EP0062372B1 - Textilweichmacher-Zusammensetzungen - Google Patents

Textilweichmacher-Zusammensetzungen Download PDF

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Publication number
EP0062372B1
EP0062372B1 EP82200358A EP82200358A EP0062372B1 EP 0062372 B1 EP0062372 B1 EP 0062372B1 EP 82200358 A EP82200358 A EP 82200358A EP 82200358 A EP82200358 A EP 82200358A EP 0062372 B1 EP0062372 B1 EP 0062372B1
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EP
European Patent Office
Prior art keywords
alkyl
carbon atoms
mixture
compositions
softening
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Expired
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EP82200358A
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English (en)
French (fr)
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EP0062372A1 (de
Inventor
Kathleen Jeannette Dzialo Nee Brown
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Procter and Gamble Co
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Procter and Gamble Co
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Priority to AT82200358T priority Critical patent/ATE20359T1/de
Publication of EP0062372A1 publication Critical patent/EP0062372A1/de
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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/26Organic compounds containing nitrogen
    • C11D3/30Amines; Substituted amines ; Quaternized amines
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005Other compounding ingredients characterised by their effect
    • C11D3/001Softening compositions

Definitions

  • This invention relates to solid detergent compositions which clean well in cool water and at the same time provide softening to the laundered fabrics in a home laundering operation.
  • a fabric softening detergent composition comprising by weight:
  • compositions of this invention contain from 3% to 40%, preferably from 5% to 25%, most preferably from 10% to 20%, of an organic surfactant selected from anionic, nonionic, cationic, amphoteric, and zwitterionic surfactants, and mixtures thereof as disclosed in U.S. Patent No. 3,929,678.
  • Anionic surfactants are much preferred for optimum combined cleaning and textile softening performance but the other classes of organic surfactants and mixtures thereof may be used.
  • anionic surfactants it is preferred that nonionic and other classes of surfactant be absent but, if mixtures containing anionics are used, it is preferred that the anionic surfactant forms the major part of the mixture.
  • Suitable anionic non-soap surfactants are water soluble salts of alkyl benzene sulfonates, alkyl toluene sulfonates, alkyl sulfates, alkyl polyethoxy ether sulfates, paraffin sulfonates, alpha-olefin sulfonates, alpha-sulfocarboxylates and their esters, alkyl glyceryl ether sulfonates, fatty acid monoglyceride sulfates and sulfonates, alkyl phenol polyethoxy ether sulfates, 2-acyloxy-alkane-1-sulfonates, and beta-alkyloxy alkane sulfonates. Soaps are also suitable anionic surfactants.
  • Especially preferred alkyl benzene sulfonates have 9 to 15 carbon atoms in a linear or branched alkyl chain, more especially 11 to 13 carbon atoms (especially valuable are linear straight chain alkyl benzene sulfonates in which the average of the alkyl groups is 11.8 carbon atoms and commonly abbreviated as C 11.8 LAS).
  • Suitable alkyl sulfates have 10 to 22 carbon atoms in the alkyl chain, more especially from 12 to 18 carbon atoms.
  • Suitable alkyl polyethoxy ether sulfates have 9 to 18 carbon atoms in the alkyl chain and have an average of 1 to 12-CHZCH20-groups (abbr. as EO) per molecule, especially 9 to 16 carbon atoms in the alkyl chain and an average of 1 to 8 -CH 2 CH 2 0- groups per molecule.
  • Suitable paraffin sulfonates are essentially linear and contain from 8 to 24 carbon atoms, more especially from 14 to 18 carbon atoms.
  • Suitable alpha-olefin sulfonates have 10 to 24 carbon atoms, more especially 14 to 16 carbon atoms; alpha-olefin sulfonates can be made by reaction with sulfur trioxide followed by neutralization under conditions such that any sultones present are hydrolyzed to the corresponding hydroxy alkane sulfonates.
  • Suitable alpha-sulfocarboxylates contain from 6 to 20 carbon atoms; included herein are not only the salts of alpha-sulfonated fatty acids but also their esters made from alcohols containing 1 to 14 carbon atoms.
  • Suitable alkyl glyceryl ether sulfates are ethers of alcohols having 10 to 18 carbon atoms, more especially those derived from coconut oil and tallow.
  • Suitable alkyl phenol polyethoxy ether sulfates have 8 to 12 carbon atoms in the alkyl chain and an average of about 1 to about 6-CH 2 CH 2 0- groups per molecule.
  • Suitable 2-acyloxy-alkane-1-sulfonates contain from 2 to 9 carbon atoms in the acyl group and 9 to 23 carbon atoms in the alkane moiety.
  • Suitable beta-alkyloxy alkane sulfonates contain 1 to 3 carbon atoms in the alkyl group and 8 to 20 carbon atoms in the alkane moiety.
  • alkyl chains of the foregoing non-soap anionic surfactants can be derived from natural sources such as coconut oil or tallow, or can be made synthetically as for example using the Ziegler or Oxo processes. Water solubility can be achieved by using alkali metal, ammonium, or alkanol-ammonium cations; sodium is preferred. Mixtures of anionic surfactants are contemplated by this invention; a satisfactory mixture contains alkyl benzene sulfonate having 11 to 13 carbon atoms in the alkyl group and alkyl sulfate having 12 to 18 carbon atoms in the alkyl group.
