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WO1995033043A1 - Compositions de blanchiment comprenant des tensioactifs de type sarcosinate d'oleoyle - Google Patents

Compositions de blanchiment comprenant des tensioactifs de type sarcosinate d'oleoyle Download PDF

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Publication number
WO1995033043A1
WO1995033043A1 PCT/US1995/006296 US9506296W WO9533043A1 WO 1995033043 A1 WO1995033043 A1 WO 1995033043A1 US 9506296 W US9506296 W US 9506296W WO 9533043 A1 WO9533043 A1 WO 9533043A1
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WO
WIPO (PCT)
Prior art keywords
bleach
bleaching
compositions
valerolactam
caprolactam
Prior art date
Application number
PCT/US1995/006296
Other languages
English (en)
Inventor
Suzanne Powell
Christian Leo Marie Vermote
Barry Thomas Ingram
Original Assignee
The Procter & Gamble Company
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Filing date
Publication date
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to DE69513974T priority Critical patent/DE69513974D1/de
Priority to AT95919235T priority patent/ATE187766T1/de
Priority to EP95919235A priority patent/EP0763096B1/fr
Priority to AU25177/95A priority patent/AU2517795A/en
Priority to MX9606047A priority patent/MX9606047A/es
Priority to JP8500949A priority patent/JPH10501566A/ja
Priority to BR9507831A priority patent/BR9507831A/pt
Publication of WO1995033043A1 publication Critical patent/WO1995033043A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3932—Inorganic compounds or complexes
    • 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
    • C11D1/10—Amino carboxylic acids; Imino carboxylic acids; Fatty acid condensates 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds

Definitions

  • the present invention relates to cleaning and bleaching compositions which employ oleoyl sarcosinate surfactants to boost performance. Bleaching, fabric laundering, automatic dishwashing and sanitizing compositions with improved oxygen bleach activity are provided.
  • formulators of cleaning compositions to include bleaching agents such as sodium perborate or sodium percarbonate in such compositions for their bleach effect. Such bleaches are widely recognized for their ability to remove various stains and soils from fabrics.
  • formulators of automatic dishwashing compositions have found that various bleaching agents can assist in the removal of tea stains, proteinaceous soils, and the like, from dishware.
  • Various fabric bleach and/or pre-soaking compositions also comprise percarbonate or perborate bleaches.
  • bleaching agents do not function optimally under all usage conditions.
  • perborate and percarbonate bleaches are more effective in hot water than in cold.
  • bleach activators typically comprise organic molecules which interact with perborate or percarbonate to release "per-acid" bleaching species.
  • the combination of bleach-plus-activator functions well over a wide range of water temperatures and usage conditions.
  • transition metal cations such as manganese, have the potential to function as bleach activators, presumably by virtue of their catalytic interaction with peroxide or per-acid bleaching species.
  • compositions seem to deter fabric damages caused by the peracids, catalysts and bleach activators.
  • the oleoyl sarcosinate is particularly effective at solubilizing the bleaching compounds and dispersing it throughout the wash liquor, especially at cooler temperatures (less than about 60°C). Thus, the precipitation of bleaching compounds in the wash liquor is reduced.
  • Oleoyl sarcosinate is described in the following patents and publications: U.S. 2,542,385; U.S. 3,402,990; U.S. 3,639,568; U.S. 4,772,424; U.S. 5, 186,855; European Patent Publication 505,129; British Patent Publication 1,211,545; Japanese Patent Publication 59/232194; Japanese Patent Publication 62/295997; Japanese Patent Publication 02/18081 1 ; and Chemical Abstracts Service abstracts No.s 61:3244q, 70:58865x, and 83:181020p.
  • amido-derived bleach activators in laundry detergents is described in U.S. Patent 4,686,063 and U.S. Patent 4,634,551.
  • 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.
  • the present invention encompasses bleach compositions comprising oleoyl sarcosinate surfactant and a bleaching agent.
  • the present invention also encompasses bleach compositions comprising oleoyl sarcosinate surfactant, a bleaching agent, especially a bleach which is a member selected from the group consisting of H2O2, perborate, percarbonate, persulfate and peracid bleaches, and one or more selected bleach activators.
  • a bleaching agent especially a bleach which is a member selected from the group consisting of H2O2, perborate, percarbonate, persulfate and peracid bleaches, and one or more selected bleach activators.
  • Preferred bleaching agents comprise percarbonate or perborate bleach, or mixtures thereof.
  • Preferred bleach activators are selected from acyl lactam-type activators, amido-derived activators, benzoaxin-type activators, tetraacetylethylene-diamine (TAED), alkanoyloxybenzenesulfonates, including nonanoyloxybenzene-sulfonate (NOBS), and benzoyloxybenzenesulfo ⁇ ate (BOBS), and mixtures thereof.
  • Peracids may also be included in the present compositions.
  • Suitable peracids include amido peracids, cationic peracids, nonylamide of peroxyadipic acid (NAPAA), and mixtures thereof Additionally, the present invention further encompasses bleach compositions comprising oleoyl sarcosinate surfactant, a bleaching agent, one or more selected bleach activators, and a catalytically-effective amount of one or more bleach catalysts, especially metal bleach catalysts
  • Preferred activators which are optionally employed in the present invention include benzoyl caprolactam, nonanoyl caprolactam, benzoyl valerolactam, nonanoyl valerolactam, 3,5,5-trimethylhexanoyI caprolactam, 3,5,5-trimethyl-hex- anoyl valerolactam, octanoyl caprolactam, octanoyl valerolactam, decanoyl caprolactam, decanoyl valerolactam, undecenoyl caprolactam, undecenoyl valerol ⁇ actam, (6-octanamidocaproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)-oxy- benzenesulfonate, (6-decanamidocaproyl)oxybenzenesulfonate, nonanoyloxy-ben- zenesulfonate, benzoy
  • Examples of highly preferred substituted benzoyl lactams include methylbenzoyl caprolactam, methylbenzoyl valerolactam, ethylbenzoyl caprolac ⁇ tam, ethylbenzoyl valerolactam, propylbenzoyl caprolactam, propylbenzoyl valerol- actam, isopropylbenzoyl caprolactam, isopropylbenzoyl valerolactam, butylbenzoyl caprolactam, butylbenzoyl valerolactam, tert-butylbenzoyl caprolactam, tert- butylbenzoyl valerolactam, pentylbenzoyl caprolactam, pentylbenzoyl valerolactam, hexylbenzoyl caprolactam, hexylbenzoyl valerolactam, ethoxybenzoyl caprolactam, e
  • bleach activators selected from the group consist ⁇ ing of benzoyl caprolactam, benzoyl valerolactam, nonanoyl caprolactam, nonanoyl valerolactam, 4-nitrobenzoyl caprolactam, 4-nitrobenzoyl valerolactam, octanoyl caprolactam, octanoyl valerolactam, decanoyl caprolactam, decanoyl valerolactam, undecenoyl caprolactam, undecenoyl valerolactam, 3,5,5-trimethyl-hexanoyl caprolactam, 3,5,5-trimethylhexanoyl valerolactam, dinitrobenzoyl capro-lactam, dinitrobenzoyl valerolactam, terephthaloyl dicaprolactam, terephthaloyl divalerolac ⁇ tam, (6-octanamidocaproyl)
  • the molar ratio of hydrogen peroxide yielded by the peroxygen bleaching compound to bleach activator is greater than about 1.0. Most preferably, the molar ratio of hydrogen peroxide to bleach activator is at least about 1.5.
  • Preferred compositions herein are those wherein the bleach catalyst is a metal-based catalyst.
  • the invention also encompasses detergent compositions, especially laundry detergents, comprising otherwise conventional surfactants and other detersive ingredients.
  • the invention also encompasses detergent or bleach compositions comprising oleoyl sarcosinate surfactant, a bleaching agent, and a catalytically effective amount of a water-soluble manganese salt.
  • the invention also encompasses a method for improving the bleaching performance of oxygen or per-acid bleach compositions, comprising adding thereto oleoyl sarcosinate surfactant in the presence of selected ligands and a catalytically effective amount of manganese cations.
  • This provides a method for removing stains from fabrics, comprising contacting said fabrics with an aqueous medium comprising said compositions.
  • compositions comprise oleoyl sarcosinate, in its acid and/or salt form selected as desired for the compositions and uses herein, having the following formula:
  • M is hydrogen or a cationic moiety.
  • M are hydrogen and alkali metal salts, especially sodium and potassium.
  • Oleoyl sarcosinate is commercially available, for example as Hamposyl O supplied by W. R. Grace & Co.
  • Bleaching compositions according to the present invention comprise at least about 0.1%, typically from about 0.1% to about 55%, preferably from about 1% to about 20%, and most preferably from about 3% to about 15%, of oleoyl sarcosinate by weight of the composition.
  • oleoyl sarcosinate useful herein can also preferably be prepared from the ester (preferably the methyl ester) of oleic acid and a sarcosine salt (preferably the sodium salt) under anhydrous reaction conditions in the presence of a base catalyst with a basicity equal to or greater than alkoxide catalyst (preferably sodium methoxide).
  • a base catalyst with a basicity equal to or greater than alkoxide catalyst preferably sodium methoxide
  • This salt may optionally be neutralized to form the oleoyl sarcosinate in its acid form.
  • the preferred method for preparing oleoyl sarcosinate is conducted at a temperature from about 80°C to about 200°C, especially from about 120°C to about 200°C. It is preferred to conduct the reaction without solvent although alcohol solvents which have a boiling point of at least 100°C and are stable to the reaction conditions (ie. glycerol is not acceptable) can be used.
  • the reaction may proceed in about 85% yield with a molar ratio of methyl ester reactant to sarcosine salt reactant to basic catalyst of about 1 : 1 :0.05-0.2.
  • Methyl ester mixtures derived from high oleic content natural oils are especially preferred as starting materials. Examples include high-oleic sunflower and rapeseed/canola oil. In addition, a high- oleic methyl ester fraction derived from either palm kernel oil or tallow is acceptable. It is to be understood that such oils typically will contain some levels of impurities, including some fatty acid impurities that may be converted to sarcosinate compounds by this synthesis method.
  • commodity canola rapeseed oil may comprise a majority of oleic acid, and a mixture of fatty acid impurities such as palmitic, stearic, linoleic, linolenic and/or eicosenoic acid, some or all of which are converted to the sarcosinate by this reaction method. If desired for formulation purposes, some or all of such impurity materials may be excluded from the starting oil before preparing the oleoyl sarcosinate to be used in the present compositions.
  • sarcosine remaining in the reaction mixture can be converted to an amide by addition of maleic or acetic anhydride to the mixture, thereby minimizing the sarcosine content and any potential for formation of undesired nitrogen- containing impurities.
  • the synthesis of oleoyl sarcosinate may be carried out as follows to prepare the sodium oleoyl sarcosinate.
  • reaction mixture is heated to 170°C for 1 hr to drive off any water.
  • the reaction is initiated by the addition of sodium methoxide 25% in methanol (15.4 g, 0.0714 mol). Reaction is kept at 170°C for 2.5 hr during which methanol is collected in the Dean-Stark trap. The reaction is allowed to cool slightly and then methanol (200 g) is added. Maleic anhydride (9.43 g, 0.095 mol) is added to the methanol solution and the reaction is stirred at 60°C for 0.5 hr. Then most of the methanol is removed by rotary evaporation and acetone (2 L) is added to precipitate the product.
  • the product is collected by suction filtration and allowed to air dry to give an off-white solid. Analysis of the reaction mixture by GC indicates the majority of the product is oleoyl sarcosinate, with minor amounts of the following impurities: sarcosine, oleic acid, and the sarcosinates derived from palmitic acid, stearic acid, and linoleic acid.
  • bleaching compositions herein also contain bleaching agents or bleaching mixtures containing a bleaching agent and one or more bleach activators, in an amount sufficient to provide bleaching of the stain or stains of interest.
  • Bleaching agents will typically be at levels of from about % to about 80%, more typically from about 5% to about 20%, of the detergent composition, especially for fabric laundering.
  • Bleach and pre-soak compositions may comprise from 5% to 99% of the bleaching agent. 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 mixture 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 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.
  • Peroxygen bleaching agents are preferably used in the compositions. 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.
  • compositions of the present invention may also comprise mixtures of bleaching activators.
  • 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.
  • Alkanoyloxybenzenesulfonates - Suitable alkanoyloxybenzenesulfonate bleach activators which can be employed in the present invention are of the formula:
  • R -C(O)- contains from about 8 to about 12, preferably from about 8 to about 1 1, carbon atoms and M is a suitable cation, such as an alkali metal, ammonium, or substituted ammonium cation, with sodium and potassium being most preferred.
  • hydrophobic alkanoyloxybenzenesulfonates are selected from the group consisting of nonanoyloxybenzenesulfonate, 3,5,5-trimethylhexanoyl- oxybenzenesulfonate, 2-ethylhexanoyloxybenzenesulfonate, octanoyloxybenzenesul- fonate, decanoyloxybenzenesulfonate, dodecanoyloxybenzenesulfonate, and mixtures thereof.
  • Amido Derived Bleach Activators The amido derived bleach activators which can be employed in the present invention are amide substituted compounds of the general formulas'
  • R is an alkyl, aryl, or alkaryl group containing from
  • R is an alkylene, arylene or alkarylene group containing from about 1 to about 14 carbon atoms
