US2303363A - Process for rendering textiles water-repellent and product therefrom - Google Patents
Process for rendering textiles water-repellent and product therefrom Download PDFInfo
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- US2303363A US2303363A US76738A US7673836A US2303363A US 2303363 A US2303363 A US 2303363A US 76738 A US76738 A US 76738A US 7673836 A US7673836 A US 7673836A US 2303363 A US2303363 A US 2303363A
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- isocyanate
- water
- repellent
- aliphatic
- carbon atoms
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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
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Description
Patented Dec. 1,
WATER-BEPEILEN T THEREFROM AND PRODUCT Walther Kaase and Ernst Waltmann, Krefeld, Germany, assignors to Heberlein Patent Corporation, New York, N. Y., a corporation of New York No Drawing. Application April 28, 1936, Serial Claims.
This invention relates to processes for producing water-repellent fibrous materials and products therefrom.
It has been suggested heretofore that water- 'repellence be produced in cellulose-containing materials by treatment with esterifying agents such as fatty acid chlorides or fatty acid anhydrides. In the execution of these processes, however, difiiculties have been encountered due to unfavorable reaction conditions whereby the appearance and feel of the goods is changed. These processes also require considerable time and expense for operation. The treatment of the material to render it water-repellent or drop-proof is carried out ordinarily as the final treatment in finishing the material. It is accordingly necessary from the standpoint of practical mass production that the process be carried out with considerable rapidity and be accomplished in a short period instead of requiring hours as heretofore.
In Germany May 2, 1935 The principal object of the present invention I is to provide a simple process to increase waterresistance in materials, such as, for example, but without limitation, cotton, jute, linen, hemp and various artificial silks and wool, in a relatively short time and with less expense than that of the chlorides and anhydrides mentioned above; and to produce materials having improved characteristics.
The invention accordingly comprises the novel products as well as the novel processes and steps of processes according to which such products are manufactured, the specific embodiments of which are described hereinafter by way of example and in accordance with which we now prefer to practice the invention.
Now We have found in accordance with our invention that treatment of textile materials, including cellulose-containing materials and wool, with the extremely reactive isocyanic acid esters of the aliphatic, mixed aliphatic-aromatic or naphthenic series produces remarkably fine effects, including resistance to wetting by water. For this purpose only the isocyanic acid esters of the series mentioned having at least 10 carbon atoms for instance decylisocyanate, hexadecylisocyanate, heptadecylisocyanate, heneicosylisocyanate, octadecylisocyanate, docosylisocyanate etc. are to be employed. These substances may be prepared by well-known processes such as described in Berichte der Deutschen Chemischen Gesellschaft, 42d year, 1909, vol. 3 page 3359, cf. the article by Schroeter, Ueber Umlagerungen. In the appended claims, certain of these isocyanates have been designated by the formula R.N=C=0, where R is an allphatic radical containing more than 10 carbon atoms. There are suitable also other isocyanates which are obtained by transposition of saturated amines or mixtures of such saturated amines of high molecular weight with phosgene. Such amines of high molecular weight are commercially obtainable in the way described in German Patent No. 611,924 or French Patent No.
This transposition is effected as follows: The amine, for example stearylamine is dissolved in hot toluene, the solution is saturated with gaseous hydrochloric acid, whereby stearylamine hydrochloride separates out; then phosgene is passed into the mixture until solution occurs. The reactions which occur appear to be as follows:
It is not necessary to use pure saturated airlines as mixtures of saturated amines of high molecular weight are well suitable, for instance the the corresponding isocyanic-acid esters of they naphthenic acids having at least 10 carbon atoms in an aliphatic portion are also suitable, for example a naphthenic acid from Galician naphtha corresponding to the formula:
or a bicyclic naphthenic acid CzoHsqCOOI-I derived from Roumanian naphtha.
There may also be employed the isocyanate obtainable from montanic acid. Montanic or hep-, tacosyl acid which corresponds to the formula: C21H55COOH, is converted into heptacosyl isocyanate in the usual way:
The statement above made that the aliphatic, mixed aliphatic-aromatic or naphthenic acids which form part of the esters should have at least 10 carbon atoms, means that there should be at least carbon atoms in the aliphatic portions of such esters. From ten carbon atoms upwards representing an even number or an uneven number of carbon atoms may be so present.
