EP0221855B1 - Diquaternary ammonium salts, their preparation and their use as textile finishing agents - Google Patents
Diquaternary ammonium salts, their preparation and their use as textile finishing agents Download PDFInfo
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- EP0221855B1 EP0221855B1 EP86810499A EP86810499A EP0221855B1 EP 0221855 B1 EP0221855 B1 EP 0221855B1 EP 86810499 A EP86810499 A EP 86810499A EP 86810499 A EP86810499 A EP 86810499A EP 0221855 B1 EP0221855 B1 EP 0221855B1
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- ammonium salt
- alkylene
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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
- D06M13/402—Amides imides, sulfamic acids
- D06M13/405—Acylated polyalkylene polyamines
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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
- D06M13/332—Di- or polyamines
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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
- D06M13/46—Compounds containing quaternary nitrogen atoms
- D06M13/467—Compounds containing quaternary nitrogen atoms derived from polyamines
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- 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
- Y10T442/2762—Coated or impregnated natural fiber fabric [e.g., cotton, wool, silk, linen, etc.]
- Y10T442/277—Coated or impregnated cellulosic fiber fabric
Definitions
- the present invention relates to diquaternary ammonium salts, a process for their preparation and their use as textile finishing agents, the diquaternary ammonium salts according to the invention e.g. be prepared from dialkylaminoalkyl behenic acid amides and aliphatic epoxy compounds and thus have aliphatic bridge members between the two quaternary nitrogen atoms, which are always substituted by at least one hydroxyl group.
- DE-AS 1 092 878 discloses diquaternary ammonium salts which are prepared from dialkylaminoalkyl fatty acid amides and an epoxy compound, the fatty acids, however, having at most 18 carbon atoms as starting components.
- the known diquaternary ammonium salts are used as dyeing aids, in particular as leveling agents for dyeings on polyacrylonitrile fibers.
- diquaternary ammonium salts which e.g. from dialkylaminoalkyl behenic acid amides and aliphatic dihalo compounds, e.g. ⁇ , ⁇ '-Dibromodiethyl ether are produced and thus have aliphatic bridge members between the two quaternary nitrogen atoms, which are free of hydroxyl substituents.
- diquaternary ammonium salts are used in hair cosmetics, in particular shampoos and rinsing agents.
- Diquaternary ammonium salts have been found which, because of their properties, are used as textile finishing agents.
- alkylene radicals A 1 and A 2 in formula (1) are straight-chain or branched.
- 2,2-Dimethylpropylene also called neopentylene
- n-butylene tetramethylene
- n-propylene trimethylene
- Suitable substituents R 1 to R 4 are straight-chain or branched alkyl radicals, such as, for example, tert-butyl, isobutyl, n-butyl, isopropyl, n-propyl or, above all, ethyl or methyl.
- the corresponding hydroxyalkyl radicals for example hydroxyethyl, are also suitable .
- the alkoxyalkyl radicals each have 1 to 4 carbon atoms in the alkyl part and alkoxy part. Alkyoxyalkyl radicals thus contain a total of 2 to 8 carbon atoms. Examples include hydroxyethyl and ethoxyethyl. Unsubstituted alkyl radicals of the type indicated above are preferred
- Y 1 n ⁇ represents, if n is 1, the monovalent anion, and if n 2 is the divalent anion of a strong acid, in formula (1) depending on the value of n either 1 divalent anion or 2 monovalent anions are present.
- the monovalent or divalent anion of basically any water-soluble, inorganic or organic acid comes into consideration as the definition of Y 1 n ⁇ .
- the anion of an inorganic acid or an organic sulfonic acid is preferred.
- Halide, sulfate, methyl sulfate or ethyl sulfate ions are mentioned as representatives of such anions, with halide anions, especially the chloride anion, being of primary interest.
- the bridge member Zi in formula (1) is always interrupted by hydroxyl groups, especially 1 to 4 hydroxyl groups and optionally by 2 to 6 oxygen atoms, and preferably has 3 to 24 carbon atoms.
- Bridge members with, for example, 3 or 4 carbon atoms are mainly substituted by 1 or 2 hydroxy groups and are generally not interrupted by oxygen atoms, while bridge members with about 8 to 24 carbon atoms are primarily substituted by 2, 3 or 4 hydroxyl groups and preferably by oxygen atoms, especially by 2 up to 6 oxygen atoms are interrupted.
- Bridge members of particular interest are derived from an epihalohydrin, preferably epichlorohydrin, from an aliphatic diepoxide, especially a diepoxyalkane such as 1,2,3,4-diepoxybutane (also called butadiene dioxide) or 1,4-butanediol diglycidyl ether or a diglycidyl ether, that of an epihalohydrin, especially epichlorohydrin, and a lower alkylene glycol with preferably at most 4 carbon atoms, such as tetramethylene glycol (1,4-butanediol), dimethylethylene glycol (2,3-butanediol), trimethylene glycol (1,3-propanediol), especially propylene glycol (1,2-propanediol) or in particular ethylene glycol (1,2-ethanediol) is obtained, such diglycidyl ethers being monomers or oligomers which contain 2 to 4 units -CH 2
- the two leftovers in formula (1) stand for the rest of preferably technical behenic acid, which contains a smaller amount of, for example, arachidic acid and erucic acid and, above all, represents the hydrolysis product of the unsaturated C 22 acids from rapeseed oil.
- Such technical behenic acids have molecular weights of about 326 to about 354.
- the bridge members -At-Qt- on the one hand and ⁇ A 2 ⁇ Q 2 - on the other hand preferably have the same meanings in formula (1).
- the alkylene chain in Z 2 can be interrupted by 2 to 6 oxygen atoms.
- ammonium salts of formula (2) are prepared by adding about 2 moles of a dialkylaminoalkyl behenic acid amide or ester of the formula wherein A 1 , Q 1 , R s and R 6 have the meanings given, with about 1 mol of an epoxy compound of the formula wherein X 1 and X 2 have the meanings given and Z "optionally alkylene having 1 to 20 carbon atoms substituted by 1 or 2 hydroxyl groups and optionally interrupted by 2 to 6 oxygen atoms, or, if X 2 is an epoxy group, Z" also for is direct bond, in the presence of an acid of the formula where Y 2 and n have the meanings given.
- ammonium salts of formula (3) are prepared by adding about 2 moles of a dialkylaminoalkyl behenic acid amide or ester of the formula wherein Ai, 0 1 and Rs have the meanings given, with about 1 mol of an epoxy compound of the formula wherein Xi and X 2 have the meanings given and Z "is methylene or, if X 2 is an epoxy group, the direct bond or interrupted by 2 to 6 oxygen atoms and optionally substituted by 1 or 2 hydroxyl groups alkylene having 4 to 20 carbon atoms, in the presence an acid of the formula where Y 3 and n have the meanings given.
- ammonium salts of formula (4) are prepared by adding about 2 moles of a dialkylaminoalkyl behenic acid amide or ester of the formula wherein Aa, 0 1 and R 7 have the meanings given, with 1 mol of epichlorohydrin, 1,2,3,4-diepoxybutane, 1,4-butanediol diglycidyl ether or a diglycidyl ether, which is obtained from ethylene glycol and epichlorohydrin, in the presence of an acid Formula- where Y 4 ⁇ has the meanings given.
- dialkylaminoalkyl behenic acid amides or esters of the formulas (7), (8), (11), (14) and (17) are known per se and are prepared by known methods by adding behenic acid with approximately equimolar amounts of corresponding dialkylaminoalkylamines or dialkylaminoalkanols elevated temperature above 100 ° C, for example 150 to 180 ° C, with removal from the reaction mixture of the water formed by the reaction.
- the reaction of the compounds of formulas (7), (8) and (9) in the presence of the acid of formula (10) are preferably carried out at elevated temperature, e.g. 50 to 90 ° C, generally in an aqueous medium and optionally in the presence of a polar solvent, preferably a low molecular weight amide or ether, such as e.g. Dimethylformamide, diethylene glycol monobutyl ether or especially a low molecular weight alkanol such as e.g. Ethanol, especially butylgycol or especially isopropanol.
- a polar solvent preferably a low molecular weight amide or ether, such as e.g. Dimethylformamide, diethylene glycol monobutyl ether or especially a low molecular weight alkanol such as e.g. Ethanol, especially butylgycol or especially isopropanol.
