US2380133A - Process for rendering textiles water-repellent - Google Patents

Process for rendering textiles water-repellent Download PDF

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US2380133A
US2380133A US183234A US18323438A US2380133A US 2380133 A US2380133 A US 2380133A US 183234 A US183234 A US 183234A US 18323438 A US18323438 A US 18323438A US 2380133 A US2380133 A US 2380133A
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repellent
water
grams
compound
textiles
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US183234A
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Waltmann Ernst
Wolf Edgar
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Heberlein Patent Corp
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Heberlein Patent Corp
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
    • D06M13/248—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing sulfur
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen

Definitions

  • An object of the invention accordingly, is to provide an improved process for producing waterrepellence in textiles employing materials of the type mentioned and to produce an improved series of water-repellent textiles thereby.
  • Another object is to provide a simple process for the manufacture of chemicals for producing such water-repellence and an improved repertoire of such chemicals.
  • the invention accordingly, consists in 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.
  • alpha-methyl halide derivatives mentioned above may be employed either in a nonaqueous solvent or in water solution. In the latter case we prefer to employ quaternary ammonium compounds mentioned above. produced by combining the alpha-methyl halide derivatives with pyridine.
  • the nitrogenous derivatives of higher fatty acids which contain a removable hydrogen atom linked to nitrogen or oxygen.
  • the nitrogenous derivatives of carbon dioxide which contain an aliphatic radical of at least ten carbon atoms. Accordingly for example hydroxamic acids, amidines, urethanes, hydrazides, derivatives of urea or dimethylol-urea which are acylated unilaterally with higher fatty acid chlorides, or which are acylated unilaterally with higher fatty chlorocarbonic acidesters may be employed.
  • the aforesaid compounds are converted preferably by combining the derivatives just mentioned with trioxymethylene or formaldehyde or other polymer with a halogen material such as hydrochloric acid gas, thereby converting into methyl chloride compounds, and the latter are converted by double decomposition with tertiary bases into water soluble quaternary ammonium compounds.
  • a halogen material such as hydrochloric acid gas
  • methyl chloride compounds they are particularly suitable for the etherification of cellulose or cellulose derivative fibrous material.
  • cellulose-derivative fiber material such as cotton, or cellulose-derivative fiber material, such as the various forms of artificial silk, but may be also applied to animal fibers such as wool.
  • aqueous solutions of the aforesaid compounds are employed, there may also be added to such compounds the water-soluble buffer salts of the alkalis or alkaline earths with weak acids. such as sodium acetate and similar compounds.
  • weak acids such as sodium acetate and similar compounds.
  • a fabric for wearing apparel made of spun rayon (viscose) is passed through an aqueous solution which contains 20 grams per liter of a quaternary pyridinium compound of the methyl chloride derivative prepared from carbamic ester of octadecylalcohol CIBHS'IO.CO.NH2 trioxymethylene (CI-I20): and dry hydrogen chloride, as more specifically described hereinafter.
  • the said fabric is passed through the said aqueous solution while the latter is at about 35 C. Thereafter the impregnated material is dried and thereupon subjected to heat treatment in a drying chamber at about 95 C. for 5 hours.
  • Dyed cotton yarn is introduced at 50 C.
  • Cotton calico is passed through an aqueous solution which contains 15 grams per liter of a quaternary pyridinium compound of the methyl chloride derivative prepared from stearic acid hydrazide C1'lHa5.CO.NH.NH2 trioxymethylene (CH-i0): and dry hydrogen chloride; as more specifically described hereinafter.
  • the said 'fabric is passed through the said aqueous solution while the latter is at about 40 C. Thereafter the impregnated material is dried and thereupon subjected to heat treatment in a drying chamber at about 85 C. for 6 hours.
  • a plush fabric consisting of cotton in warp and weft an artificial silk spun fiber in the pile, is passed through an aqueousbath which contains per liter 250 grams of 9, formaldehydeurea condensation product which is on the market under the name Kaurit," 6 grams of primary sodium phosphate. 6 grams of secondary sodium phosphate, 2 grams of tartaric acid, and 15 grams of the quaternary pyridine salt obtained by double decomposition of pyridine with the methyl chloride compound formed from carbamic ester of octadecylalcohol C1aH3'iO.CO.NI-Iz trioxymethylene (CI-I); and dry hydrogen chloride, as more specifically described hereinafter.
  • the said fabric is passed through the said aqueous solution while the latter is about C. Thereafter the impregnated material is squeezed out,
  • the material is subjected to a heat treatment in a drying chamber at about 120 C. for 2 hours, then.
  • methyl chloride compounds without pyridine may be employed in benzene or like solvent to treat textiles in a manner similar to that set forth in Examples 1 to 5.
  • the conversion of the other materials given below for the production of chemicals and the use of such chemicals in the form of their alpha methyl halide compounds is effected in the same manner as given in the above examples.
  • the other substances referred to are as follows:
  • the textiles produced in accordance with the above examples show a high degree of water-repellence.
  • the fibers of the textiles have a superficial etheriilcation. They show improved properties with respect to known textiles treated with fatty acid anhydrides including greater durability towards dry-cleaning with benzene and soap washing.
  • the feel and hang of the material having waterrepellence as produced above is not substantially altered.
  • the artificial silks have -resistance to swelling agents and wetting agents.
  • halogen as used in the appended claims is intended to include halogen elements, such as chlorine or bromine.
  • textile material used herein is intended to cover fibers, yarns, fabrics including velvet; and other pile fabrics, or other forms of cotton, Jute, linen, hemp 0r rayon, including viscose, cuprammonium or other precipitated cellulose or derivatives of cellulose such as acetyl cellulose and animal fiber such as for example wool.
  • a process for rendering textile material water-repellent which comprises heating the material with a compound of the formula R.Y.CH:.I-Ialogen where R is an aliphatic radical containing at least 10 carbon atoms from the group consisting of NH.CO.NH,
  • a process for rendering textile material watext-repellent which comprises impregnating the material with a compound of the formula where R is an aliphatic radical containing at least 10 carbon atoms. and then heating the impregnated material in the absence of moisture until itbecomes water-repellent.
  • a process for rendering textile material water-repellent which comprises impregnating the material with a compound of the formula R.CO.NH.CO.NH.CH:.C1
  • R is an aliphatic radical containing at least 10 carbon atoms, and then heating the impregnated material in the absence of moisture until it becomes water-repellent.
  • a process for rendering textile material water-repellent which comprises impregnating the material with a compound of the formula R.O.CO.NH.CO.NH.CH:.CI
  • R. is an aliphatic radical containing at least 10 carbon atoms, and then heating the impregnated material in the absence of moisture until it becomes water-repellent.
  • Y is a radical selected

