WO1996006908A1 - Ethylenediamine disuccinate utilise comme detergent - Google Patents

Ethylenediamine disuccinate utilise comme detergent Download PDF

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Publication number
WO1996006908A1
WO1996006908A1 PCT/US1995/010519 US9510519W WO9606908A1 WO 1996006908 A1 WO1996006908 A1 WO 1996006908A1 US 9510519 W US9510519 W US 9510519W WO 9606908 A1 WO9606908 A1 WO 9606908A1
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compositions
composition according
agents
weight
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PCT/US1995/010519
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Frederick Anthony Hartman
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The Procter & Gamble Company
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Publication of WO1996006908A1 publication Critical patent/WO1996006908A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids

Definitions

  • the present invention relates to detergent compositions comprising ethylenediamine disuccinate as a detergency builder.
  • Most conventional detergent compositions contain mixtures of various detersive surfactants in order to remove a * wide variety of soils and stains from surfaces.
  • various anionic surfactants are useful for removing particulate soils
  • various nonionic surfactants are useful for removing greasy soils.
  • mixtures of anionic and nonionic surfactants are used in many modem detergent compositions.
  • such compositions typically comprise various other materials which are designed to provide an improved cleaning function.
  • the formulator often employs detersive enzymes, bleaches, soil release agents, and the like, to further boost performance.
  • High performance, so-called “heavy duty” detergent compositions will also typically comprise one or more ingredients which enhance, or “build”, detergency performance.
  • Such builders function by one or more mechanisms, including, but not limited to: sequestration of calcium hardness in the wash liquor; soil peptization; soil antiredeposition; pH adjustment; and the like, all of which enhance cleaning performance.
  • a detergent builder One of the main functions of a detergent builder is to remove excess calcium hardness ions from the laundering liquor. It might have been expected that conventional chelators, many of which are known for their ability to sequester calcium ions, would be widely used as builders. However, it transpires that many such materials are not particularly useful since they lack many of the functional attributes of truly effective builders Moreover, many chelators are non- biodegradable or are otherwise unsuitable for high volume usage. Accordingly, while chelators are often listed for use in detergents, their main purpose is to remove traces of iron, copper and manganese from laundry liquors. Accordingly, such chelators are typically used at relatively low, non-builder levels, which are usually less than about 10% of the finished detergent formulation.
  • ethylenediamine disuccinate when used at concentrations above 10%, performs well as a detergent builder. Moreover, it has further been discovered that the tendency of EDDS to undesirably remove magnesium ions from the wash liquor can be offset by the incorporation of certain grease removing surfactants in the compositions. Accordingly, good cleaning performance of a variety of soils and stains can be achieved by the optimized compositions herein.
  • the present invention encompasses detergent compositions, comprising: (a) greater than 10%, by weight, of ethylenediamine disuccinate builder; (b) one or more detersive surfactants; and
  • compositions comprising adjunct ingredients and optional carriers.
  • Preferred compositions herein contain a water-soluble cationic surfactant as component (b).
  • Other preferred compositions are those which comprise as component (b) a polyhydroxy fatty acid amide surfactant, oleoyl sarcosinate, or mixtures thereof, or mixtures with the aforesaid cationic surfactant.
  • adjunct ingredients useful in the present compositions include enzymes, especially cellulases and proteases.
  • Other useful adjunct ingredients include members selected from the group consisting of soil release agents, dye transfer inhibiting agents, bleach, clay soil removal and anti-redeposition agents, suds suppressors, optical brighteners, clay fabric softeners, and mixtures thereof.
  • the invention herein employs ingredients which are known materials, or which can be synthesized in the manner described hereinafter.
  • Ethylenediamine Disuccinate ⁇ DDS1 -
  • the EDDS builder used herein also known as ethylenediamine-N,N'-disuccinate is the material described in U.S. Patent
  • EDDS can be inexpensively prepared using maleic anhydride and ethylenediamine.
  • the preferred biodegradable [S,S] isomer of EDDS can be prepared by reacting L-aspartic acid with 1,2-dibromoethane.
  • the EDDS employed herein as a builder is typically in its salt form, i.e., wherein one or more of the four acidic hydrogens are replaced by a water-soluble cation M, such as sodium, potassium, ammonium, triethanolammonium, and the like.
  • the EDDS builder is typically used in the present compositions at levels from about 12% to about 50%, by weight.
  • the preferred surfactants for use in the present compositions include the water-soluble cationics, oleoyl sarcosinate and the polyhydroxy fatty acid amides. Such preferred surfactants will typically comprise at least about 1%, preferably from about 3% to about 35%, by weight, of the total compositions.
  • the water-soluble cationic surfactants are known articles of commerce, the most common of which may be represented by the formula
  • R is typically CJO to about C20 hydrocarbyl, especially alkyl and alkenyl
  • each of R', R" and R"' is independently C1-C3 alkyl or hydroxyalkyl, especially methyl and hydroxyethyl
  • X is any convenient, water-soluble anion, e.g., chloride, bromide, methylsulfate and the like.
  • water-soluble cationic surfactants for use herein include: lauryl trimethylammonium chloride; myristyl trimethylammonium bromide; palmityl trimethylammonium methylsulfate; mixed coconut (C 12- 18) trimethylammonium chloride; coconut triethylammonium chloride; C12- 16 dimethyl hydroxyethylammonium chloride; and the like.
  • Oleoyl sarcosinate has the formula wherein M is any convenient water-soluble cation, e.g., sodium (preferred), potassium, ammonium, triethanolammonium, and the like.
  • Oleoyl sarcosinate is commercially available as HAMPOSYL O, supplied by W. R. Grace & Co.
  • Oleoyl sarcosinate can be prepared by reacting the methyl ester of oleic acid with the sodium salt of sarcosine under anhydrous conditions in the presence of sodium methoxide catalyst. The reaction is preferably conducted at a temperature from about 120°C to about 200°C using a molar ratio of methyl ester reactant: sarcosine salt reactant:base catalyst of about 1 : 1 :0.05-0.2.
