EP0326702B1 - Amine salts as stabilizers for the oil and water repellent finishing of fibre materials - Google Patents
Amine salts as stabilizers for the oil and water repellent finishing of fibre materials Download PDFInfo
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- EP0326702B1 EP0326702B1 EP88121350A EP88121350A EP0326702B1 EP 0326702 B1 EP0326702 B1 EP 0326702B1 EP 88121350 A EP88121350 A EP 88121350A EP 88121350 A EP88121350 A EP 88121350A EP 0326702 B1 EP0326702 B1 EP 0326702B1
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/325—Amines
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- the present invention relates to the use of certain water-soluble amine salts as an additive to aqueous liquors in the context of the oil- and / or water-repellent finishing of fiber materials.
- the amine salts act as liquor stabilizers.
- amine salts as emulsifiers for compositions which contain waxes, aluminum salts and fatty acids, the fatty acids being used as stabilizers.
- the present invention has set itself the task for the oil and / or water-repellent finishing of fiber materials by means of aqueous liquors, which at least one silicone or an organic Contain fluorine compound as additives such liquor stabilizers that do not have the disadvantages shown.
- aqueous liquors which at least one silicone or an organic Contain fluorine compound as additives such liquor stabilizers that do not have the disadvantages shown.
- selected amine salts which are usually present in an aqueous medium, are extremely effective liquor stabilizers.
- These amine salts are dispersants for a wide variety of purposes, for example as anticoagulants (JP application 45/24710 ref. In Derwent CPI ref. No.
- R1, R2 and R3 independently of one another are an alkyl radical having 1 to 22 carbon atoms or hydrogen, with the proviso that at least 1 alkyl radical having at least 8 carbon atoms is present and the sum of the carbon atoms in the alkyl radicals is at most 33, is preferably at most 22,
- An is an anion and x is an integer corresponding to the negative charges of the anion, as an additive to aqueous liquors for the water- and / or oil-repellent finishing of fiber materials, the aqueous liquors containing at least one silicone or an organic fluorine compound.
- the liquor stabilizers of the present invention are the amines of the formula (I a) underlying, wherein R1, R2 and R3 independently of one another are an alkyl radical having 1 to 22 carbon atoms or hydrogen, with the proviso that at least 1 alkyl radical having at least 8 carbon atoms and the sum of the carbon atoms in the alkyl radicals is at most 33 , preferably at most 22, and the condition is fulfilled that the stabilizers obtained therefrom are soluble in water.
- examples of such amines are: Octylamine, Stearylamine, Behenylamine, Octadecyldimethylamine, Dodecyldiethylamine, Palmityldimethylamine, Dipalmitylmethylamine.
- acids succinic acid, maleic acid, sulfuric acid, particularly monovalent acids such as propionic acid, formic acid, glycolic acid, lactic acid, hydrochloric acid, nitric acid and very particularly acetic acid.
- the acetates in particular have proven to be particularly effective as liquor stabilizers.
- the solutions of the liquor stabilizers are generally between 10 and 30, in particular 18 to 25,% by weight of amine salt.
- this procedure is complex and the products obtained are sometimes less effective, so that the resulting aqueous formulations are preferably used immediately as such.
- the efficacy of the liquor stabilizers which can be used according to the invention is broad. However, the effects can still be improved by adding the usual emulsifiers to the same, in amounts of 5 to 55% by weight, in particular 10 to 40% by weight, based on the amine salt.
- the emulsifiers used are known to the person skilled in the art. These are, in particular, nonionic and / or weakly cationic emulsifiers.
- Ethylene oxide adducts of fatty alcohols in particular those of primary and / or secondary, linear to branched alcohols having 8 to 16 C atoms and ethoxylated C, are suitable as emulsifiers 6 to C12 alkylphenols, the number of ethylene oxide units being between 6 and 30, suitable.
- emulsifiers examples include: 2,6,8-Trimethyl-4-Nonyloxihexaethylenoxiethanol, Isotridecylethoxilat with an average of 8 ethylene oxide units, with an average of 12 moles of ethylene oxide ethoxylated secondary dodecyl alcohol or n-decyl alcohol and nonylphenol polyglycol ether with an average of 10 ethylene oxide units.
- nitrogen-containing emulsifiers such as those formed by ethoxylation of fatty amines or fatty acid amides, are also suitable, it being possible for these compounds to be present in salt form by adding acids.
- the liquor stabilizers which can be used according to the invention have a tendency to foam, and it has therefore proven expedient proven to add the same defoamer.
- the commercially available products are suitable in commercially available amounts, silicone-free defoamers being preferred.
- Defoamers which are known to those skilled in the art, such as octadecanol, isotridecanol, tributyl phosphate, higher ketones and the usual defoamers based on silicones or mixtures of the various compounds, may be mentioned.
- the liquor stabilizers which can be used according to the invention are used in the course of oil and / or water-repellent finishing of fiber materials.
- the various known chemicals based on organic fluorine compounds are used for the oil-repellent finish.
- the person skilled in the art knows the polymers or copolymers based on perfluoroalkyl acrylates and also the other compounds used for oil repellency, as described, for example, in EP-B-073 364, US Pat. No. 3,356,628, US Pat. No. 3,968,066 and US-A-4 054 592 and DE-A-34 35 618.
- the extenders used together with the fluorochemicals are also described on a case-by-case basis (see also DE-PS-1 233 874).
