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Publication numberUS2171791 A
Publication typeGrant
Publication dateSep 5, 1939
Filing dateMay 13, 1936
Priority dateMay 16, 1935
Publication numberUS 2171791 A, US 2171791A, US-A-2171791, US2171791 A, US2171791A
InventorsErnst Waltmann, Walther Kaase
Original AssigneeHeberlein Patent Corp
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Process for rendering textiles water repellent
US 2171791 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

Patented Sept. 5,1939

PROCESS FOR RENDERING TEXTILES WATER REPELLENT Walther Kaase and Ernst Waltmann, Kr'efelrl,

Germany, assignors to Heberlein Patent Corporation, New York, N. Y., a. corporation of I New York No Drawing. Application May 13, 1936, Serial No. 79,496. In Germany May lfl, 1935 12 Claims. (01. a' 11s)' This invention relates to increasing water-repellence in textile materials.

For rendering certain textiles water-repellent there have been suggested processes which are based mainly on the surface treatment of the said materials with fatty-acid chlorides and fattyacid anhydrides. In the carrying out of these prior processes however difficulties have been encountered and the appearance and feel of the goods have been changed. These processes also required considerable time for their operation, requiring-several hours to produce the results obtained.

The principal object of the present invention is to provide a simple process to increase water-resistance in various textile materials including cotton, jute, linen, hemp and various artificial silks and wool in a considerably shorter length of time with correspondingly less expense than that of 0 the chlorides and anhydrides mentioned; and to produce materials having improved characteristics thereby.

The invention accordingly comprises the novel processes and steps of processes, specific embodimentsof which are described hereinafter by way of example and in accordance with which we now prefer to practice the invention. In our copending application Ser. No. 66,498, filed February 29, 1936, we have described and claimed the use of asymmetric fatty-acid anhydrides containing a long acyl radical of at least 10 carbon atoms and a considerably shorter acyl radical. In that copending application 'we have pointed out the use of asymmetric fattyacid anhydrides as applicable to various textile materials and have mentioned specifically cellulose-containing materials for treatment. We have now found that Wool may also be subjected to the process 4 described in said copending application, the materials employed and the conditions of treatment being otherwise substantiallythe same as mentioned in said application.

In the present application we describe and claim 45 the use for producing water-repeilence in textiles, particularly cellulose-containing and wool ma-- terials of unsymmetrical fatty-acid anhydrides of the general formula In the formula R1 represents a fatty-acid radical containing at least 10 carbon atoms in a straight 55 or derived chain or a naphthenic acid radical coritaining at least 10 carbon atoms regardless of substitutions in such chain or ring. R2 represents a radical containing at least 1 carbon atom and that part of the anhydride represented by the formula R2.O.C2O is volatile when heated in g the presence of the textile material preferably at temperatures of over about 100 C. The number of carbon atoms in R2 may be increased so long as the material is not prevented from volatilizing in the presence of the textile at temperatures below the point where the textile material would be injured. We also claim herein broadly the treatment of wool with the materials described in said copending application Ser. No. 66,498.

Substances falling under the above formula with their structural formulae are as follows: Unsymmetrical stearic-acid carbonic-acid ethylester anhydride having the structural formula i1 u.C:O

o CgHu.0.C20; Unsymmetrical palmitic-acid carbonic-acid butylester anhydride having the structural formula 0 0 15.000; Unsymmetrical adlpic-acid cetyl-alcohol-ester carbonic-acid ethyl-ester anhydride having the structural formula C uHu.O.CO(CHI)LCO o C:H|.O.CZO; Unsymmetrical stearic-acid carbonic-acid methyl-ester anhydride having the structural formula Ci'IHu.C:O 4

OHa.O.C:O;

Unsymmetrical behenic-acid-carbonlc-acid methyl-ester anhydride having the structural formula CIIHILCO on=.o.o=o

These compounds may be prepared according to known methods for conversion of fatty-acids of the kind mentioned above with chloro-carbonicacid alkyl-esters, as described by E. .Fischer (Berichte 46, 2659) and German Patent 117,267. The straight carbon chain of R1 may be interrupted by atoms or atomic groups 0, S, N,

S02.NR, in which R may be equal to hydrogen or any desired hydrogen or. any desired hydrocar- C a.O.C: 0

Heptadecylamino acetic acid carbonic acid methyl-ester anhydride;

one NH. .00

CH:O.CO

Dodecylaminobenzoic-acid carbonicracid methylester anhydride.

The impregnation of the textile material with the anhydrides described may be performed in any desired manner, with or without the employment of organic solvents by means of soaking, spraying or the like. The products claimed may also be converted into an aqueous solution by means of suitable emulsifiers and as prepared inaqueous solution, may be employed for impregnation of the textiles.

