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Publication numberUS2327760 A
Publication typeGrant
Publication dateAug 24, 1943
Filing dateJul 19, 1941
Priority dateJul 19, 1940
Publication numberUS 2327760 A, US 2327760A, US-A-2327760, US2327760 A, US2327760A
InventorsBestian Herbert, Schurmann Max Otto
Original AssigneeBestian Herbert, Schurmann Max Otto
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Fibrous materials
US 2327760 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

Patented Aug. 24, 1943 FIBROUS MATERIALS Herbert Bestian, Frankfort-on-the-Main-Hochst,

and Max Otto Sch'iirmann, Dormagen, Germany; vested in the Alien Property Custodian No Drawing. Application July 19, 1941, Serial' No. 403,232. In Germany July 19, 1940 18 Claims.

The present invention relates to fibrous materials. More particularly it relates to a process of improving the properties of cellulosic fibrous material and to the products thus obtained. We have found that the wearing strength and the other properties for the practical use of 11- brous materials from natural or regenerated cellulose or mixtures containing such fibrous material may be improved to a large extent by treating them with a member of the group consisting of compounds of the general formula:

Inc on,

wherein R stands for a member of the group consisting of aliphatic and carbocyclic radicals,

- and the derivatives of said compounds, wherein of the fibrous material are simultaneously im-- proved which are of importance for the practical use of the material. For instance the tensile strength of regenerated cellulose in the dry or wet conditionis remarkably enhanced. This improvement of the tensile strength is not decreased even by the usual washing operations, .whereas the resistance to tearing in the dry and wet state of non-treated regenerated cellulose "is diminished by a repeated washing. filextile fibers have, as is known, the tendency of swelling in the wet state. marked with fibers of regenerated cellulose, a broadening of the cross section andin consequence thereof a closing of the pores of the tissue being due to said swelling. By treating the fibrous material with the derivatives of di-urea named above a considerable reduction of the swelling property is attained and the spaces in the tissues are well maintained when the material becomes wet; in consequence thereof the permeability to air so important from the hygienic point of view is hardly impaired. Con- .trary to a non-treated material, a tissue which has been treated according to the present. invention has only a slight tendency of shriniring on washing it in an aqueous liquor. The resistance to crumbling of .the tissue is, therefore, considerably enhanced.

There exist a series of fibrous materials which,

This property is particularly- This phenomenon is particularly evident with staple fibers from viscose which were subjected to an extensive after-stretching, furthermore with artificial silk and staple fiber which were prepared according to a process of spinning by stretching; said process consists in stretching the fibers in a slowly coagulating spinning bath before hardening the threads. The phenomenon just named may produce. an undesirable and a disadvantageous efiect particularly if, for instance, during a dyeing process the tissue is subjected to a scraping or rubbing or if the finished textile material is rubbed on washing. The optic behaviour of the surface of the material is altered due to the split single fibers and a whitish shimmer is produced which may give the impression of an uneven dyeing, especially in those cases where fabrics uniformly dyed in dark shades are concerned. By treating the fibrous material according to the present invention said drawback has been satisfactorily overcome.

It must furthermore be emphasized that by the treatment herein described the'resistance to creasing of the fibrous material is considerably improved. Owing to the good resistance to washing of the impregnation the improvement of the resistance to creasing is evident even after a repeated washing. I

As already stated above, the fibrous goods show, when being wet, a reduced swellin P er.

- Moreover, there is simultaneously observed that when being rubbed in the wet state, have the characteristic that the singular fibers split into very fine fibrils and the material becomes downy.

the impregnated material distinctly possesses water-repellent properties. By the treatment according tothe present invention it is.attained that the fibrous goods are only difiicultly wetted by the action of moisture. In case the material has become wet dueto a prolonged action of water, it takes up only a small portion of water owing to the reduced swelling power; it, therefore, .can rapidly be dried again.

Gloss and embossed effects produced by calendering on textile goods disappear, as is known,

more or less completely, when the material becomes wet; if, before the calendering, them/aterial is impregnated with the derivatives of diurea named and subsequently subjected to a heat treatment, the effects are retained not only after a treatment with water, but even after one washing operation or after a repeated washing with a aqueous soap liquor or the solution i of another washing agent, even if the material is simultaneously subjectedto a mechanical treatment. By a moist ordry'ironing of the washed goods, the embossed or glossy patterns do not disappear. What is said above about calendering of tissues holds also true when fibers are given a fonn, for instance, by curling.

The treatment described herein ends in the surprising result that the cellulose material is improved in various respects for the practical use. The resistance to tearing and creasing and the water-repellent properties are enhanced; the tendency of splitting, shrinking and swelling is diminished. The impregnation described may be carried out with fibrous goods consisting of pure cellulose; but mixed fibrous materials from natural or regenerated cellulose and other vegetable, animal or. synthetic fibrous materials may be subjected to the said treatment.