- the ammonium salts according to the invention are used as water repellents, wrinkle-free
- the textile material which is finished according to the invention can be processed in any processing stage, i.e. as yarns, staple fibers, continuous threads, non-wovens, especially as woven or knitted fabrics, dyed or undyed, treated with or without an optical brightener or available as a further processed garment.
- Fully synthetic, semi-synthetic and natural fibers can be considered as textile fibers. Mixtures of synthetic and natural fibers are also possible.
- Examples of synthetic fibers are rayon, rayon, viscose, cellulose di- and triacetate, polyacrylonitrile, acrylonitrile copolymers, polyamide, in particular fibers made of poly-2-caprolactam, polyhexylmethylene diamide adipate or poly- ⁇ -aminoundecanoic acid and polyester, in particular fibers, which differ from the Derive terephthalic acid, e.g. Poly (ethylene glycol terephthalate) or poly (1,4-cyclohexylenedimethylene terephthalate), and examples of natural fibers include linen, hemp, ramie, wool and cotton.
- Derive terephthalic acid e.g. Poly (ethylene glycol terephthalate) or poly (1,4-cyclohexylenedimethylene terephthalate)
- natural fibers include linen, hemp, ramie, wool and cotton.
- wool, polyacrylonitrile, polyamide, polyester or cotton fabrics or knits as well as fabrics or knitted fabrics made from mixtures of the fibers mentioned can be refined.
- preparations which contain a diquaternary ammonium salt according to the invention are applied to the textile materials by customary processes.
- the preparations can be sprayed or puffed onto the textile materials.
- the textile materials are preferably padded with the preparations or treated by the exhaust process.
- the application takes place at room temperature or at elevated temperatures of, for example, 30 to 100 ° C. for about 5 to 120 minutes.
- the textile materials are then dried at room temperature or preferably at an elevated temperature, for example at 50 to 150 ° C.
- the diquaternary ammonium salts according to the invention are expediently used in amounts of 0.05 to 5% by weight, preferably 0.1 to 4% by weight, based on the textile material to be finished.
- the diquaternary ammonium salts according to the invention have the essential advantage of bringing about good finishing effects of the above-mentioned various types which can be applied to a large number of textile materials.
- dialkylaminoalkyl behenic acid amides or esters with the corresponding amine numbers are obtained in an analogous manner if behenic acid is reacted with the dialkylaminoalkylamines or dialkylaminoalkanols also listed in Table I:
- Example 1 A solution of 12.3 g of concentrated hydrochloric acid in 73 g of water and 43 g of isopropanol are added at 60 ° C. to 106.25 g of dimethylaminoethylbehenic acid amide according to preparation instruction B (0.25 mol). 11.6 g of epichlorohydrin (0.125 mol) are then added over the course of 15 minutes, and the temperature is then raised to 75 ° C. The reaction solution is kept at this temperature for 10 hours while stirring. After this time, the amine and epoxy values are 0. The reaction solution is then evaporated to dryness. 122 g of the diquaternary ammonium compound of the formula are obtained
- Example 2 101 g of dimethylamino-n-propylbehenic acid ester according to specification C (0.25 mol) are mixed at 60 ° C. with a solution of 12.3 g of concentrated hydrochloric acid in 73 g of water and 43 g of isopropanol. 11.6 g of epichlorohydrin (0.125 mol) are then added over the course of 15 minutes, and the temperature is then raised to 75 ° C. The reaction solution is kept at this temperature for 10 hours while stirring. After this time, the amine and epoxy values are 0. The reaction product is then evaporated to dryness.
- Example 3 A solution of 12.3 g of concentrated hydrochloric acid in 73 g of water and 43 g of isopropanol is added at 60 ° C. to 104.5 g of diethylaminoethylbehenic acid amide according to instruction D (0.25 mol). 11.6 g of epichlorohydrin (0.125 mol) are then added over the course of 15 minutes, and the temperature is then raised to 75 ° C. The reaction solution is kept at this temperature for 10 hours while stirring. After this time, the amine and epoxy values are 0. Then the reaction solution is evaporated to dryness. 120 g of the diquaternary ammonium compound of the formula are obtained
- Example 4 109.75 g of dimethylamino-n-propylbehenic acid amide according to instruction A (0.25 mol) are dissolved in 44 g of isopropanol with heating and then a solution of 12.3 g of concentrated hydrochloric acid in 74 g of water is added. 11.6 g of epichlorohydrin (0.125 mol) are added at 55 ° C. in the course of 15 minutes. The temperature of the reaction solution is then raised to 75 ° C. and the reaction solution is kept at this temperature for 3 hours with stirring. After this time, the amine and epoxy values are 0. 251 g of a 50% strength reaction solution of the diquaternary ammonium compound of the formula which is waxy at room temperature are obtained
- Example 5 65.6 g of dimethylamino-n-propylbehenic acid amide according to instruction A (0.15 mol) are melted at 80 ° C., and 14.8 g of 37% hydrochloric acid in 758.6 g of water are added. 16.35 g of 1,4-butanediol diglycidyl ether, which has an epoxide number of 4.6 (0.075 mol), are then added to the reaction mixture at 60 ° C. in the course of 10 minutes. The reaction mixture is then heated to 70 ° C. and kept at this temperature with stirring for one hour. After this time, the amine and epoxide values are 0. 855 g of a 10% strength solution of the diquaternary ammonium salt of the formula are obtained
- Example 6 65.6 g of dimethylamino-n-propylbehenic acid amide (0.15 mol) according to instruction A are melted at 80 ° C. and 5.1 g of sulfuric acid in 1083.6 g of water are added. 16.35 g (0.075 mol) of 1,4-butanediol diglycidyl ether, which has an epoxide number of 4.6, are then added to the reaction mixture at 60 ° C. in the course of 10 minutes. The reaction mixture is then heated to 70 ° C. and kept at this temperature with stirring for 10 hours. After this time the amine value is 28 and the epoxy value 0. 1170 g of a 7% solution are obtained which predominantly contains the diquaternary ammonium salt of the following formula:
- Example 7 45.8 g of dimethylaminoneopentylbehenic acid amide (0.1 mol) according to instruction E are heated together with 9.9 g of concentrated hydrochloric acid in 500.4 g of water to an internal temperature of 75 ° C. Then 10.9 g (0.05 mol) of 1,4-butanediol diglycidyl ether, which has an epoxide number of 4.6, are added in the course of 15 minutes and the mixture is stirred at 77-78 ° C. for 12 hours and epoxy values 0. 567 g of a 10% solution of the diquaternary ammonium salt of the formula are obtained:
- Example 8 42.3 g of diisopropylaminoethyl behenic acid amide (0.1 mol) according to instruction F are heated to 75 ° C. together with 9.9 g of concentrated hydrochloric acid in 479.8 g of water. Then 10.9 g (0.05 mol) of 1,4-butanediol dyglycidyl ether, which has an epoxide number of 4.6, are added within 15 minutes and the mixture is stirred at 75 ° C. for 12 hours. After this time, the amine and Epoxy values 0. 542 g of a 10% solution of the diquaternary ammonium salt of the formula are obtained
- Example 9 1 kg of cotton jersey is treated in the liquor ratio 1:30 in the exhaust process with a liquor at 40 ° C. for 20 minutes, which contains 4% of the diquaternary ammonium salt according to Example 4 and has a pH of 5.5 by adding acetic acid .
- the jersey is then dried without rinsing.
- To check the sewability use a long-fiber mower made of polyester with a sewing machine (Overlock Union Spezial type 39500) at 6000 stitches / min. a seam of 50 cm is attached. A needle with a Nm 70 tip is used. The number of holes along the seam is assessed. It was compared to a cotton jersey that was not treated.
- Table II The results are summarized in Table II below:
- Example 10 The knitted fabrics tested for sewability in Example 9 were also subjected to a soiling test. Dry soiling is assessed according to the following test: substrate; Size 9 x 12 cm (several test specimens) filter dust 15% on product weight apparatus Turbula running time 30 min. vacuum with a vacuum cleaner
- Example 11 100 kg of cotton jersey in 4000 liters of water, which contains a commercial wetting agent, are pretreated at 50 ° C. in a reel runner.
