Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
  • C11D17/0004—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
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/83—Mixtures of non-ionic with anionic compounds
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • 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
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/02—Anionic compounds
  • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
  • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic 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
  • C11D1/66—Non-ionic compounds
  • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

• This invention relates to liquid laundry detergent products which are nonaqueous in nature and which are in the form of stable dispersions of particulate material such as bleaching agents and/or other detergent composition adjuvants.
• Liquid detergent products are often considered to be more convenient to use than are dry powdered or particulate detergent products. Liquid detergents have therefore found substantial favor with consumers. Such liquid 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, liquid 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.
• liquid 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 in a liquid, and especially in an aqueous liquid, environment.
• 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.
• WO92/02610 describes stable, substantially non-aqueous washing agents which contain nonionic surfactants, at least 8% by weight of anionic surfactants and a peroxy bleach in wich the weight ratio of nonionic to anionic surfactants is 4:1 to 1:2,5 and which are obtained by the wet-grinding of a mixture of these ingredients.
• the present invention provides nonaqueous liquid detergent compositions comprising a stable suspension of solid, substantially insoluble particulate material dispersed throughout a structured, surfactant-containing liquid phase.
• Such compositions comprise A) from 35% to 99% by weight of the composition of a nonaqueous liquid phase; and B) from 1% to 65% by weight of the composition of one or more types of particulate materials.
• the nonaqueous liquid phase itself comprises from 30% to 65% by weight of this liquid phase of a certain type of dissolved anionic surfactant.
• This anionic surfactant component comprises a material selected from the alkali metal salts of C 10 -C 16 alkylbenzene sulfonic acids.
• the nonaqueous liquid phase of the compositions herein also comprises from 35% to 70% by weight of the liquid phase of a nonaqueous liquid diluent.
• a nonaqueous liquid diluent comprises both i) alcohol alkoxylates of the formula R 1 (OC m H 2m ) n OH wherein R 1 is a C 8 -C 16 alkyl group, m is from 2 to 4, and n is from about 2 to 12; and ii) a nonaqueous, low-polarity organic solvent selected from (1) mono, di, tri, tetra C 2 -C 3 alkylene glycol mono C 2 -C 6 alkyl ethers and (2) non-vicinal alkylene glycols containing from 4 to 8 carbon atoms.
• These components are present in the nonaqueous liquid diluent in an alcohol alkoxylate to organic solvent weight ratio of from 50:1 to 1:50.
• the particulate material suspended in the nonaqueous liquid phase of the compositions herein ranges in size from 0.1 to 1500 microns and is substantially insoluble in the nonaqueous compositions herein.
• This insoluble particulate material preferably comprises a peroxygen bleaching agent, but may also comprise bleach activators, ancillary anionic surfactants, organic detergent builders, inorganic alkalinity sources and combinations of these particulate material types.
• nonaqueous liquid detergent compositions of this invention comprise a surfactant - and low-polarity solvent-containing liquid phase having dispersed therein as a solid phase certain types of particulate materials.
• a surfactant - and low-polarity solvent-containing liquid phase having dispersed therein as a solid phase certain types of particulate materials.
• the liquid phase will generally comprise from 35% to 99% by weight of the detergent compositions herein. More preferably, the liquid phase will comprise from 50% to 95% by weight of the compositions. Most preferably, the liquid phase will comprise from 45% to 75% by weight of the compositions herein.
• the liquid phase of the detergent compositions herein essentially contains relatively high concentrations of a certain type anionic surfactant combined with a certain type of nonaqueous, liquid diluent.
• the anionic surfactant essentially utilized as an essential component of the nonaqueous liquid phase is one selected from the alkali metal salts of alkylbenzene sulfonic acids in which the all group contains from about 10 to 16 carbon atoms, in straight chain or branched chain configuration.
• alkali metal salts of alkylbenzene sulfonic acids in which the all group contains from about 10 to 16 carbon atoms, in straight chain or branched chain configuration.
• LAS sodium and potassium linear straight chain alkylbenzene sutfonates
• Sodum C 11 -C 14 LAS is especially preferred.
• the alkylbenzene sulfonate anionic surfactant will be dissolved in the nonaqueous liquid diluent which makes up the second essential component of the nonaqueous phase.
