusual- In particular, these fibers do not have the ability to Liehe property, from aqueous baths under Er- such an aqueous treatment bath on its active creation of the baths to exhaust the above synthetic material.

textile fibers and on wool. You 20 The treatment of textile fibers with aqueous

also give cellulose fibers a particularly good bath can be divided into two types of treatment

water-repellent quality, if they consist of one thing, namely the padding and the exhaustion of the bath,

aqueous bath according to the usual padding process. A padding is generally used for padding

applied to the fibers. concentrated aqueous bath. The fabric is made with

The property of repelling water was previously soaked in the treatment bath and then squeezed out,

with textile fibers with the help of two general classes up to a certain amount of the aqueous treatment

achieved by means, namely with physically acting fluid in relation to the fiber weight in the

agents such as paraffin wax or silicones that remain in the tissue. The fiber can e.g. B. up to one

generally be squeezed onto the fabric from an aqueous bath, absorption of 100%. In this

which contains a dilute suspension of the agent, the 3 ° trap the fiber takes on its own weight

be padded up, and with chemically or physically the same amount of the treatment bath, and if

Chemical-active agents, such as stearamido- the padded fiber is dried, remains in

methylpyridinium chloride, N-methylolstearamide or its interior (or on it) a percentage by weight

Distearamidomethane, which is in the form of an aqueous solution of the treatment agent, which is equal to the original

solutions, aqueous dispersions or solutions in 35 borrowed concentration of the treatment bath.

organic solvents are used, and on the other hand, the fiber has an affinity for the

when using them, the padded fiber after the treatment agent, as is usually the case with dyeing

Pressing and drying generally a warming of cellulose fibers or wool with compounds of the

treatment at 105 to 15O ⁰ C is subjected to case, which (in contrast to pigments) is real

chemical changes in the agent cause 40 dyes, then the tissue is generally extracted

or a chemical reaction between the agent mean the agent from the bath until the bath in the

and bring about the fiber. essential is exhausted. In this case the

Each of these classes of agents has its advantages. and disadvantages; the general problem, however, is sorbed (provided that one has a sufficient in both cases in that the water-repellent effect applied 45 amount of fiber), essentially the same some degree of durability, d. H. Total amount of the agent originally added to the bath resistance to washing. It's been added. The amount of treatment agent Standardized test methods have been developed to which is therefore independent of the amount of the fiber Degree of water repellency taken up initially, with or without like and the degree of water repellency 50 Express. In these cases the will initially be too to measure the amount of treatment agent added to the bath according to one or more standardized amounts Washing processes is still retained. After these "on the fiber weight", i. H. on the weight of the standardized test methods, generally referred to as dry fiber.

Spray test are referred to, the degree of this shows that treatments in which water repellency takes place after a rating 55 bath exhaustion are more economical on a scale from 100 to 50, with 100 rated as exceptional than block treatments; for they permit the application (in that no water at all adheres to the dung of dilute aqueous baths, and tissues are often suitable); the closest values to these for uses in fields where scale are 90, 80, 70 and 50; are inapplicable after the value 50. However, the method for comes the value zero, since the range between ⁶ ° could make water repellent z. B. so far has only been considered so bad in 50 and zero that it is not worthwhile to make differences in this area to a very limited extent in household appliances. It is carried out by machines because it has often been asserted that the above-mentioned agents are not economical enough for this method of operation, physico-chemical agents according to this, during the bath exhaustion process, as far as the standardized scale knows the initial values of the water repellency β5, neither with physically acting agents still achieved with a fortune of 100, which after a chemically or physico-chemically acting number of washing processes was not previously applicable.
80 or 70 go down. With the physically acting It has now been found that the practical properties

3 4

Shafts of aqueous suspensions (dispersions of surface-active copolymer compound or emulsions) of waxes, as we think physically, assume the surprising property of kenden means to make water repellent, without exhaustion on hydrophobic textile fibers and, expectedly, significantly improved or modified wool. This depletion effect is considered so that a much better water repellency is achieved, especially strong in spun polyester fibers, and when these suspensions are in this hydrophilic as well as organophilic unfit against aqueous treatment processes, such as units, both of which were from monomeric acrylic acid dyeing, but which are derived in the esters of the invention. In particular, it has been found that an aqueous agent is also often capable of being absorbed onto a suspension of paraffin wax or a carbon cellulose fiber such as cotton when the bath is exhausted R '"and R ^IV short-chain that they are initially stronger, more uniform and radicals, such as methyl or ethyl radicals,
More washable water repellency in textile 15 The dispersions according to the invention are produced for the fibers if they are a cationic, polymeric, commercially produced aqueous concentrate containing 10 to surface-active copolymer which contains 50% solids. They have a remarkable shelf life of two types of monomeric acrylic acid esters and can easily be combined with water. Dilute dilute treatment baths, without the subject matter of the invention is therefore an aqueous dispersion for making textiles water-repellent, showing signs of instability.

