WO1997012027A1 - Compositions de lessives aqueuses structurees contenant des oxydes d'amine - Google Patents

Compositions de lessives aqueuses structurees contenant des oxydes d'amine Download PDF

Info

Publication number
WO1997012027A1
WO1997012027A1 PCT/US1996/015523 US9615523W WO9712027A1 WO 1997012027 A1 WO1997012027 A1 WO 1997012027A1 US 9615523 W US9615523 W US 9615523W WO 9712027 A1 WO9712027 A1 WO 9712027A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition
amine oxide
alkyl
anionic surfactant
oxide
Prior art date
Application number
PCT/US1996/015523
Other languages
English (en)
Inventor
Yueqian Zhen
Original Assignee
The Procter & Gamble Company
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 The Procter & Gamble Company filed Critical The Procter & Gamble Company
Publication of WO1997012027A1 publication Critical patent/WO1997012027A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/0026—Structured liquid compositions, e.g. liquid crystalline phases or network containing non-Newtonian phase
    • 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
    • C11D1/75—Amino oxides
    • 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
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or salts thereof
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers

Definitions

  • the present invention relates to stable, aqueous heavy duty liquid laundry detergent compositions comprising anionic surfactants and amine oxide surfactants in a specific ratio to provide exceptional cleaning and softening benefits.
  • the detergent compositions herein are structured and have strong suspension properties.
  • the anionic surfactant component comprises alkyl sulfates and alkyl ethoxylated sulfates.
  • liquid laundry detergent compositions capable of suspending solids in the past have included the use of clays or polymers which act to form a shear thinning composition. While these compositions are capable of suspending particles, many have been found to have poor physical product characteristics, including phase split. Moreover, formulators were limited to a small selection of suitable detergent ingredients in relatively low concentrations.
  • aqueous, heavy duty liquid detergent compositions containing certain anionic surfactants and amine oxide surfactants provide excellent cleaning performance, softening benefits, and attractive product characteristics, i.e., are structured, phase stable, and have a rheology which allows for the suspension of particles while being easy to pour from the product container.
  • these novel compositions have an internal structure which comprises liquid crystalline surfactant particles, also known as lamellar droplets. These particles are dispersed in the aqueous phase and are capable of suspending solids. Lamellar droplets are known in the art, e.g., H. A. Barnes, “Detergents”, in K. Walters (Ed), “Rheometry: Industrial Applications”, J. Wiley & Sons, Letchworth 1980.
  • the presence of such surfactant droplets or particles in detergent compositions may be determined by optical means or by electronic microscope, such as a transmission or scanning electron microscope.
  • Amine oxide surfactants have long been known as useful additives in laundry detergent compositions. See U.S. Patent No. 5,075,501; 5,071,594.
  • the present invention encompasses a structured, heavy duty liquid laundry detergent compositions having a pH of from about 5 to about 9, at 10% dilution, and comprising, by weight ofthe composition: a) from about 10% to about 40% of an anionic surfactant component which comprises, by weight ofthe composition:
  • alkyl sulfate or alkyl polyethoxylate sulfates wherein the alkyl group contains from about 10 to about 22 carbon atoms and the polyethoxylate chain contains from 0 to about 15, preferably from 0 to about 5, more preferably from 0 to about 4, ethylene oxide moieties;
  • R' is selected from hydrogen, methyl and -CH2OH
  • R 1 is a primary or branched hydrocarbyl moiety which can be saturated or unsaturated and contain from about 8 to about 24 carbons, x is from 0 to about 6, y and z are intergers such that x+y+z is from about 0 to about 10; q is from 0 to about 2;
