DE10242762A1 - Aqueous dispersion of copolymerisates and emulsifiers which when combined with fluorinated compounds enable the proportion of these to be decreased without impairing hydrophobization efficiency of fibers and textiles - Google Patents
Aqueous dispersion of copolymerisates and emulsifiers which when combined with fluorinated compounds enable the proportion of these to be decreased without impairing hydrophobization efficiency of fibers and textiles Download PDFInfo
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- DE10242762A1 DE10242762A1 DE10242762A DE10242762A DE10242762A1 DE 10242762 A1 DE10242762 A1 DE 10242762A1 DE 10242762 A DE10242762 A DE 10242762A DE 10242762 A DE10242762 A DE 10242762A DE 10242762 A1 DE10242762 A1 DE 10242762A1
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
- C08L33/16—Homopolymers or copolymers of esters containing halogen atoms
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
- C09D133/16—Homopolymers or copolymers of esters containing halogen atoms
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
-
- 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
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/10—Repellency against liquids
- D06M2200/12—Hydrophobic properties
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Textile Engineering (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Materials Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Colloid Chemistry (AREA)
Abstract
Description
Die vorliegende Anmeldung betrifft wässrige Dispersionen, die fluorhaltige und fluorfreie Poly(meth)acrylate enthalten sowie die Verwendung derartiger Dispersionen zur hydrophobierenden Ausrüstung von Fasern und textilen Flächengebilden.The present application relates aqueous dispersions, which contain fluorine-containing and fluorine-free poly (meth) acrylates as well the use of such dispersions for the hydrophobic finishing of Fibers and textile fabrics.
Es ist bekannt und in der Textiltechnik üblich, Fasern
und textile Flächengebilde
mit wässrigen
Dispersionen zu behandeln, die fluorhaltige Copolymere auf Basis
von Perfluoracrylaten enthalten. Perfluoracrylate vermitteln Textilien
Materialien gleichzeitig stark hydrophobe und stark oleophobe Schutzeigenschaften.
Derartige Perfluoracrylate werden beispielsweise in der
Zwar führt die Ausrüstung der Textilien mit den Perfluoracrylaten oder anderen geeigneten polyfluorierten Verbindungen zu den gewünschten Eigenschaften der textilen Materialien, allerdings sind die fluorierten Verbindungen nach wie vor sehr teuer. Es besteht daher ein Bedarf, die hydrophobe Ausrüstung von Textilien preiswerter zu gestalten, ohne dass dabei die Wirksamkeit der Ausrüstung verloren geht.The equipment of the Textiles with the perfluoroacrylates or other suitable polyfluorinated Connections to the desired Properties of the textile materials, however, are the fluorinated ones Connections are still very expensive. There is therefore a need the hydrophobic finish of textiles to make them cheaper without losing their effectiveness the equipment get lost.
Es wurde nun gefunden, dass durch Kombination von an sich bekannten polymeren Perfluoracrylaten mit nicht fluorierten polymeren Acrylaten der Anteil der teuren fluorierten Produkte verringert werden kann, ohne dass das Ergebnis der hydrophoben Ausrüstung sich verschlechtert.It has now been found that by Combination of polymeric perfluoroacrylates known per se with non-fluorinated polymeric acrylates the proportion of expensive fluorinated Products can be reduced without the result of being hydrophobic equipment worsens.
Gegenstand der vorliegenden Erfindung sind somit wässrige Dispersionen, enthalten mindestens
- a) ein Copolymerisat aus Verbindungen der Formel (I) R1-O-CO-CR2=CH2 (I) in der R1 einen verzweigten oder unverzweigten Alkylrest mit 8 bis 22 C-Atomen bedeutet und R2 für ein Wasserstoffatom oder einen Alkylrest mit 1 bis 4 C-Atomen steht, mit Monomeren, ausgewählt aus Verbindungen der Formel (Ia) R3-O-CO-CR4=CH2 (Ia) in der R3 einen verzweigten oder unverzweigten Alkylrest mit 1 bis 6 C-Atomen bedeutet und R4 für ein Wasserstoffatom oder einen Alkylrest mit 1 bis 4 C-Atomen steht, und
- b) ein Copolymerisat aus Verbindungen der Formel (II) CnF2 n-CH2-CH2-O-CO-CR5=CH2 in der R5 für ein Wasserstoffatom oder einen Alkylrest mit 1 bis 4 C-Atomen steht und n eine Zahl von 4 bis 12 bedeutet, mit Monomeren, ausgewählt aus Verbindungen der Formel (Ia) steht, und
- c) Emulgatoren mit der Maßgabe, dass das Gewichtsverhältnis zwischen den Copolymeren zu a) zu den Copolymeren zu b) 10 : 1 bis 1 : 10 beträgt.