- oil-repellent agents are generally used in the form of aqueous emulsions, the emulsions generally containing 15 to 35% by weight of active substance.
- silicones are used for the water-repellent finish.
- the silicones are primarily dispersions of known polydimethylsiloxanes and hydrogen methylpolysiloxane cans are mainly used for economic reasons, but other known silicones can also be used within the scope of the invention.
- oleophobicizing or hydrophobicizing agents which can be used in the context of the invention are within the scope known to the person skilled in the art.
- finishing liquors can contain customary additives, in particular crease-free agents and fillers, e.g. Softening agents and the associated catalysts are added in customary amounts.
- the molten amine is added to the 1st vessel in a thin stream with vigorous stirring in such a way that the temperature is between 85 and 95 ° C. After the amine addition has ended, the mixture is stirred for a further 10 minutes at the temperature mentioned and then bottled.
- the product solidifies into a transparent, highly viscous mass at room temperature.
- the viscosity of a 1:10 dilution with water of this mass is 720 mPa.s (at 20 ° C).
- Example 1 the following liquor stabilizers are prepared in aqueous medium by converting 1 mol of the amines with 1.25-1.3 mol of the corresponding acids (concentration of amine salt approx. 18%): Octadecyldimethylammonium formate, Hexadecylammonium lactate, Octyldiethylammonium glycolate and Behenylammonium chloride.
- the described emulsifier can easily be replaced by 15 g of stearyl alcohol polyglycol ether (ethoxylated with an average of 15 moles of ethylene oxide per mole of alcohol).
- 25g®FUMEXOL B from CIBA-GEIGY AG are also suitable.
- these liquor stabilizers are outstandingly suitable for stabilizing liquors for oil- and / or water-repellent finishing, whereby the inexpensive stabilizers, which can be produced in a simple manner, are easy to process and do not cause any odor nuisance, and also during drying and condensation of the treated fiber materials no adverse fissile materials occur.
- a polyester jacketed poplin (approx. 200 g / m2) is padded with the following liquors (liquor absorption 55 to 60%) and completed by drying (10 minutes at 110 ° C) and condensation (5 minutes at 150 ° C).
- the following fleets were used for the equipment:
- 3 g / l and 5 g / l of the products according to Example 1 and Example 2 are added to each of these liquors A and B to stabilize the liquors.
- 3 g / l or 5 g / l of a commercially available stabilizing agent (approx. 20% octadecyloximethylpyridinium chloride; comparative product) are also added to the individual liquors.
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Description
Die vorliegende Erfindung betrifft die Verwendung bestimmter wasserlöslicher Aminsalze als Zusatz zu wäßrigen Flotten im Rahmen der öl- und/oder Wasserabweisenden Ausrüstung von Fasermaterialien. Die Aminsalze fungieren hierbei als Flottenstabilisatoren.The present invention relates to the use of certain water-soluble amine salts as an additive to aqueous liquors in the context of the oil- and / or water-repellent finishing of fiber materials. The amine salts act as liquor stabilizers.
Die Stabilisierung von wäßrigen Flotten bei der öl- und/oder wasserabweisenden Ausrüstung ist längst bekannt. Sie ist erforderlich, um bei den empfindlichen Flotten Abscheidungen zu verhindern, die zu Flecken auf den auszurüstenden Fasermaterialien führen. Die Verwendung von Emulgatoren allein ist dabei durch Beeinträchtigung der Effekte nicht möglich. So werden für dieses Einsatzgebiet nach dem Stand der Technik vor allem quaternäre Ammoniumverbindungen, insbesondere Octadecyloximethylpyridiniumchlorid empfohlen. Diese Verbindungen sind nur in einem relativ umständlichen und damit teuren Herstellungsprozess zu gewinnen und weisen auch von Fall zu Fall einen unangenehmen Eigengeruch auf. Das bevorzugt verwendete Octadecyloximethylpyridiniumchlorid ist dabei durch eine höhere Lösungstemperatur zusätzlich noch umständlich in der Handhabung und bei der Verarbeitung durch Abspaltung von Formaldehyd und Pyridin als problematisch einzustufen.The stabilization of aqueous fleets in the oil and / or water repellent finish has long been known. It is necessary to prevent deposits from forming in the sensitive liquors, which lead to stains on the fiber materials to be finished. The use of emulsifiers alone is not possible by impairing the effects. Quaternary ammonium compounds, in particular octadecyloximethylpyridinium chloride, are recommended for this area of use according to the prior art. These compounds can only be obtained in a relatively cumbersome and therefore expensive manufacturing process and also have an unpleasant odor from case to case. The preferably used octadecyloximethylpyridinium chloride is also cumbersome to handle due to a higher solution temperature and can be classified as problematic in handling and processing by splitting off formaldehyde and pyridine.
Aus der GB-A-602 109 ist es bekannt, Aminsalze als Emulgatoren für Zusammensetzungen zu verwenden, welche Wachse, Aluminiumsalze und Fettsäuren enthalten, wobei die Fettsäuren als Stabilisatoren dienen sollen.From GB-A-602 109 it is known to use amine salts as emulsifiers for compositions which contain waxes, aluminum salts and fatty acids, the fatty acids being used as stabilizers.
