DE1419376A1 - Use of copolymers for impregnating and printing fiber material - Google Patents

Description

Use of copolymers for impregnating and printing company material. It is known to use aqueous dispersions of copolymers for impregnation and as binders when printing fiber material. Copolymers have already been used that contain groups of atoms capable of crosslinking reactions and can thus be made particularly resistant to solvents by subsequent crosslinking. Such copolymer dispersions have the disadvantage that their position is limited; for example, the pH value and fine division gradually change to such an extent that satisfactory impregnations or prints are no longer obtained with the dispersions; During prolonged storage, especially under the influence of greater temperature fluctuations, the dispersions become unusable for use because the copolymers coagulate. It was therefore the task of looking for cross-linkable one Mi'schpolymerisaten that nothing lose, even during prolonged storage prior to use for impregnating and printing fiber material on usability and in the application by customary I% rfahren impregnations and prints revealed their Fastness properties are approximately equivalent * to those obtained with known copolymers. It has been found that copolymers which contain groups capable of crosslinking and hydrophilic groups and which have been converted into powder form by spray-drying their aqueous dispersions meet the requirements and moreover give impregnations and prints with particularly good fastness properties.

Groups capable of networking are those who allow it Molecules of the copolymers during impregnation and printing or afterwards under the application conditions that are technically possible in the presence of FaE # ermaterial to combine so that the products obtained in chemically inert organic solvents, such as benzene, acetone, ethyl acetate and chlorinated hydrocarbons, become insoluble.

The groups capable of crosslinking can be linked to one another directly or with the aid of polyfunctional compounds. In any case, it is advisable to bring about the crosslinking by heating the treated fiber material to, for example, 80 to 150 ° C., depending on the type of crosslinking. Catalysts, for example acids, acid donors or bases, can in many cases promote the crosslinking process. Polyfunctional compounds which, depending on their nature, bring about crosslinking with or without catalysts, include, for example, formaldehyde, urea, melamine, urethane and phenol-aldehyde resins and their ethers, polyamines, polyimines and polyalcohols.

Groups which are capable of crosslinking and must be present in the copolymers are therefore preferably those which form homeopolar bonds at a higher temperature, optionally in the presence of catalysts and / or polyfunctional compounds. Such groups are, for example, carboxamide groups of the general formula in which Ri - H or alkyl, R2 - Hg -CH2OH9 -CH2-0-alkyl, -CH2-N (alkyl) 2 -CH2-N (alkyl ) 3 or -CO-alkyl or instead of or nitrogen-containing heteroeyeles of the general formula in which R3 can be a short-chain - optionally substituted - alkylene group.

There are also substances of the general formula in T - # - traiht, 'In which Rh, a short-chain alkylene or a cyclo- hexylene group and R 5 represents a short-chain alkylene or a phenylene group. Epoxy groups, isoeyanate groups masked by chlorohydrin groups, hydroxyl groups and sulfhydryl groups are also capable of crosslinking. The polymer layers can contain one type or more types of the groups mentioned or corresponding groups.

For the production of the copolymers suitable monomers with reactive ones Groups that are capable of crosslinking reactions are e.g. c # "ß-unsaturated # e Carboxamides, ke methaeric acid. &. amide, N-methylacrylic acid amide, N-methylol- (meth) acrylic acid amide, N-diethylaminomethylene acrylic acid amide, N-trimethylammonium-meth-ylene acrylic acid amide, Maleic acid imide, cY. "Ss-unsaturated carboxamides of ethyleneimine, N-methaeryloyltriazine, N-acryloyl-Nf-methyloltriazine, acrylic acid glyaidyl ester, butanediol monoacrylic acid ester. The monomers mentioned are only examples of reactive monomers of these Kind, however, there can also be other reactive monomers for the production of the mixed polymer salts can be used if they are used at higher temperatures in the association of the Misehpolymerisate with itself or with polyfunctional compounds with the formation of chemical compounds Attachments are able to react. Copolymers to be used according to the invention can also be obtained from several monomers with reactive groups be.

For the usability of the copolymers for the purpose according to this invention, it is necessary that the macromolecules of the nischpolymeeisat a contain hydrophilic groups in addition to the groups capable of crosslinking, so that the polymer powders produced by spray drying are uniformly in an aqueous medium before use to diaper. Although some of the groups capable of crosslinking are hydrophilic, riB. to use small amounts of aaryl acid or maleic acid in the preparation of the copolymers. Since the way in which the copolymers are produced is not of decisive importance for their usability according to this invention, "if the polymer molecules are substituted by groups of the type specified and if the copolymers have been converted into powder form by spray-drying", such copolymers can also be used. which, for example, contain hydrolyzed portions of acrylonitrile in the copolymer assembly.