  • EO represents ethyleneoxy; PO represents propyleneoxy; and BO represents butyleneoxy; when x+y+z is 0, R 1 is a hydrocarbyl moiety having chainlength of from about 8 to about 18; when x+y+z is different from 0, R-- may be somewhat longer, having a chainlength in the range C12-C24; c) no more than about 10%, by weight, of solvents or hydrotropes; and d) from 0% to about 10% of
  • compositions herein have a viscosity at 20 s"l shear rate of from about
  • 100 cp to about 4,000 cp preferably from about 100 cp to about 2,000 cp, more preferably from about 200 cp to about 1,000 cp and are stable upon storage.
  • a stable, aqueous heavy duty liquid detergent composition is su ⁇ risingly formed when certain anionic surfactants and amine oxide surfactants are combined at a certain pH range and in relative proportions specified hereinafter.
  • compositions herein are structured and have a specific rheology.
  • the term "structured” indicates a heavy duty liquid composition having liquid crystalline surfactant particles and an infinite shear viscosity ( ⁇ o) value between 0 and about 3,000cp (centipoise), a shear index ( ⁇ ) value of less than about 0.6, a consistency value, K, of above about 1,000, and a viscosity ( ⁇ ) measured at 20" • ⁇ of less than about 10,000cp, preferably less than about 5,000cp.
  • a “zero shear” viscosity is above about 100,000cp wherein “zero shear” is meant a shear rate of 0.001 s"l or less.
  • the yield value of the compositions herein, obtained by plotting viscosity versus stress, is larger than 0.2Pa.
  • compositions herein are capable of suspending insoluble particles which can be in a solid, liquid, or liquid crystalline phase.
  • sustained is meant the ability to avoid settling or physical separation of particles of up to approximately 200 microns for a period of at least about 30 days.
  • the rate of particle sedimentation is inversely proportional to the viscosity, i.e., the higher the viscosity, the more stable the suspension will be.
  • a high "zero shear" viscosity is preferred, i.e., for this invention a zero shear viscosity of above about 100,000cp, preferably above about 500,000cp, even more preferably above about l,000,000cp is desired.
  • compositions herein The rheology and the suspending ability of these compositions are believed to be caused by the formation, in the specific compositions of this invention, of a space filling network of liquid crystalline surfactant particles (also known in the art as liposomes or vesicles) having a typical size of about 0.1 to about 10 microns.
  • the rheological property of the compositions herein is believed to be due in part to the presence in specific amounts of certain electrolytes, including sodium sulfate and citrate. Without being limited by theory, it is believed that the presence of electrolytes acts to control the size of the liquid crystalline surfactant particles.
  • the structured nature of the compositions herein are affected by the choice of surfactants and by the amount of electrolytes present.
  • compositions will further comprise from 0% to about 10%, more preferably from about 2% to about 6%, even more preferably from about 3% to about 5%, of a suitable electrolyte or acid equivalent thereof.
  • Sodium citrate is a highly preferred electrolyte for use herein.
  • compositions herein contain less than about 10%, preferably less than about 7%, more preferably less than about 5%, by weight of solvents and hydrotropes. Without being limited by theory, it is believed that the presence of solvents and hydrotropes can affect the structured versus isotropic nature of the compositions; compositions containing over about 10% solvents and/or hydrotrope lose the ability to remain in a single "phase", i.e., the composition will appear to separate into two or more layers.
  • solvent is meant the commonly used solvents in the detergent industry, including alkyl monoalcohol, di-, and tri- alcohols, ethylene glycol, propylene glycol, glycerine, etc.
  • hydrotrope is meant the commonly used hydrotropes in the detergent industry, including short chain surfactants that help solubilize other surfactants.
  • Other examples of hydrotropes include cumene, xylene, or toluene sulfonate, urea, Cg or shorter chain alkyl carboxylates, and C$ or shorter chain alkyl sulfate and ethoxylated sulfates.
