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US2277174A - Process for producing water-repellent textile materials and product therefrom - Google Patents

Process for producing water-repellent textile materials and product therefrom Download PDF

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US2277174A
US2277174A US142623A US14262337A US2277174A US 2277174 A US2277174 A US 2277174A US 142623 A US142623 A US 142623A US 14262337 A US14262337 A US 14262337A US 2277174 A US2277174 A US 2277174A
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water
textile
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repellent
textile materials
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Waltmann Ernst
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Heberlein Patent Corp
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Heberlein Patent Corp
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    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322Treating 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

  • This invention relates to processes for producing water-repellent textile materials and products therefrom.
  • the principal object of the present invention is to increase water-repellence in textile material by a simple process; and to produce products having improved characteristics thereby.
  • the invention accordingly comprises the novel products as well as the novel processes and steps of processes according to which such products aremanufactured, the specific embodiments of which are described hereinafter by way of example and in accordance with which I now prefer to practice the invention.
  • water-repellence is accomplished by the impregnation of textile with water-soluble quaternary ammonium compounds of methyl halogen ethers of higher fatty alcohols having the general formula Room NX.halogen in which R is an aliphatic radical containing at least carbonatoms, and NX stands for a tertiary amine, with subsequent heating.
  • tertiary amines used for the formation of the quaternary ammonium salts those tertiary amines are used which are sufficiently volatile, in order that they may volatilize off during the subsequent treatment.
  • the heterocyclic bases which contain a tertiary nitrogen atom in the ring such as pyridine, quinoline and isoquinoline or homologues or substitution products thereof.
  • aliphatic tertiary amines such as trimethylamine (CH2) 3N or triethylamine (C2H5) 3N.
  • NX.halogcn The quaternary ammonium salts of these ethers are prepared as follows:
  • the halogen ethers are first prepared.
  • methyl chloride ether of octadecane is prepared as follows: Dry hydrochloric acid gas is introduced at ordinary temperarature into a mixture containing 2'70 parts of octadecylalcohol, 810 parts of benzol, and 30 parts of trioxymethylene, until the formation of the octadecylchlormethylether occurs which can be clearly recognized by the benzol solution becoming clear.
  • the water from the reaction which accumulates at the bottom of the vessel is run off, the benzol and the surplus hydrochloric acid are removed in a vacuum.
  • the reaction which occurs may be represented by: CH3. (CH2) 16.CH2OH+CH2O+HC1 CH3.(CH2) 1e.CH2.O.CH2.Cl+H2O r
  • the quaternary ammonium salt of the ether for example with pyridine, is formed in the following manner: 319 parts of the octadecylchlormethylether are stirred with parts ofv pyridine. The mixture solidifies immediately and the quaternary pyridinium salt of octadecylchlormethylether results:
  • textiles particularly natural or regenerated cellulose
  • these quaternary ammonium salts of the halogen ethers can be rendered water-repellent by treatment with these quaternary ammonium salts of the halogen ethers.
  • the materials herein described are all soluble in water and the treatment may be accordingly carried out in this medium, thereby avoiding the use of expensive organic solvents and recovery apparatus therefor.
  • the pyridine and other tertiary amines liberated by the reaction of the chemicals on the textile materials treated by the above examples is volatilized when the textile is heated at the temperatures therein mentioned.
  • the process is also applicable to textiles of animal origin such as wool and silk, etc. as shown for instance in the examples below.
  • the impregnation of the textile material by the products set forth can be effected in any desired inanner, by immersion of the material to be treated or by spraying it or other like procedure.
  • the impregnation is preferably accomplished at a temperature slightly above that of room temperature, and thereafter upon drying the material is usually heated at a temperature above the drying temperature and in the neighbor hood of 100 C. to affect water-repellence.
  • Ihe spun rayon remains for about 15 minutes in this bath, is then removed, centrifuged and dried at 90 C. After the drying has taken place the spun rayon is preferably heated for several hours at 90 C.
  • the spun rayon which has been treated in this way shows a water-repellence which resists washing with soap and Water and also resists dry-cleaning by benzine. In the presence of soap or other wetting agents the water-repellent material so produced may be dyed hot; after thorough rinsing of the wetting agent or soap the water-repellent effect reappears.
  • a dyed dress material having a warp of cotton and a filling of viscose silk is treated in an aqueous solution of grams per liter of docosoxymethyl pyridinium chloride at a temperature of about C. It is then removed, squeezed and dried at about C. After the drying it is preferably heated for several hours at about 100 C. in a drying chamber.
  • the treated material shows water-repellence which is resistant to dry-cleaning as by benzine and washing with soap.
