EP0833887B1 - Nichtwässerige, körnchen enthaltende waschmittelzusammensetzungen - Google Patents

Nichtwässerige, körnchen enthaltende waschmittelzusammensetzungen Download PDF

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Publication number
EP0833887B1
EP0833887B1 EP95924005A EP95924005A EP0833887B1 EP 0833887 B1 EP0833887 B1 EP 0833887B1 EP 95924005 A EP95924005 A EP 95924005A EP 95924005 A EP95924005 A EP 95924005A EP 0833887 B1 EP0833887 B1 EP 0833887B1
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Prior art keywords
nonaqueous
alkyl
compositions
detergent composition
detergent
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French (fr)
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EP0833887A1 (de
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Jean-Pol Boutique
Michael Eugene Burns
James Pyott Johnston
Axel Meyer
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Procter and Gamble Co
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Procter and Gamble Co
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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
    • C11D3/3907—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0004—Non aqueous liquid compositions comprising insoluble particles
    • 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
    • C11D3/3915—Sulfur-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • C11D3/3917—Nitrogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/525—Carboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain two or more hydroxy groups per alkyl group, e.g. R3 being a reducing sugar rest

Definitions

  • This invention relates to nonaqueous laundry detergent products which are in the form of a liquid, gel or paste and which are in the form of stable dispersions of particulate material such as bleaching agents and bleach activators.
  • Detergent products in the form of liquid, gel or paste are often considered to be more convenient to use than are dry powdered or particulate detergent products. Said detergents have therefore found substantial favor with consumers. Such detergent products are readily measurable, speedily dissolved in the wash water, capable of being easily applied in concentrated solutions or dispersions to soiled areas on garments to be laundered and are non-dusting. They also usually occupy less storage space than granular products. Additionally, such detergents may have incorporated in their formulations materials which could not withstand drying operations without deterioration, which operations are often employed in the manufacture of particulate or granular detergent products.
  • detergents have a number of advantages over granular detergent products, they also inherently possess several disadvantages.
  • detergent composition components which may be compatible with each other in granular products may tend to interact or react with each other.
  • such components as enzymes, surfactants, perfumes, brighteners, solvents and especially bleaches and bleach activators can be especially difficult to incorporate into liquid detergent products which have an acceptable degree of chemical stability.
  • Nonaqueous liquid detergent compositions including those which contain reactive materials such as peroxygen bleaching agents, have been disclosed for example, in Hepworth et al., U.S. Patent 4,615,820, Issued October 17, 1986; Schultz et al., U.S. Patent 4,929,380, Issued May 29, 1990; Schultz et al., U.S.
  • EP-A-339 995 describes a non-aqueous liquid detergent composition comprising a persalt bleach and a precursor therefore, the composition containing a capped alkoxylated nonionic surfactant.
  • EP-A-540 090 proposes to use a bleach precursor which is relatively insoluble in the non aqueous liquid phase of the liquid detergent composition.
  • a difficulty associated with the stability of bleach activators is that, upon dilution in the wash liquor, the bleach activators still need to have a certain degree of solubility high enough to be effective as a bleaching species in the wash liquor.
  • a nonaqueous detergent composition which is in the form of a liquid, gel or paste, containing a bleaching agent and a bleach activator which is present as a divalent metal salt, a trivalent metal salt, a mixed metal salt whereby at least one of the salts is a divalent or a trivalent metal salt, or mixtures thereof.
  • the present invention provides a nonaqueous heavy-duty detergent composition which is in the form of a liquid, gel or paste, said composition comprising a bleaching agent and a bleach activator, characterized in that said bleach activator is present as a divalent metal salt, a trivalent metal salt, a mixed metal salt whereby at least one of the salts is a divalent or a trivalent metal salt, or mixtures thereof.
  • the bleaching agents used herein can be any of the bleaching agents useful for detergent or bleaching compositions in textile cleaning, hard surface cleaning, or other cleaning purposes that are now known or become known, and are useful for bleaching compositions as used in the present invention to treat fabrics. These include oxygen bleaches as well as other bleaching agents.
  • Perborate bleaches e.g., sodium perborate (e.g., mono- or tetrahydrate) can be used herein.
  • Peroxygen bleaching agents are preferably used in the compositions. Suitable peroxygen bleaching compounds include perborate, 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.
  • the bleach activators according to the present invention are present as a divalent and/or trivalent metal salt.
  • the bleach activator salt can be added as a powder dispersed in the non-aqueous base.
  • the bleach activator salt can also be premixed with a liquid non-aqueous ingredient such as a nonionic surfactant, organic solvent and/or mixtures thereof.
  • the bleach activator salts can be obtained by any method known to prepare divalent metal salts of anionic surface active solutions.
  • the bleach activator salts of the present invention can comprise mixed salts whereby at least one of the salts is a divalent or trivalent salt.
  • the mixed salts are obtained by cocrystallization of the bleach activator salts.
  • the mixed salts can comprise a monovalent salt. Examples of these salts are Na 3 Mg 4-[N-nonanoyl-6-aminohexanoyloxy benzene sulfonate] 5 .