• the alkylbenzene sulfonate anionic surfactant is generally present to the extent of from 30% to 65% by weight of the liquid phase. More preferably, the alkylbenzene sulfonate anionic surfactant will comprise from 35% to 50% by weight of the nonaqueous liquid phase of the compostions herein. Utilization of this anionic surfactant in these concentrations corresponds to an anionic surfactant concentration in the total composition of from 15% to 60% by weight, more preferably from 20% to 40% by weight, of the composition.
• the hereinbefore described alkylbenzene sulfonate anionic surfactant is combined with a nonaqueous liquid diluent which contains two essential components. These two components are a liquid alcohol alkoxylate materiat and a nonaqueous, low-polarity organic solvent.
• One essential component of the liquid diluent used 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 about 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 matesiats 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 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 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 11. Such products have also been commercially marketed by Shell Chemical Company.
• the alcohol alkoxylate component which is essentially utilized as part of the liquid diluent in the nonaqueous compositions herein will generally be present to the extent of from 1% to 60% of the liquid phase composition. More preferably, the alcohol alkoxylate component will comprise 5% to 40% of the liquid phase. Most preferably, the essentially utilized alcohol alkoxylate component will comprise from 5% to 30% of the detergent composition liquid phase. Utilization of alcohol alkoxytate in these concentrations in the liquid phase corresponds to an alcohol alkoxylate concentration in the total composition of from 1% to 60% by weight, more preferably from 2% to 40% by weight, and most preferably from 5% to 25% by weight, of the composition.
• a second essential component of the liquid diluent which forms part of the liquid phase of the detergent compositions herein comprises nonaqueous, low-polarity organic solvent(s).
• 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 liquid phase, other components will be present as particulate material dispersed within the “solvent"-containing liquid 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 the non-vicinal C 4 -C 8 branched or straight chain alkylene glycols.
• hexylene glycol (4-methyl-2,4-pentanediol), 1,6-hexanediol, 1,3-butylene glycol and 1,4-butylene glycol.
• Hexylene glycol is the most preferred.
• the mono-, di-, tri-, or tetra- C 2 -C 3 alkylene glycol mono C 2 -C 6 alkyl ethers include diethytene 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.
• 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 1% to 70% by weight of the liquid phase.
• the nonaqueous, low-polarity organic solvent will comprise from 10% to 60% by weight of the liquid phase, most preferably from 20% to 50% by weight, of the liquid phase of the composition. Utilization of this organic solvent in these concentrations in the liquid phase corresponds to a solvent concentration in the total composition of from 1% to 50% by weight, more preferably from 5% to 40% by weight, and most preferably from 10% to 30% by weight, of the composition.
• the ratio of alcohol alkoxylate to organic solvent within the liquid diluent can be used to vary the theological properties of the detergent compositions eventually formed.
• the weight ratio of alcohol alkoxylate to organic solvent will range from 50:1 to 1:50. More preferably, this ratio will range from 3:1 to 1:3.
• the amount of total liquid diluent in the nonaqueous liquid phase herein will be determined by the type and amounts of other composition components and by the desired composition properties.
• the liquid diluent will comprise from 35% to 70% of the nonaqueous liquid phase of the compositions herein. More preferably, the liquid diluent will comprise from 50% to 65% of the nonaqueous liquid phase. This corresponds to a nonaqueous liquid diluent concentration in the total composition of from 15% to 70% by weight, more preferably from 20% to 50% by weight, of the composition.
• the nonaqueous detergent compositions herein also essentially comprise from 1% to 65% by weight, more preferably from 5% to 50% by weight, of a solid phase of particuste material which is dispersed and suspended within the liquid phase.
• a solid phase of particuste 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:
• the most preferred type of paniculate material useful for forming the solid phase of the detergent compositions herein comprises particles of a peroxygen bleaching agent.
• a peroxygen bleaching agent may be organic or inorganic in nature. Inorganic peroxygen bleaching agents are frequently utilized in combination with a bleach activator.
• Useful organic peroxygen bleaching agents include percarboxylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of metachloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid.