substances, which is characterized in that they are

Solid component a wax and a surface-known, homopolymers made of quaternary ammo

active copolymer compound in the form of an acrylic acid ester containing nium groups, in the

Salt or a quaternary compound of a 25 still reactive after its preparation

Copolymer has been introduced from 20 to 80 percent by weight alkoxymethyl group, from aqueous

basic acrylic acid ester units, the secondary ger solution to be applied to textiles as a finish

or contain tertiary nitrogen atoms, the general one in order to give them antistatic properties,

formula The treatment, which is carried out with relatively concentrated

ß / »30 th (10%) aqueous solutions of the polymers

/ needs to be done does not serve the purpose that

CH ₂ = CCOR N., (1) to make fabrics water-repellent, and is done too

Il '' RiV not with the help of physically acting water

R 'O repellants such as wax.

35 The German Auslegeschrift 1010 051 describes a two-stage process for water-repellent

in which R 'is a hydrogen atom or a methyl group, impregnation of fabrics, in which the fabric R "is an alkylene radical with 2 to 4 carbon atoms, in the first stage with an aqueous dispersion of an R'" an alkyl radical with 1 to 22 carbon atoms from a copolymer Acrylic acid or methund R ¹ V denotes a hydrogen atom or a lower acrylic acid ester and acrylonitrile and in the second alkyl radical with 1 to 4 carbon atoms or stage with a metal salt precipitating the dispersion in which the group is treated. This treatment requires cautious

R »'nismatically large amounts of the expensive mixed

/ polymer, as the tissue is quite concentrated

~ * ^ \ 45 th solutions must be soaked while the

Riv dispersions according to the present invention are essential be used in a more dilute state and

as a whole, the remainder of a 5- or o-membered hetero- moreover as an effective component that considerably

represents cyclic ring compound, which contain lower-priced wax given,

if it can contain another heteroatom, 50 US Pat. No. 2,206,090 describes water-

z. B. piperidine, morpholine or pyrrolidine, and 80 bis repellent compositions described in

20 percent by weight of neutral acrylic acid ester units in aqueous dispersion in addition to waxes, oils or fats

the general formula amphoteric metal salts and fatty acid compounds,

for example, Amidostearyldiäthylenamin contain.

CR ₉ = CC O —R ^v 55 According to French patent specification 1109 321

: ι , γ. can similar water repellants z. B. off

n, Q is the reaction product of stearic acid and tri-

ethanolamine and a mixture of a Fischer-Tropsch wax and stearic acid.

in which R 'contains a hydrogen atom or the methyl group 60, as the comparative experiments show below

and R ^{v is} an aliphatic hydrocarbon radical with one with the irt of the American or French

1 to 22 carbon atoms denotes water-repellent agents described in a patent specification

weight ratio of mixed polymer compound to made of cotton fabrics or polyester-cotton

Wax from 0.067: 1 to 1: 1 and a total concentration of mixed fabrics, although a certain water repellency,

Tration of organic substances from 10 to 50 weight- 65 which, however, is lost after washing. So

percent of the total dispersion. It was more surprising that the dispersions of the

It was further found that this aqueous invention under otherwise identical conditions

Dispersions which, according to the invention, contain a wax and a water that remains even after several washes

cause rejection. It is just as unexpected, however, that the dispersions according to the invention together can be used with agents for anti-crease finishing, while dispersions according to of the two aforementioned patents coagulate when adding melamine formaldehyde resin and therefore cannot be applied to textiles together with such an agent.

Finally, from German Auslegeschrift 1 002 281, a solvent layer is known which has a Contains polymer of an acrylic acid ester and applied to the fabric in solution in white spirit got to.

The invention makes it possible to obtain a concentrated, permanent dispersion for rendering water repellent to put on the market which can be diluted in the treatment bath to any desired degree, without wax or any other solid precipitating. The treatment bath thus obtained can be used for treatment of fibers can be used by the padding method or by the exhaustion method. In in both cases the agent imparts synthetic fibers such as polyamides, cellulose acetate, acrylic fibers and Polyester fibers, which up to now have become difficult to water repellent even with chemically acting treatment agents make goods, water-repellent texture. The main water repellent agent settles on the fiber in even layers, so that the treated fiber does not have streaky deposits and does not easily leave a trace on the deposit when scratched (which is usually referred to as "staining").

The initial degree of water repellency naturally depends on whether it is sufficient Amount of agent deposited on the fiber. When the treatment bath is composed like this is. that there is 1 to 3% active water repellant on the fiber, based on dry weight the fiber, separates (where both the amount by weight of the wax and the amount by weight of the cationic copolymer is included), then the value for the water repellency is Usually 100 initially and 70 or more after three washes.