  • Preferred salts according to the present invention are Ca, Mg and Al salts. Highly preferred are Ca and Mg salts or mixtures thereof.
  • the bleach activators suitable for the present invention are the anionic bleach activators described in the literature, such as in the GB Patents 836,988; 864,798; 907,356; 1,003,310 and 1,519,351; German Patent 3,337,921; EP-A-0185522; EP-A-0174132; EP-A-0120591; and U.S. Pat. Nos. 1,246,339; 3,332,882; 4,128,494; 4,412,934 and 4,675,393.
  • anionic bleach activators is that as disclosed in U.S. Pat. Nos. 4,751,015 and 4,397,757, in EP-A-284292, EP-A-331,229 and EP-A-03520.
  • anionic peroxyacid bleach activators include sodium-4-benzoyloxy benzene sulphonate; sodium-1-methyl-2-benzoyloxy benzene-4-sulphonate; sodium nonanoyloxybenzene sulphonate; sodium 3,5,5,-trimethyl hexanoyloxybenzene sulphonate.
  • Bleach activators also useful in the present invention are amide substituted compounds of the general formulas: or mixtures thereof, wherein R 1 is an alkyl, aryl, or alkaryl group containing from 1 to 14 carbon atoms, R 2 is an alkylene, arylene or alkarylene group containing from 1 to 14 carbon atoms, R 5 is H or an alkyl, aryl, br alkaryl group containing from 1 to 10 carbon atoms, and L can be 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 perhydroxide anion.
  • 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 4 to 13, preferably from 6 to 11 and most preferably from 8 to 11.
  • Preferred bleach activators are those of the above general formula wherein R 1 , R 2 and R 5 are as defined for the peroxyacid and L is selected from the group consisting of: and and mixtures thereof, wherein R 1 is an alkyl, aryl, or alkaryl group containing from 1 to 14 carbon atoms, R 3 is an alkyl chain containing from 1 to 8 carbon atoms, R 4 is H or R 3 , and Y is a solubilizing anionic group.
  • the solubilizing groups are -SO 3 - , -CO 2 - , SO 4 - , and most preferably -SO 3 - and -CO 2 - wherein R 3 is an alkyl chain containing from 1 to 4 carbon atoms.
  • Preferred anionic bleach activators are those of the above general formula wherein L is selected from the group consisting of: wherein R 3 is as defined above and Y is -SO 3 - or -CO 2 - .
  • bleach activators of the above formulae include 4-[N-octanoyl-6-aminohexanoyloxy]benzene sulfonate, 4-[N-nonanoyl-6-aminohexanoyloxy]benzene sulfonate, 4-[N-decanoyl-6-aminohexanoyloxy]benzene sulfonate and mixtures thereof. Said activators are described in US-A-4,634,551 and US-A-4,852,989.
  • anionic 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.
  • this ring-opening reaction in certain activators involves attack at the lactam ring carbonyl by hydrogen peroxide or its anion. Since attack of an acyl lactam by hydrogen peroxide or its anion occurs preferably at the exocyclic carbonyl, obtaining a significant fraction of ring-opening may require a catalyst.
  • Another example of ring-opening bleach activators can be found in other activators, such as those disclosed in U.S. Patent 4,966,723, Hodge et al, issued Oct. 30, 1990.
  • the bleach activators of the present invention in contrast with monovalent bleach activator salts, are chemically stable in the concentrate, while at the same time being effective as a bleach species in the wash liquor.
  • bleach activators when agglomerated with certain acid such as citric acid, are more chemically stable.
  • the nonaqueous detergent compositions of this invention may further comprise a surfactant- and low-polarity solvent-containing liquid gel phase having dispersed therein the bleach activator salt.
  • a surfactant- and low-polarity solvent-containing liquid gel phase having dispersed therein the bleach activator salt.
  • the amount of the surfactant mixture component of the detergent compositions herein can vary depending upon the nature and amount of other composition components and depending upon the desired rheological properties of the ultimately formed composition. Generally, this surfactant mixture will be used in an amount comprising from 10% to 90% by weight of the composition. More preferably, the surfactant mixture will comprise from 15% to 50% by weight of the composition.
  • Preferred anionic surfactants include the alkyl sulfate surfactants hereof are water soluble salts or acids of the formula ROSO 3 M wherein R preferably is a C 10 -C 24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C 10 -C 18 alkyl component, more preferably a C 12 -C 15 alkyl or hydroxyalkyl, and M is H or a cation, e.g., an alkali metal cation (e.g. sodium, potassium, lithium), or ammonium or substituted ammonium (quaternary ammonium cations such as tetramethyl-ammonium and dimethyl piperdinium cations).
