EP0607529A2 - Aqeous softeners for the treatment of textiles - Google Patents

Aqeous softeners for the treatment of textiles Download PDF

Info

Publication number
EP0607529A2
EP0607529A2 EP93118805A EP93118805A EP0607529A2 EP 0607529 A2 EP0607529 A2 EP 0607529A2 EP 93118805 A EP93118805 A EP 93118805A EP 93118805 A EP93118805 A EP 93118805A EP 0607529 A2 EP0607529 A2 EP 0607529A2
Authority
EP
European Patent Office
Prior art keywords
fabric softener
softener according
cationic
mono
nonionic surfactant
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP93118805A
Other languages
German (de)
French (fr)
Other versions
EP0607529B1 (en
EP0607529A3 (en
Inventor
Heike Dr. Kelkenberg
Michael Dr. Brock
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wintershall Dea International AG
Original Assignee
Huels AG
Chemische Werke Huels AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=6478581&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0607529(A2) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Huels AG, Chemische Werke Huels AG filed Critical Huels AG
Publication of EP0607529A2 publication Critical patent/EP0607529A2/en
Publication of EP0607529A3 publication Critical patent/EP0607529A3/en
Application granted granted Critical
Publication of EP0607529B1 publication Critical patent/EP0607529B1/en
Anticipated expiration legal-status Critical
Revoked legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/667—Neutral esters, e.g. sorbitan esters
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/662—Carbohydrates or derivatives
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/001—Softening compositions
    • C11D3/0015—Softening compositions liquid
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/227—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin with nitrogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3773—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines in liquid compositions
    • 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
    • D06M13/10—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 oxygen
    • D06M13/165—Ethers
    • D06M13/17—Polyoxyalkyleneglycol ethers
    • 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
    • D06M13/10—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 oxygen
    • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
    • 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
    • D06M13/10—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 oxygen
    • D06M13/224—Esters of carboxylic acids; Esters of carbonic acid
    • 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
    • D06M13/10—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 oxygen
    • D06M13/224—Esters of carboxylic acids; Esters of carbonic acid
    • D06M13/2243—Mono-, di-, or triglycerides
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • D06M15/03—Polysaccharides or derivatives thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • D06M15/03—Polysaccharides or derivatives thereof
    • D06M15/11—Starch or derivatives thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/285—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides
    • D06M15/29—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides containing a N-methylol group or an etherified N-methylol group; containing a N-aminomethylene group; containing a N-sulfidomethylene group

Definitions

  • DMDMAC distearyldimethylammonium chloride
  • plasticizer emulsions are applied here in a relatively high concentration (10-50 g / l) according to various methods such as spraying, application or exhausting, depending on which soft effect is desired.
  • a good household laundry softener is required to draw on the textiles to be treated as quantitatively as possible from a highly diluted washing liquor emulsion (0.2 to 0.7 g / l).
  • the known good effect of the classic cationic fabric softener is based above all on the pronounced chemisorptivity of the emulsified cationic particles, which are absorbed by the ionic interaction with the anionic fiber surface on the fiber. It is known from the literature that good fabric softening effects can be achieved by mixing nonionic and cationic plasticizers. So z. B.
  • the object of the invention was to produce a new fabric softener that is free of the traditional quaternary ammonium bases with their known disadvantages.
  • the solution to the problem is to add a cationic protective colloid to emulsions of nonionic hydrophobic surfactants.
  • the surfactant vesicles present in the emulsion are cationized superficially, so that they are drawn up substantively onto the textile fiber to be rinsed.
  • the invention therefore relates to an aqueous fabric softener for the treatment of textiles based on water-insoluble nonionic surfactants, the emulsions or dispersions of which are stabilized by the addition of protective colloids which contain cationic groups.
  • nonionic fabric softening agents in particular as a hydrophobic component two similarly long C chains - the chain length of which can be C10 - C22 - and as a hydrophilic component a nonionic polyether or polyol chain or a sugar chain or polysacchrid derivative.
  • Guerbet alcohols which are produced by alkaline condensation of fatty alcohols.
  • the suitable degree of hydrophilization can be set by adding ethylene oxide or propylene oxide.
  • An ecologically interesting class of substances are saccharide difatty acid esters or fatty alkyl polyglycoside fatty acid esters, which can also be present in a mixture. If necessary, the degree of hydrophilization can also be increased with ethylene oxide or propylene oxide.
  • Another known class of substances are the fatty acid esters of sorbitol or sorbitan, which are preferably a mixture of mono-, di- and triesters available.
  • the degree of hydrophilization can also be varied here by addition of alkylene oxide.
  • the diglycerides belong to the most ecologically and economically interesting class of substances because they can be produced on the basis of cheap natural fats and oils and are easily biodegradable.
  • the appropriate degree of hydrophilization is set by alkoxylation.
  • Their manufacture is state of the art (DE 38 26 179).
  • cationic protective colloid in fabric softener formulations is not yet known.
  • colloidal solutions can be considerably stabilized using hydrophilic protective colloids.
  • the protective colloid wraps itself around the particle to be protected like a film and forms a shell of water molecules.
  • Known protective colloids are gelatin, protein hydrolyzate, glue and others.
  • a suitable example of a cationic protective colloid is the technically accessible cationic starch (I). It is used, among other things, in the paper industry. It has the advantage over the electroneutral protective colloids that it draws substantially onto the negatively charged cellulose fiber of the paper.
  • Chitosan has gained economic importance as a renewable raw material mainly in Japan and the USA in recent years. It is produced by deacetylation of chitin, a waste product from crab fishing. Chitin is the second most common polysaccharide on earth after cellulose. Chitosan has a molecular weight of 300 to 500,000 and has a higher positive charge density than the cationic starch. As a primary polyamine, it is only effective as a cationic protective colloid in acidic systems.
  • synthetic polymers are also suitable as protective colloid additives according to the invention, such as, for example, polymers or copolymers of dimethylaminopropyl acrylamide or methacrylamide, which are technically accessible (III).
  • the nonionic water-insoluble surfactants exemplified are prepared in concentrations of 5 to 20% with the aid of small amounts of conventional emulsifiers such as fatty alcohol ethoxylates and, if appropriate, with the addition of acetic acid or lactic acid as solubilizer, aqueous emulsions.
  • the cationic protective colloids mentioned as examples are added to this emulsion in amounts of 0.1 to 50%, based on the nonionic active substance. The preferred amount is 1 to 20%.
  • the protective colloids can also be added to the water before the emulsification process.
  • chitosan In the case of chitosan, the addition of organic acid as a solubilizer is necessary to ensure a pH of 4 to 5 in the rinse liquor.
  • a primary polyamine As a primary polyamine, chitosan is only effective as a cationic protective colloid in an acid medium.
  • the fabric softener emulsions thus produced are diluted so heavily during laundry treatment that the active substance combination is present in the rinse liquor in a concentration of 0.1 to 1 g / l.
  • Fabric softener tests carried out have shown that nonionic surfactants with at least two long hydrophobic chains in combination with small amounts of cationic protective colloid show good fabric softening effects.
  • alkoxylated diglycerides based on natural fats in combination with the natural product chitosan are particularly suitable.
  • the system is readily biodegradable and contains no quaternary amine functions.
  • the softening effect of the fabric softener claimed was carried out in the form of a sensory soft handle test with 6 test persons as follows: A batch of 72 terry towels (44 cm x 30 cm, approx. 60 g, from WFK-Testgewebe GmbH), even if not all 72 towels were used (for reasons of even wear), once with 100 g of a commercially available heavy-duty detergent (PERSIL) machine washed at 95 ° C, rinsed and spun. This is followed by a washing process at 95 ° C. without detergent, including rinsing and a brief spin-on, so that clean, moist cloths containing approximately 2.5 times their dry weight of water could be removed for manual fabric softening.
  • PERSIL heavy-duty detergent
  • test subjects were each presented with 3 wipes in encrypted form according to the test plan according to Table A (so-called triangular test).
  • the task for the examiner was to find out the differently treated cloth after sensory assessment.
  • the result is expressed with the help of 3 numbers: The 1st number indicates the number of examiners who found the wipes treated with the standard to be softer or those with the test substance as harder. The second number indicates the number of examiners who found the wipes treated with the standard to be harder or those with the test substance as softer. The third number finally indicates the number of examiners who, due to the small sensory differences between the wipes treated with the test substance and the standard, could not determine the wipe treated differently or did not give the correct answer.
  • the ecologically and economically interesting diglycerides based on natural fats were the preferred test substances.
  • a palm oil propoxylated with 15% by weight of propylene oxide and a skin fat from Stockhausen propoxylated with 15% by weight of propylene oxide were tested.
  • a synthetic, with 22 wt .-% EO ethoxylated C18 diglyceride (21% triglyceride) was used.
  • a Guerbet alcohol oxidized with 12 EO was used, which was synthesized by alkaline condensation of a technical C 16/18 fatty alcohol.
  • a technical product with a degree of cationization of 0.02 to 0.03 from Cerestar was selected as the cationic starch.
  • the chitosan was used as a cold-soluble hydrochloride (Kyowa Oil and Fat, Japan).
  • a technical polyaminoacrylamide copolymer with an acrylic acid content of 10% by weight and a molecular weight of approx. 1 million from the company Stockhausen was used as the synthetic protective colloid.
  • the active ingredients could easily be added 1 to 5% by weight of a common fatty acid oxyethylate as an emulsifier in the presence of the protective colloids emulsify.
  • Acetic acid or lactic acid was used as the solubilizer, which was used in such quantities that a pH of 4.5 to 5.0 was ensured in the diluted rinsing liquor.
  • chitosan 20% good flowable, stable emulsions could be produced.
  • the cationic starch and the polyamine alkyl acrylamide the emulsions were 10%.
  • Table 1 shows the test results compared to an untreated cloth. In all cases the addition of cation causes.
  • Protective colloid has a significant soft feel. In comparison to a commercially available ester quat, the same softness is achieved if the rinse liquor concentration is doubled (see Table 2).
  • Table 1 Sensory soft grip test with 6 test persons according to DIN 10951 (so-called triangle test) Comparison against untreated cloths washed with PERSIL Washing liquor Triangle test Test substance 0.35 g / l cation.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Textile Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Wood Science & Technology (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Emergency Medicine (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)