Die vorliegende Erfindung hat sich die Aufgabe gestellt, für die öl- und/oder wasserabweisende Ausrüstung von Fasermaterialien mittels wäßriger Flotten, welche mindestens ein Silikon oder eine organische Fluorverbindung enthalten, als Zusätze solche Flottenstabilisatoren zu verwenden, welche die aufgezeigten Nachteile nicht aufweisen. Überraschenderweise wurde gefunden, daß ausgewählte Aminsalze, die üblicherweise in wässerigem Medium vorliegen, äußerst wirksame Flottenstabilisatoren sind. Diese Aminsalze sind für die unterschiedlichsten Zwecke, z.B. als Antikoagulationsmittel (JP-Anmeldung 45/24710 ref. in Derwent CPI-Ref.-Nr. 39182 Q), Dispergiermittel (siehe Aufsatz "Study on Textile Dyeing Additives - Dyeing Additive for Polyester Fibres", referiert in CA 90 (18) 138.939 c) und Vorbehandlungsmittel (FR-A 2 090 205) bekannt, doch konnte aus diesen Einsatzgebieten keineswegs auf den Gegenstand der Erfindung geschlossen werden. Die Lösung der gestellten Aufgabe besteht somit gemäß Anspruch 1 in der Verwendung von wasserlöslichen Salzen von Aminen der allgemeinen Formel (I)
In der R₁, R₂ und R₃ unabhängig voneinander einen Alkylrest mit 1 bis 22 C-Atomen oder Wasserstoff bedeuten mit der Maßgabe, daß mindestens 1 Alkylrest mit mindestens 8 C-Atomen zugegen ist und die Summe der C-Atome in den Alkylresten höchstens 33, vorzugsweise hochstens 22 ausmacht, An ein Anion und x eine ganze Zahl entsprechend den negativen Ladungen des Anions bedeuten,
als Zusatz zu wäßrigen Flotten für die wasser- und/oder ölabweisende Ausrüstung von Fasermaterialien, wobei die wäßrigen Flotten mindestens ein Silikon oder eine organische Fluorverbindung enthalten.In which R₁, R₂ and R₃ independently of one another are an alkyl radical having 1 to 22 carbon atoms or hydrogen, with the proviso that at least 1 alkyl radical having at least 8 carbon atoms is present and the sum of the carbon atoms in the alkyl radicals is at most 33, is preferably at most 22, An is an anion and x is an integer corresponding to the negative charges of the anion,
as an additive to aqueous liquors for the water- and / or oil-repellent finishing of fiber materials, the aqueous liquors containing at least one silicone or an organic fluorine compound.
In den Unteransprüchen 2 bis 10 werden bevorzugte Ausführungsformen der Erfindung erläutert.Preferred embodiments of the invention are explained in subclaims 2 to 10.
Den Flottenstabilisatoren der vorliegenden Erfindung liegen die Amine der Formel (I a)
zugrunde, wobei R₁, R₂ und R₃ unabhängig voneinander einen Alkylrest mit 1 bis 22 C-Atomen oder Wasserstoff bedeuten, mit der Maßgabe, daß mindestens 1 Alkylrest mit mindestens 8 C-Atomen zugegen und die Summe der C-Atome in den Alkylresten höchstens 33, vorzugsweise höchstens 22 ausmacht, sowie die Bedingung erfüllt ist, daß die daraus erhaltenen Stabilisatoren in Wasser löslich sind. Als Beispiele für derartige Amine seien genannt:
Octylamin,
Stearylamin,
Behenylamin,
Octadecyldimethylamin,
Dodecyldiethylamin,
Palmityldimethylamin,
Dipalmitylmethylamin.The liquor stabilizers of the present invention are the amines of the formula (I a)
underlying, wherein R₁, R₂ and R₃ independently of one another are an alkyl radical having 1 to 22 carbon atoms or hydrogen, with the proviso that at least 1 alkyl radical having at least 8 carbon atoms and the sum of the carbon atoms in the alkyl radicals is at most 33 , preferably at most 22, and the condition is fulfilled that the stabilizers obtained therefrom are soluble in water. Examples of such amines are:
Octylamine,
Stearylamine,
Behenylamine,
Octadecyldimethylamine,
Dodecyldiethylamine,
Palmityldimethylamine,
Dipalmitylmethylamine.