  • R preferably is a C 10 -C 24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C 10 -C 18 alkyl component, more preferably a C 12 -C 15 alkyl or hydroxyalkyl
  • M is H or a
  • alkyl alkoxylated sulfate surfactants hereof are water soluble salts or acids of the formula RO(A) m SO3M wherein R is an unsubstituted C 10 -C 24 alkyl or hydroxyalkyl group having a C 10 -C 24 alkyl component, preferably a C 12 -C 18 alkyl or hydroxyalkyl, more preferably C 12 -C 15 alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically between 0.5 and 6, more preferably between 0.5 and 3, and M is H or a cation which can be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted-ammonium cation.
  • R is an unsubstituted C 10 -C 24 alkyl or hydroxyalkyl group having a C 10 -C 24 alkyl component, preferably a C 12
  • Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein.
  • substituted ammonium cations include quaternary ammonium cations such as tetramethyl-ammonium and dimethyl piperdinium cations
  • Exemplary surfactants are C 12 -C 15 alkyl polyethoxylate (1.0) sulfate (C 12 -C 15 E(1.0)M), C 12 -C 15 alkyl polyethoxylate (2.25) sulfate (C 12 -C 15 E(2.25)M), C 12 -C 15 alkyl polyethoxylate (3.0) sulfate (C 12 -C 15 E(3.0)M), and C 12 -C 15 alkyl polyethoxylate (4.0) sulfate (C 12 -C 15 E(4.0)M), wherein M is conveniently selected from sodium and potassium.
  • alkyl ester sulfonate surfactants including linear esters of C 8 -C 20 carboxylic acids (i.e., fatty acids) which are sulfonated with gaseous SO 3 according to "The Journal of the American Oil Chemists Society", 52 (1975), pp. 323-329.
  • Suitable starting materials would include natural fatty substances as derived from tallow, palm oil, etc.
  • the preferred alkyl ester sulfonate surfactant especially for laundry applications, comprise alkyl ester sulfonate surfactants of the structural formula : wherein R 3 is a C 8 -C 20 hydrocarbyl, preferably an alkyl, or combination thereof, R 4 is a C 1 -C 6 hydrocarbyl, preferably an alkyl, or combination thereof, and M is a cation which forms a water soluble salt with the alkyl ester sulfonate.
  • Suitable salt-forming cations include metals such as sodium, potassium, and lithium, and substituted or unsubstituted ammonium cations.
  • R 3 is C 10 -C 16 alkyl
  • R 4 is methyl, ethyl or isopropyl.
  • methyl ester sulfonates wherein R 3 is C 10 -C 16 alkyl.
  • anionic surfactants useful for detersive purposes can also be included in the laundry detergent compositions of the present invention.
  • These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap, C 9 -C 20 linear alkylbenzenesulfonates, C 8 -C 22 primary of secondary alkanesulfonates, C 8 -C 24 olefinsulfonates, sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed product of alkaline earth metal citrates, e.g., as described in British patent specification No.
  • alkylpolyglycolethersulfates (containing up to 10 moles of ethylene oxide); alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates such as the acyl isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinates (especially saturated and unsaturated C 12 -C 18 monoesters) and diesters of sulfosuccinates (especially saturated and unsaturated C 6 -C 12 diesters), sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside
  • Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tall oil. Further examples are described in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A variety of such surfactants are also generally disclosed in U.S. Patent 3,929,678, issued December 30, 1975 to Laughlin, et al. at Column 23, line 58 through Column 29, line 23.
  • the detergent compositions of the present invention typically comprise from 1% to 40%, preferably from 5% to 25% by weight of such anionic surfactants.
  • One class of nonionic surfactants useful in the present invention are condensates of ethylene oxide with a hydrophobic moiety to provide a surfactant having an average hydrophilic-lipophilic balance (HLB) in the range from 8 to 17, preferably from 9.5 to 14, more preferably from 12 to 14.
  • HLB hydrophilic-lipophilic balance
  • the hydrophobic (lipophilic) moiety may be aliphatic or aromatic in nature and the length of the polyoxyethylene group which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
  • Especially preferred nonionic surfactants of this type are the C 9 -C 15 primary alcohol ethoxylates containing 3-12 moles of ethylene oxide per mole of alcohol, particularly the C 12 -C 15 primary alcohols containing 5-8 moles of ethylene oxide per mole of alcohol.
  • Nonionic surfactants comprises alkyl polyglucoside compounds of general formula RO (C n H 2n O) t Z x wherein Z is a moiety derived from glucose; R is a saturated hydrophobic alkyl group that contains from 12 to 18 carbon atoms; t is from 0 to 10 and n is 2 or 3; x is from 1.3 to 4, the compounds including less than 10% unreacted fatty alcohol and less than 50% short chain alkyl polyglucosides.
  • Compounds of this type and their use in detergent are disclosed in EP-B 0 070 077, 0 075 996 and 0 094 118.
  • nonionic surfactants are poly hydroxy fatty acid amide surfactants of the formula wherein R 1 is H, or R 1 is C 1-4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof, R 2 is C 5-31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof.
  • R 1 is methyl
  • R 2 is a straight C 11-15 alkyl or alkenyl chain such as coconut alkyl or mixtures thereof
  • Z is derived from a reducing sugar such as glucose, fructose, maltose, lactose, in a reductive amination reaction.