- a) a copolymer of compounds of the formula (I) R 1 -O-CO-CR 2 = CH 2 (I) in which R 1 is a branched or unbranched alkyl radical having 8 to 22 carbon atoms and R 2 is a hydrogen atom or is an alkyl radical with 1 to 4 carbon atoms, with monomers selected from compounds of the formula (Ia) R 3 -O-CO-CR 4 = CH 2 (Ia) in which R 3 is a branched or unbranched alkyl radical with 1 to 6 Is C atoms and R 4 represents a hydrogen atom or an alkyl radical having 1 to 4 C atoms, and
- b) a copolymer of compounds of the formula (II) C n F 2 n -CH 2 -CH 2 -O-CO-CR 5 = CH 2 in which R 5 represents a hydrogen atom or an alkyl radical having 1 to 4 carbon atoms and n represents a number from 4 to 12, with monomers selected from compounds of the formula (Ia), and
- c) emulsifiers with the proviso that the weight ratio between the copolymers to a) to the copolymers to b) is 10: 1 to 1:10.
Sowohl die Verbindungen der Formeln (I) und (Ia) als auch die Verbindungen der Formel (II) sind an sich bekannt. Es handelt sich dabei um Derivate der Acrylsäure bzw: der Methacrylsäure, speziell um deren Ester.Both the compounds of the formulas (I) and (Ia) as well as the compounds of formula (II) are per se known. These are derivatives of acrylic acid or: methacrylic acid, especially for their esters.
Die Herstellung der perfluorierten Verbindungen gemäß Formel (II) erfolgt dabei in der Regel auf Basis von Tetrafluorethan, welches polymerisiert und jodiert wird und Verlauf einer Grignard-Reaktion mit Ethylenoxid zu einem perfluorierten Alkohol umgesetzt wird. Dieser wird in einem letzten Reaktionsschritt mit Acrylsäure oder Methacrylsäure zu den gewünschten perfluorierten Acrylaten bzw. Methacrylatestern umgesetzt. Bei der Auswahl der Verbindungen der Formel (II) ist es vorteilhaft, solche perfluorierten Verbindungen der Formel (II) einzusetzen, bei denen der Index n für eine Zahl von 6 bis 10 steht.The production of the perfluorinated Compounds according to formula (II) is usually based on tetrafluoroethane, which is polymerized and iodized and course of a Grignard reaction is reacted with ethylene oxide to form a perfluorinated alcohol. In a final reaction step, this is done using acrylic acid or methacrylic acid to the ones you want perfluorinated acrylates or methacrylate esters implemented. In the Selection of the compounds of formula (II) it is advantageous to use such to use perfluorinated compounds of the formula (II) in which the index n for is a number from 6 to 10.
Bei den Verbindungen der Formel (I) handelt es sich um ebenfalls bekannte Ester der Acryl- bzw. Methacrylsäure mit Fettalkoholen, wobei die Fettalkohole 8 bis 22 C-Atome aufweisen müssen.In the compounds of the formula (I) are also known esters of acrylic or methacrylic acid with Fatty alcohols, the fatty alcohols having 8 to 22 carbon atoms have to.
Die Monomeren der Formeln (I) und (II) werden unabhängig voneinander mit den Acryl- bzw. Methacrylsäureestern der Formel (Ia), in der Regel durch Emulsionspolymerisation in wässerigem Medium zu Copolymeren umgesetzt, wobei jeweils Emulgatoren c) zum Einsatz kommen, und anschließend werden die zwei Komponenten a) und b), die Herstellungsbedingt bereits die Emulgatoren enthalten, zu den erfindungsgemäßen Dispersionen vermischt.The monomers of the formulas (I) and (II) become independent from each other with the acrylic or methacrylic of formula (Ia), usually by emulsion polymerization in aqueous Medium converted to copolymers, each with emulsifiers c) Come in, and then be the two components a) and b), the manufacturing already which contain emulsifiers, mixed to form the dispersions according to the invention.
