US2242051A - Process for producing water-repellent textile materials and products therefrom - Google Patents

Description

Patented May 13, 1941 PROCESS FOR PRODUCING WATER-REPEIl- LENT TEXTILE MATERIALS AND PROD- UCTS THEREFROM Hans Beck, Krefeld, Germany, assignor to Heberlein Patent Corporation, New York, N. Y., a corporation of New York No Drawing. Application May 22, 1937, Serial No. 144,304. In Germany May 27, 1936 7 Claims.

This invention relates to processes for producing water-repellent textile materials and products therefrom. Matter not herein claimed is claimed in my copending application Serial No. 267,339, filed April 11, 1939.

In the copending application of Walther Kaase et al. Ser. No. 73,976, filed April 11, 1936, Patent No. 2,207,740, there is described a treatment of textile materials with aldehydes having at least 10 carbon atoms to produce a surface etherification.

The principal object of the present invention is to increase water-resistance in wool and cellulose-containing materials such as cotton, jute, linen, hemp and various artificial silks, by a simple process employing aldehydes of a different type than that described in the copending application mentioned; and to produce products having improved characteristics thereby. Another object of the invention is to provide a simple process for the manufacture of Water-repellent chemicals and to produce such chemicals thereby.

The invention accordingly comprises the novel products as Well as the novel processes and steps of processes according to which such products are manufactured, the specific embodiments of which are described hereinafter by Way of example and in accordance with which I now prefer to practice the invention.

It is believed in accordance with the present invention that slight etherification of cellulose or its derivatives or wool by means of the aldehydes herein described produces water-repellence and an improvement in the beauty of the goods; at the same time the feel of the goods is not substantially altered. In making the statement that slight etherification occurs, I do not wish to be bound by such theory as it is possible that some other reaction occurs to produce water-repellence.

In accordance with the invention I treat the textile material with a dialdehyde reaction product containing an aliphatic radical having at least 10 carbon atoms in the straight chain, to increase its water-repellence. The expression dialdehyde reaction product refers to the reaction product of a dialdehyde with fatty acid amides, fatty amines or fatty alcohols, including wool-fat alcohol. In order that the nature of these reaction products may be better understood, the following represent typical examples of reactions of dialdehydes with the substances mentioned, although it will be understood that mention of these substances is purely for illustrative purposes and without intention of restricting the invention thereto, except as indicated in the claims:

Stearic acid amide Monomeric-glyoxal H Cl7H35-C O.NH.O CH2.C=O Condensate of stearic acid amide and monomeric glyoxal (1) Or reaction with two molecules of the acid amide is as follows: i

H H C|7H35.CONH2 b C 7H35.CONHz Stcaricacid amide Monomeric-glyoxul V Ci1H:5.CONH:-H I H o.o +1120 Ci1Ha5.CONH o Condensate of 2 mols stearic acid amide and monomericglyoxal H H 2Cl7H35-NH2 O= 3C l=O Stearyl amine Monomeric glyoxal C11H35NH H H 3( l=O+HzO l formed as herein described appears to have ing equation:-

. .Cellulosc R.C1IO+21IO.Ccllulose R.C Diuldchyde reaction product ggaelulose Cellulose ecetal It is believed that a similar reaction occurs with wool. The dialdehyde reaction product great reactivity towards textile materials including cellulose, its derivatives and wool. Catalysts such as lactic acid and glycolic acid are employed in connection with the reaction. Formation of acetals is accelerated as it is known by the addition of acids. Advantageously there may be employed organic acids because textile fibres cannot be damaged by them.

The impregnation of the textile material with the products herein described can be efiected in any desired manner with or without the use of organic solvents by emulsifying the dialdehyde reaction product in aqueous solution by immersion of the material to be treated or by spraying it or by like procedure. If a solvent is emnloyed, it is preferably removed. After the material is impregnated it is heated for a short while at a temperature above approximately 100 0., preferably 100160 C.

The process may be carried out on yarns, fabrics or on textile material in other condition as desired. In connection with artificial silk the process may be employed for example with acetyl cellulose to produce the water repellence during the spinning process. In this case a solution of the aldehyde is added to the solution of acetyl cellulose in acetone or the like and the spinning follows in the customary manner. It is'also possible to effect water-repellence immediately after the spinning process by passing the spun threads through the solution of the aldehyde.

The aldehydes herein mentioned can be prepared in accordance with the following examples.

The examples given are to be regarded as illustrative and the invention is not to beconsidered restricted thereto except as indicated in the appended claims:

Example 1.-284 grams of stearic acid amide CrzHzsCONI-Iz are dissolved in 1 liter of carbon tetrachloride and there are added thereto 58 grams of monomeric-glyoxal The mixture is heated for about 30 minutes to 70 C. (158 F.). With decoloration of the solution the dialdehyde reaction product having a straight chain of more than 10 carbon atoms is formed.

Example 2.-58 grams of polyglyoxal Example 3.--58 grams of polyglyoxal are dissolved in stirred together with amide C15H31.CO.NH2

O H H are dissolved in 1 liter of carbon tetrachloride and to it there are added 284 grams of stearic acid amide C1'1H35CONH2. The mixture is heated for a time. A dialdehyde reaction product having a straight chain of more than 10 carbon atoms of high molecular weight is formed. The product is:

Example 5.-270 grams of octadecyl alcohol CraHarOH are dissolved in 2 liters of benzine, 30 grams of monomeric glyoxal are added thereto, and dry hydrochloric acid gas is introduced into the solution. A dialdehyde reaction product having a straight chain of more than 10 carbon atoms of high molecular weight is formed. The product is:

H (ll-octadecyl semi acctal of glyoxal (CiaHi10)z.CH.C

In place of stearic acid amide and palmitic acid amide other aliphatic amides may be employed, for instance lauric acid amide, montanic acid amide, naphthenic acid amide may be employed. Instead of these amides, amines may be employed such as stearyl amine or mixtures of primary saturated amines which are obtained by the hydration of train oils, for example as described in D. R. P. 611,924 or French Patent No. 761,952. In place of the amides or amines, alcohols may be employed such as octadecyl alcohol, myricyl alcohol, etc. The production of the aldehydes from amines and alcohols is efiected in the same manner as from the amides and presents no peculiarity.