Selbstverständlich können auch technische Gemische der vorliegenden Amine zur Herstellung der Flottenstabilisatoren herangezogen werden. Als besonders wirksam haben sich Amine erwiesen, in denen R₁ einen gesättigten Alkylrest mit 8 bis 10 bzw. 16 bis 18 C-Atomen und R₂ und R₃ Wasserstoff oder den Methylrest bedeuten. Die Stabilisatoren mit C₈₋₁₀-Alkylresten sind besonders gut löslich und schaumarm und diejenigen mit C₁₆₋₁₈-Alkylresten sind besonders effektstark. Die Herstellung von erfindungsgemäß verwendbaren Flottenstabilisatoren gelingt in wässeriger Lösung dadurch, daß die beschriebenen Amine mit einem geringen Überschuß an Säuren weitgehend umgesetzt werden. Im allgemeinen werden auf 1 Mol des Amins 1,1 bis 1,45 Äquivalente an Säure zur Reaktion gebracht. Als Säuren seien dabei genannt: Bernsteinsäure, Maleinsäure, Schwefelsäure, besonders einwertige Säuren wie Propionsäure, Ameisensäure, Glykolsäure, Milchsäure, Salzsäure, Salpetersäure und ganz besonders Essigsäure. Gerade die Acetate haben sich als Flottenstabilisatoren als besonders wirksam erwiesen. Die Lösungen der Flottenstabilisatoren fallen im allgemeinen zwischen 10 und 30, insbesondere 18 bis 25 Gew.% an Aminsalz an. Es ist jedoch auch möglich, durch Entfernen des Wassers, z.B. durch Verdampfen oder durch Sprühtrocknung, pulverförmige Flottenstabilisatoren zu erhalten. Diese Arbeitsweise ist jedoch aufwendig und die erhaltenen Produkte sind teilweise weniger wirksam, so daß bevorzugt die anfallenden wässerigen Formulierungen als solche sofort eingesetzt werden.Of course, technical mixtures of the present amines can also be used to prepare the liquor stabilizers. Amines have proven to be particularly effective in which R 1 is a saturated alkyl radical having 8 to 10 or 16 to 18 carbon atoms and R 2 and R 3 are hydrogen or the methyl radical. The stabilizers with C₈₋₁₀ alkyl residues are particularly soluble and low-foaming and those with C₁₆₋₁₈ alkyl residues are particularly effective. The liquor stabilizers which can be used according to the invention are prepared in aqueous solution by largely reacting the amines described with a slight excess of acids. In general, 1.1 to 1.45 equivalents of acid are reacted per mole of the amine. The following may be mentioned as acids: succinic acid, maleic acid, sulfuric acid, particularly monovalent acids such as propionic acid, formic acid, glycolic acid, lactic acid, hydrochloric acid, nitric acid and very particularly acetic acid. The acetates in particular have proven to be particularly effective as liquor stabilizers. The solutions of the liquor stabilizers are generally between 10 and 30, in particular 18 to 25,% by weight of amine salt. However, it is also possible to remove the water e.g. to obtain pulverulent liquor stabilizers by evaporation or by spray drying. However, this procedure is complex and the products obtained are sometimes less effective, so that the resulting aqueous formulations are preferably used immediately as such.
Die Wirksamkeit der erfindungsgemäß verwendbaren Flottenstabilisatoren ist in einem weiten Rahmen gegeben. Eine Verbesserung der Effekte ist jedoch noch dadurch zu erzielen, daß denselben übliche Emulgatoren zugesetzt werden, und zwar in Mengen von 5 bis 55 Gew.%, insbesondere 10 bis 40 Gew.%, bezogen auf das Aminsalz. Die verwendeten Emulgatoren sind dem Fachmann bekannt. Es handelt sich dabei insbesondere um nicht-ionische und/oder schwach kationische Emulgatoren.The efficacy of the liquor stabilizers which can be used according to the invention is broad. However, the effects can still be improved by adding the usual emulsifiers to the same, in amounts of 5 to 55% by weight, in particular 10 to 40% by weight, based on the amine salt. The emulsifiers used are known to the person skilled in the art. These are, in particular, nonionic and / or weakly cationic emulsifiers.
Als Emulgatoren sind Ethylenoxidaddukte von Fettalkoholen, insbesondere solche von primären und/oder sekundären, linearen bis verzweigten Alkoholen mit 8 bis 16 C-Atomen und ethoxilierte C
2,6,8-Trimethyl-4-Nonyloxihexaethylenoxiethanol, Isotridecylethoxilat mit durchschnittlich 8 Ethylenoxideinheiten, mit durchschnittlich 12 Mol Ethylenoxid ethoxilierter sekundärer Dodecylalkohol oder n-Decylalkohol und Nonylphenolpolyglykolether mit durchschnittlich 10 Ethylenoxideinheiten. Daneben sind in gleicher Weise auch stickstoffhaltige Emulgatoren, wie sie durch Ethoxilierung von Fettaminen oder Fettsäureamiden entstehen, geeignet, wobei diese Verbindungen durch Zugabe von Säuren auch in Salzform vorliegen können.
Als Beispiele, wiederum ohne Anspruch auf Vollständigkeit, seien folgende Verbindungen genannt:
Dodecyloxypropylamin ethoxiliert mit 12 bis 15 Mol Ethylenoxid in Form des Acetats, Stearylamin ethoxiliert mit durchschnittlich 20 Mol Ethylenoxid, Hexadecylamin ethoxiliert mit durchschnittlich 15 Mol Ethylenoxid in Form des Acetats und Stearinsäureamid ethoxiliert mit 25 Mol Ethylenoxid.Ethylene oxide adducts of fatty alcohols, in particular those of primary and / or secondary, linear to branched alcohols having 8 to 16 C atoms and ethoxylated C, are suitable as emulsifiers
2,6,8-Trimethyl-4-Nonyloxihexaethylenoxiethanol, Isotridecylethoxilat with an average of 8 ethylene oxide units, with an average of 12 moles of ethylene oxide ethoxylated secondary dodecyl alcohol or n-decyl alcohol and nonylphenol polyglycol ether with an average of 10 ethylene oxide units. In addition, nitrogen-containing emulsifiers, such as those formed by ethoxylation of fatty amines or fatty acid amides, are also suitable, it being possible for these compounds to be present in salt form by adding acids.
The following compounds are mentioned as examples, again without claim to completeness:
Dodecyloxypropylamine ethoxylates with 12 to 15 moles of ethylene oxide in the form of the acetate, stearylamine ethoxylates with an average of 20 moles of ethylene oxide, hexadecylamine ethoxylates with an average of 15 moles of ethylene oxide in the form of the acetate and stearic acid amide with 25 moles of ethylene oxide.