  • the heavy duty liquid laundry detergent compositions herein contain an anionic surfactant component and an amine oxide surfactant as essential ingredients.
  • Anionic Surfactant Component - The detergent compositions herein comprise from about 10% to about 40%, preferably from about 15% to about 25%, by weight of the detergent composition, of an anionic surfactant component.
  • the anionic surfactant component contains alkyl sulfates and/or alkyl polyethoxylate sulfates, and may contain other non-soap anionic surfactants, or mixtures thereof.
  • the anionic surfactant components should not contain more than about 5%, preferably less than about 1%, more preferably substantially free, of fatty acids.
  • anionic surfactants useful herein are disclosed in U.S. Patent No. 4,285,841, Barrat et al, issued August 25, 1981, and in U.S. Patent No. 3,919,678, Laughlin et al, issued December 30, 1975, both incorporated herein by reference.
  • Useful anionic surfactants include the water-soluble salts, particularly the alkali metal, ammonium and alkylolammonium (e.g., monoethanolammonium or triethanolammonium) salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 10 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group.
  • water-soluble salts particularly the alkali metal, ammonium and alkylolammonium (e.g., monoethanolammonium or triethanolammonium) salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 10 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group.
  • alkyl is the alkyl portion of aryl groups.
  • alkyl sulfates especially those obtained by sulfating the higher alcohols (Cg- C i g carbon atoms) such as those produced by reducing the glycerides of tallow or coconut oil.
  • anionic surfactants herein are the water-soluble salts of alkyl phenol ethylene oxide ether sulfates containing from about 1 to about 4 units of ethylene oxide per molecule and from about 8 to about 12 carbon atoms in the alkyl group.
  • Other useful anionic surfactants herein include the water-soluble salts of esters of ⁇ -sulfonated fatty acids containing from about 6 to 20 carbon atoms in the fatty acid " group and from about 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxy-alkane-l -sulfonic acids containing from about 2 to 9 carbon atoms in the acyl group and from about 9 to about 23 carbon atoms in the alkane moiety; water-soluble salts of olefin sulfonates containing from about 12 to 24 carbon atoms; and ⁇ -alkyloxy alkane sulfonates containing from about 1 to 3 carbon atoms in the alkyl group and from about 8 to 20 carbon atoms in the alkane moiety.
  • Particularly preferred anionic surfactants herein are the alkyl polyethoxylate sulfates of the formula
  • RO(C 2 H 4 O) x SO3-M + wherein R is an alkyl chain having from about 10 to about 22 carbon atoms, saturated or unsaturated, M is a cation which makes the compound water-soluble, especially an alkali metal, ammonium or substituted ammonium cation, and x averages from about 1 to about 15.
  • Preferred alkyl sulfate surfactants are the non-ethoxylated Cj2-15 primary and secondary alkyl sulfates. Under cold water washing conditions, i.e., less than abut 65°F (18.3°C), it is preferred that there be a mixture of such ethoxylated and non- ethoxylated alkyl sulfates.
  • the anionic surfactant component ofthe present compositions comprises from about 5% to about 40%, preferably from about 7% to about 36%, most preferably from about 10% to about 25%, by weight of the detergent composition, of alkyl sulfates or alkyl polyethoxylate sulfates as described above.
  • the anionic surfactant component herein must comprise no more than about 5% of fatty acids.
  • the detergent compositions herein contain no fatty acids. These include saturated and/or unsaturated fatty acids obtained from natural sources or synthetically prepared. Examples of fatty acids include capric, lauric, myristic, palmitic, stearic, arachidic, and behenic acid. Other fatty acids include palmitoleic, oleic, linoleic, linolenic, and ricinoleic acid.
  • compositions herein also contain from about 1% to about 10%, preferably from about 2% to about 7%, more preferably from about 3% to about 5% by weight of an amine oxide surfactant ofthe formula: Rl(EO) x (PO) y (BO) z N(O)(CH 2 R , )2.qH2 ⁇ (I)
  • the structure (I) provides one long-chain moiety R 1 (EO) x (PO)y(BO) z and two short chain moieties, CH2R'.
