EP0607529B1 - Use of aqeous softeners for the treatment of textiles - Google Patents

Use of aqeous softeners for the treatment of textiles Download PDF

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Publication number
EP0607529B1
EP0607529B1 EP93118805A EP93118805A EP0607529B1 EP 0607529 B1 EP0607529 B1 EP 0607529B1 EP 93118805 A EP93118805 A EP 93118805A EP 93118805 A EP93118805 A EP 93118805A EP 0607529 B1 EP0607529 B1 EP 0607529B1
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EP
European Patent Office
Prior art keywords
treatment
conditioning composition
fabric conditioning
textiles according
cationic
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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.)
Revoked
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EP93118805A
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German (de)
French (fr)
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EP0607529A2 (en
EP0607529A3 (en
Inventor
Heike Dr. Kelkenberg
Michael Dr. Brock
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Wintershall Dea International AG
Original Assignee
Huels AG
Degussa Huels AG
Chemische Werke Huels AG
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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

  • 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 well-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.
  • US-A-4 179 382 describes a combination of a conventional cationic fabric softener active ingredient such as tetraalkylammonium salts or alkylimidazolinium salts with a small amount of a polymeric special cationic salt such as cationic starch or cationic polyvinylpyrrolidone copolymers.
  • Textile laundry detergents with a stiffening effect are described in EP-A-0 017 120. They contain non-ionic and / or zwitterionic surfactants, water-soluble quaternary ammonium groups containing amino ethers of polysaccharides as well as framework salts and / or solvents which bind calcium ions.
  • a skin-mild shampoo contains a combination of the nonionic surfactant alkyl polyglycoside and a cationic polymer.
  • the mixture leads to excellent creamy foam.
  • a liquid detergent containing discoloration-inhibiting additives is described in EP-A-0 044 003.
  • the detergent contains two different nonionic surfactants, one of which is an ethoxylated C 13 -C 15 oxo alcohol with 55-65% by weight ethylene oxide and the other an ethoxylated C 9 -C 12 oxo or fatty alcohol with 60-70% by weight.
  • % Is ethylene oxide, laundry softening quaternary ammonium compounds such as distearyldimethylammonium chloride or quaternary imidazolinium compounds and cationic starch ethers as discoloration inhibitors.
  • the object of the invention was to produce a new fabric softener that is free of traditional quaternary ammonium bases with their known disadvantages.
  • the solution to the problem is emulsions of nonionic hydrophobic To add surfactants with a cationic protective colloid. That way the surfactant vesicles present in the emulsion are superficially cationized, so that the Tucked onto the textile fiber to be rinsed substantively.
  • nonionic fabric softening agents in particular as a hydrophobic component two similarly long C chains - the chain length of which can be C 10 - C 22 - and as a hydrophilic component a nonionic polyether or polyol chain or one Sugar or polysacchrid derivative included.
  • 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 present as a mixture of mono-, di- and triesters.
  • the degree of hydrophilization can be varied 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-A-38 26 179).
  • cationic protective colloid in fabric softener formulations is not yet known Generally colloidal Solutions can be stabilized considerably by means of hydrophilic protective colloids.
  • the Protective colloid forms a film around the particle to be protected and forms one Shell of water molecules from known protective colloids are gelatin, protein hydrolyzate, Glue etc.
  • a suitable cationic protective colloid is the technically accessible cationic starch (I). You can find it in the Paper industry use. Compared to the electroneutral protective colloids the advantage that they are substantive to the negatively charged cellulose fiber of the paper is raising.
  • Suitable cationic protective colloids in fabric softener formulations are the natural product chitosan (II) and chitosan derivatives.
  • 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 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 rinsing liquor.
  • 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 in Form of a sensory soft grip test with 6 test persons as follows carried out:
  • test subjects were each given 3 wipes in encrypted form after the Test plan according to table A (so-called triangular test) submitted.
  • the task for the The examiner consisted of the differently treated cloth after sensory assessment find out.
  • the examiner noted whether the different cloth was softer or feels harder. If at least 5 or 6 examiners found the cloth treated differently (T according to DIN 10 951 with examiners 1 to 3, S with examiners 4 to 6) a probability of greater than 95% between the test substance and the Standard a significant difference. The result is calculated using 3 numbers Expressed: The 1st number indicates the number of examiners who with the standard treated wipes felt softer or those with the test substance harder.
  • the 2nd number indicates the number of examiners who treated the wipes treated with the standard perceived as harder or that with the test substance as softer
  • the 3rd number gives finally the number of examiners due to the low sensory Differences in the wipes treated with the test substance or the standard cloth treated differently could not determine or the correct answer gave.
  • 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 C 18 diglyceride (21% triglyceride) ethoxylated with 22% by weight EO was used.
  • a Guerbet alcohol ethoxylated 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 by adding 1 to 5% by weight of a common one Emulsify fatty acid ethoxylate as an emulsifier in the presence of the protective colloids.
  • Solubilizer served acetic acid or lactic acid, used in such amounts was that a pH of 4.5 to 5.0 was ensured in the diluted rinse liquor.
  • chitosan 20% strength, stable, flowable emulsions could be produced will.
  • the cationic starch and the polyamine alkyllacrylamide those were Emulsions 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).
  • 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.

