EP0429983B1 - Water and oil repellant composition - Google Patents
Water and oil repellant composition Download PDFInfo
- Publication number
- EP0429983B1 EP0429983B1 EP90121949A EP90121949A EP0429983B1 EP 0429983 B1 EP0429983 B1 EP 0429983B1 EP 90121949 A EP90121949 A EP 90121949A EP 90121949 A EP90121949 A EP 90121949A EP 0429983 B1 EP0429983 B1 EP 0429983B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- carbon atoms
- compositions
- component
- polyurethane
- groups
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 239000000203 mixture Substances 0.000 title claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title description 11
- 239000004753 textile Substances 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 239000006185 dispersion Substances 0.000 claims description 11
- 239000004814 polyurethane Substances 0.000 claims description 11
- 229920002635 polyurethane Polymers 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 10
- 229910052731 fluorine Inorganic materials 0.000 claims description 10
- 239000011737 fluorine Substances 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 9
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 7
- 239000004606 Fillers/Extenders Substances 0.000 claims description 6
- 150000007945 N-acyl ureas Chemical group 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 229920001228 polyisocyanate Polymers 0.000 claims description 4
- 239000005056 polyisocyanate Substances 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229920000058 polyacrylate Polymers 0.000 claims 1
- 239000004744 fabric Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 229920000742 Cotton Polymers 0.000 description 7
- -1 methylol compounds Chemical class 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000005871 repellent Substances 0.000 description 6
- 206010034912 Phobia Diseases 0.000 description 5
- 238000009472 formulation Methods 0.000 description 5
- 208000019899 phobic disease Diseases 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 101000623895 Bos taurus Mucin-15 Proteins 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 4
- 239000012188 paraffin wax Substances 0.000 description 4
- 230000002940 repellent Effects 0.000 description 4
- 229920003002 synthetic resin Polymers 0.000 description 4
- 239000000057 synthetic resin Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 150000002222 fluorine compounds Chemical class 0.000 description 3
- 230000002262 irrigation Effects 0.000 description 3
- 238000003973 irrigation Methods 0.000 description 3
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- IUUONVQOMMQAEH-UHFFFAOYSA-N 1-methyl-2,3-dihydro-1$l^{5}-phosphole 1-oxide Chemical compound CP1(=O)CCC=C1 IUUONVQOMMQAEH-UHFFFAOYSA-N 0.000 description 2
- MQLQAXIVFGHSDE-UHFFFAOYSA-N 1-methyl-2,5-dihydro-1$l^{5}-phosphole 1-oxide Chemical compound CP1(=O)CC=CC1 MQLQAXIVFGHSDE-UHFFFAOYSA-N 0.000 description 2
- ZEYUSQVGRCPBPG-UHFFFAOYSA-N 4,5-dihydroxy-1,3-bis(hydroxymethyl)imidazolidin-2-one Chemical compound OCN1C(O)C(O)N(CO)C1=O ZEYUSQVGRCPBPG-UHFFFAOYSA-N 0.000 description 2
- NNTWKXKLHMTGBU-UHFFFAOYSA-N 4,5-dihydroxyimidazolidin-2-one Chemical compound OC1NC(=O)NC1O NNTWKXKLHMTGBU-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 2
- 210000002268 wool Anatomy 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- 235000021357 Behenic acid Nutrition 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- JQALNNOQTGZTJZ-UHFFFAOYSA-N [[4,6-bis[bis(methoxymethyl)amino]-1,3,5-triazin-2-yl]-(methoxymethyl)amino]methanol Chemical compound COCN(CO)C1=NC(N(COC)COC)=NC(N(COC)COC)=N1 JQALNNOQTGZTJZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical group 0.000 description 1
- METKIMKYRPQLGS-UHFFFAOYSA-N atenolol Chemical compound CC(C)NCC(O)COC1=CC=C(CC(N)=O)C=C1 METKIMKYRPQLGS-UHFFFAOYSA-N 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 229960000448 lactic acid Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 235000019809 paraffin wax Nutrition 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 235000019271 petrolatum Nutrition 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 238000009988 textile finishing Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- 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
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
-
- 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
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
- D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine
-
- 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
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
- Y10T442/2164—Coating or impregnation specified as water repellent
- Y10T442/2172—Also specified as oil repellent
Definitions
- the present invention relates to water repellents and oil repellents based on perfluoroalkyl group-containing polymers.
- fluorine compounds are rarely used alone in equipment formulations.
- urea resins, melamine resins or other resins mostly based on methylol compounds.
- fluorine compounds are combined with extenders, e.g. with paraffin fractions or paraffin waxes and / or fatty acid esters and melamine resins (cf. Chwala / Anger: "Handbuch der Textilosstoff", Verlag Chemie-Weinheim-New York 1977, pages 745 to 747, 721).
- Suitable components A) are commercially available perfluoroalkyl polymers from the series of perfluofalkyl group-containing vinyl, styryl, vinylidene, acrylic, methacrylic and ⁇ -chloroacrylic polymers with 4 to 20 carbon atoms in the perfluoroalkyl radical.
- Preferred compounds are acrylate (co) polymers with a fluorine content of 20 to 45, in particular 35 to 45% by weight.
- Such compounds were preferably used in the form of their aqueous emulsions or dispersions.
- the cationically modified polyurethanes are very particularly preferably used in the form of their aqueous solutions or dispersions and contain a content of incorporated ternary or quaternary ammonium groups which ensures their solubility or dispersibility in water, and, if appropriate, of built-in ethylene oxide units present within a polyether chain, the content of ternaries or quaternary ammonium compounds at 2 to 300 milliequivalents per 100 g of solid and the content of the ethylene oxide units mentioned is from 0 to 25% by weight, based on the solid.
- the agents according to the invention serve in particular as textile finishing agents for the phobing of textiles. They are in the form of aqueous dispersions with a solids content of 10 to 50%, preferably 15 to 40%. With a solids content of 15% this is Mixing ratio of perfluoro compound A) to cationically modified polyurethanes B) in the finishing liquor, for example at 0.5: 1 to 10: 1, in particular at 1: 1 to 5: 1, based on the solids content.