The monomeric starting compounds may be obtained by reaction of aliphatic, cycloaliphatic, aromatic and araliphatic diisocyanates with ethylene imine or the homologues thereof. For instance the following compounds may be named: aliphatic diisocyanates with a straight and a branched carbon chain, for instance ethylenel.2-diisocyanate, propylene 1.3 diisocyanate, butylene 1.4 diisocyanate, hexamethy1ene-1.6- diisocyanate, octamethylene 1.8 diisocyanate,- decamethylene-1.10-diisocyanate, trimethylpenq tyIene-LS-diisocyanate, 2-methyl-butylene-L4- diisocyanate, or the like. The carbon'chain of the aliphatic diisocyanates may be interrupted radicals, hydrocarbon radicals, for instance methyl, ethyl, propyl, butyl, decyl, benzyl, phenyl and others.

The ethylene ureae may be used alone or in mixture with each other. According to the solubility of the compounds, the impregnation may be performed in aqueous solutions or suspensions. They may be operated with dilute or with concentrated liquors. For instance'a quantity of 10-200 grams per liter of the derivatives of diurea may be used, but with inferior concentrations a distinct improvement of the properties of the material treated is also attained. The impregnation may be carried out at room temperature or at a raised temperature, if necessary in the presence of wetting agents. The impregnating devices suitable for the present purpose are for instance a foulard, a washer-Jigger, a boiling and crabbing machine. After the impregnation, the material is squeezed or centrifuged and then dried. For this purpose the material is suitably heated to an elevated temperature, if necessary after a previous drying at a low temperature.

The diethylene-ureae may also be used together with monoethylene-urea, as they are prepared by condensation of monoiso-cyanic acid esters with ethyleneimine and the homologues thereof.

Furthermore they may be used in combination with other adjuvants for the textile industry, for

instance with the usual hydrophobing agents and softening agents or dressing agents, such as polyvinyl alcohol, sodium polyacrylate, ammonium poly-methacrylate, water-soluble salts of interpolymerization products from vinyl compounds, for instance vinyl chloride, vinyl acetate, styrene,

or the like, and maleic acid or the anlrvdride' thereof; furthermore interpolymerization products, the one component of which is acrylic acid or crotonic acid; starch, cellulose-s1ycolic ether acid, condensation products from urea or melamine and formaldehyde, and the like. The treat- The material is squeezed between rubber rollers sothatthe tissue still contains 100 per cent of liquor. The material is then dried at 50 C. and the dried tissue is further heated for 20 minutes at 140 C. The impregnated tissue shows an improvement of the resistance to tearing in the dry and wet state which remains unaltered even after a three-times washing (the ,fabric was washed for 20 minutes at 90 C. with 5 grams of soap per liter of water). I i

2. A fabric of spun rayon is impregnated at 30 C. in a liquor containing per liter 150 grams of the diurea of the following formula:

CHI

H2 The material is thoroughly squeezed between rubber rollers so that the tissue still contains 100 per cent of liquor. The material is then dried at 50 C. and-the dried tissue is further heated for '20 minutes at 140, C. v The tissue thus obtained is substantially resistant to creasing. The resistance to creasing is substantially retained even after a three times washing (the material was washed for 20 minutes at C. with 5 grams of soap per liter of water) 3. A fabric of cotton or staple fiber from viscose is impregnated at 30 C. in a liquor containing per liter grams of the diurea of the following formula:

H2 HI The material is squeezed between rubber rollers so that it still contains 100 per cent of liquor. The fabric is then preliminarily dried at 50 C. and finally calendered at C. .with application of a pressure of the rollers of 10,000 kilograms. The fabric is further heated for half an hour at C. A stamping is produced which is resistant to washing and boiling.

4. A fabric of staple fiber from viscose is impregnated at 30 C. with a liquor containing per liter 100 grams of the diurea of the following formula:

The material is squeezed, dried and further baked for half an hourat 130 C. A tissue is thus obtained which, contrary to the non-treated v fabric, has only an insignificant swelling power in water or dilute alkalies and which, on washing,

permanently fast to washing and boiling for 15 minutes with grams of soap and 2 grams of sodium carbonate per liter of water.

no longer shrinks, i. e., the fabric is resistant to shrinking.

' 5. A tissue of staple fiber from viscose is impregnated at 25 C. in a liquor containing in suspension per liter 10 grams of the diurea of the following formula:

The fabric is squeezed, pre-dried at 80 C. and then further heated for minutes at 140 C. The tissue thus treated shows a strongly hydrophobic character which is retained even when the tissue treated is washed.