  • Suitable soaps contain 8 to 24 carbon atoms, more especially 12 to 18 carbon atoms.
  • Soaps can be made by direct saponification of natural fats and oils such as coconut oil, tallow and fish oil, or by the neutralization of free fatty acids obtained from either natural or synthetic sources.
  • the soap cation can be alkali metal, ammonium or alkanolammonium; sodium is preferred.
  • the organic fabric softening agent is the organic fabric softening agent
  • the second essential ingredient of this invention is a mixture of water insoluble tertiary amines which comprises from 4% to 12% of the mixture.
  • the mixture of water insoluble tertiary amines comprises approximately 67% of a tertiary amine having the formula R,R 2 R 3 N wherein R 1 and R 2 are independently selected from C 16 to C 22 alkyl or alkenyl groups and R 3 represents a methyl group, and approximately 33% of a tertiary amine having the formula R 4 R,R 6 N wherein R 4 and R 5 are independently selected from C 8 to C 14 alkyl groups, and R 6 represents a methyl group.
  • Suitable tertiary amines wherein R 1 and R 2 are selected from C, 6 to C 22 groups include dicetyl methylamine, distearyl methylamine, diarachidyl methylamine, dibehenyl methylamine, di(mixed arachidyl/behenyl) methylamine and di(tallowyl) methylamine. Especially preferred is di-hydrogenated tallowyl methylamine. This is commercially available as Kemamine@ T9701 from Humko Sheffield Chemical, a division of Kraft Inc.
  • Suitable tertiary amines wherein R 4 and R 5 are selected from C 8 to C 14 groups include dioctyl methylamine, didecyl methylamine, dilauryl methylamine, dimyristyl methylamine, di(mixed lauryl/ myristyl) methylamine and dicoconut methylamine. Especially preferred is dicoconut methylamine. This is commercially available as Kemamine@ T6501.
  • compositions of the invention contain from 10% to 80% of water soluble salts, preferably from 20% to 70%, and most usually from 30% to 60%, and these may be any which are such that the detergent composition in a 0.5% by weight aqueous solution has pH in the specified range, that is from 8.5 to 11, preferably from 9.5 to 10.5. At this pH the tertiary amines of the invention are in anionic form and are therefore compatible with anionic surfactants.
  • the water soluble salts are detergency builders and these can be of the polyvalent inorganic and polyvalent organic types, or mixtures thereof.
  • suitable water-soluble, inorganic alkaline detergent builder salts include the alkali metal carbonates, borates, phosphates, polyphosphates, tripolyphosphates, bicarbonates, and silicates.
  • Specific examples of such salts include the sodium and potassium tetraborates, bicarbonates, carbonates, tripolyphosphates, pyrophosphates, orthophosphates, pentapolyphosphates and hexametaphosphates. Sulfates are usually also present.
  • Suitable organic alkaline detergency builders salts are:
  • Mixtures of organic and/or inorganic builders can be used herein.
  • One such mixture of builders is disclosed in Canadian Patent No. 755,038, e.g. a ternary mixture of sodium tripolyphosphate, trisodium nitrilotriacetate, and trisodium ethane-1-hydroxy-1,1-diphosphonate.
  • Such "seeded builder" compositions are fully disclosed in British Patent Specification No. 1,424,406. ⁇
  • Preferred water soluble builders are sodium tripolyphosphate and sodium silicate, and usually both are present.
  • a substantial proportion, for instance from 3 to 15% by weight of the composition of sodium silicate (solids) of ratio (weight ratio Si0 2 :Na 2 O) from 1:1 to 3.5:1 be employed.
  • a further class of detergency builder materials useful in the present invention are insoluble sodium aluminosilicates, particularly those described in Belgian Patent 814,874, issued November 12, 1974.
  • the compositions contain from 20% to 70% of builders, more usually 30% to 60% by weight. If present, incorporation of about 5% to about 25% by weight of aluminosilicate is suitable, partially replacing water soluble builder salts, provided that sufficient water soluble alkaline salts remain to provide the specified pH of the composition in aqueous solution.
  • a valuable optional component of the present compositions consists of particular smectite clay materials, namely the alkali metal and certain alkaline earth metal varieties of montmorillonites, saponites, and hectorites. These materials are also useful in providing softening and antistatic benefits to fabrics. These materials are described in U.S. Patent 3,936,537.
  • the suitable smectite clays can be included at levels of from 1 % to 25%, preferably from 2% to 20%, and most preferably from 3% to 10%, of the composition.
  • the suitable clay materials can be described as impalpable, expandable, three-layer clays, in which a sheet of aluminum/oxygen atoms or magnesium oxygen atoms lies between two layers of silicon/ Q xygen atoms, i.e., alumino-silicates and magnesium silicates, having an ion exchange capacity of at least 50 meq./100 g., preferably at least 60 meq./100 g., of clay.