  • R' is preferably selected from hydrogen, methyl and -CH2OH.
  • R-- is a primary or branched hydrocarbyl moiety which can be saturated or unsaturated, preferably, Rl is a primary alkyl moiety.
  • R-* is a hydrocarbyl moiety having chainlength of from about 8 to about 18.
  • R* When x+y+z is different from 0, R* may be somewhat longer, having a chainlength in the range Ci2 _ C24*
  • the invention also encompasses amine oxides wherein x+y+z is different from zero, specifically x+y+z is from about 1 to about 10, Rl is a primary alkyl group containing 8 to about 24 carbons, preferably from about 12 to about 16 carbon atoms; in these embodiments y + z is preferably 0 and x is preferably from about 1 to about 6, more preferably from about 2 to about 4; EO represents ethyleneoxy; PO represents propyleneoxy; and BO represents butyleneoxy.
  • amine oxides can be prepared by conventional synthetic methods, e.g., by the reaction of alkylethoxysulfates with dimethylamine followed by oxidation of the ethoxylated amine with hydrogen peroxide.
  • Highly preferred amine oxides herein are solids at ambient temperature, more preferably they have melting-points in the range 30°C to 90°C.
  • Amine oxides suitable for use herein are made commercially by a number of suppliers, including Akzo Chemie, Ethyl Corp., and Procter & Gamble. See McCutcheon's compilation and Kirk-Othmer review article for alternate amine oxide manufacturers.
  • Preferred commercially available amine oxides are the solid, dihydrate ADMOX 16 and ADMOX 18, ADMOX 12 and especially ADMOX 14 from Ethyl Corp.
  • Preferred embodiments include dodecyldimethylamine oxide dihydrate, hexadecyldimethylamine oxide dihydrate, octadecyldimethylamine oxide dihydrate, hexadecyltris(ethyleneoxy)dimethyl-amine oxide, tetradecyldimethylamine oxide dihydrate, and mixtures thereof.
  • R' is H
  • R' is CH2OH, such as hexadecylbis(2- hydroxyethyl)amine oxide, tallowbis(2-hydroxyethyl)amine oxide, stearylbis(2- hydroxyethyl)amine oxide and oleylbis(2- hydroxyethylamine oxide.
  • Inventions herein comprise the detergent composition wherein the weight ratio of anionic surfactant component to amine oxide surfactant is from about 1.5:1 to about 5:1, preferably from about 1.5:1 to about 4.5:1, more preferably from about 2 : 1 to about 4:1, even more preferably from about 2 : 1 to about 3.5:1.
  • compositions of the present invention can also preferably contain up to about 10%, preferably from 0% to about 5%, more preferably from 0% to about 3%, by weight of an ethoxylated nonionic surfactant.
  • ethoxylated alcohols and ethoxylated alkyl phenols of the formula R(OC2H4)nOH, wherein R is selected from the group consisting of aliphatic hydrocarbon radicals containing from about 8 to about 15 carbon atoms and alkyl phenyl radicals in which the alkyl groups contain from about 8 to about 12 carbon atoms, and the average value of n is from about 5 to about 15.
  • R is selected from the group consisting of aliphatic hydrocarbon radicals containing from about 8 to about 15 carbon atoms and alkyl phenyl radicals in which the alkyl groups contain from about 8 to about 12 carbon atoms, and the average value of n is from about 5 to about 15.
  • R is selected from the group consisting of aliphatic hydrocarbon radicals containing from about 8 to about 15 carbon atoms and alkyl phenyl radicals in which the alkyl groups contain from about 8 to about 12 carbon atoms, and the average value of n is from about 5 to about
  • compositions herein also preferably contain up to about 30%, more preferably from about 1% to about 20%, most preferably from about 1% to about 10%, by weight of a non-citrate, non-fatty acid detergent builder material. While all manner of detergent builders known in the art can be used in the present compositions, the type and level of builder should be selected such that the final composition has an initial pH of from about 5 to about 9, preferably from about 6 to about 8, at a concentration of about 10% by weight in water at 20°C.
  • Detergent builders are described in U.S. Patent No. 4,321,165, Smith et al, issued March 23, 1982, inco ⁇ orated herein by reference.
  • Preferred builders for use in liquid detergents herein are described in U.S. Patent No. 4,284,532, Leikhim et al, issued August 18, 1981, inco ⁇ orated herein by reference.