The following are examples of application of the dialdehyde reaction products to textile materials:

Example 8.A textile fabric consisting of a warp of viscose and a weft of viscose crepe is treated for 5 minutes at 40 C. (104 F.) in a bath which contains 5 grams of lactic acid (60%) as catalyst per liter of Water. The fabric is then dried and is thereupon passed through a solution of heavy benzine, B. P. C. (230 F.), at a temperature of 60 C. (140 R), which contains per liter 10 grams of the dialdehyde reaction product formed in accordance with Example 1. After the evaporation of the benzine by heating at 110 C. the fabric is subjected for 1 hour to a temperature of C. (248 F.).

Example 9.A cloak fabric composed of pure wool is treated for minutes at 50 C. (122 F.) in a bath which contains per liter 4 grams of glycolic acid as catalyst. Thereupon the fabric is dried and is passed through a solution of-carbon tetrachloride at a temperature of 60 C. (140 R), which contains per liter grams of the dialdehyde reaction product produced in accordance with Example 5. After the evaporation of the solvent the fabric is subjected for 1 hour to a temperature of 110 C. (230 F.)

The process is also suitable for the rendering water-repellent of thin sheets or films composed of cellulose.

Example 10.Cellulose film for example Cellophane made from viscose or reprecipitated cellulose from cuprammonium cellulose is passed through a bath at a temperature of 40 C. (104 F.), which contains per liter 5 grams of lactic acid (60%) as catalyst. The cellulose film is then dried and is thereupon passed through a solution of heavy benzine 110 C. (230 F.), at a temperature of 60 C. (140 E), which contains per liter 10 grams of the dialdehyde reaction product formed in accordance with Example 1. After the evaporation of the solvent the film is subjected for 10 minutes to a temperature of 140 C. (284 F.).

By aliphatic amine, as employed in the appended claims, is intended aliphatic substances which contain an NH: group, but do not contain another N group which under the reaction conditions included herein will result in a product favorable to the absorption of water.

The process of the invention, particularly as set forth in the specific embodiments above, may be carried out with simple apparatus at relatively small expense and in.a relatively short time. The products show an improved appearance, their feel as compared with similar untreated material is not substantially altered, and have a high degree of water-repellence which does not rapidly disappear upon cleansing by laundering or otherwise of the materials produced/ In the claims where the expression "textile material is employed, it isintended to cover wool or cellulose-containing materials including fibers, films, yarns, fabrics or other forms of cotton, jute, linen, hemp or rayon, including viscose, cuprammonium, or other precipitated cellulose, or derivatives of cellulose such as acetyl cellulose.

While the invention has been described in detail according to the preferred manner of carrying out the process, it will be obvious to those skilled in the art after understanding the invention, that changes and modifications may be made therein without departing from the spirit or scope of the invention; and it is intended in the appended claims to cover all such changes and modifications.

is claimed as new and desired to be secure-L3 by Letters Patent is:

A process for the ennoblement of textile material which comprises treating the textile material with a dialdehyde combined through one aldehyde group with a substance selected from the group consisting of: an aliphatic acid amide, an aliphatic amine, an aliphatic alcohol, a wool fat alcohol, a naphthenic acid amide, said substance having at least 10 carbon atoms in a straight chain or ring, and heating the so-treated textile material to increase the water-repellence thereof.

2. A process for the ennoblement of textile material which comprises treating the textile material with a dialdehyde combined through one aldehyde group with an aliphatic acid, amide, said aliphatic acid amide having at least 10 carbon atoms in a straight chain and heating the so treated textile material to increase the waterrepellence of said textile material.

3. A process for the ennobling of textile material which comprises impregnating the textile material with lactic acid and the reaction product of stearic acid amide and monomeric glyoxal,

. H I 0.1mm ONH.O cmc o and heating the material to a temperature above C. to produce water-repellence therein.

4. A process for the ennobling of textile material which comprises impregnating the textile material with lactic acid and the reaction product of stearic acid amide and polygiyoxal, said amide being combined with said polyglyoxal through one aldehyde group of the latter, and heating the material to a temperature above 100 C. to produce water-repellence therein.

5. A process for the ennobling of textile material which comprises impregnating the textile material with glycolic acid and the reaction product of stearic acid amide and terephthalic aldenyde H CI7H:5.CONH.0.CH2.CsHi.C

and heating the material to a temperature above 100 C. to produce water-repellence therein.

6. Textile material containing the products obtainable by heating said textile material in contact with a dialdehyde combined through one aldehyde group with a substance selected from the group consisting of an aliphatic acid amide, an aliphatic amine, an aliphatic alcohol, woolfat alcohol, a naphthenic acid amide, said substance having at least 10 carbon atoms in a straight chain or ring, said textile material being water-repellent.

7. Textile material containing the products obtainable by heating said textile material in contact with a dialdehyde combined through one aldehyde group with an aliphatic acid amide, said aliphatic acid amide havin at least 10 carbon atoms in a straight chain, said textile material being water-repellent.

HANS BECK.