The materials generally and specifically mentioned above as employed in the carrying out of our invention may be used for the impregnation of various textile materials including cellulosecontaining materials such as cotton, jute, linen, hemp or rayon, including viscose, cuprammonium or other precipitated cellulose or derivatives of cellulose such as .acetyl cellulose and also wool. The materials may be treated in the form of fibers, yarns, fabric or other manufactured products.

In the case of acetyl cellulose the materials herein mentioned may be added to the spinning solution itself, thus combining the process of rendering water-repellent with the spinning process.

In carrying out the invention, catalysts such as pyridine may be employed, although they are not'absolutely necessary.

The following are examples of embodiments of the invention as we now prefer to practice it. The invention is not to be restricted thereto except as indicated in the appended claims.

Examples .1. A linen fabric dyed with indanthrene is passed through an 0.5% solution of unsymmetrical stearic-acid carbonic-acid ethyl-ester anhydride in benzine at room temperature and after evaporation of the benzine is subjected for 60 minutes to a temperature of 110 C.

2. A viscose satin having .a warp of viscose and a filler of viscose crepe is passed through a 1% solution of unsymmetrical palmitic-acid carbonic-acid butyl-ester anhydride in benzine at room temperature, and after evaporation of benzine is immediately subjected for 5 minutes to a temperature of 140 C.

3. A printed matt crepe having a warp of spinning-matt acetate silk and a filler of viscose crepe is passed through a 1% solution of unsym- 00.0, o.co, NR, NR.CO, com so=, NRSOz,

metrical adipic-acid cetyl alcohol-ester carbonicacid ethyl-ester anhydride in benzine at room temperature, and after evaporation of benzine is immediately subjected for 2 minutes to a temperature of 140 C.

4. Wool muslin is sprayed with a 2% solution of stearic-acid carbonic-acid methyl-ester anhydride in benzine, the solvent evaporated and the fabric subjected for 60 minutes to a temperature of C.

5. A wool muslin is passed through a 1% solution of asymmetric-stearic-acid-acetic acid anhydride in benzine at room temperature, said anhydride having the structural formula cn ssCg /O CHBC O which is a substance having 2 acyl radicals, one acyl radical of more than 10 carbon atoms and the other of not more than 4 carbon atoms; the muslin is then suction filtered and thereupon exposed for 5 minutes to a temperature of C. This is followed by a treatment at 150 C. for 5 minutes.

6. A wool muslin is sprayed with a 1% solution of adipic-acid-stearic-alcohol ester-acetic acid anhydride having the structural formula CmHnOIJ 0 (CHz)4. C 0

/O CHa.OO

in benzine, and thereupon treated for 4 minutes at 100 C. This is followed by treatment at 100 C. for 5 minutes.

7. A velvet from mercerized cotton is passed through a 1% solution of unsymmetrical octocosan-acid-carbonic-acid-ethyl-ester anhydride in benzine at room temperature, and after evaporation of benzine is immediately subjected for 2 minutes to a temperature of 140 C.

8. A clothing material -consisting of acetate silk as warp and viscose crepe as weft is sprayed with a 0.5% solution of behenic-acid-carbonicacid methyl-ester anhydride in benzine, the solvent evaporated and the fabric subjected for 60 minutes to a temperature of C.

9. A cotton tent-cloth is passed through a 1% solution of naphthenic acid carbonic acid methyl-ester anhydride in benzine, the solvent evaporated and the fabric subjected for 60 minutes to a temperature of 100 C.

10. T0 1000 liters of a 20% solution of acetyl cellulose in acetone 1000 grams of stearic-acidcarbonic-acid methyl-ester anhydride are added and this mixture spun as usual in order to produce water-repellence in the spun filaments.

' The process of the invention particularly as set forth in the specific embodiments above can 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 dry-cleaning.

In the claims where the expression "cellulosecontaining material is employed it is intended to cover fibers, 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.

The expression "textile material as used in the claims is intended to cover such cellulosecontaining material, as well as wool.

The expression "fatty-acid radical" as employed in the claims is intended to cover not only a straight carbon chain but also naphthenic acid ring structures, each of which may be substituted or unsubstituted by aliphatic or aromatic groups.

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.

What is claimed as new and desired to be secured by Letters Patent is:

1. A process for the ennobling of textile material which comprises heating the textile material with an unsymmetric fatty-acid carbonicacid ester anhydride, the fatty acid radical having at least ten carbon atoms and the carbonic acid ester having at least two carbon atoms to volatilize the carbonic acid radical having the lower number of carbon atoms, and to increase the water-repellence of said textile material.

2. A process for the ennobling of textile material which comprises treating the textile material with an unsymmetric fatty-acid carbonic-- acid ester anhydride, the fatty. acid radical having at least 10 carbon atoms and the carbonicacid ester radical having at least 2 carbon atoms, removable by heating without injury to said textile material, and heating the textile material to a temperature above about C. for several minutes to remove said last named radical to increase the water-repellence and to decrease tendency to spotting of said material.