• Such bleaching agents are disclosed in U.S. Patent 4,483,781, Hartman, Issued November 20, 1984; European Patent Application EP-A-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 (NAPAA) as described in U.S. Patent 4,634,551, Issued January 6, 1987 to Bums et al.
• NAPAA 6-nonylamino-6-oxoperoxycaproic acid
• Inorganic peroxygen bleaching agents may also be used in particulate form in the detergent compositions herein.
• Inorganic bleaching agents are in fact preferred.
• Such inorganic peroxygen compounds include alkali metal perborate and percarbonate materials, most preferably the percarbonates.
• sodium perborate e.g. mono- or tetra-hydrate
• Suitable inorganic bleaching agents can also include sodium or potassium carbonate peroxyhydrate and equivalent "percarbonate" bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide.
• Persulfate bleach e.g., OXONE, manufactured commercially by DuPont
• OXONE manufactured commercially by DuPont
• inorganic peroxygen bleaches will be coated with silicate, borate, sulfate or water-soluble surfactants.
• coated percarbonate particles are available from various commercial sources such as FMC, Solvay Interox, Tokai Denka and Degussa.
• Inorganic peroxygen bleaching agents e.g., the perborates, the percarbonates, etc.
• bleach activators which lead to the in situ production in aqueous solution (i.e., during use of the compositions herein for fabric laundering/bleaching) of the peroxy acid corresponding to the bleach activator.
• Various non-limiting examples of activators are disclosed in U.S. Patent 4,915,854, Issued April 10, 1990 to Mao et al.; and U.S. Patent 4,412,934 Issued November 1, 1983 to Chung et al.
• NOBS nonanoyloxybenzene sulfonate
• TAED tetraacetyl ethylene diamine
• R 1 N(R 5 )C(O)R 2 C(O)L or R 1 C(O)N(R 5 )R 2 C(O)L wherein R 1 is an alkyl group containing from about 6 to about 12 carbon atoms, R 2 is an alkylene containing from 1 to about 6 carbon atoms, R 5 is H or alkyl, aryl, or alkaryl containing from about 1 to about 10 carbon atoms, and L is any suitable leaving group.
• a leaving group is any group that is displaced from the bleach activator as a consequence of the nucleophilic attack on the bleach activator by the perhydrolysis anion.
• a preferred leaving group is phenol sulfonate.
• bleach activators of the above formulae include (6-octanamido-caproyl)oxybenzenesulfonate, (6-nonanamidocaproyl) oxybenzenesulfonate, (6-decanamido-caproyl)oxybenzenesulfonate and mixtures thereof as described in the hereinbefore referenced U.S. Patent 4,634,551. Such mixtures are characterized herein as (6-C 8 -C 10 alkamido-caproyl)oxybenzenesulfonate.
• Another class of useful bleach activators comprises the benzoxazin-type activators disclosed by Hodge et al. in U.S. Patent 4,966, 723, Issued October 30, 1990, incorporated herein by reference.
• a highly preferred activator of the benzoxazin-type is:
• Still another class of useful bleach activators indudes the acyl lactam activators, especially acyl caprolactams and acyl valerolactams of the formulae: wherein R 6 is H or an alkyl, aryl, alkoxyaryl, or alkaryl group containing from 1 to about 12 carbon atoms.
• lactam activators include benzoyl caprolactam, octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, benzoyl valerolactam, octanoyl valerolactam, decanoyl valerolactam, undecenoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam and mixtures thereof. See also U.S. Patent 4,545,784, Issued to Sanderson, October 8, 1985, incorporated herein by reference, which discloses acyl caprolactams, including benzoyl caprolactam, adsorbed into sodium perborate.
• peroxygen bleaching agents are used as all or part of the essentially present particulate material, they will generally comprise from 1% to 30% by weight of the composition. More preferably, peroxygen bleaching agent will comprise from 1% to 20% by weight of the composition. Most preferably, peroxygen bleaching agent will be present to the extent of from 3% to 15% by weight of the composition.
• bleach activators can comprise from 0.5% to 20%, more preferably from 1% to 10%, by weight of the composition. Frequently, activators are employed such that the molar ratio of bleaching agent to activator ranges from 1:1 to 10:1, more preferably from 1.5:1 to 5:1. In addition, it has been found that bleach activators, when agglomerated with certain acids such as citric acid, are more chemically stable.