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Description

Patented July 10, 1945 UNITED STATES PATENT orrice PROCESS FOR RENDERING TEXTILES WATER-REPELLENT Ernst Waltmann and Edgar Wolf. Krefeld, Germany, assignors to Heberlein Patent Corporation, New York, N. Y., a corporation of New York No Drawing. Application January 3, 1938, Serial No. 183,234. In Germany January 6, 1937 7 Claims. (CI. 8-1162) Serial No. 177,054, filed November 29, 1937, now
Pat. No. 2,294,435, there is described the preparation of compounds from alpha-methyl halide derivatives obtained from higher fatty acid or .naphthenic acid amides or their methylol compounds, or higher alkyl amines with formaldehyde or its polymers and a halogen or hydrogen halide; and the use of these materials for combining with textile materials.
We have found in accordance with the hereindescribed invention that the above-described reaction can be extended to an additional series of s prefer to employ these materials in water-soluble form and this may be effected by employing them as their quaternary ammonium compounds.
An object of the invention, accordingly, is to provide an improved process for producing waterrepellence in textiles employing materials of the type mentioned and to produce an improved series of water-repellent textiles thereby.
Another object is to provide a simple process for the manufacture of chemicals for producing such water-repellence and an improved serie of such chemicals. Other objects will be in part obvious and in part pointed out hereinafter.
The invention. accordingly, consists in 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.
In accordance with our invention we have found that the alpha-methyl halide derivatives mentioned above may be employed either in a nonaqueous solvent or in water solution. In the latter case we prefer to employ quaternary ammonium compounds mentioned above. produced by combining the alpha-methyl halide derivatives with pyridine.
We have found suitable for our purpose in carrying out the treatment of textiles, the nitrogenous derivatives of higher fatty acids which contain a removable hydrogen atom linked to nitrogen or oxygen. Further there can be employed the nitrogenous derivatives of carbon dioxide which contain an aliphatic radical of at least ten carbon atoms. Accordingly for example hydroxamic acids, amidines, urethanes, hydrazides, derivatives of urea or dimethylol-urea which are acylated unilaterally with higher fatty acid chlorides, or which are acylated unilaterally with higher fatty chlorocarbonic acidesters may be employed. The aforesaid compounds are converted preferably by combining the derivatives just mentioned with trioxymethylene or formaldehyde or other polymer with a halogen material such as hydrochloric acid gas, thereby converting into methyl chloride compounds, and the latter are converted by double decomposition with tertiary bases into water soluble quaternary ammonium compounds. As methyl chloride compounds they are particularly suitable for the etherification of cellulose or cellulose derivative fibrous material.
The processis applicable not only to cellulose,
such as cotton, or cellulose-derivative fiber material, such as the various forms of artificial silk, but may be also applied to animal fibers such as wool.
In the treatment of artificial silk there is secured not only a water-repelling effect, but there also is effected a diminution of the capabilit of swelling in the presence of the swelling agents and an increase in resistance to wetting. The effects produced on textiles in accordance with our invention are resistant to dry cleaning and washing with soap. A remarkable feature in all the treatments or impregnations made in accordance with ourinvention is the increase in wet tensile strength of artificial silk and an increase in the fastness of the dyes on all textiles. and particularly the fastness to washing of dyed textiles of various types including cotton, artificial silk and animal fibers. These materials resist shrinking when subjected to mild shrinking as in laundering and also more severe shrinkage by concentrated caustic alkali.
If aqueous solutions of the aforesaid compounds are employed, there may also be added to such compounds the water-soluble buffer salts of the alkalis or alkaline earths with weak acids. such as sodium acetate and similar compounds. By means of these additions, possible damage to the fiber, particularly at high temperatures is avoided. When operating at higher temperatures, the reaction between the textile material and the alphamethyl-halide derivatives is accelerated and may be satisfactorily completed for water-repellent purposes in a shorter time than where lower temperatures are employed.