  • the polyhydroxy fatty acid amide surfactants comprise N-alkoxy or N- aryloxy of the formula:
  • polyhydroxy fatty acid amide surfactants used herein also comprise N-alkyl, N- hydroxyalkyl or N-alkenyl materials of the formula:
  • R 3 -C-N-Z (II) wherein in formulas (I) and (II): R- is C7-C21 hydrocarbyl, preferably C9-C17 hydrocarbyl, including straight-chain and branched-chain alkyl and alkenyl, or mixtures thereof; R-* is C2-C8 hydrocarbyl including straight-chain, branched-chain and cyclic (including aryl), and is preferably C2-C4 alkylene, i.e., -CH2CH2-, - CH2CH2CH2- and -CH2(CH2)2CH2S R 2 is C i-Cg straight-chain, branched-chain and cyclic hydrocarbyl including aryl and oxy-hydrocarbyl, and is preferably C1-C4 alkyl or phenyl; R ⁇ is Cj-Cg alkyl, alkenyl or hydroxyalkyl, including methyl (preferred), ethyl, propyl, isoprop
  • Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose, as well as glyceraldehyde.
  • nonlimiting examples of the amine substituent group -R'-O-R 2 can be, for example: 2-methoxyethyl-, 3- methoxypropyl-, 4-methoxybutyl-, 5-methoxypentyl-, methoxybenzyl, 2-methoxy- propyl, and the like.
  • R-CO-N ⁇ can be, for example, cocamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, tallowamide, etc.
  • any unreacted amino polyol remaining in the product can be acylated with an acid anhydride, e.g., acetic anhydride, maleic anhydride, or the like, in water at 50°C-85°C to minimize the overall level of such residual amines in the product.
  • an acid anhydride e.g., acetic anhydride, maleic anhydride, or the like
  • Residual sources of straight-chain primary fatty acids which can suppress suds, can be depleted by reaction with, for example, monoethanolamine at 50°C-85°C.
  • Preparing the polyhydroxy fatty acid amides directly from triglyceride feedstocks, rather than methyl esters, avoiding methanol solvent and using sodium glycolate catalyst helps avoid the formation of fatty acids in the final product.
  • the water solubility of the solid polyhydroxy fatty acid amide surfactants herein can be enhanced by quick cooling from a melt. While not intending to be limited by theory, it appears that such quick cooling re-solidifies the melt into a metastable solid which is more soluble in water than the pure crystalline form of the polyhydroxy fatty acid amide.
  • Such quick cooling can be accomplished by any convenient means, such as by use of chilled (0°C-10°C) rollers, by casting the melt onto a chilled surface such as a chilled steel plate, by means of refrigerant coils immersed in the melt, or the like.
  • Fully-formulated detergent compositions especially those intended for use in laundering fabrics, will typically also comprise various adjunct ingredients to enhance overall cleaning performance, to provide additional fabric care benefits, or to improve the processability and/or aesthetics of the compositions.
  • adjunct ingredients to enhance overall cleaning performance, to provide additional fabric care benefits, or to improve the processability and/or aesthetics of the compositions. The following is included for the convenience of the formulator to illustrate such adjunct ingredients, but is not intended to be limiting thereof.
  • bleaching agents may be at levels of from about 1% to about 30%, more typically from about 5% to about 20%, of the detergent composition, especially for fabric laundering. If present, the amount of bleach activators will typically be from about 0.1% to about 60%, more typically from about 0.5% to about 40% of the bleaching composition comprising the bleaching agent-plus-bleach activator.
  • the bleaching agents used herein can be any of the bleaching agents useful for detergent compositions in textile cleaning, hard surface cleaning, or other cleaning purposes that are now known or become known. These include oxygen bleaches as well as other bleaching agents.
  • Perborate bleaches e.g., sodium perborate (e.g., mono- or tetra-hydrate) can be used herein.
  • bleaching agent that can be used without restriction encompasses percarboxylic acid bleaching agents and salts thereof Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of metachloro perbenzoic acid, 4-nonylamino-4- oxoperoxybutyric acid and diperoxydodecanedioic acid.
  • Such bleaching agents are disclosed in U.S. Patent 4,483,781, Hartman, issued November 20, 1984, U.S. Patent Application 740,446, Burns et al, filed June 3, 1985, European Patent Application 0, 133,354, Banks et al, published February 20, 1985, and U.S. Patent 4,412,934, Chung et al, issued November 1, 1983.
  • Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S. Patent 4,634,551, issued January 6, 1987 to Burns et al.
  • Peroxygen bleaching agents can also be used. Suitable peroxygen bleaching compounds include sodium carbonate peroxyhydrate and equivalent "percarbonate” bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide. Persulfate bleach (e.g., OXONE, manufactured commercially by DuPont) can also be used.
  • a preferred percarbonate bleach comprises dry particles having an average particle size in the range from about 500 micrometers to about 1,000 micrometers, not more than about 10% by weight of said particles being smaller than about 200 micrometers and not more than about 10% by weight of said particles being larger than about 1,250 micrometers.
  • the percarbonate can be coated with silicate, borate or water-soluble surfactants.
  • Percarbonate is available from various commercial sources such as FMC, Solvay and Tokai Denka. Mixtures of bleaching agents can also be used.
  • Peroxygen bleaching agents, the perborates, the percarbonates, etc. are preferably combined with bleach activators, which lead to the in situ production in aqueous solution (i.e., during the washing process) of the peroxy acid corresponding to the bleach activator.
  • bleach activators Various nonlimiting examples of activators are disclosed in U.S. Patent 4,915,854, issued April 10, 1990 to Mao et al, and U.S. Patent 4,412,934.
  • the nonanoyloxybenzene sulfonate (NOBS) and tetraacetyl ethylene diamine (TAED) activators are typical, and mixtures thereof can also be used See also U.S. 4,634,551 for other typical bleaches and activators useful herein.