There may also be employed substances which are easily converted into the isocyanic acid esters upon treating the textiles herein mentioned with such substances under reaction conditions. For example we may employ the corresponding fatty acid azides such as palmitic acid azide CH3 (CH2) 14CO.N:
These substances become converted with elimination of nitrogen into the corresponding isocyanic acid esters, as described in Journal flir praktische Chemie" (2) vol. 64, page 430, cf. the article by Curtius Dellschaft.
Fatty acid azides occur as intermediate products if the way of preparing fatty acid chlorides and treating same with sodium azide is adopted, as is shown in the reactions on the preceding page of this specification. Furthermore fatty acid azides may be obtained, as is well known, by treating fatty acid hydrazides with nitrous acid HNOz. I
In accordance with our invention it has further been found that there may also be employed aliphatic isocyanates whose carbon chains are interrupted by the atoms or atomic groups 0, S, N, C0.0, 0.00, NR, NR.CO, CO.NR', S02, NR'.SO2, SO2.NR' in which R. may be equal to hydrogen or may be any desired hydrocarbon radical (cf. French Patent No. 787,785). It is known that all carboxylic acid chlorides are easily converted into the corresponding azides and isocyanates by the Curtius method.
For the same purpose mixed aliphatic-aromatic isocyanic acid esters may also be used, in so far as they contain a saturated aliphatic radical of at least 10 carbon atoms. The active --N=C=O group may in this connection be tied directly to the aromatic ring, 1. e., for example which is 1-stearyl-oxy-phenylene-4-isocyanate.
' The aromatic radical may be hydrogenated, chlorinated, or otherwise replaced, and the hydrogenated compound, for example, may be represented which is 4-carboctadecoxy tetrahydrophenyl isocyanate.
It is also possible to successfully use for waterrepellence, isocyanates which contain in the alkyl radical the radical of a saturated or unsaturated alcohol of the sterol series. As a technological starting material for the alcohol of the sterol series there is advantageously employed the sterol mixtures contained in the unsaponiflable part of wool fat. Such mixtures may be prepared for instance in the manner described in German Patent No. 617,975. For the purpose of introduction of the active N=C=O group these alcohols are converted into esteror ether-carboxylic acids and the chlorides of these esteror ether-carboxylic acids are converted by the Curtius method. Thus for example cholesterol which is an alcohol,
occurring in the unsaponiflable part of wool fat is transposed by means of adipic acid chloride according to the following reaction:
whereby cholesterol-adipic acid ester isocyanate is formed.
The new substances mentioned are distinguished by an extremely high rapidity of action towards textile materials, particularly towards cellulose and cellulose derivatives, such as has not heretofore been observed in connection with any of the known methods. 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 isocyanic acid esters in benzine or a suitable solvent and immediately thereafter it is subjected for several min utes to a high temperature to produce waterrepellence.
An action between the textile material and the treating substance occurs in accordance with our invention to produce water-repellence but we do not wish to be understood to state unqualifiedly that a chemical reaction occurs between the textile material and the chemical compound employed in accordance with the invention, as we are not sure that such is the case.
One may also treat the fibers of cellulose or cellulose derivatives immediately after the spinning process with the esters herein mentioned, to obtain water-repellence.
Impregnation of the textile materials with the esters herein mentioned may be carried put in any desired manner with or without the use of organic solvents or of aqueous emulsions of the esters applied by soaking, spraying or the like. The addition of catalytic agents for the purpose of securing the desired effect may be made, but it is not necessary.
The water-repellent effect produced in accordance with our invention resists domestic washing. After thorough rinsing out of the soap employed for this purpose and drying, the textile material again manifests water-repellent properties. It is also resistant to dry cleaning.
The following are examples of embodiments of the invention as we now prefer to carry it out. It is to be understood that these examples are not to be construed as limiting the invention, except as indicated in the appended claims.
Examples 1. A printed crepe, having delustered viscose rayon as warp and viscose crepe as weft, is passed through a 0.5% solution of octodecyl isocyanate, CmHsvN=C=O in benzine. The time of passage is about 3 seconds and the solution is at room temperature. Immediately thereafter the so-treated material is subjected for one minute to a temperature of C. (212 F.) and then for two minutes to a temperature of 140 C. (284 F.).
2. Acetate satin having acetate silk as warp and viscose crepe as weft is sprayed with a 1% solution of heptacosyl (or montanyl) isocyanate, C21H55N=C=O, in benzine at room temperature. The solvent is evaporated off, and the so-treated material is subjected for two minutes to a temperature of C.