Die Emulsionspolymerisation stellt ein Spezialverfahren der Polymerisation dar, bei dem wasserunlösliche Monomere mit Hilfe von Emulgatoren in Wasser emulgiert und unter Verwendung wasserlösliche Initiatoren (z. B. Kaliumpersulfat; Redoxinitiatoren) polymerisiert werden. Besonders bevorzugte Monomeren der Formel (Ia) sind ausgewählt aus der Gruppe der aus der Gruppe der Methyl-, Ethyl-, n-Propyl-, i-Propyl- und/oder Butylester der Acryl- bzw. Methacrylsäure. Dabei können die Verbindungen der Formel (Ia) unabhängig voneinander zur Herstellung der Polymerdispersionen a) und b) verwendet werden. Bei der Polymerisation zu den Komponente a) und b) ist es vorteilhaft wenn der Anteil an Monomeren der Formeln (I) bzw. (II) in Bezug auf die Comonomeren (Ia) mindestens 50 Gew.-%, vorzugsweise mindestens 70 Gew.-% beträgt. Es ist auch möglich nur Monomeren der Formeln (I) bzw. (II) zu polymerisieren. Bevorzugt beträgt der Anteil an Comonomeren der Formel (Ia) bei der Polymerisation aber mindestens 5 Gew.-%.The emulsion polymerization provides is a special process of polymerization in which water-insoluble monomers emulsified in water with the help of emulsifiers and using water-soluble Initiators (e.g. potassium persulfate; redox initiators) polymerized become. Particularly preferred monomers of the formula (Ia) are selected from the group consisting of the group consisting of methyl, ethyl, n-propyl, i-propyl and / or butyl esters of acrylic or methacrylic acid. The Compounds of formula (Ia) independently of one another for the preparation the polymer dispersions a) and b) can be used. During the polymerization to components a) and b) it is advantageous if the proportion of monomers of formulas (I) or (II) with respect to the comonomers (Ia) at least 50% by weight, preferably at least 70% by weight. It is also possible to polymerize only monomers of the formulas (I) or (II). Prefers is the proportion of comonomers of the formula (Ia) in the polymerization, however at least 5% by weight.
Erfindungswesentlich ist, dass das Gewichtsverhältnis zwischen den Komponente a) und b) im Bereich von 10 : 1 bis 1 : 10, vorzugsweise aber im Bereich von 5 : 1 bis 1 : 3 liegt. Besonders bevorzugt sind die Bereiche 3 : 1 bis 1 : 1.It is essential to the invention that weight ratio between components a) and b) in the range from 10: 1 to 1: 10, but preferably in the range from 5: 1 to 1: 3. Especially the ranges 3: 1 to 1: 1 are preferred.
Die erfindungsgemäßen Dispersionen enthalten zur Stabilisierung zwingend Emulgatoren c). Die Emulgatoren sind ausgewählt vorzugsweise aus den nichtionischen und/oder kationischen Emulgatoren. Bei den Emulgatoren sind besonders bevorzugt die kationischen Emulgatoren, wobei es sich hierbei um solche Verbindungen handelt, die eine positive Ladung in Form einer quaternierten Amoniumgruppe enthalten oder aber eine ladungsneutrale Amingruppe, die beim Ansäuern des Gesamtsystems in die ionisch protonierte Form übergehen. Beispiele für derartige kationische Verbindungen finden sich in der WO 88/00991 auf den Seiten 2 und 3. Aber auch andere dem Fachmann bekannte quaternierte Verbindungen, insbesondere sogenannte Esterquats, d. h. quaternierte Alkylammoniumverbindungen, die mindestens eine Estergruppe in der Alkylgruppe tragen, sind zur Stabilisierung der erfindungsgemäßen Dispersionen geeignet.The dispersions according to the invention necessarily contain emulsifiers c) for stabilization. The emulsifiers are preferably selected from the nonionic and / or cationic emulsifiers. The emulsifiers are particularly preferably the cationic emulsifiers, which are compounds which contain a positive charge in the form of a quaternized ammonium group or a charge-neutral amine group which change to the ionically protonated form when the overall system is acidified. Examples of such cationic compounds can be found in WO 88/00991 on pages 2 and 3. But also other quaternized compounds known to the person skilled in the art, in particular so-called ester quats, ie quaternized alkylammonium compounds which carry at least one ester group in the alkyl group, are used to stabilize the dispersions according to the invention suitable.
