US2173029A - Process for rendering textiles water-repellent and products therefrom - Google Patents
Process for rendering textiles water-repellent and products therefrom Download PDFInfo
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- US2173029A US2173029A US126521A US12652137A US2173029A US 2173029 A US2173029 A US 2173029A US 126521 A US126521 A US 126521A US 12652137 A US12652137 A US 12652137A US 2173029 A US2173029 A US 2173029A
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- United States
- Prior art keywords
- water
- repellent
- acid
- weight
- isocyanate
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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
- D06M13/322—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
- D06M13/395—Isocyanates
Definitions
- This invention relates to processes for producing water-repellent fibrous materials andproducts therefrom.
- the principal object of the present invention is to provide a simple process to increase waterrepellence in materials such as cotton, jute, linen, hemp and various artificial silks and wool, presenting advantages over the known fatty acid chloride and fatty acid anhydride processes referred to in said copending application.
- 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 byway of example and in accordance with which we now prefer to practice the invention.
- R is intended to designate an alkyl, cycloalkyl or aralkyl radical containing a saturated alkyl radical of at least 10 carbon atoms or signifies the saturated or unsaturated radical of an alcohol of the steroi series.
- Textile materials such as cotton, jute, linen, hemp and various ar- 40 tificial silks and wool may be treated with such materials to produce a slight surface combinathe case of cellulose it is believed that there is a reaction with the cellulose molecule by the here pidity of reaction toward textile materials, particularly towards cellulose and cellulose deriva- In Germany February tion to produce the desired water-repellenoe.
- Impregnation of the textile materials with the esters herein mentioned may be carried out in any desired manner with or without the use of organic solvents by means of emulsification in an aqueous solution by soaking, spraying or the iike. It is also possible in the case of acetyl cellulose to add the isocyanates mentioned herein to the spinning solution itself in order thus to combine the process of producing water-repelience with the spinning process. Also one may treat the fibers of cellulose or cellulose derivatives immediately after the spinning process with the esters herein mentioned to obtain water-repeilence. The addition of catalytic agents, such as pyridine for the purpose of securing the desired effect, may be made but such addition is not necessary.
- catalytic agents such as pyridine for the purpose of securing the desired effect
- the textile materials are advantageously treated before impregnation takes place with weak aqueous solutions of sodium hydroxide, sodium carbonate or sodium acetate.
- organic bases such as pyridine may be added to the solutions of acyl carbamic chlorides in organic solvents.
- a raincoat material having spun viscose rayon as warp and weft, is passed through a 1% solution of stearic acid isocyanate in benzol for 3 seconds at a temperature of C., and after evaporating of the benzol is heated for 5 minutes to 140 0. (284 F.). The material then becomes water-repellent. The effect is proof to washing with soap, as well as to the solvents customary in dry cleaning.
- a poplin from mercerized cotton is passed through 1% solution of stearic acid-butyl-carbamic acid chloride in benzol for 4 seconds at a temperature of 25 C.
- the solution also contains 10 grams of pyridine per liter. After evaporating of the benzol the material is heated for 60 minutes to 60 C. (140 F.). The resulting efl'ect is similar to that of Example 1.
- a cotton tent cloth is passed through an aqueous solution of 16' grams per liter of sodium acetate, dried, and then passed through a 1% solution of palmitic acid methyl carbamic acid chloride CIsTiaCO.N.CO.Cl
- a clothing material of cuprammonium silk is passed through a 1% solution of phenylstearic acid isocyanate in benzol for 3 seconds at a temperature of 25 C., and after evaporating of the benzol is heated for 5 minutes to 140 C. (284 F.). The material then becomes waterrepellent. The effect is proof to washing with soap, as well as to the solvents customary in dry cleaning (manufacture of phenyl-steariq acid 0. f. United States Patent No. 1,972,568).
- acyl-isocyanates which are obtained by transposition of higher fatty acid amides with phosgene. This transposition is effected as follows:
- Carbamic acid chlorides may be made as follows: 300 parts by weight of stearlc acid butylamide are dissolved in 700 parts by weight of toluene, 80 parts by weight of pyridine and 100 parts by weight of phosgene are added. The mixture is heated in an autoclave to 150 C. for
- the amount of the ester deposited in all 0 the above examples on the textile materials will naturally vary with the weight of the material and its reactability. We have found that ordinarlly an amount of the ester equal to about 1% of the material is sufficient to give the effect. Corresponding amounts of the chlorides are also deposited.