Die erfindungsgemäß verwendbaren Flottenstabilisatoren neigen zum Schäumen, und es hat sich deshalb als zweckmäßig erwiesen, denselben Entschäumer zuzusetzen. Als solche sind die handelsüblichen Produkte in handelsüblichen Mengen geeignet, wobei silikonfreie Entschäumer bevorzugt eingesetzt werden. Als Entschäumer seien dem Fachmann bekannte Verbindungen, wie Octadecanol, Isotridecanol, Tributylphosphat, höhere Ketone und die üblichen Entschäumer auf Basis von Silikonen bzw. Mischungen der verschiedenen Verbindungen genannt.The liquor stabilizers which can be used according to the invention have a tendency to foam, and it has therefore proven expedient proven to add the same defoamer. As such, the commercially available products are suitable in commercially available amounts, silicone-free defoamers being preferred. Defoamers which are known to those skilled in the art, such as octadecanol, isotridecanol, tributyl phosphate, higher ketones and the usual defoamers based on silicones or mixtures of the various compounds, may be mentioned.
Die erfindungsgemäß verwendbaren Flottenstabilisatoren werden im Rahmen der öl- und bzw. oder wasserabweisenden Ausrüstung von Fasermaterialien eingesetzt. Für die ölabweisende Ausrüstung kommen die verschiedenen bekannten Chemikalien auf Basis organischer Fluorverbindungen zum Einsatz. Der Fachmann kennt die Polymeren bzw. Copolymeren auf Basis von Perfluoralkylacrylaten und auch die anderen zur Ölabweisung verwendeten Verbindungen, wie sie z.B. in der EP-B-073 364, der U.S.-A-3 356 628, der U.S.-A-3 968 066 und der U.S.-A-4 054 592, und der DE-A-34 35 618 beschrieben werden. In diesen Druckschriften werden von Fall zu Fall auch die zusammen mit den Fluorchemikalien eingesetzten Extender beschrieben (siehe hierzu auch DE-PS-1 233 874). Diese ölabweisenden Mittel werden im allgemeinen in Form von wässerigen Emulsionen angewandt, wobei die Emulsionen in der Regel 15 bis 35 Gew.% an Aktivsubstanz enthalten. Neben den bereits angesprochenen Extendern kommen zur wasserabweisenden Ausrüstung Silikone zum Einsatz. Diese Produkte bzw. die zur Anwendung kommenden Dispersionen derselben sind dem Fachmann bekannt und er wird keine Mühe haben, die entsprechenden Ausrüstungsmittel auszuwählen.The liquor stabilizers which can be used according to the invention are used in the course of oil and / or water-repellent finishing of fiber materials. The various known chemicals based on organic fluorine compounds are used for the oil-repellent finish. The person skilled in the art knows the polymers or copolymers based on perfluoroalkyl acrylates and also the other compounds used for oil repellency, as described, for example, in EP-B-073 364, US Pat. No. 3,356,628, US Pat. No. 3,968,066 and US-A-4 054 592 and DE-A-34 35 618. In these publications, the extenders used together with the fluorochemicals are also described on a case-by-case basis (see also DE-PS-1 233 874). These oil-repellent agents are generally used in the form of aqueous emulsions, the emulsions generally containing 15 to 35% by weight of active substance. In addition to the extenders already mentioned, silicones are used for the water-repellent finish. These products or the dispersions used thereof are known to the person skilled in the art and he will have no trouble selecting the appropriate finishing agents.
Bei den Silikonen handelt es sich in erster Linie um Dispersionen bekannter Polydimethylsiloxane und Wasserstoffmethylpolysiloxane Dose werden aus wirtschaftlichen Gründen vorwiegend eingesetzt jedoch sind auch andere bekannte Silikone durchaus im Rahmen der Erfindung verwendbar.The silicones are primarily dispersions of known polydimethylsiloxanes and hydrogen methylpolysiloxane cans are mainly used for economic reasons, but other known silicones can also be used within the scope of the invention.
Die im Rahmen der Erfindung einsetzbaren Mengen an Oleophobierungs- oder Hydrophobierungsmittel bewegen sich in dem dem Fachmann bekannten Rahmen.The amounts of oleophobicizing or hydrophobicizing agents which can be used in the context of the invention are within the scope known to the person skilled in the art.
Selbstverständlich können den Ausrüstungsflotten, wie das der Fachmann gewohnt ist, übliche Zusatzstoffe, insbesondere Knitterfreimittel und Füllmittel, z.B. Weichgriffmittel und die dazugehörigen Katalysatoren in üblichen Mengen zugesetzt werden.Of course, as is known to the person skilled in the art, the finishing liquors can contain customary additives, in particular crease-free agents and fillers, e.g. Softening agents and the associated catalysts are added in customary amounts.
Es ist überraschend und war dem Stand der Technik keineswegs zu entnehmen, daß durch die Verwendung dieser einfachen Aminsalze hervorragende Flottenstabilisatoren zur Verfügung gestellt werden können. Diese Verbindungen zeichnen sich durch eine einfache und damit kostengünstige Herstellung aus, sind nahezu geruchsneutral und durch die niedrigere Lösungstemperatur einfach in der Handhabung. Besonders hervorzuheben ist aber, daß störende Spaltprodukte bei der Verwendung dieser Produkte nicht auftreten und somit durch den Einsatz dieser einfachen Verbindungen ein wesentlicher ökologischer Fortschritt erzielt wird.