  • R is H or an alkyl, aryl, or alkaryl group containing from about 1 to about 10 carbon atoms
  • L is essentially any suitable leaving group
  • a leaving group is any group that is displaced from the bleaching activator as a consequence of the nucleophilic attack on the bleach activator by the perhydroxide anion. This, the perhydrolysis reaction, results in the formation of the peroxycarboxylic acid.
  • a group to be a suitable leaving group it must exert an electron attracting effect. It should also form a stable entity so that the rate of the back reaction is negligible. This facilitates the nucleophilic attack by the perhydrox.... r.ion.
  • the L group must be sufficiently reactive for the reaction to occur within the optimum time frame (e.g., a wash cycle). However, if L is too reactive, this activator will be difficult to stabilize for use in a bleaching composition.
  • pKa of the conjugate acid of the leaving group although exceptions to this convention are known. Ordinarily, leaving groups that exhibit such behavior are those in which their conjugate acid has a pKa in the range of from about 4 to about 13, preferably from about 6 to about 11 and most preferably from about 8 to about 11.
  • Preferred bleach activators are those of the above general formula wherein R 1 , R ?2 aanndd RR 5 are as defined for the peroxyacid and L is selected from the group consisting of:
  • R is an alkyl, aryl, or alkaryl group containing from about I to about 14 carbon atoms, R is an alkyl chain containing from 1 to about
  • R 4 is H or R 3
  • Y is H or a solubilizing group.
  • the preferred solubilizing groups are -SO-, M , -CO- M , -SO, M ,
  • R is an alkyl chain containing from about 1 to about 4 carbon atoms
  • M is a cation which provides solubility to the bleach activator
  • X is an anion which provides solubility to the bleach activator.
  • M is an alkali metal, ammonium or substituted ammonium cation, with sodium and potassium being most preferred
  • X is a halide, hydroxide, methylsulfate or acetate anion.
  • Preferred bleach activators are those of the above general formula wherein L is selected from the group consisting of:
  • R is as defined above and Y is -SO-, " M or -C0 2 " M wherein M is as defined above.
  • bleach activators of the above formulae include (6- octanamidocaproyl)oxybenzenesulfonate, ( ⁇ -nonanamidocaproyl)oxybenzenesulfo- nate, (6-decanamidocaproyl)oxybenzenesulfonate, and mixtures thereof.
  • Another important class of bleach activators provide organic peracids as described herein by ring-opening as a consequence of the nucleophilic attack on the carbonyl carbon of the cyclic ring by the perhydroxide anion. For instance, this ring-opening reaction in lactam activators involves attack at the lactam ring carbonyl by hydrogen peroxide or its anion.
  • ring-opening bleach activators can be found in activators, such as those disclosed in U.S. Patent 4,966,723, Hodge et al, issued Oct. 30, 1990.
  • Such activator compounds disclosed by Hodge include the activators of the benzoxazi ⁇ -type, having the formula:
  • R is H, alkyl, alkaryl, aryl, arylalkyl, and wherein R ⁇ , R ⁇ >, R 4 , and Re may be the same or different substituents selected from H, halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxyl, amino, alkyl amino, COOR 6 (wherein R 6 is H or an alkyl group) and carbonyl functions.
  • a preferred activator of the benzoxazin-type is:
  • washing solutions wherein the pH of such solution is between about 8.5 and 10.5 and preferably between 9.5 and 10.5 in order to facilitate the perhydrolysis reaction.
  • pH can be obtained with substances commonly known as buffering agents, which are optional components of the bleaching systems herein.
  • Still another class of preferred bleach activators includes the acyl lactam activators, especially acyl caprolactams and acyl valerolactams of the formulae:
  • R ⁇ is H, an alkyl, aryl, alkoxyaryl, or alkaryl group containing from 1 to about 12 carbon atoms, or a substituted phenyl group containing from about 6 to about 18 carbons.
  • R ⁇ is H, an alkyl, aryl, alkoxyaryl, or alkaryl group containing from 1 to about 12 carbon atoms, or a substituted phenyl group containing from about 6 to about 18 carbons.
  • activators which may also comprise the bleach compositions disclosed herein include those in U.S. Patent 4,915,854, issued April 10, 1990 to Mao et al, and U.S. Patent 4,412,934. See also U.S. 4,634,551 for other typical bleaches and activators useful herein.
  • bleaching agent Another optional, yet preferable, category of 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 (INTEROX), the magnesium salt of metachloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid.
  • INTEROX magnesium monoperoxyphthalate hexahydrate
  • Such bleaching agents are disclosed in U.S. Patent 4,483,781, Hartman, issued November 20, 1984; U.S. Pat. App. 740,446, Burns et al, filed June 3, 1985; European Pat. App. 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
  • Suitable amidoperoxyacids are of the formula:
  • R5 R5 wherein R 1 , R2 , and R 5 are as defined for the amido-derived type bleach activators described above.
  • Preferred organic peroxyacids are selected from the group consisting of 4- nonylamino-4-oxoperoxybutyric acid; 6-(nonyl-amino)-6-oxoperoxycaproic acid; decylsulphonylperpropionic acid; and heptyl, octyl-, nonyl-, decyl-sulphonyl- perbutyric acid; and mixtures thereof.
  • Example 1 of U.S. Pat. 4,686,063 contains one description of the synthesis fo NAPSA, from col. 8, line 40 to col. 9, line 5, and NAPAA, from col. 9 line 15 to col. 9, line 65.
  • the superior bleaching/cleaning action of the present compositions is achieved with safety to natural rubber machine parts and other natural rubber articles, including fabrics containing natural rubber and natural rubber elastic materials.
  • the bleaching mechanism and, in particular, the surface bleaching mechanism are not completely understood. However, it is generally believed that the bleach activator undergoes nucleophilic attack by a perhydroxide anion, which is generated from the hydrogen peroxide evolved by the peroxygen bleach, to form a peroxycarboxylic acid. This reaction is commonly referred to as perhydrolysis.
  • amido-derived and lactam bleach activators herein can also be used in combination with rubber-safe, enzyme-safe, hydrophilic activators such as TAED, typically at weight ratios of amido-derived or caprolactam activators:TAED in the range of 1:5 to 5: 1, preferably about 1 : 1.
  • TAED rubber-safe, enzyme-safe, hydrophilic activators
  • the bleach catalyst material used herein can comprise the free acid form, the salts, and the like. It is to be appreciated that the bleach catalyst does not function as a bleach by itself. Rather, it is used as a catalyst to enhance the performance of conventional bleaches and, in particular, oxygen bleaches such as perborate, percarbonate, persulfate, and the like, especially in the presence of bleach activators.
  • One type of bleach catalyst is a catalyst system comprising a heavy metal cation of defined bleach catalytic activity, such as copper, iron or manganese cations, an auxiliary metal cation having little or no bleach catalytic activity, such as zinc or aluminum cations, and a sequestrant having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra(methylenephosphonic acid) and water-soluble salts thereof.
  • a heavy metal cation of defined bleach catalytic activity such as copper, iron or manganese cations
  • an auxiliary metal cation having little or no bleach catalytic activity such as zinc or aluminum cations
  • a sequestrant having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra(methylenephosphonic acid) and water-soluble salts thereof.
  • bleach catalysts include the manganese-based complexes disclosed in U.S. Pat. 5,246,621 and U.S. Pat. 5,244,594. Preferred examples of these catalysts include Mn ⁇ V 2( u -0)3( ⁇ 4 > ⁇ "methyl- 1,4, 7-triazacyclononane)2- (PFgt ⁇ , Mn ⁇ i 2(u-O) i (u-OAc)2( 1 ,4,7-trimethyl- 1 ,4,7-triazacyclononane)2 (004)2, Mn IV 4 (u-O)6( 1 ,4,7-triazacyclononane)4(ClO )4, Mn ⁇ Mn IV 4 (u-O) ] (u-OAc) 2 .
  • ligands suitable for use herein include l,5,9-trimethyl- l ,5,9-triazacycIododecane, 2-methyl-l,4,7-triaza- cyclononane, 2-methyl- 1 ,4,7-triazacyclononane, 1 ,2,4,7-tetramethyl- 1 ,4,7-triaza- cyclononane, and mixtures thereof.
  • bleach catalysts useful in machine dishwashing compositions and concentrated powder detergent compositions may also be selected as appropriate for the present invention.
  • suitable bleach catalysts see U.S. Pat. 4,246,612 and U.S. Pat. 5,227,084. See also U.S. Pat. 5, 194,416 which teaches mononuclear manganese (IV) complexes such as Mn IV (l,4,7-trimethyl-l,4,7-triazacyclononane)- (OQ ⁇ PFg).
  • Still another type of bleach catalyst is a water-soluble complex of manganese (II), (III), and/or (IV) with a ligand which is a non-carboxylate polyhydroxy compound having at least three consecutive C-OH groups.
  • Preferred ligands include sorbitol, iditol, dulsitol, mannitol, xylithol, arabitol, adonitol, meso-erythritol, meso-inositol, lactose, and mixtures thereof.
  • U.S. Pat. 5,1 14,61 1 teaches a bleach catalyst comprising a complex of transition metals, including Mn, Co, Fe, or Cu, with an non-(macro)-cyclic ligand.
  • Said ligands are of the formula: R2 R3
  • Preferred ligands include pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole, and triazole rings.
  • said rings may be substituted with substituents such as alkyl, aryl, alkoxy, halide, and nitro.
  • Particularly preferred is the ligand 2,2'-bispyridylamine.
  • Preferred bleach catalysts include Co, Cu, Mn, Fe,-bispyridylmethane and -bispyridylamine complexes.
  • Highly preferred catalysts include Co(2,2'-bispyridylamine)Cl2, Di(isothiocyanato)bispyridylamine-coba!t (II), trisdipyridylamine-cobalt(II) per- chlorate, Co(2,2-bispyridylamine)2.
  • O2CIO4 Bis-(2 1 2'-bispyridylamine) copper(II) perchlorate, tris(di-2-pyridyl-amine) iron(II) perchlorate, and mixtures thereof.
  • the bleach catalysts of the present invention may also be prepared by combining a water-soluble ligand with a water-soluble manganese salt in aqueous media and concentrating the resulting mixture by evaporation. Any convenient water-soluble salt of manganese can be used herein.
  • Manganese (II), (III), (IV) and/or (V) is readily available on a commercial scale. In some instances, sufficient manganese may be present in the wash liquor, but, in general, it is preferred to add Mn cations in the compositions to ensure its presence in cataiytically-effective amounts.
  • the sodium salt of the ligand and a member selected from the group consisting of MnS04, n(ClO4)2 or MnCb (least preferred) are dissolved in water at molar ratios of ligand:Mn salt in the range of about 1 :4 to 4: 1 at neutral or slightly alkaline pH.
  • the water may first be de-oxygenated by boiling and cooled by sparging with nitrogen.
  • the resulting solution is evaporated (under N2, if desired) and the resulting solids are used in the bleaching and detergent compositions herein without further purification.
  • the water-soluble manganese source such as MnSO4
  • MnSO4 is added to the bleach/cleaning composition or to the aqueous bleaching/cleaning bath which comprises the ligand.
  • Some type of complex is apparently formed in situ, and improved bleach performance is secured. In such an in situ process, it is convenient to use a considerable molar excess of the ligand over the manganese, and mole ratios of ligand:Mn typically are 3: 1 to 15: 1.
  • the additional ligand also serves to scavenge vagrant metal ions such as iron and copper, thereby protecting the bleach from decomposition.
  • One possible such system is described in European Pat. App. Pub. No. 549,271.
  • the bleach-catalyzing manganese-complexes of the present invention have not been elucidated, it may be speculated that they comprise chelates or other hydrated coordination complexes which result from the interaction of the carboxyl and nitrogen atoms of the ligand with the manganese cation.
  • the oxidation state of the manganese cation during the catalytic process is not known with certainty, and may be the (+11), (+III), (+IV) or (+V) valence state. Due to the ligands' possible six points of attachment to the manganese cation, it may be reasonably speculated that multi-nuclear species and/or "cage" structures may exist in the aqueous bleaching media. Whatever the form of the active Mn-ligand species which actually exists, it functions in an apparently catalytic manner to provide improved bleaching performances on stubborn stains such as tea, ketchup, coffee, blood, and the like.