The following examples are illustrative and the invention is not to be considered as limited thereto except as indicated in the appended claims.
Examples for textile treatment 1. A fabric for wearing apparel made of spun rayon (viscose) is passed through an aqueous solution which contains 20 grams per liter of a quaternary pyridinium compound of the methyl chloride derivative prepared from carbamic ester of octadecylalcohol CIBHS'IO.CO.NH2 trioxymethylene (CI-I20): and dry hydrogen chloride, as more specifically described hereinafter. The said fabric is passed through the said aqueous solution while the latter is at about 35 C. Thereafter the impregnated material is dried and thereupon subjected to heat treatment in a drying chamber at about 95 C. for 5 hours.
2. Dyed cotton yarn is introduced at 50 C.
, into an aqueous solution of grams per liter of the quaternary pyridine compound of the methyl chloride derivative prepared from stea- ,royl urea Ci'7I'L'l5.C0-NH.CO.NH2 trioxymethylene solution while the latter is at about 40 C. Thereafter the impregnated material is dried and thereupon subjected to heat treatment in a drying chamber at about 85 C. for 6 hours.
4. Cotton calico is passed through an aqueous solution which contains 15 grams per liter of a quaternary pyridinium compound of the methyl chloride derivative prepared from stearic acid hydrazide C1'lHa5.CO.NH.NH2 trioxymethylene (CH-i0): and dry hydrogen chloride; as more specifically described hereinafter. The said 'fabric is passed through the said aqueous solution while the latter is at about 40 C. Thereafter the impregnated material is dried and thereupon subjected to heat treatment in a drying chamber at about 85 C. for 6 hours.
5. A plush fabric, consisting of cotton in warp and weft an artificial silk spun fiber in the pile, is passed through an aqueousbath which contains per liter 250 grams of 9, formaldehydeurea condensation product which is on the market under the name Kaurit," 6 grams of primary sodium phosphate. 6 grams of secondary sodium phosphate, 2 grams of tartaric acid, and 15 grams of the quaternary pyridine salt obtained by double decomposition of pyridine with the methyl chloride compound formed from carbamic ester of octadecylalcohol C1aH3'iO.CO.NI-Iz trioxymethylene (CI-I); and dry hydrogen chloride, as more specifically described hereinafter. The said fabric is passed through the said aqueous solution while the latter is about C. Thereafter the impregnated material is squeezed out,
brushed, and dried. The material is subjected to a heat treatment in a drying chamber at about 120 C. for 2 hours, then.
Ez'ramples for chemicals pyridinium salt of the methyl chloride derivative.
of carbamic ester of octadecylalcohol is formed having the formula:
(115E310 C O.NH.CH1.N.C1
7. Into a mixture, at a temperature of about 20 C., of 327 grams of stearoyl urea 1500 grams of benzene, and 60 grams of trioxymethylene, dry hydrochloric acid gas is introduced until the formation of the methyl chloride compound takes place. This compound is treated as stated in Example 6 and is stirred with grams of pyridine at room temperature. The quaternary pyridinium salt of the methyl chloride derivative of'stearoyl urea is formed having the formula:
8. Into a mixture, at a temperature of about 20 C. of 356 grams of allophanic octadecylester C1aHJ'IO.CO.NH.CO.NH2 (Liebigs Annalen der Chemie 244, 41), 2000 grams of benzene, and 60 grams trioxymethylene, dry hydrochloric acid gas is introduced until the formation of the methyl chloride compound takes place. This compound is treated as stated in Example 6 and is stirred with 100 grams of pyridine at room temperature. The quaternary pyridinium salt of the methyl chloride derivative of allophanic octadecylester is formed having the formula:
The above methyl chloride compounds without pyridine may be employed in benzene or like solvent to treat textiles in a manner similar to that set forth in Examples 1 to 5. The conversion of the other materials given below for the production of chemicals and the use of such chemicals in the form of their alpha methyl halide compounds is effected in the same manner as given in the above examples. The other substances referred to are as follows:
stearo-hydroxamic acid C17Ha5.CO.N.HOH