  • amido-derived bleach activators are those of the formulae: R !N(R 5 )C(O)R 2 C(O)L or R 1 C(O)N(R 5 )R 2 C(O)L wherein Rl is an alkyl group containing from about 6 to about 12 carbon atoms, R 2 is an alkylene containing from 1 to about 6 carbon atoms, R- 5 is H or alkyl, aryl, or alkaryl containing from about 1 to about 10 carbon atoms, and L is any suitable leaving group.
  • a leaving group is any group that is displaced from the bleach activator as a consequence of the nucleophilic attack on the bleach activator by the perhydrolysis anion.
  • a preferred leaving group is phenyl sulfonate.
  • Preferred examples of bleach activators of the above formulae include (6- octanamido-caproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)oxybenzenesul- fonate, (6-decanamido-caproyl)oxybenzenesulfonate, and mixtures thereof as described in U.S. Patent 4,634,551, incorporated herein by reference.
  • Another class of bleach activators comprises the benzoxazin-type activators disclosed by Hodge et al in U.S. Patent 4,966,723, issued October 30, 1990, incorporated herein by reference.
  • a highly preferred activator of the benzoxazin-type is:
  • acyl caprolactams especially acyl valerolactams of the formulae:
  • R 6 is H or an alkyl, aryl, alkoxyaryl, or alkaryl group containing from 1 to about 12 carbon atoms.
  • Highly preferred lactam activators include benzoyl caprolactam, octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyi caprolactam, benzoyl valerolactam, octanoyl valerolactam, decanoyl valerolactam, undecenoyi valerolactam, nonanoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam and mixtures thereof. See also U.S. Patent 4,545,784, issued to Sanderson, October 8, 1985, incorporated herein by reference, which discloses acyl caprolactams, including benzoyl caprolactam, adsorbed into sodium per
  • Bleaching agents other than oxygen bleaching agents are also known in the an and can be utilized herein.
  • One type of non-oxygen bleaching agent of particular interest includes photoactivated bleaching agents such as the sulfonated zinc and/or aluminum phthalocyanines. See U.S. Patent 4,033,718, issued July 5, 1977 to Holcombe et al. If used, detergent compositions will typically contain from about 0 025% to about 1.25%, by weight, of such bleaches, especially sulfonate zinc phthalocyanine.
  • the bleaching compounds can be catalyzed by means of a manganese compound.
  • a manganese compound Such compounds are well known in the art and include, for example, the manganese-based catalysts disclosed in U.S. Pat. 5,246,621, U.S. Pat. 5,244,594; U.S. Pat. 5, 194,416; U.S. Pat. 5,1 14,606; and European Pat. App. Pub. Nos. 549,271A1, 549,272A1, 544,440A2, and 544.490A1; Preferred examples of these catalysts include Mn ⁇ 2( u -C')3(l,4,7-trimethyl-l,4,7-triazacyclononane)2.
  • metal-based bleach catalysts include those disclosed in U.S. Pat. 4,430,243 and U.S. Pat. 5, 114,61 1
  • the use of manganese with various complex ligands to enhance bleaching is also reported in the following United States Patents: 4,728,455; 5,284,944; 5,246,612, 5,256,779; 5,280,1 17; 5,274,147; 5,153,161; and 5,227,084.
  • compositions and processes herein can be adjusted to provide on the order of at least one part per ten million of the active bleach catalyst species in the aqueous washing liquor, and will preferably provide from about 0 1 ppm to about 700 ppm, more preferably from about 1 ppm to about 500 ppm, of the catalyst species in the laundry liquor
  • Nonlimiting examples of surfactants useful herein typically at levels from about 1% to about 55%, by weight, include the conventional Ci j -C j g alkyl benzene sulfonates ("LAS") and primary, branched-chain and random C ⁇ ) -C20 alkyl sulfates (“AS”), the Cio-Cig secondary (2,3) alkyl sulfates of the formula CH3(CH2) x (CHOSO 3 " M + ) CH 3 and CH 3 (CH 2 )y(CHOSO3 " M + ) CH2CH3 where x and (y + I) are integers of at least about 7, preferably at least about 9, and M is a water-solubilizing cation, especially sodium, unsaturated sulfates such as oleyl sulfate, the C jo-C ig alkyl alkoxy sulfates ("AE X S"; especially EO 1-7 ethoxy sulf
  • the conventional nonionic and amphoteric surfactants such as the Ci2-Cj alkyl ethoxylates ("AE") including the so-called narrow peaked alkyl ethoxylates and Cg-C ⁇ alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), C ⁇ -Cj g betaines and sulfobetaines ("sultaines"), Cjo-Ci amine oxides, and the like, can also be included in the overall compositions.
  • the C j o-C j g N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include the C ⁇ -Cjg N-methylglucamides.
  • sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as i Q -C j g N- (3-methoxypropyI) glucamide.
  • the N-propyl through N-hexyl C ⁇ -Cjg glucamides can be used for low sudsing.
  • C10-C20 conventional soaps may also be used. If high sudsing is desired, the branched-chain C ⁇ Q-C ⁇ Q soaps may be used. Mixtures of anionic and nonionic surfactants are especially useful. Other conventional useful surfactants are listed in standard texts.
  • Enzymes - Enzymes can be included in the formulations herein for a wide variety of fabric laundering purposes, including removal of protein-based, carbohydrate-based, or triglyceride-based stains, for example, and for the prevention of refugee dye transfer, and for fabric restoration.
  • the enzymes to be incorporated include proteases, amylases, lipases, cellulases, and peroxidases, 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 incorporated at levels sufficient to provide up to about
  • compositions herein will typically comprise from about 0.001% to about 5%, preferably 0.01%-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.
  • proteases are the subtilisins which are obtained from particular strains of B subtilis and B cheniforms 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 trade name ESPERASE The preparation of this enzyme and analogous enzymes is described in British Patent Specification No 1,243,784 of Novo Proteolytic enzymes suitable for removing protein-based stains that are commercially available include those sold under the tradena es ALCALASE and SAVTNASE by Novo Industries A/S (Denmark) and MAXATASE by International Bio-Synthetics, Inc (The Netherlands) Other 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), RAPID ASE, 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 DSM1800 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 Corp , U S A and Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli The
  • Peroxidase enzymes are used in combination with oxygen sources, e.g., percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for "solution bleaching," i.e. to prevent transfer of dyes or pigments removed from substrates during wash operations to other substrates in the wash solution.
