US2289275A - Process of waterproofing textiles - Google Patents

Description

Patented July 7, 1942 2,289,275 FlCE 2,289,275 PROCESS OF WATERPROOFING TEXTILES Ludwig Orthner and Gerhard Balle, Frankforton-the-Main, Jo

hann Rosenbach, Wiesbaden,

. and Kurt Bonstedt, Frankfort-on-the-Main, by mesne assignments, to

Germany, .assignors,

General Aniline &

Film

Corporation, New

York, N, Y., a corporati n of Delaware No Drawing.- Application March 25, 1939, Serial No. 264,176. In Germany April 2', 1938 4 Claims. (01. 3-120) The present invention relates to water-proof textile material and to a process of preparing'it. e have found that natural or artificial fibrous materials of animal or vegetable origin as well as products made therefrom may be rendered water-repellent by treating them with a solution vor a dispersion of a condensation product of b'etaine-like structure substituted .at the betain nitrogen by the group and subjecting the material thus impregated to a heat treatment between 80 C. and 150 C.

In the above formula R means a hydrocarbon radical with at least 12 carbon atoms which may.

be interrupted by hetero-atoms, for instance An alternative method of manufacturing waterrepellent textile materials by means of the condensation products of betaine-like constitution here in question consists in adding oneof the condensation products of betaine-like constitution above described to the spinning solution whichis to serve as the making artificial threads.

It is often of special advantage to impregnate the textile material in the presence of agents of feebly acid action, such as lactic acid, tartaric oxygen or sulfur and X means oxygen or sulfur.

'The compounds which are to be used in the process may be preparedas described in our copending application Serial No. 261,760, Patent No. 2,217,846. Compounds suitable for treating the fibrous materials are, for instance, condensation products of betaine-like structure prepared from aminocarboxylieacids disubstituted atthe nitrogen atom and for instance the following halogen methyl compounds: dodecyl chloromethyl ether, octadecyl chloromethyl ether, dodecyl bromomethyl ether, octylcyclo hexyl chloromethyl ether, the chloromethyl ethers of i iso-octylphenol-monoglycol ether, dodecyldiglycol ether, dodecylhydroxy ethyl sulfide, montanalcohol, abietinol and di-hydro'abietinol. are, likewise, suitable sation products from thio-ethers such as, for instance, dodecyl chloromethylsulfide and octadecyl chloromethyl sulfide.

, From the amino-carboxylic acids having tertiary nitrogen, whose products of reaction withthe above mentioned compounds are suitable for' rendering textiles water-repellent, there may be mentioned, for instance, dimethylamino-acetic acid, dibutylamino-acetic acid, piperidino-acetic acid, morpholino-acetic acid, al'pha-dimethyl-l amino-prop-ionic butyrlc acid.

The textile material is impregnated .with a solution or dispersion of the condensation prodacid and gamma-diethylaminoas water-proofing agent, the excess of the solution is removed by squeezing or centrifuging andthe material thus treated is then exposed for some time to a temperature of 80 C. to 150 C.-

The degree of temperature necessary for obtaining a of the waterproofing agent used. Ins'ome cases it may be advantageous first to dry the 1mpregnated material at low temperature and then to heat to a higher temperature.

satisfactory efiect depends upon the kind acid, glycolic acid, boric acid or the like. .It is possible thereby to reduce the duration of the subsequent heat treatment or to obtain a satisfactory eifect even at essentially lower ripening temperature. The textile material may be treated with the acid agents also before or after the im- Dregnation proper.

The condensation products of betaine-like, structure may also be used in admixturewith other water-proofing agents, for instance, with the methylol-amides of acids of high molecular weight, isocyanates of high molecular weight or v the addition products of halogen methylethers or halogen methylamides of high molecular weight with tertiary bases. Furthermore, it is possible to enhance the waterproofing effect of the condensation products used in the present invention There. the corresponding condenby adding to the impregnation liquors resin-like condensation products or the pre-condensation products thereof, for instance, condensates of urea, thiourea, aniline, melamine, dicyandiamide, phenyliminodiacetic acid-diamide or the like with aldehydes, especially formaldehyde and glyoxal.

In this case not only the water-repellent property of the fibrous material may be enhanced but the not of betaine-like structure which is to be used not diminished even by material acquires a considerable fastness to creasing. The treatment may also be combined with other processes, for instance, by adding to the above described baths softening agents, delustering agents, agents known to enhance resistance to creasing, filling and dressing agents and other agents usually applied in the of textiles.

Various special effects may be obtained which are several washing operations. 7

The following examples serve to illustrate the 'invention butthey are not intended to limit it thereto: Y 7

(l) Artificial silk crepe is impregnated at 60 C. with an aqueous solution of 1 per cent strength of octadecyloxybetaine of the formula heated for hour at C. to C. Thereby, the material becomes very water-repellent.

The material lsthen squeezed and parent material 4 for acid methyl ester and wfirst pre-dried at 50 squeezed and heated for 1 hour at 105 (2) Artificial silk fabric is impregnated for 10 minutes at 50 C. with a bath containing per litre of water 10 grams of octadecyloxybetaine (which has likewise been applied in Example 1) and 6 cc. of lactic acid of 75 per cent strength. The fabric is then squeezed and subjected for /2 hour to 105 C. to 110 C. After this material becomes very water-proof and water poured thereon immediately runs off in drops. The effect remains undiminished even after several washing operations. I

(3) Artificial silk crepe is impregnated with an alcoholic solution containing per litre 6 'cc. of lactic acid and 10 grams of octadecyloxybetaine. The fabric is then freed from the excess of the adherent solvent by centrifuging and heated for 30 minutes at 120 C..