and derivatives of urea, thiourea, or dimethylolurea which contain. an aliphatic radical of at least ten carbon atoms, for example:
N-n-heptadecyl-urea Cl'IH3li.NH.CO-NHI r stearoyl-thiourea Cl'1Has.CO.NH.CS.NH2 or allophanlc ester thiourea, for example curnaoconncsmn The amount of the reaction product deposited when uncombined with a tertiary amine in Examples l to on the textile material will naturally vary with the weight of the material and its reactability. I have found that, ordinarily an amount equal to 0.5-1.5 per cent of the material is sufllclent to give the effect. When combined to form a quaternary ammonium salt, approximately 1-2 per cent, based on the weight of the material will give the desired eifect. The textiles produced in accordance with the above examples show a high degree of water-repellence. The fibers of the textiles have a superficial etheriilcation. They show improved properties with respect to known textiles treated with fatty acid anhydrides including greater durability towards dry-cleaning with benzene and soap washing. The feel and hang of the material having waterrepellence as produced above is not substantially altered. In additio', the artificial silks have -resistance to swelling agents and wetting agents.
simple apparatus at relatively small expense.
The term "halogen" as used in the appended claims is intended to include halogen elements, such as chlorine or bromine.
The expression textile material" used herein is intended to cover fibers, yarns, fabrics including velvet; and other pile fabrics, or other forms of cotton, Jute, linen, hemp 0r rayon, including viscose, cuprammonium or other precipitated cellulose or derivatives of cellulose such as acetyl cellulose and animal fiber such as for example wool.
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 invenquinoline, or an N-alkyl-piperidine ortion. 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 modiiications.
What is claimed as new and desired to be secured by Letters Patent is:
1. A process for rendering textile material water-repellent which comprises heating the material with a compound of the formula R.Y.CH:.I-Ialogen where R is an aliphatic radical containing at least 10 carbon atoms from the group consisting of NH.CO.NH,
CO.NHCONH, CONHNH, CO.NHCSNH.
O.C0.NH, O.CO.NHCONH, O.CONHCSNH, and CO.NHO, to render it water-repellent.
2. A process for rendering textile material watext-repellent which comprises impregnating the material with a compound of the formula where R is an aliphatic radical containing at least 10 carbon atoms. and then heating the impregnated material in the absence of moisture until itbecomes water-repellent.
3. A process for rendering textile material water-repellent which comprises impregnating the material with a compound of the formula R.CO.NH.CO.NH.CH:.C1
where R is an aliphatic radical containing at least 10 carbon atoms, and then heating the impregnated material in the absence of moisture until it becomes water-repellent.
4. A process for rendering textile material water-repellent which comprises impregnating the material with a compound of the formula R.O.CO.NH.CO.NH.CH:.CI
where R. is an aliphatic radical containing at least 10 carbon atoms, and then heating the impregnated material in the absence of moisture until it becomes water-repellent.
5 A process according to claim 2 in which the compound employed for impregnation has the 6. A process according to claim 3 in which the compound employed for impregnation has the formula Ci1Has.CO.NH.CO.NH.CHa-.Cl
CisI'Is'1.O.CO.NH.CO.NH.CH:.C1
ERNST WALTMANN. EDGAR WOLF.
and Y is a radical selected
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2518266A (en) * 1946-08-14 1950-08-08 Ici Ltd Quaternary ammonium textile treatment agents and method of application thereof
US2965436A (en) * 1956-05-17 1960-12-20 Toulmin And Toulmin Process for improving the wet strength of products obtained from cellulosic pulp
US4323602A (en) * 1980-05-14 1982-04-06 Roberts Consolidated Industries, Inc. Water repellent and preservative for wood products

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2518266A (en) * 1946-08-14 1950-08-08 Ici Ltd Quaternary ammonium textile treatment agents and method of application thereof
US2965436A (en) * 1956-05-17 1960-12-20 Toulmin And Toulmin Process for improving the wet strength of products obtained from cellulosic pulp
US4323602A (en) * 1980-05-14 1982-04-06 Roberts Consolidated Industries, Inc. Water repellent and preservative for wood products

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