  • a dyed cloak material made of spun cuprammonium rayon is treated in an aqueous solution of 15 grams per liter of trimethyl octadecoxymethyl ammonium chloride Ngcl at a temperature of about 45 C. It is then removed, squeezed and dried at about C. and after drying is preferably exposed for several hours at a temperature of about C.
  • the resulting material has substantially the same properties as described for materials in Examples 1 and 2.
  • a wool muslin is treated in an aqueous solution of 15 grams per liter of hexadecoxymethyl pyridinium bromide at a temperature of about 45 C. It is then removed, squeezed and dried at about 90 C. and
  • the resulting material has substantially the same properties as described for materials in Examples 1 and 2.
  • a velvet weave consisting of a real silk warp and weft and a viscose pile is passed through a bath which contains per liter 20 grams of docosoxymethyl pyridinium chloride at a temperature of about 45 C. It is then squeezed and dried at about 80 C. After the drying it is preferably heated for several hours at about 100 C. in a drying chamber.
  • the velvet material shows water-repellence which is resistant to dry-cleaning as by benzene and washing with soap.
  • a velvet weave consisting of real silk in the warp and weft and having a viscose pile is passed through a bath which consists per liter 2Q grams of octadecoxymethyl pyridine bromide at a temperature of about 45 C. It is then squeezed and dried at about 80 C. After the drying it is preferably heated for several hours at about 100 C. in a drying chamber.
  • the velvet material shows water-repellence which is resistant to dry-cleaning as by benzine and washing with soap.
  • halogen as used in the appended claims is intended to designate one of the three elements-chlorine. bromine, iodine.
  • the process of the invention 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 the have a high degree of water-repellence which does not rapidly disappear upon cleansing by laundering or otherwise of the materials produced.
  • cellulose-containing material as herein employed 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.
  • fibers of animal origin may m employed in various similar forms.
  • a process for treating textiles which comprises subjecting a textile material of animal origin to a water-soluble quaternary ammonium compound of methyl halogen ether of a higher fatty alcohol having the general formula R.O.CH
  • NX.halogen in which R is an aliphatic radical containing at least 10 carbon atoms, and NX stands for a teriary amine, and heating the so treated textile material to increase the water-repellence thereof.
  • a process for treating textiles which comprises subjecting a textile material of animal origin to a water-soluble pyridinlum methyl chloride ether of a higher fatty alcohol containing an aliphatic radical of at least 10 carbon atoms, and heating the sotreated textile material to increase the water-repellence thereof.
  • a process for treating textiles which comprises subjecting a textile material to a watersoluble pyridinium methyl chloride thioether of -'a.higher fatty thioalcohol containing an aliphatic radical of at leastlO carbon atoms, and heating the so treated textile material to increase the water-repelience thereof.
  • a process for treatment of cellulose-containing material which comprises subjecting the cellulose-containing material to a water solution of the quaternary pvridinium salt of octadecyl methyl chloride thioether, drying the treated cellulose-containingmaterial and heating it to about c. to produce a water-repellence in said cellulose-containing material.
  • R--SCHz-NX-halogen in which R stands for an aliphatic radicalcontaming at least twelve carbon atoms and NK for ylene quaternary ammonium compound having the formula R-CHaNX-halogen in which R stands for an aliphatic radical containing at least twelve carbon atoms and NK for a tertiary amine, and then heating the impregnated material in the absence of moisture at a temperature suflicient to decompose the quaternary ammonium compound with the liberation of the tree amine.
  • a process for rendering textile material of animal origin water-repellent which comprises impregnating the material with a quaternary ammonium compound having the formula RS-CH2NX-halogen in which R stands for an aliphatic radical containing at least twelve carbon atoms and NX tor a tertiary amine, and then heating the material in the absence of moisture at a temperature sufficlent to decompose the quaternary ammonium compound with th liberation of the free amine.
  • a process for treatment of textiles which comprises subjecting a textile material of animal origin to octadecoxymethyl pyridinium halide and then heating the treated material in the absence oi! moisture at a temperature sufllcient to decompose the compound with the liberation of the free amine.
  • a process for treatment of textile material of animal origin which comprises impregnating the material with a water solution of hexadecoxymethyl pyridinium halide and heating the dried material to a temperature of the order of C. to produce water-repellence therein.
  • a process for treatment oi. textile material of animal origin which comprises impregnating the material with a water solution of octadecoxymethyl pyridinium halide and heating the dried material to a temperature of the order of 100 C; to produce water-repellence therein.
