US2588640A - Hydrofugation of textile materials - Google Patents
Hydrofugation of textile materials Download PDFInfo
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- US2588640A US2588640A US58370A US5837048A US2588640A US 2588640 A US2588640 A US 2588640A US 58370 A US58370 A US 58370A US 5837048 A US5837048 A US 5837048A US 2588640 A US2588640 A US 2588640A
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- condensation
- carbon atoms
- fatty alcohol
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- 239000004753 textile Substances 0.000 title claims description 21
- 239000000463 material Substances 0.000 title claims description 16
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 45
- 239000000047 product Substances 0.000 claims description 33
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 30
- 239000007859 condensation product Substances 0.000 claims description 24
- 150000002191 fatty alcohols Chemical class 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 18
- 229940015043 glyoxal Drugs 0.000 claims description 15
- -1 METHYLOL GROUPS Chemical group 0.000 claims description 13
- 238000009833 condensation Methods 0.000 claims description 12
- 230000005494 condensation Effects 0.000 claims description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 9
- 239000004202 carbamide Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 230000002708 enhancing effect Effects 0.000 claims description 8
- 229920000877 Melamine resin Polymers 0.000 claims description 7
- 150000001408 amides Chemical class 0.000 claims description 7
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 7
- YIKSCQDJHCMVMK-UHFFFAOYSA-N Oxamide Chemical compound NC(=O)C(N)=O YIKSCQDJHCMVMK-UHFFFAOYSA-N 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 2
- 238000000034 method Methods 0.000 description 24
- 239000002609 medium Substances 0.000 description 23
- 125000004432 carbon atom Chemical group C* 0.000 description 17
- 230000002209 hydrophobic effect Effects 0.000 description 15
- 238000005406 washing Methods 0.000 description 15
- 239000004744 fabric Substances 0.000 description 13
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 10
- 239000003995 emulsifying agent Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000000839 emulsion Substances 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000003368 amide group Chemical group 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- AVFZOVWCLRSYKC-UHFFFAOYSA-N 1-methylpyrrolidine Chemical compound CN1CCCC1 AVFZOVWCLRSYKC-UHFFFAOYSA-N 0.000 description 1
- 229920002955 Art silk Polymers 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- 241000272201 Columbiformes Species 0.000 description 1
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 1
- AHVYPIQETPWLSZ-UHFFFAOYSA-N N-methyl-pyrrolidine Natural products CN1CC=CC1 AHVYPIQETPWLSZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229940097275 indigo Drugs 0.000 description 1
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- MNQOPPDTVHYCEZ-UHFFFAOYSA-N n-(hydroxymethyl)formamide Chemical compound OCNC=O MNQOPPDTVHYCEZ-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N sulfurochloridic acid Chemical compound OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 229960002415 trichloroethylene Drugs 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- 229940099259 vaseline Drugs 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
- C08G12/10—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with acyclic compounds having the moiety X=C(—N<)2 in which X is O, S or —N
- C08G12/12—Ureas; Thioureas
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
- C08G12/22—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with carboxylic acid amides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
- C08G12/30—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with substituted triazines
- C08G12/32—Melamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/40—Chemically modified polycondensates
- C08G12/42—Chemically modified polycondensates by etherifying
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
- Y10S8/17—Glyoxal and polyaldehyde treatment of textiles
Definitions
- the efiects obtained are perfectly resisting not only to the known washing methods but also to most tinctorial baths, so that the treatment may be eifected at any finishing stage of the textile materials. Since the treatment is efiected in an only slightly acid medium, it does not cause any modification of the dye nor any damage to the fibre. Moreover the hydrophobic effect obtained does not affect in any manner the air permeability of the fabrics.
- the preparation of the products intended for thetreatment according to the invention may be effected by dissolving when heated and in an aqueous medium into a product prepared according to the method described in the above mentioned. application, Serial No. 58,156, a small amount less-than 7%, for example about 1%, of an emulsifying agent preferably a sulphonate of a fatty alcohol, after which the said solution is emulsified with such an amount of a monovalent fatty alcohol containing a number of carbon atoms greater than ten, preferably from C15 to C20, for instance n-octadecyl alcohol that only a part of the methylol groups present may be etherified by the said alcohol, then, after acidification, the mixture is heated with reflux while vigorously stirring, until the reaction is completed. When cooling a white paste easily emulsifiable in distilled water is obtained.