- aqueous dispersions according to the invention can contain further components such as other textile auxiliaries, e.g. Synthetic resins.
- These further constituents are preferably nonionic or cationic in nature.
- the aqueous dispersions are diluted with water before use on the textile materials.
- the application amounts are chosen so that a coating amount of 0.5 to 15 g, preferably 0.5 to 5 g and in particular 0.5 to 1.5 g of solids of the substance according to the invention per kg of textile material is obtained.
- natural and synthetic materials such as fibers, filaments, yarns, nonwovens, fabrics, knitted fabrics and knitted fabrics made in particular of cellulose and its derivatives but also of polyester, polyamide and polyacrylonitrile materials, wool or silk can be successfully finished.
- hydrophobized or oleophobicized textile structures such as nonwovens or, in particular, fabrics are used, for example, for the production of umbrella coverings, tents, water-repellent clothing or covers, balloon envelopes, awnings, textile floor coverings, packaging materials or footwear,
- the finishing is carried out by known methods, preferably by the pull-out or padding method, for example between room temperature and 40 ° C., but also by splashing or spraying with a subsequent temperature treatment at 80 to 180, preferably 120 to 150 ° C.
- a cotton gabardine fabric with a m2 weight of approx. 240 g was equipped with the following formulations:
- the cotton fabric was soaked in a chassis with the liquors and squeezed between 2 rubber rollers (foulard).
- the liquor absorption was 70% based on the textile weight.
- the samples were dried at 100 ° C and condensed at 150 ° C for 5 minutes.
- the grade for oil repellency corresponds to the highest numbered test liquid that does not wet the fiber material within 30 seconds: Grade 1 lowest value Grade 8 highest value.
- Component I added according to the invention already gives this increase with use, based on solid substance, of 1.5 g / l, while component III, which is not in accordance with the invention, is effective only when 10 g / l is used.
- the cotton swatches finished in Example 1 were washed 5 times at 40 ° C. on a Miele washing machine type W 763 washed with an easy care program with the addition of a household detergent and dried at 80 ° C in a Miele household dryer.
- Component I added in accordance with the invention improves the wash resistance of fluorine finishes in such a way that even after 5 machine washes, the phobia values are retained, while the finishes without extender or with component III drop significantly.
- a dyed polyester / cotton poplin fabric (67% PES / 33% cotton) with a weight of approx. 160 g m2 was equipped with the following formulations on the foulard:
- Component I added according to the invention improves the wash resistance in such a way that even after 5 machine washes, the phobic values are almost completely retained,
- a wool fabric with a weight of 280 g / m2 is padded as follows:
- the fleet uptake was 80%. After treatment at 100 ° C, the tissues are treated for 3 minutes at 140 ° C:
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyurethanes Or Polyureas (AREA)
Description
Die vorliegende Erfindung betrifft Hydrophobierungs- und Oleophobierungsmittel auf der Basis von Perfluoralkylgruppen enthaltenden Polymeren.The present invention relates to water repellents and oil repellents based on perfluoroalkyl group-containing polymers.
Derartige Fluorverbindungen werden in der Praxis in Ausrüstungsformulierungen selten allein eingesetzt. So werden zur besseren Fixierung der Fluorprodukte sowie auch zur Verbesserung der Dimensionsstabilität der Textilsubstrate Harnstoffharze, Melaminharze oder sonstige Harze zumeist auf Basis Methylolverbindungen eingesetzt. Zur Unterstützung der Phobiewerte, meistens Hydrophobiewerte, werden Fluorverbindungen mit Extendern kombiniert, z.B. mit Paraffinfraktionen bzw. Paraffinwachsen und/oder Fettsäureestern und Melaminharzen (vgl. Chwala/Anger: "Handbuch der Textilhilfsmittel", Verlag Chemie-Weinheim-New York 1977, Seiten 745 bis 747, 721).Such fluorine compounds are rarely used alone in equipment formulations. For better fixation of the fluorine products and also to improve the dimensional stability of the textile substrates, urea resins, melamine resins or other resins, mostly based on methylol compounds, are used. To support the phobia values, mostly hydrophobicity values, fluorine compounds are combined with extenders, e.g. with paraffin fractions or paraffin waxes and / or fatty acid esters and melamine resins (cf. Chwala / Anger: "Handbuch der Textilhilfsmittel", Verlag Chemie-Weinheim-New York 1977, pages 745 to 747, 721).
Solche Formulierungen erreichen auch bei herabgesetzten Gehalten an Fluorkomponenten gelegentlich ausreichende bis gute Phobieeffekte auf verschiedenen Substraten, jedoch ist die Permanenz dieser Ausrüstungseffekte gegen Mehrfachwäschen bei 40 oder 60°C in Haushaltswaschmaschinen mit üblichen Haushaltswaschmitteln nicht ausreichend.Such formulations sometimes achieve sufficient levels even when the fluorine component content is reduced to good phobia effects on various substrates, but the durability of these finishing effects against multiple washing at 40 or 60 ° C in household washing machines with common household detergents is not sufficient.
Es ist jedoch wünschenswert, daß eine erhöhte Phobiewirkung durch Zusatz von Extendern erreicht wird und nicht durch Erhöhung der Fluorkomponente. Gleichzeitig sollte bei einer deutlichen Reduzierung der teuren Fluorkomponente der Extender eine normalerweise auftretende Reduzierung der Phobiewerte ausgleichen. In beiden Fällen sollte jedoch eine ausreichende Waschpermanenz gegeben sein.However, it is desirable that an increased phobia effect is achieved by adding extenders and not by increasing the fluorine component. At the same time, a significant reduction in the phobia values should compensate for a significant reduction in the expensive fluorine component of the extenders. In both cases, however, there should be sufficient washing resistance.