3. A process accordingto claim 3 in which the anhydride is combined with the textile material in solution and is thereafter heated for several minutes at a temperature above about 100 C. to cause partial esterification of the material to produce a water-repellent property in said material.

4. A process for the ennobling of cellulosecontaining material which comprises heating the cellulose-containing material with an anhydride to a temperature of the order of 90-160 C. for a suflicient time to cause a reaction therebetween, said anhydride being an unsymmetric fatty-acid carbonic-acid ester anhydride, the fatty-acid radical having at least 10 carbon atoms therein and the ester radical having at least two carbon atoms therein, said heating causing removal re 7. A process for ennobling cellulose-containhydride, and thereafter subjecting the treated wool to a temperature of about loo- C.

9. A process for the ennobling of textile matterial which comprises heating the textile material with an unsymmetrlc fatty-acid carbonicacid alkyl-ester anhydride of the general formula in which R1 represents a radical containing an aliphatic group of at least ten carbon atoms and R2 a radical having an aliphatic member of at least one carbon atom, said heating being conducted at atemperature to split of! the radical containing the lower member of carbon atoms and to cause the remainder of the anhydride to react with the textile material to increase the water-repellence thereof.

10. A process for the ennobling of wool which comprises heating the wool with an asymmetric fatty-acid anhydride containing a long acyl radical of at least ten carbon atoms and a considerably shorter acyl radical, said heating being conducted at a temperature to cause the shorter acyl radical to volatilize and the remainder of the anhydride to react with the wool to increase the water-repellence and decrease tendency of spotting of said wool.

11. A process for the ennobling of wool which comprises treating wool with an asymmetric fatty-acid 'anhydride having on acyl radical ,of at least 10 carbon atoms and the other acyl radical having not more than 4 carbon atoms and heating;. the wool so treated to volatilize the acyl radical" having the-lower number of carbon atoms, to increase thewater-repellence and to decrease tendency to spotting of said wool.

12. A process for the ennobling of textile materials which comprises heating the textile material with an unsymmetric fatty-acid carbonicacid alkyl-ester anhydride of the general formula in which formula R1 represents a radical of at least 10 carbon atoms interrupted by atoms or atomic groups 0, S, N, 00.0, O.CO, NR, NR.C0,

S02, NR.SO2, SO2.NR, in which R may be equal to hydrogen or any desired hydrocarbon radical, and R2 a radical having 'at least 1 carbon atom, said heating being conducted to volatilize said radical having the smaller number of carbon .atoms and to cause. the remainder of the anhydride to react with the textile material to increase the water-repellence of said textile material.

WAL'I'HER KAABE. ERNST WALTMANN.

CERTIFICATE OF CORRECTION. Fatent No. 2,171,791. September 5, 19 9.

WALTHER KAASE, ET AL. f It is hereby certified that error appears in the; printed specification of the above numbered patent requiring correction as follows: Page 2, first column, line 5, strike out the words "hydrogen or desired"; and second column, line 55, for "100" second occurrence, 'read 160; page 5, first column, line L Z, claim 5, for the claim reference numeral "5" read 2; and

I second column, line 1 2, claim 11, for "on" read one; and that the said Letters Patent should be read with this correction therein 'that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 5rd day of October, A. D. 1959.

, Henry Van Arsdale, (Seal) Acting Commissionerof Patents.

Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US2499653 *Oct 17, 1946Mar 7, 1950American Cyanamid CoTreatment of protein-containing textile materials and products thereof
US2689863 *Oct 7, 1948Sep 21, 1954Union Carbide & Carbon CorpEster-anhydrides and the production thereof
US2986445 *Jan 6, 1960May 30, 1961Koenig Nathan HTreatment of wool with acid anhydrides in the presence of dimethylformamide
US3097052 *Aug 25, 1961Jul 9, 1963Koenig Nathan HTreatment of wool with acid anhydrides in the presence of acetic acid
US3219684 *Dec 17, 1962Nov 23, 1965Celanese CorpMixed anhydrides
US6485530 *Jun 1, 2000Nov 26, 2002Nano-Tex, LlcModified textile and other materials and methods for their preparation
US6607564 *Jul 17, 2002Aug 19, 2003Nano-Tex, LlcModified textiles and other materials and methods for their preparation
Classifications
U.S. Classification8/194, 8/115.7, 554/63, 8/120, 558/275, 8/127.6, 106/243, 8/128.1, 8/129, 558/276, 8/128.3, 8/196, 562/887
International ClassificationD06M13/224, D06M13/188, D06M13/00
Cooperative ClassificationD06M13/224, D06M13/188
European ClassificationD06M13/188, D06M13/224