  • impalpable as used herein means that the individual clay particles are of such a size that they cannot be perceived tactilely. Such particle sizes are within the range below about 0.1 mm in effective diameter. In general, the clays herein have an ultimate particle size within the range from 0.001 mm to 0.05 mm.
  • expandable as used to describe clays relates to the ability of the layered clay structures to be swollen, or expanded on contact with water.
  • a further property of the suitable clay materials used herein is that they exhibit a true 14 ⁇ 10 -10 m diffraction pattern.
  • fabric softening smectite clay minerals are: sodium montmorillonite sold under the trade names Brock, Volclay BC, Gelwhite GP, Thixo-Jel No. 1, Ben-A-Gel; sodium hectorite sold under the trade names Veegum F and Laponite SP; sodium saponite sold under the trade name Barasym NAS100; calcium montmorillonite sold underthe tradenames Soft Clark and Gelwhite L; and lithium hectorite sold under the tradename Barasym LIH200.
  • smectite clays useful in the compositions herein are commercially available under various tradenames, for example, Brock, Gelwhite GP and Thixo-Jel No. 1 from Georgia Kaolin Co., Elizabeth, New Jersey; Volclay BC and Volclay No. 325, from American Colloid Co., Skokie, Illinois; and Veegum F from R. T. Vanderbilt. It is to be recognized that such smectite minerals obtained under the foregoing tradenames can comprise mixtures of the various discrete mineral entities. Such mixtures are suitable for use herein.
  • Additional suitable optional fabric softening/anti-static agents in this invention are the conventionally water-insoluble quaternary ammonium compounds of the formula R 1 R 2 R 3 R 4 N + Y - wherein R 1 and R 2 represent hydrocarbyl groups of from 10 to 22 carbon atoms, R 3 and R 4 represent hydrocarbyl groups containing from 1 to 4 carbon atoms, and Y represents an anion, (e.g., fluoride, chloride, bromide, or methylsulfate).
  • R 1 and R 2 represent hydrocarbyl groups of from 10 to 22 carbon atoms
  • R 3 and R 4 represent hydrocarbyl groups containing from 1 to 4 carbon atoms
  • Y represents an anion, (e.g., fluoride, chloride, bromide, or methylsulfate).
  • Examples of these compounds include dioctadecyldimethylammonium chloride, ditallow- dimethylammonium chloride, ditallowdiethylammonium bromide, cetyldecylmethylethylammonium chloride, bis-docosyldimethylammonium chloride, and the like.
  • R 1 is C 10 to C 22 alkyl or alkenyl, preferably C 16 to C 20 alkyl
  • R 2 , R 3 , and R 4 are C 1 to C 4 alkyl groups, or acyl groups such as benzyl
  • Y is defined as above.
  • quaternary ammonium compounds are those having a single long chain wherein R 1 is a C 10 to C 22 alkyl group, R 2 is a C 1 to C 4 alkyl group or hydrogen R 3 is ⁇ (C 2 H 4 O) x H, and R 4 is ⁇ (C 2 H 4 O) y H wherein x and y are at least 1 and (x+y) is from 2 to 25. Examples are and the like. Substances of this sort are sold under the trade name "Ethoquads".
  • compositions of this invention can contain up to 10%, preferably from 0.5% to 5% of the above quaternary ammonium compounds.
  • R 1 and preferably R 2 represent an organic radical containing a group selected from a C 16- C 22 aliphatic radical or an alkyl phenyl or alkyl benzyl radical having from 10 to 16 carbon atoms in the alkyl chain
  • R 3 and R 4 represent hydrocarbyl groups containing from 1 to 4 carbon atoms
  • Y- represents an anion.
  • bleaching agents such as sodium perborate, sodium percarbonate and other perhydrates, at levels from 5% to 35% by weight of the composition
  • activators therefor such as tetra acetyl ethylene diamine, tetra acetyl glycoluril and others known in the art
  • stabilisers therefor such as magnesium silicate, and ethylene diamine tetra acetate.
  • a usual optional component is a processing aid, especially for the anionic surfactant.
  • Such components include from 0.1 % to 9%, preferably 0.5% to 3%, of sodium toluene sulfonate and/or sodium xylene sulfonate.
  • Suds controlling agents are often present. These include suds boosting or suds stabilising agents such as mono- or di-ethanolamides of fatty acids. More often in modern detergent compositions, suds suppressing agents are required. Soaps especially those having 16-22 carbon atoms, or the corresponding fatty acid, can act as effective suds suppressors if included in the anionic surfactant component of the present compositions. Usually 1 % to 4% of such soap is effective as suds suppressor. Very suitable soaps when suds suppression is a primary reason for their use, are those derived from Hyfac (Trade name for hardened marine oil fatty acids, predominantly C 18 to C 20 ).
  • non-soap suds suppressors are preferred in synthetic detergent based compositions of the invention since soap or fatty acid is less effective in cool water washing and tends to give rise to a characteristic odour in these compositions.
  • Preferred suds suppressors comprise silicones.
  • a particulate suds suppressor comprising silicone and silanated silica releasably enclosed in water soluble or dispersible substantially non-surface active detergent impermeable carrier.
  • Suds suppressing agents of this sort are disclosed in British patent specification 1,407,997.