Dieses Ziel kann gemäß allgemeinem Stand der Technik jedoch nur erreicht werden, wenn man die Fluorverbindung in der Phobierungsformulierung deutlich erhöht und entsprechend hohe Mengen der Kunstharzkomponente zur besseren Fixierung hinzufügt.According to the general state of the art, however, this goal can only be achieved if the fluorine compound in the phobing formulation is significantly increased and correspondingly large amounts of the synthetic resin component are added for better fixation.
Überraschenderweise wurde nun gefunden, daß man auf verschiedensten Textilsubstraten Phobierungseffekte von hoher Qualität und Permanenz ohne den genannten Nachteil erhält, wenn man als Extender ein kationisch modifiziertes Polyurethan einsetzt.Surprisingly, it has now been found that phobizing effects of high quality and permanence are obtained on a wide variety of textile substrates without the disadvantage mentioned, if a cationically modified polyurethane is used as the extender.
Gegenstand der Erfindung sind somit Hydrophobierungs- und Oleophobierungsmittel enthaltend
- A) ein Perfluoralkylgruppen enthaltendes Polymeres und
- B) ein kationisch modifiziertes Polyurethan, das Acylharnstoffgruppen der Formel
- R
- einen gesättigten oder ungesättigten aliphatischen Kohlenwasserstoffrest mit bis zu 35 Kohlenstoffatomen, vorzugsweise mit 9 bis 22 Kohlenstoffatomen oder einen aromatischen Kohlenwasserstoffrest mit 6 bis 10 Kohlenstoffatomen oder einen araliphatischen Kohlenwasserstoffrest mit 7 bis 10 Kohlenstoffatomen bedeutet.
- A) a polymer containing perfluoroalkyl groups and
- B) a cationically modified polyurethane, the acylurea groups of the formula
- R
- is a saturated or unsaturated aliphatic hydrocarbon residue having up to 35 carbon atoms, preferably having 9 to 22 carbon atoms, or an aromatic hydrocarbon residue having 6 to 10 carbon atoms or an araliphatic hydrocarbon residue having 7 to 10 carbon atoms.
Geeignete Komponenten A) sind handelsübliche Perfluoralkylpolymere aus der Reihe der perfluofalkylgruppenhaltigen Vinyl-, Styryl-, Vinyliden-, Acryl-, Methacryl- und α-Chloracrylpolymeren mit 4 bis 20 C-Atomen im Perfluoralkylrest. Beispiele für diese Produkte sind Polymerisate und Copolymerisate von folgenden Verbindungen:
C₅F₁₁CH₂O₂CC(CH₃)=CH₂
C₇F₁₅CH₂O₂CC(CH₃)=CH₂
C₉F₁₉CH₂O₂CCH=CH₂
C₈F₁₇SO₂N(C₂H₅)C₂H₄O₂CC(CH₃)=CH₂
C₈F₁₇SO₂N(CH₃)C₂H₄O₂CCH=CH₂
C₈F₁₇CON(C₂H₅)C₂H₄O₂CC(CH₃)=CH₂
C₈F₁₇C₂H₄O₂CC(CH₃)=CH₂
C₈F₁₇SO₂N(CH₃)COC(CH₃)=CH₂
C₈F₁₇C₂H₄O₂CCH=CHCO₂C₂H₄C₈H₁₇
C₈F₁₇SO₂N(C₃H₇)C₂H₄OCOH=CH₂
C₈F₁₇SO₂N(CH₃)C₁₁H₂₂OCOCH=CH₂
C₈F₁₇SO₂N(CH₃)C₁₀H₂₀OCOCH=CH₂
C₈F₁₇SO₂N(CH₃)C₁₁H₂₂OCOC(CH₃)=CH₂
C₅F₁₁CH₂OCOC(CH₃)=CH₂
C₇F₁₅CH₂OCOC(CH₃)=CH₂
C₈F₁₇SO₂N(C₂H₅)C₂H₄COOCH=CH₂
C₇F₁₅C₃H₆COOH=CH₂
C₄F₉COOCH₂CH=CH₂
C₈F₁₇SO₂N(C₂H₅)COCH=CH₂
C₇F₁₅CH₂O₂CCH=CHCO₂CH₂C₇F₁₅
C₃F₇CH₂O₂OCF=CH₂
C₃F₇CH₂O₂CCF=CF₂
(C₃F₇)₃CCH₂O₂CCH=CH₂
C₈F₁₇(CH₂)₃O₂CCH=CH₂
C₆F₁₇COCH₂CH₂CH₂O₂CCH=CH₂
C₈F₁₇(CH₂)₁₁O₂CC(CH₃)=CH₂
C₈F₁₇SO₂CH₂CH₂O₂CCH=CH₂
C₈F₁₇SOCH₂CH₂O₂CCH=CH₂
C₈F₁₇CON(C₂H₅)(CH₂)₂O₂CC(CH₃)=CH₂
C₁₂F₂₅SO₂NH(CH₂)₁₁O₂CC(CH₃)=CH₂
C₁₂F₂₅SO₂C₆H₄CH=CH₂
N-Butylperfluoroctansulfonamidoethylacrylat,
N-Ethylperfluoroctansulfonamidoethylmethacrylat,
N-Methylperfluorbutansulfonamidobutylacrylat,
N-Ethylperfluoroctansulfonamidoethyl-α-chloracrylat,
1,1-Dihydroperfluorhexylacrylat,
1,1-Dihydroperfluordecylmethacrylat,
1,1-Dihydroperfluoroctyl-ω-chloracrylat,
3-(Perfluoroctyl)-propylacrylat,
2-(Perfluorheptyl)-ethylmethacrylat,
11-(Perfluoroctyl)-undecylacrylat und
3-(Perfluorheptyl)-propylchloracrylat.Suitable components A) are commercially available perfluoroalkyl polymers from the series of perfluofalkyl group-containing vinyl, styryl, vinylidene, acrylic, methacrylic and α-chloroacrylic polymers with 4 to 20 carbon atoms in the perfluoroalkyl radical. Examples of these products are polymers and copolymers of the following compounds:
C₅F₁₁CH₂O₂CC (CH₃) = CH₂