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  • 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 in the past few years due to its aquatic toxicity Environmental discussion. It is now due to quaternary containing ester or amide Ammonium bases or imidazolinium salts have been displaced from the market, which in their Environmental behavior can be classified as better.

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 Lanolin und einer traditionellen quaternären Ammoniumbase vorgeschlagen, die in der Wäschebehandlung gute Weichspüleffekte zeigen (EP-A-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-A-0 056 695; EP-A-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 well-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 lanolin and a traditional quaternary ammonium base, which show good fabric softening effects in laundry treatment (EP-A-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 nonionic additives, such as, for example, alkylene oxide adducts of fatty alcohols, fatty acid amides and fatty acid esters and natural fats (EP-A-0 056 695; EP-A-0 159 919). Standard fabric softeners today contain about 15% co-softeners such as. B. glycerol monostearate or fatty alcohol oxyethylates (Surfactants Surf. Det. 27, 34-40 (1990)).

Eine Kombination aus einem üblichen kationischen Weichspülerwirkstoff wie Tetraalkylammoniumsalzen oder Alkylimidazoliniumsalzen mit einer kleinen Menge eines polymeren speziellen kationischen Salzes wie kationischer Stärke oder kationischen Polyvinylpyrrolidon-Copolymeren beschreibt US-A-4 179 382.
Appretierend wirkende Textilwaschmittel mit steifender Wirkung werden in EP-A-0 017 120 beschrieben. Sie enthalten nichtionische und/oder zwitterionische Tenside, in Wasser lösliche quartäre Ammoniumgruppen aufweisende Aminoether von Polysacchariden sowie Calciumionen bindende Gerüstsalze und/oder Lösemittel.
Ein hautmildes Shampoo enthält nach EP-A-0 337 354 eine Kombination aus dem nichtionischen Tensid Alkylpolyglycosid und einem kationischen Polymer. Die Mischung führt zu ausgezeichnetem cremigen Schaum.
Ein flüssiges Waschmittel mit einem Gehalt an verfarbungsinhibierenden Zusätzen wird in EP-A-0 044 003 beschrieben. Das Waschmittel enthält zwei verschiedene nichtionische Tenside, von denen eines ein ethoxylierter C13-C15-Oxoalkohol mit 55 - 65 Gew.-% Ethylenoxid und das andere ein ethoxylierter C9-C12-Oxo- oder Fettalkohol mit 60 - 70 Gew.% Ethylenoxid ist, wäscheweichmachende quartäre Ammoniumverbindungen wie Distearyldimethylammoniumchlorid oder quartäre Imidazoliniumverbindungen und kationische Stärkeether als Verfarbungsinhibitoren.US-A-4 179 382 describes a combination of a conventional cationic fabric softener active ingredient such as tetraalkylammonium salts or alkylimidazolinium salts with a small amount of a polymeric special cationic salt such as cationic starch or cationic polyvinylpyrrolidone copolymers.
Textile laundry detergents with a stiffening effect are described in EP-A-0 017 120. They contain non-ionic and / or zwitterionic surfactants, water-soluble quaternary ammonium groups containing amino ethers of polysaccharides as well as framework salts and / or solvents which bind calcium ions.
According to EP-A-0 337 354, a skin-mild shampoo contains a combination of the nonionic surfactant alkyl polyglycoside and a cationic polymer. The mixture leads to excellent creamy foam.
A liquid detergent containing discoloration-inhibiting additives is described in EP-A-0 044 003. The detergent contains two different nonionic surfactants, one of which is an ethoxylated C 13 -C 15 oxo alcohol with 55-65% by weight ethylene oxide and the other an ethoxylated C 9 -C 12 oxo or fatty alcohol with 60-70% by weight. % Is ethylene oxide, laundry softening quaternary ammonium compounds such as distearyldimethylammonium chloride or quaternary imidazolinium compounds and cationic starch ethers as discoloration inhibitors.