  • the hereinbefore described surfactant may be combined with a nonaqueous liquid diluent such as a liquid alcohol alkoxylate material or a nonaqueous, low-polarity organic solvent.
  • a nonaqueous liquid diluent such as a liquid alcohol alkoxylate material or a nonaqueous, low-polarity organic solvent.
  • One component of the liquid diluent suitable to form the compositions herein comprises an alkoxylated fatty alcohol material.
  • Such materials are themselves also nonionic surfactants.
  • Such materials correspond to the general formula: R 1 (C m H 2m O) n OH wherein R 1 is a C 8 - C 16 alkyl group, m is from 2 to 4, and n ranges from 2 to 12.
  • R 1 is an alkyl group, which may be primary or secondary, that contains from 9 to 15 carbon atoms, more preferably from 10 to 14 carbon atoms.
  • the alkoxylated fatty alcohols will be ethoxylated materials that contain from 2 to 12 ethylene oxide moieties per molecule, more preferably from 3 to 10 ethylene oxide moieties per molecule.
  • the alkoxylated fatty alcohol component of the liquid diluent will frequently have a hydrophilic-lipophilic balance (HLB) which ranges from 3 to 17. More preferably, the HLB of this material will range from 6 to 15, most preferably from 8 to 15.
  • HLB hydrophilic-lipophilic balance
  • fatty alcohol alkoxylates useful as one of the essential components of the nonaqueous liquid diluent in the compositions herein will include those which are made from alcohols of 12 to 15 carbon atoms and which contain about 7 moles of ethylene oxide. Such materials have been commercially marketed under the trade names Neodol 25-7 and Neodol 23-6.5 by Shell Chemical Company.
  • Neodols include Neodol 1-5, an ethoxylated fatty alcohol averaging 11 carbon atoms in its alkyl chain with about 5 moles of ethylene oxide; Neodol 23-9, an ethoxylated primary C 12 - C 13 alcohol having about 9 moles of ethylene oxide and Neodol 91-10, an ethoxylated C 9 - C 11 primary alcohol having about 10 moles of ethylene oxide. Alcohol ethoxylates of this type have also been marketed by Shell Chemical Company under the Dobanol tradename.
  • Dobanol 91-5 is an ethoxylated C 9 -C 11 fatty alcohol with an average of 5 moles ethylene oxide and Dobanol 25-7 is an ethoxylated C 12 -C 15 fatty alcohol with an average of 7 moles of ethylene oxide per mole of fatty alcohol.
  • Suitable ethoxylated alcohols include Tergitol 15-S-7 and Tergitol 15-S-9 both of which are linear secondary alcohol ethoxylates that have been commercially marketed by Union Carbide Corporation.
  • the former is a mixed ethoxylation product of C 11 to C 15 linear secondary alkanol with 7 moles of ethylene oxide and the latter is a similar product but with 9 moles of ethylene oxide being reacted.
  • Alcohol ethoxylates useful in the present compositions are higher molecular weight nonionics, such as Neodol 45-11, which are similar ethylene oxide condensation products of higher fatty alcohols, with the higher fatty alcohol being of 14-15 carbon atoms and the number of ethylene oxide groups per mole being about 11. Such products have also been commercially marketed by Shell Chemical Company.
  • the alcohol alkoxylate component when utilized as part of the liquid diluent in the nonaqueous compositions herein will generally be present to the extent of from 1% to 60% by weight of the composition. More preferably, the alcohol alkoxylate component will comprise 5% to 40% by weight of the compositions herein. Most preferably, the alcohol alkoxylate component will comprise from 10% to 25% by weight of the detergent compositions herein.
  • solvent is used herein to connote the non-surface active carrier or diluent portion of the liquid phase of the composition. While some of the essential and/or optional components of the compositions herein may actually dissolve in the “solvent"-containing phase, other components will be present as particulate material dispersed within the “solvent”-containing phase. Thus the term “solvent” is not meant to require that the solvent material be capable of actually dissolving all of the detergent composition components added thereto.
  • nonaqueous organic materials which are employed as solvents herein are those which are liquids of low polarity.
  • low-polarity liquids are those which have little, if any, tendency to dissolve one of the preferred types of particulate material used in the compositions herein, i.e., the peroxygen bleaching agents, sodium perborate or sodium percarbonate.
  • relatively polar solvents such as ethanol should not be utilized.
  • Suitable types of low-polarity solvents useful in the nonaqueous liquid detergent compositions herein do include alkylene glycol mono lower alkyl ethers, lower molecular weight polyethylene glycols and lower molecular weight methyl esters and amides.
  • a preferred type of nonaqueous, low-polarity solvent for use herein comprises the mono-, di-, tri-, or tetra-C 2 -C 3 alkylene glycol mono C 2 -C 6 alkyl ethers.
  • the specific examples of such compounds include diethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, dipropolyene glycol monoethyl ether, and dipropylene glycol monobutyl ether.
  • Diethylene glycol monobutyl ether and dipropylene glycol monobutyl ether are especially preferred.