Dabei ist aber die Wirksamkeit in vollem Umfang gegeben. So bleiben die ansonsten empfindlichen Flotten über mehrere Stunden stabil, was vor allem unter den rauheren Bedingungen der Praxis von Bedeutung ist. Außerdem werden durch den erfindungsgemäßen Zusatz der Aminsalze als Flottenstabilisatoren Walzenbeläge weitgehend vermieden, ohne daß ein negativer Einfluß auf die Ausrüstungseffekte zu beobachten ist. Durch Walzenbeläge entstehen Flecken auf der ausgerüsteten Ware, so daß der Einsatz von Flottenstabilisatoren für die öl- und/oder wasserabweisende Ausrüstung unumgänglich ist.It is surprising and was by no means apparent from the prior art that excellent liquor stabilizers can be provided by using these simple amine salts. These compounds are characterized by simple and therefore inexpensive production, are almost odorless and easy to handle due to the lower solution temperature. It should be particularly emphasized, however, that disruptive fission products do not occur when these products are used, and consequently significant ecological progress is achieved through the use of these simple compounds.
However, the effectiveness is fully available. In this way, the otherwise sensitive fleets remain stable for several hours, which is particularly important under the harsher conditions in practice. In addition, the addition of the amine salts as liquor stabilizers according to the invention largely prevents roller coatings without having a negative influence on the finishing effects can be observed. Roll coverings cause stains on the finished goods, so that the use of liquor stabilizers for the oil- and / or water-repellent finish is unavoidable.
Die Erfindung wird durch die nachfolgenden Beispiele erläutert. In diesen Beispielen bedeuten % = Gewichtsprozent und Teile = Gewichtsteile.The invention is illustrated by the following examples. In these examples,% = percent by weight and parts = parts by weight.
1300 g Wasser, 138 g 60%-ige Essigsäure und 34 g eines handelsüblichen Silikonentschäumers (Wirksubstanz 40 Gew.%) werden in einem 4-Liter-4-Halskolben (1. Gefaß) mit wirksamem Rührer, Innenthermometer und Rückflußkühler auf 85°C erwärmt.
In einem 2. Gefäß werden 265 g (1 Mol) hydriertes Talgfettamin (dest.; 98% primäres Amin folgender Zusammensetzung: 5% C₁₄, 32% C₁₆, 60% C₁₈, 3% ungesättigt C₁₈, Aminzahl 208 - 223) geschmolzen und ebenfalls auf 85°C erwärmt. Nach Entfernen der Heizquelle wird das geschmolzene Amin in dünnem Strahl unter kräftigem Rühren in der Weise dem 1. Gefäß zugefügt, daß die Temperatur zwischen 85 und 95°C betragt. Nach Ende der Aminzugabe wird noch 10 Minuten bei der genannten Temperatur gerührt und dann abgefüllt. Das Produkt erstarrt bei Zimmertemperatur zu einer durchsichtigen, hochviskosen Masse. Die Viskosität einer Verdünnung 1:10 mit Wasser dieser Masse liegt bei 720 mPa.s (bei 20°C). Der pH-Wert der 20%-igen Lösung beträgt ca. 4,9 (=Produkt 1).1300 g of water, 138 g of 60% acetic acid and 34 g of a commercially available silicone defoamer (active substance 40% by weight) are brought to 85 ° C. in a 4 liter 4-necked flask (1st vessel) with an effective stirrer, internal thermometer and reflux condenser warmed up.
In a second vessel 265 g (1 mol) of hydrogenated tallow fatty amine (dest .; 98% primary amine of the following composition: 5% C₁₄, 32% C₁₆, 60% C₁₈, 3% unsaturated C₁₈, amine number 208-223) are melted and also heated to 85 ° C. After removing the heating source, the molten amine is added to the 1st vessel in a thin stream with vigorous stirring in such a way that the temperature is between 85 and 95 ° C. After the amine addition has ended, the mixture is stirred for a further 10 minutes at the temperature mentioned and then bottled. The product solidifies into a transparent, highly viscous mass at room temperature. The viscosity of a 1:10 dilution with water of this mass is 720 mPa.s (at 20 ° C). The pH of the 20% solution is approximately 4.9 (= product 1).
500 g Fettaminacetatlösung nach Beispiel 1, in der der Silikonentschäumer durch 19 g Tributylphosphat ersetzt wurde, werden mit 20 g Emulgator (Dodecyloxypropylamin ethoxyliert mit 12 bis 15 Mol Ethylenoxid in Form des Acetats) unter Rühren auf 80°C erwärmt, 15 Minuten bei dieser Temperatur gehalten und dann abgefüllt. Das bei 80°C dünnflüssige Produkt (pH-Wert 4,5) erstarrt beim Abkühlen zu einer pastösen Masse. Die Viskosität dieser Lösung nach einer Verdünnung 1:10 liegt bei 600 mPa.s (=Produkt 2).500 g of fatty amine acetate solution according to Example 1, in which the silicone defoamer was replaced by 19 g of tributyl phosphate, are heated to 80 ° C. with 20 g of emulsifier (dodecyloxypropylamine ethoxylated with 12 to 15 mol of ethylene oxide in the form of the acetate), with stirring, for 15 minutes at this temperature held and then bottled. The product, which is thin at 80 ° C (pH 4.5), solidifies on cooling to a pasty mass. The viscosity of this solution after dilution 1:10 is 600 mPa.s (= product 2).