  • Enzymes Enzymes can be included in the formulations herein for a wide variety of fabric laundering pu ⁇ oses, including removal of protein-based, carbohydrate-based, or triglyceride-based stains, for example, and for fabric restoration.
  • the enzymes to be inco ⁇ orated include proteases, amylases, lipases, and cellulases, as well as mixtures thereof.
  • Other types of enzymes may also be included. They may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. However, their choice is governed by several factors such as pH-activity and/or stability optima, thermostability, stability versus active detergents, builders and so on. In this respect bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases.
  • Enzymes are normally inco ⁇ orated at levels sufficient to provide up to about 5 mg by weight, more typically about 0.01 mg to about 3 mg, of active enzyme per gram" of the composition. Stated otherwise, the compositions herein will typically comprise from about 0.001% to about 5%, preferably 0.01% to 1% by weight of a commercial enzyme preparation. Protease enzymes are usually present in such commercial preparations at levels sufficient to provide from 0.005 to 0.1 Anson units (AU) of activity per gram of composition.
  • AU Anson units
  • proteases are the subtilisins which are obtained from particular strains of B. subtilis and B. licheniforms. Another suitable protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold by Novo Industries A/S under the registered tradename ESPERASE. The preparation of this enzyme and analogous enzymes is described in British Patent Specification No. 1,243,784 of Novo.
  • protealytic enzymes suitable for removing protein-based stains that are commercially available include those sold under the trade names ALCALASE and SAVINASE by Novo Industries A/S (Denmark) and MAXATASE by International Bio-Synthetics, Inc. (The Netherlands).
  • proteases include Protease A (see European Patent Application 130,756, published January 9, 1985) and Protease B (see European Patent Application Serial No. 87303761.8, filed April 28, 1987, and European Patent Application 130,756, Bott et al, published January 9, 1985).
  • Amylases include, for example, ⁇ -amylases described in British Patent Specification No. 1,296,839 (Novo), RAPIDASE, International Bio-Synthetics, Inc. and TERMAMYL, Novo Industries.
  • the cellulase usable in the present invention include both bacterial or fungal cellulase. Preferably, they will have a pH optimum of between 5 and 9.5.
  • Suitable cellulases are disclosed in U.S. Patent 4,435,307, Barbesgoard et al, issued March 6, 1984, which discloses fungal cellulase produced from Humicola insolens and Humicola strain DSM 1800 or a cellulase 212-producing fungus belonging to the genus Aeromonas, and cellulase extracted from the hepatopancreas of a marine mollusk (Dolabella Auricula Solander). Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832. CAREZYME (Novo) is especially useful.
  • Suitable lipase enzymes for detergent usage include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent 1,372,034. See also lipases in Japanese Patent Application 53,20487, laid open to public inspection on February 24, 1978. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano,” hereinafter referred to as "Amano-P.” Other commercial lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var.
  • lipolyticum NRRLB 3673 commercially available from Toyo Jozo Co., Tagata, Japan; and further Chromobacter viscosum lipases from U.S. Biochemical Co ⁇ ., U.S.A. and Diosynth Co., The Netherlands, and lipases ex Pseudomonas gladioli.
  • the LIPOLASE enzyme derived from Humicola lanuginosa and commercially available from Novo is a preferred lipase for use herein.
  • Patent 3,600,319 issued August 17, 1971 to Gedge, et al, and European Patent Application Publication No. 0 199 405, Application No. 86200586.5, published October 29, 1986, Venegas. Enzyme stabilization systems are also described, for example, in U.S. Patent 3,519,570.
  • the enzymes employed herein may be stabilized by the presence of water- soluble sources of calcium and/or magnesium ions in the finished compositions which provide such ions to the enzymes.