  • Peroxidase enzymes are known in the art, and include, for example, horseradish peroxidase, ligninase, and haloperoxidase such as chloro- and bromo-peroxidase.
  • Peroxidase-containing detergent compositions are disclosed, for example, in PCT International Application WO 89/099813, published October 19, 1989, by O. Kirk, assigned to Novo Industries A S.
  • 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.
  • Enzyme Stabilizers The enzymes employed herein are 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.
  • natural water hardness may suffice.
  • the foregoing levels of calcium and/or magnesium ions are sufficient to provide enzyme stability. More calcium and/or magnesium ions can be added to the compositions to provide an additional measure of grease removal performance. Accordingly, as a general proposition the 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.
  • compositions herein may also optionally, but preferably, contain various additional stabilizers, especially borate-type stabilizers.
  • 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 3%, 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.
  • alkali metal borates e.g., sodium ortho-, meta- and pyroborate, and sodium pentaborate
  • Substituted boric acids e.g., phenylboronic acid, butane boronic acid, and p-bromo phenylboronic acid
  • boric acid e.g., phenylboronic acid, butane boronic acid, and p-bromo phenylboronic acid
  • compositions of the present invention can also optionally contain water-soluble ethoxylated amines having clay soil removal and antiredeposition properties.
  • Granular detergent compositions which contain these compounds typically contain from about 0.01% to about 10.0% by weight of the water-soluble ethoxylates amines; liquid detergent compositions typically contain about 0.01% to about 5%.
  • the most prefe ⁇ ed soil release and anti-redeposition agent is ethoxylated tetraethylenepentamine.
  • Exemplary ethoxylated amines are further described in U S Patent 4,597,898, VanderMeer, issued July 1, 1986.
  • Another group of preferred clay soil removal-antiredeposition agents are the cationic compounds disclosed in European Patent Application 1 1 1,965, Oh and Gosselink, published June 27, 1984
  • Other clay soil removal/antiredeposition agents which can be used include the ethoxylated amine polymers disclosed in European Patent Application 1 1 1,984, Gosselink, published June 27, 1984; the zwitterionic polymers disclosed in European Patent Application 1 12,592, Gosselink, published July 4, 1984; and the amine oxides disclosed in U.S.
  • Other clay soil removal and/or anti redeposition agents known in the art can also be utilized in the compositions herein.
  • Another type of preferred antiredeposition agent includes the carboxy methyl cellulose (CMC) materials. These materials are well known in the art.
  • Suds Suppressors - Compounds for reducing or suppressing the formation of suds can be incorporated into the compositions of the present invention. Suds suppression can be of particular importance in the so-called "high concentration cleaning process" as described in U.S. 4,489,455 and 4,489,574 and in front-loading European-style washing machines.
  • a wide variety of materials may be used as suds suppressors, and suds suppressors are well known to those skilled in the art.
  • One category of suds suppressor of particular interest encompasses monocarboxylic fatty acid and soluble salts therein. See U.S. Patent 2,954,347, issued September 27, 1960 to Wayne St. John.
  • the monocarboxylic fatty acids and salts thereof used as suds suppressor typically have hydrocarbyl chains of 10 to about 24 carbon atoms, preferably 12 to 18 carbon atoms.
  • Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts.
  • the detergent compositions herein may also contain non-surfactant suds suppressors.
  • non-surfactant suds suppressors include, for example, high molecular weight hydrocarbons such as paraffin, fatty acid esters (e.g., fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C ⁇ -C4o ketones (e.g., stearone), etc.
  • suds inhibitors include N-alkylated amino triazines such as tri- to hexa-alkylmelamines or di- to tetra-alkyldiamine chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, and monostearyl phosphates such as monostearyl alcohol phosphate ester and monostearyl di-alkali metal (e.g., K, Na, and Li) phosphates and phosphate esters.
  • the hydrocarbons such as paraffin and haloparaffin can be utilized in liquid form.
  • the liquid hydrocarbons will be liquid at room temperature and atmospheric pressure, and will have a pour point in the range of about -40°C and about 50°C, and a minimum boiling point not less than about 110°C (atmospheric pressure). It is also known to utilize waxy hydrocarbons, preferably having a melting point below about 100°C.
  • the hydrocarbons constitute a preferred category of suds suppressor for detergent compositions. Hydrocarbon suds suppressors are described, for example, in U S Patent 4,265,779, issued May 5, 1981 to Gandolfo et al.
  • the hydrocarbons thus, include aliphatic, alicyclic, aromatic, and heterocyclic saturated or unsaturated hydrocarbons having from about 12 to about 70 carbon atoms.
  • the term "paraffin,” as used in this suds suppressor discussion, is intended to include mixtures of true paraffins and cyclic hydrocarbons.
  • Non-surfactant suds suppressors comprises silicone suds suppressors.
  • This category includes the use of polyorganosiloxane oils, such as polydimethylsiloxane, dispersions or emulsions of polyorganosiloxane oils or resins, and combinations of polyorganosiloxane with silica particles wherein the polyorganosiloxane is chemisorbed or fused onto the silica.
  • Silicone suds suppressors are well known in the art and are, for example, disclosed in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al and European Patent Application No. 89307851.9, published February 7, 1990, by Starch, M. S.
  • Patent Application DOS 2, 124,526 Silicone defoamers and suds controlling agents in granular detergent compositions are disclosed in U.S. Patent 3,933,672, Bartolotta et al, and in U.S. Patent 4,652,392, Baginski et al, issued March 24, 1987.