Die Produkte aus Beispiel 1 und 2 sind, wie nachfolgende Ausrüstungsbeispiele zeigen, in hervorragender Weise zur Stabilisierung von Ausrüstungsflotten geeignet.The products from Examples 1 and 2, as the following equipment examples show, are outstandingly suitable for stabilizing equipment fleets.
In der im Beispiel 1 beschriebenen Weise werden durch Umsatz von 1 Mol der Amine mit 1,25 - 1,3 Mol der entsprechenden Säuren folgende Flottenstabilisatoren in wäßrigem Medium hergestellt (Konzentration an Aminsalz ca. 18%):
Octadecyldimethylammoniumformiat,
Hexadecylammoniumlactat,
Octyldiethylammoniumglykolat und
Behenylammoniumchlorid.In the manner described in Example 1, the following liquor stabilizers are prepared in aqueous medium by converting 1 mol of the amines with 1.25-1.3 mol of the corresponding acids (concentration of amine salt approx. 18%):
Octadecyldimethylammonium formate,
Hexadecylammonium lactate,
Octyldiethylammonium glycolate and
Behenylammonium chloride.
Der beschriebene Emulgator kann ohne weiteres durch 15g Stearylalkoholpolyglykolether (ethoxiliert mit durchschnittlich 15 Mol Ethylenoxid je Mol Alkohol) ersetzt werden. Anstelle der genannten Entschäumungsmittel sind ebenso 25g®FUMEXOL B der Firma CIBA-GEIGY AG geeignet.
Diese Flottenstabilisatoren sind ebenso wie im Beispiel 1 in hervorragender Weise zur Stabilisierung von Flotten zur öl- und/oder wasserabweisenden Ausrüstung geeignet, wobei die in einfacher Weise herstellbaren, preisgünstigen Stabilisatoren leicht zu verarbeiten sind und keine Geruchsbelästigungen entstehen und auch bei der Trocknung und Kondensation der behandelten Fasermaterialien keine nachteiligen Spaltstoffe auftreten.The described emulsifier can easily be replaced by 15 g of stearyl alcohol polyglycol ether (ethoxylated with an average of 15 moles of ethylene oxide per mole of alcohol). Instead of the defoaming agents mentioned, 25g®FUMEXOL B from CIBA-GEIGY AG are also suitable.
As in Example 1, these liquor stabilizers are outstandingly suitable for stabilizing liquors for oil- and / or water-repellent finishing, whereby the inexpensive stabilizers, which can be produced in a simple manner, are easy to process and do not cause any odor nuisance, and also during drying and condensation of the treated fiber materials no adverse fissile materials occur.
Es werden 1 Mol n-Decylamin und 1 Mol Bernsteinsaure in 765g Wasser bei 70°C unter Temperaturerhöhung zu einer wasserklaren niedrigviskosen Lösung (pH-Wert 4,3) umgesetzt, die beim Abkühlen zu einer kristallinen, weißen Masse mit guter Wasserlöslichkeit erstarrt.1 mol of n-decylamine and 1 mol of succinic acid are reacted in 765 g of water at 70 ° C. while increasing the temperature to give a water-clear, low-viscosity solution (pH 4.3), which solidifies on cooling to a crystalline, white mass with good water solubility.
Ein Polyester-Mantelpopeline (ca. 200 g/m²) wird mit den nachfolgend genannten Flotten foulardiert (Flottenaufnahme 55 bis 60%) und durch Trocknen (10 Minuten bei 110°C) und Kondensieren (5 Minuten bei 150°C) fertiggestellt. Zur Ausrüstung wurden folgende Flotten herangezogen:A polyester jacketed poplin (approx. 200 g / m²) is padded with the following liquors (liquor absorption 55 to 60%) and completed by drying (10 minutes at 110 ° C) and condensation (5 minutes at 150 ° C). The following fleets were used for the equipment:
20 g/l einer ca. 70%-igen, wässerigen Lösung von mit Methanol verethertem Dimethyloldihydroxyethylenharnstoff (enthält ca. 6% Alkalichlorid) (Komponente 1),
5 ml/l einer wässrigen, ca. 55%-igen Zinkchloridlösung (pH-Wert ca. 2,2) (Komponente 2), 2 ml/l Essigsäure 60%-ig, 30 g/l eines handelsüblichen Extenders (ca. 12% fettmodifizierter Hexamethylolmelaminmethylether, ca. 1% Emulgator, ca. 5% Propylenglykol),
25 g/l eines handelsüblichen ca. 20%-igen Oleophobierungsmittels (®SCOTCHGARD FC 251 der 3 M-Company)20 g / l of an approximately 70% aqueous solution of dimethylol dihydroxyethylene urea etherified with methanol (contains approximately 6% alkali metal chloride) (component 1),
5 ml / l of an aqueous, approx. 55% zinc chloride solution (pH approx. 2.2) (component 2), 2 ml / l acetic acid 60%, 30 g / l of a commercially available extender (approx. 12 % fat-modified hexamethylolmelamine methyl ether, approx. 1% emulsifier, approx. 5% propylene glycol),
25 g / l of a commercially available approx. 20% oleophobicizing agent (®SCOTCHGARD FC 251 from the 3 M company)
- 20 g/l20 g / l
- Komponente (1),Component (1),
- 5 ml/l5 ml / l
- Komponente (2),Component (2),
- 2 ml/l2 ml / l
- Essigsäure 60%-ig60% acetic acid
- 20 g/l20 g / l
- einer handelsüblichen, wässerigen, schwach kationischen, ca. 40%-igen Wasserstoffmethylpolysiloxanemulsion unda commercially available, aqueous, weakly cationic, approx. 40% hydrogen methyl polysiloxane emulsion and
- 15 g/l15 g / l
- einer handelsüblichen, wässerigen, schwach kationischen, ca. 25%-igen Dimethylpolysiloxanemulsion.a commercially available, aqueous, weakly cationic, approx. 25% dimethylpolysiloxane emulsion.
