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EP0763096A1 - Compositions de blanchiment comprenant des tensioactifs de type sarcosinate d'oleoyle - Google Patents

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

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Publication number
EP0763096A1
EP0763096A1 EP95919235A EP95919235A EP0763096A1 EP 0763096 A1 EP0763096 A1 EP 0763096A1 EP 95919235 A EP95919235 A EP 95919235A EP 95919235 A EP95919235 A EP 95919235A EP 0763096 A1 EP0763096 A1 EP 0763096A1
Authority
EP
European Patent Office
Prior art keywords
bleach
bleaching
compositions
valerolactam
caprolactam
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP95919235A
Other languages
German (de)
English (en)
Other versions
EP0763096B1 (fr
Inventor
Suzanne Powell
Christian Leo Marie Vermote
Barry Thomas Ingram
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
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Publication date
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Publication of EP0763096A1 publication Critical patent/EP0763096A1/fr
Application granted granted Critical
Publication of EP0763096B1 publication Critical patent/EP0763096B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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

  • 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.
  • 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
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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%.
  • 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.
  • 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.
  • 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.
  • 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 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 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.
  • 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:
  • 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
  • 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
  • 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

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EP95919235A 1994-06-01 1995-05-18 Compositions de blanchiment comprenant des tensioactifs de type sarcosinate d'oleoyle Expired - Lifetime EP0763096B1 (fr)

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US6235695B1 (en) * 1996-04-01 2001-05-22 Henkel Kommanditgesellschaft Auf Aktien Cleaning agent with oligoammine activator complexes for peroxide compounds
DE19620411A1 (de) 1996-04-01 1997-10-02 Henkel Kgaa Übergangsmetallamminkomplexe als Aktivatoren für Persauerstoffverbindungen
DE102006036889A1 (de) * 2006-08-04 2008-02-07 Clariant International Limited Verwendung von Aminoacetonen und deren Salzen als Bleichkraftverstärker für Persauerstoffverbindungen
US7759300B2 (en) * 2007-07-02 2010-07-20 Ecolab Inc. Solidification matrix including a salt of a straight chain saturated mono-, di-, or tri- carboxylic acid
GB201117252D0 (en) * 2011-10-06 2011-11-16 Croda Int Plc Improved treatment of hard surfaces
WO2015058803A1 (fr) 2013-10-24 2015-04-30 Ecolab Inc. Compositions et procédés pour éliminer les salissures sur des 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
EP4151093A1 (fr) 2018-12-28 2023-03-22 Diversey, Inc. Compositions désinfectantes synergiques ayant une efficacité antimicrobienne et une stabilité améliorées, et leurs procédés d'utilisation
EP4097209A1 (fr) * 2020-01-31 2022-12-07 Ecolab USA Inc. Synergie d'amylase avec un agent de blanchiment à l'oxygène dans une application de lavage de vaisselle
ES3004149T3 (en) * 2020-10-23 2025-03-11 Chemische Fabrik Dr Weigert Gmbh & Co Kg Liquid detergent concentrate, ready-to-use application solution, uses of same and cleaning methods

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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
GB9102507D0 (en) * 1991-02-06 1991-03-27 Procter & Gamble Peroxyacid bleach precursor compositions
US5244593A (en) * 1992-01-10 1993-09-14 The Procter & Gamble Company Colorless detergent compositions with enhanced stability
EP0634483B1 (fr) * 1993-07-14 2000-09-13 The Procter & Gamble Company Compositions de blanchiment stabilisées
EP0639639B2 (fr) * 1993-08-17 2010-07-28 The Procter & Gamble Company Compositions détergentes contenant des percarbonates comme agents de blanchiment
EP0659876A3 (fr) * 1993-12-24 1996-12-04 Procter & Gamble Composition additive pour détergent.
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