[go: up one dir, main page]

EP0062372B1 - Fabric softening compositions - Google Patents

Fabric softening compositions Download PDF

Info

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
Authority
EP
European Patent Office
Prior art keywords
alkyl
carbon atoms
mixture
compositions
softening
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.)
Expired
Application number
EP82200358A
Other languages
German (de)
French (fr)
Other versions
EP0062372A1 (en
Inventor
Kathleen Jeannette Dzialo Nee Brown
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.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
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
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to AT82200358T priority Critical patent/ATE20359T1/en
Publication of EP0062372A1 publication Critical patent/EP0062372A1/en
Application granted granted Critical
Publication of EP0062372B1 publication Critical patent/EP0062372B1/en
Expired legal-status Critical Current

Links

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.

Landscapes

  • 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)

Abstract

Laundry detergent compositions are provided which contain an effective textile softening agent for through the wash softening. The softening agent comprises a mixture of two specified classes of tertiary amines.

Description

    Technical field
  • 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.
  • It is common practice for homemakers to provide a softened quality to laundered fabrics by treating laundered fabrics with a softening composition during the rinse cycle to deposit the softening agent on the fabric. By providing a detergent composition which can at the same time provide a softening quality to the fabrics while being washed makes the home laundering operation more convenient.
  • Background
  • Numerous attempts have been made to formulate laundry detergent compositions which provide the good cleaning performance expected of them and which also have textile softening properties. Thus, attempts have been made to incorporate cationic textile softeners in anionic surfactant-based built detergent compositions employing various means of overcoming the natural antagonism between the anionic and cationic surfactant species. For instance, in British patent specification 1,518,529, detergent compositions are described comprising organic surfactant, builders, and in particulate form, a quaternary ammonium softener combined with a poorly water-soluble dispersion inhibitor which inhibits premature dispersion of the cationic in the wash liquor. Even in these compositions, some compromise between cleaning and softening effectiveness has to be accepted. Another approach to providing anionic detergent compositions with textile softening ability has been the use of smectite-type clays, as described in British patent specification 1,400,898. These compositions, although they clean well, require rather large contents of clay for effective softening, perhaps because the clay is not very efficiently deposited on the fabrics in the presence of anionic surfactants. Yet another approach to providing built detergent compositions with softening ability has been to employ nonionic surfactants instead of anionic with cationic softeners, and compositions of this type have been described in, for example, British patent specification 1,079,388, German Auslegeschrift 1,220,956 and US patent 3,607,763. However, it is found that if enough nonionic surfactant is employed to provide good cleaning, it impairs the softening effect of the cationic softener, so that, once again, a compromise between cleaning and softening effectiveness must be accepted.
  • The use of clay together with a water insoluble cationic compound and an electrically conductive metal salt as a softening composition adapted for use with anionic, nonionic, zwitterionic and amphoteric surfactants has been described in British patent specification 1,483,627. U.S. Patent No. 4,292,035 which issued on September 29, 1981 to Charles F. Battrell describes granular textile softening compositions comprising a complex of a cationic softener and a smectite-type clay subsequently treated with an anionic surfactant. These compositions are intended primarily as rinse additives, where their cleaning performance is not of primary interest.
  • Recently it has been disclosed in British Patent specification 1,514,276 that certain tertiary amines with two long chain alkyl or alkenyl groups and one short chain alkyl group are effective fabric softeners in detergent compositions when chosen to have an isoelectric point in the pH range such that they are in anionic form in a normal alkaline wash liquor and are more in cationic form at the lower pH of a rinse liquor, and so become substantive to fabrics. Use of amines of this class, amongst others, in detergent compositions for foam control has also been previously disclosed in British patent specification 1,286,054. Use of amines of the class specified in GB-A-1,286,054 together with a smectite-type clay for laundry detergent compositions providing through-the-wash softening is claimed in European Application No. 79200656.1 Publication No. 0011340.
  • It has now been found that the combination of a di-long chain (Cl67-C22) tertiary amine with a di-shorter chain (CS-C14) tertiary amine in specific ratios provides improved softening compared to either tertiary amine alone.
  • Summary of the invention
  • According to the present invention there is provided a fabric softening detergent composition comprising by weight:
    • (a) from 3% to 40% of an organic surfactant;
    • (b) from 4% to 12% of a mixture of tertiary amines containing twoCgto C22 alkyl or alkenyl groups and a methyl group, attached to the nitrogen atom; and
    • (c) from 10% to 80% of one or more water soluble salts, wherein the pH of a 0.5% by weight aqueous solution of the composition is in the range of from 8.5 to 11;
      wherein the tertiary amine fabric softening agent (b) is a mixture of tertiary amines wherein approximately 67% of the mixture is a di- C16-C22 alkyl or alkenyl methylamine, and approximately 33% of the mixture is a di CS-C14 alkyl methylamine.
    Detailed description of the invention Organic surfactant
  • The 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. When anionic surfactants are employed 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 C11.8LAS). 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 -CH2CH20- 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-CH2CH20- 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.
  • The 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
  • 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,R2R3N wherein R1 and R2 are independently selected from C16 to C22 alkyl or alkenyl groups and R3 represents a methyl group, and approximately 33% of a tertiary amine having the formula R4R,R6N wherein R4 and R5 are independently selected from C8 to C14 alkyl groups, and R6 represents a methyl group.