- the jersey After a further 45 min. at 80 ° C the jersey is rinsed with hot and then with cold water and then with 4000 liters of a liquor in a liquor ratio of 1:40 for 20 min. Washed at cooking temperature, the 4 kg of an adduct of 1 mole of nonylphenol and 9 moles of ethylene contains oxide and 4 kg of diquaternary ammonium salt according to Example 4. The jersey is then rinsed and dried again. In the monsanto picture as a measure for the wrinkle-free finishing of the treated jersey, the grade 4 is obtained. If the jersey is treated as stated above, but without the addition of the diquaternary ammonium salt in the dyebath and in the post-wash liquor, grade 2 is obtained in the monsanto picture.
- Example 13 A washing machine with a filling of approx. 4 kg is loaded with the following material:
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Abstract
Description
Die vorliegende Erfindung betrifft diquatemäre Ammoniumsalze, ein Verfahren zu ihrer Herstellung sowie ihre Verwendung als Textilveredelungsmittel, wobei die erfindungsgemässen, diquatemären Ammoniumsalze z.B. aus Dialkylaminoalkylbehensäureamiden und aliphatischen Epoxyverbindungen hergestellt werden und somit zwischen den beiden quatemären Stickstoffatomen aliphatische Brückenglieder aufweisen, die stets durch mindestens eine Hydroxylgruppe substituiert sind.The present invention relates to diquaternary ammonium salts, a process for their preparation and their use as textile finishing agents, the diquaternary ammonium salts according to the invention e.g. be prepared from dialkylaminoalkyl behenic acid amides and aliphatic epoxy compounds and thus have aliphatic bridge members between the two quaternary nitrogen atoms, which are always substituted by at least one hydroxyl group.
Aus DE-AS 1 092 878 sind diquatemären Ammoniumsalze bekannt, die aus Dialkylaminoalkylfettsäureamiden und einer Epoxyverbindung hergestellt werden, wobei die Fettsäuren als Ausgangskomponenten jedoch höchstens 18 Kohlenstoffatome aufweisen. Die bekannten, diquatemären Ammoniumsalze finden Verwendung als Färbereihilfsmittel, insbesondere als Egalisiermittel für Färbungen auf Polyacrylnitrilfasem.DE-AS 1 092 878 discloses diquaternary ammonium salts which are prepared from dialkylaminoalkyl fatty acid amides and an epoxy compound, the fatty acids, however, having at most 18 carbon atoms as starting components. The known diquaternary ammonium salts are used as dyeing aids, in particular as leveling agents for dyeings on polyacrylonitrile fibers.
Aus US-A-4 312 813 sind ebenfalls diquatemäre Ammoniumsalze bekannt, die z.B. aus Dialkylaminoalkylbehensäureamiden und aliphatischen Dihalogenverbindungen, z.B. β,β'-Dibromodiethyl-ether hergestellt werden und somit zwischen den beiden quatemären Stickstoffatomen aliphatische Brückenglieder aufweisen, die von Hydroxylsubstituenten frei sind. Diese bekannten diquatemären Ammoniumsalze finden in haarkosmetischen Mitteln, insbesondere Shampoos und Nachspülmitteln Verwendung.From US-A-4 312 813 diquaternary ammonium salts are also known which e.g. from dialkylaminoalkyl behenic acid amides and aliphatic dihalo compounds, e.g. β, β'-Dibromodiethyl ether are produced and thus have aliphatic bridge members between the two quaternary nitrogen atoms, which are free of hydroxyl substituents. These known diquaternary ammonium salts are used in hair cosmetics, in particular shampoos and rinsing agents.
Es wurden diquatemäre Ammoniumsalze gefunden, die aufgrund ihrer Eigenschaften als Textilveredelungsmittel Verwendung finden.Diquaternary ammonium salts have been found which, because of their properties, are used as textile finishing agents.
Gegenstand der Erfindung sind somit diquatemäre Ammoniumsalze, die dadurch gekennzeichnet sind, dass sie der Formel
- A1 und A2 unabhängig voneinander Alkylen mit jeweils 2 bis 5 Kohlenstoffatomen,
- Q1 and Q2 unabhängig voneinander jeweils -NH- oder -O-,
- R1, R2, R3 und R4 unabhängig voneinander jeweils Alkyl, Hydroxyalkyl oder Alkoxyalkyl mit 1 bis 4 Kohlenstoffatomen in jedem Alkylteil,
- Y1 n⊖ das Anion einer starken Säure,
- Z1 durch Hydroxyl substituiertes und gegebenenfalls durch Sauerstoffatome unterbrochenes Alkylen mit 3 bis 24 Kohlenstoffatomen und
- n 1 oder 2 bedeuten.
- A 1 and A 2 independently of one another alkylene each having 2 to 5 carbon atoms,
- Q 1 and Q 2 are each independently of the other -NH- or -O-,
- R 1 , R 2 , R 3 and R 4 independently of one another each alkyl, hydroxyalkyl or alkoxyalkyl with 1 to 4 carbon atoms in each alkyl part,
- Y 1 n⊖ the anion of a strong acid,
- Z 1 substituted by hydroxyl and optionally interrupted by oxygen atoms alkylene having 3 to 24 carbon atoms and
- n is 1 or 2.
Weitere Gegenstände der Erfindung bilden die Herstellung nach an sich bekannten Methoden der neuen, erfindungsgemässen, diquatemären Ammoniumsalze und deren Verwendung als Textilveredelungsmittel.Further objects of the invention are the production according to methods known per se of the new, diquaternary ammonium salts according to the invention and their use as textile finishing agents.
Die Alkylenreste A1 und A2 in Formel (1) sind geradkettig oder verzweigt. Als mögliche Vertreter seien 2,2-Dimethylpropylen (auch Neopentylen genannt), n-Butylen (Tetramethylen) und vor allem n-Propylen (Trimethylen) und Ethylen erwähnt.The alkylene radicals A 1 and A 2 in formula (1) are straight-chain or branched. 2,2-Dimethylpropylene (also called neopentylene), n-butylene (tetramethylene) and especially n-propylene (trimethylene) and ethylene are mentioned as possible representatives.
Als Substituenten R1 bis R4 kommen geradkettige oder verzweigte Alkylreste, wie z.B. tert.-Butyl, Isobutyl, n-Butyl, Isopropyl, n-Propyl oder vor Allem Ethyl oder Methyl in Betracht Die entsprechenden Hydroxyalkylreste, z.B. Hydroxyethyl, kommen auch in Frage. Die Alkoxyalkylreste weisen je 1 bis 4 Kohlenstoffatome im Alkylteil und Alkoxyteil auf. Alkyoxyalkylreste enthalten somit insgesamt 2 bis 8 Kohlenstoffatome. Als Beispiele seien Hydroxyethyl und Ethoxyethyl genannt. Unsubstituierte Alkylreste der vorstehend angegebenen Art sind bevorzugtSuitable substituents R 1 to R 4 are straight-chain or branched alkyl radicals, such as, for example, tert-butyl, isobutyl, n-butyl, isopropyl, n-propyl or, above all, ethyl or methyl. The corresponding hydroxyalkyl radicals, for example hydroxyethyl, are also suitable . The alkoxyalkyl radicals each have 1 to 4 carbon atoms in the alkyl part and alkoxy part. Alkyoxyalkyl radicals thus contain a total of 2 to 8 carbon atoms. Examples include hydroxyethyl and ethoxyethyl. Unsubstituted alkyl radicals of the type indicated above are preferred
Y1 n⊖ stellt, falls n 1 ist, das einwertige Anion, und falls n 2 ist das zweiwertige Anion einer starken Säure, wobei in Formel (1) je nach Wert von n entweder 1 zweiwertiges Anion oder 2 einwertige Anionen vorhanden sind.Y 1 n⊖ represents, if n is 1, the monovalent anion, and if n 2 is the divalent anion of a strong acid, in formula (1) depending on the value of n either 1 divalent anion or 2 monovalent anions are present.