(4) W001 piece goods aretreated with an aqueous solution of the octadecyloxybetaine of the formula:

(5) Loose viscose artificial silk fibre is im-- short time with an aqueous solution of 1 per cent strength of the product obtained by saponification of the condensation alpha-dimethyl-amino-propionic dodecyl chloromethyl ether. After centrifuging, the textile material is C. and then heated for 1 product from hourat 130 C.

(6) A mixed fabric wool and artificial silk made from equal parts of staple fibre is treated for A minutes with an aqueous solution containing per litre 20 grams of the betaine on, on; 0111115. 5 CHI-N10111:. o o o and 8 grams of lactic acid. The material is then C. ('7) Artificial silk fabric is impregnated for a short time with an aqueous dispersion of l per cent strength of a mixture consisting of equal parts of octadecyloxybetaine (cf. Example 1) and stearic acid methylolamide. The material is then squeezed and heated for /2 hour at 135 C.

(8) Fabric from artificial silk staple fibre is impregnated with an aqueous solution containing per litre 100 grams of dimethylol urea, 5

1 grams of tartaric acid and 10 grams of octadecyloxybetaine (of. Example 1). The excess of the impregnating liquor is then removed by centrifuging and the material exposed to a temperature of 135 C. to 140 C. i

(9) A'fabric from viscose staple fiber is impregnated on the foulard with carbon tetrachloride containing per litre 10 grams of an in-- terpolymerization product from maleic acid anhydride and vinyloctadecyi ether in the dissolved state. The fabric is then further impregnated, likewise on the foulard, in a second bath containing per litre of water 20 grams of octadecyloxybetaine of the formula:

and 5 grams of lactic acid, dried and heated for treatment the 10 minutes at 150 C. A fabric is obtained which is very water-repellent, even being resistant to a boiling soap-treatment.

' (10) A fabric prepared from viscose artificial silk and artificial silk staple fiber made according to the viscose process is treated for a short time at 50 C. to 60 C. with an aqueous solution containing per litre 10 grams of octadecyloxybetaine and'6 cc. of lactic acidof '75 per cent strength. The material is then squeezed, predried for 1 hour at 60 C. and then heated for 20 minutes at 140 C. 4

'(11) Cotton fabric is impregnated with an aqueous solution heated to 60 C. containing per litre 6 cc. of lactic acid of '75 per cent strength and 10 grams of the betaine of the following constitution V he material is then centrifuged, pre-dried at 50 C. and heated for /z hour at 13 5 C. to 140 Cg: CH3 CuHasO-O.CH;.CH.O.CH1.CH.O.CHrliCHaCOO- The material is squeezed and heated for 1 hour at 140 C.

(13) 11.2 grams of the compound made by saponifying the reaction product from octadecylchloromethyl ether and piperidino-acetic acidmethyl ester are added in the form of an aqueous solution of 20 per cent strength to 5 kilograms of a viscose solution ready for spinning containing 7.5 per cent of cellulose and 6.5 per cent of alkali and the solution is spun in the usual manner, for instance according to the twobath-process. The fiber is washed until neutral, dipped into a lactic acid bath of 0.3 per cent strength, dried and subjected for 45 minutes at 110 C. to a ripening process.

(14) 10 grams of the compound made by saponifying the reaction product from octadecylchloromethyl ether and dimethylamino-acetic acid-methyl ester are added in the form of an aqueous solution of 10 per cent strength to 5 kilograms of a viscose solution ready for spinning containing 7.5 per cent of cellulose and 6.5 per cent of alkali and the solution is spun in the usual manner, for instance according to the twobath-process. The fiber is washed until neutral, dipped into a lactic acid bath of 0.3 per cent strength, dried and subjected for 45 minutes at 110 C. to a ripening process.

' saponifying "7.5 per cent of cellulose and 6.5 per cent of alkali and the solution is spun in the usual manner in a Mullen-bath. The desulfurized and acidified fiber iswashed until neutral, dipped into a solution of tartaric acid of 0.3 per cent strength and h ated-for 1 hour at C.

nating the textile material 1. The process of manufacturing water repel- I lent textile materialwhich comprises impregnating the textile material with a liquor containing a condensation product of betaine-like constitution substituted at the betaine nitrogen atom by the group 7 R. X. CH2- wherein R stands for a member of the group consisting of hydrocarbon radicals and hydrocarbon radicals containing hetero atoms as members of their carbon structure the radicals having at least 12 carbon atoms,- X stands for a member of the group consisting of oxygen and sulfur, removingthe excess of the liquor from the textile material and exposing the textile material to a temperature between'about 80 C. and about 150 C.

2. The process of manufacturing-water'repellent textile material which comprises impregwith a liquor containing a weak acid and a condensation product of betaine-like constitution substituted at the betaine nitrogen atom by the group R. 2: CH2- wherein R stands for a member of the group consisting of hydrocarbon radicals and hydrocarbon radicals containing hetero atoms as mem-' bers of their carbon structure the radicals having. at least 12 carbon atoms, X stands for a member of the group consisting of oxygen, and sulfur, removing the excess of the liquor from the textile material and exposing the textile material to a temperature between about C. v

and about C.

3. A modification of the process described in claim 1 which consists in treating the textile material with a weak acid before impregnating it with the liquor containing the condensation product of betaine-like constitution.

4. A modification of the process described in claim 1 which consists in treating the textile 7 material with a weak acid after impregnating it with the liquor containing the condensation product of betaine-like constitution.

LUDWIG ORTHNER. GERHARD BAILE. JOHANN ROSENBACH. KURT BONSTED'I'.