- the materials produced in accordance with the above examples show a high degree of waterrepellence. They show a lesser absorption of moisture as compared with the known processes for treatment with fatty acid chlorides and fatty acid anhydrldes. They show also greatly improved durability toward dry-cleaning, soap washing, etc. as compared with these previous materials. The feel and hang of the materials having water-repellence as produced above, have not been substantially altered.
- cellulose-containing materials including cotton
- cuprammonium or other precipitated cellulose or derivatives of cellulose such as acetyl cellulose.
- a process for ennobiing textile materia which comprises subjecting the material to reaction with stearyl isocyanate at a temperature of about 150 C. for about 5 minutes to increase the water-repellence of said material.
- cuprammonium or other precipitated cellulose or derivatives of cellulose such as acetyl cellulose.
- a process for ennobiing textile materia which comprises subjecting the material to reaction with stearyl isocyanate at a temperature of about 150 C. for about 5 minutes to increase the water-repellence of said material.
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Description
Patented Sept. 12, 1939 UNITED STATES PATENT OFFICE PROCESS FOR RENDERING TEXTILES WA- TER-REPELIENT AND PRODUCTS THERE- FROM York
No Drawing. Application February 18, 1937, Se-
rial No. 126,521. 1936 6 Claims.
This invention relates to processes for producing water-repellent fibrous materials andproducts therefrom.
In our copending application Serial No. 76,738,
filed April 28, 1936, there is described a process for treating material with an isocyanate to increase the water-repellence thereof and the product obtained therefrom. We have now found that isocyanates of another formula may be employed for the production of water-repellent fibrous materials, and have also found novel processes for producing the substances employed for rendering the materials water-repellent.
The principal object of the present invention is to provide a simple process to increase waterrepellence in materials such as cotton, jute, linen, hemp and various artificial silks and wool, presenting advantages over the known fatty acid chloride and fatty acid anhydride processes referred to in said copending application.
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 byway of example and in accordance with which we now prefer to practice the invention.
We have found in accordance with our invention that isocyanatc derivatives having the general formula R.CO.N=C:O can be employed with great success for rendering textiles waterrepellent. In the formula just mentioned and in the appended claims in which said formula is employed, R is intended to designate an alkyl, cycloalkyl or aralkyl radical containing a saturated alkyl radical of at least 10 carbon atoms or signifies the saturated or unsaturated radical of an alcohol of the steroi series. Textile materials such as cotton, jute, linen, hemp and various ar- 40 tificial silks and wool may be treated with such materials to produce a slight surface combinathe case of cellulose it is believed that there is a reaction with the cellulose molecule by the here pidity of reaction toward textile materials, particularly towards cellulose and cellulose deriva- In Germany February tion to produce the desired water-repellenoe. In
tives. It is necessary only to bring the textile material in contact with the isocyanate as by passing the textile material briefly through a solution of the substance in benzine or a suitable solvent and immediately thereafter subjecting it for several minutes to a high temperature, usually C. or above.
Impregnation of the textile materials with the esters herein mentioned may be carried out in any desired manner with or without the use of organic solvents by means of emulsification in an aqueous solution by soaking, spraying or the iike. It is also possible in the case of acetyl cellulose to add the isocyanates mentioned herein to the spinning solution itself in order thus to combine the process of producing water-repelience with the spinning process. Also one may treat the fibers of cellulose or cellulose derivatives immediately after the spinning process with the esters herein mentioned to obtain water-repeilence. The addition of catalytic agents, such as pyridine for the purpose of securing the desired effect, may be made but such addition is not necessary. The
water-repellent effect secured by these treatments resists domestic washing. After thorough rinsing out with soap employed in such washing and drying, the textile material again manifests water-repellent properties. It is also resistant to dry cleaning.
The substances falling under the above formula may be obtained by the action of isocyanates upon acid chlorides (cf. Ber. 36, page 3213, C. Billcter). The reaction proceeds according to the following formula:
R.COCI+AE (NCO) R.CONCO +AgCl RCONH2+COCI2-R.CO.NH.COCI+HCI ZREONH COCl+Ca0-- 2RCON=C=O+H20+CaCl2 According to a modification of the process the said higher acyl-isocyanates may be replaced by the corresponding acyl-carbamic-acid chlorides. These compounds may be obtained by treating fatty acid amides with phosgene (cf. German Patent No. 566,603)
Employing higher acyl-carbamic acid chlorides instead of the corresponding acyl-isocyanates the textile materials are advantageously treated before impregnation takes place with weak aqueous solutions of sodium hydroxide, sodium carbonate or sodium acetate.