  • Compounds of the type have been commercially marketed under the tradenames Dowanol, Carbitol, and Cellosolve.
  • nonaqueous, low-polarity organic solvent useful herein comprises the lower molecular weight polyethylene glycols (PEGs).
  • PEGs polyethylene glycols
  • Such materials are those having molecular weights of at least about 150.
  • PEGs of molecular weight ranging from about 200 to 600 are most preferred.
  • non-polar, nonaqueous solvent comprises lower molecular weight methyl esters.
  • Such materials are those of the general formula: R 1 -C(O)-OCH 3 wherein R 1 ranges from 1 to 18.
  • suitable lower molecular weight methyl esters include methyl acetate, methyl propionate, methyl octanoate, and methyl dodecanoate.
  • the nonaqueous, low-polarity organic solvent(s) employed should, of course, be compatible and non-reactive with other composition components, e.g., bleach and/or activators, used in the liquid detergent compositions herein.
  • a solvent component will generally be utilized in an amount of from about 1% to 60% by weight of the composition. More preferably, the nonaqueous, low-polarity organic solvent will comprise from 5% to 40% by weight of the composition, most preferably from 10% to 25% by weight of the composition.
  • the amount of total liquid diluent in the compositions herein will be determined by the type and amounts of other composition components and by the desired composition properties. Generally, the liquid diluent will comprise from 20% to 80% by weight of the compositions herein. More preferably, the liquid diluent will comprise from 40% to 60% by weight of the composition.
  • the nonaqueous detergent compositions herein may further comprise a solid phase of particulate material which is dispersed and suspended within the liquid phase.
  • particulate material will range in size from 0.1 to 1500 microns. More preferably such material will range in size from 5 to 200 microns.
  • the particulate material utilized herein can comprise one or more types of detergent composition components which in particulate form are substantially insoluble in the nonaqueous liquid phase of the composition.
  • the types of particulate materials which can be utilized are described in detail as follows:
  • Another possible type of particulate material which can be suspended in the nonaqueous liquid detergent compositions herein includes ancillary anionic surfactants which are fully or partially insoluble in the nonaqueous liquid phase.
  • anionic surfactant with such solubility properties comprises primary or secondary alkyl sulfate anionic surfactants.
  • Such surfactants are those produced by the sulfation of higher C 8 -C 20 fatty alcohols.
  • R typically a linear C 8 - C 20 hydrocarbyl group, which may be straight chain or branched chain
  • M is a water-solubilizing cation.
  • R is typically a C 10 - C 14 alkyl
  • M is alkali metal.
  • R is about C 12 and M is sodium.
  • Conventional secondary alkyl sulfates may also be utilized as the essential anionic surfactant component of the solid phase of the compositions herein.
  • Conventional secondary alkyl sulfate surfactants are those materials which have the sulfate moiety distributed randomly along the hydrocarbyl "backbone" of the molecule. Such materials may be depicted by the structure CH 3 (CH 2 ) n (CHOSO 3 - M + ) (CH 2 ) m CH 3 wherein m and n are integers of 2 or greater and the sum of m + n is typically 9 to 15, and M is a water-solubilizing cation.
  • ancillary anionic surfactants such as alkyl sulfates will generally comprise from 1% to 10% by weight of the composition, more preferably from 1% to 5% by weight of the composition.
  • Alkyl sulfate used as all or part of the particulate material is prepared and added to the compositions herein separately from the unalkoxylated alkyl sulfate material which may form part of the alkyl ether sulfate surfactant component essentially utilized as part of the liquid phase herein.
  • particulate material which can be suspended in the nonaqueous liquid detergent compositions herein comprises an organic detergent builder material which serves to counteract the effects of calcium, or other ion, water hardness encountered during laundering/bleaching use of the compositions herein.
  • organic detergent builder material which serves to counteract the effects of calcium, or other ion, water hardness encountered during laundering/bleaching use of the compositions herein.
  • examples of such materials include the alkali metal, citrates, succinates, malonates, fatty acids, carboxymethyl succinates, carboxylates, polycarboxylates and polyacetyl carboxylates. Specific examples include sodium, potassium and lithium salts of oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids and citric acid.
  • organic phosphonate type sequestering agents such as those which have been sold by Monsanto under the Dequest tradename and alkanehydroxy phosphonates. Citrate salts are highly preferred.
  • suitable organic builders include the higher molecular weight polymers and copolymers known to have builder properties.
  • such materials include appropriate polyacrylic acid, polymaleic acid, and polyacrylic/polymaleic acid copolymers and their salts, such as those sold by BASF under the Sokalan trademark.
  • Another suitable type of organic builder comprises the water-soluble salts of higher fatty acids, i.e., "soaps".
  • these include alkali metal soaps such as the sodium, potassium, ammonium, and alkylolammonium salts of higher fatty acids containing from 8 to 24 carbon atoms, and preferably from 12 to 18 carbon atoms.
  • Soaps can be made by direct saponification of fats and oils or by the neutralization of free fatty acids.
  • Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap.
  • insoluble organic detergent builders can generally comprise from 2% to 20% by weight of the compositions herein. More preferably, such builder material can comprise from 4% to 10% by weight of the composition.
  • particulate material which can be suspended in the nonaqueous liquid detergent compositions herein can comprise a material which serves to render aqueous washing solutions formed from such compositions generally alkaline in nature.
  • Such materials may or may not also act as detergent builders, i.e., as materials which counteract the adverse effect of water hardness on detergency performance.
  • alkalinity sources examples include water-soluble alkali metal carbonates, bicarbonates, borates, silicates and metasilicates.
  • water-soluble phosphate salts may also be utilized as alkalinity sources. These include alkali metal pyrophosphates, orthophosphates, polyphosphates and phosphonates. Of all of these alkalinity sources, alkali metal carbonates such as sodium carbonate are the most preferred.
  • the alkalinity source if in the form of a hydratable salt, may also serve as a desiccant in the nonaqueous liquid detergent compositions herein.
  • the presence of an alkalinity source which is also a desiccant may provide benefits in terms of chemically stabilizing those composition components such as the peroxygen bleaching agent which may be susceptible to deactivation by water.
  • the alkalinity source will generally comprise from 1% to 15% by weight of the compositions herein. More preferably, the alkalinity source can comprise from 2% to 10% by weight of the composition. Such materials, while water-soluble, will generally be insoluble in the nonaqueous detergent compositions herein. Thus such materials will generally be dispersed in the nonaqueous liquid phase in the form of discrete particles.
  • the detergent compositions herein can, and preferably will, contain various optional components.
  • Such optional components may be in either liquid or solid form.
  • the optional components may either dissolve in the liquid phase or may be dispersed within the liquid phase in the form of fine particles or droplets.
  • the detergent compositions herein may also optionally contain one or more types of inorganic detergent builders beyond those listed hereinbefore that also function as alkalinity sources.
  • optional inorganic builders can include, for example, aluminosilicates such as zeolites. Aluminosilicate zeolites, and their use as detergent builders are more fully discussed in Corkill et al., U.S. Patent No. 4,605,509; Issued August 12, 1986. Also crystalline layered silicates, such as those discussed in this '509 U.S. patent, are also suitable for use in the detergent compositions herein.
  • optional inorganic detergent builders can comprise from 2% to 15% by weight of the compositions herein.
  • the detergent compositions herein may also optionally contain one or more types of detergent enzymes.
  • Such enzymes can include proteases, amylases, cellulases and lipases. Such materials are known in the art and are commercially available. They may be incorporated into the nonaqueous liquid detergent compositions herein in the form of suspensions, "marumes" or "prills".
  • Another suitable type of enzyme comprises those in the form of slurries of enzymes in nonionic surfactants. Enzymes in this form have been commercially marketed, for example, by Novo Nordisk under the tradename "LDP.”
  • Enzymes added to the compositions herein in the form of conventional enzyme prills are especially preferred for use herein.
  • Such prills will generally range in size from 100 to 1,000 microns, more preferably from 200 to 800 microns and will be suspended throughout the nonaqueous liquid phase of the composition.
  • Prills in the compositions of the present invention have been found, in comparison with other enzyme forms, to exhibit especially desirable enzyme stability in terms of retention of enzymatic activity over time.
  • compositions which utilize enzyme prills need not contain conventional enzyme stabilizing such as must frequently be used when enzymes are incorporated into aqueous liquid detergents.
  • nonaqueous liquid detergent compositions herein will typically comprise from 0.001% to 5%, preferably from 0.01% to 1% by weight, of a commercial enzyme preparation.
  • Protease enzymes for example, 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.
  • the detergent compositions herein may also optionally contain a chelating agent which serves to chelate metal ions, e.g., iron and/or manganese, within the nonaqueous detergent compositions herein.
  • a chelating agent which serves to chelate metal ions, e.g., iron and/or manganese, within the nonaqueous detergent compositions herein.
  • Such chelating agents thus serve to form complexes with metal impurities in the composition which would otherwise tend to deactivate composition components such as the peroxygen bleaching agent.
  • Useful chelating agents can include amino carboxylates, phosphonates, amino phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures thereof.
  • Amino carboxylates useful as optional chelating agents include ethylenediaminetetraacetates, N-hydroxyethylethylene-diaminetriacetates, nitrilotriacetates, ethylenediamine tetrapropionates, triethylenetetraaminehexacetates, diethylenetriaminepentaacetates, ethylenediaminedisuccinates and ethanoldiglycines.
  • the alkali metal salts of these materials are preferred.
  • Amino phosphonates are also suitable for use as chelating agents in the compositions of this invention when at least low levels of total phosphorus are permitted in detergent compositions, and include ethylenediaminetetrakis (methylene-phosphonates) as DEQUEST.
  • these amino phosphonates do not contain alkyl or alkenyl groups with more than 6 carbon atoms.