Abstract

Aqueous softeners for the treatment of textiles based on non-ionic surfactants which are insoluble in water, their emulsions or dispersions, are stabilised by addition of protective colloids which contain cationic groups.

Description

Das klassische Wäscheweichspülmittel - Distearyldimethylammonium-chlorid (DSDMAC) - ist in den letzten Jahren aufgrund seiner aquatischen Toxizität in die Umweltdiskussion geraten. Es ist inzwischen durch ester- oder amidhaltige quaternäre Ammoniumbasen bzw. Imidazoliniumsalze vom Markt verdrängt worden, die in ihrem Umweltverhalten als besser eingestuft werden.The classic fabric softener - distearyldimethylammonium chloride (DSDMAC) - has been the subject of environmental discussion in recent years due to its aquatic toxicity. It has now been pushed out of the market by quaternary ammonium bases or imidazolinium salts containing ester or amide, which are classified as better in terms of their environmental behavior.

In der Textilausrüstung werden für die Weichmachung in großen Mengen auch nichtkationische Hilfsmittel wie sulfierte Fette, Ethoxylate, Silikone und Wachse mit Erfolg eingesetzt. Im Unterschied zur Wäscheweichspülung im Haushalt werden hier die Weichmacheremulsionen in relativ hoher Konzentration (10-50 g/l) nach verschiedenen Verfahren wie Sprühung, Auftrags- oder Ausziehverfahren appliziert, je nachdem welcher Weicheffekt gewünscht wird.In textile finishing and non-cationic aids such as sulfonated fats, ethoxylates, silicones and waxes are used with success for the softening in large quantities. In contrast to the soft fabric rinse in the household, the plasticizer emulsions are applied here in a relatively high concentration (10-50 g / l) according to various methods such as spraying, application or exhausting, depending on which soft effect is desired.

Dagegen wird von einem guten Haushaltswäscheweichspüler gefordert, daß er aus einer hochverdünnten Spülflottenemulsion (0.2 bis 0.7 g/l) möglichst quantitativ auf die zu behandelnden Textilien aufzieht. Die bekanntermaßen gute Wirkung der klassischen kationaktiven Weichspüler beruht vor allem auf der ausgeprägten Chemisorptivität der emulgierten kationischen Partikel, die über die ionische Wechselwirkung mit der anionischen Faseroberfläche auf die Faser aufziehen. Aus der Literatur ist bekannt, daß sich durch Abmischen von nichtionischen und kationischen Weichmachern gute Weichspüleffekte erzielen lassen. So werden z. B. Weichspülemulsionen auf Basis eines Gemisches von Lanolin oder propoxyliertem Lanonin und einer traditionellen quaternären Ammoniumbase vorgeschlagen, die in der Wäschebehandlung gute Weichspüleffekte zeigen (EP 0 086 104). Ein weiterer Vorteil dieser Mischemulsionen ist, daß sie sich als hochkonzentrierte Emulsionen handhaben lassen, ohne einzudicken, was bei den rein kationischen Wirkstoffemulsionen häufig zu Problemen führt. Die gleiche Wirkung wird auch durch andere nichtionogene Zusätze, wie z. B. Alkylenoxid-Addukte von Fettalkolen, Fettsäureamiden und Fettsäureestern sowie natürlichen Fetten, erreicht (EP 0 056 695; EP 0 159 919). Marktübliche Weichspülmittel enthalten heute ca. 15 % Co- Weichmacher wie z. B. Glycerinmonostearat oder Fettalkoholoxethylate (Tenside Surf. Det. 27, 34-40 (1990)).A good household laundry softener, on the other hand, is required to draw on the textiles to be treated as quantitatively as possible from a highly diluted washing liquor emulsion (0.2 to 0.7 g / l). The known good effect of the classic cationic fabric softener is based above all on the pronounced chemisorptivity of the emulsified cationic particles, which are absorbed by the ionic interaction with the anionic fiber surface on the fiber. It is known from the literature that good fabric softening effects can be achieved by mixing nonionic and cationic plasticizers. So z. B. fabric softener emulsions based on a mixture of lanolin or propoxylated lanonin and a traditional quaternary ammonium base are proposed, which show good fabric softening effects in laundry treatment (EP 0 086 104). Another advantage of these mixed emulsions is that they can be handled as highly concentrated emulsions without thickening, which often leads to problems with the purely cationic active ingredient emulsions. The same effect is also achieved by other non-ionic additives, such as. B. alkylene oxide adducts of fatty alcohols, fatty acid amides and fatty acid esters and natural fats achieved (EP 0 056 695; EP 0 159 919). Standard fabric softener today contain approx. 15% co-plasticizers such as B. glycerol monostearate or fatty alcohol oxyethylates (Surfactants Surf. Det. 27 , 34-40 (1990)).

Aufgabe der Erfindung war es, ein neues Weichspülmittel herzustellen, daß frei von den traditionellen quaternären Ammnoniumbasen mit ihren bekannten Nachteilen ist.The object of the invention was to produce a new fabric softener that is free of the traditional quaternary ammonium bases with their known disadvantages.

Die Lösung der Aufgabe besteht darin, Emulsionen von nichtionischen hydrophoben Tensiden mit einem kationischen Schutzkolloid zu versetzen. Auf diese Weise werden die in der Emulsion vorhandenen Tensidvesikel oberflächlich kationisiert, so daß das Aufziehen auf die weichzuspülende Textilfaser substantiv erfolgt.The solution to the problem is to add a cationic protective colloid to emulsions of nonionic hydrophobic surfactants. In this way, the surfactant vesicles present in the emulsion are cationized superficially, so that they are drawn up substantively onto the textile fiber to be rinsed.

Gegenstand der Erfindung ist daher ein wäßriges Weichspülmittel für die Behandlung von Textilien auf Basis wasserunlöslicher nichtionischer Tenside, deren Emulsionen oder Dispersionen durch Zusatz von Schutzkolloiden, die kationische Gruppen enthalten, stabilisiert sind.The invention therefore relates to an aqueous fabric softener for the treatment of textiles based on water-insoluble nonionic surfactants, the emulsions or dispersions of which are stabilized by the addition of protective colloids which contain cationic groups.