Also in a modification organic bases such as pyridine may be added to the solutions of acyl carbamic chlorides in organic solvents.
The following examples represent preferred embodiments of the invention for producing water-repellence in accordance with the manner in which we now prefer to practice it. It is to be understood that these examples are illustrative and the invention is not to be considered as limited thereto except as indicated in the appended claims.
Examples (1) A raincoat material, having spun viscose rayon as warp and weft, is passed through a 1% solution of stearic acid isocyanate in benzol for 3 seconds at a temperature of C., and after evaporating of the benzol is heated for 5 minutes to 140 0. (284 F.). The material then becomes water-repellent. The effect is proof to washing with soap, as well as to the solvents customary in dry cleaning.
(2) A cellulose hydrate web is passed through a 1% solution of palmitic acid isocyanate in benzol for 4 seconds at a temperature of 25 C. and after evaporating of the benzol is heated for minutes to 120 C. (248 F.) The resulting effect is similar to that of Example 1.
(3) A wool muslin is passed through a 1% solution of stearic acld-isocyanate in carbon tetrachloride for 3 seconds at a temperature of 25 C. and after evaporating of the solvent is heated for 60 minutes to 120" C. (248 F.). The result is similar to that of Example 1.
(4) A poplin from mercerized cotton is passed through 1% solution of stearic acid-butyl-carbamic acid chloride in benzol for 4 seconds at a temperature of 25 C. The solution also contains 10 grams of pyridine per liter. After evaporating of the benzol the material is heated for 60 minutes to 60 C. (140 F.). The resulting efl'ect is similar to that of Example 1.
(5) A cotton tent cloth is passed through an aqueous solution of 16' grams per liter of sodium acetate, dried, and then passed through a 1% solution of palmitic acid methyl carbamic acid chloride CIsTiaCO.N.CO.Cl
in carbon tetrachloride for 4 seconds at a temperature of 25 C. After evaporating of the solvent the material is heated 60 minutes to C. (158 F.). The resulting eflect is similar to that of Example 1.
(6) A clothing material of cuprammonium silk is passed through a 1% solution of phenylstearic acid isocyanate in benzol for 3 seconds at a temperature of 25 C., and after evaporating of the benzol is heated for 5 minutes to 140 C. (284 F.). The material then becomes waterrepellent. The effect is proof to washing with soap, as well as to the solvents customary in dry cleaning (manufacture of phenyl-steariq acid 0. f. United States Patent No. 1,972,568).
For the production of the substances for producing water-repellence, the following are examples of the way in which we now prefer to practice the invention. The invention is not to be restricted thereto, however, except as indicated in the appended claims.
(7) A mixture of 284 parts by weight of stearic acid chloride and 150 parts by weight oi silver cyanate are heated in 300 parts by weight of toluene at the reflux condenser for 60 minutes. The solution of stearic acid isocyanate C11H:sCO.N=C=O is liberated from the precipitated chloride by filtration.
(8) A mixture of 256 parts by weight of palmitic acid chloride and 82 parts by weight of potassium cyanate dissolved in a small quantity of water are heated in 300 parts by weight of toluene at the reflux condenser for 30 minutes. Palmitic acid isocyanate CisHJ1CO.N=C=O is liberated from the precipitated potassium chloride by filtration.
There are suitable also the acyl-isocyanates which are obtained by transposition of higher fatty acid amides with phosgene. This transposition is effected as follows:
(9) 250 parts by weight of stearic acid amide are dissolved in 700 parts by weight of 'toluene parts by weight of pyridine and parts by weight of phosgene are added. The mixture is heated in an autoclave to C. for three hours. Stearic acid-carbamic acid chloride is obtained. The corresponding isocyanate is obtained by dissolving the acyl-carbamic acid chloride in benacne and heating it with calcium oxide.
, (10) Carbamic acid chlorides may be made as follows: 300 parts by weight of stearlc acid butylamide are dissolved in 700 parts by weight of toluene, 80 parts by weight of pyridine and 100 parts by weight of phosgene are added. The mixture is heated in an autoclave to 150 C. for
a few hours. Stearic acid-butyl-carbamic acid chloride C|1H:|CO.N.CO.CI
is obtained.