  • Calcium ions are generally somewhat more effective than magnesium ions and are preferred herein if only one type of cation is being used.
  • Additional stability can be provided by the presence of various other art-disclosed stabilizers, especially borate species. See Severson, U.S. 4,537,706.
  • Typical detergents, especially liquids will comprise from about 1 to about 30, preferably from about 2 to about 20, more preferably from about 5 to about 15, and most preferably from about 8 to about 12, millimoles of calcium ion per liter of finished composition.
  • the level of calcium or magnesium ions should be selected so that there is always some minimum level available for the enzyme, after allowing for complexation with builders, fatty acids, etc., in the composition.
  • Any water-soluble calcium or magnesium salt can be used as the source of calcium or magnesium ions, including, but not limited to, calcium chloride, calcium sulfate, calcium malate, calcium maleate, calcium hydroxide, calcium formate, and calcium acetate, and the corresponding magnesium salts.
  • a small amount of calcium ion generally from about 0.05 to about 0.4 millimoles per liter, is often also present in the composition due to calcium in the enzyme slurry and formula water.
  • the formulation may include a sufficient quantity of a water-soluble calcium ion source to provide such amounts in the laundry liquor. In the alternative, natural water hardness may suffice.
  • compositions herein will typically comprise from about 0.05% to about 2% by weight of a water- soluble source of calcium or magnesium ions, or both.
  • the amount can vary, of course, with the amount and type of enzyme employed in the composition.
  • the compositions herein may also optionally, but preferably, contain various additional stabilizers, especially borate-type stabilizers.
  • such stabilizers will be used at levels in the compositions from about 0.25% to about 10%, preferably from about 0.5% to about 5%, more preferably from about 0.75% to about 4%, by weight of boric acid or other borate compound capable of forming boric acid in the composition (calculated on the basis of boric acid).
  • Boric acid is preferred, although other compounds such as boric oxide, borax and other alkali metal borates (e.g., sodium ortho-, meta- and pyroborate, and sodium pentaborate) are suitable.
  • Substituted boric acids e.g., phenylboronic acid, butane boronic acid, and p-bromo phenylboronic acid
  • liquid detergents herein are the neutralizing agents, buffering agents, phase regulants, polyacids, suds regulants, opacifiers, dispersants, such as ethoxylated tetraethylene pentaamine, antioxidants, bactericides, dyes, soil release polymers, perfumes, and brighteners described in the U.S. Patent No. 4,285,841, Barrat et al, issued August 25, 1981, inco ⁇ orated herein by reference.
  • Preferred neutralizing agents for use herein are organic bases, especially triethanolamine and monoethanol amine, which results in better detergency performance than inorganic bases such as sodium and potassium hydroxides.
  • compositions herein are suitable for suspending insoluble particles.
  • Particles for suspension include alkyl amine-anionic surfactant ion pair particles, as disclosed in U.S. pat. no. 4,861,502; builders s ⁇ ch as zeolites; bleach particles; perfume particles; encapsulated detergent additives; and other known insouble laundry additives.
  • Liquid detergent compositions were prepared according to the following formulas.
  • Amine oxide is a mixture of 80% C12 alkyl dimethyl amine oxide, 16% C14 alkyl dimethyl amine oxide, and 4%C ⁇ g alkyl dimethyl amine oxide.
  • the detergent samples are made by the following procedure.
  • the anionic surfactant paste is first mixed with alkyl ethoxylate, C14.15EO7 (if present) according to the formula composition, which is followed by the addition of of sodium hydroxide. Citric acid is added immediately after NaOH to bring the pH to about 5-9 at 10% solution. The amine oxide is then added. Immediately after the addition ofthe amine oxide, an opaque, lamellar droplet-filled suspension sample is formed. Water and other ingredients are added at the end to complete the formulation.
  • compositions of Examples I and II have a viscosity/rheology capable of suspending solids and are stable for more than 30 days.