Als nichtionische Weichspül-Wirkstoffe kommt eine Vielzahl an sich bekannter Stoffklassen infrage, die insbesondere als hydrophoben Anteil zwei ähnlich lange C-Ketten - deren Kettenlänge C₁₀ - C₂₂ sein kann - und als hydrophilen Anteil eine nichtionische Polyether- oder Polyol-Kette oder einen Zucker- oder Polysacchrid-Abkömmling enthalten.A large number of substance classes known per se are suitable as nonionic fabric softening agents, in particular as a hydrophobic component two similarly long C chains - the chain length of which can be C₁₀ - C₂₂ - and as a hydrophilic component a nonionic polyether or polyol chain or a sugar chain or polysacchrid derivative.

Eine dieser Stoffklassen stellen die technisch verfügbaren Guerbet-Alkohole dar, die durch alkalische Kondensation von Fettalkoholen hergestellt werden. Der geeignete Hydrophilierungsgrad läßt sich durch Ethylenoxid- oder Propylenoxid-Addition einstellen.
Eine ökologisch interessante Stoffklasse stellen die Saccharid-Difettsäureester oder die Fettalkylpolyglycosid-Fettsäureester dar, die auch im Gemisch vorliegen können. Bei Bedarf kann auch hier der Hydrophilierungsgrad zusätzlich mit Ethylenoxid oder Propylenoxid erhöht werden.
Eine andere bekannte Stoffklasse stellen die Fettsäureester des Sorbitols oder des Sorbitans dar, die bevorzugt als Gemisch von Mono- Di- und Triester vorliegen. Auch hier kann der Hydrophilierungsgrad durch Alkylenoxid-Addition variiert werden.
Die Diglyceride zählen zu der ökologisch und wirtschaftlich interessantesten Stoffklasse, da sie sich auf Basis billiger natürlicher Fette und Öle herstellen lassen und biologisch gut abbaubar sind. Auch hier wird der geeignete Hydrophilierungsgrad durch Alkoxylierung eingestellt. Ihre Herstellung ist Stand der Technik (DE 38 26 179).One of these substance classes is the technically available Guerbet alcohols, which are produced by alkaline condensation of fatty alcohols. The suitable degree of hydrophilization can be set by adding ethylene oxide or propylene oxide.
An ecologically interesting class of substances are saccharide difatty acid esters or fatty alkyl polyglycoside fatty acid esters, which can also be present in a mixture. If necessary, the degree of hydrophilization can also be increased with ethylene oxide or propylene oxide.
Another known class of substances are the fatty acid esters of sorbitol or sorbitan, which are preferably a mixture of mono-, di- and triesters available. The degree of hydrophilization can also be varied here by addition of alkylene oxide.
The diglycerides belong to the most ecologically and economically interesting class of substances because they can be produced on the basis of cheap natural fats and oils and are easily biodegradable. Here too, the appropriate degree of hydrophilization is set by alkoxylation. Their manufacture is state of the art (DE 38 26 179).

Der erfindungsgemäße Zusatz von kationischem Schutzkolloid in Wäscheweichspülformulierungen ist bisher nicht bekannt. Allgemein können kolloidale Lösungen durch hydrophile Schutzkolloide beträchtlich stabilisiert werden. Das Schutzkolloid legt sich wie ein Film um das zu schützende Teilchen und bildet eine Hülle von Wassermolekülen aus. Bekannte Schutzkolloide sind Gelatine, Eiweißhydrolysat, Leim u.a. Ein geeignetes Beispiel für ein kationisches Schutzkolloid ist die technisch zugängliche kationische Stärke (I). Sie findet unter anderem in der Papierindustrie Verwendung. Sie hat gegenüber den elektroneutralen Schutzkolloiden den Vorteil, daß sie substantiv auf die negativ geladene Cellulosefaser des Papiers aufzieht.The addition of cationic protective colloid according to the invention in fabric softener formulations is not yet known. In general, colloidal solutions can be considerably stabilized using hydrophilic protective colloids. The protective colloid wraps itself around the particle to be protected like a film and forms a shell of water molecules. Known protective colloids are gelatin, protein hydrolyzate, glue and others. A suitable example of a cationic protective colloid is the technically accessible cationic starch (I). It is used, among other things, in the paper industry. It has the advantage over the electroneutral protective colloids that it draws substantially onto the negatively charged cellulose fiber of the paper.

Ein weiteres Beispiel für den erfindungsgemäßen Zusatz eines kationischen Schutzkolloides in Wäscheweichspülformulierungen ist das Naturprodukt Chitosan (II).
Chitosan hat in den letzten Jahren als nachwachsender Rohstoff hauptsächlich in Japan und USA an wirschaftlicher Bedeutung gewonnen. Es wird durch Deacetylierung von Chitin, einem Abfallprodukt aus der Krabbenfischerei produziert. Chitin ist nach der Cellulose das zweithäufigste Polysaccharid der Erde.
Chitosan hat ein Molgewicht von 300 bis 500 000 und hat im Vergleich zur kationischen Stärke eine höhere positive Ladungsdichte. Als primäres Polyamin ist es als kationisches Schutzkolloid nur in sauren Systemen wirksam.
Neben den natürlichen kationischen Polymeren sind auch synthetische Polymere als erfindungsgemäßer Schutzkolloid-Zusatz geeignet, wie beispielsweise Polymere oder Copolymere des Dimethylaminopropyl-acrylamids oder -methacrylamids, die technisch zugänglich sind (III).Another example of the addition of a cationic protective colloid according to the invention in fabric softener formulations is the natural product chitosan (II).
Chitosan has gained economic importance as a renewable raw material mainly in Japan and the USA in recent years. It is produced by deacetylation of chitin, a waste product from crab fishing. Chitin is the second most common polysaccharide on earth after cellulose.
Chitosan has a molecular weight of 300 to 500,000 and has a higher positive charge density than the cationic starch. As a primary polyamine, it is only effective as a cationic protective colloid in acidic systems.
In addition to the natural cationic polymers, synthetic polymers are also suitable as protective colloid additives according to the invention, such as, for example, polymers or copolymers of dimethylaminopropyl acrylamide or methacrylamide, which are technically accessible (III).

Zur Herstellung des erfindungsgemäßen wäßrigen Weichspülmittels werden die beispielhaft aufgeführten nichtionischen wasserunlöslichen Tenside in Konzentrationen von 5 bis 20 % unter Zuhilfenahme kleiner Mengen üblicher Emulgatoren wie Fettalkoholethoxylate und gegebenenfalls unter Zugabe von Essigsäure oder Milchsäure als Lösungsvermittler wäßrige Emulsionen hergestellt. Zu dieser Emulsion werden die als Beispiele genannten kationischen Schutzkolloide in Mengen von 0.1 bis 50 %, bezogen auf die nichtionische Wirksubstanz, hinzugegeben.
Die bevorzugte Menge beträgt 1 bis 20 %. Die Schutzkolloide können dem Wasser auch vor dem Emulgierungsprozeß zugesetzt werden. Im Falle des Chitosans ist die Zugabe von organischer Säure als Lösungsvermittler erforderlich, um einen pH von 4 bis 5 in der Spülflotte zu gewährleisten. Als primäres Polyamin ist Chitosan nur in saurem Medium als kationisches Schutzkolloid wirksam.To prepare the aqueous fabric softener according to the invention, the nonionic water-insoluble surfactants exemplified are prepared in concentrations of 5 to 20% with the aid of small amounts of conventional emulsifiers such as fatty alcohol ethoxylates and, if appropriate, with the addition of acetic acid or lactic acid as solubilizer, aqueous emulsions. The cationic protective colloids mentioned as examples are added to this emulsion in amounts of 0.1 to 50%, based on the nonionic active substance.
The preferred amount is 1 to 20%. The protective colloids can also be added to the water before the emulsification process. In the case of chitosan, the addition of organic acid as a solubilizer is necessary to ensure a pH of 4 to 5 in the rinse liquor. As a primary polyamine, chitosan is only effective as a cationic protective colloid in an acid medium.