, The crosslinkable copolymers contain the elements with groups capable of crosslinking and possibly also with hydrophilic groups Elements made from monomers that do not contain reactive groups. These monomers can basically all copolymerizable, ethylqnically unsaturated compounds be, e.g. ' Vinyl chloride, vinylidene chloride, styrene, acrylonitrile, acrylic acid or Methacrylic acid esters, vinyl esters and butadiene.

The composition is chosen so that sticking cannot occur either during spray drying or during storage of the polymer powder under elevated temperature conditions. Furthermore, the composition of the copolymers is matched to the desired properties of the impregnations or prints. For example, impregnations and prints with a particularly soft hand are obtained if the copolymers have been produced using sufficient, but not sticky, amounts of plasticizing components such as butadiene or butyl acrylate. , apart from the need to avoid unwanted bonding, th e average number appended to reactive, - networking inducing groups should have the molecule of züi use-.the copolymers »on the composition of Mischpolymerisatg and the desired effect from. Copolymers are preferably used which have been prepared with 1 to 10 wt., Cg, based on the total amount of monomers, monomers containing reactive groups. In special cases, ., P of monomers can be exceeded with these limits. Dis, Peng 1, drophile groups can be up to 7.5%, for example, but can be exceeded in individual cases.

Some copolymers are listed in the following table by specifying the starting monomers, for example: Amount amount amount amount amount amount Styrene 76% 60; 9 '17550, 21 r, 5w, 75% Acrylic acid butyl ester 1595 Acrylic acid iso- bittylester 15% Acrylic acid tert. butylestpr - .3 O, 'yj - Acrylsäureni- - tril 15% 15% 15% - 15%, 15% Aarylsäurp 5, 'y 5% 5% 6% - 5% Methacr.vls.! - ure * - - - 5% - Butyl ether of XM, Pthylolacryl- 5% - acid amide Ät, hyläthftr from N-MP, thyfolmeth-4.4 anrylic acid amide A-Grylsäuremethyl- est-rr 35% Me.thao4säkt-re.r ", 10% methyle ## '. er Amount amount amount amount amount amount Acrylamide Methacrylamide 4 N-methylol- methacrylic acid- 5 amide 2-liydroxy - 3-chloro - 5% propyl acrylate The copolymers to be used according to the invention can be converted into powder form by processes known per se. The procedural-en generally consist in the fact that the material to be dried Disnersionen verso UHT or verdUst and the thus obtained fine Fliissigkeitetröpfchen (50 to 150 0 C unFefähr) and concentrated in vacuo egg usually at higher Tpmperaturen are dried in Rchwebezustand. The spraying takes place in a closed container with a roller speed. that the water vapor and the dry powder can be separated mechanically. This separation generally takes place by separating the powder in a cyclone. The following examples - the parts mentioned therein 4 - are parts by weight. Example A.

A 40% aqueous dispersion of a copolymer of 74 parts of styrene, 15 parts of acrylonitrile, 6 parts of acrylic acid and 5 parts of N-methylol methacrylamide is prepared in a conventional manner by emulsion polymerization, diluted with water to a solids content of 20% and poured into a a pressure of about 600 Torr, heated to 130 0 C dryer. The water vapor and the resulting powder are separated in a cyclone.

100 parts of the resulting fine and almost colorless powder are re-emulsified in 150 parts of water, which has been adjusted to p111 8 to 8.5 with ammonia, with vigorous stirring using a homogenizer. This mixture is then kept at room temperature for 12 to 24 hours. The pH value is then corrected to 8 to 8.05 if necessary. With the help of the homogenizer, 50 parts of dibutyl phthalate and at the same time 50 parts of water are stirred in. You can leave the vegetables to stand for another 12 to 24 hours and then stir again thoroughly. The dispersion obtained in this way gives a thin, transparent, relatively soft and pliable film on drying, which is, however, still soluble in organic solvents. If 50 parts of the secondary dispersion are mixed with 3 parts on Ammonium nitrate, lets this mixture dry in a thin layer on glass and heated to 150 ° C. for 5 minutes, a soft, transparent film is obtained that is resistant to organic solvents. Example B.