Das ein- oder zweiwertige Anion von grundsätzlich jeglicher wasserlöslichen, anorganischen oder organischen Säure kommt als Definition von Y1 n⊖ in Betracht Bevorzugt ist das Anion einer anorganischen Säure oder einer organischen Sulfonsäure. Als Vertreter so Icher Anionen seien das Halogenid-, Sulfat-, Methylsulfat- oder Ethylsulfation gennant, wobei Halogenidanionen, vor allem das Chloridanion im Vordergrund des Interesses stehen.The monovalent or divalent anion of basically any water-soluble, inorganic or organic acid comes into consideration as the definition of Y 1 n⊖. The anion of an inorganic acid or an organic sulfonic acid is preferred. Halide, sulfate, methyl sulfate or ethyl sulfate ions are mentioned as representatives of such anions, with halide anions, especially the chloride anion, being of primary interest.
Das Brückenglied Zi in Formel (1) ist stets durch Hydroxylgruppen, vor allem 1 bis 4 Hydroxylgruppen und gegebenenfalls durch 2 bis 6 Sauerstoffatome unterbrochen und weist vorzugsweise 3 bis 24 Kohlenstoffatome auf. Brückenglieder mit z.B. 3 oder 4 Kohlenstoffatomen sind vor allem durch 1 oder 2 Hydroxyigruppen substituiert und im allgemeinen nicht durch Sauerstoffatome unterbrochen, während Brückenglieder mit etwa 8 bis 24 Kohlenstoffatomen vor allem durch 2, 3 oder 4 Hydroxylgruppen und vorzugsweise durch Sauerstoffatome, vor allem durch 2 bis 6 Sauerstoffatome, unterbrochen sind. Brückenglieder von besonderem Interesse leiten sich ab von einem Epihalogenhydrin, vorzugsweise Epichlorhydrin, von einem aliphatischen Diepoxyd, vor allem einem Diepoxyalkan wie z.B. 1,2,3,4-Diepoxybutan (auch Butadiendioxid genannt) oder 1,4-Butandioldiglycidylether oder einem Diglycidylether, der aus einem Epihalogenhydrin, vor allem Epichlorhydrin, und einem niederen Alkylenglykol mit vorzugsweise höchstens 4 Kohlenstoffatomen wie z.B. Tetramethylenglykol (1,4-Butandiol), Dimethylethylenglykol (2,3-Butandiol), Trimethylenglykol (1,3-Propandiol), vor allem Propylenglykol (1,2-Propandiol) oder insbesondere Ethylenglykol (1,2-Ethandiol) erhalten wird, wobei solche Diglycidylether Monomere oder Oligomere darstellen, die 2 bis 4 Einheiten -CH2-CH(OH)-CH2-O-(C2-C4-Alkylen)-O- oder insbesondere 2 bis 4 Einheiten ―CH2―CH(OH)―CH2―O―(CH2)2―O― aufweisen.The bridge member Zi in formula (1) is always interrupted by hydroxyl groups, especially 1 to 4 hydroxyl groups and optionally by 2 to 6 oxygen atoms, and preferably has 3 to 24 carbon atoms. Bridge members with, for example, 3 or 4 carbon atoms are mainly substituted by 1 or 2 hydroxy groups and are generally not interrupted by oxygen atoms, while bridge members with about 8 to 24 carbon atoms are primarily substituted by 2, 3 or 4 hydroxyl groups and preferably by oxygen atoms, especially by 2 up to 6 oxygen atoms are interrupted. Bridge members of particular interest are derived from an epihalohydrin, preferably epichlorohydrin, from an aliphatic diepoxide, especially a diepoxyalkane such as 1,2,3,4-diepoxybutane (also called butadiene dioxide) or 1,4-butanediol diglycidyl ether or a diglycidyl ether, that of an epihalohydrin, especially epichlorohydrin, and a lower alkylene glycol with preferably at most 4 carbon atoms, such as tetramethylene glycol (1,4-butanediol), dimethylethylene glycol (2,3-butanediol), trimethylene glycol (1,3-propanediol), especially propylene glycol (1,2-propanediol) or in particular ethylene glycol (1,2-ethanediol) is obtained, such diglycidyl ethers being monomers or oligomers which contain 2 to 4 units -CH 2 -CH (OH) -CH 2 -O- (C 2 -C 4 -alkylene) -O- or in particular 2 to 4 units ―CH 2 ―CH (OH) ―CH 2 ―O― (CH 2 ) 2 ―O―.
Die beiden Reste
Vorzugsweise haben die Brückenglieder -At-Qt- einerseits und ―A2―Q2― andererseits in Formel (1) die gleichen Bedeutungen.The bridge members -At-Qt- on the one hand and ―A 2 ―Q 2 - on the other hand preferably have the same meanings in formula (1).
Demgemäß entsprechen bevorzugte, diquatemäre Ammoniumsalze der Formel
- Rs und Re unabhängig voneinander Alkyl mit jeweils 1 bis 4 Kohlenstoffatomen,
- Y2n⊖ das Anion einer anorganischen Säure oder einer Sulfonsäure und Z2 durch 1 bis 4 Hydroxylgruppen substituiertes und gegebenenfalls durch Sauerstoffatome unterbrochenes Alkylen mit 3 bis 24 Kohlenstoffatomen bedeuten und
- A1, Q1 und n die angegebenen Bedeutungen haben.
- Rs and R e independently of one another alkyl each having 1 to 4 carbon atoms,
- Y 2 n⊖ is the anion of an inorganic acid or a sulfonic acid and Z 2 is substituted by 1 to 4 hydroxyl groups and optionally interrupted by oxygen atoms, alkylene having 3 to 24 carbon atoms and
- A 1 , Q 1 and n have the meanings given.
Je nach der Kohlenstoffatomzahl kann die Alkylenkette in Z2 durch 2 bis 6 Sauerstoffatome unterbrochen sein.Depending on the number of carbon atoms, the alkylene chain in Z 2 can be interrupted by 2 to 6 oxygen atoms.
Vorzugsweise sind C1―C4-Alkylsubstituenten in Formel (2) identisch. Somit entsprechen Ammoniumsalze von besonderem Interesse vor allem der Formel (2), worin
- Y2n⊖ ein Halogenid-, Sulfat-, Methylsulfat- oder Ethylsulfation, und
- Z2 durch 1 oder 2 Hydroxylgruppen substituiertes Alkylen mit 3 oder 4 Kohlenstoffatomen oder durch 2 bis 4 Hydroxylgruppen substituiertes und durch 2 bis 6 Sauerstoffatome unterbrochenes Alkylen mit 8 bis 24 Kohlenstoffatomen bedeuten und Rs und R6 gleich sind.
- Y 2 n⊖ a halide, sulfate, methyl sulfate or ethyl sulfate, and
- Z 2 denotes alkylene having 3 or 4 carbon atoms substituted by 1 or 2 hydroxyl groups or alkylene having 8 to 24 carbon atoms substituted by 2 to 4 hydroxyl groups and interrupted by 2 to 6 oxygen atoms and R s and R 6 are identical.
Ammoniumsalze die sich besonders gut dazu eignen, als Textilveredelungsmittel verwendet zu werden, entsprechen der Formel (2), worin
- A1 Ethylen, n-Propylen, n-Butylen oder 2,2-Dimethylpropylen,
- Rs gleich Rs ist und Methyl, Ethyl oder Isopropyl und
- Z2 ―CH2―CH(OH)―CH2, ―CH2―CH(OH)―CH(OH)―CH2― oder ―CH2―CH(OH)―CH2―O―(CH2)4―O― CH2―CH(OH)―CH2―
- bedeuten.
- A 1 ethylene, n-propylene, n-butylene or 2,2-dimethylpropylene,
- Rs is Rs and is methyl, ethyl or isopropyl and
- Z 2 ―CH 2 ―CH (OH) ―CH 2 , ―CH 2 ―CH (OH) ―CH (OH) ―CH 2 - or ―CH 2 ―CH (OH) ―CH 2 ―O― (CH 2 ) 4 ―O― CH 2 ―CH (OH) ―CH 2 -
- mean.
Im Vordergrund des Interesses stehen diquatemäre Ammoniumsalze der Formel
- A1 Ethylen, n-Propylen, n-Butylen oder 2,2-Dimethylpropylen und
- Rs Methyl, Ethyl oder Isopropyl bedeuten und
- Q1 die angegebene Bedeutung hat.
- A 1 ethylene, n-propylene, n-butylene or 2,2-dimethylpropylene and
- Rs denote methyl, ethyl or isopropyl and
- Q 1 has the meaning given.