Die so hergestellten Weichspülemulsionen werden bei der Wäschebehandlung so stark verdünnt, daß die Wirkstoffkombination in der Spülflotte in einer Konzentration von 0.1 bis 1 g/l vorliegt.
Durchgeführte Weichspülteste haben gezeigt, daß nichtionische Tenside mit mindestens zwei langen hydrophoben Ketten in Kombination mit kleinen Mengen an kationischem Schutzkolloid gute Wäscheweichspüleffekte zeigen. Aus ökologischer Sicht sind insbesondere alkoxylierte Diglyceride auf Basis natürlicher Fette in Kombination mit dem Naturprodukt Chitosan geeignet. Das System ist biologisch gut abbaubar und enthält keine quaternären Aminfunktionen.The fabric softener emulsions thus produced are diluted so heavily during laundry treatment that the active substance combination is present in the rinse liquor in a concentration of 0.1 to 1 g / l.
Fabric softener tests carried out have shown that nonionic surfactants with at least two long hydrophobic chains in combination with small amounts of cationic protective colloid show good fabric softening effects. From an ecological point of view, alkoxylated diglycerides based on natural fats in combination with the natural product chitosan are particularly suitable. The system is readily biodegradable and contains no quaternary amine functions.

Die durchgeführten Weichspülversuche werden im folgenden Text genauer beschrieben und sollen die Erfindung näher erläutern.The fabric softener tests carried out are described in more detail below and are intended to explain the invention in more detail.

Beschreibung der Testmethode der weichmachenden Wirkung (Dreiecksprüfung)Description of the test method of the softening effect (triangular test)

Die weichmachende Wirkung des beanspruchten Wäscheweichspülmittels wurde in Form einer sensorischen Weichgriff-Prüfung mit 6 Testpersonen wie folgt durchgeführt:
Eine Charge von 72 Stück Frotteehandtüchern (44 cm · 30 cm, ca. 60 g, von der WFK-Testgewebe GmbH) wurden, auch wenn nicht alle 72 Tücher gebraucht wurden (aus Gründen gleichmäßiger Abnutzung), einmal mit 100 g eines handelsüblichen Vollwaschmittels (PERSIL) maschinell bei 95 °C gewaschen, gespült und geschleudert. Anschließend folgt ein Waschvorgang bei 95 °C ohne Waschmittel einschließlich Spülen und kurze Anschleuderung, so daß saubere, feuchte, etwa das 2,5fache ihres Trockengewichtes an Wasser enthaltene Tücher für manuelles Weichspülen entnommen werden konnten.The softening effect of the fabric softener claimed was carried out in the form of a sensory soft handle test with 6 test persons as follows:
A batch of 72 terry towels (44 cm x 30 cm, approx. 60 g, from WFK-Testgewebe GmbH), even if not all 72 towels were used (for reasons of even wear), once with 100 g of a commercially available heavy-duty detergent ( PERSIL) machine washed at 95 ° C, rinsed and spun. This is followed by a washing process at 95 ° C. without detergent, including rinsing and a brief spin-on, so that clean, moist cloths containing approximately 2.5 times their dry weight of water could be removed for manual fabric softening.

Für einen Versuchsplan analog Tabelle A wurden jeweils 9 Tücher in 9 Spülflotten mit dem Standard (= S) und 9 Tücher in 9 Spülflotten mit der Testsubstanz (= T) weichgespült. Dazu wurden in Plastikschüsseln jeweils 2 l Leitungswasser und 0.00 bzw. 0,35 g/l Standard (Aktivsubstanz gerechnet) bzw. eine frei zu wählende Menge der Testsubstanz vordispergiert und die feuchten Tücher 10 min. darin belassen. Nach 5 min. wurden die Tücher einmal gewendet. Die weichgespülten Tücher wurden einzeln jeweils 30 sek. geschleudert und auf dem Wäscheständer in ruhender Luft getrocknet. Tabelle A Versuchsplan für die sensorische Weichgriffprüfung mit 6 Prüfern. Tücherkombination mit verschlüsselter Kennzeichnung 1 SST 2 SST 3 SST 4 STT 5 STT 6 STT S = Vergleichssubstanz (Standard); T = Erfindung (Testsubstanz) For a test plan analogous to Table A, 9 wipes in 9 washing liquors with the standard (= S) and 9 wipes in 9 washing liquors with the test substance (= T) were rinsed soft. For this purpose, 2 l tap water and 0.00 or 0.35 g / l standard (active substance calculated) or a freely selectable amount of the test substance were predispersed in plastic bowls and the wet wipes for 10 min. leave in it. After 5 min. the towels were turned over once. The rinsed cloths were individually 30 sec each. flung and dried on the drying rack in still air. Table A Experimental plan for the sensory soft grip test with 6 examiners. Cloth combination with encrypted labeling 1 SST 2nd SST 3rd SST 4th STT 5 STT 6 STT S = reference substance (standard); T = invention (test substance)

Den Prüfpersonen wurden jeweils 3 Tücher in verschlüsselter Form nach dem Versuchsplan gemäß Tabelle A (sog. Dreieckstest) vorgelegt. Die Aufgabe für den Prüfer bestand darin, das abweichend behandelte Tuch nach sensorischer Begutachtung herauszufinden.The test subjects were each presented with 3 wipes in encrypted form according to the test plan according to Table A (so-called triangular test). The task for the examiner was to find out the differently treated cloth after sensory assessment.

War dies möglich, vermerkte der Prüfer, ob sich das abweichende Tuch weicher oder härter anfühlt. Fanden mindestens 5 oder 6 Prüfer das abweichend behandelte Tuch (T bei den Prüfern 1 bis 3, S bei den Prüfern 4 bis 6) heraus, besteht nach DIN 10 951 mit einer Wahrscheinlichkeit von größer 95 % zwischen der Testsubstanz und dem Standard ein signifikanter Unterschied. Das Ergebnis wird mit Hilfe von 3 Zahlen ausgedrückt: Die 1. Zahl gibt die Anzahl der Prüfer an, die die mit dem Standard behandelten Tücher als weicher empfanden bzw. die mit der Testsubstanz als härter. Die 2. Zahl gibt die Anzahl der Prüfer an, die die mit dem Standard behandelten Tücher als härter empfanden bzw. die mit der Testsubstanz als weicher. Die 3. Zahl gibt schließlich die Anzahl der Prüfer an, die aufgrund der geringen sensorischen Unterschiede der mit der Testsubstanz bzw. dem Standard behandelten Tücher das abweichend behandelte Tuch nicht bestimmen konnte bzw. nicht die richtige Antwort gab.If this was possible, the examiner noted whether the different cloth felt softer or harder. If at least 5 or 6 examiners found the cloth treated differently (T for examiners 1 to 3, S for examiners 4 to 6), there is a significant difference between the test substance and the standard according to DIN 10 951 with a probability of greater than 95% . The result is expressed with the help of 3 numbers: The 1st number indicates the number of examiners who found the wipes treated with the standard to be softer or those with the test substance as harder. The second number indicates the number of examiners who found the wipes treated with the standard to be harder or those with the test substance as softer. The third number finally indicates the number of examiners who, due to the small sensory differences between the wipes treated with the test substance and the standard, could not determine the wipe treated differently or did not give the correct answer.

Als Testsubstanzen wurden die ökologisch und wirtschaftlich interessanten Diglyceride auf Basis natürlicher Fette bevorzugt untersucht.
Zur Ausprüfung kam ein mit 15 Gew.-% Propylenoxid propoxyliertes Palmöl und ein mit 15 Gew.-% Propylenoxid propoxyliertes Hautfett der Firma Stockhausen. Daneben wurde ein synthetisches, mit 22 Gew.-% EO oxethyliertes C₁₈-Diglycerid (21 % Triglycerid) eingesetzt. Als weiteres Beispiel wurde ein mit 12 EO oxethyllierter Guerbet-Alkohol eingesetzt, der durch alkalische Kondensation eines technischen C16/18-Fettalkohols synthetisiert wurde.
Als kationische Stärke wurde ein technisches Produkt mit einem Kationisierungsgrad von 0.02 bis 0.03 der Firma Cerestar ausgewählt. Das Chitosan wurde als kaltlösliches Hydrochlorid eingesetzt (Firma Kyowa Oil and Fat, Japan). Als synthetisches Schutzkolloid diente ein technisches Polyaminoacrylamid-Copolymerisat mit einem Acrylsäureanteil von 10 Gew.-% und einem Molgewicht von ca. 1 Mio. von der Firma Stockhausen.The ecologically and economically interesting diglycerides based on natural fats were the preferred test substances.
A palm oil propoxylated with 15% by weight of propylene oxide and a skin fat from Stockhausen propoxylated with 15% by weight of propylene oxide were tested. In addition, a synthetic, with 22 wt .-% EO ethoxylated C₁₈ diglyceride (21% triglyceride) was used. As a further example, a Guerbet alcohol oxidized with 12 EO was used, which was synthesized by alkaline condensation of a technical C 16/18 fatty alcohol.
A technical product with a degree of cationization of 0.02 to 0.03 from Cerestar was selected as the cationic starch. The chitosan was used as a cold-soluble hydrochloride (Kyowa Oil and Fat, Japan). A technical polyaminoacrylamide copolymer with an acrylic acid content of 10% by weight and a molecular weight of approx. 1 million from the company Stockhausen was used as the synthetic protective colloid.