A conventionally prepared aqueous dispersion of a mixed polymer of 40 parts of styrene, 36 parts of methyl methgeryl ester, 15 parts of acrylonitrile, 5 parts of acrylic acid and 4 parts of methaerylamide is diluted with water to a solids content of 20% by weight and, as in Example 1 described, spray-dried.

100 parts of the resulting powder are re-emulsified as described in Example 1 and burned with 50 parts of dibutyl phthalate, 10 parts of a urea-formaldehyde resin and 1 part of ammonium nitrate. Excluding this mixture in a thin layer to dry and heated to 140 0 C anschlbßend 15'Minuten, one obtains a relatively soft Filn Although the swell somewhat in orgailischen solvents but not dissolve --SiCH more.

EXAMPLE An aqueous dispersion prepared in a customary manner from 50 parts of tertiary butyl acrylate, 45 parts of methyl methacrylate and -5 parts of N-methylolmethaerylamide-n-butyl ether is spray-dried. colorless 100 parts of the dust-fine / I> ulver obtained are divided into 300 parts Dissolved ethyl acetate, mixed with 0.1 part of phosphoric acid, dried in a thin layer on glass at 8o 0 C and 15 minutes. th heated to 150 0 C. The film obtained is colorless and hard and no longer dissolves in organic solvents.

Example D. One made in a conventional manner. Dispersion of a copolymer of 70 parts of styrene, 15 parts of acrylonitrile, 5 parts of acrylic acid and 10 parts of 3-chloro 1,2-propanediol acrylate is diluted with water to a solids content of 25% and spray-dried. 100 parts of the powder obtained are re-emulsified in ammonia water in the manner described in Example 1 , 50 parts of di-2-ethylhexyl phthalate are added and the mixture is homogenized. Now the mixture is adjusted to pH = 12 with sodium hydroxide solution and left to dry in a thin layer at room temperature. This gives a soft film that is insoluble in organic solvents.

Aqueous emulsion polymers are expediently used as the starting material for spray drying. which are obtained in a conventional manner by copolymerization of the monomers in an aqueous emulsion. Further information can be found in the Belgian patent specification 627 700 (priority of the German patent application .B 65 709 1Vd / 3q c dated January 30, 1962-). Before use, the powders are redispersed in water and the dispersions obtained are provided with the necessary and any other desired additives. The water can, for example, also contain alcohols such as glycerine or ethanol. It is customary to incorporate plasticizers into the dispersants for the impregnation and for the printing so that the copolymers have increased film-forming properties. All substitutes that are compatible with the copolymers and the other additives and suitable for plasticization are used as plasticizers Consider, for example, Pi-ithaljs. * - iureefter, mixed polymer latex - which are already sufficiently soft on their own, can also be processed without these kissers, if the "intended purpose" and the desired effect allow it. The amount of plasticizer can therefore be 0 to! ÖO Cnw.%. based on the mixed catalyst. bet-agen.

The dispersions of the invention, ## ß To use -. # Copolymers, other auxiliaries required for impregnations and prints, such as paring agents, pigments, optical brighteners, emulsifiers, can also be used. Protective colloids and thickeners or fillers can be added. In the presence of special emulsifiers, e.g. the sulfated addition product of approximately 25 moles of ethylene oxide and 1 mole of sperm oil alcohol, reserve or caustic agents such as aluminum sulfate, tin (II) chloride or the sodium salt of oxymethanesulfinic acid can also be used. Basic or acidic compounds, such as triethanolamine or tartaric acid, or potentially acidic compounds, such as ammonium nitrate, diammonium phosphate or ammonium rhodanide, and, if desired, curable precondensates, can also be added to the dispersions. Such precondensates are e.g. methylol derivatives of urea, urea derivatives, melamine and urethanes. If the use of polyfunctional, small compounds of the type mentioned above is necessary for the crosslinking of the copolymers, then these are also added to the copolymer dispersion.

If one wants to use the copolymers to be used according to the invention To produce emulsion thickenings, heavy gasoline is emulsified in the dispersions and / or other water-insoluble organic liquids.