  • a very suitable granular tprilled) suds suppressing product comprises 7% silica/silicone (85% by weight silanated silica, 15% silicone, obtained from Messrs. Dow Corning), 65% sodium tripolyphosphate, 25% tallow alcohol condensed with 25 molar proportions of ethylene oxide, and 3% moisture.
  • silica/silicone suds suppressor employed depends upon the degree of suds suppression desired but is often in the range from 0.01 % to -0.5% by weight of the detergent composition.
  • Other suds suppressors which may be used are water insoluble, preferably microcrystalline, waxes having melting point in the range from 35 to 120°C and saponification value less than 100, as described in British patent specification 1,492,938.
  • suds suppressing systems are mixtures of hydrocarbon oil, a hydrocarbon wax and hydrophobic silica as described in European laid open patent application No. 0000216 published January 10, 1979 and, especially, particulate suds suppressing compositions comprising such mixtures, combined with a nonionic ethoxylate having hydrophilic lipophilic balance in the range from 14-19 and a compatibilising agent capable of forming inclusion compounds, such as urea.
  • a compatibilising agent capable of forming inclusion compounds such as urea.
  • Soil suspending agents are usually present at 0.1 to 10%, such as water soluble salts of carboxymethylcellulose, carboxyhydroxymethyl cellulose, polyethylene glycols of molecular weight from 300 to 10000, polyacrylic acid, hydroxybutyl methyl cellulose and derivatives thereof, and copolymers of methylvinylether and maleic anhydride or acid, available from the General Aniline and Film Corporation under the Trade Name Gantrez.
  • Optical brighteners which can be anionic, cationic, or nonionic types, are usually present at 0.01 to 1 %.
  • Especially suitable brighteners include the derivatives of sulfonated triazinyl diamino stilbene such as 4,4 1 - bis[(6 - anilino - 4 - morpholino - 1.3.5 - triazin - 2 - yl)amino]stilbene - 2,2 1 - disulfonate and the diphenyl type such as disodium 4,4' - bis(2 - sulfostyryl)diphenyl.
  • These brighteners tend to cause yellowing of granular products, especially on aging, and it has been found useful to incorporate into the composition from 0.1 % to 7% of polyethylene glycol of molecular weight of 300 to 1500 to prevent such yellowing.
  • proteolytic may be present.
  • a further useful additive is a photo activated bleach comprising a mixture of the tri and tetra sulphonated derivatives of zinc phthalocyanine as described in GB-A-1372035 and 1408144.
  • potassium, lithium or ammonium or amine salts may be used instead if their extra cost etc. are justified for special reasons.
  • the detergent compositions may be prepared in any way, as appropriate to their physical form, as by mixing the components, co-agglomerating them or dispersing them in a liquid carrier.
  • the compositions are granular and are prepared by spray drying an aqueous slurry of the non-heat-sensitive components to form spray dried granules into which may be admixed the heat sensitive components such as persalts, enzymes, perfumes, etc.
  • the tertiary and quaternary amines are preferably included in the slurry for spray drying, they can be incorporated by being sprayed in liquid form on the spray dried granules before or after other heat sensitive solids have been dry mixed with them.
  • the granules so made are surprisingly crisp and free flowing even though the amines are a combination of a waxy solid of low melting point and a liquid.
  • the amines in liquid form may be sprayed onto any particulate component or components of the composition which are able to act as carrier granules.
  • the clay component may be added to the slurry for spray drying or may be dry mixed, as preferred for reasons unrelated to its softening effect, such as for optimum colour of the product.
  • the fabric softening performance of a composition containing tertiary amines of this invention was determined by washing test terry towels (84% cotton/16% polyester) in a top-loading semiautomatic machine with the agitation provided by an impeller with reversing agitation and an extractor adjacent to the wash tub.
  • the washing was done in 21°C water whose hardness was 51 ppm (as CaC0 3 ) (3 gr./U.S. gal.) with the Ca/Mg ratio being 3/1.
  • the product concentration was 0.15%, the water capacity of the wash was 30 liters and the water: cloth ratio was 30:1 and the cloth load was 1 kg.
  • test terry towels each 305x457 mm and weighing about 50 g.
  • the fabric load was washed for 10 minutes, extracted for 2 minutes and then rinsed, extracted again and line dried.
  • the test towels were then graded for softness in a round-robin panel test using 3 experienced judges who were not advised of the test details. Included in the test were a set of test towels wherein no organic fabric softener was present in the wash.
  • the scale used by the judges was a 4 point scale wherein the scale had the following meaning: 0-no difference; 1-guess that there is a difference; 2-small difference; 3-modest difference; 4-large difference.
  • a statistically significant difference between treatments at the 95% confidence level is 0.5 panel score units.
  • composition of the product was as follows:
  • compositions are prepared:
  • compositions are prepared.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Detergent Compositions (AREA)