Die Wirkstoffe ließen sich problemlos unter Zusatz von 1 bis 5 Gew.-% eines gängigen Fettsäureoxethylats als Emulgator in Gegenwart der Schutzkolloide emulgieren. Als Lösungsvermittler diente Essigsäure oder Milchsäure, die in solchen Mengen eingesetzt wurde, daß ein pH von 4.5 bis 5.0 in der verdünnten Spülflotte gewährleistet war. Im Falle des Chitosans konnten so 20 %ige gut fließfähige, stabile Emulsionen hergestellt werden. Im Falle der kationischen Stärke und des Polyaminalkylacrylamids waren die Emulsionen 10 %ig.The active ingredients could easily be added 1 to 5% by weight of a common fatty acid oxyethylate as an emulsifier in the presence of the protective colloids emulsify. Acetic acid or lactic acid was used as the solubilizer, which was used in such quantities that a pH of 4.5 to 5.0 was ensured in the diluted rinsing liquor. In the case of chitosan, 20% good flowable, stable emulsions could be produced. In the case of the cationic starch and the polyamine alkyl acrylamide, the emulsions were 10%.

Als Vergleichssubstanz wurde ein marktübliches Esterquat von der Firma Stepan (STEPANTEX VR 85) ausgewählt.A commercially available esterquat from Stepan (STEPANTEX VR 85) was selected as the reference substance.

Die Versuchsergebnisse sind in den folgenden zwei Tabellen zusammengefaßt.The test results are summarized in the following two tables.

In Tabelle 1 sind die Prüfergebnisse im Vergleich zu einem unbehandelten Tuch zusammengestellt. In allen Fällen bewirkt der Zusatz von kation. Schutzkolloid einen signifikannten Weichgriff. Im Vergleich zu einem marktgängigen Esterquat wird der gleiche Weichgriff erreicht, wenn die Spülflottenkonzentration verdoppelt ist (vgl. Tabelle 2). Dabei zeigte das Chitosan als kationisches Schutzkolloid die beste Wirkung. Bereits ein Zusatz von nur 2,5 %, bezogen auf Testsubstanz, genügt, um einen synergistischen Effekt zu erzielen. Tabelle 1 Sensorische Weichgriffprüfung mit 6 Prüfpersonen nach DIN 10951 (sog. Dreieckstest) Vergleich gegen unbehandelte mit PERSIL gewaschene Tücher Spülflotte Dreiecksprüfung Testsubstanz 0.35 g/l kation. Schutzkolloid Gew.-% bez. auf Testsubstanz unbehandelt weicher Testsubstanz weicher kein Unterschied C32/36-Guerbitol + 12 EO ---- 0 1 5 + 15 % kat. Stärke 0 5 1 Palmöl/15 % PO ----- 0 2 4 + 13 % kat. Stärke 0 5 1 Hautfett/15 % PO ----- 0 3 3 + 10 % kat. Stärke 0 6 0 C₁₈-Diglycerid/22 % EO ----- 0 1 5 + 10 % kat. Stärke 0 5 1 ------ + 100 % Chitosan 0 3 3 Palmöl/15 % PO + 5 % Chitosan 0 5 1 Hautfett/15 % PO + 5 % Chitosan 0 6 0 C₁₈-Diglycerid/22 % EO + 5 % Chitosan 0 6 0 ------ + 10 % Polyaminoacrylamid 1 2 3 Palmöl/15 % PO + 5 % Polyaminoacryamid 0 5 1 Hautöl/15 % PO + 5 % Polyyaminoacrylamid 0 4 2 C₁₈-Diglycerid/22 % EO + 10 % Polyamino- 0 5 1 Tabelle 2 Sensorische Weichgriffprüfung mit 6 Prüfpersonen nach DIN 10951 (sog. Dreieckstest) Vergleich gegen marktübliches Esterquat*(0.18 g/l STEPANTEX VR 85) Spülflotte Dreiecksprüfung Testsubstanz 0.35 g/l kation. Schutzkolloid Gew.% bez.auf Testsubstanz Esterquat weicher Testsubstanz weicher kein Unter schied Palmöl/15 % PO ---- 4 0 2 Palmöl/15 % PO + 5 % Chitosan 1 0 5 Palmöl/15 % PO 2.5 % Chitosan 1 0 5 Hautfett/15 % PO ---- 5 0 1 Hautfett/15 % PO + 5 % Chitosan 1 0 5 C₁₈-Diglycerid/22 % EO ---- 4 0 2 C₁₈-Diglycerid/22 % EO + 5 % Chitosan 1 0 5 * Quaternierter Fettsäureester des Triethanolamins Table 1 shows the test results compared to an untreated cloth. In all cases the addition of cation causes. Protective colloid has a significant soft feel. In comparison to a commercially available ester quat, the same softness is achieved if the rinse liquor concentration is doubled (see Table 2). The chitosan, as a cationic protective colloid, had the best effect. An addition of only 2.5%, based on the test substance, is sufficient to achieve a synergistic effect. Table 1 Sensory soft grip test with 6 test persons according to DIN 10951 (so-called triangle test) Comparison against untreated cloths washed with PERSIL Washing liquor Triangle test Test substance 0.35 g / l cation. Protective colloid% by weight on test substance untreated softer Test substance softer no difference C 32/36 Guerbitol + 12 EO ---- 0 1 5 + 15% cat. Strength 0 5 1 Palm oil / 15% PO ----- 0 2nd 4th + 13% cat. Strength 0 5 1 Skin fat / 15% PO ----- 0 3rd 3rd + 10% cat. Strength 0 6 0 C₁₈ diglyceride / 22% EO ----- 0 1 5 + 10% cat. Strength 0 5 1 ------ + 100% chitosan 0 3rd 3rd Palm oil / 15% PO + 5% chitosan 0 5 1 Skin fat / 15% PO + 5% chitosan 0 6 0 C₁₈ diglyceride / 22% EO + 5% chitosan 0 6 0 ------ + 10% polyaminoacrylamide 1 2nd 3rd Palm oil / 15% PO + 5% polyaminoacryamide 0 5 1 Skin oil / 15% PO + 5% polyaminoacrylamide 0 4th 2nd C₁₈ diglyceride / 22% EO + 10% polyamino 0 5 1 Sensory soft grip test with 6 test persons according to DIN 10951 (so-called triangle test) Comparison against commercially available esterquat * (0.18 g / l STEPANTEX VR 85) Washing liquor Triangle test Test substance 0.35 g / l cation. Protective colloid% by weight based on test substance Esterquat softer Test substance softer no difference Palm oil / 15% PO ---- 4th 0 2nd Palm oil / 15% PO + 5% chitosan 1 0 5 Palm oil / 15% PO 2.5% chitosan 1 0 5 Skin fat / 15% PO ---- 5 0 1 Skin fat / 15% PO + 5% chitosan 1 0 5 C₁₈ diglyceride / 22% EO ---- 4th 0 2nd C₁₈ diglyceride / 22% EO + 5% chitosan 1 0 5 * Triethanolamine quaternized fatty acid ester

Claims (18)