C₇F₁₅CH₂O₂CC (CH₃) = CH₂
C₉F₁₉CH₂O₂CCH = CH₂
C₈F₁₇SO₂N (C₂H₅) C₂H₄O₂CC (CH₃) = CH₂
C₈F₁₇SO₂N (CH₃) C₂H₄O₂CCH = CH₂
C₈F₁₇CON (C₂H₅) C₂H₄O₂CC (CH₃) = CH₂
C₈F₁₇C₂H₄O₂CC (CH₃) = CH₂
C₈F₁₇SO₂N (CH₃) COC (CH₃) = CH₂
C₈F₁₇C₂H₄O₂CCH = CHCO₂C₂H₄C₈H₁₇
C₈F₁₇SO₂N (C₃H₇) C₂H₄OCOH = CH₂
C₈F₁₇SO₂N (CH₃) C₁₁H₂₂OCOCH = CH₂
C₈F₁₇SO₂N (CH₃) C₁₀H₂₀OCOCH = CH₂
C₈F₁₇SO₂N (CH₃) C₁₁H₂₂OCOC (CH₃) = CH₂
C₅F₁₁CH₂OCOC (CH₃) = CH₂
C₇F₁₅CH₂OCOC (CH₃) = CH₂
C₈F₁₇SO₂N (C₂H₅) C₂H₄COOCH = CH₂
C₇F₁₅C₃H₆COOH = CH₂
C₄F₉COOCH₂CH = CH₂
C₈F₁₇SO₂N (C₂H₅) COCH = CH₂
C₇F₁₅CH₂O₂CCH = CHCO₂CH₂C₇F₁₅
C₃F₇CH₂O₂OCF = CH₂
C₃F₇CH₂O₂CCF = CF₂
(C₃F₇) ₃CCH₂O₂CCH = CH₂
C₈F₁₇ (CH₂) ₃O₂CCH = CH₂
C₆F₁₇COCH₂CH₂CH₂O₂CCH = CH₂
C₈F₁₇ (CH₂) ₁₁O₂CC (CH₃) = CH₂
C₈F₁₇SO₂CH₂CH₂O₂CCH = CH₂
C₈F₁₇SOCH₂CH₂O₂CCH = CH₂
C₈F₁₇CON (C₂H₅) (CH₂) ₂O₂CC (CH₃) = CH₂
C₁₂F₂₅SO₂NH (CH₂) ₁₁O₂CC (CH₃) = CH₂
C₁₂F₂₅SO₂C₆H₄CH = CH₂
N-butyl perfluorooctanesulfonamidoethyl acrylate,
N-ethyl perfluorooctanesulfonamidoethyl methacrylate,
N-methyl perfluorobutanesulfonamidobutylacrylate,
N-ethyl perfluorooctanesulfonamidoethyl-α-chloroacrylate,
1,1-dihydroperfluorohexyl acrylate,
1,1-dihydroperfluorodecyl methacrylate,
1,1-dihydroperfluorooctyl-ω-chloroacrylate,
3- (perfluorooctyl) propyl acrylate,
2- (perfluoroheptyl) ethyl methacrylate,
11- (perfluorooctyl) undecyl acrylate and
3- (perfluoroheptyl) propyl chloroacrylate.
Bevorzugte Verbindungen sind Acrylat-(Co)Polymere mit einem Fluorgehalt von 20 bis 45, insbesondere 35 bis 45 Gew.-%.Preferred compounds are acrylate (co) polymers with a fluorine content of 20 to 45, in particular 35 to 45% by weight.
Verbindungen dieser Art werden beispielsweise in DE-A 1 595 017, 1 595 018, 2 134 978 und 2 939 549 beschrieben.Compounds of this type are described for example in DE-A 1 595 017, 1 595 018, 2 134 978 and 2 939 549.
Derartige Verbindungen wurden vorzugsweise in Form ihrer wäßrigen Emulsionen- bzw. Dispersionen eingesetzt.Such compounds were preferably used in the form of their aqueous emulsions or dispersions.
Die Polyurethan-Komponenten B sind Umsetzungsprodukte von
- a) organischen Polyisocyanaten mit
- b) gegenüber Isocyanatgruppen reaktionsfähige Gruppen aufweisenden Verbindungen
als Aufbaukomponente a) und/oder b) zumindest anteilig Acylharnstoffgruppen der Formel
aufweisende Verbindungen verwendet werden, deren Menge so bemessen wird, daß in dem Polyisocyanat-Additionsprodukt von 0,1 bis 20 Gew.-%, bezogen auf Feststoff-Anteil, der genannten Acylharnstoffgruppen bildenden Struktureinheit der Formel
vorliegen und wobei
- R
- einen gesättigten oder ungesättigten aliphatischen Kohlenwasserstoffrest mit bis zu 35 Kohlenstoffatomen, vorzugsweise mit 9 bis 22 Kohlenstoffatomen oder einen aromatischen Kohlenwasserstoffrest mit 6 bis 10 Kohlenstoffatomen oder einen araliphatischen Kohlenwasserstoffrest mit 7 bis 10 Kohlenstoffatomen bedeutet, oder wobei bei Vorliegen von mehreren Resten R im gleichen Molekül gleichzeitig unterschiedliche, der genannten Definition entsprechende, Reste vorliegen können.
- a) with organic polyisocyanates
- b) compounds having groups which are reactive toward isocyanate groups
as structural component a) and / or b) at least partially acylurea groups of the formula
containing compounds are used, the amount of which is such that in the polyisocyanate addition product from 0.1 to 20% by weight, based on the solids content, of the structural unit of the formula mentioned forming acylurea groups
present and where
- R
- a saturated or unsaturated aliphatic hydrocarbon residue with up to 35 carbon atoms, preferably with 9 to 22 carbon atoms or an aromatic hydrocarbon radical having 6 to 10 carbon atoms or an araliphatic hydrocarbon radical having 7 to 10 carbon atoms, or where, when there are several radicals R in the same molecule, different radicals which correspond to the definition mentioned can be present at the same time.