Powdered auxiliaries of the abovementioned type, if they are compatible with the mixed polymer powders, can also be admixed before dispersing. The content of the dispersions in the copolymers to be used according to the invention is to be adapted to the intended use. Dilute liquors are prepared for impregnation. The liquors, which can contain dyes, pigments and / or curable resins and plasticizers, for example, are used to soak or puke tissue, after which it is dried. Pressure approaches are obtained by adding thickenings in the form of low-body natural or synthetic thickeners such as tragacanth, alginate or salts of polyacrylic acid, or in the form of an oil-in-water or water-in-oil emulsion to the dispersions of the Copolymers. In addition, dyes or pigments and other desired or necessary H4 [.lfsh # ttel are added. The water-insoluble solvent can also be emulsified directly into the dispersion to produce an oil-in-water emulsion thickener. The printing plate is used to print fabric, whereupon m an ef dries. After the impregnated or printed fabric has dried, the interpolymer applied to the fiber material is crosslinked and the impregnation or print is therefore extremely fast Post-treatment referred to as fixation depends primarily on the type of compound used, the type of crosslinking reaction, and the desired level of fastness. For example, when using copolymers with reactive groups which react in the sapric medium at elevated temperature, e.g. mixed polymers with amide or methylolamide groups in the presence of an acidic catalyst, the fiber material is heated to 125 ° C. for 5 minutes. When using alkaline cross-linking groups such as chlorohydrin "5 minutes at 0 in the presence of alkali, for example, about 102 C attenuated, In jedem.Fall: is the upper temperature Turgi., ienze 4urch.die temperature sensitivity" determined le treated fiber material.

The amount of fiber that can be treated with the mixed polymers used according to the invention are threads, woven fabrics, knitted fabrics and nonwovens made of natural and synthetic fibers, for example cotton and cellulose wool, wool and silk, cellulose acetate and livestock, polyafflower. , Polyester and polyacrylonitrile, asbestos-9 glass and metal fibers. The use of mixed polymer resins of the type described here for. The impregnation and printing of fiber material * has numerous advantages over the agents used up to now. The use of mixed polymer powder as a starting material simplifies storage and considerably reduces transport problems. It is no longer * necessary to send mixed polymer dispersions with their high water content. As a result, Ttana port space is saved and better-wasted. In addition, simpler and cheaper packaging, eg bags or sacks, can be used instead of liquid containers. The most important factor in practice is the almost unlimited storage stability of the mixed polymer powders. It is particularly surprising9 that the mixed polymer powders despite their content of reactive groups Even after longer storage, there is nothing of the reactivity necessary for networking on the other hand, but extremely real impregnation and prints on iPasormatertal result.

.Even in view of the present in the Mischpolymertsaten hydrophilic Gruppenji although the Redlopei # gierbgrkeit the powder be-94niett4q4,4 .: But in alligen'etnen also dte Quellbarkeit.der. Miaoh polymort. sati -increased and the high-beauty of the impregnation and bruaks astonishing. Depending on the amount of powder, particularly platical prints are obtained which, for example, are particularly bright with metal powder as pigment. The following exemplary embodiments provide an overview of the numerous possible uses of the copolymers used in accordance with the invention for impregnating and printing fiber material. The amounts given are parts by weight.

Example 1.

20 parts of a powder obtained by spray drying of a copolymer of 60% styrene, 15% acrylic acid isobutyl ether, 15% aaryl acid nitrile, 5% acrylic acid and 5% of the butyl ether vön.N-methylolacrylic acid amide are dispersed in 80 parts of water with stirring. The homogeneous dispersion obtained in this way is adjusted to a PI value of 8 with ammonia and 5 parts of di-butyl phthalate are added while stirring on a stainless steel stirrer. Another 40 parts of a 20% strength aqueous solution of ammonium chloride are added and the volume is made up to 1 liter with water.

Using the thus obtained fleet a Bau'mwollgewebe is padded, additions, 0 fixed closing and dried 5 minutes at 150 C. The * impregnation is very washable and gives the fabric a full riff.

-Se: or if 10 parts of a 20% strength pigment paste of chlorinated copper phthaloeyanine and 10 parts of a 5% strength aqueous solution of sodium alginate are added before filling up with water, a uniform green coloration with good fastness properties is obtained.