  • a textile material or animal origin having water-repellent properties and being the product of a process as defined in claim 15.-

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

Description

Patented Mar. 24, 1942- 2,277,174 FFICE I PROCESS FOR PRODUCING WATER-REPEL- LENT TEXTILE MATERIALS AND PROD- UCT THEREFRQM Ernst Waltmann, Krefeld, Germany, assignor to Heberlein Patent Corporation, New York, N. Y., a corporation of New York No Drawing.
Application May 14, 1937, Serial No. 142,623. In .Germany May 19, 1936 .17 Claims.
This invention relates to processes for producing water-repellent textile materials and products therefrom.
The principal object of the present invention is to increase water-repellence in textile material by a simple process; and to produce products having improved characteristics thereby.
The invention accordingly comprises the novel products as well as the novel processes and steps of processes according to which such products aremanufactured, the specific embodiments of which are described hereinafter by way of example and in accordance with which I now prefer to practice the invention.
According to the present invention water-repellence is accomplished by the impregnation of textile with water-soluble quaternary ammonium compounds of methyl halogen ethers of higher fatty alcohols having the general formula Room NX.halogen in which R is an aliphatic radical containing at least carbonatoms, and NX stands for a tertiary amine, with subsequent heating.
As tertiary amines used for the formation of the quaternary ammonium salts those tertiary amines are used which are sufficiently volatile, in order that they may volatilize off during the subsequent treatment. There may be advantageous- 1y employed the heterocyclic bases which contain a tertiary nitrogen atom in the ring such as pyridine, quinoline and isoquinoline or homologues or substitution products thereof. There may also be employed aliphatic tertiary amines such as trimethylamine (CH2) 3N or triethylamine (C2H5) 3N.
There may also be employed the quaternary ammonium salts of methyl-halogen-thioethers of higher fatty thioalcohols having the general formula:
R.S.CH2
NX.halogcn The quaternary ammonium salts of these ethers are prepared as follows: The halogen ethers are first prepared. For example methyl chloride ether of octadecane is prepared as follows: Dry hydrochloric acid gas is introduced at ordinary temperarature into a mixture containing 2'70 parts of octadecylalcohol, 810 parts of benzol, and 30 parts of trioxymethylene, until the formation of the octadecylchlormethylether occurs which can be clearly recognized by the benzol solution becoming clear. The water from the reaction which accumulates at the bottom of the vessel is run off, the benzol and the surplus hydrochloric acid are removed in a vacuum. The reaction which occurs may be represented by: CH3. (CH2) 16.CH2OH+CH2O+HC1 CH3.(CH2) 1e.CH2.O.CH2.Cl+H2O r The quaternary ammonium salt of the ether, for example with pyridine, is formed in the following manner: 319 parts of the octadecylchlormethylether are stirred with parts ofv pyridine. The mixture solidifies immediately and the quaternary pyridinium salt of octadecylchlormethylether results:
CHa.(CH2)m-CH2.0.CH2
CH3. (CH2) w.CH .O.CH2+HO.cellulose Quaternary pyridiuium salt of octadecylmethyl chloride ether C Ha. (CH2) m. CH2. 0 C Hz .cellu1ose+ +H 01 Quaternary pyridinium salt of hexadecylmethylchloride thiocthcr omrcnmomsom N 0.ccl1ulose+/ +H01 The pyridine formed in the above reaction is volatilized as above stated during the heating to which the textile materials are subjected after reaction, as given for instance in the examples below.
It has been found that textiles, particularly natural or regenerated cellulose, can be rendered water-repellent by treatment with these quaternary ammonium salts of the halogen ethers. The materials herein described are all soluble in water and the treatment may be accordingly carried out in this medium, thereby avoiding the use of expensive organic solvents and recovery apparatus therefor.
The pyridine and other tertiary amines liberated by the reaction of the chemicals on the textile materials treated by the above examples is volatilized when the textile is heated at the temperatures therein mentioned.
Where the context permits the expression ethers as used in the appended claims designates either an ordinary ether or thioether.
The process is also applicable to textiles of animal origin such as wool and silk, etc. as shown for instance in the examples below.
The impregnation of the textile material by the products set forth can be effected in any desired inanner, by immersion of the material to be treated or by spraying it or other like procedure. The impregnation is preferably accomplished at a temperature slightly above that of room temperature, and thereafter upon drying the material is usually heated at a temperature above the drying temperature and in the neighbor hood of 100 C. to affect water-repellence.
The following are examples of the invention as I now prefer to practice it. It is to be understood that these examples are illustrative and that the invention is not limited thereto except as indicated in the appended claims:
Examples 1. Undyed, unbrightened, loose spun viscose rayon is introduced into an aqueous bath heated to about 40 C. containing per liter grams of octadecoxymethyl pyridinium chloride.