• 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 is typically a linear C 8 - C 20 hydrocarbyl group, which may be straight chain or branched chain, and M is a water-solubilizing cation.
• R is typically a linear C 8 - C 20 hydrocarbyl group, which may be straight chain or branched chain, and M is a water-solubilizing cation.
• R is a C 10 - C 14 alkyl, and M is alkali metal. Most preferably 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 about 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.
• 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.
• rnataials 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 seguestering 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 ".
• soaps include alkali metal soaps such as the sodium, potassium, ammonium, and alkylolammonium salts of higher fatty adds containing from about 8 to about 24 carbon atoms, and preferably from about 12 to about 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 about 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, potyphosphates 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 25% by weight of the compositions herein. More preferably, the alkalinity source can comprise from about 2% to 15% 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, in addition to the optional alkyl sulfates hereinbefore described, also contain other types of surfactant materials.
• additional optional surfactants must, of course, be compatible with other composition components and must not substantially adversely affect composition rheology, stability or performance.
• Optional surfactants can be of the anionic, nonionic, cationic, and/or amphoteric type. If employed, optional surfactants will generally comprise from 1% to 20% by weight of the compositions herein, more preferably from 5% to 10% by weight of the compositions herein.
• alkyl polyalkoxylate sulfates are also known as alkoxylated alkyl sulfates or alkyl ether sulfates.
• Such materials are those which correspond to the formula R 2 -O-(C m H 2m O) n -SO 3 M wherein R 2 is a C 10 -C 22 alkyl group, m is from 2 to 4, n is from about 1 to 15, and M is a salt-forming cation.
• R 2 is a C 12 -C 18 alkyl, m is 2, n is from about 1 to 10, and M is sodium, potassium, ammonium, alkylammonium or alkanolammonium. Most preferably, R 2 is a C 12 -C 16 , m is 2, n is from about 1 to 6, and M is sodium. Ammonium, alkylammonium and alkanolammonium counterions are preferably avoided when the solid phase materials used in the compositions herein include a peroxygen bleaching agent.
• anionic surfactant material which may be optionally added to the detergent compositions herein comprises carboxylate-type anionics.
• Carboxylate-type anionics include the C 10 -C 18 alkyl alkoxy carboxylates (especially the EO 1 to 5 ethoxycarboxylates) and the C 10 -C 18 sarcosinates, especially oleoyl sarcosinate.
• anionic surfactant material which may be optionally employed comprises other sulfonated anionic surfactants such as the C 8 -C 18 paraffin sulfonates and the C 8 -C 18 olefin sulfonates.
• a preferred type of optional nonionic surfactant comprises surfactants which are ethylene oxide (EO) - propylene oxide (PO) block polymers.
• Materials of this type are well known nonionic surfactants which have been marketed under the tradename Pluronic. These materials are formed by adding blocks of ethylene oxide moieties to the ends of polypropylene glycol chains to adjust the surface active properties of the resulting block polymers.
• Pluronic block polymer nonionics of this type are described in greater detail in Davidsohn and Milwidsky; Synthetic Detergents, 7th Ed. ; Longman Scientific and Technical (1987) at pp. 34-36 and pp. 189-191 and in U.S. Patents 2,674,619 and 2,677,700. All of these publications are incorporated herein by reference.
• Pluronic type nonionic surfactants are believed to function as effective suspending agents for the particulate material which is dispersed in the liquid phase of the detergent compositions herein.
• Materials of this type of nonionic surfactant are those which conform to the formula: wherein R is a C 9-17 alkyl or alkenyl, p is from 1 to 6, and Z is glycityl derived from a reduced sugar or alkoxylated derivative thereof.
• Such materials include the C 12 -C 18 N-methyl glucamides. Examples are N-methyl N-1-deoxyglucityl cocoamide and N-methyl N-1-deoxyglucityl oleamide. Processes for making polyhydroxy fatty acid, amides are know and can be found, for example, in Wilson, U.S.
• Patent 2,965,576 and Schwartz U.S. Patent 2,703,798, the disclosures of which are incorporated herein by reference.