Ganz besonders bevorzugt werden die kationisch modifizierten Polyurethane in Form ihrer wäßrigen Lösungen oder Dispersionen eingesetzt und enthalten einen ihre Löslichkeit oder Dispergierbarkeit in Wasser gewährleistenden Gehalt an eingebauten ternären oder quaternären Ammoniumgruppen, sowie gegebenenfalls an eingebauten, innerhalb einer Polyetherkette vorliegenden Ethylenoxideinheiten, wobei der Gehalt an ternären oder quaternären Ammoniumverbindungen bei 2 bis 300 Milliäquivalenten pro 100 g Feststoff und der Gehalt an den genannten Ethylenoxideinheiten bei 0 bis 25 Gew.-%, bezogen auf Feststoff, liegt.The cationically modified polyurethanes are very particularly preferably used in the form of their aqueous solutions or dispersions and contain a content of incorporated ternary or quaternary ammonium groups which ensures their solubility or dispersibility in water, and, if appropriate, of built-in ethylene oxide units present within a polyether chain, the content of ternaries or quaternary ammonium compounds at 2 to 300 milliequivalents per 100 g of solid and the content of the ethylene oxide units mentioned is from 0 to 25% by weight, based on the solid.
Derartige Lösungen oder Dispersionen sind an sich bereits bekannt und werden in DE-A 35 23 856 beschrieben.Such solutions or dispersions are already known per se and are described in DE-A 35 23 856.
Die erfindungsgemäßen Mittel dienen insbesondere als Textilausrüstungsmittel für die Phobierung von Textilien. Sie liegen als wäßrige Dispersionen mit einem Feststoffgehalt von 10 bis 50 %, vorzugsweise 15 bis 40 % vor. Bei einem Feststoffgehalt von 15 % beträgt das Mischungsverhältnis von Perfluorverbindung A) zu kationisch modifizierten Polyurethanen B) in der Ausrüstungsflotte beispielsweise bei 0,5:1 bis 10:1, insbesondere bei 1:1 bis 5:1 bezogen auf Feststoffgehalt.The agents according to the invention serve in particular as textile finishing agents for the phobing of textiles. They are in the form of aqueous dispersions with a solids content of 10 to 50%, preferably 15 to 40%. With a solids content of 15% this is Mixing ratio of perfluoro compound A) to cationically modified polyurethanes B) in the finishing liquor, for example at 0.5: 1 to 10: 1, in particular at 1: 1 to 5: 1, based on the solids content.
Die erfindungsgemäßen wäßrigen Dispersionen können weitere Bestandteile wie andere Textilhilfsmittel, z.B. Kunstharze, enthalten.The aqueous dispersions according to the invention can contain further components such as other textile auxiliaries, e.g. Synthetic resins.
Bevorzugt sind diese weiteren Bestandteile nichtionischer oder kationischer Natur.These further constituents are preferably nonionic or cationic in nature.
Die wäßrigen Dispersionen werden vor der Anwendung auf den Textilmaterialien mit Wasser verdünnt. Die Anwendungsmengen werden so gewählt, daß daraus eine Auflagemenge von 0,5 bis 15 g, vorzugsweise 0,5 bis 5 g und insbesondere 0,5 bis 1,5 g Feststoff der erfindungsgemäßen Substanz pro kg Textilmaterial erzielt wird.The aqueous dispersions are diluted with water before use on the textile materials. The application amounts are chosen so that a coating amount of 0.5 to 15 g, preferably 0.5 to 5 g and in particular 0.5 to 1.5 g of solids of the substance according to the invention per kg of textile material is obtained.
Überraschend zeigt es sich, daß bereits mit diesen relativ geringen Auflagemengen hervorragende Hydro- und Oleophobierungseffekte erzielt werden können.Surprisingly, it turns out that excellent hydro- and oleophobicizing effects can be achieved even with these relatively small quantities.
Mit den erfindungsgemäßen Mischungen können natürliche und synthetische Materialien wie Fasern, Filamente, Garne, Vliese, Gewebe, Gewirke und Gestricke aus insbesondere Cellulose und ihren Derivaten aber auch aus Polyester-, Polyamid- und Polyacrylnitrilmaterialien, Wolle oder Seide erfolgreich ausgerüstet werden.With the mixtures according to the invention, natural and synthetic materials such as fibers, filaments, yarns, nonwovens, fabrics, knitted fabrics and knitted fabrics made in particular of cellulose and its derivatives but also of polyester, polyamide and polyacrylonitrile materials, wool or silk can be successfully finished.
Die hydrophobierten bzw, oleophobierten textilen Gebilde, etwa Vliese oder insbesondere Gewebe finden z.B, Einsatz zur Herstellung von Regenschirmbespannungen, Zelten, wasserabweisenden Bekleidungen oder Bezügen, Ballonhüllen, Markisen, textilen Bodenbelägen, Verpackungsmaterialien oder Schuhwerk,The hydrophobized or oleophobicized textile structures, such as nonwovens or, in particular, fabrics are used, for example, for the production of umbrella coverings, tents, water-repellent clothing or covers, balloon envelopes, awnings, textile floor coverings, packaging materials or footwear,
Die Ausrüstung erfolgt nach bekannten Verfahren, vorzugsweise nach dem Auszieh- oder Foulardverfahren beispielsweise zwischen Raumtemperatur und 40°C, aber auch durch Pflatschen oder Besprühen mit einer nachgeschalteten Temperaturbehandlung bei 80 bis 180, vorzugsweise 120 bis 150°C`The finishing is carried out by known methods, preferably by the pull-out or padding method, for example between room temperature and 40 ° C., but also by splashing or spraying with a subsequent temperature treatment at 80 to 180, preferably 120 to 150 ° C.