(11) 250 parts by weight of palmitlc acid methylamide are dissolved in 700 parts by weight of toluene, 80 parts by weight of pyridine and 100 parts by weight of phosgene are added. The mixture is heated in an autoclave to 150 C. for a few hours. Palmitic acid methyl carbamic acid chloride c,.H,..co,N.c0.ci
is obtained.
The amount of the ester deposited in all 0 the above examples on the textile materials will naturally vary with the weight of the material and its reactability. We have found that ordinarlly an amount of the ester equal to about 1% of the material is sufficient to give the effect. Corresponding amounts of the chlorides are also deposited.
The materials produced in accordance with the above examples show a high degree of waterrepellence. They show a lesser absorption of moisture as compared with the known processes for treatment with fatty acid chlorides and fatty acid anhydrldes. They show also greatly improved durability toward dry-cleaning, soap washing, etc. as compared with these previous materials. The feel and hang of the materials having water-repellence as produced above, have not been substantially altered.
. cellulose-containing materials including 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 or carrying out the process, it will be obvious to those skilled in the art aiter 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.
Subject matter not claimed herein is claimed in our copending applications: Serial No. 76,738, filed April 28, 1936; Serial No. 289,394, filed August 10, 1939; Serial No. 289,395, filed August 10,
1939; and Serial No. 289,396, filed August 10, 1939.
What is claimed as new and desired to be secured by Letters Patent, is:
1. A process for ennobling textile material which comprises impregnating the material with an isocyanlc acid ester having the formula R.CO.N=C=O in which formula R signifies an alkyl, cycloalkyl or aralkyl radical containing a saturated alkyl radical of at least 10 carbon atoms or signifies a saturated or unsaturated radical of an alcohol the sterol series and heating the impregnated material to increase the water-repelience thereof.
2. A process for ennobling textile material which comprises impregnating the material with an isocyanic acid ester of an organic acid having a saturated alkyl radical of at least 10 carbon atoms in which the lsocyanate group N=C=O is directly linked to the carbonyl group CO and heating the impregnated material to increase the water-repellence thereof.
3. A process for ennobiing textile material which comprises impregnating the material with an isocyanic acid ester of an organic acid containing a sterol group in which the isocyanate group N=C=O is linked directly with the carbonyl group CO, and heating the impregnated material to increase the water-repellence.
4. A process for ennobiing textile materia which comprises subjecting the material to reaction with stearyl isocyanate at a temperature of about 150 C. for about 5 minutes to increase the water-repellence of said material.
5. A textile material partially chemically a1- tered with an isocyanate of the formula R.CO.N=C=O and in which formula R signifies an alkyl, cycloalkyl or aralkyl radical containing a saturated alkyl radical of at least carbon atoms or signifies the saturated or unsaturated radicaloi' an alcohol of the sterol series, said material having a water-repellent property but in appearance and feel being substantially the same as similar material untreated, said material being also capable of withstanding ordinary house laundering and other cleaning.
6. A textile material treated with an isocyanic acid ester of an organic acid having a saturated alkyl radical of at least 10 carbon atoms in which the isocyanate group N=C=O is directly linked to the carbonyl group C0, to produce in said material, a water-repellent property, said material in appearance and feel being substantially the same as similar material untreated, said material being also capable of withstanding ordinary house laundering and dry cleaning.
ERNST WALTMANN. EDGAR WOLF.
CERTIFICATE OF GORRBC'I'IOH.
Patent No. 2,173,029.
Septqnber 12, 1939- ERIIST HALTHAHH, ET AL. It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page 2, sec- 0nd column, lines 3|;end55, strike out the words and colon carbonic acid chlorides. may be made as follows and ineertthe same as a separate paragraph arter' 'oxided, line M10 9; and can the in Letters Patent should be read with this correction therein that the one my custom to the record of the case in the Patent ornce.
Signed. and peeled this rd as; of October, A. n; 1959.
(Mill liens-y Van Airedale, Acting dc-ieeioner ot Patentecellulose-containing materials including 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 or carrying out the process, it will be obvious to those skilled in the art aiter 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.
Subject matter not claimed herein is claimed in our copending applications: Serial No. 76,738, filed April 28, 1936; Serial No. 289,394, filed August 10, 1939; Serial No. 289,395, filed August 10,
1939; and Serial No. 289,396, filed August 10, 1939.
What is claimed as new and desired to be secured by Letters Patent, is:
1. A process for ennobling textile material which comprises impregnating the material with an isocyanlc acid ester having the formula R.CO.N=C=O in which formula R signifies an alkyl, cycloalkyl or aralkyl radical containing a saturated alkyl radical of at least 10 carbon atoms or signifies a saturated or unsaturated radical of an alcohol the sterol series and heating the impregnated material to increase the water-repelience thereof.