C1sHs1. 0. CH2
Ihe spun rayon remains for about 15 minutes in this bath, is then removed, centrifuged and dried at 90 C. After the drying has taken place the spun rayon is preferably heated for several hours at 90 C. The spun rayon which has been treated in this way shows a water-repellence which resists washing with soap and Water and also resists dry-cleaning by benzine. In the presence of soap or other wetting agents the water-repellent material so produced may be dyed hot; after thorough rinsing of the wetting agent or soap the water-repellent effect reappears.
2. A dyed dress material having a warp of cotton and a filling of viscose silk is treated in an aqueous solution of grams per liter of docosoxymethyl pyridinium chloride at a temperature of about C. It is then removed, squeezed and dried at about C. After the drying it is preferably heated for several hours at about 100 C. in a drying chamber. The treated material shows water-repellence which is resistant to dry-cleaning as by benzine and washing with soap.
3. A dyed cloak material made of spun cuprammonium rayon is treated in an aqueous solution of 15 grams per liter of trimethyl octadecoxymethyl ammonium chloride Ngcl at a temperature of about 45 C. It is then removed, squeezed and dried at about C. and after drying is preferably exposed for several hours at a temperature of about C. The resulting material has substantially the same properties as described for materials in Examples 1 and 2.
5. A wool muslin is treated in an aqueous solution of 15 grams per liter of hexadecoxymethyl pyridinium bromide at a temperature of about 45 C. It is then removed, squeezed and dried at about 90 C. and
after drying is preferably exposed for several hours at a temperature of about 100 C. The resulting material has substantially the same properties as described for materials in Examples 1 and 2.
6. A velvet weave consisting of a real silk warp and weft and a viscose pile is passed through a bath which contains per liter 20 grams of docosoxymethyl pyridinium chloride at a temperature of about 45 C. It is then squeezed and dried at about 80 C. After the drying it is preferably heated for several hours at about 100 C. in a drying chamber. The velvet material shows water-repellence which is resistant to dry-cleaning as by benzene and washing with soap.
7. A velvet weave consisting of real silk in the warp and weft and having a viscose pile is passed through a bath which consists per liter 2Q grams of octadecoxymethyl pyridine bromide at a temperature of about 45 C. It is then squeezed and dried at about 80 C. After the drying it is preferably heated for several hours at about 100 C. in a drying chamber. The velvet material shows water-repellence which is resistant to dry-cleaning as by benzine and washing with soap.
The term halogen" as used in the appended claims is intended to designate one of the three elements-chlorine. bromine, iodine.
The process of the invention, particularly as set forth in the specific embodiments, 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 the have a high degree of water-repellence which does not rapidly disappear upon cleansing by laundering or otherwise of the materials produced.
The term "textiles" as herein employed is intended to include wool, silk and' other animal fiber, as well as cellulose-containing material. The expression cellulose-containing material" as herein employed 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
fibers of animal origin may m employed in various similar forms.
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 treating textiles which comprises subjecting a textile material of animal origin to a water-soluble quaternary ammonium compound of methyl halogen ether of a higher fatty alcohol having the general formula R.O.CH|
NX.halogen in which R is an aliphatic radical containing at least 10 carbon atoms, and NX stands for a teriary amine, and heating the so treated textile material to increase the water-repellence thereof.
3. A process for treating textiles which comprises subjecting a textile material of animal origin to a water-soluble pyridinlum methyl chloride ether of a higher fatty alcohol containing an aliphatic radical of at least 10 carbon atoms, and heating the sotreated textile material to increase the water-repellence thereof.
4. A process for treating textiles which comprises subjecting a textile material to a watersoluble pyridinium methyl chloride thioether of -'a.higher fatty thioalcohol containing an aliphatic radical of at leastlO carbon atoms, and heating the so treated textile material to increase the water-repelience thereof.
5. A process for treatment of cellulose-containing material which comprises subjecting the cellulose-containing material to a water solution of the quaternary pvridinium salt of octadecyl methyl chloride thioether, drying the treated cellulose-containingmaterial and heating it to about c. to produce a water-repellence in said cellulose-containing material.
6. A textile material of animal origin treated with a water-soluble ammonium compound of the methyl halogen ether of a higher fatty alcohol having the general formula NXhalogen in which R is an aliphatic radical containing at least 10 carbon atoms, and NX stands for a tertiary amine, said material having a water-repellent property but its appearance and feel being substantially the same as similar material untreated, said property also being capable of withstanding ordinary house laundering and dry cleaning being the product of a process as defined inclaim 1.