6. A cotton fabric is impregnated at 40 C.-

9. Staple fiber obtained from ammoniacal copper oxide spinning solution by spinning in water, subsequently hardening it in dilute sulfuric acid and further treating it in the usual manner, is

dried at about 40 C. and soaked with an aqueous solution of 50 grams of the compound per liter of liquor. The fiber is centrifuged, dried in a current of air at 80 C.-90 C. and then heated for 10 minutes to 130 C.'-140 C. When compared with the non-treated fibers the fibers treated as herein described are 200 times more resistant to splitting when they are subjected to mechanical stress in the wet state. a

10. Spun rayon is soaked, after having been cut, with a solution of 25 grams of hexamethylene-diethylene-urea per liter of water, vigorously squeezed and carefully dried at atemperature of about 50 C. The artificial silk staple fiber is then curled by pressing it with grooved rollers and the curled fibers are hardened by subsequently heating them for 15 minutes to 120 C.

- The curling thus obtained is fast to washing.

liter 100 grams of the diurea of the following formula:

H20 on,

NC0NH--(CHz)s-NHC0-N l l H: H: and 10 grams of octadecyl-N'-N-ethylene-urea. The material is squeezed and, after a pre-drying at 80 C., heated for minutes at 120 C. The tissue thus obtained is distinguished, contrary to the non-treated tissue, by an agreeable and a soft touch, by a considerably improved resistance to tearing in the wet and dry state, by an essential reduction of the swelling power of the individual fibers, by a substantial resistance to creasing and shrinking and by its highly hydrophobic character. The effects produced possess an excellent resistance to washing and -fulling. Instead of 10 grams of N-octadecyl- N'.N'-ethylene-urea there may be used 10 grams of stearic acid methylolamide.

8. A fabric of staple fiber prepared from viscose or according to the ammoniacal copper oxide process is impregnated at 40 C. in a liquor containing per liter of water 120 grams of dimethylol-urea, 25 grams of diethylene urea of the formula:

and furthermore 3 grams of glycolic acid. The fabric is centrifugedaor squeezed, dried and then heated for 20 minutes at 120 C. In comparison 11. Artificial silk staple fiber prepared according to the amfnoniacal copper oxide process is treated in a bath containing per liter of water 50 grams of. tetra-methylene-diethylene-urea and 10 grams of stearyl-ethylene-urea. The fibers are centrifuged, carefully dried and then curled by stamping at a temperature of 130 C. between rollers provided with a pattern. The fibers are subsequently heated for 5 minutes at 130 C. A curled staple fiber is obtained which is not brittle. The curling is resistant to washing with soap.

12. A viscose artificial silk yarn is twisted and wound in this state on perforated bobbins. The artificial silk is then impregnated with a solution of 30 grams of hexamethylene-diethylene-urea per liter of water, and carefullydried on the bobbins. The yam is then twisted again in a twister and finally heated for half an hour to C. A curling resistant to washing is obtained.

13. A fabric of viscose staple fiber is impregnated at 25 C. in a liquor containing per liter 50 grams of the diurea of thefollowing formula:

and 25 grams of sodium polyacrylate. The faband 30 grams of the ammonium salt of an intermlymerlzation product of equal parts of vinyl-' methyl-ether and maleic anhydride. The fabric pregnating the material with a member of the group consistingof compounds of the general formula:

mo CH: l N-C ONH-RNH--C N i Ha H: wherein R stands for a member of the group consisting of aliphatic and carbocyclic radicals, and the derivatives of the said compounds, wherein at least one hydrogen atom of the nuclear bound ethylene group is substituted by a hydrocarbon radical, and subsequently drying and baking the impregnated material in order to simultaneously enhance tensile strength, crease-resistance, hydrophobic properties and to diminish the tendency to splitting, shrinking and swelling of'the cellulose material.

2. The process of preventing the tendency of splitting of cellulose fibers which become downy when used, especially on rubbing in a wet condition which comprises impregnating the material with a member of the group consisting of compounds of the general formula:

wherein R stands for a member of the group consisting of aliphatic and carbocyclic radicals, and the derivatives of the said compounds, wherein at least one hydrogen atom of the nuclear bound ethylene group is substituted by a hydrocarbon radical, and subsequently drying and baking the impregnated material.

3. The process of producing gloss and embossing eifects fast to washing on fibrous material containing cellulose which comprises impregnating the material with a member of the group con sisting of compounds of the general formula:

group consisting of compounds of the general formula:

HzC CH:

wherein R stands for a member of the group consisting of aliphatic and carbocyclic radicals, and the derivatives of the said compounds,

wherein at least one hydrogen atom of the nuand subsequently drying and hiking the impregnated material.