Die in den folgenden Beispielen angegebenen Teile und Prozente beziehen sich auf das Gewicht, sofern nichts anderes vermerkt ist,The parts and percentages given in the following examples relate to the weight, unless stated otherwise,
Dabei wurden die nachstehend aufgeführten Produkte verwendet:The products listed below were used:
Kationisch modifiziertes Polyurethan (B)
- Komponente I:
- ca, 15 %ige wäßrige kationisch modifizierte PU-Dispersion gemäB DE-A 35 23 856 (Beispiel 1), d.h. ein auf folgende Weise hergestelltes Produkt:
- Component I:
- approx. 15% aqueous cationically modified PU dispersion according to DE-A 35 23 856 (Example 1), ie a product produced in the following way:
Perfluoralkylgruppenhaltiges Phobiermittel (A)
- Komponente II:
- Ein als 15 %ige wäßrige Dispersion vorliegendes Perfluoralkan-Gruppen enthaltendes Acrylat-Copolymeres mit einem Fluorgehalt von ca. 40 % im Feststoff,
- Komponente III:
- Mischung aus 50 % Kondensationsprodukt aus 1 Mol Hexamethylol-melamin-pentamethylether, 1,5 Mol Behensäure und 0,9 Mol Methyldiethanolamin bei 130°C während 3 Stunden und 50 % Paraffin (Schmp.: 52°C).
- Component II:
- An acrylic copolymer containing perfluoroalkane groups as a 15% aqueous dispersion with a fluorine content of about 40% in the solid,
- Component III:
- Mixture of 50% condensation product from 1 mol of hexamethylol melamine pentamethyl ether, 1.5 mol of behenic acid and 0.9 mol of methyldiethanolamine at 130 ° C for 3 hours and 50% paraffin (mp: 52 ° C).
Für die Flächenstabilisierung der Textilsubstrate aus Baumwolle und Baumwolle/Synthesefasern bzw. zur Griffgestaltung der PAC-Markisenstoffe werden handelsübliche Kunstharze und entsprechende Katalysatoren mitverwendet.
- Kunstharz X:
- Fixapret CPN® (Methylolierungsprodukt von Glyoxalmonourein)
- Kunstharz Y:
- ACRAFIX MF® (Melamin-/Formaldehydkondensat)
- Katalysator:
- Zinknitrat
- Resin X:
- Fixapret CPN® (methylolation product of Glyoxalmonourein)
- Synthetic resin Y:
- ACRAFIX MF® (melamine / formaldehyde condensate)
- Catalyst:
- Zinc nitrate
Ein Baumwoll-Gabardinegewebe mit einem m²-Gewicht von ca. 240 g wurde mit folgenden Formulierungen ausgerüstet:
Die Baumwollware wurde in einem Chassis mit den Flotten getränkt und zwischen 2 Gummiwalzen (Foulard) abgequetscht. Die Flottenaufnahme betrug 70 % bezogen auf das Textilgewicht. Die Muster wurden bei 100°C getrocknet und während 5 Minuten bei 150°C kondensiert.The cotton fabric was soaked in a chassis with the liquors and squeezed between 2 rubber rollers (foulard). The liquor absorption was 70% based on the textile weight. The samples were dried at 100 ° C and condensed at 150 ° C for 5 minutes.
Die Prüfung der ausgerüsteten Ware erfolgte nach folgender Methode:
Nach einer 24-stündigen Klimatisierung bei 20°C ± 2°C und 65 % relativer Luftfeuchtigkeit werden die ausgerüsteten Textilmuster den entsprechenden Prüfungen unterzogen:
- 1. Beregnungsprüfung erfolgt in Anlehnung an DIN 53 888 mit dem Beregnungsprüfgerät nach Dr. Bundesmann.
Bewertung- a) Abperlzeit in Minuten
- b) Abperleffekt in Noten 5-1 Note 5 bedeutet höchster Abperleffekt Note 1 bedeutet geringster Abperleffekt
- c) Wasseraufnahme
- d) Wasserdurchschlag in cm³
- 2. Die Wasserdichtheitsprüfung erfolgt in Anlehnung an DIN 53 886 (Schoppertest).
- 3. Der Ölabweisungstest erfolgt in Anlehnung an AATCC Test Method 118-1978.
After a 24-hour air conditioning at 20 ° C ± 2 ° C and 65% relative humidity, the finished textile samples are subjected to the appropriate tests:
- 1. Irrigation test is carried out in accordance with DIN 53 888 with the irrigation tester according to Dr. Bundesmann.
rating- a) beading time in minutes
- b) Beading off effect in notes 5-1. Note 5 means the highest beading effect. Note 1 means the lowest beading effect
- c) water absorption
- d) water penetration in cm³
- 2. The water tightness test is based on DIN 53 886 (Schoppertest).
- 3. The oil repellency test is based on AATCC Test Method 118-1978.
Die Note für die Ölabweisung entspricht der am höchsten nummerierten Testflüssigkeit, die das Fasermaterial innerhalb 30 Sekunden nicht benetzt:
Note 1 niedrigster Wert
Note 8 höchster Wert.The grade for oil repellency corresponds to the highest numbered test liquid that does not wet the fiber material within 30 seconds:
Grade 1 lowest value
Grade 8 highest value.
Die Prüfung ergab folgende Werte:
Die Auswertung zeigt, daß die Menge der eingesetzten Fluorkomponente II allein für eine wasserabweisende Ausrüstung zu gering ist.The evaluation shows that the amount of fluorine component II used alone is too small for a water-repellent finish.
Der Zusatz der Komponenten I und III ergibt bei der Prüfung der Wasserabweisung 1a-d) Werte, die dem Standard einer Regenbekleidungsausrüstung entsprechen.The addition of components I and III results in the test of water repellency 1a-d) values which correspond to the standard of rainwear equipment.