  • bleach catalysts are described, for example, in European Pat. App. Pub. Nos. 408, 131 (cobalt complex catalysts), 384,503, and 306,089 (metallo-porphyrin catalysts), U.S. 4,728,455 (manganese/multidentate ligand catalyst), U.S. 4,711,748 and European Pat. App. Pub. No. 224,952, (absorbed manganese on aluminosilicate catalyst), U.S. 4,601,845 (aluminosilicate support with manganese and zinc or magnesium salt), U.S. 4,626,373 (manganese/ligand catalyst), U.S. 4, 119,557 (ferric complex catalyst), German Pat.
  • the bleach catalyst is used in a catalytically effective amount.
  • catalytically effective amount is meant an amount which is sufficient, under whatever comparative test conditions are employed, to enhance bleaching and removal of the stain or stains of interest from the target substrate.
  • the target substrate will typically be a fabric stained with, for example, various food stains.
  • the target substrate may be, for example, a porcelain cup or plate with tea stain or a polyethylene plate stained with tomato soup.
  • the test conditions will vary, depending on the type of washing appliance used and the habits of the user. Thus, front-loading laundry washing machines of the type employed in Europe generally use less water and higher detergent concentrations than do top-loading U.S.
  • 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.
  • compositions herein can optionally include one or more other detergent adjunct materials or other materials for assisting or enhancing cleaning performance, treatment of the substrate to be cleaned, or to modify the aesthetics of the detergent composition (e.g., perfumes, colorants, dyes, etc.).
  • other detergent adjunct materials e.g., perfumes, colorants, dyes, etc.
  • the following are illustrative examples of such adjunct materials.
  • Detersive Surfactants typically at levels from about 1% to about 55%, by weight, include the conventional C ⁇ i-Cjg alkyl benzene sulfonates ("LAS") and primary, branched-chain and random C10-C20 a ' sulfates ("AS"), the C io-Cjg secondary (2,3) alkyl sulfates of the formula CH3(CH2) x (CHOSO 3 " M + ) CH 3 and CH 3 (CH 2 ) y (CHOS ⁇ 3 " M + ) CH 2 CH 3 where x and (y + 1) 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 Cio-Cj alkyl alkoxy sulfates ("AE X S"; especially x up to about
  • LAS C ⁇ i-Cjg alkyl benzene sul
  • the conventional nonionic and amphoteric surfactants such as the C12-C18 alkyl ethoxyiates ("A£") including the so-called narrow peaked alkyl ethoxylates and C5- C12 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), Ci2-C] 8 betaines and sulfobetaines ("sultaines”), C ⁇ Q-C ⁇ g amine oxides, and the like, can also be included in the overall compositions.
  • the CiQ-C ⁇ N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include the C12- Cj N-methylglucamides. See WO 9,206,154.
  • sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as Cjo-Cig N-(3- methoxypropyl) 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 ]o-C ]6 soaps may be used. Mixtures of anio ⁇ ic and nonionic surfactants are especially useful. Other conventional useful surfactants are listed in standard texts.
  • Builders - Detergent builders can optionally be included in the compositions herein to assist in controlling mineral hardness. Inorganic as well as organic builders can be used. Builders are typically used in fabric laundering compositions to assist in the removal of particulate soils.
  • the level of builder can vary widely depending upon the end use of the composition and its desired physical form. When present, the compositions will typically comprise at least about 1% builder. Liquid formulations typically comprise from about 5% to about 50%, more typically about 5% to about 30%, by weight, of detergent builder Granular formulations typically comprise from about 10% to about 80%, more typically from about 15% to about 50% by weight, of the detergent builder Lower or higher levels of builder, however, are not meant to be excluded.
  • Inorganic or P-containing detergent builders include, but are not limited to, the alkali metal, ammonium and aikanolammonium salts of polyphosphates (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta- phosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates, and aluminosilicates.
  • polyphosphates exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta- phosphates
  • phosphonates phosphonates
  • phytic acid e.g., silicates
  • carbonates including bicarbonates and sesquicarbonates
  • sulphates sulphates
  • aluminosilicates aluminosilicates.
  • non-phosphate builders are required in some locales.
  • compositions herein function surprisingly well even in the presence of the so-called “weak” builders (as compared with phosphates) such as citrate, or in the so-called “underbuilt” situation that may occur with zeolite or layered silicate builders.
  • silicate builders are the alkali metal silicates, particularly those having a Si ⁇ 2:Na2 ⁇ ratio in the range 1.0.1 to 3.2: 1 and layered silicates, such as the layered sodium silicates described in U.S. Patent 4,664,839, issued May 12, 1987 to H. P. Rieck.
  • NaSKS-6 is the trademark for a crystalline layered silicate marketed by Hoechst (commonly abbreviated herein as "SKS-6").
  • Hoechst commonly abbreviated herein as "SKS-6”
  • the Na SKS-6 silicate builder does not contain aluminum.
  • NaSKS-6 has the delta- Na2Si ⁇ 5 morphology form of layered silicate.
  • SKS-6 is a highly preferred layered silicate for use herein, but other such layered silicates, such as those having the general formula NaMSi x ⁇ 2 x +j yH2 ⁇ wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0 can be used herein.
  • Various other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-1 1, as the alpha, beta and gamma forms.
  • delta-Na2Si ⁇ 5 (NaSKS-6 form) is most preferred for use herein.
  • Other silicates may also be useful such as for example magnesium silicate, which can serve as a crispening agent in granular formulations, as a stabilizing agent for oxygen bleaches, and as a component of suds control systems.
  • carbonate builders are the alkaline earth and alkali metal carbonates as disclosed in German Patent Application No. 2,321,001 published on November 15, 1973.
  • Aluminosilicate builders are useful in the present invention. Aluminosilicate builders are of great importance in most currently marketed heavy duty granular detergent compositions, and can also be a significant builder ingredient in liquid detergent formulations. Aluminosilicate builders include those having the empirical formula:
  • z and y are integers usually of at least 6, the molar ratio of z to y is in the range from 1.0 to 0, and x is an integer from 0 to about 264, and M is a Group IA or IIA element, e.g., Na, K, Mg, Ca with valence n.
  • aluminosilicate ion exchange materials are commercially available. These aluminosilicates can be crystalline or amorphous in structure and can be naturally-occurring aluminosilicates or synthetically derived. A method for producing aluminosilicate ion exchange materials is disclosed in U.S. Patent 3,985,669, Krummel, et al, issued October 12, 1976. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In an especially preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula:
  • Organic detergent builders suitable for the purposes of the present invention include, but are not restricted to, a wide variety of polycarboxylate compounds. As used herein, "polycarboxylate” refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates.
  • Polycarboxylate builder can generally be added to the composition in acid form, but can also be added in the form of a neutralized salt.
  • alkali metals such as sodium, potassium, and lithium, or alkanolammonium salts are preferred.
  • polycarboxylate builders include a variety of categories of useful materials.
  • One important category of polycarboxylate builders encompasses the ether polycarboxylates, including oxydisuccinate, as disclosed in Berg, U.S. Patent 3, 128,287, issued April 7, 1964, and Lamberti et al, U.S. Patent 3,635,830, issued January 18, 1972. See also "TMS/TDS" builders of U.S. Patent 4,663,071, issued to Bush et al, on May 5, 1987.
  • Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S.
  • Other useful detergency builders include the ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1, 3, 5- trihydroxy benzene-2, 4, 6-trisulphonic acid, and carboxymethyloxysuccinic acid, the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid, as well as polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.
  • Citrate builders e.g., citric acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders of particular importance for heavy duty liquid detergent formulations due to their availability from renewable resources and their biodegradability. Citrates can also be used in granular compositions, especially in combination with zeolite and/or layered silicate builders. Oxydisuccinates are also especially useful in such compositions and combinations.
  • succinic acid builders include the C5-C20 alkyl and alkenyl succinic acids and salts thereof.
  • a particularly preferred compound of this type is dodecenylsuccinic acid.
  • succinate builders include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2- dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like.
  • Laurylsuccinates are the preferred builders of this group, and are described in European Patent Application 86200690.5/0,200,263, published November 5, 1986.
  • Other suitable polycarboxylates are disclosed in U.S. Patent 4, 144,226, Crutchfield et al, issued March 13, 1979 and in U.S. Patent 3,308,067, Diehl, issued March 7, 1967. See also Diehl U.S. Patent 3,723,322.
  • Fatty acids e.g., Cj2-C ⁇ s monocarboxylic acids such as oleic acid and/or its salts
  • Cj2-C ⁇ s monocarboxylic acids such as oleic acid and/or its salts
  • oleic acid and/or its salts can also be incorporated into the compositions alone, or in combination with the aforesaid builders, especially citrate and/or the succinate builders, to provide additional builder activity.
  • Such use of fatty acids will generally result in a diminution of sudsing, which should be taken into account by the formulator.
  • the various alkali metal phosphates such as the well-known sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate can be used.
  • Phosphonate builders such as ethane- 1- hydroxy-l, l-diphosphonate and other known phosphonates (see, for example, U.S. Patents 3, 159,581; 3,213,030; 3,422,021; 3,400, 148 and 3,422, 137) can also be used.
  • 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, upases, 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%-2% 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. 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 trade name 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 tradenames 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).
  • 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).
  • Other proteases include Protease A (see European Patent Application 130,756, published January 9, 1985) and Protease B (see European Patent Application Serial No.
  • Protease C is a variant of an alkaline serine protease from Bacillus, particularly Bacillus lentus. in which arginine replaced lysine at position 27, tyrosine replaced valine at position 104, serine replaced asparagine at position 123, and alanine replaced threonine at position 274.
  • Protease C is described in EP 90915958:4; U.S. Patent No. 5, 185,250; and U.S. Patent No. 5,204,015.
  • protease which are described in copending application U.S. Serial No.
  • 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 hepato pancreas 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 upases 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 Upases include Amano-CES, Upases ex Chromobacter viscosum, e.g. Chromobacter viscosum var.
  • lipolyticum NRRLB 3673 commercially available from Toyo Jozo Co., Tagata, Japan; and further Chromobacter viscosum Upases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and Upases ex Pseudomonas gladioli.
  • the LIPOLASE enzyme derived from Humicola lanuginosa and commercially available from Novo is a preferred lipase for use herein.
  • 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.
  • 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. It may be desired to use, in combination with these peroxidases, materials viewed as being peroxidase accelerators such as phenolsulfonate and/or phenothiazine.