The way in which the agent is applied to the fiber depends on the nature of the fiber. As stated earlier, the new agents can be applied to fibers of all types using the padding process. For fibers made of wool or synthetic hydrophobic fibers such as fibers made of polyamides, polyesters, acrylic fibers or Cellulose ester fibers. Depletion method application is possible and preferred. With this type of application, the amount of the to be added Means calculated not according to the weight of the treatment bath, but according to the weight of the fiber, and it is unnecessary to squeeze the impregnated fiber up to a precisely calculated degree of absorption. However, the fiber must be kept in contact with the treatment bath longer than that Block method. A treatment time of 3 to 10 minutes is usually sufficient.

On Cclluliisefaser all can be in the frame the invention falling treatment agents are applied by the padding process, while the Application by pulling up with exhaustion of the bath is only applicable when certain types of copolymers defined above are used for the preparation of the treatment agent, for. B.

those where the group

^X RIV

of component (1) is a dimethyl or diethylamino group is. Therefore, in textile mills that are set up for the padding process, this process can be used preferred, while the exhaustion method is preferred for home laundry, what dispersions can be brought onto the market for which contain copolymer compounds, where the group

RIV

of the copolymer meets the above condition.

The preparation of the cationic, surface-active copolymer compounds used according to the invention can according to the known processes for the preparation of copolymers of these general Kind by polymerization in bulk, in an organic solvent or in aqueous emulsion.

In emulsion polymerization, the respective mixture of monomers is emulsified in an aqueous solution of a cationic or nonionic surface active agent, the polymerization catalyst is added and the mass is heated to 65 to 75 ⁰ C. Further details of this process and a detailed discussion of the catalysts and surface-active agents which can be used for this purpose can be found in US Pat. No. 2,879,178. At the end of the polymerization process, the aqueous mass is acidified so that an acid addition salt is formed, as described below in individual is described.

In solvent polymerization, 1 part of the respective monomer mixture is generally dissolved in about 1 to 10 parts of an organic liquid or a low-melting solid substance which is at the same time a solvent for the monomers and for the copolymer formed therefrom; Examples of such organic solvents are paraffin wax, heptane, solvent naphtha, and ethanol. Benzene or toluene. To the solution of the monomers is a soluble in the solvent or peroxide Azonitrilkatalysator is added, after which can polymerize the solution at temperatures of about 25 to 150 ⁰ C. If a volatile solvent, such as ethanol or heptane, is used, the copolymer can be isolated by evaporating off the solvent and then dissolved or dispersed in an aqueous acid solution to form the salt of the cationic copolymer. This solution or dispersion can then be used to emulsify a wax in order to obtain a salable mass containing such a wax.

When - the monomers have been polymerized in a molten wax as a solvent, the mixture of wax and copolymer obtained in this way can be placed directly in an aqueous acidic solution are dispersed, which contains so much acid that the acid salt of the copolymer is formed.

By converting the copolymer into a

Salt, as described in the last two

drive, the polymer becomes water-soluble or water-dispersible, making it an effective emulsifier for the wax represents. In addition, this treatment gives the copolymer the same effect as before unknown nature of a bath depletion agent, d. i.e., it acquires the Ability to absorb the textile fiber from an aqueous bath when the bath is exhausted, and it also has the effect that the wax is absorbed onto the same tissue when the bath is exhausted. Suitable acids for converting the copolymer into these salts are, for. B. hydrochloric acid, sulfuric acid, sulphurous acid, phosphoric acid, nitric acid, hydrofluoric acid, formic acid, acetic acid, Propionic acid, butyric acid, acrylic acid, methacrylic acid, chloroacetic acid, benzenesulfonic acid, oxalic acid or tartaric acid. Weak, volatile acids, such as acetic acid, are preferred because they affect cellulose fibers have less of a degrading effect than the stronger acids and because they are easier to drive out. Strong, non-volatile acids, which are used to form salts, can be applied to the fabric with a weak alkali, such as sodium carbonate or sodium phosphate, neutralized and thus harmless after the acid does its job, the copolymer is in solution or dispersion to bring has met.

Instead of converting the copolymer into a salt, it can also be quaternized in the usual way, so that an ionizable quaternary derivative of the tertiary amino group is formed. The general procedure for this purpose is to use the b ^ i of Emulsion polymerization resulting mixed polymer dispersion and dilute it at about room temperature with or without the addition of an acid-binding agent, such as caustic soda, which quaternize all tertiary nitrogen atoms of the copolymer amount of the quaternizing agent (or im In the case of dialkyl sulfates a little less) to be added.

Suitable quaternizing agents for this purpose are e.g. B_. Dimethyl sulfate, diethyl sulfate, methyl bromide, Ethyl iodide, p-toluenesulfonic acid methyl ester, Triethyl phosphate or benzyl chloride.