Die erfindungsgemäß zugesetzte Komponente I ergibt diese Steigerung schon bei einem Einsatz, bezogen auf Festsubstanz, von 1,5 g/l, während die nichterfindungsgemäße Komponente III erst bei 10 g/l Einsatzmenge wirksam ist.Component I added according to the invention already gives this increase with use, based on solid substance, of 1.5 g / l, while component III, which is not in accordance with the invention, is effective only when 10 g / l is used.
Die unter Beispiel 1 ausgerüsteten Baumwollmuster wurden 5 mal bei 40°C auf einer Miele-Waschmaschine Typ W 763 mit Pflegeleichtprogramm unter Zusatz eines haushaltsüblichen Waschmittels gewaschen und bei 80°C in einem Miele-Haushaltstrockner getrocknet.The cotton swatches finished in Example 1 were washed 5 times at 40 ° C. on a Miele washing machine type W 763 washed with an easy care program with the addition of a household detergent and dried at 80 ° C in a Miele household dryer.
Die Prüfung ergab folgende Werte:
Die erfindungsgemäß zugesetzte Komponente I verbessert die Waschbeständigkeit von Fluorausrüstungen dergestalt, daß selbst nach 5 Maschinenwäschen ein Erhalt der Phobierwerte gegeben ist, während die Ausrüstungen ohne Extender bzw. mit Komponente III deutlich abfallen.Component I added in accordance with the invention improves the wash resistance of fluorine finishes in such a way that even after 5 machine washes, the phobia values are retained, while the finishes without extender or with component III drop significantly.
Eine gefärbte Polyester/Baumwolle-Popelineware (67 % PES/33 % Baumwolle) mit einem m²-Gewicht von ca. 160 g wurde mit folgenden Formulierungen auf dem Foulard ausgerüstet:
Die Flottenaufnahme betrug 65 %, die nachfolgende Behandlung erfolgte wie bei Beispiel 1 beschrieben.The liquor absorption was 65%, the subsequent treatment was as described in Example 1.
Die Prüfung ergab folgende Werte:
Die erfindungsgemäß zugesetzte Komponente I verbessert die Waschbeständigkeit derart, daß selbst nach 5 Maschinenwäschen ein fast vollständiger Erhalt der Phobierwerte gegeben ist,Component I added according to the invention improves the wash resistance in such a way that even after 5 machine washes, the phobic values are almost completely retained,
Ein Wollgewebe mit einem Gewicht von 280 g/m² wird foulardmäßig wie folgt ausgerüstet:
Die Flottenaufnahme betrug 80 %. Nach einer Behandlung bei 100°C werden die Gewebe 3 Minuten bei 140°C behandelt:
Ergebnis:
Während bei der Fluorkomponente II keine Hydrophobwerte erzielt werden, erreicht die erfindungsgemäße Beimischung der Komponente I sehr gute Beregnungswerte. Durch die Komponente III wird nur eine geringfügige Verbesserung gegenüber der nur mit Komponente II ausgerüsteten Textilware erzielt.Result:
While no hydrophobic values are achieved with fluorine component II, the addition of component I according to the invention achieves very good irrigation values. Component III achieves only a slight improvement over the textile goods that are only equipped with component II.
Claims (7)
- Hydrophobizing and oleophobizing compositions containingA) a polymer containing perfluoroalkyl groups andB) a polyurethane, characterized in that the polyurethane is cationically modified and contains structural components containing acylurea groups of the formula
R denotes a saturated or unsaturated aliphatic hydrocarbon radical having up to 35 carbon atoms, preferably having 9 to 22 carbon atoms, or an aromatic hydrocarbon radical having 6 to 10 carbon atoms or an araliphatic hydrocarbon radical having 7 to 10 carbon atoms. - Compositions according to Claim 1, characterized in that polymers containing a perfluoroalkyl group having 4 to 20 carbon atoms, which can be interrupted by oxygen, are employed as component A).
- Compositions according to Claim 1 or 2, characterized in that component A) is an acrylate polymer having a fluorine content of 20 to 45% by weight.
- Compositions according to Claim 1 to 3, characterized in that the polyurethane component B) is used in the form of aqueous solutions or dispersions.
- Process for finishing textiles, characterized in that compositions of Claims 1 to 4 are used.
- Process for finishing textiles with hydrophobizing and/or oleophobizing compositions based on polymers containing perfluoroalkyl groups, characterized in that a cationically modified polyurethane is used as an extender.