- the sulphonate .used as an emulsifier may conveniently be that of the alcohol used for the condensation.
- emulsifier which may be prepared, for example by condensing n-octadecyl alcohol with about moles of ethylene oxide.
- the amount of emulsifier to be added depends on the hardness of the used water and the harder the said Water the greater the added amount of emulsifier. As an illustration, for a water having a hydrotimetric of 20-40 there will be-added 0.5 to 1% in weight of emulsifier.
- condensation products with a moderately soft parafin, having for example a melting point of about to C. a natural wax or a similar material easily soluble in fatty alcohols and producing a highly hydrophobic effect, the said substance, according to the quite unexpected findings of the applicant are then fixed upon the fibre and form thereon a combination which resists perfectly to the known washing methods.
- a moderately soft parafin having for example a melting point of about to C. a natural wax or a similar material easily soluble in fatty alcohols and producing a highly hydrophobic effect
- the treatment of textile fabrics or materials with the products obtained according to the method described above is effected according to a mode of operation similar to that described in the patent application hereinbefore mentioned: the condensation products are set into a milky emulsion with water, then a catalyst such as ammonium nitrate is added and the textile product or fabric is impregnated with the said emulsion after which the product is wrung, dried and heated at a temperature preferably of about 110 to 120 C. for about 15 minutes.
- the hydrophobic efiect obtained on the textile products thus treated is materially stronger than that obtained on the same textile products by the known methods.
- the most remarkable fact is however that this hydrophobic eifect as already mentioned above resists in a manner substantially absolute to the known washing method (washing at ebullition with soap sodium carbonate, chemical washing and the like) as well as to the tinctorial baths even to the aggressive baths used for the indigo and sulphur colouring matters.
- Example 1.6 kg. urea is dissolved into 5.8 kg. of diluted aqueous glyoxal solution.
- the mixture is then acidified, for example by means of a small amount of high concentration hydrochloric acid and heated to ebullition.
- the mixture is allowed to cool down.
- the white precipitate of. glyoxal-diurea is separated and then mixed with an alkaline aqueous solution of formaldehyde at 30% and the product thus obtained is then heated at ebuliition until the formaldehyde is combined.
- the textile material to be treated was for example a regenerated cellulose fabric, after having been treated it is soft, agreeable and fleecy to the touch.
- the hydrophobic effect obtained with the method according to the invention is about 9 to 10 times higher than the effect obtained with the best methods heretofore known.
- an ebullition with soap-sodium carbonate the hydrophobic eifect obtained with the present method remains substantially unchanged, while the effect obtained with the best methods heretofore known drops after one single washing with soap-sodium carbonate at only 60 C., to of its original value.
- the swelling power drops from the original value l00'to value 50 after the treatment; the said value of 50 is no more varied by the washings at ebullition with soap-sodium carbonate.
- a method according to claim 7 in-which the number of carbon atoms is comprised between 15 and 20.
- a method of treating textile materials with a view to hydrophobing the same consisting in impregnating the textile product to be treated with a solution of a condensation product according to claim 7 in the presence of a catalyst whereupon the said textile product is wrung, dried and heated.
- a method of manufacturing condensation products easily emulsifiable in water intended for enhancing the qualities of textile materials and more particularly for hldrophobing the same consisting in heating in an acid medium a monovalent fatty alcohol containing at least 10 carbon atoms and not more than 20 carbon atoms, with a condensation product resulting from two steps: the first of which consists in the condensation of an amide selected from the group consisting of urea, melamine and oxamide, in an acid medium, with glyoxal; and the second step consisting in condensing the product thus obtained with formaldehyde in an alkaline medium, the amount of fatty alcohol used being such that only a portion of the methylol groups present is etherified.