  • Preferred chelating agents include hydroxyethyldiphosphonic acid (HEDP), diethylene triamine penta acetic acid (DTPA), ethylenediamine disuccinic acid (EDDS) and dipicolinic acid (DPA) and salts thereof.
  • the chelating agent may, of course, also act as a detergent builder during use of the compositions herein for fabric laundering/ bleaching.
  • the chelating agent if employed, can comprise from 0.1% to 4% by weight of the compositions herein. More preferably, the chelating agent will comprise from 0.2% to 2% by weight of the detergent compositions herein.
  • the detergent compositions herein may also optionally contain a polymeric material which serves to enhance the ability of the composition to maintain its solid particulate components in suspension.
  • a polymeric material which serves to enhance the ability of the composition to maintain its solid particulate components in suspension.
  • Such materials may thus act as thickeners, viscosity control agents and/or dispersing agents.
  • Such materials are frequently polymeric polycarboxylates but can include other polymeric materials such as polyvinylpyrrolidone (PVP) and polymeric amine derivatives such as quaternized, ethoxylated hexamethylene diamines.
  • PVP polyvinylpyrrolidone
  • polymeric amine derivatives such as quaternized, ethoxylated hexamethylene diamines.
  • 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 of monomeric segments, containing no carboxylate radicals such as vinylmethyl ether, styrene, ethylene, etc. is suitable provided that such segments do not constitute more than 40% by weight of the polymer.
  • 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 2,000 to 10,000, more preferably from 4,000 to 7,000, and most preferably from 4,000 to 5,000.
  • Water-soluble salts of such acrylic acid polymers can include, for example, the alkali metal, salts.
  • Soluble polymers of this type are known materials. Use of polyacrylates of this type in detergent compositions has been disclosed, for example, Diehl, U.S. Patent 3,308,067, issued March 7, 1967. Such materials may also perform a builder function.
  • the optional thickening, viscosity control and/or dispersing agents should be present in the compositions herein to the extent of from 0.1% to 4% by weight. More preferably, such materials can comprise from 0.5% to 2% by weight of the detergents compositions herein.
  • the detergent compositions herein may also optionally contain conventional brighteners, suds suppressors, silicone oils, bleach catalysts, and/or perfume materials.
  • Such brighteners, suds suppressors, silicone oils, bleach catalysts, and perfumes must, of course, be compatible and non-reactive with the other composition components in a nonaqueous environment. If present, brighteners suds suppressors and/or perfumes will typically comprise from 0.1% to 2% by weight of the compositions herein.
  • Suitable bleach catalysts include the manganese based complexes disclosed in US-A-5,246,621, US-A-5,244,594, US-A-5,114,606 and US-A-5,114,611.
  • the particulate-containing liquid detergent compositions of this invention are substantially nonaqueous (or anhydrous) in character. While very small amounts of water may be incorporated into such compositions as an impurity in the essential or optional components, the amount of water should in no event exceed 5% by weight of the compositions herein. More preferably, water content of the nonaqueous detergent compositions herein will comprise less than 1% by weight.
  • the particulate-containing nonaqueous detergent compositions herein will be in the form of a liquid, gel or paste.
  • nonaqueous detergent compositions herein can be prepared by combining the bleach activator salts and optional components thereof in any convenient order and by mixing, e.g., agitating, the resulting component combination to form the phase stable compositions herein.
  • compositions of this invention can be used to form aqueous washing solutions for use in the laundering and bleaching of fabrics.
  • an effective amount of such compositions is added to water, preferably in a conventional fabric laundering automatic washing machine, to form such aqueous laundering/bleaching solutions.
  • the aqueous washing/bleaching solution so formed is then contacted, preferably under agitation, with the fabrics to be laundered and bleached therewith.
  • An effective amount of the liquid detergent compositions herein added to water to form aqueous laundering/bleaching solutions can comprise amounts sufficient to form from 500 to 7, 000 ppm of composition in aqueous solution. More preferably, from 1,000 to 3,000 ppm of the detergent compositions herein will be provided in aqueous washing/bleaching solution.
  • a bleach-containing nonaqueous laundry detergent is prepared having the composition as set forth in Table I.
  • This composition is a stable anhydrous liquid laundry detergent wherein the bleach activator is stable in the concentrate and wherein the bleach activator is effective in the wash liquor.

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Claims (9)

  1. Nichtwäßrige Waschmittelzusammensetzung, welche in Form einer Flüssigkeit, Paste oder eines Gels vorliegt, wobei die nichtwäßrige Waschmittelzusammensetzung ein Bleichmittel und einen Bleichaktivator umfaßt, dadurch gekennzeichnet, daß der Bleichaktivator als zweiwertiges Metallsalz, dreiwertiges Metallsalz, gemischtes Metallsalz, wobei mindestens eines der Salze ein zweiwertiges oder ein dreiwertiges Metallsalz ist, oder Mischungen hiervon vorliegt.
  2. Nichtwäßrige Waschmittelzusammensetzung nach Anspruch 1, wobei das zweiwertige Salz aus Ca und/oder Mg gewählt ist.
  3. Nichtwäßrige Waschmittelzusammensetzung nach Anspruch 1, wobei das gemischte Metallsalz ein einwertiges Metall umfaßt.