  • 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 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.
  • 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.
  • 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
  • such materials may also be used in formulations as the sole stabilizer as well as being used in combination with added calcium and/or magnesium ions.
  • 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) oxypropylene or polyoxypropylene segments with a degree of polymerization of from 2 to 10, wherein said hydrophile segment does not encompass any oxypropylene 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 oxypropylene 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 oxypropylene 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(vinyi ester), e.g., C ] -Cg vinyl esters, preferably poly(vinyl acetate) grafted onto polyalkylene oxide backbones, such as polyethylene oxide backbones.
  • poly(vinyi ester) e.g., C ] -Cg vinyl esters
  • poly(vinyl acetate) grafted onto polyalkylene oxide backbones such as polyethylene oxide backbones.
  • 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 MILEASE 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.
  • These 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
  • 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 3 1, 1989 to Maldonado et al, which discloses anionic, especially sulfoarolyl, end-capped terephthalate esters.
  • Still another preferred soil release agent is an oligomer with repeat units of terephthaloyl units, sulfoisoterephthaloyi 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.
  • 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%.
  • the detergent compositions herein may also optionally contain one or more iron and/or manganese chelating agents.
  • chelating agents can be selected from the group consisting of amino carboxylates, amino phosphonates, polyfiinctionally-substituted aromatic chelating agents and mixtures therein, all as hereinafter defined. Without intending to be bound by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove iron and manganese ions from washing solutions by formation of soluble chelates.
  • Amino carboxylates useful as optional chelating agents include ethylenediaminetetracetates, N-hydroxyethylethylenediaminetriacetates, nitrilotri- acetates, ethylenediamine tetraproprionates, triethylenetetraaminehexacetates, diethylene-triaminepentaacetates, and ethanoldiglycines, alkali metal, ammonium, and substituted ammonium salts therein and mixtures therein.
  • Amino phosphonates are also suitable for use as chelating agents in the compositions of the invention when at lease low levels of total phosphorus are permitted in detergent compositions, and include ethylenediaminetetrakis (methylenephosphonates) as DEQUEST. Preferred, these amino phosphonates to not contain alkyl or alkenyl groups with more than about 6 carbon atoms.
  • Polyfunctionally-substituted aromatic chelating agents are also useful in the compositions herein. See U.S. Patent 3,812,044, issued May 21, 1974, to Connor et al.
  • Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as l,2-dihydroxy-3,5-disulfobenzene.
  • EDDS ethylenediamine disuccinate
  • these chelating agents will generally comprise from about 0.1% to about 10% by weight of the detergent compositions herein. More preferably, if utilized, the chelating agents will comprise from about 0. 1% to about 3.0% by weight of such compositions.
  • Clav Soil Removal/Anti-redeposition Agents The 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 preferred 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.
  • CMC carboxy methyl cellulose
  • Polymeric Dispersing Agents can advantageously be utilized at levels from about 0.1% to about 7%, by weight, in the compositions herein. Suitable polymeric dispersing agents include polymeric polycarboxylates and polyethylene glycols, although others known in the art can also be used. Polymeric polycarboxylate materials can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid form.
  • Unsaturated monomeric acids that can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid.
  • the presence in the polymeric polycarboxylates herein or monomeric segments, containing no carboxylate radicals such as vinylmethyl ether, styrene, ethylene, etc. is suitable provided that such segments do not constitute more than about 40% by weight.
  • Particularly suitable polymeric polycarboxylates can be derived from acrylic acid.
  • acrylic acid-based polymers which are useful herein are the water-soluble salts of polymerized acrylic acid.
  • the average molecular weight of such polymers in the acid form preferably ranges from about 2,000 to 10,000, more preferably from about 4,000 to 7,000 and most preferably from about 4,000 to 5,000.
  • Water-soluble salts of such acrylic acid polymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble polymers of this type are known materials. Use of polyacrylates of this type in detergent compositions has been disclosed, for example, in Diehl, U.S. Patent 3,308,067, issued March 7, 1967.
  • Acrylic/maleic-based copolymers may also be used as a preferred component of the dispersing/anti-redeposition agent.
  • Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid.
  • the average molecular weight of such copolymers in the acid form preferably ranges from about 2,000 to 100,000.
  • a preferred copolymer has an average molecular weight of about 2,000 to 15,000, more preferably about 6,000 to about 13,000, and most preferably about 7,000 to about 12,000.
  • Other preferred copolymers have an average molecular weight from about 5,000 to 75,000, most preferably from about 7,000 to 65,000.
  • the ratio of acrylate to maleate segments in such copolymers will generally range from about 30: 1 to about 1 :2, more preferably from about 10: 1 to 1 : 1 , and most preferably about 2.5:1 to 1 : 1.
  • Water-soluble salts of such acrylic acid/maleic acid copolymers can include, for example, the alkali metal, ammonium and substituted ammonium salts.
  • Soluble acrylate/maleate copolymers of this type are known materials which are described in European Patent Application No. 66915, published December 15, 1982, as well as in EP 193,360, published September 3, 1986, which also describes such polymers comprising hydroxypropylacrylate.
  • Still other useful dispersing agents include the maleic/acrylic/vinyl alcohol terpolymers.
  • Such materials are also disclosed in EP 193,360, including, for example, the 45/45/10 terpolymer of acrylic/maleic/vinyl alcohol.
  • Particularly preferred dispersant polymers are low molecular weight modified polyacrylate copolymers.
  • Such copolymers contain as monomer units: a) from about 90% to about 10%, preferably from about 80% to about 20% by weight acrylic acid or its salts and b) from about 10% to about 90%, preferably from about 20% to about 80% by weight of a substituted acrylic monomer or its salt and have the general formula: -[(C(R 2 )C(R 1 )(C(0)OR 3 )]- wherein the incomplete valencies inside the square braces are hydrogen and at least one of the substituents Rl, R ⁇ or R ⁇ , preferably R' or R-, is a 1 to 4 carbon alkyl or hydroxyalkyl group, R !
  • R2 can be a hydrogen and R J can be a hydrogen or alkali metal salt.
  • R J can be a hydrogen or alkali metal salt.
  • Most preferred is a substituted acrylic monomer wherein R 1 is methyl, R 2 is hydrogen and R ⁇ is sodium.
  • the low molecular weight polyacrylate dispersant polymer preferably has a molecular weight of less than about 15,000, preferably from about 500 to about 10,000, most preferably from about 1,000 to about 5,000.
  • the most preferred polyacrylate copolymer for use herein has a molecular weight of 3500 and is the fully neutralized form of the polymer comprising about 70% by weight acrylic acid and about 30% by weight methacrylic acid.
  • Suitable modified polyacrylate copolymers include the low molecular weight copolymers of unsaturated aliphatic carboxylic acids disclosed in U.S. Patents 4,530,766, and 5,084,535, both incorporated herein by reference.
  • Agglomerated forms of the present invention may employ aqueous solutions of polymer dispersants as liquid binders for making the agglomerate (particularly when the composition consists of a mixture of sodium citrate and sodium carbonate).
  • aqueous solutions of polymer dispersants as liquid binders for making the agglomerate (particularly when the composition consists of a mixture of sodium citrate and sodium carbonate).
  • polyacrylates with an average molecular weight of from about 1,000 to about 10,000
  • acrylate/maleate or acrylate/ fumarate copolymers with an average molecular weight of from about 2,000 to about 80,000 and a ratio of acrylate to maleate or fumarate segments of from about 30: 1 to about 1 :2.
  • Examples of such copolymers based on a mixture of unsaturated mono- and dicarboxylate monomers are disclosed in European Patent Application No. 66,915, published December 15, 1982, incorporated herein by reference.
  • dispersant polymers useful herein include the polyethylene glycols and polypropylene glycols having a molecular weight of from about 950 to about 30,000 which can be obtained from the Dow Chemical Company of Midland, Michigan. Such compounds for example, having a melting point within the range of from about 30° to about 100°C can be obtained at molecular weights of 1450, 3400, 4500, 6000, 7400, 9500, and 20,000. Such compounds are formed by the polymerization of ethylene glycol or propylene glycol with the requisite number of moles of ethylene or propylene oxide to provide the desired molecular weight and melting point of the respective polyethylene glycol and polypropylene glycol.
  • the polyethylene, polypropylene and mixed glycols are referred to using the formula HO(CH 2 CH2 ⁇ ) m (CH2CH(CH3)0) n (CH(CH3)CH 2 0) 0 H wherein m, n, and o are integers satisfying the molecular weight and temperature requirements given above.
  • dispersant polymers useful herein include the cellulose sulfate esters such as cellulose acetate sulfate, cellulose sulfate, hydroxyethyl cellulose sulfate, methylcellulose sulfate, and hydroxypropylcellulose sulfate.
  • cellulose sulfate esters such as cellulose acetate sulfate, cellulose sulfate, hydroxyethyl cellulose sulfate, methylcellulose sulfate, and hydroxypropylcellulose sulfate.
  • Sodium cellulose sulfate is the most preferred polymer of this group.
  • Suitable dispersant polymers are the carboxylated polysaccharides, particularly starches, celluloses and alginates, described in U.S. Pat. No. 3,723,322, Diehl, issued Mar. 27, 1973, the dextrin esters of polycarboxylic acids disclosed in U.S. Pat. No. 3,929, 107, Thompson, issued Nov. 1 1, 1975; the hydroxyalkyl starch ethers, starch esters, oxidized starches, dextrins and starch hydrolysates described in U.S. Pat No. 3,803,285, Jensen, issued Apr. 9, 1974; the carboxylated starches described in U.S. Pat. No. 3,629, 121, Eldib, issued Dec.
  • cellulose-derived dispersant polymers are the carboxymethyl celluloses.
  • organic dispersant polymers such as polyaspartate.
  • PEG polyethylene glycol
  • PEG can exhibit dispersing agent performance as well as act as a clay soil removal-antiredeposition agent.
  • Typical molecular weight ranges for these purposes range from about 500 to about 100,000, preferably from about 1,000 to about 50,000, more preferably from about 1,500 to about 10,000.
  • Polyaspartate and polyglutamate dispersing agents may also be used, especially in conjunction with zeolite builders.
  • compositions containing detergent builders it is believed, though it is not intended to be limited by theory, that polymeric dispersing agents enhance overall detergent builder performance, especially zeolite and or silicate builders, when used in combination with other builders (including lower molecular weight polycarboxylates) by crystal growth inhibition, particulate soil release peptization, and anti-redeposition.
  • Dispersing agents such as polyaspartate preferably have a molecular weight (avg.) of about 10,000.
  • 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. Zahradnik, Published by John Wiley & Sons, New York (1982).
  • 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 PHOR WHITE series of brighteners from Verona Other brighteners 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, iocated in Italy; the 2- (4-stryl-phenyl)-2H-napthol[l,2-d]triazoles; 4,4'-bis- (l,2,3-triazol-2-yl)-stil- benes; 4,4'-bis(stryl)bisphenyls; and the aminocoumarins.