Wäßriges Weichspülmittel für die Behandlung von Textilien auf Basis wasserunlöslicher nichtionischer Tenside,
dadurch gekennzeichnet,
daß deren Emulsionen oder Dispersionen durch Zusatz von Schutzkolloiden, die kationische Gruppen enthalten, stabilisiert sind.Aqueous fabric softener for the treatment of textiles based on water-insoluble non-ionic surfactants,
characterized,
that their emulsions or dispersions are stabilized by the addition of protective colloids which contain cationic groups. Weichspülmittel nach Anspruch 1,
dadurch gekennzeichnet,
daß das kationische Schutzkolloid Chitosan oder ein Chitosan-Derivat darstellt.Fabric softener according to claim 1,
characterized,
that the cationic protective colloid is chitosan or a chitosan derivative. Weichspülmittel nach Anspruch 2,
dadurch gekennzeichet,
daß das Weichspülmittel zusätzlich organische Säuren enthält.Fabric softener according to claim 2,
characterized by
that the fabric softener also contains organic acids. Weichspülmittel nach Anspruch 1,
dadurch gekennzeichnet,
daß das kationische Schutzkolloid eine kationische Stärke darstellt.Fabric softener according to claim 1,
characterized,
that the protective cationic colloid is a cationic starch. Weichspülmittel nach Anspruch 1,
dadurch gekennzeichnet,
daß das kationische Schutzkolloid ein synthetisches Polymeres oder Copolymeres darstellt, welches kationische Gruppen enthält.Fabric softener according to claim 1,
characterized,
that the cationic protective colloid is a synthetic polymer or copolymer containing cationic groups. Weichspülmittel nach Anspruch 5,
dadurch gekennzeichnet,
daß das kationische Schutzkolloid ein Polymeres oder Copolymeres auf Basis von Aminoalkylacrylamid darstellt.Fabric softener according to claim 5,
characterized,
that the cationic protective colloid is a polymer or copolymer based on aminoalkylacrylamide. Wäßriges Weichspülmittel nach Anspruch 1,
dadurch gekennzeichnet,
daß die wasserunlöslichen nichtionischen Tenside ein bis vier, bevorzugt zwei lange hydrophobe Ketten und als hydrophile Gruppe einen Glycose- oder Polysaccharid-Rest, eine Polyol-Kette oder eine Polyether-Kette enthalten.Aqueous fabric softener according to claim 1,
characterized,
that the water-insoluble nonionic surfactants contain one to four, preferably two long, hydrophobic chains and, as the hydrophilic group, a glycose or polysaccharide residue, a polyol chain or a polyether chain. Weichspülmittel nach Anspruch 7,
dadurch gekennzeichnet,
daß das nichtionische Tensid einen alkoxylierten verzweigten Alkohol der allgemeinen Formel
Figure imgb0001
 darstellt, in der R¹ und R² verzweigte oder geradkettige C₁₀-C₂₂-Alkylreste bedeuten und gleich oder verschieden sein können und R³ für Wasserstoff oder Methyl-Rest steht und n eine Zahl von 1 bis 30 ist.Fabric softener according to claim 7,
characterized,
that the nonionic surfactant is an alkoxylated branched alcohol of the general formula
Figure imgb0001
 represents in which R¹ and R² are branched or straight-chain C₁₀-C₂₂-alkyl radicals and may be the same or different and R³ is hydrogen or methyl radical and n is a number from 1 to 30. Weichspülmittel nach Anspruch 7,
dadurch gekennzeichnet,
daß das nichtionische Tensid einen Mono-, Di-, Tri-, oder Tetra-, bevorzugt Di-Fettsäureester eines Monosaccharids oder Polysaccharids darstellt, in dem die Acyl-Reste verzweigte oder lineare Ketten von C₁₀-C₂₂ sind und gleich oder verschieden sein können.Fabric softener according to claim 7,
characterized,
that the nonionic surfactant is a mono-, di-, tri-, or tetra-, preferably di-fatty acid ester of a monosaccharide or polysaccharide, in which the acyl radicals are branched or linear chains of C₁₀-C₂₂ and can be the same or different. Weichspülmittel nach Anspruch 7,
dadurch gekennzeichnet,
daß das nichtionische Tensid einen Mono-, Di-, Tri-, bevorzugt Mono-Fettsäureester eines Fettalkyl-Glycosids oder Fettalkyl-polyglycosids darstellt, in dem die Acyl-Reste und die Fettalkylreste verzweigte oder lineare C₁₀₋C₂₂-Ketten sind und gleich oder verschieden sein können.Fabric softener according to claim 7,
characterized,
that the nonionic surfactant is a mono-, di-, tri-, preferably mono-fatty acid ester of a fatty alkyl glycoside or fatty alkyl polyglycoside in which the acyl radicals and the fatty alkyl radicals are branched or linear C₁₀₋C₂₂ chains and are the same or different could be. Weichspülmittel nach den Ansprüchen 9 und 10,
dadurch gekennzeichnet,
daß die nichtionischen Tenside noch zusätzlich mit Ethylenoxid oder Propylenoxid alkoxyliert sind.Fabric softener according to claims 9 and 10,
characterized,
that the nonionic surfactants are additionally alkoxylated with ethylene oxide or propylene oxide. Weichspüler nach Anspruch 7,
dadurch gekennzeichnet,
daß das nichtionische Tensid einen Mono-, Di-, Tri-, bevorzugt Di-Fettsäureester eines Polyols der allgemeinen Formel



        HOCH₂-(CHOH)m-CH₂OH



darstellt und in der m eine Zahl von 1-4 ist, und die Acylreste verzweigte oder geradlinige C₁₀-C₂₂-Ketten sind und gleich oder verschieden sein können.Fabric softener according to claim 7,
characterized,
that the nonionic surfactant is a mono-, di-, tri-, preferably di-fatty acid ester of a polyol of the general formula



HOCH₂- (CHOH) m -CH₂OH



represents and in which m is a number from 1-4, and the acyl radicals are branched or rectilinear C₁₀-C₂₂ chains and may be the same or different. Weichspüler nach Anspruch 12,
dadurch gekennzeichnet,
daß die nichtionischen Tenside noch zusätzlich mit Ethylenoxid oder Propylenoxid alkoxyliert sind.Fabric softener according to claim 12,
characterized,
that the nonionic surfactants are additionally alkoxylated with ethylene oxide or propylene oxide. Weichspülmittel nach Anspruch 13,
dadurch gekennzeichnet,
daß die nichtionischen Tenside Difettsäureester oder Gemische von Mono-, Di- und Trifettsäureester des Glycerins darstellen.Fabric softener according to claim 13,
characterized,
that the nonionic surfactants are difatty acid esters or mixtures of mono-, di- and trifatty acid esters of glycerol. Weichspülmittel nach den Ansprüchen 12 bis 14,
dadurch gekennzeichnet,
daß die nichtionischen Tenside aus alkoxylierten natürlichen Fetten, Ölen und/oder deren Mischungen mit freien Fettsäuren, Mono- und/oder Diglyceriden bestehen.Fabric softener according to claims 12 to 14,
characterized,
that the nonionic surfactants consist of alkoxylated natural fats, oils and / or their mixtures with free fatty acids, mono- and / or diglycerides. Weichspülmittel nach Anspruch 1,
dadurch gekennzeichnet,
daß das Schutzkolloid in Mengen von 0.1 bis 50 %, bevorzugt 1 bis 20 %, bezogen auf das nichtionische Tensid, zugesetzt wird.Fabric softener according to claim 1,
characterized,
that the protective colloid is added in amounts of 0.1 to 50%, preferably 1 to 20%, based on the nonionic surfactant. Weichspülmittel nach Anspruch 1,
dadurch gekennzeichnet,
daß das nichionische Tensid in Mengen von 5 bis 30 %, bevorzugt 5 bis 20 %, bezogen auf die Emulsion, zugesetzt wird.Fabric softener according to claim 1,
characterized,
that the nonionic surfactant is added in amounts of 5 to 30%, preferably 5 to 20%, based on the emulsion. Verwendung des Weichspülmittels nach den Ansprüchen 1 bis 17 in einer Konzentration von 0.1 bis 1 g/l Wirkstoffkombination in der Spülflotte bei der Wäschebehandlung.Use of the fabric softener according to claims 1 to 17 in a concentration of 0.1 to 1 g / l combination of active ingredients in the washing liquor in the laundry treatment.
EP93118805A 1993-01-20 1993-11-23 Use of aqeous softeners for the treatment of textiles Revoked EP0607529B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4301459A DE4301459A1 (en) 1993-01-20 1993-01-20 Aqueous fabric softener for the treatment of textiles
DE4301459 1993-01-20

Publications (3)