The fabric can also be equipped in combination with condensation resins if, for example, only 10 parts of the mixed polymer powder and 100 parts of a. 50% aqueous . Solution of dimethylolethylene urea used.-Example-2. 10 parts of a powder of a mixed polymer of 75% styrene, 15% acrylonitrile, 5% acrylic acid and 5% N-methylolmethaeryl acid amide obtained by spray-drying are dispersed in 25 parts of water with stirring; pi -value 8 and stirred with 5 parts of phthalic acid dibutyl ester. 4 parts of a 30% strength aqueous pigment paste of Küpferphthaloeyanin, 2 parts of a 5-0% strength aqueous solution of ammonium nitrate and 54 parts of a thickener emulsion are added by stirring 78% heavy gasoline (hydrocarbon mixture with a boiling range 140 to 220 0 C, flash point according to Abel-Pensky 3Q 0 C and aromatic content <15%) on a high speed stirrer (number of revolutions _3000 - 6000 rpm) in a solution of 0 , 5 % of the adduct of 25 moles of ethylene oxide with 1 mole of sperm oil alcohol, 0.2 % of cellulose etherified with methanol and 21.3% of water are obtained.

This printing paste is used to print a cotton or cellulose fabric on the roller blind printing machine; it is dried at about 50oC and fixed for 5 minutes at 1400e. A brilliant print with good fastness to rubbing, washing and dry cleaning is obtained. The aging resistance is flawless. Example .3.

6 parts of the mixed polymer powder mentioned in Example 2 are dispersed in 20 parts of water with stirring. The pH of the dispersion is adjusted to 9 with ammonia and 6 parts of a 66 2/3% solution of octyl phthalate in toluene are stirred in with a high-speed stirrer. After adding 1 part of the addition products of -2-5 mol of ethylene oxide to 1 mol of sperm oil alcohol and 3 parts of an aqueous tragacanth solution, 58 parts of heavy gasoline (self-adhesive as in Example 1 ) are added with the counter .at about 3000 rpm. stirred.-Xan gives 3 parts of a 25% w.gorigen, # Pig'ment / dough . it consists of monobromis, odibenzanthron, which still contains 15% of an etherified urea-formaldehyde precondensate, and the second part of a 50% aqueous solution of ammonium nitrate; The printing paste obtained is used to print fabrics made of cotton, viscose and polyester fibers by film printing, then drying at about 50 ° C. and fixing at 1200 ° C. for 5 minutes. Brilliant prints with good fastness properties are obtained. If a white pigment is added to the print batch, matt color prints are obtained, if the abovementioned color pigment is omitted, matt white prints are obtained on uncolored ones. but also dyed fabrics.

For example 14 parts of a powder of a copolymer of 45 % styrene and 35% methyl acrylate obtained by spray drying. 10% methyl methacrylate, 6% acrylic acid and 4 % methaeryl amide are dispersed in 50 parts of water with stirring. The homogeneous dispersion obtained is adjusted to a pH of 9 with ammonia and 6 parts of adipic acid dioate acid are added while stirring with a high-speed stirrer. 3 parts of a 20% aqueous solution of the additive product of 25 moles of ethyi'epoxide to 1 mole of sperm oil alcohol, 10 parts of a 4% aqueous solution of sodium alginate are added. aqueous 12 parts of silver bronze, 3 parts of a 33 1/3% Igen / solution of diammonium phosphate and 2 parts of an approximately migh aqueous solution of an etherified urea - '. formaldehyde precondensate added.

A black acetate fabric is printed with the resulting paste, dried and fixed at 1200C for 5 minutes. A brilliant silver overprint with good wash fastness is obtained.

Example 5.

20 parts of a powder obtained by spray drying, a copolymer of 76 Styrlgl ", 15% acrylonitrile, 5% acrylic acid and 4 % of the ethyl ether of N-methylolmethaeryl acid amide, are dispersed in 34 parts of water with stirring. The homogeneous dispersica obtained is with ammonia to - a p. value of 8 * and mixed with 12 parts of phthalic acid dibutyl ester with stirring with the high speed stirrer. The dispersion is mixed with - 13 parts of an aqueous solution of a cellulose methylate, 3 parts of a 20% aqueous solution of the Anlagerungsprodukbes of 25 moles of ethylene oxide Toggle 1 mole of sperm oil, 15 parts of gold bronze mnd 3 parts of a 33 1/3% solution of Dia. mmoniumphosphat.hinzu.

With the received printing patron. A black viscose rayon fabric and a black acetate fabric are printed. It is then dried and fixed at 120 ° C. for 5 minutes. A very plastic, luminous gold print with good wash fastness is obtained. Example 6.