- a method of manufacturing condensation products easily emulsifiable in water intended for enhancing the qualities of textile materials and more particularly for hydrophobing the same consisting in heating in an acid medium a monovalent fatty alcohol containing at least 10 carbon atoms and not more than 20 carbon atoms, with a condensation product resulting from two steps: the first of which consists in the condensation of an amide selected from the group consisting of urea, melamine and oxamide, in an acid medium, with such an amount of glyoxal that at most 50% of the hydrogen atoms of the amide groups present are substituted from the glyoxal; the second step consisting in condensing the product thus obtained with formaldehyde in an alkaline medium, the amount of fatty alcohol used being such that only a portion of the methylol groups present is etherified.
- a method of manufacturing condensation products easily emulsifiable in water intended for enhancing the qualities of textile materials and more particularly for hydrophobing the same consisting in heating in an acid medium a monovalent fatty alcohol containing at least 10 carbon atoms and not more than 20 carbon atoms, with a condensation product resulting from two steps: the first of which consists in the condensation of urea in an acid medium with glyoxal; and the second step consisting in condensing the product thus obtained with formaldehyde in an alkaline medium, the amount of fatty alcohol used being such that only a portion of the methylol groups present is etherified.
- a method of manufacturing condensation products easily emulsifiable in water intended for enhancing the qualities of textile materials and more particularly for hydrophobing the same consisting in heating in an acid medium a monovalent fatty alcohol containing at least 10 carbon atoms and not more than 20 carbon atoms, with a condensation product resulting from two steps: the first of which consists in the condensation of urea in an acid medium with such an amount of glyoxal that at most 50% of the hydrogen atoms of the amide groups present are substituted from the glyoxal; the second step consisting in condensing the product thus obtained with formaldehyde in an alkaline medium, the amount of fatty alcohol used being such that only a portion of the methylol groups present is etherified.
- a method of manufacturing condensation products easily emulsifiable in water intended for enhancing the qualities of textile materials and more particularly for hydrophobing the same consisting in heating in an acid medium a monovalent fatty alcohol containing at least 10 carbon atoms and not more than 20 carbon atoms, with a condensation product resulting from two steps: the first of which consists in the condensation of melamine in an acid medium with glyoxal; and the second step consisting in condensing the product thus obtained with formaldehyde in an alkaline medium, the amount of fatty alcohol used being such that only a portion of the methylol groups present is etherified.
- a method of manufacturing condensation products easily emulsifiable in water intended for enhancing the qualities of textile materials and more particularly for hydrophobing the same consisting in heating in an acid medium a monovalent fatty alcohol containing at least 10 carbon atoms and not more than 20 carbon atoms, with a condensation product resulting from two steps: the first of which consists in the condensation of melamine in an acid medium with such an amount of glyoxal that at most 50% of the hydrogen atoms of the amide groups present are substituted from the glyoxal; the second step consisting in condensing the product thus obtained with formaldehyde in an alkaline medium, the amount of fatty alcohol used being such that only a portion of the methylol groups present is etherified.
- the condensation products obtained by heating in an acid medium a monovalent fatty alcohol containing at least 10 carbon atoms and not more than 20 carbon atoms with a condensation product resulting from two steps: the first of which consists in the condensation of an amide selected from the group consisting of urea, melamine and oxamide, in an acid medium with glyoxal; and the second step consisting in condensing the product thus obtained with formaldehyde in an alkaline medium, the amount of fatty alcohol used being such that only a portion of the methylol groups present is etherified.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Description
Patented Mar. 11, 1952 HYDROFUGATION OF TEXTILEMATERIALS Ren Lon Lehmann, Paris, and Josef Lintner, La Garenne Colombes, France, assignors to Bozel-Maletra Societe Industrielle dc Produits Chimiques, Paris, France, a corporation of France No Drawing. Application November 4, 1948, Se-
rial No. 58,370. In France April 26, 1948 13 Claims. (01. zen-67.6)
Some methods have already been proposed with a view to hydrophobing fabrics but, up to the present time none of them has made it possible to obtain a fibre which is both hydrophobic and strong, has a stable form and the hydrophobic efiect of which is resisting to washing.
Now the applicants have found that it is possible to obtain in a simple manner both a strong unshrinkable fibre and, on the said fibre, a hydrophobic efiect resisting to the known washing methods (such as the Washing at ebullition with soap and sodium carbonate usually used for ordinary cotton, cellulose cotton and artificial silk or the chemical washing generally used for W001) by treating the textile fabrics or materials with stuffs obtained by condensing with a monovalent fatty alcohol containing a number of carbon atoms greater than 10, preferably from C15 to C in the presence of a weak acid, the products obtained according to the method described in the United'States patent application No. 58,156 filed November 3, 1948 now Patent No. 2,574,114, issued November 6, 1951, for Water-soluble condensation products for enhancing the qualities of textile materials viz the products resulting from the condensation of an amide selected from the group consisting of urea, melamine and oxamide successively with glyoxal and with formaldehyde. In said copending application it is taught that by condensing an amide such as urea,
portion, preferably not exceeding 50%, of the reactive nitrogen of the amide and by then treating the condensation products thus obtained in an alkaline medium with an amount of formaldehyde at least equal to the amount, stoichiometrically, to fix the remaining reactive nitrogen, it is very easy to obtain water soluble products containing in dry weight up to 45% of formaldehyde in combined form and having certain remarkable properties resulting from the presence of the glyoxal in the molecule; although the formaldehyde is thus combined in.the molecule as a methylol group fixed on the nitrogen and although these said products are stable, nonvolatile and not entrainable by aqueous vapor, nevertheless they still provide all chemical reactions of free formaldehyde without the risk of self-condensation into products having a higher molecular weight which would be difiicultly soluble in water. In particular these methylols very easily form acetals with the hydroxyl groups of cellulose, everiin the presence of water and even under the mere action of only slightly acid catalysts, such as ammonium nitrate. of hydrophobing is distinguishable from the known-methods bybeing easier to embody and by its remarkable effects: the reagents are used in an aqueous solution, which is a great advantage.
On the other hand, the efiects obtained are perfectly resisting not only to the known washing methods but also to most tinctorial baths, so that the treatment may be eifected at any finishing stage of the textile materials. Since the treatment is efiected in an only slightly acid medium, it does not cause any modification of the dye nor any damage to the fibre. Moreover the hydrophobic effect obtained does not affect in any manner the air permeability of the fabrics.
- The preparation of the products intended for thetreatment according to the invention may be effected by dissolving when heated and in an aqueous medium into a product prepared according to the method described in the above mentioned. application, Serial No. 58,156, a small amount less-than 7%, for example about 1%, of an emulsifying agent preferably a sulphonate of a fatty alcohol, after which the said solution is emulsified with such an amount of a monovalent fatty alcohol containing a number of carbon atoms greater than ten, preferably from C15 to C20, for instance n-octadecyl alcohol that only a part of the methylol groups present may be etherified by the said alcohol, then, after acidification, the mixture is heated with reflux while vigorously stirring, until the reaction is completed. When cooling a white paste easily emulsifiable in distilled water is obtained.
.The sulphonate .used as an emulsifier may conveniently be that of the alcohol used for the condensation.
It is also possible to operate without any emulsifier. In this case a product prepared according to the above mentioned patent application is dissolved into solvents having a good afiinity for water and a good dissolving power for fatty alcohols but which does not react with the methyl- 01 groups of the above products, e. g. N-methyl pyrrolidine, dimethyl formamide, methylol formamide, or other similar solvent, after which the water is first separated from the mixture by distillation, then the necessary amount of fatty alcohol is added and then, after acidification, the mixture is heated for a few hours. There is thus obtained nearly colourless products which dissolve in water to give a milky emulsion. I
In order that the emulsions of the products thus obtained be stable even with hard water, it is advisable to add further the said products with This method a small quantity of an emulsifier which may be prepared, for example by condensing n-octadecyl alcohol with about moles of ethylene oxide. The amount of emulsifier to be added depends on the hardness of the used water and the harder the said Water the greater the added amount of emulsifier. As an illustration, for a water having a hydrotimetric of 20-40 there will be-added 0.5 to 1% in weight of emulsifier.
In order to obtain a maximum hydrophobic effect it is also advisable to add the condensation products with a moderately soft parafin, having for example a melting point of about to C. a natural wax or a similar material easily soluble in fatty alcohols and producing a highly hydrophobic effect, the said substance, according to the quite unexpected findings of the applicant are then fixed upon the fibre and form thereon a combination which resists perfectly to the known washing methods.
The treatment of textile fabrics or materials with the products obtained according to the method described above is effected according to a mode of operation similar to that described in the patent application hereinbefore mentioned: the condensation products are set into a milky emulsion with water, then a catalyst such as ammonium nitrate is added and the textile product or fabric is impregnated with the said emulsion after which the product is wrung, dried and heated at a temperature preferably of about 110 to 120 C. for about 15 minutes.
The hydrophobic efiect obtained on the textile products thus treated is materially stronger than that obtained on the same textile products by the known methods. The most remarkable fact is however that this hydrophobic eifect as already mentioned above resists in a manner substantially absolute to the known washing method (washing at ebullition with soap sodium carbonate, chemical washing and the like) as well as to the tinctorial baths even to the aggressive baths used for the indigo and sulphur colouring matters.
When treating, in particular cellulose fibres, there is obtained simultaneously with the hydrophobic effect a reduction of the swelling power, an increase of the resistance to friction and an absolute form stability (unshrinkability).
The following example illustrates the invention but does not limit its scope in any manner.
Example 1.6 kg. urea is dissolved into 5.8 kg. of diluted aqueous glyoxal solution. The mixture is then acidified, for example by means of a small amount of high concentration hydrochloric acid and heated to ebullition. As soon as the glyoxal is combined, the mixture is allowed to cool down. The white precipitate of. glyoxal-diurea is separated and then mixed with an alkaline aqueous solution of formaldehyde at 30% and the product thus obtained is then heated at ebuliition until the formaldehyde is combined.
0.055 kg. of a moderately concentrated sulphonate obtained by a sulphonation of n-octadecyl alcohol with chlorosulphonic acid followed by a neutralization with caustic soda lie is dissolved while stirring at -80 G. into 5.3
kg. of an aqueous solution at about 50% of the condensation product prepared as described above. There is then added, while stirring, 0.54 kg. n-octadecyl alcohol and the whole is acidified with acetic acid. The mixture is then heated with reflux, while vigorously stirring until the reaction is completed. Finally one dissolves into the mixture 0.75% by weight of the condensation product of about 20 moles of ethylene oxide with 1 mole of n-octadecyl-alcohol and paraffin having a melting point of 43 to 46 C. is finally also introduced. The still warm mixture is removed into an emulsioning apparatus and cooled down slowly therein to the room temperature. After cooling the paste should be homogeneous and its aspect should be similar with that off Vaseline.
One then prepares in the cold, while stirring, with water having a hydrotimetric degree of 30, a milky emulsion containing per litre of water 50 g. of the above condensation product. ammonium nitrate per litre are dissolved into the said emulsion, then the fabric to be treated is immersed into the solution while stirring for a few minutes. The fabric is then wrung until it remains on the fibre only a weight of solution equal to the weight of the original dry fabric. The fabric is then dried at C. in a hot air current and finally the dry fabric is further heated for about 15 minutes at about C.
Under the condition of this example, if the textile material to be treated was for example a regenerated cellulose fabric, after having been treated it is soft, agreeable and fleecy to the touch.
The hydrophobic effect obtained has been compared, before and after washing, with the effect obtained on the same fabric with the best hydrophobing methods known up to the present time:
Before the first washing, the hydrophobic effect obtained with the method according to the invention is about 9 to 10 times higher than the effect obtained with the best methods heretofore known. After five washings an ebullition with soap-sodium carbonate the hydrophobic eifect obtained with the present method remains substantially unchanged, while the effect obtained with the best methods heretofore known drops after one single washing with soap-sodium carbonate at only 60 C., to of its original value.
Even after 25 to 30 washings at ebullition, which however will probably never occur in the practice, the hydrophobic effect obtained with the present method is still about 50% of its original value; it thus remains still materially higher than the hydrophobic effect obtained with the best methods heretofore known.
In the above example the swelling power drops from the original value l00'to value 50 after the treatment; the said value of 50 is no more varied by the washings at ebullition with soap-sodium carbonate.
Similarly, the hydrophobic effect and the swelling power remain unchanged after extraction of the fabric with trichloro ethylene.
All above values are given to make the matter clear. In some cases, far more better results may be obtained.
What we claim is:
1. A method according to claim 7 in-which the number of carbon atoms is comprised between 15 and 20.
2. A method according to claim 7 in which the condensation with the alcohol is effected without emulsifier but in the presence of a solvent having a good dissolving power for fatty alcohols and the product to be condensed with the alcohol but which does not react on the methylol groups of the product to be condensed with the alcohol. 1
3. A method of treating textile materials with a view to hydrophobing the same, consisting in impregnating the textile product to be treated with a solution of a condensation product according to claim 7 in the presence of a catalyst whereupon the said textile product is wrung, dried and heated.
4. A method according to claim 3 in which the catalyst is ammonium nitrate.
5. A method according to claim 3 in which the heating of the textile material is made at a temperature of 110 to 120 C. for about 15 minutes.
6. As new products of manufacture the hydrophobed textile products obtained by the method according to claim 3.
7. A method of manufacturing condensation products easily emulsifiable in water intended for enhancing the qualities of textile materials and more particularly for hldrophobing the same, consisting in heating in an acid medium a monovalent fatty alcohol containing at least 10 carbon atoms and not more than 20 carbon atoms, with a condensation product resulting from two steps: the first of which consists in the condensation of an amide selected from the group consisting of urea, melamine and oxamide, in an acid medium, with glyoxal; and the second step consisting in condensing the product thus obtained with formaldehyde in an alkaline medium, the amount of fatty alcohol used being such that only a portion of the methylol groups present is etherified.
8. A method of manufacturing condensation products easily emulsifiable in water intended for enhancing the qualities of textile materials and more particularly for hydrophobing the same, consisting in heating in an acid medium a monovalent fatty alcohol containing at least 10 carbon atoms and not more than 20 carbon atoms, with a condensation product resulting from two steps: the first of which consists in the condensation of an amide selected from the group consisting of urea, melamine and oxamide, in an acid medium, with such an amount of glyoxal that at most 50% of the hydrogen atoms of the amide groups present are substituted from the glyoxal; the second step consisting in condensing the product thus obtained with formaldehyde in an alkaline medium, the amount of fatty alcohol used being such that only a portion of the methylol groups present is etherified.
9. A method of manufacturing condensation products easily emulsifiable in water intended for enhancing the qualities of textile materials and more particularly for hydrophobing the same, consisting in heating in an acid medium a monovalent fatty alcohol containing at least 10 carbon atoms and not more than 20 carbon atoms, with a condensation product resulting from two steps: the first of which consists in the condensation of urea in an acid medium with glyoxal; and the second step consisting in condensing the product thus obtained with formaldehyde in an alkaline medium, the amount of fatty alcohol used being such that only a portion of the methylol groups present is etherified.
10. A method of manufacturing condensation products easily emulsifiable in water intended for enhancing the qualities of textile materials and more particularly for hydrophobing the same, consisting in heating in an acid medium a monovalent fatty alcohol containing at least 10 carbon atoms and not more than 20 carbon atoms, with a condensation product resulting from two steps: the first of which consists in the condensation of urea in an acid medium with such an amount of glyoxal that at most 50% of the hydrogen atoms of the amide groups present are substituted from the glyoxal; the second step consisting in condensing the product thus obtained with formaldehyde in an alkaline medium, the amount of fatty alcohol used being such that only a portion of the methylol groups present is etherified.
11. A method of manufacturing condensation products easily emulsifiable in water intended for enhancing the qualities of textile materials and more particularly for hydrophobing the same, consisting in heating in an acid medium a monovalent fatty alcohol containing at least 10 carbon atoms and not more than 20 carbon atoms, with a condensation product resulting from two steps: the first of which consists in the condensation of melamine in an acid medium with glyoxal; and the second step consisting in condensing the product thus obtained with formaldehyde in an alkaline medium, the amount of fatty alcohol used being such that only a portion of the methylol groups present is etherified.