  • these brighteners include 4-methyl-7-diethyl- amino coumarin; l,2-bis(-venzimidazol-2- yl)ethylene; 1 ,3-diphenyl-phrazolines; 2,5-bis(benzoxazol-2-yl)thiophene; 2-stryl- napth-[l,2-d]oxazole; and 2-(stilbene-4-yl)-2H-naphtho- [ l,2-d]triazole. See also U.S. Patent 3,646,015, issued February 29, 1972 to Hamilton. Anionic brighteners are preferred herein.
  • 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.
  • suds suppressors are well known to those skilled in the art See, for example, Kirk Othmer Encyclopedia of Chemical Technology, Third Edition, Volume 7, pages 430- 447 (John Wiley & Sons, Inc., 1979).
  • 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 J 8-C40 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 1 10°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, 1 81 to Gandolfo et al and European Patent Application No. 89307851.9, published February 7, 1990, by Starch, M. S.
  • silicone and silanated silica are described, for instance, in German 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: (i) polydimethylsiloxane fluid having a viscosity of from about 20 cs. to about 1,500 cs. at 25°C; (ii) from about 5 to about 50 parts per 100 parts by weight of (i) of siloxane resin composed of (CH3) SiO j/2 units of Si ⁇ 2 units in a ratio of from (CH3)3 SiOj/2 units and to Si ⁇ 2 units of from about 0.6: 1 to about 1.2: 1 ; and (iii) from about 1 to about 20 pans per 100 pans by weight of (i) of a solid silica gel.
  • 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. Similar amounts can be used in granular compositions, gels, etc. See also U
  • 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 glycol opolymer 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 LIOI .
  • 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 C -C ⁇ alkyl alcohols having a C ] -C j 6 chain.
  • a preferred 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 weli 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.
  • compositions of the present invention 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, pyrrolidine, piperidine and derivatives thereof.
  • the N-0 group can be represented by the following general structures:
  • GV- z wherein R ⁇ , R2, R3 are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof; x, y and z are 0 or 1; and the nitrogen of the N-0 group can be attached or form part of any of the aforementioned groups.
  • the amine oxide unit of the polyamine N-oxides has a pKa ⁇ I0, 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.
  • polymeric backbones examples include 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.
  • the number of amine oxide groups present in the polyamine oxide poiymer 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.
  • 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".
  • 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-vinyiimidazole to N-vinylpyrrolidone 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 poiyvinyl-pyrrolidone (“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.
  • 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 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, chloro and amino; and M is a salt-forming cation such as sodium or potassium.
  • Rj 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.
  • This particular brightener species 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-anilino-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.
  • 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'-sti!benedisulfonic 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, Tinopal-PLC, 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. Without being bound by theory, it is believed that such brighteners work 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.
  • compositions can optionally be used in the present compositions to provide conventional fabric "brightness" benefits, rather than a true dye transfer inhibiting effect.
  • Such usage is conventional and well-known to detergent formulations.
  • Other Ingredients A wide variety of other ingredients useful in detergent compositions can be included in the compositions herein, including other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, solvents for liquid formulations, solid fillers for bar compositions, etc. If high sudsing is desired, suds boosters such as the C ⁇ Q-C ⁇ Q alkanolamides can be incorporated into the compositions, typically at 1%-I0% levels.
  • the C 10-C14 monoethanol and diethanol amides illustrate a typical class of such suds boosters.
  • Use of such suds boosters with high sudsing adjunct surfactants such as the amine oxides, betaines and sultaines noted above is also advantageous.
  • soluble magnesium salts such as MgCl2, MgS ⁇ 4, and the like, can be added at levels of, typically, 0.1%-2%, to provide additional suds and to enhance grease removal performance.
  • detersive ingredients employed in the present compositions optionally can be further stabilized by absorbing said ingredients onto a porous hydrophobic substrate, then coating said substrate with a hydrophobic coating.
  • the detersive ingredient is admixed with a surfactant before being absorbed into the porous substrate.
  • the detersive ingredient is released from the substrate into the aqueous washing liquor, where it performs its intended detersive function.
  • a porous hydrophobic silica (trademark SIPERNAT D10, DeGussa) is admixed with a proteolytic enzyme solution containing 3%-5% of C 13.15 ethoxylated alcohol (EO 7) nonionic surfactant.
  • EO 7 ethoxylated alcohol
  • the enzyme/surfactant solution is 2.5 X the weight of silica.
  • the resulting powder is dispersed with stirring in silicone oil (various silicone oil viscosities in the range of 500- 12,500 can be used).
  • silicone oil various silicone oil viscosities in the range of 500- 12,500 can be used.
  • the resulting silicone oil dispersion is emulsified or otherwise added to the final detergent matrix.
  • ingredients such as the aforementioned enzymes, bleaches, bleach activators, bleach catalysts, photoactivators, dyes, fluorescers, fabric conditioners and hydrolyzable surfactants can be "protected” for use in detergents, including liquid laundry detergent compositions.
  • Liquid detergent compositions can contain water and other solvents as carriers.
  • Low molecular weight primary or secondary alcohols exemplified by methanol, ethanol, propanol, and isopropanol are suitable.
  • Monohydric alcohols are preferred for solubilizing surfactant, but polyols such as those containing from 2 to about 6 carbon atoms and from 2 to about 6 hydroxy groups (e.g., 1,3-propanediol, ethylene glycol, glycerine, and 1,2-propanedioI) can also be used.
  • the compositions may contain from 5% to 90%, typically 10% to 50% of such carriers.
  • Granular detergents can be prepared, for example, by spray-drying (final product density about 520 g/1) or agglomerating (final product density above about 600 g/1) the Base Granule.
  • the remaining dry ingredients can then be admixed in granular or powder form with the Base Granule, for example in a rotary mixing drum, and the liquid ingredients (e.g., nonionic surfactant and perfume) can be sprayed on.
  • the detergent compositions herein will preferably be formulated such that, during use in aqueous cleaning operations, the wash water will have a pH of between about 6.5 and about 1 1 , preferably between about 7.5 and 10.5.
  • Liquid dishwashing product formulations preferably have a pH between about 6.8 and about 9.0. Laundry products are typically at pH 9- 1 1. Techniques for controlling pH at recommended usage levels include the use of buffers, alkalis, acids, etc., and are well known to those skilled in the art.
  • compositions according to the invention but are not intended to be limiting thereof.
  • a dry laundry bleach is as follows:
  • the sodium percarbonate can be replaced by an equivalent amount of perborate
  • the bleach activator can be replaced by an equivalent amount of the following activators: benzoyl valerolactam, nonanoyl caprolactam, nonanoyl valerolactam, 4-nitro- benzoyl caprolactam, 4-nitrobenzoyl valerolactam, octanoyl caprolactam, octanoyl valerolactam, decanoyl caprolactam, decanoyl valerolactam, undecenoyl caprolactam, undecenoyl valerolactam, 3,5,5-trimethylhexanoyl caprolactam, 3,5,5- trimethylhexanoyl valerolactam, dinitrobenzoyl caprolactam, dinitrobenzoyl valerolactam, terephthaloyl dicaprolactam, terephthaloyl divalerolactam, (6-octan- amidocaproyl)oxybenzene
  • compositions of Example I can be used per se as a bleach, or can be added to a pre-soak or surfactant-containing detergent composition to impart a bleaching benefit thereto.
  • compositions are employed in conventional manner and at conventional concentration
  • compositions are placed in an aqueous liquor at levels which may range from about
  • compositions can further be modified by adding an equivalent amount of a bleach catalysts identified in Example I.
  • compositions can be modified by replacing the nonanoyl capro ⁇ lactam with an equivalent amount of the bleach activators identified in Example I.
  • a bleaching system useful as a bleach additive, is prepared comprising the following ingredients.
  • compositions can be modified by the addition of lipase enzymes.
  • the above compositions can also be modified by replacing the nonanoyl valerolactam bleach activator with an equivalent amount of the bleach activators identified in Example I and/or with the addition of 0.1% metal catalyst.
  • the above compositions can also be modified by replacing the percarbonate with an equivalent amount of perborate.
  • a laundry bar with bleach is prepared by standard extrusion processes and comprises: Oleoyl Sarcosinate (20%); sodium tripolyphosphate (20%); sodium silicate (7%); sodium perborate monohydrate (10%); ( ⁇ -decanamidocaproyl)oxy- benzenesulfonate ( 10%); ( 1.0%); MgS ⁇ 4 or talc filler; and water (5%).
  • compositions can be modified by the addition of lipase enzymes.
  • the above compositions can also be modified by replacing the (6- decanamidocaproyl)oxybenzenesulfonate bleach activator with an equivalent amount of the bleach activators identified in Example I and/or with the addition of 0.1% metal catalyst.
  • the above compositions can also be modified by replacing the perborate with an equivalent amount of percarbonate
  • An automatic dishwashing composition is as follows. Ingredient % (Wt. ⁇ )
  • the perborate can be replaced by an equivalent amount of percarbonate.
  • the bleach catalyst can be replaced by an equivalent amount of preformed bleach catalyst, as identified in Example I, or with metal cations and ligands to form the bleach catalysts identified in Example I.
  • compositions can also be modified by replacing the benzoyl caprolactam with an equivalent amount of the bleach activators identified in Example I.
  • the surfactant may be replaced by an equivalent amount of any low-foaming, nonionic surfactant.
  • Example include low-foaming or non-foaming ethoxylated straight-chain alcohols such as Plurafac ⁇ M RA series, supplied by Eurane Co., LutensojTM LF series, supplied by BASF Co., Triton ⁇ M DF series, supplied by Rohm & Haas Co., and SynperonicTM LF series, supplied by
  • ICI Co. Automatic dishwashing compositions may be in granular, tablet, bar, or rinse aid form. Methods of making granules, tablets, bars, or rinse aids are known in the art. See, for instance, U.S. Pat. Serial Nos. 08/106,022, 08/147,222, 08/147,224, 08/147,219, 08/052,860, 07/867,941. All of the foregoing granular compositions may be provided as spray-dried granules or high density (above 600 g/I) granules or agglomerates.
  • the Mn-catalyst may be adsorbed onto and into water-soluble granules to keep the catalyst separate from the balance of the compositions, thus providing additional stability on storage.
  • Such granules (which should not contain oxidizable components) can comprise, for example, water-soluble silicates, carbonates and the like.
  • compositions are typical of those useful herein, it is most preferred that: ( 1) the compositions not contain STPP builder; (2) that the nonionic.anionic surfactant ratio be greater than 1 : 1, preferably at least 1.5: 1; and (3) that at least 1% perborate or other chlorine scavenger be present in the compositions to minimize formation of Mn ⁇ 2 in use.
  • the catalyzed bleaching systems herein can be employed under any circumstance where improved oxygen bleaching is desired.
  • the technology of this invention may be used, for example, to bleach paper pulp, to bleach hair, to cleanse and sanitize prosthetic devices such as dentures, in dentifrice compositions to clean teeth and kill oral bacteria, and in any other circumstances where bleaching is advantageous to the user.

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  • Chemical Kinetics & Catalysis (AREA)
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  • Wood Science & Technology (AREA)
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Abstract

L'invention concerne des compositions de blanchiment et de lavage comprenant un composé de blanchiment, un tensioactif de type sarcosinate d'oléolyle et facultativement, mais de préférence, un catalyseur de blanchiment ainsi qu'un ou plusieurs activateurs de blanchiment. Ainsi, des compositions détergentes de blanchissage comprenant du perborate, du percarbonate et de préférence des activateurs tels que le caprolactame de benzoyle présentent un meilleur rendement en présence de sarcosinate d'oléoyle.
PCT/US1995/006296 1994-06-01 1995-05-18 Compositions de blanchiment comprenant des tensioactifs de type sarcosinate d'oleoyle WO1995033043A1 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
DE69513974T DE69513974D1 (de) 1994-06-01 1995-05-18 Oleoylsarcosinattenside enthaltende bleichmittelzusammensetzungen
AT95919235T ATE187766T1 (de) 1994-06-01 1995-05-18 Oleoylsarcosinattenside enthaltende bleichmittelzusammensetzungen
EP95919235A EP0763096B1 (fr) 1994-06-01 1995-05-18 Compositions de blanchiment comprenant des tensioactifs de type sarcosinate d'oleoyle
AU25177/95A AU2517795A (en) 1994-06-01 1995-05-18 Bleach compositions comprising oleoyl sarcosinate surfactants
MX9606047A MX9606047A (es) 1995-05-18 1995-05-18 Composiciones de blanqueo que contienen agentes tensioactivos de sarcosinato de oleoilo.
JP8500949A JPH10501566A (ja) 1994-06-01 1995-05-18 オレオイルサルコシネート界面活性剤を含む漂白組成物
BR9507831A BR9507831A (pt) 1994-06-01 1995-05-18 Composições alvejantes compreendendo tensoativos sarcosinato de oleoíla

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US25204094A 1994-06-01 1994-06-01
US08/252040 1994-06-01

Publications (1)

Publication Number Publication Date
WO1995033043A1 true WO1995033043A1 (fr) 1995-12-07

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PCT/US1995/006296 WO1995033043A1 (fr) 1994-06-01 1995-05-18 Compositions de blanchiment comprenant des tensioactifs de type sarcosinate d'oleoyle

Country Status (12)

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EP (1) EP0763096B1 (fr)
JP (1) JPH10501566A (fr)
CN (1) CN1200758A (fr)
AT (1) ATE187766T1 (fr)
AU (1) AU2517795A (fr)
BR (1) BR9507831A (fr)
CA (1) CA2191439A1 (fr)
DE (1) DE69513974D1 (fr)
IL (1) IL113880A0 (fr)
MA (1) MA23569A1 (fr)
WO (1) WO1995033043A1 (fr)
ZA (1) ZA954278B (fr)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0790297A1 (fr) * 1996-02-16 1997-08-20 The Procter & Gamble Company Compositions de blanchiment
WO1997036988A1 (fr) * 1996-04-01 1997-10-09 Henkel Kommanditgesellschaft Auf Aktien Complexes d'ammine et de metaux de transition utilises comme activateurs pour les composes de peroxyde
WO1997036986A1 (fr) * 1996-04-01 1997-10-09 Henkel Kommanditgesellschaft Auf Aktien Detergents contenant des complexes activateurs a base d'oligoammine pour composes de peroxy
EP0869769A1 (fr) * 1995-12-29 1998-10-14 The Procter & Gamble Company Compositions pour decolorants capillaires
WO2013050743A1 (fr) * 2011-10-06 2013-04-11 Croda International Plc Traitement amélioré de surfaces dures
JP2015172195A (ja) * 2007-07-02 2015-10-01 エコラボ インコーポレイティド 直鎖飽和モノ−、ジ−、またはトリ−カルボン酸の塩を含む凝固基材
JP2016540841A (ja) * 2013-10-24 2016-12-28 エコラボ ユーエスエー インコーポレイティド 表面から汚れを除去する組成物及び方法
WO2019186457A1 (fr) * 2018-03-29 2019-10-03 Pilon, Randall Andrew Compositions antimicrobiennes contenant un composé peroxygéné et un tensioactif anionique a base d'alkylsarcosine
US11330819B2 (en) 2018-12-28 2022-05-17 Diversey, Inc. Synergistic disinfectant compositions having enhanced antimicrobial efficacy and stability, and methods of using the same
US12152219B2 (en) 2020-10-23 2024-11-26 Chemische Fabrik Dr. Weigert Gmbh & Co. Kg Liquid cleaning agent concentrate comprising a fatty alcohol-based EO/PO copolymer and a C10-C18 amino acid-based surfactant mixture

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102006036889A1 (de) * 2006-08-04 2008-02-07 Clariant International Limited Verwendung von Aminoacetonen und deren Salzen als Bleichkraftverstärker für Persauerstoffverbindungen
JP7417753B2 (ja) * 2020-01-31 2024-01-18 エコラボ ユーエスエー インコーポレイティド ウェア洗浄用途における酸素漂白剤とのアミラーゼ相乗効果

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GB459039A (en) * 1934-03-24 1936-12-28 Ig Farbenindustrie Ag Manufacture of washing agents and detergents
JPS55102697A (en) * 1979-02-01 1980-08-06 Jiyonson Kk Oxygen type detergent bleaching composition
US4772424A (en) * 1986-01-08 1988-09-20 The Proctor & Gamble Company Shampoo containing mixtures of sulfate and/or sulfonate, sarcosinate and betaine surfactants
WO1992013798A1 (fr) * 1991-02-06 1992-08-20 The Procter & Gamble Company Compositions precurseurs d'agents de blanchiment au peroxyacide
US5244593A (en) * 1992-01-10 1993-09-14 The Procter & Gamble Company Colorless detergent compositions with enhanced stability
EP0634483A1 (fr) * 1993-07-14 1995-01-18 The Procter & Gamble Company Compositions de blanchiment stabilisées
EP0639639A1 (fr) * 1993-08-17 1995-02-22 The Procter & Gamble Company Compositions détergentes contenant des percarbonates comme agents de blanchiment
EP0659876A2 (fr) * 1993-12-24 1995-06-28 The Procter & Gamble Company Composition additive pour détergent
EP0672749A1 (fr) * 1994-03-17 1995-09-20 The Procter & Gamble Company Compositions de blanchiment

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GB459039A (en) * 1934-03-24 1936-12-28 Ig Farbenindustrie Ag Manufacture of washing agents and detergents
JPS55102697A (en) * 1979-02-01 1980-08-06 Jiyonson Kk Oxygen type detergent bleaching composition
US4772424A (en) * 1986-01-08 1988-09-20 The Proctor & Gamble Company Shampoo containing mixtures of sulfate and/or sulfonate, sarcosinate and betaine surfactants
WO1992013798A1 (fr) * 1991-02-06 1992-08-20 The Procter & Gamble Company Compositions precurseurs d'agents de blanchiment au peroxyacide
US5244593A (en) * 1992-01-10 1993-09-14 The Procter & Gamble Company Colorless detergent compositions with enhanced stability
EP0634483A1 (fr) * 1993-07-14 1995-01-18 The Procter & Gamble Company Compositions de blanchiment stabilisées
EP0639639A1 (fr) * 1993-08-17 1995-02-22 The Procter & Gamble Company Compositions détergentes contenant des percarbonates comme agents de blanchiment
EP0659876A2 (fr) * 1993-12-24 1995-06-28 The Procter & Gamble Company Composition additive pour détergent
EP0672749A1 (fr) * 1994-03-17 1995-09-20 The Procter & Gamble Company Compositions de blanchiment

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DATABASE WPI Section Ch Week 8038, Derwent World Patents Index; Class D25, AN 80-66785C *

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0869769A1 (fr) * 1995-12-29 1998-10-14 The Procter & Gamble Company Compositions pour decolorants capillaires
EP0869769A4 (fr) * 1995-12-29 2000-07-12 Procter & Gamble Compositions pour decolorants capillaires
EP0790297A1 (fr) * 1996-02-16 1997-08-20 The Procter & Gamble Company Compositions de blanchiment
WO1997036988A1 (fr) * 1996-04-01 1997-10-09 Henkel Kommanditgesellschaft Auf Aktien Complexes d'ammine et de metaux de transition utilises comme activateurs pour les composes de peroxyde
WO1997036986A1 (fr) * 1996-04-01 1997-10-09 Henkel Kommanditgesellschaft Auf Aktien Detergents contenant des complexes activateurs a base d'oligoammine pour composes de peroxy
US6200946B1 (en) 1996-04-01 2001-03-13 Henkel Kommanditgesellschaft Auf Aktien Transition metal ammine complexes as activators for peroxide compounds
US6235695B1 (en) * 1996-04-01 2001-05-22 Henkel Kommanditgesellschaft Auf Aktien Cleaning agent with oligoammine activator complexes for peroxide compounds
JP2015172195A (ja) * 2007-07-02 2015-10-01 エコラボ インコーポレイティド 直鎖飽和モノ−、ジ−、またはトリ−カルボン酸の塩を含む凝固基材
WO2013050743A1 (fr) * 2011-10-06 2013-04-11 Croda International Plc Traitement amélioré de surfaces dures
US9222062B2 (en) 2011-10-06 2015-12-29 Croda International Plc Treatment of hard surfaces
JP2016540841A (ja) * 2013-10-24 2016-12-28 エコラボ ユーエスエー インコーポレイティド 表面から汚れを除去する組成物及び方法
US11566207B2 (en) 2013-10-24 2023-01-31 Ecolab Usa Inc. Compositions and methods for removing soil from surfaces
US12221594B2 (en) 2013-10-24 2025-02-11 Ecolab Usa Inc. Compositions and methods for removing soil from surfaces
WO2019186457A1 (fr) * 2018-03-29 2019-10-03 Pilon, Randall Andrew Compositions antimicrobiennes contenant un composé peroxygéné et un tensioactif anionique a base d'alkylsarcosine
US11330819B2 (en) 2018-12-28 2022-05-17 Diversey, Inc. Synergistic disinfectant compositions having enhanced antimicrobial efficacy and stability, and methods of using the same
US11758906B2 (en) 2018-12-28 2023-09-19 Diversey, Inc. Synergistic disinfectant compositions having enhanced antimicrobial efficacy and stability, and methods of using the same
US11871744B2 (en) 2018-12-28 2024-01-16 Diversey, Inc. Synergistic disinfectant compositions having enhanced antimicrobial efficacy and stability, and methods of using the same
US12152219B2 (en) 2020-10-23 2024-11-26 Chemische Fabrik Dr. Weigert Gmbh & Co. Kg Liquid cleaning agent concentrate comprising a fatty alcohol-based EO/PO copolymer and a C10-C18 amino acid-based surfactant mixture

Also Published As

Publication number Publication date
IL113880A0 (en) 1995-08-31
ATE187766T1 (de) 2000-01-15
JPH10501566A (ja) 1998-02-10
DE69513974D1 (de) 2000-01-20
ZA954278B (en) 1996-01-24
EP0763096A1 (fr) 1997-03-19
CN1200758A (zh) 1998-12-02
CA2191439A1 (fr) 1995-12-07
BR9507831A (pt) 1997-09-16
MA23569A1 (fr) 1995-12-31
AU2517795A (en) 1995-12-21
EP0763096B1 (fr) 1999-12-15

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