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)
  • Crystallography & Structural Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention concerne des compositions détergentes liquides à grand rendement contenant un tensioactif anionique et un tensioactif d'oxyde d'amine. Le tensioactif anionique contient, par rapport au poids de la composition, 5 à 40 % en poids de sulfates d'alkyle ou de sulfates de polyéthoxylate d'alkyle. Ces compositions sont structurées et présentent un excellent pouvoir détachant, un excellent pouvoir assouplissant et permettent la mise en suspension de particules d'une dimension allant jusqu'à environ 200 microns pendant au moins un mois environ.
PCT/US1996/015523 1995-09-29 1996-09-27 Compositions de lessives aqueuses structurees contenant des oxydes d'amine WO1997012027A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US454595P 1995-09-29 1995-09-29
US60/004,545 1995-09-29

Publications (1)

Publication Number Publication Date
WO1997012027A1 true WO1997012027A1 (fr) 1997-04-03

Family

ID=21711311

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1996/015523 WO1997012027A1 (fr) 1995-09-29 1996-09-27 Compositions de lessives aqueuses structurees contenant des oxydes d'amine

Country Status (1)

Country Link
WO (1) WO1997012027A1 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2355015A (en) * 1999-08-02 2001-04-11 Procter & Gamble Structured liquid detergents with selected perfume fragrance materials
US20060135627A1 (en) * 2004-08-17 2006-06-22 Seren Frantz Structured surfactant compositions
US20090324520A1 (en) * 2007-07-27 2009-12-31 Jonathan Robert Cetti Personal-care article for sequentially dispensing compositions with variable concentrations of partitioned benefit or suspended benefit agents
US7749332B2 (en) 2004-08-23 2010-07-06 Henkel Kgaa Detergent/cleaning agents with a gellan gum thickening system, methods for using the same and cleaning substrates containing the same
US7901152B2 (en) * 2003-11-13 2011-03-08 The Sun Products Corporation Fabric cleaning fluid and dispensing device
WO2016112984A1 (fr) * 2015-01-15 2016-07-21 Ecolab Inc. Mousse de nettoyage longue durée
EP3284805A1 (fr) * 2016-08-17 2018-02-21 The Procter & Gamble Company Composition de nettoyage
CN113164800A (zh) * 2018-11-26 2021-07-23 株式会社资生堂 洗涤剂组合物

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4155871A (en) * 1973-01-19 1979-05-22 Lever Brothers Company Detergent compositions
EP0092363A1 (fr) * 1982-04-13 1983-10-26 Albright & Wilson Limited Compositions d'oxydes d'amines
GB2179054A (en) * 1985-08-16 1987-02-25 Unilever Plc Detergent gel compositions
US5039451A (en) * 1978-05-26 1991-08-13 Albright & Wilson Limited Manufacturing concentrated surfactant compositions
US5071594A (en) * 1989-10-02 1991-12-10 Ethyl Corporation Free flowing granular laundry detergent comprising tert-amine oxide dihydrate
US5075501A (en) * 1989-10-02 1991-12-24 Ethyl Corporation Mixed tert-amine oxide dihydrates
WO1995005440A1 (fr) * 1993-08-13 1995-02-23 The Procter & Gamble Company Detergent granuleux pour lave-vaisselle contenant des oxydes d'amines a longue chaine

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4155871A (en) * 1973-01-19 1979-05-22 Lever Brothers Company Detergent compositions
US5039451A (en) * 1978-05-26 1991-08-13 Albright & Wilson Limited Manufacturing concentrated surfactant compositions
EP0092363A1 (fr) * 1982-04-13 1983-10-26 Albright & Wilson Limited Compositions d'oxydes d'amines
GB2179054A (en) * 1985-08-16 1987-02-25 Unilever Plc Detergent gel compositions
US5071594A (en) * 1989-10-02 1991-12-10 Ethyl Corporation Free flowing granular laundry detergent comprising tert-amine oxide dihydrate
US5075501A (en) * 1989-10-02 1991-12-24 Ethyl Corporation Mixed tert-amine oxide dihydrates
WO1995005440A1 (fr) * 1993-08-13 1995-02-23 The Procter & Gamble Company Detergent granuleux pour lave-vaisselle contenant des oxydes d'amines a longue chaine