6. The process of improving the properties of cellulose fibrous material which comprises impregnating the material with hexamethylene dipregnating the material and subsequently nated material.

drying and baking the impreg- 7. The process of improving the properties of and subsequently drying and baking the nated material.

8. The process of improving the properties 01. cellulose fibrous material which comprises impregnating the material-with the product of the formula: v CH:

impreg- H2 H wherein R stands for a member of the group consisting of aliphatic and carbocyclic radicals, and the derivatives 01' the said compounds, wherein at least'one hydrocarbon atom of the nuclear bound ethylene group is substituted by a hydrocarbon radical drying and baking the impregnated mater a 10. Cellulose fibers having the tendency to become downy in their usual condition, impregnated with a member of the group consisting of compounds of the general formula:

H20 CH2 i NC ONH'RNH-C ON l HI Hz wherein R stands for a member 01' the group consistmg of aliphatic and carbocyclic radicals, and the derivatives of the said compounds, wherein at least one hydrocarbon atom of the nuclear bound ethylene group is substituted by a hydrocarbon radical, said fibers being dried and baked after impregnation, the treated material having no tendency to split.

11. Glossy and embossed fibrous materials containing cellulose obtained by impregnating the material with a'member of the group consisting of compounds of the general formula:

H:C\ /CH1 N-C NHR-NHC0N l/ \l H Hz wherein R stands for a member of the group consisting of aliphatic and carbocyclic radicals, and the derivatives or the said compounds, wherein at least one hydrocarbon atom or the nuclear bound ethylene group is substituted by a hydrocarbon radical, and after previously drying, calendering and heating.

l2. Cellulose fibrous material obtained by impregnating with an alkylene diethylene urea having the general formula:

NC O*NH-alkylene-NHC O-N l i H: H! and subsequently drying and baking the impregnated material.

13. Cellulose fibrous material obtained by impregnating with hexamethylene diethylene urea of the formula:

and subsequently drying and baking the impregnated material.

14. Cellulose fibrous material obtained by impregnating with tetramethylene diethylene urea and subsequently drying and baking the impre nated material.

15. Cellulose fibrous material obtained by impregnating with the product of the formula Cg: 9H: l N-co-NHOcHrONH-c O-N\l 'r BESTIAN. MAX o'rro scntlRMANN.

Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US2518963 *Mar 18, 1946Aug 15, 1950Libbey Owens Ford Glass CoProduction of thermosetting aldehyde reaction products
US2650172 *Jan 21, 1949Aug 25, 1953American Viscose CorpMoistureproofing of nonfibrous cellulosic material
US2893892 *Dec 7, 1954Jul 7, 1959Ct Tech Ind Dit I Textile De FMethod for the coating of glass threads and tissues with artificial resin
US3009831 *Feb 9, 1959Nov 21, 1961Basf AgImpregnated films of regenerated cellulose
US3038776 *May 17, 1960Jun 12, 1962Chance Leon HWrinkle resistant cellulose textiles and processes for producing same
US3039167 *Sep 2, 1959Jun 19, 1962Courtaulds North America IncMethod for improving the properties of fabrics containing cross-linked regenerated cellulose material
US3197463 *Mar 10, 1961Jul 27, 1965Stevens & Co Inc J PCertain aziridine compounds
US3218792 *Oct 2, 1961Nov 23, 1965Courtaulds LtdCellulosic textile material
US3519381 *Aug 22, 1966Jul 7, 1970Chevron ResMethod of imparting permanent crease to fabrics containing free hydroxyl groups
US3542505 *Oct 13, 1967Nov 24, 1970Us AgricultureTreatment of textiles with aziridine-modified polyurethanes
US3642571 *Dec 8, 1969Feb 15, 1972Sun Chemical CorpA method of sizing cellulosic fibers using an n,n,-(x-alkyl)-n-carbamate{13 (n{11 {40 ,n{11 {40 -alkylen)urea
US4011613 *Nov 18, 1975Mar 15, 1977The United States Of America As Represented By The Secretary Of AgricultureDurable-press properties in cotton containing fabrics via polymeric N-methylol reagents
US4954540 *Mar 3, 1988Sep 4, 1990Polyplastics Co., Ltd.Fireproof, bisaziridine derivatives
Classifications
U.S. Classification428/171, 427/359, 8/115.6, 8/191, 524/86, 8/183, 427/381, 428/362, 442/148, 28/166, 548/964, 8/185
International ClassificationD06M13/487, D06M15/61, C07D203/20
Cooperative ClassificationC07D203/20, D06M15/61, D06M13/487
European ClassificationC07D203/20, D06M13/487, D06M15/61