Diesen Flotten A und B werden jeweils 3 g/l bzw. 5 g/l der Produkte nach Beispiel 1 bzw. Beispiel 2 zur Stabilisierung der Flotten zugesetzt. Zum Vergleich werden den einzelnen Flotten ebenfalls 3 g/l bzw. 5 g/l eines handelsüblichen Stabilisierungsmittels (ca. 20% Octadecyloximethylpyridiniumchlorid; Vergleichsprodukt) beigefügt. Die mit diesen Flotten erhaltenen Ausrüstungen sind in der nachfolgenden Tabelle zusammengefaßt (Prüfung der Wasserabweisung nach DIN 53888 bzw. dem Spraytest entsprechend AATCC 22-1974 und der Ölabweisung nach AATCC 118-1972):
Die gesamten Ergebnisse des Ausrüstungsbeispiels zeigen, daß die erfindungsgemäßen Flottenstabilisatoren keinen negativen Einfluß auf die Hydrophobier- und Oleophobiereffekte haben und auch in hohem Maße wirksam sind, denn selbst unter extremen Betriebsbedingungen sind, die Ausrüstungsflotten mindestens 8 Stunden haltbar.The overall results of the equipment example show that the liquor stabilizers according to the invention have no negative influence on the hydrophobizing and oleophobicizing effects and are also highly effective, because even under extreme operating conditions, the finishing liquors are stable for at least 8 hours.
Claims (10)
- Use of water-soluble salts of amines of the general formula (I)
- Use according to Claim 1, characterised in that the salts are employed in amounts of 1 to 10, in particular 2 to 6 g/l.
- Use according to Claim 1 or 2, characterised in that R, denotes an alkyl radical having 8 to 10 or 16 to 18 C atoms and R₂ and R₃ denote hydrogen or the methyl radical.
- Use according to one or more of Claims 1 to 3, characterised in that An denotes a monovalent anion and x accordingly denotes 1.
- Use according to one or more of Claims 1 to 4, characterised in that An denotes formate, glycolate, lactate, chloride, nitrate or, in particular, acetate.
- Use according to one or more of Claims 1 to 5, characterised in that stearylammonium acetate, octylammonium acetate, tallow fat-ammonium acetate and/or octadecyldimethylammonium acetate is used as the amine salt.
- Use according to one or more of Claims 1 to 6, characterised in that the salts are employed in the form of aqueous solutions which contain 10 to 30, in particular 18 to 25% by weight of amine salt (calculated as the solid).
- Use according to one or more of Claims 1 to 7, characterised in that the liquors additionally contain customary emulsifiers, in particular non-ionic and/or weakly cationic emulsifiers.
- Use according to Claim 8, characterised in that the emulsifiers have been added in amounts of 10 to 40% by weight, based on the amine salt.
- Use according to one or more of Claims 1 to 9, characterised in that the liquors additionally contain customary foam suppressants in the customary amounts.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3802878A DE3802878A1 (en) | 1988-02-01 | 1988-02-01 | FLEET STABILIZERS FOR OIL AND / OR WATER REPELLENT EQUIPMENT OF FIBER MATERIALS AND THEIR USE |
DE3802878 | 1988-02-01 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0326702A2 EP0326702A2 (en) | 1989-08-09 |
EP0326702A3 EP0326702A3 (en) | 1991-07-03 |
EP0326702B1 true EP0326702B1 (en) | 1993-06-02 |
Family
ID=6346375
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP88121350A Expired - Lifetime EP0326702B1 (en) | 1988-02-01 | 1988-12-21 | Amine salts as stabilizers for the oil and water repellent finishing of fibre materials |
Country Status (2)
Country | Link |
---|---|
EP (1) | EP0326702B1 (en) |
DE (2) | DE3802878A1 (en) |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB602109A (en) * | 1944-06-14 | 1948-05-20 | E F Houghton And Co | Wax emulsions and method of preparing the same |
CH544839A (en) * | 1970-05-22 | 1973-05-15 | Ciba Geigy Ag | Process for producing multi-tone effects on fiber material made of polyacrylonitrile or polyacrylonitrile copolymers |
US3869250A (en) * | 1970-05-22 | 1975-03-04 | Ciba Geigy Ag | Process for the production of differential effects on polymeric or copolymeric acrylonitrile fibers |
US3968066A (en) * | 1974-04-18 | 1976-07-06 | Ciba-Geigy Corporation | Oil and water repellent textile composition containing a fluorochemical polyurethane resin and a quaternary ammonium salt |
-
1988
- 1988-02-01 DE DE3802878A patent/DE3802878A1/en not_active Withdrawn
- 1988-12-21 EP EP88121350A patent/EP0326702B1/en not_active Expired - Lifetime
- 1988-12-21 DE DE8888121350T patent/DE3881505D1/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
EP0326702A3 (en) | 1991-07-03 |
EP0326702A2 (en) | 1989-08-09 |
DE3802878A1 (en) | 1989-08-10 |
DE3881505D1 (en) | 1993-07-08 |
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