Instead of first preparing the basic copolymer and then converting it into a salt, as described above or to convert a quaternary compound, one can also first use the monomeric basic ester of the above formula (1) into the desired salt or quaternary derivative and then converted into carry out the copolymerization in a manner known per se. The copolymer obtained in this way is then obtained directly in cationic form (i.e. with ionizable ammonium groups) and can be used directly for the purposes of the invention.

The basic monomers for the purposes of the invention are the acrylic and methacrylic esters of the following basic alcohols:

2-methylaminoethanol,

2-dimethylaminoethanol,

2-diethylaminoethanol,

2- ⁱ EthyIaminoethanoI,

2-propylaminoethanol,

2-dipropylaminoethanol,

2-diisopropylaminoethanol,

2-tert-butylaminoethanol,

2-diisobutylaminoethanol,

60

65 2- (N-methyl-N-cyclohexylamino) ethanol,

2-morpholinoethanol,

2- (N-methyl-N-dodecylamino) ethanol,

2- (N-ethyl-N-octadecylamino) -ethanol,

2- (N-ethyl-N-2-ethylhexylamino) -ethanol,

2-piperidinoethanol,

3-diethylaminopropanol- (l),

2-diethylaminopropanol- (l),

l-dimethylaminopropanol- (2),

4-diethylaminobutanol- (l),

4-diisobutylaminobutanol- (l),

l-dimethylaminobutanol- (2),

4-diethylaminobutanol- (2),

1-ethylamino-2-methylpropanol- (2).

These esters can be prepared according to U.S. Patent 2,138,763.

Suitable neutral monomeric esters of the formula (2) are, for. B. the acrylic and methacrylic esters of Butanol- (l), butanol- (2), 2-methylpropanol- (2), butene - (3) - oil - (1), pentanol - (1), hexanol - (1), Hexen- (3) -ol- (l), octanol- (l), 5,5-dimethylhexen- (2) -ol- (2), octen- (3) -ol- (l), 2-ethylhexanol- (l), dodecanol- (l), 2,6-dimethylocten- (5) -ol- (2), hexadecanol- (1), octadecanol- (1), octadecen- (9) -ol- (1) or docosanol- (1).

Any natural or synthetic wax can be used as the water repellent. Examples Suitable waxes are natural hydrocarbon waxes such as paraffin wax, ozokerite and palm wax or mixtures of such waxes with natural or synthetic waxes, e.g. B. beeswax or polyethylene.

The proportion is 1 to 15 parts of wax to 1 part of the cationic surface-active copolymer, and the two components are preferably made into a technical one by the manufacturer Emulsion mixed, which is diluted by the end user with water to the desired concentration can be. For this purpose, the wax can be mixed with the monomers before these are polymerized, or it can be in an aqueous solution or dispersion of the acid salt or of the quaternary salt of the copolymer is emulsified will. If the wax with the acrylic or methacrylic acid esters before their polymerization When mixed, it can act in a molten state at the same time as a solvent for the reactants serve, or it can be used together with the monomers in a common solvent, like heptane.

The water-repellent-making dispersion obtained in this way can be applied to the most varied of textile fibers, yarns or tissue are applied.

The amount of the water repellent agent to be used may range from 0.5 to 10 percent by weight vary in total solids based on fiber weight.

After treating the fiber with the dilute treatment bath (and the pressing, when working according to the padding process), the material is 20 minutes to 100 to 200 ⁰ C, preferably to 125 to 165 ° C, heated for 0.5 to the To make coating insoluble. When used in household washing machines, this heating takes place automatically and simply by subsequent ironing of the treated item of clothing or by using a household tumble dryer.

109 639/329

ίο

The invention is further enhanced by the following examples, in which parts refer to amounts by weight explain.

example 1

Persulfate as a polymerization catalyst, mixed polymer dispersions are prepared from χ parts of 2-diethylaminoethyl methacrylate and y parts of butyl methacrylate. The value χ is varied in the range from 10 to 78 and the value y in the range from 90 to 22.

Each of these basic copolymers is then converted into the corresponding acetic acid salt, adding the dispersion with the same amount of weight

butyronitrile added in small portions over the course of 6 to 10 hours. After the last addition of the Polymerisationserregers the reaction mass is held for 2 hours at 75 ° C and then V ₈ hour at 100 ⁰ C ". 5 The charge is then diluted with 2000 parts of melted paraffin wax (melting point = 60 to 51 ^° C.) in a ratio of wax to copolymer of 3: 1 and poured into small blocks for easy handling.

In 100 parts of this mixture of wax and copolymer 4 parts of glacial acetic acid are stirred after melting by heating at 65 to 7O ⁰ C. Then the wax copolymer mass is long-

In a vessel equipped with a stirrer, a solution of 300 parts of 2-diethylaminoethyl methacrylate is added and 700 parts of octyl methacrylate in 1000 parts of at one temperature

of 75 ° C located molten paraffin- »° water is diluted and added to each dispersion wax (melting point = 60 to 61 ° C) 10 parts of 2,2'-azodiiso- vigorous stirring, a lot of glacial acetic acid is added,

equal to half the calculated weight of the original basic monomer in the diluted one Is dispersion.