12. A method of manufacturing condensation products easily emulsifiable in water intended for enhancing the qualities of textile materials and more particularly for hydrophobing the same, consisting in heating in an acid medium a monovalent fatty alcohol containing at least 10 carbon atoms and not more than 20 carbon atoms, with a condensation product resulting from two steps: the first of which consists in the condensation of melamine in an acid medium with such an amount of glyoxal that at most 50% of the hydrogen atoms of the amide groups present are substituted from the glyoxal; the second step consisting in condensing the product thus obtained with formaldehyde in an alkaline medium, the amount of fatty alcohol used being such that only a portion of the methylol groups present is etherified.
13. As new products of manufacture, the condensation products obtained by heating in an acid medium a monovalent fatty alcohol containing at least 10 carbon atoms and not more than 20 carbon atoms, with a condensation product resulting from two steps: the first of which consists in the condensation of an amide selected from the group consisting of urea, melamine and oxamide, in an acid medium with glyoxal; and the second step consisting in condensing the product thus obtained with formaldehyde in an alkaline medium, the amount of fatty alcohol used being such that only a portion of the methylol groups present is etherified.
, RENE LEON LEHMANN.
J OSEF LINTNER.
REFERENCES CITED The following references are of record in the file of this patent:
UNITED STATES PATENTS Number Name Date 2,427,504 Morgan Sept. 16, 1947 FOREIGN PATENTS a Number Country Date 494,700 Great Britain 7.-.- Oct. 13, 1938
Claims (1)
- 7. A METHOD OF MANUFACTURING CONDENSATION PRODUCTS EASILY EMULSIFIABLE IN WATER INTENDED FOR ENHANCING THE QUALITIES OF TEXTILE MATERIALS AND MORE PARTICULARLY FOR HLDROPHOBING THE SAME, CONSISTING IN HEATING IN AN ACID MEDIUM A MONOVALENT FATTY ALCOHOL CONTAINING AT LEAST 10 CARBON ATOMS AND NOT MORE THAN 20 CARBON ATOMS, WITH A CONDENSATION PRODUCT RESULTING FROM TWO STEPS: THE FIRST OF WHICH CONSISTS IN THE CONDENSATION OF AN AMIDE SELECTED FROM THE GROUP CONSISTING OF UREA, MELAMINE AND OXAMIDE, IN AN ACID MEDIUM, WITH GLYOXAL; AND THE SECOND STEP CONSISTING IN CONDENSING THE PRODUCT THUS OBTAINED WITH FORMALDEHYDE IN AN ALKALINE MEDIUM, THE AMOUNT OF FATTY ALCOHOL USED BEING SUCH THAT ONLY A PORTION OF THE METHYLOL GROUPS PRESENT IS ETHERIFIED.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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FR2588640X | 1948-04-26 |
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US2588640A true US2588640A (en) | 1952-03-11 |
Family
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Application Number | Title | Priority Date | Filing Date |
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US58370A Expired - Lifetime US2588640A (en) | 1948-04-26 | 1948-11-04 | Hydrofugation of textile materials |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2731364A (en) * | 1951-08-18 | 1956-01-17 | Basf Ag | Process for improving cellulose textile materials and product thereof |
US3645667A (en) * | 1970-05-22 | 1972-02-29 | Us Agriculture | Nonaqueous cross linking of cellulose with a methylolated urea in the absence of an acidic catalyst |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB494700A (en) * | 1936-05-01 | 1938-10-31 | Du Pont | Improvements in or relating to the production of urea-aldehyde synthetic resins |
US2427504A (en) * | 1944-07-22 | 1947-09-16 | American Maize Prod Co | Producing aldehyde-prolamine reaction products |
-
1948
- 1948-11-04 US US58370A patent/US2588640A/en not_active Expired - Lifetime
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB494700A (en) * | 1936-05-01 | 1938-10-31 | Du Pont | Improvements in or relating to the production of urea-aldehyde synthetic resins |
US2427504A (en) * | 1944-07-22 | 1947-09-16 | American Maize Prod Co | Producing aldehyde-prolamine reaction products |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2731364A (en) * | 1951-08-18 | 1956-01-17 | Basf Ag | Process for improving cellulose textile materials and product thereof |
US3645667A (en) * | 1970-05-22 | 1972-02-29 | Us Agriculture | Nonaqueous cross linking of cellulose with a methylolated urea in the absence of an acidic catalyst |
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