Publication Number Publication Date
EP0607529A2 true EP0607529A2 (en) 1994-07-27
EP0607529A3 EP0607529A3 (en) 1995-03-22
EP0607529B1 EP0607529B1 (en) 1998-06-24

Family

ID=6478581

Family Applications (1)

Application Number Title Priority Date Filing Date
EP93118805A Revoked EP0607529B1 (en) 1993-01-20 1993-11-23 Use of aqeous softeners for the treatment of textiles

Country Status (8)

Country Link
US (1) US5447643A (en)
EP (1) EP0607529B1 (en)
JP (1) JPH06294073A (en)
AT (1) ATE167698T1 (en)
CA (1) CA2113687A1 (en)
DE (2) DE4301459A1 (en)
ES (1) ES2119850T3 (en)
NO (1) NO940182L (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0903402A1 (en) * 1997-09-22 1999-03-24 Hüls Aktiengesellschaft Washing or cleaning agent formulations containing chitin or chitosan derivatives as soil release polymers
WO2008077395A1 (en) * 2006-12-22 2008-07-03 Lothar Ernst Wilhelm Weber Fabric softener

Families Citing this family (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4433597C2 (en) * 1993-09-28 1996-10-02 Clariant Finance Bvi Ltd Process for increasing the wet lubricity of textile material and wet lubricant therefor
DE4440620A1 (en) * 1994-11-14 1996-05-15 Henkel Kgaa Textile softeners
DE4446137A1 (en) * 1994-12-23 1996-06-27 Huels Chemische Werke Ag Quaternized triethanolamine difatty acid esters
JP3069884B2 (en) * 1995-01-24 2000-07-24 日本コーンスターチ株式会社 Cationized starch and size liquid for papermaking and methods for producing them
DE19532542B4 (en) * 1995-09-04 2008-12-18 Henkel Ag & Co. Kgaa Rinse aid with cationic polymers
DE19607847C1 (en) * 1996-03-01 1997-11-20 Suedzucker Ag Aliphatic carboxylic acid esters of inulin
DE19712978A1 (en) * 1997-03-27 1998-10-01 Henkel Kgaa Chitosan microspheres
KR100462336B1 (en) * 1997-12-26 2005-05-31 주식회사 엘지생활건강 Transparent liquid fabric softener composition
AU5547299A (en) * 1998-08-07 2000-02-28 Reichhold, Inc. Novel latex compositions for deposition on various substrates
GB9911437D0 (en) 1999-05-17 1999-07-14 Unilever Plc Fabric softening compositions
GB9930435D0 (en) * 1999-12-22 2000-02-16 Unilever Plc Fabric softening compositions
EP1274825A1 (en) * 2000-04-20 2003-01-15 The Procter & Gamble Company Yarn strength enhancing agents and compositions and methods employing same
GB2363614A (en) * 2000-04-20 2002-01-02 Procter & Gamble Modified chitosan fabric treatment agents
KR100419603B1 (en) * 2001-02-21 2004-02-25 주식회사 아르테크플러스 The textile softener containing aroma capsule and chitosan
US6849586B2 (en) 2001-10-26 2005-02-01 S. C. Johnson & Son, Inc. Hard surface cleaners containing chitosan
GB0213263D0 (en) * 2002-06-10 2002-07-17 Unilever Plc Improvements relating to fabric detergent compositions
US6949500B2 (en) † 2002-12-16 2005-09-27 Colgate-Palmolive Company Fabric softener compositions containing a mixture of cationic polymers as rheology modifiers
US7135451B2 (en) * 2003-03-25 2006-11-14 The Procter & Gamble Company Fabric care compositions comprising cationic starch
ATE520717T1 (en) * 2003-05-21 2011-09-15 Basf Se METHOD FOR PRODUCING ESTERS OF CARNITINE AND USE THEREOF.
US7491753B2 (en) * 2003-07-03 2009-02-17 Mallard Creek Polymers, Inc. Antimicrobial and antistatic polymers and methods of using such polymers on various substrates
US7981946B2 (en) 2003-07-03 2011-07-19 Mallard Creek Polymers, Inc. Antimicrobial and antistatic polymers and methods of using such polymers on various substrates
US7781498B2 (en) 2003-07-03 2010-08-24 Mallard Creek Polymers, Inc. Cationic latex as a carrier for bioactive ingredients and methods for making and using the same
CA2439436A1 (en) * 2003-09-03 2005-03-03 George Sutherland Treatment of aqueous compositions containing contaminants
JP4342899B2 (en) * 2003-10-14 2009-10-14 花王株式会社 Wrinkle remover composition for textile products
US7776813B2 (en) * 2004-09-15 2010-08-17 The Procter & Gamble Company Fabric care compositions comprising polyol based fabric care materials and deposition agents
WO2006132872A1 (en) * 2005-06-03 2006-12-14 The Procter & Gamble Company Fabric care compositions
US20070048249A1 (en) 2005-08-24 2007-03-01 Purdue Research Foundation Hydrophilized bactericidal polymers
EP2079762B1 (en) * 2005-12-08 2012-10-03 Chemigate Oy A process for the preparation of hydroxy polymer esters and their use
CN102124092B (en) 2008-08-15 2014-06-18 宝洁公司 Benefit compositions comprising polyglycerol esters
EP3404086B1 (en) * 2017-05-18 2020-04-08 The Procter & Gamble Company Fabric softener composition
EP3629731A1 (en) 2017-05-27 2020-04-08 Poly Group LLC Dispersible antimicrobial complex and coatings therefrom
WO2018232417A1 (en) 2017-06-16 2018-12-20 Poly Group LLC Polymeric antimicrobial surfactant
CN112813691B (en) * 2020-12-31 2023-05-12 武汉奥克特种化学有限公司 Refining agent and preparation method thereof

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4179382A (en) * 1977-11-21 1979-12-18 The Procter & Gamble Company Textile conditioning compositions containing polymeric cationic materials
EP0017120A1 (en) * 1979-03-26 1980-10-15 Henkel Kommanditgesellschaft auf Aktien Textile detergent acting as a finishing agent
EP0017149A1 (en) * 1979-03-31 1980-10-15 Henkel Kommanditgesellschaft auf Aktien Use of a liquid composition for cleaning hard surfaces
EP0044003A1 (en) * 1980-07-10 1982-01-20 Henkel Kommanditgesellschaft auf Aktien Liquid washing agent with a content of discolouration inhibiting additives
EP0086104A2 (en) * 1982-02-10 1983-08-17 Unilever N.V. Method of softening fabrics
EP0115252A2 (en) * 1982-12-29 1984-08-08 Ciba-Geigy Ag Mixtures of quaternary polymer ammonium salts, surfactants and fatty acids, their preparation and use in cosmetic compositions
EP0337354A1 (en) * 1988-04-12 1989-10-18 Kao Corporation Low-irritation detergent composition
EP0530959A1 (en) * 1991-09-06 1993-03-10 Colgate-Palmolive Company Fabric softening compositions based on pentaerythritol compound and dispersant for such a compound

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FI57987C (en) * 1977-07-01 1980-11-10 Valmet Oy DRAWING FOER TRYCK- OCH VISKOSITETSSTOERNINGAR I MASSASUSPENSIONSSTROEMMEN TILL INLOPPSLAODAN I EN PAPPERSMASKIN
GR67665B (en) * 1979-05-21 1981-09-02 Unilever Nv
US4311601A (en) * 1980-08-13 1982-01-19 Merck & Co., Inc. Use of heteropolysaccharide S-119 as a warp size
PH18436A (en) * 1980-11-07 1985-07-08 Unilever Nv A fabric softening composition and a process for preparing it
DE3263800D1 (en) * 1981-01-16 1985-07-04 Procter & Gamble Textile treatment compositions
GB8410322D0 (en) * 1984-04-19 1984-05-31 Unilever Plc Aqueous concentrated fabric softening composition
US4851141A (en) * 1984-12-12 1989-07-25 Colgate-Palmolive Company Concentrated stable nonaqueous fabric softener composition
GB8722540D0 (en) * 1987-09-24 1987-10-28 Unilever Plc Composition for softening fabrics
US4795032A (en) * 1987-12-04 1989-01-03 S. C. Johnson & Son, Inc. Wash-added, rinse-activated fabric conditioner and package
JPH0227279A (en) * 1988-07-15 1990-01-30 Sharp Corp Superconductor magnetic measuring apparatus
GB8909069D0 (en) * 1989-04-21 1989-06-07 Bp Chem Int Ltd Fabric conditioners
US5290475A (en) * 1990-05-08 1994-03-01 Colgate Palmolive Liquid softening and anti-static nonionic detergent composition with soil release promoting PET-POET copolymer
US5246611A (en) * 1990-05-09 1993-09-21 The Procter & Gamble Company Non-destructive carriers for cyclodextrin complexes
US5185088A (en) * 1991-04-22 1993-02-09 The Procter & Gamble Company Granular fabric softener compositions which form aqueous emulsion concentrates