3. Dyed stockings of Bemberg silk (cuprammonium silk) are immersed in a 0.3% solution of heneicosylisocyanate C21H4aN=C=0, in benzine at room temperature for approximately 10 seconds, then taken out and. after evaporation of the solvent, treated for 1% minutes at 150C. 4. A cotton tent cloth is passed through, a 1% solution of naphthenic isocyanate,
in benzine. After the passage which lasts about 4 seconds, the solvent is evaporated off and the material is heated for 2 minutes to a temperature of 150 C.
5. A fabric, suitable for rucksacks, consisting of linen and cotton is treated with a 0.75% solution of bicyclic naphthen isocyanate,
from Roumanian naphtha in benzine in the same way as described in Example 4.
6. A viscose spun rayon fabric is treated with an 0.5% solution in benzine of l-stearyl-oxyphenylene-4-isocyanate,
in the same way as in Example 1.
7. A poplin from mercerized cotton, suitable for rain-proof overcoats is passed through 9 0.5% solution of octocosan-acid azide in benzine. The solvent is then removed by heating the fabric to about 100 C. for a short time. Afterwards the material is exposed for two minutes to a temperature of 140.
8. A mixture of amines obtainable by hydrating train oil acids (see page 1)- is converted into a mixture of isocyanie esters by means of phosgene as above described and a 0.5% solution in benzine therefrom is prepared. A mixed fabric consisting of mercerized cotton and viscose spun rayon is treated with this solution in the same way as described in Example 7.
9. A fabric consisting of "Vistra (spun viscose rayon) is treated with a 0.5% solution of cholesterol-adipic acid ester isocyanate.
in benzine as described in Example 7.
10. A wool muslin is treated with a 0.5% solution of cholesterol-adipic acid ester azide in benzine (see page 2), C21H45O.CO(CH2)4CON3, as de-. scribed in Example '7.
11. A worsted fabric is treated with a 0.5% solution of octocosan acid az de in benzine. as described in Example 7.
12. A strong cotton fabric is passed during 3 seconds through a 0.5% solution of heptacosyl (montanyl) isocyanate, C27H5sN==C=O, in benzine, the solvent is evaporated off and the material is exposed for 2 minutes to a temperature of 150 C.
The amount of the ester deposited in all of the above examples on the materials will naturally vary with the weight of the material. We have found that ordinarily an amount of the ester equal to about 0.5% of the material being treated, is sufficient to give the effect.
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 employing fatty acid chlorides and fatty acid anhydrides. 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 waterrepellence as produced above, is about the same as that of the untreated material. Rayons especially, when treated in accordance with the invention, show an increase in tensile strength.
The process of the invention, particularly as set forth in the specific embodiments above, may be carried out with simple apparatus at relatively small expense and in a relatively short time.
In the claims and elsewhere where the expression cellulose-containing material is employed, it is intended to 'cover fibersjyarns, fabrics or other forms of cotton, jute, linen, hemp or rayon including viscose, cuprammonium, or other pre cipitated cellulose or derivatives of cellulose such as acetyl cellulose. Similarly, the expression textile material is intended to include such cellulose-containing material" and similar forms of wool or other animal material.
The expression isocyanate, as used in the claims, is intended to include not only isocyanates but also azides which are capable of liberating nitrogen to produce isocyanates and when applied to textiles and heated, for example, above C. will act thereon to produce water-repellence therein.
Subject matter not herein claimed is claimed in our copending applications Serial No. 196,622, filed March 18, 1938, and Serial No. 221,994, filed July 29, 1938.
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 inven tion, 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 ennobling textile material which comprises subjecting the material to an isocyanate of the group consisting of aliphatic isocyanates, mixed aliphatic-aromatic isocyanates, and naphthenic isocyanates, which contain an aliphatic radical of at least 10 carbon atoms, and heating the material with the isocyanate to increase the water-repellence of said material.
2. A process for ennobling textile material which comprises subjecting the material to a naphthenic isocyanate having a naphthene radical containing an aliphatic radical of at least 10 carbon atoms, and heating the material with the isocyanate to increase the water-repellence of said material.
3. A process for ennobling textile material which comprises impregnating the material with an isocyanate of the group consisting of aliphatic isocyanates, mixed aliphatic-aromatic isocyanates, and naphthenic isocyanates, which contain an aliphatic radical of at least 10 carbon atoms, and heating the impregnated material for a short period at a temperature above 100 C. to increase the water-repellence of said material.
4. A process for ennobling artificial silk which comprises heating the artificial silk with an isocyanate of the group consisting of aliphatic isocyanates, mixed aliphatic-aromatic isocyanates, and naphthenic isocyanates, which contain an aliphatic radical of at least 10 carbon atoms capable of acting upon said material, for a short period at a temperature above 100 C., to increase the water-repellence of said silk.