Die wässrigen Dispersionen gemäß der vorliegenden erfindungsgemäßen Lehre enthalten die Komponenten a) und b) in Summe in Mengen von 0,1 bis 50 Gew. %, vorzugsweise in Mengen von 1 bis 35 Gew. %, jeweils bezogen auf das Gesamtgewicht der wässrigen Dispersion. Die Emulgatoren c) sind dabei in Mengen von 0,1 bis 10 Gew. %, vorzugsweise 0,5 bis 5 Gew.-%, jeweils bezogen auf das Gesamtgewicht der Dispersion enthalten. Es kann vorteilhaft sein, neben den Komponente a) und b) sowie den Emulgatoren c) noch wassermischbare organische Lösungsmittel einzusetzen. Dabei handelt es sich vorzugsweise um Polyole mit 2 bis 6 C-Atomen und 2 bis 6 Hydroxylgruppen, den Alkylethern oder Teilakylethern dieser Polyole oder den vollständig oder teilweise alkoxylierten Derivaten der Polyole oder um Aceton.The aqueous dispersions according to the present teaching according to the invention contain components a) and b) in total in amounts from 0.1 to 50% by weight, preferably in amounts of 1 to 35% by weight, in each case based on the total weight of the aqueous Dispersion. The emulsifiers c) are in amounts from 0.1 to 10 wt.%, Preferably 0.5 to 5 wt .-%, each based on the Total weight of the dispersion included. It can be beneficial in addition to components a) and b) and the emulsifiers c) also water-miscible organic solvents use. These are preferably polyols with 2 up to 6 carbon atoms and 2 to 6 hydroxyl groups, the alkyl ethers or Partial alkyl ethers of these polyols or the fully or partially alkoxylated Derivatives of the polyols or around acetone.
Die Herstellung der erfindungsgemäßen Dispersionen erfolgt dahingehend, dass zunächst eine wässrige kationisch oder nichtionisch stabilisierte Dispersion a) mit einer wässrigen, kationisch oder nichtionisch stabilisierte Dispersion b) vermischt wird. Anschließend kann die so enthaltene Mischung in an sich geeigneter und bekannter Art und Weise auf Textilien und Fasern aufgetragen werden. Geeignete textile Materialien sind sowohl Baumwolle als auch Polyester oder Polyamidfasern sowie Mischgewebe. Die wässrigen erfindungsgemäßen Dispersionen werden mittels gängiger Applikationstechnik, beispielsweise einer Foulardwalze, auf die Fasern bzw. das Gewebe aufgebracht. Dabei beträgt die Wirkstoffkonzentration vorzugsweise zwischen 1 bis 5g pro Liter bezogen auf die Flotte.The preparation of the dispersions according to the invention is done in that first an aqueous cationically or nonionically stabilized dispersion a) with a aqueous, cationically or nonionically stabilized dispersion b) is mixed. Subsequently can the mixture contained in a suitable and known per se Way to be applied to textiles and fibers. suitable Textile materials are both cotton and polyester or Polyamide fibers and blended fabrics. The aqueous dispersions according to the invention are using common Application technology, for example a paddle roller, on the Fibers or the fabric applied. The active ingredient concentration is preferably between 1 to 5 g per liter based on the liquor.
Ein weiterer Gegenstand der vorliegenden Erfindung betrifft die Verwendung von wässrigen Dispersionen, wie oben beschrieben, zur hydrophobierenden Ausrüstung von Fasern und textilen Flächengebilden.Another object of the present invention concerns the use of aqueous Dispersions as described above for the hydrophobizing finish of Fibers and textile fabrics.