  • An exemplary silicone based suds suppressor for use herein is a suds suppressing amount of a suds controlling agent consisting essentially of:
  • polydimethylsiloxane fluid having a viscosity of from about 20 cs. to about 1,500 cs. at 25°C;
  • siloxane resin composed of (CH3)3SiO ⁇ /2 units of Si ⁇ 2 units in a ratio of from (CH3)3 SiO ⁇ /2 units and to Si ⁇ 2 units of from about 0.6.1 to about
  • the solvent for a continuous phase is made up of certain polyethylene glycols or polyethylene- polypropylene glycol copolymers or mixtures thereof (preferred), or polypropylene glycol.
  • the primary silicone suds suppressor is branched/crosslinked and preferably not linear
  • typical liquid laundry detergent compositions with controlled suds will optionally comprise from about 0.001 to about 1, preferably from about 0.01 to about 0 7, most preferably from about 0.05 to about 0.5, weight % of said silicone suds suppressor, which comprises ( 1 ) a nonaqueous emulsion of a primary antifoam agent which is a mixture of (a) a polyorganosiloxane, (b) a resinous siloxane or a silicone resin-producing silicone compound, (c) a finely divided filler material, and (d) a catalyst to promote the reaction of mixture components (a), (b) and (c), to form silanolates; (2) at least one nonionic silicone surfactant; and (3) polyethylene glycol or a copolymer of polyethylene-polypropylene glycol having a solubility in water at room temperature of more than about 2 weight %; and without polypropylene glycol.
  • a primary antifoam agent which is a mixture of (a) a polyorgan
  • the silicone suds suppressor herein preferably comprises polyethylene glycol and a copolymer of polyethylene glycol/polypropylene glycol, all having an average molecular weight of less than about 1,000, preferably between about 100 and 800.
  • the polyethylene glycol and polyethylene/polypropylene copolymers herein have a solubility in water at room temperature of more than about 2 weight %, preferably more than about 5 weight %.
  • the preferred solvent herein is polyethylene glycol having an average molecular weight of less than about 1,000, more preferably between about 100 and 800, most preferably between 200 and 400, and a copolymer of polyethylene glycol polypropylene glycol, preferably PPG 200 PEG 300.
  • Preferred is a weight ratio of between about 1 : 1 and 1 : 10, most preferably between 1 :3 and 1 :6, of polyethylene glycolxopolymer of polyethylene-polypropylene glycol.
  • the preferred silicone suds suppressors used herein do not contain polypropylene glycol, particularly of 4,000 molecular weight. They also preferably do not contain block copolymers of ethylene oxide and propylene oxide, like PLURONIC L101.
  • suds suppressors useful herein comprise the secondary alcohols (e.g., 2-alkyl alkanols) and mixtures of such alcohols with silicone oils, such as the silicones disclosed in U.S. 4,798,679, 4,075, 1 18 and EP 150,872.
  • the secondary alcohols include the Cg-C j ⁇ alkyl alcohols having a C J -C J O chain.
  • a prefened alcohol is 2- butyl octanol, which is available from Condea under the trademark ISOFOL 12.
  • Mixtures of secondary alcohols are available under the trademark ISALCHEM 123 from Enichem.
  • Mixed suds suppressors typically comprise mixtures of alcohol + silicone at a weight ratio of 1 :5 to 5: 1.
  • suds should not form to the extent that they overflow the washing machine.
  • Suds suppressors when utilized, are preferably present in a "suds suppressing amount.
  • Suds suppressing amount is meant that the formulator of the composition can select an amount of this suds controlling agent that will sufficiently control the suds to result in a low-sudsing laundry detergent for use in automatic laundry washing machines.
  • compositions herein will generally comprise from 0% to about 5% of suds suppressor.
  • monocarboxylic fatty acids, and salts therein will be present typically in amounts up to about 5%, by weight, of the detergent composition.
  • from about 0.5% to about 3% of fatty monocarboxylate suds suppressor is utilized.
  • Silicone suds suppressors are typically utilized in amounts up to about 2.0%, by weight, of the detergent composition, although higher amounts may be used. This upper limit is practical in nature, due primarily to concern with keeping costs minimized and effectiveness of lower amounts for effectively controlling sudsing.
  • from about 0.01% to about 1% of silicone suds suppressor is used, more preferably from about 0.25% to about 0.5%.
  • these weight percentage values include any silica that may be utilized in combination with polyorganosiloxane, as well as any adjunct materials that may be utilized.
  • Monostearyl phosphate suds suppressors are generally utilized in amounts ranging from about 0.1% to about 2%, by weight, of the composition.
  • Hydrocarbon suds suppressors are typically utilized in amounts ranging from about 0.01% to about 5.0%, although higher levels can be used.
  • the alcohol suds suppressors are typically used at 0.2%-3% by weight of the finished compositions.
  • Fabric Softeners Various through-the-wash fabric softeners, especially the impalpable smectite clays of U.S. Patent 4,062,647, Storm and Nirschl, issued December 13, 1977, as well as other softener clays known in the art, can optionally be used typically at levels of from about 0.5% to about 10% by weight in the present compositions to provide fabric softener benefits concurrently with fabric cleaning.
  • Clay softeners can be used in combination with amine and cationic softeners as disclosed, for example, in U.S. Patent 4,375,416, Crisp et al, March 1, 1983 and U.S. Patent 4,291,071, Harris et al, issued September 22, 1981.
  • Polymeric Soil Release Agent Any polymeric soil release agent known to those skilled in the art can optionally be employed in the compositions and processes of this invention.
  • Polymeric soil release agents are characterized by having both hydrophilic segments, to hydrophilize the surface of hydrophobic fibers, such as polyester and nylon, and hydrophobic segments, to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles and, thus, serve as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to treatment with the soil release agent to be more easily cleaned in later washing procedures.
  • the polymeric soil release agents useful herein especially include those soil release agents having: (a) one or more nonionic hydrophile components consisting essentially of (i) polyoxyethylene segments with a degree of polymerization of at least 2, or (ii) oxypropyiene or polyoxypropylene segments with a degree of polymerization of from 2 to 10, wherein said hydrophile segment does not encompass any oxypropyiene unit unless it is bonded to adjacent moieties at each end by ether linkages, or (iii) a mixture of oxyalkylene units comprising oxyethylene and from 1 to about 30 oxypropyiene units wherein said mixture contains a sufficient amount of oxyethylene units such that the hydrophile component has hydrophilicity great enough to increase the hydrophilicity of conventional polyester synthetic fiber surfaces upon deposit of the soil release agent on such surface, said hydrophile segments preferably comprising at least about 25% oxyethylene units and more preferably, especially for such components having about 20 to 30 oxypropyiene units, at least about 50% oxyethylene units; or
  • the polyoxyethylene segments of (a)(i) will have a degree of polymerization of from about 200, although higher levels can be used, preferably from 3 to about 150, more preferably from 6 to about 100.
  • Suitable oxy C4-C6 alkylene hydrophobe segments include, but are not limited to, end-caps of polymeric soil release agents such as M ⁇ 3S(CH2) n OCH2CH2 ⁇ -, where M is sodium and n is an integer from 4-6, as disclosed in U.S. Patent 4,721,580, issued January 26, 1988 to Gosselink.
  • Polymeric soil release agents useful in the present invention also include cellulosic derivatives such as hydroxyether cellulosic polymers, copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, and the like. Such agents are commercially available and include hydroxyethers of cellulose such as METHOCEL (Dow). Cellulosic soil release agents for use herein also include those selected from the group consisting of C 1-C4 alkyl and C4 hydroxyalkyl cellulose; see U.S. Patent 4,000,093, issued December 28, 1976 to Nicol, et al.
  • Soil release agents characterized by poly(vinyl ester) hydrophobe segments include graft copolymers of poly( vinyl ester), e.g., C j -Cg vinyl esters, preferably poly(vinyl acetate) grafted onto polyalkylene oxide backbones, such as polyethylene oxide backbones.
  • poly(vinyl ester) e.g., C j -Cg vinyl esters
  • poly(vinyl acetate) grafted onto polyalkylene oxide backbones such as polyethylene oxide backbones.
  • Commercially available soil release agents of this kind include the SOKALAN type of material, e.g., SOKALAN HP-22, available from BASF (West Germany).
  • One type of preferred soil release agent is a copolymer having random blocks of ethylene terephthalate and polyethylene oxide (PEO) terephthalate.
  • the molecular weight of this polymeric soil release agent is in the range of from about 25,000 to about 55,000. See U.S. Patent 3,959,230 to Hays, issued May 25, 1976 and U.S. Patent 3,893,929 to Basadur issued July 8, 1975.
  • Another preferred polymeric soil release agent is a polyester with repeat units of ethylene terephthalate units contains 10-15% by weight of ethylene terephthalate units together with 90-80% by weight of polyoxyethylene terephthalate units, derived from a polyoxyethylene glycol of average molecular weight 300-5,000.
  • this polymer include the commercially available material ZELCON 5126 (from Dupont) and MLLEASE T (from ICI). See also U.S. Patent 4,702,857, issued October 27, 1987 to Gosselink.
  • Another preferred polymeric soil release agent is a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and terminal moieties covalently attached to the backbone
  • soil release agents are described fully in U.S. Patent 4,968,451, issued November 6, 1990 to J.J. Scheibel and E.P. Gosselink.
  • Other suitable polymeric soil release agents include the terephthalate polyesters of U.S. Patent 4,71 1,730, issued December 8, 1987 to Gosselink et al, the anionic end- capped oligomeric esters of U.S. Patent 4,721,580, issued January 26, 1988 to Gosselink, and the block polyester oligomeric compounds of U.S. Patent 4,702,857, issued October 27, 1987 to Gosselink.
  • Preferred polymeric soil release agents also include the soil release agents of U.S. Patent 4,877,896, issued October 31, 1989 to Maldonado et al, which discloses anionic, especially sulfoaroyl, end-capped terephthalate esters.
  • Still another preferred soil release agent is an oligomer with repeat units of terephthaloyl units, sulfoisoterephthaloyl units, oxyethyleneoxy and oxy-1,2- propylene units.
  • the repeat units form the backbone of the oligomer and are preferably terminated with modified isethionate end-caps.
  • a particularly preferred soil release agent of this type comprises about one sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy and oxy-l,2-propyleneoxy units in a ratio of from about 1.7 to about 1.8, and two end-cap units of sodium 2-(2-hydroxyethoxy)- ethanesulfonate.
  • Said soil release agent also comprises from about 0.5% to about 20%, by weight of the oligomer, of a crystalline-reducing stabilizer, preferably selected from the group consisting of xylene sulfonate, cumene sulfonate, toluene sulfonate, and mixtures thereof.
  • a crystalline-reducing stabilizer preferably selected from the group consisting of xylene sulfonate, cumene sulfonate, toluene sulfonate, and mixtures thereof.
  • soil release agents will generally comprise from about 0.01% to about 10.0%, by weight, of the detergent compositions herein, typically from about 0.1% to about 5%, preferably from about 0.2% to about 3.0%.
  • Dve Transfer Inhibiting Agents may also include one or more materials effective for inhibiting the transfer of dyes from one fabric to another during the cleaning process.
  • dye transfer inhibiting agents include polyvinyl pyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine, peroxidases, and mixtures thereof. If used, these agents typically comprise from about 0.01% to about 10% by weight of the composition, preferably from about 0.01% to about 5%, and more preferably from about 0.05% to about 2%.
  • Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pynolidine, piperidine and derivatives thereof.
  • the N-O group can be represented by the following general structures:
  • the amine oxide unit of the polyamine N-oxides has a pKa ⁇ 10, preferably pKa ⁇ 7, more preferred pKa ⁇ 6.
  • Any polymer backbone can be used as long as the amine oxide polymer formed is water-soluble and has dye transfer inhibiting properties.
  • suitable polymeric backbones are polyvinyls, polyalkylenes, polyesters, polyethers, polyamide, polyimides, polyacrylates and mixtures thereof. These polymers include random or block copolymers where one monomer type is an amine N-oxide and the other monomer type is an N-oxide.
  • the amine N-oxide polymers typically have a ratio of amine to the amine N-oxide of 10: 1 to 1 : 1,000,000. However, the number of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate copolymerization or by an appropriate degree of N-oxidation.
  • the polyamine oxides can be obtained in almost any degree of polymerization Typically, the average molecular weight is within the range of 500 to 1,000,000; more preferred 1,000 to 500,000; most preferred 5,000 to 100,000. This preferred class of materials can be referred to as "PVNO".
  • the most preferred polyamine N-oxide useful in the detergent compositions herein is poly(4-vinylpyridine-N-oxide) which as an average molecular weight of about 50,000 and an amine to amine N-oxide ratio of about 1.4.
  • Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers are also preferred for use herein.
  • the PVPVI has an average molecular weight range from 5,000 to 1,000,000, more preferably from 5,000 to 200,000, and most preferably from 10,000 to 20,000. (The average molecular weight range is determined by light scattering as described in Barth, et al.. Chemical Analysis. Vol 1 13.
  • the PVPVI copolymers typically have a molar ratio of N-vinylimidazole to N-vinylpyrroIidone from 1 1 to 0 2 1, more preferably from 0 8 1 to 0 3 1, most preferably from 0 6 1 to 0 4 1
  • These copolymers can be either linear or branched.
  • compositions also may employ a polyvinylpyrrolidone ("PVP") having an average molecular weight of from about 5,000 to about 400,000, preferably from about 5,000 to about 200,000, and more preferably from about 5,000 to about 50,000 PVP's are known to persons skilled in the detergent field, see, for example, EP-A-262,897 and EP-A-256,696, incorporated herein by reference
  • PVP polyvinylpyrrolidone
  • Compositions containing PVP can also contain polyethylene glycol (“PEG”) having an average molecular weight from about 500 to about 100,000, preferably from about 1,000 to about 10,000
  • the ratio ' of PEG to PVP on a ppm basis delivered in wash solutions is from about 2: 1 to about 50.1, and more preferably from about 3 1 to about 10 1
  • the detergent compositions herein may also optionally contain from about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners which also provide a dye transfer inhibition action. If used, the compositions herein will preferably comprise from about 0.01% to 1% by weight of such optical brighteners.
  • hydrophilic optical brighteners useful in the present invention are those having the structural formula.
  • R j is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl
  • R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphilino, chJoro and amino
  • M is a salt-forming cation such as sodium or potassium.
  • R ⁇ is anilino
  • R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium
  • the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis- hydroxyethyl)-s-triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt
  • Tinopal-UNPA-GX is commercially marketed under the tradename Tinopal-UNPA-GX by Ciba-Geigy Corporation Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein.
  • R ⁇ is anilino
  • R2 is N-2-hydroxyethyl-N-2- methylamino
  • M is a cation such as sodium
  • the brightener is 4,4'-bis[(4-aniiino-6- (N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid disodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal 5BM-GX by Ciba-Geigy Corporation.
  • K ⁇ is anilino
  • R2 is morphilino
  • M is a cation such as sodium
  • the brightener is 4,4'-bis[(4-anilino-6-morphilino-s-triazine-2- yl)amino]2,2'-stilbenedisulfonic acid, sodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal AMS-GX by Ciba Geigy
  • the specific optical brightener species selected for use in the present invention provide especially effective dye transfer inhibition performance benefits when used in combination with the selected polymeric dye transfer inhibiting agents hereinbefore described.
  • the combination of such selected polymeric materials (e.g., PVNO and/or PVPVI) with such selected optical brighteners (e.g., Tinopal UNPA-GX, Tinopal 5BM-GX and/or Tinopal AMS-GX) provides significantly better dye transfer inhibition in aqueous wash solutions than does either of these two detergent composition components when used alone.
  • such brighteners WO ⁇ K this way because they have high affinity for fabrics in the wash solution and therefore deposit relatively quick on these fabrics.
  • the extent to which brighteners deposit on fabrics in the wash solution can be defined by a parameter called the "exhaustion coefficient".
  • the exhaustion coefficient is in general as the ratio of a) the brightener material deposited on fabric to b) the initial brightener concentration in the wash liquor. Brighteners with relatively high exhaustion coefficients are the most suitable for inhibiting dye transfer in the context of the present invention.
  • Brightener Any optical brighteners or other brightening or whitening agents known in the art can be incorporated at levels typically from about 0.05% to about 1.2%, by weight, into the detergent compositions herein.
  • Commercial optical brighteners which may be useful in the present invention can be classified into subgroups, which include, but are not necessarily limited to, derivatives of stilbene, pyrazoline, coumarin, carboxylic acid, methinecyanines, dibenzothiphene-5,5-dioxide, azoles, 5- and 6-membered-ring heterocycles, and other miscellaneous agents. Examples of such brighteners are disclosed in "The Production and Application of Fluorescent Brightening Agents", M.
  • optical brighteners which are useful in the present compositions are those identified in U S Patent 4,790,856, issued to Wixon on December 13, 1988 These brighteners include the PHORWHITE series of brighteners from Verona Other b ⁇ ghteners disclosed in this reference include Tinopal UNPA, Tinopal CBS and Tinopal 5BM, available from Ciba-Geigy, Artie White CC and Artie White CWD, available from Hilton-Davis, located in Italy, the 2- (4-stryI-phenyl)-2H-napthol[ l,2-d]triazoles, 4,4'-bis- (l,2,3-triazol-2-yl)-stilbenes, 4,4'-bis(stryl)bisphenyls, and the aminocoumarins Specific examples of these brighteners include 4-methyl-7-diethyl- amino coumarin, l,2-bis(-venzimidazol-2-
  • compositions herein may be in the form of granules, liquids, bars, and the like, and typically are formulated to provide an in-use pH in the range of 9 to 11
  • Various carriers such as sodium sulfate, water, water-ethanol, sodium carbonate, and the like, may be used routinely to formulate the finished products
  • Granules may be produced by spray-drying or by agglomeration, using known techniques, to provide products in the density range of 350-950 g/1
  • the compositions may also contain conventional perfumes, bactericides, hydrotropes and the like
  • conventional auxiliary builders such as citrate, zeolites (e.g., zeolites A, P, X and MAP), layered silicates (e g., SKS-6, Hoechst) and the like can be used in the present composition at levels from 1% to 50%
  • zeolites e.g., zeolites A, P, X and MAP
  • layered silicates e g
  • Lipase (Lipolase 165 KLU) 0 2 0 1 0 2
  • a laundry bar suitable for hand- washing soiled fabrics is prepared by standard extrusion processes and comprises the following:
  • a liquid laundry detergent with improved grease/oil ⁇ at 70°F (21°C) is as follows
  • N-(3-methoxypropyl) material may be substituted for the N-methyl material
  • N-hexyl material may be used.