Claims (2)

1. Eine Textilweichmacher-Detergenszusammensetzung, enthaltend, bezogen auf das Gewicht,
(a) 3% bis 40% eines organischen oberflächenaktiven Mittels;
(b) 4% bis 12% eines Gemisches von tertiären Aminen, die zwei C8―C22-Alkyl- oder -Alkenylgruppen und eine Methylgruppe an das Stickstoffatom gebunden aufweisen; und
(c) 10% bis 80% eines wasserlöslichen Salzes oder mehrerer wasserlöslicher Salze,
wobei der pH einer 0,5 gew.-%igen wässerigen Lösung der Zusammensetzung im Bereich von 8,5 bis 11 liegt; dadurch gekennzeichnet, daß das Textilweichmachermittel (b) auf Basis tertiärer Amine ein Gemisch von tertiären Aminen ist, in welchem annähernd 67% des Gemisches von einem Di-C16-C22-alkyl- oder -alkenylmethylamin, und annähernd 33% des Gemisches von einem Di-C8―C14-alkylmethylamin gebildet werden.
2. Eine Zusammensetzung nach Anspruch 1, welche zusätzlich bis zu 10% eines wasserunlöslichen, quaternären Ammoniumweichmachers mit der Formel R1R2R3R4N+Y- enthält, worin R1 und vorzugsweise R2 einen organischen Rest bedeuten, der eine aus einem aliphatischen C16-C22-Rest oder einem Alkylphenyl- oder Alkylbenzylrest mit 10 bis 16 Kohlenstoffatomen in der Alkylkette ausgewählte Gruppe enthält, R3 und R4 Kohlenwasserstoffgruppen, die 1 bis 4 Kohlenstoffatome enthalten, bedeuten, und Y- ein Anion bedeutet.
EP82200358A 1981-04-02 1982-03-24 Textilweichmacher-Zusammensetzungen Expired EP0062372B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT82200358T ATE20359T1 (de) 1981-04-02 1982-03-24 Textilweichmacher-zusammensetzungen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US25033981A 1981-04-02 1981-04-02
US250339 1981-04-02