2. A process for ennobling textile material which comprises impregnating the material with an isocyanic acid ester of an organic acid having a saturated alkyl radical of at least 10 carbon atoms in which the lsocyanate group N=C=O is directly linked to the carbonyl group CO and heating the impregnated material to increase the water-repellence thereof.
3. A process for ennobiing textile material which comprises impregnating the material with an isocyanic acid ester of an organic acid containing a sterol group in which the isocyanate group N=C=O is linked directly with the carbonyl group CO, and heating the impregnated material to increase the water-repellence.
4. A process for ennobiing textile materia which comprises subjecting the material to reaction with stearyl isocyanate at a temperature of about 150 C. for about 5 minutes to increase the water-repellence of said material.
5. A textile material partially chemically a1- tered with an isocyanate of the formula R.CO.N=C=O and in which formula R signifies an alkyl, cycloalkyl or aralkyl radical containing a saturated alkyl radical of at least carbon atoms or signifies the saturated or unsaturated radicaloi' an alcohol of the sterol series, said material having a water-repellent property but in appearance and feel being substantially the same as similar material untreated, said material being also capable of withstanding ordinary house laundering and other cleaning.
6. A textile material treated with an isocyanic acid ester of an organic acid having a saturated alkyl radical of at least 10 carbon atoms in which the isocyanate group N=C=O is directly linked to the carbonyl group C0, to produce in said material, a water-repellent property, said material in appearance and feel being substantially the same as similar material untreated, said material being also capable of withstanding ordinary house laundering and dry cleaning.
ERNST WALTMANN. EDGAR WOLF.
CERTIFICATE OF GORRBC'I'IOH.
Patent No. 2,173,029.
Septqnber 12, 1939- ERIIST HALTHAHH, ET AL. It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page 2, sec- 0nd column, lines 3|;end55, strike out the words and colon carbonic acid chlorides. may be made as follows and ineertthe same as a separate paragraph arter' 'oxided, line M10 9; and can the in Letters Patent should be read with this correction therein that the one my custom to the record of the case in the Patent ornce.
Signed. and peeled this rd as; of October, A. n; 1959.
(Mill liens-y Van Airedale, Acting dc-ieeioner ot Patente-
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2173029X | 1936-02-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2173029A true US2173029A (en) | 1939-09-12 |
Family
ID=7988536
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US126521A Expired - Lifetime US2173029A (en) | 1936-02-19 | 1937-02-18 | Process for rendering textiles water-repellent and products therefrom |
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| Country | Link |
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| US (1) | US2173029A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2468716A (en) * | 1947-04-16 | 1949-04-26 | American Cyanamid Co | Treatment of hydrogen-donor textile materials and products thereof |
| US2482578A (en) * | 1947-04-24 | 1949-09-20 | Little Inc A | Treatment of wool |
| US2537064A (en) * | 1946-08-30 | 1951-01-09 | American Cyanamid Co | Treatment of organic textile materials and products thereof |
| US2795517A (en) * | 1953-12-02 | 1957-06-11 | Ici Ltd | Modification of the properties of fibrous materials |
| US3005728A (en) * | 1956-10-19 | 1961-10-24 | Tee Pak Inc | Cellulosic laminates |
| US3213135A (en) * | 1962-09-04 | 1965-10-19 | Monsanto Co | Chloroacetyl isocyanates and their preparation |
-
1937
- 1937-02-18 US US126521A patent/US2173029A/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2537064A (en) * | 1946-08-30 | 1951-01-09 | American Cyanamid Co | Treatment of organic textile materials and products thereof |
| US2468716A (en) * | 1947-04-16 | 1949-04-26 | American Cyanamid Co | Treatment of hydrogen-donor textile materials and products thereof |
| US2482578A (en) * | 1947-04-24 | 1949-09-20 | Little Inc A | Treatment of wool |
| US2795517A (en) * | 1953-12-02 | 1957-06-11 | Ici Ltd | Modification of the properties of fibrous materials |
| US3005728A (en) * | 1956-10-19 | 1961-10-24 | Tee Pak Inc | Cellulosic laminates |
| US3213135A (en) * | 1962-09-04 | 1965-10-19 | Monsanto Co | Chloroacetyl isocyanates and their preparation |
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