Aufgabe der Erfindung war es, ein neues Weichspülmittel herzustellen, das frei von den traditionellen quaternären Ammoniumbasen mit ihren bekannten Nachteilen ist.The object of the invention was to produce a new fabric softener that is free of 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 emulsions of nonionic hydrophobic To add surfactants with a cationic protective colloid. That way the surfactant vesicles present in the emulsion are superficially cationized, so that the Tucked onto the textile fiber to be rinsed substantively.

Gegenstand der Erfindung ist daher die Verwendung eines wäßrigen Weichspülmittels für die Behandlung von Textilien auf Basis wasserunlöslicher nichtionischer Tenside, deren Emulsionen oder Dispersionen durch Zusatz von Schutzkolloiden, die kationische Gruppen enthalten, stabilisiert sind,
wobei die Emulsionen oder Dispersionen

  • 5 - 20 Gew.-% nichtionische Tenside mit hydrophoben Ketten mit je 10 - 20 Kohlenstoffatomen,
  • 0,1 - 50 % bez. auf Tensid kationische Schutzkolloide
  • ausgewählt aus der Gruppe der kationischen Stärken, Chitosane, Chitosanderivate oder synthetischen Polymeren und
  • kleine Mengen üblicher Emulgatoren
  • enthalten
  • und wobei das Mittel frei von kationischen, quartären, monomeren Ammoniumverbindungen mit 2 C12-22-Alkyl- oder Alkenylresten ist.
    • The invention therefore relates to the use of 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,
    where the emulsions or dispersions
  • 5-20% by weight of nonionic surfactants with hydrophobic chains each having 10-20 carbon atoms,
  • 0.1 - 50% cationic protective colloids on surfactant
  • selected from the group of cationic starches, chitosans, chitosan derivatives or synthetic polymers and
  • small amounts of common emulsifiers
  • contain
  • and wherein the agent is free of cationic, quaternary, monomeric ammonium compounds with 2 C 12-22 alkyl or alkenyl radicals.

    • 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 C 10 - C 22 - and as a hydrophilic component a nonionic polyether or polyol chain or one Sugar or polysacchrid derivative included.

    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 vaniert 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-A-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 present as a mixture of mono-, di- and triesters. Here, too, the degree of hydrophilization can be varied 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-A-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 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 inventive addition of cationic protective colloid in fabric softener formulations is not yet known Generally colloidal Solutions can be stabilized considerably by means of hydrophilic protective colloids. The Protective colloid forms a film around the particle to be protected and forms one Shell of water molecules from known protective colloids are gelatin, protein hydrolyzate, Glue etc. A suitable cationic protective colloid is the technically accessible cationic starch (I). You can find it in the Paper industry use. Compared to the electroneutral protective colloids the advantage that they are substantive to the negatively charged cellulose fiber of the paper is raising.

    Weitere geeignete kationische Schutzkolloide in Wäscheweichspülformulierungen sind das Naturprodukt Chitosan (II) und Chitosanderivate. 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).    Other suitable cationic protective colloids in fabric softener formulations are the natural product chitosan (II) and chitosan derivatives. 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 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 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.    To prepare the aqueous fabric softener, 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 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 rinsing liquor.

    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 in the following text 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:The softening effect of the fabric softener claimed was in Form of a sensory soft grip test with 6 test persons as follows carried out:

    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 folgte 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.A batch of 72 pieces of terry towels (44 cm cm 30 cm, approx. 60 g, of which WFK-Testgewebe GmbH), even if not all 72 wipes 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 was followed by a washing process at 95 ° C without detergent included Rinse and brief spin-on so that clean, moist, about 2.5 times yours Dry weight of water-containing cloths removed for manual fabric softening could become.