Die Herstellung der diquatemären Ammoniumsalze der Formel (1) erfolgt nach an sich bekannten Methoden indem man z.B. etwa 1 Mol eines Dialkylaminoalkylbehensäureamids oder -esters der Formel
- X1 eine Epoxygruppe
- X2 eine Epoxygruppe oder ein bewegliches Halogenatom und
- Z' gegebenenfalls durch Hydroxyl substituiertes und gegebenenfalls durch Sauerstoffatome unterbrochenes Alkylen mit 1 bis 20 Kohlenstoffatomen bedeutet, oder, sofern X2 eine Epoxygruppe ist, Z' auch für die direkte Bindung steht,
- in Gegenwart einer starken Säure der Formel
- X 1 is an epoxy group
- X 2 is an epoxy group or a movable halogen atom and
- Z 'is alkylene having 1 to 20 carbon atoms which is optionally substituted by hydroxyl and optionally interrupted by oxygen atoms, or, if X 2 is an epoxy group, Z' also represents the direct bond,
- in the presence of a strong acid of the formula
Die Ammoniumsalze der Formel (2) werden hergesellt, indem man etwa 2 Mol eines Dialkylaminoalkylbehensäureamids oder -esters der Formel
Die Ammoniumsalze der Formel (3) werden hergestellt, indem man etwa 2 Mol eines Dialkylaminoalkylbehensäureamids oder -esters der Formel
Die Ammoniumsalze der Formel (4) werden hergestellt, indem man etwa 2 Mol eines Dialkylaminoalkylbehensäureamids oder -esters der Formel
Die Dialkylaminoalkylbehensäureamide oder -ester der Formeln (7), (8), (11), (14) und (17) sind an sich bekannt und werden nach bekannten Methoden hergestellt, indem man Behensäure mit etwa äquimolaren Mengen an entsprechende Dialkylaminoalkylamine oder Dialkylaminoalkanole bei erhöhter Temperatur über 100°C, z.B. 150 bis 180°C, unter Entfernung aus dem Reaktionsgemisch des durch die Reaktion gebildeten Wassers umsetzt.The dialkylaminoalkyl behenic acid amides or esters of the formulas (7), (8), (11), (14) and (17) are known per se and are prepared by known methods by adding behenic acid with approximately equimolar amounts of corresponding dialkylaminoalkylamines or dialkylaminoalkanols elevated temperature above 100 ° C, for example 150 to 180 ° C, with removal from the reaction mixture of the water formed by the reaction.
Die Umsetzung der Verbindungen der Formeln (7), (8) und (9) in Gegenwart der Säure der Formel (10) werden vorzugsweise bei erhöhter Temperatur, z.B. 50 bis 90°C, im allgemeinen in wässrigem Medium und gegebenenfalls in Gegenwart eines polaren Lösungsmittels, vorzugsweise eines niedermolekularen Amids oder Ethers, wie z.B. Dimethylformamid, Diethylenglykolmonobutylether oder vor allem eines niedermolekularen Alkanols wie z.B. Ethanol, vor allem Butylgykol oder insbesondere Isopropanol durchgeführt. Bei ihrer Verwendung als Textilveredelungsmittel werden die erfindungsgemässen Ammoniumsalze als Hydrophobiermittel, Faltenfreimittel, Weichgriffmittel oder Mittel zur Verbesserung der Vemähbarkeit, der Spinnbarkeit oder des Anschmutzverhaltens von Textilien eingesetztThe reaction of the compounds of formulas (7), (8) and (9) in the presence of the acid of formula (10) are preferably carried out at elevated temperature, e.g. 50 to 90 ° C, generally in an aqueous medium and optionally in the presence of a polar solvent, preferably a low molecular weight amide or ether, such as e.g. Dimethylformamide, diethylene glycol monobutyl ether or especially a low molecular weight alkanol such as e.g. Ethanol, especially butylgycol or especially isopropanol. When used as textile finishing agents, the ammonium salts according to the invention are used as water repellents, wrinkle-free agents, softening agents or agents for improving the sewability, spinnability or soiling behavior of textiles
Das Textilmaterial, das erfindungsgemäss veredelt wird, kann in beliebiger Verarbeitungsstufe, d.h. als Garne, Stapfelfasem, Endlosfäden, Vliese, vor allem als Gewebe oder Gewirke, gefärbt oder ungefärbt, mit oder ohne optischen Aufhellem behandelt oder als bereits weiterverarbeitetes Kleidungsstück vorliegen.The textile material which is finished according to the invention can be processed in any processing stage, i.e. as yarns, staple fibers, continuous threads, non-wovens, especially as woven or knitted fabrics, dyed or undyed, treated with or without an optical brightener or available as a further processed garment.
Als Textilfasem kommen sowohl vollsynthetische als halbsynthetische und natürliche Fasem in Frage. Auch Mischungen von synthetischen und natürlichen Fasem kommen in Betracht.Fully synthetic, semi-synthetic and natural fibers can be considered as textile fibers. Mixtures of synthetic and natural fibers are also possible.
Als Beispiele synthetischer Fasem seien Kunstseide, Zellwolle, Viskose, Cellulosedi- und triacetat, Polyacrylnitril, Acrylnitrilmischpolymere, Polyamid, insbesondere Fasem aus Poly-2-caprolactam, Polyhexylmethylendiamid-adipat oder Poly-ω-aminoundecansäure und Polyester, insbesondere Fasem, die sich von der Terephthalsäure ableiten, z.B. Poly(ethylenglykolterephthalat) oder Poly(1,4-cyclohexy- lendimethylenterephthalat), und als Beispiele natürlicher Fasem seien Leinen, Hanf, Ramie, Wolle und Baumwolle genannt.Examples of synthetic fibers are rayon, rayon, viscose, cellulose di- and triacetate, polyacrylonitrile, acrylonitrile copolymers, polyamide, in particular fibers made of poly-2-caprolactam, polyhexylmethylene diamide adipate or poly-ω-aminoundecanoic acid and polyester, in particular fibers, which differ from the Derive terephthalic acid, e.g. Poly (ethylene glycol terephthalate) or poly (1,4-cyclohexylenedimethylene terephthalate), and examples of natural fibers include linen, hemp, ramie, wool and cotton.
Vor allem können Woll-, Polyacrylnitril-, Polyamid-, Polyester- oder Baumwollgewebe oder -gewirke sowie Gewebe oder Gewirke aus Mischungen der genannten Fasem veredelt werden.Above all, wool, polyacrylonitrile, polyamide, polyester or cotton fabrics or knits as well as fabrics or knitted fabrics made from mixtures of the fibers mentioned can be refined.
Beim Veredeln der Textilmaterialien werden Zubereitungen, die ein erfindungsgemässes, diquatemäres Ammoniumsalz enthalten, nach üblichen Verfahren auf die Textilmaterialien aufgebracht. So können z.B. die Zubereitungen auf die Textilmaterialien aufgesprüht oder aufgepflatscht werden. Vorzugsweise werden jedoch die Textilmaterialien mit den Zubereitungen foulardiert oder nach dem Ausziehverfahren behandelt. Die Applikation erfolgt bei Raumtemperatur oder auch bei erhöhten Temperaturen von z.B. 30 bis 100°C während etwa 5 bis 120 Minuten. Anschliessend werden die Textilmaterialien bei Raumtemperatur oder vorzugsweise bei erhöhter Temperatur, etwa bei 50 bis 150°C, getrocknet.When the textile materials are finished, preparations which contain a diquaternary ammonium salt according to the invention are applied to the textile materials by customary processes. For example, the preparations can be sprayed or puffed onto the textile materials. However, the textile materials are preferably padded with the preparations or treated by the exhaust process. The application takes place at room temperature or at elevated temperatures of, for example, 30 to 100 ° C. for about 5 to 120 minutes. The textile materials are then dried at room temperature or preferably at an elevated temperature, for example at 50 to 150 ° C.
Die erfindungsgemässen, diquatemären Ammoniumsalze werden zweckmässig in Mengen von 0,05 bis 5 Gew.%, vorzugsweise von 0,1 bis 4 Gew.%, bezogen auf das zu veredelnde Textilmaterial, eingesetzt.The diquaternary ammonium salts according to the invention are expediently used in amounts of 0.05 to 5% by weight, preferably 0.1 to 4% by weight, based on the textile material to be finished.