The acidified salt solution of each copolymer is then slowly added with vigorous stirring melted paraffin wax entered until 3 parts wax per part copolymer are added. To further stirring to achieve a stable, uniform wax emulsion is added to each of the masses Water diluted to a wax suspension containing about 24% solids, the ratio of Wax to copolymer is 3: 1.

Proportions of each of the above wax emulsions

sam with vigorous stirring with the aid of a mixer 5 are diluted with water to solids contents of 2, 3 or from high shear force to 294 parts of water and diluted 4% and kept at 65 to 70 ⁰ C for padding cotton. The stirring is still used according to Example 11 poplin. The treated continued for a while to complete the emulsification to fabric after the above mentioned spray test. The 25% emulsion is cooled once at the beginning and once after three normal washing temperatures and represents a finished 3 <> processes for its water repellency.

If cotton is treated according to the method in Example 11, it is found that those wax suspen-

described padding process with this dispersion, in which the value of χ is treated in the mixed poly, it assumes an initial water merisate in the range from 20 to 80 (and the repellency of 100, which after three 35 value y = 100 - χ is), provide treatment baths that reduce normal washes to 70 to 80. Cotton poplin gives an initial water repellency - if spun polyester fibers, spun capacity of 100, which goes back to 70 to 80 after three polyacrylic fibers or wool after the normal washing processes in Example 12, with the bath depletion process described during the treatment baths, which are treated with the mixing agent, If you also achieve a 4o polymerizate, in which χ is greater than 80 initial water repellency of 100, already at the beginning poor values for the water softness after three normal washing processes do not provide repellency, which already drops below 90 after one. Reduce the normal washing process to 50. The mixed

Instead, as described above, the polymerisation polymer, for which the value χ = 10, is carried out in a dye wax melt, no stable emulsion at all can be achieved.
one also an organic one in a manner known per se

Solvents, e.g. B. heptane or ethanol, use. , B e i s ρ i e 1 3

The solvent is then removed by evaporation

removed and as a viscous residue behind a suspension of 69.2 parts of methacrylic acid

Permanent copolymer in molten Paraf- 5o dodecyl ester and 30.8 parts of methacrylic acid-2-difi η wax in a proportion of wax to ethylaminoethyl ester in 180 parts of water, the tri-copolymer solved by 3: 1.

100 parts of this wax copolymer composition are then mixed with 12 parts of glacial acetic acid, and an aqueous dispersion to make water repellent manufactured.

Is used in the process described above in place of the methacrylic acid octadecyl ester Octadecen- (9) -yl methacrylate is obtained in this way

a means for waterproofing the same 6o ratio of wax to copolymer in one Nature and effectiveness. Case of 3: 1 and in another case of 4: 1

receives.

B e i s ρ i e I 2 portions of these suspensions are diluted with water

Concentrations of 4, 3 or 2% diluted. With

Samples of cotton poplin are produced by interpolymerization in aqueous emulsion 65 of these baths treated at 55 to 75 ° C using a condenser according to the padding process of Example 11, sation product of a long-chain alkylamine with All treated samples show after the spray test Ethylene oxide as a dispersant and potassium - an initial water repellency of 100,

containing methyloctadecylammonium chloride as a dispersant, is ^{polymerized at 65 0} C under nitrogen with hydrogen peroxide as a catalyst. The dispersion obtained in this way is acidified with acetic acid according to Example 2 and added together with wax to water according to the same example, so that wax mixed polymer dispersions with a solids content of 24 ° / ₀ and a consistency

11 12

which after three normal washes to 90 to 80. If polyester fiber according to Example 11 with a

going back. 2% treatment bath according to the above

Example 4 is treated, the value for the

Water repellency initially ICO and after

After the emulsion polymerization process of 5, three normal washes also 100.

Example 3, but using methacrylic. .

acid octadecyl ester instead of methacrylic acid example /

dodecyl ester, a series of dispersions is produced. You work according to Examples 3 and 6, but below

provided, in which the percentage of the basic use of 30 parts of acrylic acid-2-diethylamino-

Monomers in the range of 20 to 80. From each io ethyl ester and 70 parts of acrylic acid dodecyl ester as

After acidification according to Example 2, the dispersion is made of monomeric esters and of "," - Azobisisobutyro-

a series of aqueous wax dispersions (with amidine hydrochloride as a catalyst.