Publications (2)

Publication Number Publication Date
EP0062372A1 EP0062372A1 (de) 1982-10-13
EP0062372B1 true EP0062372B1 (de) 1986-06-11

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EP82200358A Expired EP0062372B1 (de) 1981-04-02 1982-03-24 Textilweichmacher-Zusammensetzungen

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EP (1) EP0062372B1 (de)
AT (1) ATE20359T1 (de)
DE (1) DE3271622D1 (de)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0123400A3 (de) * 1983-03-18 1987-09-09 The Procter & Gamble Company Gewebekonditionierende Mittel, Zusammensetzungen und Verfahren
GB8720937D0 (en) * 1987-09-05 1987-10-14 Boots Co Plc Depilatory compositions

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1514276A (en) * 1975-10-22 1978-06-14 Unilever Ltd Fabric-softening compositions
ATE1863T1 (de) * 1978-11-20 1982-12-15 The Procter & Gamble Company Reinigungsmittelzusammensetzung mit textilweichmachereigenschaften.
EP0013450B1 (de) * 1978-12-28 1983-04-06 THE PROCTER & GAMBLE COMPANY Wäschereinigungsmittelzusammensetzung, Verfahren zur Herstellung und Verwendung derselben
EP0023367B1 (de) * 1979-07-05 1984-11-07 THE PROCTER & GAMBLE COMPANY Detergenszusammensetzung mit Textilweichmachereigenschaft

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DE3271622D1 (en) 1986-07-17
EP0062372A1 (de) 1982-10-13
ATE20359T1 (de) 1986-06-15

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