8 parts of the copolymer powder mentioned in Example 2 are dispersed in 28 parts of water with a period of time. The dispersi . After neutralizing with ammonia, 4 parts of di-butyl phthalate, while stirring with a high-speed stirrer, and 1 part of the sodium salt of the acidic sulfuric acid ester: that is, anloLgerlungsprodukte - of 8-6 moles of ethylene oxide to 1 mole of sperm oil alcohol are mixed into the mixture 42 parts of a thickener emulsion according to Example 2 '' 1 part tartaric acid., 10 parts of a reserve paste of 50% tin (II) chloride and 50% of a 6% 1.gen aqueous tragacanth solution and 6 parts of a 30% aqueous pigment dough of an azo dye from 2 mol 2,4-dichloroaniline 1 mol 3,31-dimethy # 1-4,41-.diacetoaetylaminodJ.phenyl stirred in.

A naphtholized cotton fabric is printed with this printing paste and treated for 10 minutes at # O-OC. Then it is padded with a solution of a parbo base and treated as usual for naphthol dyeing. Brilliant, pure reserve prints with good roughness are obtained. Example 7 8 parts of the mixed polymer powder mentioned in Example 2 are dispersed in 28 parts of water by stirring. The erh.nIttenen, dispersion after Neutralisätion with ammonium-Iak 4 parts' $ Phthalsburedibutyl ester under Rübren with the Schne1.1rUh-rer and 3 positions: Sodium salt of the acid it Schwefelsäureesters the adduct 80% RON Hol ethylene oxide and 1 mole of Spermöla-Iko "% # ol in the - mixture 44 parts of a thickener emulsion # nae-h Pelspiel 2, 10 parts of a paste Xt.z -from 50 # 5j the sodium salt of Oxymetba-nsiilf in # skure and 50! 5 »of a 6% aqueous tragacanth solution, P. parts of elner-, 10%, aqueous solution of ammonium nitrate and 3 parts of a 30-age, aqueous pigment paste of an azo dye from 1 mole of 393f-die-chlorobenzi (lin + 2 moles of 2N-adetoaoetylamino-5 -chloro-1,4-dimethoxybenzene stirred in. A substantively black-colored cotton fabric is printed with this printing paste; it is then dried and steamed for 7 minutes at 1050 ° C. A brilliant discharge print with good fastness properties is obtained. Example 8th.

9 parts of a powder of a copolymer of 75% styrene, 15% acrylonitrile, 5% acrylic acid and 5% 2-hydroxy-3-chloropropyl acrylate are dispersed in 12 parts of water with stirring. The dispersion is adjusted to a pH value of 7 to 8 with ammonia and stirred with 4 parts of dibutyl flithalate. To this are added 4 parts of a 30% strength aqueous pigment paste of the azo dye composed of 2 moles of 2,4-dichloroaniline + 1 mole of 3 $ 31-dimethyl-4941-diacetoaoetylaminodiphenyl and 68 parts of a thickener emulsion according to Example 2. Finally, 3 parts of L5jK are stirred. ige caustic soda ..

The printing paste obtained is used to print a cotton fabric on the Rouleaux printing machine. It is dried at about 500 C and fixed by o 'vapors 10 min. At about 102 C. The result is a print with good Reib. and wash fastness.

Claims (6)

Patent claims 1. Use of # miscfipol.ymerii # aten.-which contain groups capable of cross-linking and hydrophilic groups -and-have been converted into powder form by spray-drying their aqueous dispersions. for the production of impregnations and prints on fiber material in a conventional manner from aqueous phase and by finishing the impregnations or prints in a conventional manner. - 2. Use of copolymers. those capable of networking Groups and hydrophilic Ci - ?, uppen 'contained and by spray drying their aqueous! gen dispersions have been fed over in powder form. together with a plasticizer zpr Manufacture of impregnations and prints on fiber material on the per-se usual Wise '-out' -, viäßri-ger phase and through'Fertir:, 2 # telle'n der - "Tmprregnationen or pressure6 in the usual way. »-. _ 3. Use of copolymers according to claim 1 or 2 for the production of impregnations and prints on fiber material, catalysts and / or polyfunctional compounds and / or precursors of curable resins that are able to react with the reactive groups of the copolymers are also used. 4. Use according to claims 1 to 3, characterized. that dyestuffs and / or. Pigments are also used. 5. Use according to claims 1 to 4. thereby gt # enG ## tichnet. da3 water-soluble natural or synthetic high-molecular substances and / or oil-in-water or water-in-oil emulsions which contain water-insoluble solvents are used as thickeners. 6. Mixtures of mixed polymer powders of the type mentioned in claim 1 with pigments. especially pigment dyes, and if desired. Tools for the impregnation or printing of fiber material.