  • composition is designed for use at 0.39 cup (92 4 mis) in a conventional U S top-loading automatic washing machine, or its equivalent
  • a liquid laundry detergent composition suitable for use at the relatively high concentrations common to front-loading automatic washing machines, especially in Europe, and over a wide range of temperatures is as follows
  • Oleoyl sarcosinate Na 10 0
  • Soil release polymer 10 0.2 Silicone (suds control) ⁇ 0 4
  • ⁇ Silane corrosion inhibitor available as A1130 from Union Carbide or DYNASYLAN TRIAMINO from HOls.
  • Polyester per U.S. Patent 4,711,730.
  • 1 Silicone suds control agent available as Q2-3302 from Dow Corning.
  • l Dispersant for silicone suds control agent available as DC-3225C from Dow Coming.
  • automatic dishwashing compositions will typically employ low- sudsing, mainly nonionic surfactants such as the well-known polymers of ethylene oxide (EO), propylene oxide (PO) and mixed EP-PO copolymers. Usage levels of such surfactants are typically rather low, generally from about 0.5% to about 5%, by weight of automatic dishwashing compositions.
  • EO ethylene oxide
  • PO propylene oxide
  • EP-PO copolymers ethylene oxide
  • Usage levels of such surfactants are typically rather low, generally from about 0.5% to about 5%, by weight of automatic dishwashing compositions.
  • An example of a typical automatic dishwashing composition is as follows.

Abstract

L'éthylènediamine disuccinate (EDDS) est utilisé dans des compositions détergentes en tant qu'adjuvant. L'enlèvement de la graisse/huile est assuré de manière plus efficace au moyen d'agents tensioactifs choisi parmi des agents cationiques hydrosolubles, des amides d'acide gras polyhydroxy et du sarcosinate d'oléoyle. Des détergents liquides, en pain et en granules sont décrits.
PCT/US1995/010519 1994-08-26 1995-08-18 Ethylenediamine disuccinate utilise comme detergent WO1996006908A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997034984A1 (fr) * 1996-03-21 1997-09-25 Unilever Plc Compositions detergentes contenant des agents sequestrants diaminoalkyle disulfosuccinate
KR20100039856A (ko) * 2007-07-26 2010-04-16 이노스펙 리미티드 조성물
WO2010069905A1 (fr) * 2008-12-19 2010-06-24 Henkel Ag & Co. Kgaa Détergent pour lave-vaisselle
JP2014227445A (ja) * 2013-05-20 2014-12-08 ライオン株式会社 食器洗い機用洗浄剤

Citations (5)

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Publication number Priority date Publication date Assignee Title
US4704233A (en) * 1986-11-10 1987-11-03 The Procter & Gamble Company Detergent compositions containing ethylenediamine-N,N'-disuccinic acid
WO1994003572A1 (fr) * 1992-08-01 1994-02-17 Procter & Gamble Company Compositions detersives
WO1994003554A1 (fr) * 1992-08-01 1994-02-17 The Procter & Gamble Company Compositions de blanchiment detersives, contenant un additif de silicate a couches et du percarbonate, stabilisees par acide ethylenediamine-n,n'-disuccinique
EP0598693A1 (fr) * 1992-11-16 1994-05-25 The Procter & Gamble Company Emulsions stables d'agents tensioactifs non-ioniques contenant un agent de contrôle de la viscosité
EP0659871A1 (fr) * 1993-12-23 1995-06-28 The Procter & Gamble Company Compositions de rinçage

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4704233A (en) * 1986-11-10 1987-11-03 The Procter & Gamble Company Detergent compositions containing ethylenediamine-N,N'-disuccinic acid
WO1994003572A1 (fr) * 1992-08-01 1994-02-17 Procter & Gamble Company Compositions detersives
WO1994003554A1 (fr) * 1992-08-01 1994-02-17 The Procter & Gamble Company Compositions de blanchiment detersives, contenant un additif de silicate a couches et du percarbonate, stabilisees par acide ethylenediamine-n,n'-disuccinique
EP0598693A1 (fr) * 1992-11-16 1994-05-25 The Procter & Gamble Company Emulsions stables d'agents tensioactifs non-ioniques contenant un agent de contrôle de la viscosité
EP0659871A1 (fr) * 1993-12-23 1995-06-28 The Procter & Gamble Company Compositions de rinçage

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997034984A1 (fr) * 1996-03-21 1997-09-25 Unilever Plc Compositions detergentes contenant des agents sequestrants diaminoalkyle disulfosuccinate
KR20100039856A (ko) * 2007-07-26 2010-04-16 이노스펙 리미티드 조성물
KR101555388B1 (ko) 2007-07-26 2015-09-23 이노스펙 리미티드 조성물
KR101579324B1 (ko) 2007-07-26 2015-12-21 이노스펙 리미티드 조성물
WO2010069905A1 (fr) * 2008-12-19 2010-06-24 Henkel Ag & Co. Kgaa Détergent pour lave-vaisselle
US8268768B2 (en) 2008-12-19 2012-09-18 Henkel Ag & Co. Kgaa Automatic dishwashing agent
JP2014227445A (ja) * 2013-05-20 2014-12-08 ライオン株式会社 食器洗い機用洗浄剤

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