  • Suitable tertiary amines wherein R1 and R2 are selected from C,6 to C22 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 R4 and R5 are selected from C8 to C14 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.
  • It was unexpected that the shorter chain length tertiary amines disclosed herein, which are liquid and have no particular value as fabric softening agents, improve cool water fabric softening through-the-wash when included with the longer chain length tertiary amines disclosed herein in a detergent composition.
  • Water-soluble salts
  • The 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.
  • Preferably the water soluble salts are detergency builders and these can be of the polyvalent inorganic and polyvalent organic types, or mixtures thereof. Non-limiting examples of 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.
  • Examples of suitable organic alkaline detergency builders salts are:
    • (1) water-soluble amino polyacetates, e.g., sodium and potassium ethylenediaminetetraacetates, nitrilotriacetates, N-(2-hydroxylethyl) nitrilodiacetates and diethylenetriamine pentaacetates;
    • (2) water-soluble salts of phytic acid, e.g. sodium and potassium phytates;
    • (3) water-soluble polyphosphates, including sodium, potassium and lithium salts of methylene- diphosphonic acid and the like and aminopolymethylene phosphonates such as ethyldiamine- tetramethylenephosphonate and diethylenetriaminepentamethylene phosphonate, and polyphosphonates as described in the commonly assigned DE-A-2816770.
    • (4) water-soluble polycarboxylates such as the salts of lactic acid, succinic acid, malonic acid, maleic acid, citric acid, carboxymethylsuccinic acid, 2-oxa-1,1,-3-propane tricarboxylic acid, 1,1,2-2-ethane tetracarboxylic acid, cyclopentane-cis, cis, cis-tetracarboxylic acid, mellitic acid and pyromellitic acid.
  • 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.
  • Another type of detergency builder material useful in the present compositions comprises a water-soluble material capable of forming a water-insoluble reaction product with water hardness cations preferably in combination with a crystallization seed which is capable of providing growth sites for said reaction product. 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. In particular it is preferred that a substantial proportion, for instance from 3 to 15% by weight of the composition of sodium silicate (solids) of ratio (weight ratio Si02:Na2O) 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.
  • This patent discloses and claims detergent compositions containing sodium aluminosilicates of the formula
    Figure imgb0001
    wherein z and y are integers equal to at least 6, the molar ratio of z to is in the range of from 1.0:1 to about 0.5:1 and x is an integer from about 15 to about 264. A preferred material is
    Figure imgb0002
  • Preferably, 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.
  • Optional components
  • 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/Qxygen 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. The term "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.
  • The term "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.
  • Specific non-limiting examples of such 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.
  • Most of the 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 R1R2R3R4N+Y- wherein R1 and R2 represent hydrocarbyl groups of from 10 to 22 carbon atoms, R3 and R4 represent hydrocarbyl groups containing from 1 to 4 carbon atoms, and 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. Also suitable are the single long chained quaternary ammonium compounds of the above formula wherein R1 is C10 to C22 alkyl or alkenyl, preferably C16 to C20 alkyl, and R2, R3, and R4 are C1 to C4 alkyl groups, or acyl groups such as benzyl, and Y is defined as above.
  • Yet other quaternary ammonium compounds are those having a single long chain wherein R1 is a C10 to C22 alkyl group, R2 is a C1 to C4 alkyl group or hydrogen R3 is―(C2H4O)xH, and R4 is―(C2H4O)yH wherein x and y are at least 1 and (x+y) is from 2 to 25. Examples are
    Figure imgb0003
    Figure imgb0004
    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.
  • Preferred compounds are those of the formula above wherein R1 and preferably R2 represent an organic radical containing a group selected from a C16-C22 aliphatic radical or an alkyl phenyl or alkyl benzyl radical having from 10 to 16 carbon atoms in the alkyl chain, R3 and R4 represent hydrocarbyl groups containing from 1 to 4 carbon atoms and Y- represents an anion.
  • The optional components usual in built laundry detergents may of course be present. These include bleaching agents such as sodium perborate, sodium percarbonate and other perhydrates, at levels from 5% to 35% by weight of the composition, and activators therefor, such as tetra acetyl ethylene diamine, tetra acetyl glycoluril and others known in the art, and 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 C18 to C20).
  • However, 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. In particular there may be employed 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. The amount of 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.
  • Yet other suitable 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. These particulate suds suppressing compositions are described in European patent application 79200472.3 Publication No. 0008830.
  • 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 4,41 - bis[(6 - anilino - 4 - morpholino - 1.3.5 - triazin - 2 - yl)amino]stilbene - 2,21 - 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, amylolytic or lipolytic enzymes, especially 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.
  • Through the description herein, where sodium salts have been referred to, potassium, lithium or ammonium or amine salts may be used instead if their extra cost etc. are justified for special reasons.
  • Preparation of the compositions
  • 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. Preferably 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. Although 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. Alternatively 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.
  • Example I
  • 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 CaC03) (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. and consisted of 8 test terry towels (each 305x457 mm and weighing about 50 g.) with the remainder of the load being soiled T-shirts. 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.
  • The composition of the product was as follows:
    Figure imgb0005
  • The results of the test are summarized in Table I.
    Figure imgb0006
  • As shown by the data the mixtures of tertiary amines of the invention surprisingly provided more softening than either amine alone with the best results observed when the ratio of ditallowmethylamine to dicoconutmethylamine being about 2:1.
  • Example II
  • The following compositions are prepared:
    Figure imgb0007
  • Example III
  • The following compositions are prepared.
    Figure imgb0008