Die erfindungsgemässen, diquatemären Ammoniumsalze weisen den wesentlichen Vorteil auf, gute Veredelungseffekte der vorstehend angegebenen, verschiedenartigen Art, die auf eine Vielzahl von Textilmaterialien anwendbar sind, zu bewirken. Zudem stellt die gute Kompatibilität der diquatemären Ammoniumsalze mit optischen Aufhellem, Farbstoffen und in der Textilindustrie üblich mitverwendeten Hilfsmitteln und Zusätzen, wie z.B. Tensiden, einen weiteren Vorteil dar.The diquaternary ammonium salts according to the invention have the essential advantage of bringing about good finishing effects of the above-mentioned various types which can be applied to a large number of textile materials. In addition, the good compatibility of the diquaternary ammonium salts with optical brighteners, dyes and auxiliaries and additives commonly used in the textile industry, such as e.g. Surfactants, another advantage.
In den nachfolgenden Herstellungsvorschriften und Beispielen beziehen sich die angegebenen Teile und Prozente auf das Gewicht.In the following manufacturing instructions and examples, the parts and percentages given relate to the weight.
Zu einer Schmelze aus 166 Teilen einer Technischen Behensäure, die ein Molekulargewicht von 332 aufweist (0,5 Mol), werden bei 160°C 56,1 Teile Dimethylaminopropylamin (0,55 Mol) in inerter Stickstoffatmosphäre innerhalb von 90 Minuten gegeben. Anschliessend wird das Reaktionsgemisch auf 170°C aufgeheizt und während 5 Stunden bei dieser Temperatur unter Rühren gehalten, wobei das durch die Reaktion gebildete Wasser aus dem Reaktionsgemisch entfernt wird. Man erhält in praktisch quantitativer Ausbeute Diethylaminopropylbehensäureamid, das die Aminzahl 128 und die Säurezahl 0 aufweist.To a melt of 166 parts of a technical behenic acid, having a molecular weight of 332 (0.5 mol), at 160 ° C 56.1 parts of dimethylaminopropylamine are (0.55 mol) was added in an inert nitrogen atmosphere over 90 minutes. The reaction mixture is then heated to 170 ° C. and kept at this temperature for 5 hours with stirring, the water formed by the reaction being removed from the reaction mixture. In practically quantitative yield, diethylaminopropyl behenic acid amide, which has an amine number of 128 and an acid number of 0, is obtained.
In analoger Weise werden die in der nachfolgenden Tabelle I bezeichneten Dialkylaminoalkylbehensäureamide oder -ester mit den entsprechenden Aminzahlen erhalten, wenn man Behensäure mit den ebenfalls in Tabelle I bezeichneten Dialkylaminoalkylaminen oder Dialkylaminoalkanolen umsetzt:
Beispiel 1: 106,25 g Dimethylaminoethylbehensäureamid gemäss Herstellungsvorschrift B (0,25 Mol) werden bei 60°C mit einer Lösung aus 12,3 g konzentrierter Salzsäure in 73 g Wasser und 43 g Isopropanol versetzt. Dann gibt man innerhalb von 15 Minuten 11,6 g Epichlorhydrin (0,125 Mol) zu und erhöht die Temperatur anschliessend auf 75°C. Die Reaktionslösung wird während 10 Stunden bei dieser Temperatur unter Rühren gehalten. Nach dieser Zeit betragen Amin-und Epoxydwerte 0. Anschliessend wird die Reaktionslösung zur Trockene eingedampft. Man erhält 122 g der diquatemären Ammoniumverbindung der Formel
Beispiel 2: 101 g Dimethylamino-n-propylbehensäureester gemäss Vorschrift C (0,25 Mol) werden bei 60°C mit einer Lösung aus 12,3 g konzentrierter Salzsäure in 73 g Wasser und 43 g Isopropanol versetzt. Dann gibt man innerhalb von 15 Minuten 11,6 g Epichlorhydrin (0,125 Mol) zu und erhöht die Temperatur anschliessend auf 75°C. Die Reaktionslösung wird während 10 Stunden bei dieser Temperatur unter Rühren gehalten. Nach dieser Zeit betragen Amin-und Epoxydwerte 0. Anschliessend wird das Reaktionsprodukt zur Trockene eingedampft.Example 2: 101 g of dimethylamino-n-propylbehenic acid ester according to specification C (0.25 mol) are mixed at 60 ° C. with a solution of 12.3 g of concentrated hydrochloric acid in 73 g of water and 43 g of isopropanol. 11.6 g of epichlorohydrin (0.125 mol) are then added over the course of 15 minutes, and the temperature is then raised to 75 ° C. The reaction solution is kept at this temperature for 10 hours while stirring. After this time, the amine and epoxy values are 0. The reaction product is then evaporated to dryness.
Man erhält 117 g der diquatemären Ammoniumverbindung der Formel
Beispiel 3: 104,5 g Diethylaminoethylbehensäureamid gemäss Vorschrift D (0,25 Mol) werden bei 60°C mit einer Lösung aus 12,3 g konzentrierter Salzsäure in 73 g Wasser und 43 g Isopropanol versetzt. Dann gibt man innerhalb von 15 Minuten 11,6 g Epichlorhydrin (0,125 Mol) zu und erhöht die Temperatur anschliessend auf 75°C. Die Reaktionslösung wird während 10 Stunden bei dieser Temperatur unter Rühren gehalten. Nach dieser Zeit betragen Amin-und Epoxydwerte 0. Danach wird die Reaktionslösung zur Trockene eingedampft. Man erhält 120 g der diquatemären Ammoniumverbindung der Formel
Beispiel 4: 109,75 g Dimethylamino-n-propylbehensäureamid gemäss Vorschrift A (0,25 Mol) werden in 44 g Isopropanol unter Erwärmen gelöst und dann mit einer Lösung aus 12,3 g konzentrierter Salzsäure in 74 g Wasser versetzt. Bei 55°C gibt man innerhalb von 15 Minuten 11,6 g Epichlorhydrin (0,125 Mol) zu. Anschliessend wird die Temperatur der Reaktionslösung auf 75°C erhöht und die Reaktionslösung während 3 Stunden bei dieser Temperatur unter Rühren gehalten. Nach dieser Zeit betragen Amin- und Epoxydwerte 0. Man erhält 251 g einer 50 %igen, bei Raumtemperatur wachsartigen Reaktionslösung der diquatemären Ammoniumverbindung der Formel
Beispiel 5: 65,6 g Dimethylamino-n-propylbehensäureamid gemäss Vorschrift A (0,15 Mol) werden bei 80°C geschmolzen und mit 14,8 g einer 37 %igen Salzsäure in 758,6 g Wasser versetzt. Nun werden zum Reaktionsgemisch 16,35 g 1,4-Butandioldiglycidylether, der eine Epoxydzahl von 4,6 aufweist (0,075 Mol), innerhalb von 10 Minuten bei 60°C gegeben. Anschliessend wird das Reaktionsgemisch auf 70°C aufgeheizt und während einer Stunde bei dieser Temperatur unter Rühren gehalten. Nach dieser Zeit betragen Amin- und Epoxydwerte 0. Man erhält 855 g einer 10 %igen Lösung des diquatemären Ammoniumsalzes der Formel
Beispiel 6: 65,6 g Dimethylamino-n-propylbehensäureamid (0,15 Mol) gemäss Vorschrift A werden bei 80°C geschmolzen und mit 5,1 g Schwefelsäure in 1083,6 g Wasser versetzt. Nun werden zum Reaktionsgemisch 16,35 g (0,075 Mol) 1,4-Butandioldiglycidylether, der eine Epoxydzahl von 4,6 aufweist innerhalb von 10 Minuten bei 60°C gegeben. Anschliessend wird das Reaktionsgemisch auf 70°C aufgeheizt und während 10 Stunden bei dieser Temperatur unter Rühren gehalten. Nach dieser Zeit beträgt der Aminwert 28 und der Epoxidwert 0. Man erhält 1170 g einer 7%-igen Lösung die vorwiegend das diquaternäre Ammoniumsalz folgender Formel enthält:
Beispiel 7: 45,8 g Dimethylaminoneopentylbehensäureamid (0,1 Mol) gemäss Vorschrift E werden zusammen mit 9,9 g konzentrierter Salzsäure in 500,4 g Wasser auf 75°C Innentemperatur erwärmt. Dann gibt man inerhalb von 15 Minuten 10,9 g (0,05 Mol) 1,4-Butandioldiglycidylether, der eine Epoxidzahl von 4,6 aufweist, zu und rührt 12 Stunden lang bei 77-78°C. Nach dieser Zeit betragen Amin-und Epoxydwerte 0. Man erhält 567 g einer 10%-igen Lösung des diquatemären Ammoniumsalzes der Formel:Example 7: 45.8 g of dimethylaminoneopentylbehenic acid amide (0.1 mol) according to instruction E are heated together with 9.9 g of concentrated hydrochloric acid in 500.4 g of water to an internal temperature of 75 ° C. Then 10.9 g (0.05 mol) of 1,4-butanediol diglycidyl ether, which has an epoxide number of 4.6, are added in the course of 15 minutes and the mixture is stirred at 77-78 ° C. for 12 hours and epoxy values 0. 567 g of a 10% solution of the diquaternary ammonium salt of the formula are obtained:
Beispiel 8: 42,3 g Diisopropylaminoethylbehensäureamid (0,1 Mol) gemäss Vorschrift F werden zusammen mit 9,9 g konzentrierter Salzsäure in 479,8 g Wasser auf 75°C aufgeheizt. Dann gibt man innerhalb von 15 Minuten 10,9 g (0,05 Mol) 1,4-Butandioldyglycidylether, der eine Epoxydzahl von 4,6 aufweist, zu und rührt 12 Stunden lang bei 75°C. Nach dieser Zeit betragen Amin- und Epoxidwerte 0. Man erhält 542 g einer 10%-igen Lösung des diquatemären Ammoniumsalzes der Formel
Beispiel 9: 1 kg Baumwolltrikot wird im Flottenverhältnis 1:30 im Ausziehverfahren mit einer Flotte bei 40°C während 20 Minuten behandelt, die 4 % des diquatemären Ammoniumsalzes gemäss Beispiel 4 enthält und durch Zusatz von Essigsäure einen pH-Wert von 5,5 aufweist. Anschliessend wird das Trikot ohne zu Spülen getrocknet. Zur Prüfung der Vemähbarkeit wird Mittels einem Langfasemähgam aus Polyester mit einer Nähmaschine (Overlock Union Spezial Typ 39500) mit 6000 Stich/min. eine Naht von 50 cm angebracht. Verwendet wird eine Nadel mit einer Spitze Nm 70. Beurteilt wird die Anzahl Löcher längs der Naht. Verglichen wurde mit einem Baumwolltrikot, welches nicht behandelt wurde. Die Ergebnisse sind in der nachfolgenden Tabelle II zusammengefasst:Example 9: 1 kg of cotton jersey is treated in the liquor ratio 1:30 in the exhaust process with a liquor at 40 ° C. for 20 minutes, which contains 4% of the diquaternary ammonium salt according to Example 4 and has a pH of 5.5 by adding acetic acid . The jersey is then dried without rinsing. To check the sewability, use a long-fiber mower made of polyester with a sewing machine (Overlock Union Spezial type 39500) at 6000 stitches / min. a seam of 50 cm is attached. A needle with a Nm 70 tip is used. The number of holes along the seam is assessed. It was compared to a cotton jersey that was not treated. The results are summarized in Table II below:
Aehnliche Ergebnisse werden auch erzielt, wenn man das Baumwolltrikot mit einer Flotte bei einem Abquetscheffekt von 100 % bei Raumtemperatur (15 bis 25°C) foulardiert, die 40 g/l diquatemäres Ammoniumsalz gemäss Beispiel 4 und 2 g/1 Essigsäure 80 % enthält und das Trikot anschliessend bei 90°C trocknet.Similar results are also achieved if the cotton jersey is padded with a liquor with a squeezing effect of 100% at room temperature (15 to 25 ° C), which contains 40 g / l diquaternary ammonium salt according to Example 4 and 2 g / 1 acetic acid 80% and the jersey then dries at 90 ° C.
Beispiel 10: Die im Beispiel 9 bezüglich Vemähbarkeit geprüften Gewirke wurden auch einem Anschmutzungstest unterworfen. Hierbei wird die Trockenanschmutzung nach folgendem Test beurteilt: Substrat; Grösse 9 x 12 cm (mehrere Prüflinge) Filterstaub 15% auf Warengewicht Apparat Turbula Laufzeit 30 min. absaugen mit StaubsaugerExample 10: The knitted fabrics tested for sewability in Example 9 were also subjected to a soiling test. Dry soiling is assessed according to the following test: substrate; Size 9 x 12 cm (several test specimens) filter dust 15% on product weight apparatus Turbula running time 30 min. vacuum with a vacuum cleaner
Die Ergebnisse sind in der nachfolgenden Tabelle III zusammengestellt:
Hierauf werden 3 kg eines Farbstoffes der Formel
- 8 kg m-Nitrobenzolsulfonsäure (Natriumsalz) und
- 4 kg diquatemäres Ammoniumsalz gemäss Beispiel 4 zugesetzt.
- 8 kg of m-nitrobenzenesulfonic acid (sodium salt) and
- 4 kg of diquaternary ammonium salt according to Example 4 were added.
Nach der gleichmässigen Verteilung dieser Zusätze werden nach und nach 160 kg Natriumchlorid zugegeben und die Temperatur auf 80°C erhöht. Darauf werden 12 g einer 30 %igen Natriumhydroxidlösung zugegeben.After the uniform distribution of these additives, 160 kg of sodium chloride are gradually added and the temperature is raised to 80 ° C. 12 g of a 30% sodium hydroxide solution are then added.
Nach einer Laufzeit von weiteren 45 min. bei 80°C wird das Trikot mit heissem und dann mit kaltem Wasser gespült und dann mit 4000 Liter einer Flotte in einem Flottenverhältnis von 1:40 während 20 min. bei Kochtemperatur nachgewaschen, die 4 kg eines Adduktes aus 1 Mol Nonylphenol und 9 Mol Ethylenoxid und 4 kg diquatemäres Ammoniumsalz gemäss Beispiel 4 enthält. Anschliessend wird das Trikot nochmals gespült und getrocknet. Im Monsantobild als Mass für die faltenfreie Ausrüstung des behandelten Trikots wird die Note 4 erhalten. Wird das Trikot wie vorstehend angegeben behandelt, jedoch ohne Zusatz des diquatemären Ammoniumsalzes im Färbebad und in der Nachwaschflotte, so erhält man die Note 2 im Monsantobild.After a further 45 min. at 80 ° C the jersey is rinsed with hot and then with cold water and then with 4000 liters of a liquor in a liquor ratio of 1:40 for 20 min. Washed at cooking temperature, the 4 kg of an adduct of 1 mole of nonylphenol and 9 moles of ethylene contains oxide and 4 kg of diquaternary ammonium salt according to Example 4. The jersey is then rinsed and dried again. In the monsanto picture as a measure for the wrinkle-free finishing of the treated jersey, the grade 4 is obtained. If the jersey is treated as stated above, but without the addition of the diquaternary ammonium salt in the dyebath and in the post-wash liquor, grade 2 is obtained in the monsanto picture.
Beispiel 12: 20 g gebleichtes Baumwoll-Frottä mit einem Flächengewicht von 330 g/m2 wird während 5 min. bei 20°C mit 400 ml Wasser von 5° dH (deutsche Härtegrade) behandelt, die 0,02 g diquatemäres Ammoniumsalz gemäss Beispiel 4 enthält. Anschliessend wird das Frotte ohne zu Spülen geschwungen und bei 70°C getrocknet. Die identische Behandlung wird mit den folgenden Textilmaterialien wiederholt:
- a) Viscosegam
- b) chloriertes Wollcablégarn
- c) Stapelgam aus Polyamid
- d) hochbauschiges Stapelgam aus Polyacrylnitril.
- a) Viscosegam
- b) chlorinated wool cablé yarn
- c) Stacking yarn made of polyamide
- d) high-bulk staple yarn made of polyacrylonitrile.