24% solids) according to Example 3, when treating cotton according to Example 6

wherein the ratio of wax to the thus obtained copolymer with 24 ° / _o aqueous suspension

3: 1.6: 1 or 10: 1. »5 from a ratio of wax to copolymer

Treating cotton poplin with a ratio of 3: 1 gives practically the same results, dilute aqueous baths of these dispersions

according to example 11 provide all treatment examples

average initial values of 100 for the water - a solution of 10 parts of methacrylic acid-3-di-

repellency, which after three normal washes ao ethylaminopropyl ester and 40 parts methacrylic acid

processes drop to 80 or 80 to 90. octadecyl ester in 117 parts of absolute ethanol

heated to 75 ^{° C.} 0.1 part of 2,2'-azo-diiso-

B e i s ρ i e 1 5 butyronitrile and passes nitrogen through the reaction mixture. The temperature will rise to 18 hours

Shares of the methacrylic acid as in Example 4 from 70 to 75 ⁰ C, whereupon a further amount of

octadecyl ester and methacrylic acid diethylamino 0.1 part catalyst added and the polymerization

Dispersions produced in _{ethyl ester} are continued in just 4.5 hours. The main crowd

known way with dimethyl sulfate in quaternary of the alcohol is now at a pressure of 1 mm Hg

Ammonium compounds transferred, with the di- or less distilled off and the residue behind

dried methyl sulfate in an amount corresponding to 90 ° / ₀ 30 remaining polymer,

of theory (based on the calculated amount of In 12 parts of the residue remaining

basic nitrogen in the dispersion), mixed polymer (a viscous mass) can be used

will. after heating to 65 ^° C., 1 part of glacial acetic acid in succession

Then the wax according to Example 3 is added and 36 parts of melted paraffin wax are stirred in,

with the difference that the resulting aqueous 35 The mixture of wax and copolymer

Wax copolymer dispersions for some then with vigorous stirring in a mixer

Samples to a solids content of 12 weight- high shear slowly to a solution of

percent and for others to a solids content of 149 parts of water and 1.5 parts of trimethyloctadecyl

24 percent by weight can be set. Of each ammonium chloride at 65 ° C added to the emulsion

Dispersion Suspensions with a mixture are allowed to cool with moderate stirring. The

ratio of wax to copolymer of 3: 1, the product is a stable 24% emulsion, the wax

6: 1 or 10: 1 produced. and mixed polymer in a weight ratio of 3: 1

Samples of cotton poplin are then included as per.

Example 11 with each of the suspensions of aqueous If cotton is treated with this emulsion in aqueous treatment baths, the concentrations of 45 baths, which, as described in Example 2, have different wax copolymer solids of 4, 3 or concentrations, is treated, receives 2 percent by weight. Then the fabric will give you practically the same results,
in all cases up to an absorption of 100%. If you work according to the compression described above. After drying and heating using 4-methacrylic acid treatment at high temperature, as described in Example 11 50 ethylaminobutyl ester instead of the corresponding one, the same values are obtained for the water-propyl compound, so similar results are obtained, repellency as in example 4.

t _D. . . , Example 9

B e 1 s ρ 1 el 6

¹ According to Example 3, 30.8 parts of methacrylic treatment are used on various fabrics
_n : 2-dimethylaminoethyl ester and 69.2 parts of meth- A wax copolymer emulsion in which the octadecyl acrylate in an aqueous emulsion co- polymerizes the ratio of wax to copolymer 3: 1, and the copolymer is then and the copolymer is the acetic acid was converted into the acetate and molten salt of a copolymer of 70 parts by _weight; emulsified _n wax, so that after cooling a ^6o octadecyl methacrylate and 30 parts by weight of 24 ° / ₀ aqueous emulsion with a content of wax methacrylic acid-2-diäthylaminoäthylester, it is after a mixed polymer of 3: 1 is formed. During loading example 4 and to various concen _u f treatment of cotton according to Example 11 with loading concentrations diluted. These baths are treated to treatment baths containing 2, 3 or 4 weight percent lung various tissues after the padding process i _n of wax copolymer solids contain, ER 65 of Example 11 is used. The long while on the fiber It tissue volumes an initial value for the percentage of active ingredient and deposited; st water repellency of 100, which dates back to three results obtained when spray test are in \ Normal washing operations on 70th Table I compiled.

13th

Table I.

tissue

Deposition

Weight percent

5.2
2.0

5.2
2.6
1.3

5.2
2.6

5.2
2.6

5.2
2.6
1.3

1.3
1.3

Value in the spray test

after

Washing 3 times

initially

100
100

100
100
100

100
100

100
100

100
100
100

100
100

90 to l00 80

80 to 90

80 to 90 80 to 90

80 to 90 80 to 90

100 100 100

100 100

You can see that the highest initial value and a

good durability of the treatment has been achieved with various cotton fabrics, but that the The durability of the treatment effect in the case of non-cellulosic synthetic fibers is unsurpassed.