- Textile structures finished with compositions of Claims 1 to 4.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3939341A DE3939341A1 (en) | 1989-11-29 | 1989-11-29 | HYDROPHOBIC AND OLEOPHOBIC AGENTS |
| DE3939341 | 1989-11-29 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0429983A2 EP0429983A2 (en) | 1991-06-05 |
| EP0429983A3 EP0429983A3 (en) | 1991-10-23 |
| EP0429983B1 true EP0429983B1 (en) | 1994-05-04 |
Family
ID=6394353
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP90121949A Expired - Lifetime EP0429983B1 (en) | 1989-11-29 | 1990-11-16 | Water and oil repellant composition |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US5164252A (en) |
| EP (1) | EP0429983B1 (en) |
| JP (1) | JPH03172337A (en) |
| DE (2) | DE3939341A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5509939A (en) * | 1989-12-29 | 1996-04-23 | E. I. Du Pont De Nemours And Company | Soil-release process |
| DE4039193A1 (en) * | 1990-12-08 | 1992-06-11 | Bayer Ag | WET-DISPERSIBLE, ELECTROLYTE-TABLE POLYETHERESTER-MODIFIED POLYURETHANIONOMERS |
| KR100214319B1 (en) * | 1991-04-02 | 1999-08-02 | 스프레이그 로버트 월터 | Fluorine-efficient oil and water repellent compositions |
| US6309752B1 (en) | 1991-04-02 | 2001-10-30 | 3M Innovative Properties Company | Substrate having high initial water repellency and a laundry durable water repellency |
| JP2608195B2 (en) * | 1991-06-24 | 1997-05-07 | セントラル硝子株式会社 | Thermoplastic urethane resin composition |
| US5403514A (en) * | 1991-10-07 | 1995-04-04 | Canon Kabushiki Kaisha | Solvent composition and water-repellent/oil-repellent composition using the same |
| JP2660312B2 (en) * | 1992-05-29 | 1997-10-08 | ヘキスト合成株式会社 | Fluorine-containing water- and oil-repellent composition |
| DE69424173T2 (en) * | 1994-11-24 | 2000-09-28 | Minnesota Mining & Mfg | Carbodiimide compounds and permanent water repellent compositions containing these compounds |
| US6495624B1 (en) | 1997-02-03 | 2002-12-17 | Cytonix Corporation | Hydrophobic coating compositions, articles coated with said compositions, and processes for manufacturing same |
| US5853894A (en) * | 1997-02-03 | 1998-12-29 | Cytonix Corporation | Laboratory vessel having hydrophobic coating and process for manufacturing same |
| US7268179B2 (en) | 1997-02-03 | 2007-09-11 | Cytonix Corporation | Hydrophobic coating compositions, articles coated with said compositions, and processes for manufacturing same |
| US8653213B2 (en) | 1997-02-03 | 2014-02-18 | Cytonix, Llc | Hydrophobic coating compositions and articles coated with said compositions |
| EP0985741A1 (en) * | 1998-09-07 | 2000-03-15 | The Procter & Gamble Company | Modulated plasma glow discharge treatments for making super hydrophobic substrates |
| DE19857106C2 (en) * | 1998-12-10 | 2000-10-26 | Heinz Neubaur | Swimwear made from a water-repellent fabric and process for its manufacture |
| US6353051B1 (en) * | 1999-03-10 | 2002-03-05 | E. I. Du Pont De Nemours And Company | Top coating for synthetic leathers |
| ITVA20000017A1 (en) * | 2000-06-08 | 2001-12-08 | Lamberti Spa | WATER DISPERSIONS OF URETHANE-ACRYLIC COPOLYMERS AND THEIR USE AS FINISHING AGENTS. |
| DE10120989A1 (en) * | 2001-04-25 | 2002-11-07 | Inst Polymerforschung Dresden | Hydrophobic permanent coatings on substrates and processes for their production |
| US6479605B1 (en) | 2001-05-15 | 2002-11-12 | E. I. Du Pont De Nemours And Company | High-durability, low-yellowing repellent for textiles |
| DE10211549B9 (en) | 2002-03-15 | 2004-11-25 | Rudolf Gmbh & Co. Kg Chemische Fabrik | Preparations based on water and / or organic solvents and their use as a finish on fabrics |
| DE10325094B4 (en) * | 2003-06-03 | 2006-02-16 | Rudolf Gmbh & Co. Kg Chemische Fabrik | Preparations for the oil and water repellent finishing of fabrics and their use |
| JP4656148B2 (en) * | 2005-09-21 | 2011-03-23 | ダイキン工業株式会社 | Paper processing agent and paper processing method |
| US8202579B2 (en) * | 2008-03-31 | 2012-06-19 | Cooley Group Holdings, Inc. | Water-resistant fabrics and methods of preparation thereof |
| WO2016184877A1 (en) * | 2015-05-18 | 2016-11-24 | Teijin Aramid Gmbh | Textile sheet material having a water-repellent finish and method for producing said sheet material |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH416670D (en) * | 1969-03-20 | |||
| US3763078A (en) * | 1970-11-30 | 1973-10-02 | Warnaco Inc | Wear resistant garments and method and composition for production thereof |
| US3949124A (en) * | 1974-07-12 | 1976-04-06 | Hca-Martin, Inc. | Method for treating textile materials and textile materials treated in such a way, and textile treating compositions |
| JPS58214586A (en) * | 1983-05-09 | 1983-12-13 | カネボウ株式会社 | Processing of fiber structure |
| DE3407362A1 (en) * | 1984-02-29 | 1985-08-29 | Bayer Ag, 5090 Leverkusen | AQUEOUS DISPERSIONS OF GRAFT POLYMERS OR COPOLYMERS, A METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS A HYDROPHOBIC AND OLEOPHOBIC AGENT FOR TEXTILES |
| DE3438563A1 (en) * | 1984-10-20 | 1986-04-24 | Bayer Ag, 5090 Leverkusen | AQUEOUS SOLUTIONS OR DISPERSIONS OF POLYISOCYANATE ADDITION PRODUCTS, A METHOD FOR THE PRODUCTION THEREOF, AND THEIR USE AS A COATING OR SIZING AGENT FOR PAPER |
| DE3523856A1 (en) * | 1985-07-04 | 1987-01-08 | Bayer Ag | AQUEOUS SOLUTIONS OR DISPERSIONS OF POLYISOCYANATE ADDITION PRODUCTS, A METHOD FOR THE PRODUCTION THEREOF, AND THEIR USE AS A COATING OR SIZING AGENT FOR PAPER |
-
1989
- 1989-11-29 DE DE3939341A patent/DE3939341A1/en not_active Withdrawn
-
1990
- 1990-11-16 EP EP90121949A patent/EP0429983B1/en not_active Expired - Lifetime
- 1990-11-16 DE DE59005615T patent/DE59005615D1/en not_active Expired - Fee Related
- 1990-11-21 US US07/616,554 patent/US5164252A/en not_active Expired - Fee Related
- 1990-11-27 JP JP2321383A patent/JPH03172337A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03172337A (en) | 1991-07-25 |
| EP0429983A2 (en) | 1991-06-05 |
| DE59005615D1 (en) | 1994-06-09 |
| DE3939341A1 (en) | 1991-06-06 |
| EP0429983A3 (en) | 1991-10-23 |
| US5164252A (en) | 1992-11-17 |
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