    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 1 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. Versuchsplan für die sensorische Weichgriffprüfung mit 6 Prüfern. Prüfer Tücherkombination mit verschlüsselter Kennzeichnung 1 SST 2 SST 3 SST 4 STT 5 STT 6 STT S = Vergleichssubstanz (Standard); T = Testsubstanz (Erfindung)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 liters of 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. Experimental plan for the sensory soft grip test with 6 examiners. tester Cloth combination with encrypted labeling 1 SST 2nd SST 3rd SST 4th STT 5 STT 6 STT S = reference substance (standard); T = test substance (invention)

    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 given 3 wipes in encrypted form after the Test plan according to table A (so-called triangular test) submitted. The task for the The examiner consisted of the differently treated cloth after sensory assessment find out.

    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 was softer or feels harder. If at least 5 or 6 examiners found the cloth treated differently (T according to DIN 10 951 with examiners 1 to 3, S with examiners 4 to 6) a probability of greater than 95% between the test substance and the Standard a significant difference. The result is calculated using 3 numbers Expressed: The 1st number indicates the number of examiners who with the standard treated wipes felt softer or those with the test substance harder. The 2nd number indicates the number of examiners who treated the wipes treated with the standard perceived as harder or that with the test substance as softer The 3rd number gives finally the number of examiners due to the low sensory Differences in the wipes treated with the test substance or the standard cloth treated differently could not determine or the correct answer gave.

    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 oxethylierter 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 C 18 diglyceride (21% triglyceride) ethoxylated with 22% by weight EO was used. As a further example, a Guerbet alcohol ethoxylated 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 Fettsäureethoxylats 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 by adding 1 to 5% by weight of a common one Emulsify fatty acid ethoxylate as an emulsifier in the presence of the protective colloids. As Solubilizer served acetic acid or lactic acid, used in such amounts was that a pH of 4.5 to 5.0 was ensured in the diluted rinse liquor. in the In the case of chitosan, 20% strength, stable, flowable emulsions could be produced will. In the case of the cationic starch and the polyamine alkyllacrylamide, those were Emulsions 10%.

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

    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 signifikanten 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. Sensorische Weichgriffprüfung mit 6 Prüfpersonen nach DIN 10951 (sog. Dreieckstest) Vergleich gegen unbehandelte mit PERSIL® gewaschene Tücher Spülflotte Dreiecksprüfung Teststubstanz 0.35 g/l kation. Schutzkolloid Gew.-% bez. auf Testsubstanz unbehandelt weicher Testsubstanz weicher kein Unterschied C32/36-Guerbitol ----- 0 1 5 + 12 EO + 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/ ----- 0 1 5 22 % EO + 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 % Polyaminoacrylamid 0 5 1 Hautöl/15 % PO + 5 % Polyaminoacrylamid 0 4 2 C18-Diglycerid/ 22 % EO + 10 % Polyaminoacrylamid 0 5 1 Sensorische Weichgriffprüfung mit 6 Prüfpersonen nach DIN 10951 (sog. Dreieckstest) Vergleich gegen marktübliches Esterquat (0.18 g/l STEPANTEX® VR 85) Spülflotte Dreiecksprüfung Teststubstanz 0.35 g/l kation. Schutzkolloid Gew.-% bez auf Testsubstanz Esterquat weicher Testsubstanz weicher kein Unterschied 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 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. 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 ----- 0 1 5 + 12 EO + 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 C 18 diglyceride / ----- 0 1 5 22% EO + 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 C 18 diglyceride / 22% EO + 5% chitosan 0 6 0 ----------- + 10% polyaminoacrylamide 1 2nd 3rd Palm oil / 15% PO + 5% polyaminoacrylamide 0 5 1 Skin oil / 15% PO + 5% polyaminoacrylamide 0 4th 2nd C 18 diglyceride / 22% EO + 10% polyaminoacrylamide 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 wt .-% 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 C 18 diglyceride / 22% EO ------ 4th 0 2nd C 18 diglyceride / 22% EO + 5% chitosan 1 0 5

    Claims (13)