ExampleO

Different waxes

Instead of the paraffin wax used in Examples 4 and 9, other waxes are added to the aqueous emulsion of the acetate of the copolymer indicated in Example 9. In all cases the temperature of the mixed polymer solution was kept 5 ° C. above the melting point of the molten wax to be emulsified in each case, and the ratio of wax to mixed polymer was in all cases 3: 1. Portions of the wax emulsions obtained in this way were diluted to form pad baths, into which samples made of polyester fabric were immersed. Then the tissues were heated for 5 minutes at 15O ⁰ C. The waxes used here and the results obtained in the spray test are summarized in Table II.

* 5 posed.

Table II

tissue

Deposition

Weight percent

Value in the spray test
after
3 times
To wash

initially

Eicosan ■;

Microcrystalline
Petroleum wax

Palm wax

Paraffin wax

Beeswax + I

Paraffin wax in a ratio of 1: 4 [

Paraffin wax +
low melting point
Polyethylene im
Ratio 80:20

90
90
90

100
100
100

100
100
100

100

70 to 80
70 to 80
70 to 80

90
100
100

100
100
100

100

It is noted that the polyester fiber waxes given give a good to excellent initial start Give water repellency. The durability in washing is also good up to excellent.

Example 11
Treatment according to the block method

An emulsion obtained according to Example 1 is mixed with water to form a pad bath with a solids content diluted by 3 percent by weight. The emulsion can be easily diluted without undocking and delivers a constant log bath. Cotton poplin is padded in this bath and then up to a take of 100% pressed, which corresponds to an absorption of 3% of solids, based on the fiber weight. Then the fabric is heated to 175 ° C for 10 minutes.

B e i s ρ i el 12

Treatment of wool or hydrophobic
synthetic fibers after the exhaustion process

In this process, the amount of the treatment agent to be added to the treatment bath depends on the percentage by weight of the to be deposited on the fiber. If z. B.

a deposition of 2.4 ° / _{0 is} desired and 100 parts of fabric are to be treated, then 10 parts of any of the wax - copolymer suspension prepared according to the preceding examples with a solids content of 24 percent by weight to any amount, e.g. B. 1000 or 2000 parts, hot water of 27 to 71 ° C is added. The fabric is kept moving in this bath for 3 to 20 minutes, then wrung out and ironed, with or without drying, or it can

simply in a household clothes drying device without subsequent ironing to be dried.

If wool serge, polyester fabric or a blend of acrylic fibers and wool as well as spun Acrylic fibers are treated according to the exhaustion process described above, result in Use of the aqueous paraffin wax dispersions according to the invention and when applying various Copolymers the values compiled in Table III.

Table III

attempt
No.

Composition of the copolymer

Initial values of water repellency and treated fabric

WoIl serge

polyester

Wool

! 55:45

Woven acrylic fiber

1
2
3
4th
5
6th
7th
8th

I. MDieth

II. MBut

I. MDieth

II. MBut

1. MDiet

II. MBut

I. MDieth

II. MMeth

I. MDieth

II. M-n-Prop

I. MDieth

II. MOct

I. MDieth

II. MOct

I. MDimeth

II. MOct

1 20:80, salt j 30:70, salt j 78:22, salt

60:40, salt 54:46, salt 60:40, Quaternary. 20:80, salt 1 30:70, salt

Notes to Table III:

MDiäth = diethylaminoethyl methacrylate MDimeth = dimethylaminoethyl methacrylate MBut = butyl methacrylate MMeth = methyl methacrylate Mn-Prop = n-propyl methacrylate MOct = octadecyl methacrylate quaternary. = converted into a quaternary ammonium salt with dimethyl sulfate
Salt = acetic acid salt

100
90
100
100
100
100
100
100

100
100
100
100
100
100
100
100

100
100
100
100
100
100
100
100

100
100
100

100
100
100
100

The ratio in the column that relates to the composition of the copolymer is the weight ratio between the two components in the order listed.

The dashes in the last vertical column mean that this fiber has not been investigated.

The wax copolymer suspension given in experiment no. 8 in the table above pulls with exhaustion well on cotton too.

The details given in the above examples can be modified as will be understood by those skilled in the art will. While the concentrates given in the examples have a solids concentration in most cases of 24 percent by weight, in one case 12 percent by weight and in one case If they have 25 percent by weight, the concentrates can of course also be used with each others are within a range of 10 to 50 percent by weight for practical purposes Solids content are produced.

Comparative experiments

A. Preparation of a water repellent composition according to U.S. Patent 2,206,090

Preparation of the surface-active compound

71.0 g of stearic acid are placed in a three-necked flask fitted with a thermometer and a water trap. The acid is melted by heating to about 100 ⁰ C, and thereto 25.7 g of diethylenetriamine are added. The mixture is ^{heated to 220 °} C. with stirring. A little more than 2.1 ml of water are formed and are removed from the system. The resulting mixture is poured into an aluminum pan, where it solidifies to a wax-like material (89.0 g).