Claims (13)
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10242762A DE10242762A1 (en) | 2002-09-14 | 2002-09-14 | Aqueous dispersion of copolymerisates and emulsifiers which when combined with fluorinated compounds enable the proportion of these to be decreased without impairing hydrophobization efficiency of fibers and textiles |
TW092123919A TW200407338A (en) | 2002-09-14 | 2003-08-29 | Aqueous dispersions for the hydrophobic finishing of fibres and flat textiles |
CNB038216167A CN1289598C (en) | 2002-09-14 | 2003-09-05 | Aqueous disperse system for drainage treatment of fibers and smooth textile |
PCT/EP2003/009854 WO2004026959A1 (en) | 2002-09-14 | 2003-09-05 | Aqueous dispersions for hydrophobically finishing fibres and flat textile materials |
EP03753386A EP1537176A1 (en) | 2002-09-14 | 2003-09-05 | Aqueous dispersions for hydrophobically finishing fibres and flat textile materials |
US10/527,244 US20050257325A1 (en) | 2002-09-14 | 2003-09-05 | Aqueous dispersions for hydrophobically finishing fibres and flat textile materials |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10242762A DE10242762A1 (en) | 2002-09-14 | 2002-09-14 | Aqueous dispersion of copolymerisates and emulsifiers which when combined with fluorinated compounds enable the proportion of these to be decreased without impairing hydrophobization efficiency of fibers and textiles |
Publications (1)
Publication Number | Publication Date |
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DE10242762A1 true DE10242762A1 (en) | 2004-03-18 |
Family
ID=31724773
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DE10242762A Withdrawn DE10242762A1 (en) | 2002-09-14 | 2002-09-14 | Aqueous dispersion of copolymerisates and emulsifiers which when combined with fluorinated compounds enable the proportion of these to be decreased without impairing hydrophobization efficiency of fibers and textiles |
Country Status (6)
Country | Link |
---|---|
US (1) | US20050257325A1 (en) |
EP (1) | EP1537176A1 (en) |
CN (1) | CN1289598C (en) |
DE (1) | DE10242762A1 (en) |
TW (1) | TW200407338A (en) |
WO (1) | WO2004026959A1 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8666056B2 (en) | 2007-12-28 | 2014-03-04 | Genesys Telecommunications Laboratories, Inc. | System for facilitating loosely configured service worker groups in a dynamic call center environment |
EP3778824A4 (en) * | 2018-03-26 | 2021-12-15 | Agc Inc. | Oil-repellent and water-repellent agent composition, article, and method for producing article |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2804391A (en) * | 1954-06-15 | 1957-08-27 | Atlantic Refining Co | Mothproofing and waterproofing composition |
US3256230A (en) * | 1961-05-03 | 1966-06-14 | Du Pont | Polymeric water and oil repellents |
US3536779A (en) * | 1967-05-16 | 1970-10-27 | Louise C Decnyf | Method for imparting a durable water resistant coating to a substrate |
DE3626051A1 (en) * | 1986-08-01 | 1988-02-11 | Pfersee Chem Fab | AQUEOUS DISPERSIONS FOR THE SIMULTANEOUS SOFTENING AND HYDROPHILIZING EQUIPMENT OF FIBER MATERIALS, METHOD FOR THEIR PRODUCTION AND THEIR USE |
DE4201603A1 (en) * | 1992-01-22 | 1993-07-29 | Bayer Ag | MIXTURES OF FLUORINE COPOLYMERISATE |
US5387640A (en) * | 1992-01-22 | 1995-02-07 | Bayer Aktiengesellschaft | Fluorine-containing copolymers and aqueous dispersions prepared therefrom |
-
2002
- 2002-09-14 DE DE10242762A patent/DE10242762A1/en not_active Withdrawn
-
2003
- 2003-08-29 TW TW092123919A patent/TW200407338A/en unknown
- 2003-09-05 CN CNB038216167A patent/CN1289598C/en not_active Expired - Fee Related
- 2003-09-05 WO PCT/EP2003/009854 patent/WO2004026959A1/en active Application Filing
- 2003-09-05 US US10/527,244 patent/US20050257325A1/en not_active Abandoned
- 2003-09-05 EP EP03753386A patent/EP1537176A1/en not_active Withdrawn
Also Published As
Publication number | Publication date |
---|---|
CN1289598C (en) | 2006-12-13 |
CN1681882A (en) | 2005-10-12 |
TW200407338A (en) | 2004-05-16 |
US20050257325A1 (en) | 2005-11-24 |
EP1537176A1 (en) | 2005-06-08 |
WO2004026959A1 (en) | 2004-04-01 |
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