  4. Nichtwäßrige Waschmittelzusammensetzung nach den Ansprüchen 1-3, wobei der Bleichaktivator 4-Benoyloxybenzolsulfonat; 1-Methyl-2-benzoyloxybenzol-4-sulfonat; Nonanoyloxybenzolsulfonat; 3,5,5-Trimethylhexanoyloxybenzolsulfonat ist.
  5. Nichtwäßrige Waschmittelzusammensetzung nach den Ansprüchen 1-3, wobei der Bleichaktivator 4-[N-Oktanoyl-6-aminohexanoyloxy]benzolsulfonat, 4-[N-Nonanoyl-6-aminohexanoyloxy]benzolsulfonat, 4-[N-Dekanoyl-6-aminohexanoyloxylbenzolsulfonat und Mischungen hiervon ist.
  6. Nichtwäßrige Waschmittelzusammensetzung nach den Ansprüchen 1-5, wobei das Bleichmittel Percarbonat ist.
  7. Nichtwäßrige Waschmittelzusammensetzung nach den Ansprüchen 1-6, umfassend weiterhin ein Polyoltensid.
  8. Nichtwäßrige Waschmittelzusammensetzung nach Anspruch 7, wobei das Polyoltensid aus Polyhydroxyfettsäureamiden gewählt ist.
  9. Nichtwäßrige Waschmittelzusammensetzung nach den Ansprüchen 1-8, umfassend weiterhin 5-25 Gew.-% anionisches Tensid.
EP95924005A 1995-06-20 1995-06-20 Nichtwässerige, körnchen enthaltende waschmittelzusammensetzungen Revoked EP0833887B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
CN95197939A CN1193994A (zh) 1995-06-20 1995-06-20 非水含颗粒洗涤剂组合物
PCT/US1995/007823 WO1997000937A1 (en) 1995-06-20 1995-06-20 Nonaqueous, particulate-containing detergent compositions
CA002225596A CA2225596A1 (en) 1995-06-20 1995-06-20 Nonaqueous, particulate-containing detergent compositions

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EP0833887B1 true EP0833887B1 (de) 2000-01-19

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EP0907710A2 (de) * 1996-06-28 1999-04-14 The Procter & Gamble Company Nichtwässrige waschmittelzusammensetzungen enthaltend bleichmittelvorstufen
CZ417498A3 (cs) † 1996-06-28 1999-06-16 The Procter & Gamble Company Nevodný tekutý čistící prostředek obsahující bělící primární látku
BR9810490A (pt) * 1997-06-27 2001-11-27 Procter & Gamble Composições detergente não-aquosas contendoalvejante
BR9810943A (pt) * 1997-06-27 2000-09-26 Procter & Gamble Composições de detergentes contendo materiais particulados não aquosos contendo alvejante
ATE241003T1 (de) * 1997-11-10 2003-06-15 Procter & Gamble Mehrschichtige waschmitteltablette mit sowohl verpresstem als auch nicht-verpresstem anteil
JP2001522933A (ja) * 1997-11-10 2001-11-20 ザ、プロクター、エンド、ギャンブル、カンパニー 洗剤タブレット
US6770615B1 (en) 1999-08-10 2004-08-03 The Procter & Gamble Company Non-aqueous liquid detergents with water-soluble low-density particles
BR0013246A (pt) * 1999-08-10 2002-04-16 Procter & Gamble Detergentes lìquidos não-aquosos com partìculas de densidade baixa solúvel em água
US8933131B2 (en) 2010-01-12 2015-01-13 The Procter & Gamble Company Intermediates and surfactants useful in household cleaning and personal care compositions, and methods of making the same
CA2827658A1 (en) 2011-02-17 2012-08-23 The Procter & Gamble Company Bio-based linear alkylphenyl sulfonates
EP2678410B1 (de) 2011-02-17 2017-09-13 The Procter and Gamble Company Zusammensetzungen mit mischungen aus c10-c13-alkylphenyl-sulfonaten
US9228158B2 (en) 2012-02-01 2016-01-05 Gurtler Industries, Inc. Composition and method for removing stains derived from chlorhexidine gluconate
DE102014218951A1 (de) * 2014-09-19 2016-03-24 Henkel Ag & Co. Kgaa Festförmige Zusammensetzung für die Textilbehandlung

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US4634551A (en) * 1985-06-03 1987-01-06 Procter & Gamble Company Bleaching compounds and compositions comprising fatty peroxyacids salts thereof and precursors therefor having amide moieties in the fatty chain
PH25878A (en) * 1987-01-27 1991-12-02 Colgate Palmolive Co Built liquid laundry detergent composition containing an alkaline earth metal or zinc salt of higher fatty acid liquifying agent
GB9123220D0 (en) * 1991-11-01 1991-12-18 Unilever Plc Liquid cleaning compositions

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EP0833887A1 (de) 1998-04-08

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