109 639/329

Preparation of the dispersion

44.0 g of paraffin wax and 3.0 g of the previously prepared Amidostearyldiäthylenamins are melted together and placed in a stirred vessel. A solution of 75.0 g of aluminum acetate in 78.0 g of water at ^{60 °} C. is added with stirring. The mixture is kept at 60.degree. The mixture is then stirred at maximum stirring speed for 10 minutes. 576 ml of water are then added at low stirring speed and an approximately stable dispersion is obtained (solids content 14.2%).

B. Manufacture of the water-repellent agent according to French patent specification 1,119,321

125 ml of water, 12.5 g of stearic acid and 12.5 g of triethanolamine are heated in a stirred vessel mixed.

50 g of a Fischer-Tropsch wax (melting point 101 ^° C. and 12.5 g of stearic acid are melted together.

The soap solution in the stirring vessel is ^{heated to 105 to HO 0} C, and the molten wax and the molten stearic acid are added rapidly at maximum stirring speed. The mixture is ^{allowed to cool to 80 °} C. and 37 ml of water are added with stirring. The mixture obtained is cooled to 40 ° C. with stirring, and a further 50 ml of water are added. The product is a thick paste with a solids content of 30.2 ° / ₀ represents.

C. According to the invention
water-repellent dispersion

Example 1 was followed up with the exception that 233 parts of water were used, whereby one a dispersion of the copolymer and the wax with a solids content of 30% was obtained.

D. Application

The following Table IV shows the water repellency effects achieved with the preparations described above. In experiments 2, 4 and 6 as well as 3, 5 and 7, the same weight amounts of active ingredients are in each case on the substance, because the dispersion according to US Pat. No. 2,206,090 contained 14%, the dispersions according to French Pat. No. 1119 321 and Example 1 of the present invention each 30% solids. The water-repellent agents were applied to a poplin fabric made of 65:35 polyester / cotton (referred to as a mixed fabric) and to 100% cotton fabric, the respective concentrations being noted in the “OWF concentration” column. The treated substances were heated to 170 ^° C. for 2 ¹ I _{2 minutes.} The treated fabrics were then tested for their water repellency after the treatment and after three or five washes using the AATCC spray test 22-1952.

Table IV

No. Water repellent agent Conc
tration
OWF (·) Mixed
tissue tree
wool \
three w
Mixed
tissue A'asserabwi
ashing
tree
wool ; isation after
five vv
Mixed
tissue 'ashes
tree
wool 1
2
3 A according to
i U.S. Patent 2,206,090 j 2.0
4.0
8.0 0
0
50 50
50
70 0
0
0 0
0
0 0
0
0 0
0
0 B according to 4th
5 \ French ί
J patent specification 1 119 321 \ 2.0
4.0 0
50 0
50 0
0 0
0 0
0 0
0 6th
7th C according to
j Example 1 I. 2.0
4.0 80
100 70
90 70
70 0
50 50
70 0
50

(·) OWF means the amount of solid constituents of the dispersion applied to the fabric, based on the Weight of the fabric.

Further experiments were carried out in order to produce preparations which contained 10% of a melamine-formaldehyde resin for the anti-crease finish and 2.0% of an acidic catalyst in addition to the amounts of the dispersions used in the table. The baths according to US Pat. No. 2,206,090 and French Pat. No. 1,119,321 coagulate and could not be applied to textiles. The baths which contained the dispersion according to the invention according to Example 1 of the present invention remain stable at 38 ° C. for 2 hours and could be applied to textiles, giving both crease resistance and a water-repellent finish.

Claims (3)

Patent claims: 1. Aqueous dispersion for making textile fabrics water-repellent, consisting of a Wax and a surface-active copolymer compound in the form of a salt or a Quaternary compound of a copolymer of 20 to 80 percent by weight of basic acrylic acid ester units of the general formula CH ₁ = CCO- R "-N ' R 'O R ' RIV and 80 to 20 percent by weight of neutral acrylic acid ester units the general formula CH ₂ = C - C - O - R ^v I I = R 'O wherein R 'is a hydrogen atom or a methyl group, R "is an alkylene radical having 2 to 4 carbon atoms, R ^{v is} an alkyl radical having 1 to 22 carbon atoms, R'" is an alkyl radical having 1 to 22 carbon atoms and R ^{IV is} a hydrogen atom or a Denotes an alkyl radical having 1 to 4 carbon atoms or in which the radicals R '"and R ^IV with the nitrogen atom to which they are attached to a five- or six-membered ring are joined together, which may also have a may contain further heteroatom, as solid constituents in a weight ratio of copolymer compound to wax from 0.067: 1 to 1: 1 and a total concentration organic matter from 10 to 50 percent by weight of the total dispersion. 2. Dispersion according to claim 1, characterized in that the wax is a hydrocarbon wax is. 3. Use of an aqueous dispersion according to claim 1 or 2 for making textile fabrics water-repellent by heating the treated textile fabrics to 100 to 200 ^° C.