• the materials themselves and their preparation are also described in greater detail in Honsa, U.S. Patent 5,174,937, Issued December 26, 1992, which patent is also incorporated herein by reference.
• 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, the disclosure of which is incorporated herein by reference. Also crystalline layered silicates, such as those discussed in this '509 U.S. patent, are also suitable for use in the detergent compositions herein. If utilized, 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, e.g., the enzymes marketed by Novo Nordisk under the tradename "SL” or the microencapsulated enzymes marketed 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 m-6 (microns), more preferably from 200 to 800 m-6 (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-substiuted aromatic chelating agents and mixtures thereof.
• Amino carboxylates useful as optional chelating agents include ethylenediaminetetraacetates, N-hydroxyethyl-ethylenediaminetriacetates, nitrilotriacetates, ethylene-diamine tetrapropionates, triethylenetetraaminehexacetates, diethylenetriaminepentaacetates, ethylenediaminedisucci-nates 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 about 6 carbon atoms.
• Preferred chelating agents include hydroxy-ethyldiphosphonic 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).
• 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 about 40% by weight of the polymer.
• Particularly suitable polymeric polyearboxylates 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, 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 about 0.1% to 4% by weight. More preferably, such materials can comprise from about 0.5% to 2% by weight of the detergents compositions herein.
• the detergent compositions herein may also optionally contain bleach activators which are liquid in form at room temperature and which can be added as liquids to the nonaqueous liquid phase of the detergent compositions herein.
• One such liquid bleach activator is acetyl triethyl citrate (ATC).
• ATC acetyl triethyl citrate
• Other examples include glycerol triacetate and nonanoyl valerolactam.
• Liquid bleach activators can be dissolved in the nonaqueous liquid phase of the compositions herein.
• the detergent compositions herein may also optionally contain conventional brighteners, suds suppressors, silicone oils, bleach catalysts, dyes and/or perfume materials.
• Such brighteners, suds suppressors, silicone oils, bleach catalysts, dyes and perfumes must, of course, be compatible and non-reactive with the other composition components in a nonaqueous environment. If present, brighteners suds suppressors, dyes and/or perfumes will typically comprise from 0.0001% to 2% by weight of the compositions herein.
• Suitable bleach catalysts include the manganese based complexes disclosed in US 5,246,621, US 5,244,594, US 5,114,606 and US 5,114,611.
• nonaqueous liquid detergent compositions herein are in the form of bleaching agent and/or other materials in particulate form as a solid phase suspended in and dispersed throughout a nonaqueous liquid phase.
• the nonaqueous liquid phase will comprise from 35% to 99%, more preferably from 50% to 95%, by weight of the composition with the dispersed solid phase comprising from 1% to 65%, more preferably from 5% to 50%, by weight of the composition.
• 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 liquid detergent compositions herein will be relatively viscous and phase stable under conditions of commercial marketing and use of such compositions Frequently the viscosity of the compositions herein will range from about 300 to 5,000 mPa/s (cps), more preferably from 500 to 3,000 mPa/s (cps). For purposes of this invention, viscosity is measured with a Brookfield Viscometer using a RV #5 spindle at 50 rpm.
• nonaqueous liquid detergent compositions herein can be prepared by combining the essential 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.
• essential and certain preferred optional components will be combined in a particular order and under certain conditions.
• an admixture of the alkylbenzene sulfonate anionic surfactant and the two essential components of the nonaqueous diluent is formed by heating a combination of these materials to a temperature from 30°C to 100°C.
• a second process step the heated admixture formed as hereinbefore described is maintained under shear agitation at a temperature from 40°C to 100°C for a period of from 2 minutes to 20 hours.
• a vaccuum can be applied to the admixture at this point.
• This second process step serves to completely dissolve the anionic surfactant in the nonaqueous liquid phase.
• this liquid phase combination of materials is cooled to a temperature of from 0°C to 35°C.
• This cooling step serves to form a structured, surfactant-containing liquid base into which the particulate material of the detergent compositions herein can be added and dispersed.
• Particulate material is added in a fourth process step by combining the particulate material with the liquid base which is maintained under conditions of shear agitation.
• the liquid base which is maintained under conditions of shear agitation.
• any optional surfactants in solid particulate form can be added in the form of particles ranging in size from 0.2 to 1,000 10 -6 m (microns).