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2355015A (en) * 1999-08-02 2001-04-11 Procter & Gamble Structured liquid detergents with selected perfume fragrance materials
US7901152B2 (en) * 2003-11-13 2011-03-08 The Sun Products Corporation Fabric cleaning fluid and dispensing device
US20060135627A1 (en) * 2004-08-17 2006-06-22 Seren Frantz Structured surfactant compositions
US7749332B2 (en) 2004-08-23 2010-07-06 Henkel Kgaa Detergent/cleaning agents with a gellan gum thickening system, methods for using the same and cleaning substrates containing the same
US20090324520A1 (en) * 2007-07-27 2009-12-31 Jonathan Robert Cetti Personal-care article for sequentially dispensing compositions with variable concentrations of partitioned benefit or suspended benefit agents
CN107257848A (zh) * 2015-01-15 2017-10-17 艺康股份有限公司 长效的清洁泡沫
WO2016112984A1 (fr) * 2015-01-15 2016-07-21 Ecolab Inc. Mousse de nettoyage longue durée
JP2018505272A (ja) * 2015-01-15 2018-02-22 エコラボ ユーエスエー インコーポレイティド 長時間残る洗浄泡
US10550355B2 (en) 2015-01-15 2020-02-04 Ecolab Usa Inc. Long lasting cleaning foam
US11208613B2 (en) 2015-01-15 2021-12-28 Ecolab Usa Inc. Long lasting cleaning foam
EP3284805A1 (fr) * 2016-08-17 2018-02-21 The Procter & Gamble Company Composition de nettoyage
WO2018034842A1 (fr) * 2016-08-17 2018-02-22 The Procter & Gamble Company Compositions de nettoyage comprenant des enzymes
US10519401B2 (en) 2016-08-17 2019-12-31 The Procter & Gamble Company Cleaning composition
CN113164800A (zh) * 2018-11-26 2021-07-23 株式会社资生堂 洗涤剂组合物

Similar Documents

Publication Publication Date Title
EP0757713B1 (fr) Compositions detergentes a lessive, aqueuses, stables et presentant des proprietes adoucissantes ameliorees
EP0757714B2 (fr) Compositions detergentes pour lessives, aqueuses, stables, presentant de meilleures proprietes adoucissantes
US5942485A (en) Stable concentrated liquid laundry detergent composition containing alkyl polyethoxylate sulfate and polyhydroxy fatty acid amide surfactants and toluene sulfonate salt
EP0151678B1 (fr) Compositions de détergents liquides stables
AU608492B2 (en) Liquid detergent containing conditioning agent and high levels of alkyl sulfate/alkyl ethoxylated sulfate
EP0095205B1 (fr) Compositions détergentes contenant de l'acide gras
JPH0763605B2 (ja) 界面活性剤組成物及びそれを含有する液体洗剤組成物
MXPA96005097A (en) Composition detergent aqueous stable paralavanderia which has smoothing propertiesimple
CA1284446C (fr) Compositions detersives liquides, concentrees et homogenes, a systeme tensio-actif ternaire
US5981466A (en) Detergent compositions containing amines and anionic surfactants
WO1997012027A1 (fr) Compositions de lessives aqueuses structurees contenant des oxydes d'amine
CA2146636A1 (fr) Composition detergente avec systeme de suppression de la mousse
EP0706371A1 (fr) Compositions detergentes liquides a faible pouvoir moussant
WO1997012019A1 (fr) Compositions de lessives aqueuses stables a proprietes de mise en suspension ameliorees
WO1997012022A1 (fr) Compositions stables de detergents aqueux pour lessive, comprenant des agents tensio-actifs quaternaires et des oxydes d'amines et presentant des proprietes de suspension ameliorees
CA1315635C (fr) Detergent liquide en suspension stable
GB2298211A (en) Liquid detergent compositions comprising anionic surfactant, nonionic surfactant and proteolytic enzyme
US6479455B1 (en) Builder agglomerates for laundry detergent powders
EP0759970A1 (fr) Composition de detergent liquide pour grosse lessive en machine, contenant un tensioactif anionique, un tensioactif du type oxyde d'amine et un acide gras
WO1995016016A1 (fr) Composition detergente contenant un tensioactif a l'oxyde d'amine sous forme d'agglomerats
CA2345737C (fr) Procede d'apport d'agglomerat chelateur a une composition de detergent afin d'ameliorer sa stabilite au stockage, son aptitude a la fluidification et la facilite avec laquelle on peut prelever des doses d'utilisation
MXPA96005487A (en) Composition liquid detergent for heavy duty laundry containing surgical anti-aging and amine oxide agents and acid gr

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): BR CA JP MX US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: CA