Claims (2)

1. A fabric softening detergent composition comprising, by weight:
(a) from 3% to 40% of an organic surfactant;
(b) from 4% to 12% of a mixture of tertiary amines containing two C8 to C22 alkyl or alkenyl groups and a methyl group, attached to the nitrogen atom; and
(c) from 10% to 80% of one or more water soluble salts, wherein the pH of a 0.5% by weight aqueous solution of the composition is in the range of from 8.5 to 11; characterised in that the tertiary amine fabric softening agent (b) is a mixture of tertiary amines wherein approximately 67% of the mixture is a di C16-C22 alkyl or alkenylmethylamine, and approximately 33% of the mixture is a di C8―C14 alkylmethylamine.
2. A composition according to claim 1 which additionally contains up to 10% of a water insoluble quaternary ammonium softener having the formula R1R2R3R4N+Y- wherein R1 and preferably R2 represent an organic radical containing a group selected from a C16―C22 aliphatic radical or an alkyl phenyl or alkyl benzyl radical having from 10 to 16 carbon atoms in the alkyl chain, R3 and R4 represent hydrocarbyl groups containing from 1 to 4 carbon atoms and Y- represents an anion.
EP82200358A 1981-04-02 1982-03-24 Fabric softening compositions Expired EP0062372B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT82200358T ATE20359T1 (en) 1981-04-02 1982-03-24 FABRIC SOFTENER COMPOSITIONS.