5. A process for ennobling textile material which comprises heating the material with an aliphatic-aromatic isocyanate, which contains a saturated aliphatic radical of at least carbon atoms, the isocyanate group N= C= =O being joined directly to the aromatic ring', to increase the water-repellence of said material.
6. A textile material heated with an isocyanate to render it water-repellent, said isocyanate being selected from the group consisting of aliphatic, mixed aliphatic-aromatic and naphthenic isocyanates, containing an aliphatic radical of at least 10 carbon atoms, said material having a waterrepellent property but in appearance and feel being substantially the same as similar material untreated.
7. A textile material heated with an aliphatic isocyanate which contains an alkyl radical of at least ten carbon atoms, said material having a water-repellent property but in appearance and feel being substantially the same as similar material untreated.
8. A textile material heated with a naphthenic isocyanate having a naphthene radical containing an aliphatic radical of at least ten carbon atoms, said material having a water-repellent property but in appearance and feel being substantially the same as similar material untreated.
9. A textile material heated with an aliphaticaromatic isocyanate which contains a saturated aliphatic radical of at least ten carbon atoms, said material having a water-repellent property but inappearance and feel beingsubstantially the same as similar material untreated.
10. A process for treating textile material which comprises impregnating the material with an isocyanate of the formula RNCO in which R is an asoases aliphatic radical containing more than 10 carbo atoms, said isocyanate being capable of actin upon said textile material to render the sam water-repellent, and heating the impregnate material to produce water-repellence therein.
11. A process for treating textile material whlc comprises impregnating the material with a isocyanate containing an aliphatic radical of e least ten carbon atoms capable of acting upo said textile material to render the same water repellent, and heating the impregnated materii to produce water-repellence therein.
12. A process for treating textile material whic comprises impregnating the. material with mixed aliphatic-aromatic isocyanate containin an aliphatic radical of more than 10 carbo atoms, and capable of acting upon said textii material to render the same water-repellent, an heating the impregnated material to produc water-repellence therein.
13. A process for treating textile material whic comprises impregnating the material with mor tanyl isocyanate and heating the so impregnate material to render the same water-repellent.
14. A process for treating textile material whic comprises impregnating the material with l-ste aryl-oxy-phenylene-i-isocyanate and heating tl CERTIFICATE -OF CORRECTION.
Patent 'No. 2,505,565. December 1, 1 9h2.,
HALTHER KAASE, ET AL.
It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction gs follows: Page 2, second column, line 5, for that portion of the formnle reading "(C H )COCl+ H01 read --(CH )L COCl+-HC1-; 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 br February, A. D. 1911.3.
(Seal) Henry Van Arsdale,
Acting Commissioner of Patents.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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DE2303363X | 1935-05-02 |
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US2303363A true US2303363A (en) | 1942-12-01 |
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US76738A Expired - Lifetime US2303363A (en) | 1935-05-02 | 1936-04-28 | Process for rendering textiles water-repellent and product therefrom |
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2482578A (en) * | 1947-04-24 | 1949-09-20 | Little Inc A | Treatment of wool |
US2768154A (en) * | 1953-10-12 | 1956-10-23 | Eastman Kodak Co | Urethane modified materials |
US2897233A (en) * | 1956-02-06 | 1959-07-28 | Armour & Co | Process for the separation of amino acids |
US2978475A (en) * | 1956-03-26 | 1961-04-04 | Aerojet General Co | Nitro-substituted diisocyanate compounds |
US3455883A (en) * | 1963-01-09 | 1969-07-15 | Gen Mills Inc | Polyisocyanates and derivatives |
-
1936
- 1936-04-28 US US76738A patent/US2303363A/en not_active Expired - Lifetime
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2482578A (en) * | 1947-04-24 | 1949-09-20 | Little Inc A | Treatment of wool |
US2768154A (en) * | 1953-10-12 | 1956-10-23 | Eastman Kodak Co | Urethane modified materials |
US2897233A (en) * | 1956-02-06 | 1959-07-28 | Armour & Co | Process for the separation of amino acids |
US2978475A (en) * | 1956-03-26 | 1961-04-04 | Aerojet General Co | Nitro-substituted diisocyanate compounds |
US3455883A (en) * | 1963-01-09 | 1969-07-15 | Gen Mills Inc | Polyisocyanates and derivatives |
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