Der Griff der behandelten Textilmaterialien wird mittels folgender Notenskala beurteilt:
- 0 = Griff unverändert
- 1 = etwas weicher als 0
- 2 = deutlich weicher als 0
- 3 = viel weicher als 0
- 4 = sehr viel weicher als 0
- 0 = handle unchanged
- 1 = slightly softer than 0
- 2 = significantly softer than 0
- 3 = much softer than 0
- 4 = much softer than 0
Die Ergebnisse sind in der nachfolgenden Tabelle IV zusammengestellt:
Aehnliche Ergebnisse werden mit den diquatemären Ammoniumsalzen gemäss Beispiel 1, 2, 3 oder 5 bis 8 erzielt.Similar results are achieved with the diquaternary ammonium salts according to Examples 1, 2, 3 or 5 to 8.
- 300 g gebleichtes Baumwoll-Frotte (Flächengewicht: 330 g/m2)300 g bleached cotton terry (basis weight: 330 g / m 2 )
- 300 g gebleichtes Baumwolltrikot mercerisiert (Flächengewicht: 150 g/m2)300 g bleached cotton jersey mercerized (basis weight: 150 g / m 2 )
- 300 g Viscose-Taffet (Flächengewicht: 105 g/m2)300 g viscose taffeta (basis weight: 105 g / m 2 )
- 300 g Helanca-Trikot aus Polyamid 6,6, Typ HE (Flächengewicht: 260 g/m2)300 g Helanca jersey made of polyamide 6.6, type HE (basis weight: 260 g / m 2 )
- 300 g Polyester Crimplene-Trikot fixiert (Flächengewicht: 225 g/m2)300 g polyester crimplene jersey fixed (basis weight: 225 g / m 2 )
- 300 g Polyacrylnitril-Trikot, Typ 42 (Flächengewicht: 175 g/m2)300 g polyacrylonitrile jersey, type 42 (basis weight: 175 g / m 2 )
Diese Füllung wird mit 80 g eines handelsüblichen Waschmittels bei 40°C gewaschen. Die Wasserhärte ist ca. 10° dH. Zum letzten Spülgang (= 20 I) wird 2 g diquatemäres Ammoniumsalz gemäss Beispiel 4, gelöst in 200 ml Wasser, zugesetzt und das Textilmaterial während 5 Minuten damit behandelt. Anschliessend wird das Textilmaterial geschwungen und bei 70°C getocknet Der Griff der so behandelten Textilmaterialien wird wie in Beispiel 12 angegeben beurteilt. Die Ergebnisse sind in der nachfolgenden Tabelle V zusammengestellt:This filling is washed with 80 g of a commercial detergent at 40 ° C. The water hardness is approx. 10 ° dH. 2 g of diquaternary ammonium salt according to Example 4, dissolved in 200 ml of water, are added to the last rinse cycle (= 20 l) and the textile material is treated with it for 5 minutes. The textile material is then swung and dried at 70 ° C. The handle of the Tex treated in this way Til materials are assessed as given in Example 12. The results are summarized in Table V below:
- Substrat behandelt ohne behandelt mit Ammoniumsalz AmmoniumsalzSubstrate treated without treated with ammonium salt ammonium salt
- Baumwoll-Frotte 0 3Cotton terry cloth 0 3
- Baumwoll-Trikot 0 2-3Cotton jersey 0 2-3
- Viscose-Taffet 0 2-3Viscose taffet 0 2-3
- Polyamid-Trikot 0 2Polyamide jersey 0 2
- Polyester-Trikot 0 2Polyester jersey 0 2
- Polyacrylnitril-Trikot 0 4Polyacrylonitrile jersey 0 4
Claims (9)
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Application Number | Priority Date | Filing Date | Title |
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CH4801/85 | 1985-11-08 | ||
CH480185 | 1985-11-08 |
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EP0221855A2 EP0221855A2 (en) | 1987-05-13 |
EP0221855A3 EP0221855A3 (en) | 1988-05-11 |
EP0221855B1 true EP0221855B1 (en) | 1990-07-11 |
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Application Number | Title | Priority Date | Filing Date |
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EP86810499A Expired - Lifetime EP0221855B1 (en) | 1985-11-08 | 1986-11-03 | Diquaternary ammonium salts, their preparation and their use as textile finishing agents |
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US (1) | US4906413A (en) |
EP (1) | EP0221855B1 (en) |
JP (1) | JPS62174042A (en) |
DE (1) | DE3672564D1 (en) |
ZA (1) | ZA868483B (en) |
Families Citing this family (9)
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AU3729893A (en) * | 1992-03-16 | 1993-10-21 | Procter & Gamble Company, The | Fabric softening compositions containing mixtures of softener material and highly ethoxylated curd dispersant |
US5670472A (en) * | 1994-04-19 | 1997-09-23 | Witco Corporation | Biodegradable ester diquaternary compounds and compositions containing them |
US5643864A (en) * | 1994-08-19 | 1997-07-01 | Rhone-Poulenc, Inc. | Anionic surfactants having multiple hydrophobic and hydrophilic groups |
GB2310659A (en) * | 1996-02-27 | 1997-09-03 | Procter & Gamble | Cationic detergent compounds |
US5944852A (en) * | 1996-10-23 | 1999-08-31 | Solutia Inc. | Dyeing process |
US5830240A (en) * | 1996-10-23 | 1998-11-03 | Solutia Inc. | Fibers and textile materials having enhanced dyeability and finish compositions used thereon |
DE19645380B4 (en) * | 1996-11-04 | 2008-04-17 | Schill + Seilacher Ag | Composition for the permanent hydrophilization of polyolefin fibers, and use of the composition |
CN101039722A (en) * | 2004-10-13 | 2007-09-19 | 宝洁公司 | Hair conditioning composition comprising an alkyl diquaternized ammonium salt cationic surfactant |
JP2010538101A (en) * | 2007-08-31 | 2010-12-09 | ザ プロクター アンド ギャンブル カンパニー | Composition and method for changing visual perception |
Family Cites Families (10)
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US2259650A (en) * | 1938-11-18 | 1941-10-21 | Du Pont | Chemical compound |
US2583772A (en) * | 1949-02-12 | 1952-01-29 | Dearborn Chemicals Co | Acid and quaternary salts of polyamides |
DE1092878B (en) * | 1956-10-10 | 1960-11-17 | Ciba Geigy | Process for dyeing polyacrylonitrile fibers |
US2891835A (en) * | 1956-10-10 | 1959-06-23 | Ciba Ltd | Diquaternary ammonium compounds used in the cationic dyeing of fibers of polyacrylonitrile |
US3074815A (en) * | 1961-01-23 | 1963-01-22 | Nalco Chemical Co | Treatment of cellulosic fibrous materials with diamide quaternaries and the resulting articles |
NO792679L (en) * | 1978-09-01 | 1980-03-04 | Bayer Ag | LIM FOR PAPER. |
US4312813A (en) * | 1980-06-26 | 1982-01-26 | Johnson & Johnson Baby Products Company | Bisquaternary ammonium compound |
DE3329444A1 (en) * | 1983-08-16 | 1985-03-07 | Bayer Ag, 5090 Leverkusen | Quaternary ammonium compounds, their preparation and use |
US4728337A (en) * | 1985-11-08 | 1988-03-01 | Ciba-Geigy Corporation | Assistant combination and use thereof as wool textile finishing agent |
US4721512A (en) * | 1985-11-25 | 1988-01-26 | Ciba-Geigy Corporation | Process for aftertreating dyed cellulosic material |
-
1986
- 1986-11-03 DE DE8686810499T patent/DE3672564D1/en not_active Expired - Lifetime
- 1986-11-03 EP EP86810499A patent/EP0221855B1/en not_active Expired - Lifetime
- 1986-11-07 ZA ZA868483A patent/ZA868483B/en unknown
- 1986-11-08 JP JP61264917A patent/JPS62174042A/en active Granted
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1988
- 1988-11-10 US US07/270,378 patent/US4906413A/en not_active Expired - Fee Related
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ZA868483B (en) | 1987-06-24 |
JPS6328417B2 (en) | 1988-06-08 |
JPS62174042A (en) | 1987-07-30 |
EP0221855A2 (en) | 1987-05-13 |
DE3672564D1 (en) | 1990-08-16 |
EP0221855A3 (en) | 1988-05-11 |
US4906413A (en) | 1990-03-06 |
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