'7. A textile material treated with a water-soluble ammonium compound of methyl halogen thioether of a higher fatty thioalcohol having the general formula in which R is an aliphatic radical containing at least 10 carbon atoms, and NX stands for a tertiary amine, said material having a water-repellent property but its appearance and feel being substantially the same as similar material untreated, said property also being capable of withstanding ordinary house laundering and dry cleaning being the product of a process as defined in claim 2.
8. A cellulose-containing material treated with a water-soluble pyridinium methyl chloride thioether of a higher fatty thioalcohol containing an aliphatic radical of at least 10 carbon atoms, having a water-repellent property but its appearance and feel being substantially the same as similar material untreated, said property also being capable of withstanding ordinary house laundering and dry cleaning. being the product R--SCHz-NX-halogen in which R stands for an aliphatic radicalcontaming at least twelve carbon atoms and NK for ylene quaternary ammonium compound having the formula R-CHaNX-halogen in which R stands for an aliphatic radical containing at least twelve carbon atoms and NK for a tertiary amine, and then heating the impregnated material in the absence of moisture at a temperature suflicient to decompose the quaternary ammonium compound with the liberation of the tree amine.
11. A process for rendering textile material of animal origin water-repellent which comprises impregnating the material with a quaternary ammonium compound having the formula RS-CH2NX-halogen in which R stands for an aliphatic radical containing at least twelve carbon atoms and NX tor a tertiary amine, and then heating the material in the absence of moisture at a temperature sufficlent to decompose the quaternary ammonium compound with th liberation of the free amine.
12. A process for treatment of textiles which comprises subjecting a textile material of animal origin to octadecoxymethyl pyridinium halide and then heating the treated material in the absence oi! moisture at a temperature sufllcient to decompose the compound with the liberation of the free amine.
13. A cellulose-containing material treated with a quaternary pyridinium salt of octadecyl methyl chloride thioether, having a water-repellent property capable of withstanding ordinary house laundering and dry cleaning but having an appearance and feel substantially the same as similar material untreated, being the product of a process as defined in claim 5.
14. A process for treatment of textile material of animal origin which comprises impregnating the material with a water solution of hexadecoxymethyl pyridinium halide and heating the dried material to a temperature of the order of C. to produce water-repellence therein.
15. A process for treatment oi. textile material of animal origin which comprises impregnating the material with a water solution of octadecoxymethyl pyridinium halide and heating the dried material to a temperature of the order of 100 C; to produce water-repellence therein.
16. A textile material of animal origin having water-repellent properties and being the product of a process as defined in claim 14.
17. A textile material or animal origin having water-repellent properties and being the product of a process as defined in claim 15.-
ERNST WAL'IMANN.
CERTIFICATE OF CORRECTION. Patent No. 2,277,17h. March 21 194.2.
' ERNST WALTMANN.
It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction asfollows! Page 1, first column, line 16-1'7, for the word "textile" read'-textiles--; and second column, line 51, for "appears" read "appear"; page 2, first column, lines .114. to 21 inclusive, strike out the following paragraphs and insert the same after 'soap." on page" 5, first column, line 16 The pyridine and other tertiary amines liberated by the reaction of the chemicals. on the textile materials treated by the aboue. examples is volatilized when the textile is heated at the temperatures therein mention ed.
wh h context permits the-expression "ethers" as used in the appended-claims designates eitheranordinary ether or thioether.- I
page 2, second column, line 21, for "popelin" read poplinline 25, before "quaternary insert -,the-; page}, first column, line 2, for'"con sists" read --contains; 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 2nd day of June, A. D. 19h2.
Henry Van Arsdale, (Seal) Acting Commissioner of Patents.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2637623A (en) * 1948-09-02 1953-05-05 Deering Milliken Res Trust Textile treating compounds and method of applying them to textiles
US3406032A (en) * 1964-07-22 1968-10-15 Pfersee Chem Fab Emulsion for hydrophobing textiles
US3437518A (en) * 1963-12-27 1969-04-08 Ugine Kuhlmann Process for flameproofing and waterproofing textile materials

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2637623A (en) * 1948-09-02 1953-05-05 Deering Milliken Res Trust Textile treating compounds and method of applying them to textiles
US3437518A (en) * 1963-12-27 1969-04-08 Ugine Kuhlmann Process for flameproofing and waterproofing textile materials
US3406032A (en) * 1964-07-22 1968-10-15 Pfersee Chem Fab Emulsion for hydrophobing textiles

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