    1. The use of a fabric conditioning composition for the treatment of textiles, characterized in that as fabric softening agents there are used emulsions or dispersions of nonionic surfactants which have been stabilized by addition of protective colloids having cationic groups, the emulsions or dispersions comprising 5-20% by weight of nonionic surfactants having hydrophobic chains of in each case 10-20 carbon atoms, 0.1-50%, relative to surfactant, of cationic protective colloids selected from the group consisting of cationic starches, chitosan, chitosan derivatives and synthetic polymers and small amounts of conventional emulsifiers, and the composition being free from cationic, quaternary, monomeric ammonium compounds having 2 C12_22-alkyl or alkenyl radicals.
    2. The use of a fabric conditioning composition for the treatment of textiles according to claim 1, characterized in that the cationic protective colloid is a chitosan or a chitosan derivative and organic acid is present.
    3. The use of a fabric conditioning composition for the treatment of textiles according to claim 1, characterized in that the cationic protective colloid is a polymer or copolymer of dimethylaminopropylacrylamide or dimethylaminopropylmethacrylamide.
    4. The use of a fabric conditioning composition for the treatment of textiles according to claim 1, characterized in that the nonionic surfactants contain two to four long hydrophobic carbon chains and a glycose or polysaccharide radical, a polyether or a polyol chain as hydrophilic group.
    5. The use of a fabric conditioning composition for the treatment of textiles according to claim 4, characterized in that the nonionic surfactant is an ethoxylated or propoxylated branched alcohol of the general formula
      Figure 00170001
      in which R1 and R2 are branched or straight-chain C10-C22-alkyl radicals and can be identical or different, and R3 represents hydrogen or a methyl radical, and n is a number from 1 to 30.
    6. The use of a fabric conditioning composition for the treatment of textiles according to claim 4, characterized in that the nonionic surfactant is a mono-, di-, tri- or tetra-fatty acid ester of a monosaccharide or polysaccharide in which the acyl radicals are branched or linear C10-C22-chains and are identical or different.
    7. The use of a fabric conditioning composition for the treatment of textiles according to claim 4, characterized in that the nonionic surfactant is a mono-, di- or tri-fatty acid ester of a fatty alkyl glycoside or fatty alkyl polyglycoside in which the acyl and the alkyl radicals are branched or linear C10-C22-chains and are identical or different.
    8. The use of a fabric conditioning composition for the treatment of textiles according to either of claims 6 or 7, characterized in that the nonionic surfactants have additionally been alkoxylated with ethylene oxide or propylene oxide.
    9. The use of a fabric conditioning composition for the treatment of textiles according to claim 4, characterized in that the nonionic surfactant is a mono-, di- or tri-fatty acid ester of a polyol of the general formula HOCH2-(CHOH)m-CH2OH in which m is a number from 1 to 4, and the acyl radicals are branched or straight-chain C10-C22-chains and are identical or different.
    10. The use of a fabric conditioning composition for the treatment of textiles according to claim 9, characterized in that the nonionic surfactants have additionally been alkoxylated with ethylene oxide or propylene oxide.
    11. The use of a fabric conditioning composition for the treatment of textiles according to claim 9, characterized in that the nonionic surfactants are di-fatty acid esters or mixtures of mono-, di- and tri-fatty acid esters of glycerol.
    12. The use of a fabric conditioning composition for the treatment of textiles according to claim 1, characterized in that the nonionic surfactants consist of alkoxylated natural fats, oils and/or mixtures thereof with free fatty acids, mono- and/or diglycerides.
    13. The use of a fabric conditioning composition for the treatment of textiles according to claims 1 to 12 in a concentration of 0.1 to 1 g/l of active compound combination in the rinse liquor of a washing operation.
    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
    DE4301459 1993-01-20
    DE4301459A DE4301459A1 (en) 1993-01-20 1993-01-20 Aqueous fabric softener for the treatment of textiles

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    EP93118805A Revoked EP0607529B1 (en) 1993-01-20 1993-11-23 Use of aqeous softeners for the treatment of textiles

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    EP (1) EP0607529B1 (en)
    JP (1) JPH06294073A (en)
    AT (1) ATE167698T1 (en)
    CA (1) CA2113687A1 (en)
    DE (2) DE4301459A1 (en)
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    Also Published As

    Publication number Publication date
    EP0607529A2 (en) 1994-07-27
    US5447643A (en) 1995-09-05
    ATE167698T1 (en) 1998-07-15
    DE59308712D1 (en) 1998-07-30
    JPH06294073A (en) 1994-10-21
    NO940182D0 (en) 1994-01-18
    DE4301459A1 (en) 1994-07-21
    CA2113687A1 (en) 1994-07-21
    NO940182L (en) 1994-07-21
    ES2119850T3 (en) 1998-10-16
    EP0607529A3 (en) 1995-03-22

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