• particles of substantially all of an organic builder e.g., citrate and/or fatty acid, and/or an alkalinity source, e.g., sodium carbonate
• an organic builder e.g., citrate and/or fatty acid
• an alkalinity source e.g., sodium carbonate
• Other solid form optional ingredients can then be added to the composition at this point. Agitation of the mixture is continued, and if necessary, can be increased at this point to form a uniform dispersion of insoluble solid phase particulates within the liquid phase.
• the particles of the highly preferred peroxygen bleaching agent can be added to the composition, again while the mixture is maintained under shear agitation.
• the peroxygen bleaching agent material By adding the peroxygen bleaching agent material last, or after all or most of the other components, and especially after alkalinity source particles, have been added, desirable stability benefits for the peroxygen bleach can be realized. If enzyme prills are incorporated, they are preferably added to the nonaqueous liquid matrix last.
• agitation of the mixture is continued for a period of time sufficient to form compositions having the requisite viscosity and phase stability characteristics. Frequently this will involve agitation for a period of from 1 to 30 minutes.
• one or more of the solid components may be added to the agitated mixture as a slurry of particles premixed with a minor portion of one or more of the liquid components.
• a premix of a small fraction of the alcohol alkoxylate and/or nonaqueous, low-polarity solvent with particles of the organic builder material and/or the particles of the inorganic alkalinity source and/or particles of a bleach activator may be separately formed and added as a slurry to the agitated mixture of composition components. Addition of such slurry premixes should precede addition of peroxygen bleaching agent and/or enzyme particles which may themselves be part of a premix slurry formed in analogous fashion.
• 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 800 to 3,000 ppm of the detergent compositions herein will be provided in aqueous washing/bleaching solution.
• a bleach-containing nonaqueous liquid laundry detergent is prepared having the composition as set forth in Table I.
• Component Wt. % Liquid Phase Na C 12 Linear alkylbenzene sulfonate (LAS) 27.3 C 12-14 , EO 5 alcohol ethoxylate 13.6 Hexylene glycol 27.3 Perfume 0.4 Solids Protease enzyme 0.4 Na 3 Citrate, anhydrous 4.3 Sodium perborate 3.4 Sodium nonanoyloxybenzene sulfonate (NOBS) 8.0 Sodium carbonate 13.9 Diethyl triamine pentaacetic acid (DTPA) 0.9 Brightener 0.4 Suds Suppressor 0.1 Minors 0.4 100%
• Such a composition is prepared by mixing the LAS, hexylene glycol and alcohol ethoxylate together at 54°C (130°F) for 1/2 hour. This mixture is then cooled to 29°C (85°F) whereupon the remaining components are added. The resulting composition is then stirred at 29°C (85°F) for another 1/2 hour.
• the resulting composition is a stable anhydrous heavy duty liquid laundry detergent which provides excellent stain and soil removal performance when used in normal fabric laundering operations.

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• 1996
  • 1996-05-28 BR BR9608998A patent/BR9608998A/pt not_active Application Discontinuation
  • 1996-05-28 CA CA002225562A patent/CA2225562C/en not_active Expired - Fee Related
  • 1996-05-28 AT AT96920530T patent/ATE231546T1/de not_active IP Right Cessation
  • 1996-05-28 DE DE69625911T patent/DE69625911T2/de not_active Revoked
  • 1996-05-28 CN CN96196174A patent/CN1192777A/zh active Pending
  • 1996-05-28 CZ CZ974036A patent/CZ403697A3/cs unknown
  • 1996-05-28 JP JP50384497A patent/JP4024297B2/ja not_active Expired - Fee Related
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  • 1996-05-28 EP EP96920530A patent/EP0842256B1/en not_active Revoked
  • 1996-05-28 WO PCT/US1996/007814 patent/WO1997000938A1/en not_active Application Discontinuation
  • 1996-06-13 DE DE19623623A patent/DE19623623A1/de not_active Withdrawn
  • 1996-06-13 GB GB9612409A patent/GB2302548B/en not_active Expired - Fee Related
  • 1996-06-20 FR FR9607676A patent/FR2735786B1/fr not_active Expired - Fee Related
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