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4179382A (en) * 1977-11-21 1979-12-18 The Procter & Gamble Company Textile conditioning compositions containing polymeric cationic materials
EP0017120A1 (en) * 1979-03-26 1980-10-15 Henkel Kommanditgesellschaft auf Aktien Textile detergent acting as a finishing agent
EP0017149A1 (en) * 1979-03-31 1980-10-15 Henkel Kommanditgesellschaft auf Aktien Use of a liquid composition for cleaning hard surfaces
EP0044003A1 (en) * 1980-07-10 1982-01-20 Henkel Kommanditgesellschaft auf Aktien Liquid washing agent with a content of discolouration inhibiting additives
EP0086104A2 (en) * 1982-02-10 1983-08-17 Unilever N.V. Method of softening fabrics
EP0115252A2 (en) * 1982-12-29 1984-08-08 Ciba-Geigy Ag Mixtures of quaternary polymer ammonium salts, surfactants and fatty acids, their preparation and use in cosmetic compositions
EP0337354A1 (en) * 1988-04-12 1989-10-18 Kao Corporation Low-irritation detergent composition
EP0530959A1 (en) * 1991-09-06 1993-03-10 Colgate-Palmolive Company Fabric softening compositions based on pentaerythritol compound and dispersant for such a compound

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0903402A1 (en) * 1997-09-22 1999-03-24 Hüls Aktiengesellschaft Washing or cleaning agent formulations containing chitin or chitosan derivatives as soil release polymers
WO2008077395A1 (en) * 2006-12-22 2008-07-03 Lothar Ernst Wilhelm Weber Fabric softener

Also Published As

Publication number Publication date
EP0607529B1 (en) 1998-06-24
ES2119850T3 (en) 1998-10-16
EP0607529A3 (en) 1995-03-22
NO940182D0 (en) 1994-01-18
DE59308712D1 (en) 1998-07-30
CA2113687A1 (en) 1994-07-21
NO940182L (en) 1994-07-21
US5447643A (en) 1995-09-05
DE4301459A1 (en) 1994-07-21
JPH06294073A (en) 1994-10-21
ATE167698T1 (en) 1998-07-15

Similar Documents

Publication Publication Date Title
EP0607529B1 (en) Use of aqeous softeners for the treatment of textiles
EP0230565B1 (en) Laundry aftertreating agent
DE2631114C3 (en) Fabric softeners
DE3046352C2 (en)
DE2151177C2 (en) Process for the production and use of a dimensionally stable and inflexible substrate coated with a conditioning agent for laundry
DE2622014C3 (en) Liquid textile treatment agents to be added to the rinse cycle in conventional automatic laundry washing
DE2920453A1 (en) LIQUID WHITENING AND TISSUE SOFTENING AGENT
EP1259672B1 (en) Crease resistant finishing of cellulose-containing textiles, and laundry post-treatment agents
DE69109579T2 (en) Fabric softener composition.
DE69100751T2 (en) METHOD FOR TREATING TEXTILES.
EP0914513B1 (en) Process for providing fibres or nonwovens with a hydrophilic coating
DE1903536A1 (en) Process to avoid agglomeration
DE60104400T2 (en) USE OF COMPOSITIONS CONTAINING PROTEINS, POLYSACCHARIDES AND ETHYLENE OXIDE DERIVATIVES AS TENSIDANTS
EP0345495A2 (en) Fabric softener
DE2812118A1 (en) TISSUE SOFTENING COMPOSITION WITH ANTISTATIC EFFECT
DE69209090T2 (en) METHOD FOR TREATING ABSORBENT FABRIC OF COTTON OR THE LIKE WITH IMPROVED SOFTENING EFFECT WITH UNCHANGED STRENGTH
DE3730444C2 (en)
DE4215689A1 (en) Nitrogen-free active ingredient in fabric softener formulations
DE1594966A1 (en) Methods and agents for treating household textiles
DE2243806C3 (en) Aqueous agent for softening textiles
DE1619182C3 (en) Process for softening textiles
EP0924291B1 (en) Aqueous softener with improved softness
DE69111829T2 (en) LAUNDRY DETERGENT AND SHEETS FOR FABRIC DRYERS.
EP0747468A1 (en) Aqueous softeners for the treatment of textiles
DE2203142C3 (en) Process for the softening of textiles

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE CH DE DK ES FR GB IT LI NL SE

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): AT BE CH DE DK ES FR GB IT LI NL SE

17P Request for examination filed

Effective date: 19950302

17Q First examination report despatched

Effective date: 19970107

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

ITF It: translation for a ep patent filed
AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE DK ES FR GB IT LI NL SE

REF Corresponds to:

Ref document number: 167698

Country of ref document: AT

Date of ref document: 19980715

Kind code of ref document: T

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REF Corresponds to:

Ref document number: 59308712

Country of ref document: DE

Date of ref document: 19980730

ET Fr: translation filed
GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 19980713

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19980924

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19980924

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2119850

Country of ref document: ES

Kind code of ref document: T3

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19981130

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19981130

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19981130

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

PLBQ Unpublished change to opponent data

Free format text: ORIGINAL CODE: EPIDOS OPPO

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

26 Opposition filed

Opponent name: UNILEVER PLC/ UNILEVER NV

Effective date: 19990324

BERE Be: lapsed

Owner name: HULS A.G.

Effective date: 19981130

NLR1 Nl: opposition has been filed with the epo

Opponent name: UNILEVER PLC/ UNILEVER NV

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

RAP2 Party data changed (patent owner data changed or rights of a patent transferred)

Owner name: DEGUSSA-HUELS AKTIENGESELLSCHAFT

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19991129

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19991130

Year of fee payment: 7

Ref country code: AT

Payment date: 19991130

Year of fee payment: 7

NLT2 Nl: modifications (of names), taken from the european patent patent bulletin

Owner name: DEGUSSA-HUELS AKTIENGESELLSCHAFT

RAP2 Party data changed (patent owner data changed or rights of a patent transferred)

Owner name: RWE-DEA AKTIENGESELLSCHAFT FUER MINERALOEL UND CHE

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20000125

Year of fee payment: 7

NLT2 Nl: modifications (of names), taken from the european patent patent bulletin

Owner name: RWE-DEA AKTIENGESELLSCHAFT FUER MINERALOEL UND CHE

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20000222

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20000417

Year of fee payment: 7

PLBQ Unpublished change to opponent data

Free format text: ORIGINAL CODE: EPIDOS OPPO

PLAB Opposition data, opponent's data or that of the opponent's representative modified

Free format text: ORIGINAL CODE: 0009299OPPO

R26 Opposition filed (corrected)

Opponent name: UNILEVER PLC/ UNILEVER NV

Effective date: 19990324

NLR1 Nl: opposition has been filed with the epo

Opponent name: UNILEVER PLC/UNILEVER NV

NLS Nl: assignments of ep-patents

Owner name: RWE-DEA AKTIENGESELLSCHAFT FUER MINERALOEL UND CHE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20001124

RDAH Patent revoked

Free format text: ORIGINAL CODE: EPIDOS REVO

REG Reference to a national code

Ref country code: FR

Ref legal event code: TP

RDAG Patent revoked

Free format text: ORIGINAL CODE: 0009271

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: PATENT REVOKED

27W Patent revoked

Effective date: 20001212

GBPR Gb: patent revoked under art. 102 of the ep convention designating the uk as contracting state

Free format text: 20001212

REG Reference to a national code

Ref country code: FR

Ref legal event code: CD

Ref country code: FR

Ref legal event code: CA

NLR2 Nl: decision of opposition
PLAB Opposition data, opponent's data or that of the opponent's representative modified

Free format text: ORIGINAL CODE: 0009299OPPO