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 (en) 1982-10-13
EP0062372B1 true EP0062372B1 (en) 1986-06-11

Family

ID=22947320

Family Applications (1)

Application Number Title Priority Date Filing Date
EP82200358A Expired EP0062372B1 (en) 1981-04-02 1982-03-24 Fabric softening compositions

Country Status (3)

Country Link
EP (1) EP0062372B1 (en)
AT (1) ATE20359T1 (en)
DE (1) DE3271622D1 (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0123400A3 (en) * 1983-03-18 1987-09-09 The Procter & Gamble Company Fabric conditioning agents, compositions and processes
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
DE2964114D1 (en) * 1978-11-20 1982-12-30 Procter & Gamble Detergent composition having textile softening properties
DE2965164D1 (en) * 1978-12-28 1983-05-11 Procter & Gamble Ltd Laundry detergent composition, method of manufacture and use thereof
DE3069588D1 (en) * 1979-07-05 1984-12-13 Procter & Gamble Detergent composition having textile softening property

Also Published As

Publication number Publication date
EP0062372A1 (en) 1982-10-13
DE3271622D1 (en) 1986-07-17
ATE20359T1 (en) 1986-06-15

Similar Documents

Publication Publication Date Title
US4294710A (en) Detergent softener with amine ingredient
US4375416A (en) Detergent composition having textile softening properties
EP0026529B1 (en) Detergent compositions
EP0026528B2 (en) Detergent compositions
US4661289A (en) Detergent compositions
US3954632A (en) Softening additive and detergent composition
US4291071A (en) Washing and softening compositions
US4292035A (en) Fabric softening compositions
CA1074966A (en) Detergent-compatible fabric softening and antistatic compositions
US4321165A (en) Detergent compositions comprising cationic, anionic and nonionic surfactants
CA1102202A (en) Granular detergent compositions for improved greasy soil removal
US5019292A (en) Detergent compositions
EP0120528B1 (en) Detergent compositions
US3993573A (en) Softening additive and detergent composition
US4308151A (en) Detergent-compatible fabric softening and antistatic compositions
GB2189817A (en) Softening detergent compositions
EP0000225A1 (en) Solid detergent composition for improved greasy soil removal
NZ225217A (en) Detergent comprising 1-25 wt% of a hectorite clay
US4960526A (en) Diammonium compound containing fabric softening and antistatic detergent composition
EP0076572B1 (en) Fabric softening detergent additive products and use thereof in detergent compositions
CA1322824C (en) Softening and bleaching detergent compositions containing amide softening agent
US4744911A (en) Dispersible fabric softeners
JPH0665719B2 (en) Laundry composition
EP0062372B1 (en) Fabric softening compositions
US6194374B1 (en) Biodegradable fabric softening compositions based on a combination of pentaerythritol esters, bentonite and a polyphosphonate compound

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

Designated state(s): AT BE DE FR GB IT NL

17P Request for examination filed

Effective date: 19830402

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE DE FR GB IT NL

REF Corresponds to:

Ref document number: 20359

Country of ref document: AT

Date of ref document: 19860615

Kind code of ref document: T

ITF It: translation for a ep patent filed
REF Corresponds to:

Ref document number: 3271622

Country of ref document: DE

Date of ref document: 19860717

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

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

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
ITTA It: last paid annual fee
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19960126

Year of fee payment: 15

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

Ref country code: AT

Payment date: 19960313

Year of fee payment: 15

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

Ref country code: GB

Payment date: 19960315

Year of fee payment: 15

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

Ref country code: NL

Payment date: 19960328

Year of fee payment: 15

Ref country code: DE

Payment date: 19960328

Year of fee payment: 15

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

Ref country code: BE

Payment date: 19960510

Year of fee payment: 15

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

Ref country code: GB

Effective date: 19970324

Ref country code: AT

Effective date: 19970324

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

Ref country code: BE

Effective date: 19970331

BERE Be: lapsed

Owner name: THE PROCTER & GAMBLE CY

Effective date: 19970331

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

Ref country code: NL

Effective date: 19971001

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19970324

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

Ref country code: FR

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

Effective date: 19971128

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 19971001

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

Ref country code: DE

Effective date: 19971202

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST