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WO1996010072A1 - Procede de preparation de compositions detergentes liquides, non aqueuses et contenant un agent de blanchiment - Google Patents

Procede de preparation de compositions detergentes liquides, non aqueuses et contenant un agent de blanchiment Download PDF

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Publication number
WO1996010072A1
WO1996010072A1 PCT/US1995/011238 US9511238W WO9610072A1 WO 1996010072 A1 WO1996010072 A1 WO 1996010072A1 US 9511238 W US9511238 W US 9511238W WO 9610072 A1 WO9610072 A1 WO 9610072A1
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Prior art keywords
weight
added
detergent composition
nonaqueous
amount sufficient
Prior art date
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PCT/US1995/011238
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English (en)
Inventor
Josephine Ling Kong-Chan
Kathleen Brenner Hunter
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The Procter & Gamble Company
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Filing date
Publication date
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to EP95933041A priority Critical patent/EP0784669A1/fr
Priority to AU35841/95A priority patent/AU3584195A/en
Priority to JP8511778A priority patent/JPH10506930A/ja
Publication of WO1996010072A1 publication Critical patent/WO1996010072A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • C11D3/3947—Liquid compositions

Definitions

  • This invention relates to the preparation of heavy duty liquid (HDL) laundry detergent products which are nonaqueous in nature and which contain a bleaching system based on peroxygen bleaching agents.
  • HDL heavy duty liquid
  • 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.
  • non-aqueous, bleach-containing liquid detergents in the form of dispersions of particulate materials in a liquid matrix, the physical stability of such compositions may also become a problem. This is because there is a tendency for such products to phase separate as dispersed insoluble solid particulate material drops from suspension and settles at the bottom of the container holding the liquid detergent product. As one consequence of this type of problem, there can also be difficulties associated with incorporating enough of the right types and amounts of surfactant materials into nonaqueous liquid detergent products.
  • Surfactant materials must, of course, be selected such that they are suitable for imparting acceptable fabric cleaning performance to such compositions but utilization of such surfactant materials must not lead to an unacceptable degree of composition phase separation. Accordingly, the process used to prepare non-aqueous liquid detergents containing suitable types of surfactants and peroxygen bleaching agents must be selected so as to minimize undesirable component chemical interaction and to maximize the phase stability of the product so prepared.
  • the present invention provides a process for preparing physically and chemically stable, nonaqueous liquid detergent compositions containing particles of peroxygen bleaching agents suspended therein. Such a process comprises the steps of:
  • Step D) nonaqueous liquid matrix to form the desired detergent compositions in the form of a uniform dispersion of particulate materials in nonaqueous liquid, wherein this dispersion has a viscosity ranging from about 300 to 5,000 cps.
  • the essentially utilized liquid nonionic surfactant is an alcohol ethoxylate of the formula R*'(OC2H4) n OH wherein R* is a C - Cig alkyl group and n is from about 1 to 80.
  • this nonionic surfactant is used in at least 51% of an amount sufficient to provide from about 1% to 60% by weight of this nonionic surfactant component in the detergent composition which is ultimately prepared.
  • the other component used to form the Step A) nonaqueous liquid matrix is a nonaqueous, low-polarity organic solvent.
  • a nonaqueous, low-polarity organic solvent is utilized in at least 51% of an amount which is sufficient to provide from about 1% to 60% by weight of this nonaqueous, low-polarity solvent in the detergent composition which is ultimately prepared.
  • the particulate material added in Step B) is one which is substantially insoluble in the nonaqueous liquid matrix to which it is added. Such particulate material ranges in particle size from about 0.2 to 1,000 microns.
  • the particulate material added in Step B) must include an anionic surfactant material comprising sulfated Cg - C20 alcohols. This anionic surfactant material is added in an amount sufficient to provide from about 10% to 40% by weight of this anionic surfactant material in the detergent composition which is ultimately prepared.
  • the particulate material added in Step B) must also include a desiccant/alkalinity source which is selected from hydratable, water-soluble alkali metal carbonates, bicarbonates, borates, silicates and metasilicates.
  • This desiccant/alkalinity source is added in an amount sufficient to provide from about 5% to 20% by weight of this desiccant/alkalinity source in the detergent composition which is ultimately prepared.
  • the peroxygen bleaching agent added in Step D) also comprises particulate material which ranges in size from about 0.2 to 1,000 microns.
  • the peroxygen bleaching agent particles are added in an amount sufficient to provide from about 2% to 30% by weight of these peroxygen bleaching agent particles in the detergent composition which is ultimately prepared.
  • the detergent composition preparation process herein may optionally include the addition to the detergent composition being prepared of additional liquids and solid particulate materials including optional nonionic surfactants, activators for the peroxygen bleaching agent, detergent builders, detergent enzymes, chelating agents, suds supressors and the like.
  • nonaqueous liquid detergent compositions prepared by the process of this invention comprise a nonionic surfactant- and low-polarity solvent-containing liquid phase having dispersed therein as a solid phase certain types of particulate materials.
  • Compositions of this type are also disclosed in the concurrently filed U. S. patent application of Josephine L. Kong-Chan and Kathleen B. Hunter, which application has U. S. Serial No. ( P&G Case No. 5436).
  • the liquid matrix formed in the first step of the detergent composition preparation process herein essentially contains certain types of nonionic surfactants and certain types of nonaqueous, low-polarity solvents.
  • the liquid matrix formed in the detergent composition preparation process of this invention essentially comprises an ethoxylated fatty alcohol nonionic surfactant.
  • a material corresponds to the general formula: wherein R* is a C - Cjg alkyl group and n ranges from about 1 to 80.
  • R* is a C - Cjg alkyl group and n ranges from about 1 to 80.
  • R! alkyl group which may be primary or secondary, contains from about 9 to 15 carbon atoms, more preferably from about 10 to 14 carbon atoms.
  • the ethoxylated fatty alcohol will contain from about 2 to 12 ethylene oxide moieties per molecule, more preferably from about 3 to 10 ethylene oxide moieties per molecule.
  • the ethoxylated fatty alcohol nonionic surfactant will frequently have a hydrophilic-lipophilic balance (HLB) which ranges from about 3 to 17. More preferably, the HLB of this material will range from about 6 to 15, most preferably from about 10 to 15.
  • HLB hydrophilic-lipophilic balance
  • fatty alcohol ethoxylates useful as the essential liquid nonionic surfactant 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 tradenames Neodol 25-7 and Neodol 23-6.5 by Shell Chemical Company.
  • Neodols include Neodol 1-5, an ethoxylated fatty alcohol averaging 1 1 carbon atoms in its alkyl chain with about 5 moles of ethylene oxide; Neodol 23-9, an ethoxylated primary ⁇ 2 - ⁇ alcohol having about 9 moles of ethylene oxide and Neodol 91- 10, an ethoxylated Co, - C ⁇ ⁇ 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 C9-C1 1 fatty alcohol with an average of 5 moles ethylene oxide and Dobanol 25-7 is an ethoxylated C12- 15 fatty alcohol with an average of 7 moles of ethylene oxide per mole of fatty alcohol.
  • Suitable ethoxylated alcohol nonionic surfactants 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 ⁇ ⁇ to C15 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 ethoxylate nonionics 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 ethoxylate nonionic which is essentially utilized to form part of the liquid matrix of the process herein will generally be present to the extent of ultimately providing from about 1% to 60% by weight of this material in the detergent composition eventually prepared. More preferably, the alcohol ethoxylate nonionic will be used in an amount that provides from about 5% to 35% by weight of this component in the compositions herein. Most preferably, the essentially utilized alcohol ethoxylate nonionic will be used in amounts sufficient to provide from about 8% to 25% by weight of this component in the detergent compositions herein.
  • a second essential component of the liquid matrix formed in the irst step of the process 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 prepared 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 the peroxygen bleach, e.g., sodium perborate, and optional bleach activators, e.g., sodium nonanoyloxybenzene sulfonate (NOBS), which are present in the nonaqueous compositions herein.
  • peroxygen bleach e.g., sodium perborate
  • optional bleach activators e.g., sodium nonanoyloxybenzene sulfonate (NOBS)
  • NOBS sodium nonanoyloxybenzene sulfonate
  • relatively polar solvents such as ethanol and propanediol 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, lower molecular weight methyl esters and amides, and the like.
  • a preferred type of nonaqueous, low-polarity solvent for use herein comprises the mono-, di-, tri- or tetra- C 2 - C3 alkylene glycol mono C 2 - C $ alkyl ethers.
  • Specific examples of such compounds include diethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, dipropylene glycol monoethyl ether and dipropylene glycol monobutyl ether.
  • Diethylene glycol monobutyl ether and dipropylene glycol monobutyl ether are especially preferred.
  • Compounds of this 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). 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.
  • Yet another preferred type of non-polar, nonaqueous solvent comprises lower molecular weight methyl esters. Such materials are those of the general formula: Rl-C(O)-OCH3 wherein Rl ranges from 1 to about 18. Examples of 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 the process herein in an amount sufficient to provide from about 1% to 60% by weight of this solvent component in the detergent composition ultimately prepared.
  • the nonaqueous, low-polarity organic solvent(s) will be used in an amount which provides from about.15% to 45% by weight of solvent in the final composition, most preferably from about 20% to 45% by weight of solvent in the final composition.
  • Step B two different types of solid particulate materials are essentially added to the liquid matrix.
  • These two essential types of materials are 1) alkyl sulfate anionic surfactant and 2) a desiccant/alkalinity source and are each described in detail as follows: (1) Essential Anionic Surfactant
  • One essential solid phase material added to the liquid matrix in the second process step herein comprises a primary or secondary alkyl sulfate anionic surfactant.
  • Such surfactants are those produced by the sulfation of higher Cg - C 2 rj fatty alcohols.
  • R is typically a linear Cg - C 2 Q hydrocarbyl group, which may be straight chain or branched chain, and M is a water-solubilizing cation.
  • R is a C ⁇ Q - C14 alkyl
  • M is alkali metal.
  • R is about C ⁇ 2 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
  • secondary alkyl sulfates are the (2,3) alkyl sulfate surfactants which can be represented by structures of formulas A and B
  • x and (y+1) are, respectively, integers of at least about 6, and can range from about 7 to about 20, preferably about 10 to about 16.
  • M is a cation, such as an alkali metal, alkaline earth metal, or the like. Sodium is typical for use as M to prepare the water-soluble (2,3) alkyl sulfates, but potassium, and the like, can also be used.
  • alkyl sulfate surfactants essentially utilized herein do not generally dissolve in the liquid phase and will hence be dispersed throughout the liquid phase as discrete particles. Such particles will typically range in size from about 0.2 to 1,000 microns, more preferably from about 1 to 800 microns.
  • the requisite alkyl sulfate anionic surfactant should be used in relatively high concentrations in order to provide suitable soil/stain removal performance and in order to provide suspension phase stability for the nonaqueous detergent compositions as prepared herein.
  • the alkyl sulfate surfactant will generally be used in amounts sufficient to provide from about 10% to 40% by weight of alkyl sulfate in the compositions prepared herein. More preferably, alkyl sulfate will be utilized to the extent needed to provide from about 16% to 30% by weight of alkyl sulfate in the composition. Frequently, alkyl sulfate surfactant will be employed in amounts sufficient to provide a liquid phase to alkyl sulfate anionic weight ratio of from about 1 : 1 to 5: 1, more preferably from about 1.5: 1 to 3.5: 1.
  • a second essential solid phase material added to the liquid matrix in the second (Step B) process step herein comprises a hydratable material which serves both as a desiccant and as material that renders generally alkaline in nature the aqueous washing solutions formed from the compositions prepared herein.
  • a hydratable material which serves both as a desiccant and as material that renders generally alkaline in nature the aqueous washing solutions formed from the compositions prepared herein.
  • 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.
  • desiccant/alkalinity sources include hydratable, water- soluble alkali metal carbonates, bicarbonates, borates, silicates and metasilicates.
  • water-soluble phosphate salts may also be utilized as alkalinity sources. These include hydratable alkali metal pyrophosphates, orthophosphates, polyphosphates and phosphonates. Of all of these desiccant/alkalinity sources, alkali metal carbonates, such as sodium carbonate, are the most preferred.
  • the desiccant/alkalinity source will generally be added in an amount such that it comprises from about 5% to 30% by weight of the compositions ultimately prepared herein.
  • the desiccant/alkalinity source can be added in amounts sufficient to provide from about 5% to 20% by weight of this component in the ultimately prepared compositions.
  • 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 non-aqueous liquid matrix is further subjected to shear agitation in Step C) to form a uniform dispersion of this solid particulate material in the nonaqueous liquid matrix.
  • particles of peroxygen bleaching agent are added.
  • peroxygen bleaching agents may be organic or inorganic in nature. Inorganic peroxygen bleaching agents are frequently utilized in combination with a bleach activator.
  • Usefiil 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 Burns et al.
  • NAPAA 6-nonylamino-6- oxoperoxycaproic acid
  • Inorganic peroxygen bleaching agents may also be used in particulate form in the preparation of the detergent compositions herein.
  • Inorganic bleaching agents are in fact preferred.
  • Such inorganic peroxygen compounds include alkali metal perborate and percarbonate materials.
  • 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
  • amido-derived bleach activators are those of the formulae: RlN(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-> is H or alkyl, aryl, or alkaryl containing from about 1 to about 10 carbon atoms, and L is any suitable " ⁇ "
  • 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.
  • 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 includes the acyl lactam activators, especially acyl caprolactams and acyl valerolactams of the formulae:
  • R*-> is H or an alkyl, aryl, alkoxyaryl, or alkaryl group containing from 1 to about 12 carbon atoms.
  • Highly preferred lactam activators include benzoyl caprolactam, octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, benzoyl valerolactam, octanoyl valerolactam, decanoyl valerolactam, undecenoyl valerolactam, 3,5,5- trimethylhexanoy] valerolactam and mixtures thereof.
  • acyl caprolactams including benzoyl caprolactam, adsorbed into sodium perborate.
  • Still another class of useful bleach activators are those which are liquid in form at room temperature and 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.
  • the peroxygen bleaching agent particles, and activator particles for those activators which are solids should have an average particle size which ranges from about 0.2 to 1,000 microns, more preferably from about 1 to 800 microns. Preferably, no more than about 10% by weight of the bleaching agent and/or activator particles will be smaller than about 1 micron and no more than about 10% by weight of such particles will be larger than about 500 microns. Both peroxygen bleaching agent, and bleach activator if a solid activator is utilized, should be in the form of particles which are substantially insoluble in the nonaqueous liquid matrix being used to form the detergent compositions herein.
  • Peroxygen bleaching agent will generally be added to the liquid matrix in amounts sufficient to provide from about 2% to 30% by weight of peroxygen bleaching in the compositions ultimately prepared. More preferably, peroxygen bleaching agent will be added in amounts sufficient to provide from about 2% to 20% by weight of peroxygen bleach agents in the compositions herein. Most preferably, peroxygen bleaching agent will be used in amounts sufficient to provide from about 3% to 15% by weight of peroxygen bleaching agents in the compositions prepared herein. If utilized, bleach activators can be added in amounts sufficient to provide from about 2% to 10% by weight of activator component in the compositions herein. Frequently, activators are employed such that the molar ratio of bleaching agent to activator ranges from about 1 : 1 to 10: 1, more preferably from about 1.5:1 to 5: 1.
  • the detergent compositions prepared by the process herein can, and preferably will, contain various optional components.
  • Such optional components may be in either liquid or solid form.
  • the solid form optional components may either dissolve in the liquid phase or may be dispersed within the liquid phase in fine particulate form, as part of the solid phase of the composition.
  • optional components can generally be added at any point in the process herein, either during or after formulation of the Step A) liquid matrix.
  • the detergent compositions prepared herein may also contain other types of surfactant materials, provided such additional surfactants are compatible with other composition components and do not substantially adversely affect composition stability or performance.
  • Optional surfactants can be of the anionic, nonionic, cationic, and/or amphoteric type. If employed, optional surfactants will generally be added so that they comprise from about 1% to 20% by weight of the compositions prepared herein, more preferably from about 5% to 10% by weight of the compositions prepared herein.
  • nonionic surfactant comprises surfactants which are ethylene oxide (EO) - propylene oxide (PO) block polymers.
  • EO ethylene oxide
  • PO propylene oxide
  • 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 ethylene oxide moieties to the ends of polypropylene glycol chains to adjust the surface active properties of the resulting block polymers.
  • EO-PO 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.
  • 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.
  • One common type of anionic surfactant which is preferably not utilized in the preparation of the compositions herein comprises the sulfonated anionics which are alkyl benzene sulfonates.
  • Such non-bleach activating sulfonated anionic surfactants like linear alkylbenzene sulfonate (LAS), tend not to provide acceptable phase properties for the nonaqueous liquid detergent compositions prepared according to this invention. Accordingly, such compositions as prepared herein will preferably be substantially free of alkyl benzene sulfonate anionic surfactant materials.
  • the detergent compositions as prepared herein may also optionally contain 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.
  • optional organic builder materials will generally be added so that they comprise from about 1% to 60%, more preferably from about 3% to 50%, most preferably from about 3% to 20%, by weight of the compositions prepared herein.
  • the detergent compositions as prepared 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 as prepared herein.
  • a chelating agent which serves to chelate metal ions, e.g., iron and/or manganese, within the nonaqueous detergent compositions as prepared 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, amino phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures thereof.
  • Amino carboxylates useful as optional chelating agents include ethylenediaminetetraacetates, N-hydroxyethylethylenediaminetriacetates, nitrilotriacetates, ethylenediamine tetrapropionates, triethylenetetra- aminehexacetates, 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) such as DEQUEST.
  • these amino phosphonates do not contain alkyl or alkenyl groups with more than about 6 carbon atoms.
  • Preferred chelating agents include diethylene triamine penta acetic acid (DTPA), ethylenediamine disuccinic acid (EDDS) and dipicolinic acid (DPA) and salts thereof.
  • DTPA diethylene triamine penta acetic acid
  • EDDS ethylenediamine disuccinic acid
  • DPA dipicolinic acid
  • 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 be added such that it comprises from about 0.1% to 4% by weight of the compositions prepared herein. More preferably, the chelating agent will be added so as to comprise from about 0.2% to 2% by weight of the detergent compositions prepared herein.
  • the detergent compositions as prepared herein may also optionally contain one or more types of detergent enzymes.
  • Such enzymes can include proteases, amylases, cellulases and Upases.
  • Such materials are known in the art and are commercially available. They may be incorporated into the nonaqueous liquid detergent compositions prepared herein in the form of suspensions, "marumes" or "prills". Since enzymes in particulate forms such as prills may be fairly fragile, enzymes, if used, should generally be added to the nonaqueous matrix last.
  • Enzymes added to the compositions prepared herein in the form of conventional enzyme prills are especially preferred for use herein.
  • Such prills will generally range in size from about 100 to 1,000 microns, more preferably from about 200 to 800 microns and will be suspended throughout the nonaqueous liquid phase of the composition.
  • Prills in the compositions prepared according to 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 as prepared herein 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 will typically comprise from about 0.001% to 5%, preferably from about 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 as prepared 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 polycarboxylates can be derived from acrylic acid.
  • acrylic acid-based polymers which are useful herein are the water-soluble salts of polymerized acrylic acid.
  • the average molecular weight of such polymers in the acid form preferably ranges from about 2,000 to 10,000, more preferably from about 4,000 to 7,000, and most preferably from about 4,000 to 5,000.
  • Water- soluble salts of such acrylic acid polymers can include, for example, the alkali metal, 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 added such that they are present in the compositions prepared herein to the extent of from about 0.1% to 4% by weight. More preferably, such materials can be added such that they comprise from about 0.5% to 2% by weight of the detergents compositions as prepared herein.
  • the detergent compositions as prepared herein may also optionally contain conventional brighteners, suds suppressors and/or perfume materials. Such brighteners, suds suppressors 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 be added such that they comprise from about 0.1% to 2% by weight of the compositions prepared herein. COMPOSITION FORM
  • the nonaqueous liquid detergent compositions prepared herein are in the form of bleaching agent and 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 about 30% to 70% by weight of the composition with the dispersed solid phase comprising from about 30% to 70% by weight of the composition.
  • size of the solid, insoluble particulate material (other than enzyme prills) dispersed in the liquid phase will range from about 0.2 to 1,000 microns, more preferably from about 1 to 800 microns.
  • the bleach-containing liquid detergent compositions prepared in accordance with this invention are substantially nonaqueous (or anhydrous) in character.
  • the amount of water should in no event exceed about 5% by weight of the compositions prepared herein. More preferably, water content of the nonaqueous detergent compositions prepared herein will comprise less than about 2% by weight.
  • the bleach-containing nonaqueous liquid detergent compositions as prepared herein will be relatively viscous and phase stable under conditions of commercial marketing and use of such compositions.
  • Generally viscosity of the compositions prepared herein will range from about 300 to 5,000 cps, more preferably from about 500 to 3,000 cps.
  • viscosity is measured with a Brookfield Viscometer using a RV #5 spindle at 50 rpm.
  • a liquid matrix is formed containing at least a major proportion, e.g., at least 51%, preferably at least 75%, and more preferably substantially all, of the liquid components, e.g., the essential alcohol ethoxylate nonionic surfactant and the nonaqueous, low-polarity organic solvent, with the liquid components being thoroughly admixed by imparting shear agitation to this liquid combination.
  • the liquid components e.g., the essential alcohol ethoxylate nonionic surfactant and the nonaqueous, low-polarity organic solvent
  • rapid stirring with a mechanical stirrer may be usefully employed.
  • alkyl sulfate anionic surfactant e.g., sodium lauryl sulfate
  • the alkyl sulfate anionic surfactant e.g., sodium lauryl sulfate
  • particles of substantially all of the desiccant/alkalinity source e.g., sodium carbonate
  • Other solid form optional ingredients can be added to the composition at this point.
  • 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 about 30 to 60 minutes.
  • the optional enzyme material e. g., prills, may be added if desired.
  • 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 nonionic surfactant and/or nonaqueous, low-polarity solvent with particles of the alkyl sulfate surfactant and/or the particles of the 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, however, precede addition of peroxygen bleaching agent particles which may themselves be part of a premix slurry formed in analogous fashion.
  • compositions prepared in accordance with 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 about 500 to 7,000 ppm of composition in aqueous solution. More preferably, from about 1,000 to 3,000 ppm of the detergent compositions herein will be provided in aqueous washing/bleaching solution.
  • a detergent composition is prepared by mixing together the ingredients listed in Table I in the proportions shown. These steps in the preparation process are described in detail folio winf Table I:
  • the finished product is an opaque, white, creamy liquid with suspended solids.
  • the blue enzyme prills are visible and give the product a speckled appearance.
  • the viscosity is 620 cps when measured on a Brookfield RV viscometer with a RV #5 spindle at 50 rpm. After 1 week at ambient temperature, the viscosity of the product reaches 1000 cps and remains relatively constant afterwards. Approximately 5% separation (clear phase on top layer) is observed after 3 days at ambient temperature. The separated phases are dispersed readily, and the dispensing properties of the product are good. Chemical stability of this product is excellent. After 4 weeks at 100°F, >85% of the original Available Oxygen is still retained.

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Abstract

L'invention concerne un procédé de préparation de compositions de détergents lessiviels liquides, non aqueux et contenant un agent de blanchiment. Lesdites compositions se présentent sous forme de suspension de matière particulaire constituée d'un agent de blanchiment au peroxygène et d'un agent tensioactif au sulfate d'alkyle, dispersée dans une phase liquide contenant un agent tensioactif non ionique à l'éthoxylate d'alcool et un solvant organique non aqueux à faible polarité. Ce procédé permet de produire des compositions présentant les caractéristiques de lavage et de blanchiment désirées pour les tissus lavés avec celles-ci et, en particulier, la stabilité chimique et de phase voulue.
PCT/US1995/011238 1994-09-26 1995-09-08 Procede de preparation de compositions detergentes liquides, non aqueuses et contenant un agent de blanchiment WO1996010072A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP95933041A EP0784669A1 (fr) 1994-09-26 1995-09-08 Procede de preparation de compositions detergentes liquides, non aqueuses et contenant un agent de blanchiment
AU35841/95A AU3584195A (en) 1994-09-26 1995-09-08 Process for preparing non-aqueous, bleach-containing liquid detergent compositions
JP8511778A JPH10506930A (ja) 1994-09-26 1995-09-08 非水性漂白剤含有液体洗剤組成物の製法

Applications Claiming Priority (2)

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US31351794A 1994-09-26 1994-09-26
US08/313,517 1994-09-26

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WO1996010072A1 true WO1996010072A1 (fr) 1996-04-04

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AU (1) AU3584195A (fr)
CA (1) CA2199816A1 (fr)
PE (1) PE18896A1 (fr)
TR (1) TR199501168A2 (fr)
TW (1) TW311932B (fr)
WO (1) WO1996010072A1 (fr)

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998000516A1 (fr) * 1996-06-28 1998-01-08 The Procter & Gamble Company Preparation de compositions detergentes liquides non aqueuses contenant des particules, a phase liquide structuree a l'aide d'un tensioactif
WO1998000514A1 (fr) * 1996-06-28 1998-01-08 The Procter & Gamble Company Compositions detergentes liquides non aqueuses contenant des particules, a phase liquide structuree a l'aide d'un tensioactif
WO1998000518A1 (fr) * 1996-06-28 1998-01-08 The Procter & Gamble Company Preparation de compositions detergents liquides non aqueuses contenant des particules, avec pretraitement des elements secs
US5814592A (en) * 1996-06-28 1998-09-29 The Procter & Gamble Company Non-aqueous, particulate-containing liquid detergent compositions with elasticized, surfactant-structured liquid phase
US5872092A (en) * 1994-09-26 1999-02-16 The Procter & Gamble Company Nonaqueous bleach-containing liquid detergent compositions
JP2002507237A (ja) * 1997-06-27 2002-03-05 ザ、プロクター、エンド、ギャンブル、カンパニー 非水性の、粒子を含む、漂白剤含有洗剤組成物
US6372703B1 (en) 1998-07-15 2002-04-16 Henkel Komanditgesellschaft Auf Aktien Non-aqueous bleach-containing liquid detergents
WO2011088089A1 (fr) 2010-01-12 2011-07-21 The Procter & Gamble Company Intermédiaires et tensioactifs utiles dans des compositions de nettoyage ménager et d'hygiène personnelle, et leurs procédés de fabrication
WO2012112828A1 (fr) 2011-02-17 2012-08-23 The Procter & Gamble Company Sulfonates d'alkylphényle linéaires d'origine biologique
WO2012138423A1 (fr) 2011-02-17 2012-10-11 The Procter & Gamble Company Compositions comprenant des mélanges de sulfonates d'alkylphényle c10-c13
US8871807B2 (en) 2008-03-28 2014-10-28 Ecolab Usa Inc. Detergents capable of cleaning, bleaching, sanitizing and/or disinfecting textiles including sulfoperoxycarboxylic acids
US9242879B2 (en) 2012-03-30 2016-01-26 Ecolab Usa Inc. Use of peracetic acid/hydrogen peroxide and peroxide-reducing agents for treatment of drilling fluids, frac fluids, flowback water and disposal water
US9253978B2 (en) 2008-03-28 2016-02-09 Ecolab USA, Inc. Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents
US9288992B2 (en) 2013-03-05 2016-03-22 Ecolab USA, Inc. Efficient stabilizer in controlling self accelerated decomposition temperature of peroxycarboxylic acid compositions with mineral acids
US9290448B2 (en) 2008-03-28 2016-03-22 Ecolab USA, Inc. Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents
EP3101106A1 (fr) * 2015-06-05 2016-12-07 The Procter and Gamble Company Composition de detergent liquide compacte pour blanchisserie
US9585397B2 (en) 2013-03-05 2017-03-07 Ecolab Usa Inc. Peroxycarboxylic acid compositions suitable for inline optical or conductivity monitoring
US9902627B2 (en) 2011-12-20 2018-02-27 Ecolab Usa Inc. Stable percarboxylic acid compositions and uses thereof
US10165774B2 (en) 2013-03-05 2019-01-01 Ecolab Usa Inc. Defoamer useful in a peracid composition with anionic surfactants
US10655093B2 (en) 2015-06-05 2020-05-19 The Procter & Gamble Company Compacted liquid laundry detergent composition
US10683474B2 (en) 2015-06-05 2020-06-16 The Procter & Gamble Company Compacted liquid laundry detergent composition
US10711225B2 (en) 2015-06-05 2020-07-14 The Procter & Gamble Company Compacted liquid laundry detergent composition
US12096768B2 (en) 2019-08-07 2024-09-24 Ecolab Usa Inc. Polymeric and solid-supported chelators for stabilization of peracid-containing compositions
US12203056B2 (en) 2008-03-28 2025-01-21 Ecolab Usa Inc. Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents

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EP0120659A2 (fr) * 1983-03-28 1984-10-03 Imperial Chemical Industries Plc Compositions détergentes
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EP0120659A2 (fr) * 1983-03-28 1984-10-03 Imperial Chemical Industries Plc Compositions détergentes
EP0253151A2 (fr) * 1986-06-27 1988-01-20 Henkel Kommanditgesellschaft auf Aktien Agent de lavage liquide et procédé pour sa production
WO1992002610A1 (fr) * 1990-08-02 1992-02-20 Henkel Kommanditgesellschaft Auf Aktien Detergents liquides
EP0534298A1 (fr) * 1991-09-25 1993-03-31 Henkel KGaA Composition liquide ou pasteuse de lavage ou de nettoyage
WO1993023521A1 (fr) * 1992-05-19 1993-11-25 Henkel Kommanditgesellschaft Auf Aktien Procede de fabrication d'un detergent se presentant sous forme de pate

Cited By (47)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5872092A (en) * 1994-09-26 1999-02-16 The Procter & Gamble Company Nonaqueous bleach-containing liquid detergent compositions
WO1998000516A1 (fr) * 1996-06-28 1998-01-08 The Procter & Gamble Company Preparation de compositions detergentes liquides non aqueuses contenant des particules, a phase liquide structuree a l'aide d'un tensioactif
WO1998000514A1 (fr) * 1996-06-28 1998-01-08 The Procter & Gamble Company Compositions detergentes liquides non aqueuses contenant des particules, a phase liquide structuree a l'aide d'un tensioactif
WO1998000518A1 (fr) * 1996-06-28 1998-01-08 The Procter & Gamble Company Preparation de compositions detergents liquides non aqueuses contenant des particules, avec pretraitement des elements secs
US5814592A (en) * 1996-06-28 1998-09-29 The Procter & Gamble Company Non-aqueous, particulate-containing liquid detergent compositions with elasticized, surfactant-structured liquid phase
US6277804B1 (en) 1996-06-28 2001-08-21 The Procter & Gamble Company Preparation of non-aqueous, particulate-containing liquid detergent compositions with surfactant-structured liquid phase
US6576602B1 (en) 1996-06-28 2003-06-10 The Procter & Gamble Company Nonaqueous, particulate-containing liquid detergent compositions with surfactant-structured liquid phase
JP2002507237A (ja) * 1997-06-27 2002-03-05 ザ、プロクター、エンド、ギャンブル、カンパニー 非水性の、粒子を含む、漂白剤含有洗剤組成物
US6372703B1 (en) 1998-07-15 2002-04-16 Henkel Komanditgesellschaft Auf Aktien Non-aqueous bleach-containing liquid detergents
US12203056B2 (en) 2008-03-28 2025-01-21 Ecolab Usa Inc. Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents
US10669512B2 (en) 2008-03-28 2020-06-02 Ecolab Usa Inc. Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents
US10017720B2 (en) 2008-03-28 2018-07-10 Ecolab Usa Inc. Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents
US8871807B2 (en) 2008-03-28 2014-10-28 Ecolab Usa Inc. Detergents capable of cleaning, bleaching, sanitizing and/or disinfecting textiles including sulfoperoxycarboxylic acids
US11827867B2 (en) 2008-03-28 2023-11-28 Ecolab Usa Inc. Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents
US11015151B2 (en) 2008-03-28 2021-05-25 Ecolab Usa Inc. Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents
US9253978B2 (en) 2008-03-28 2016-02-09 Ecolab USA, Inc. Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents
US9676711B2 (en) 2008-03-28 2017-06-13 Ecolab Usa Inc. Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents
US9290448B2 (en) 2008-03-28 2016-03-22 Ecolab USA, Inc. Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents
US9359295B2 (en) 2008-03-28 2016-06-07 Ecolab USA, Inc. Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents
US10323218B2 (en) 2008-03-28 2019-06-18 Ecolab Usa Inc. Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents
US10077415B2 (en) 2008-03-28 2018-09-18 Ecolab Usa Inc. Detergents capable of cleaning, bleaching, sanitizing and/or disinfecting textiles including sulfoperoxycarboxylic acids
US9540598B2 (en) 2008-03-28 2017-01-10 Ecolab Usa Inc. Detergents capable of cleaning, bleaching, sanitizing and/or disinfecting textiles including sulfoperoxycarboxylic acids
WO2011088089A1 (fr) 2010-01-12 2011-07-21 The Procter & Gamble Company Intermédiaires et tensioactifs utiles dans des compositions de nettoyage ménager et d'hygiène personnelle, et leurs procédés de fabrication
WO2012138423A1 (fr) 2011-02-17 2012-10-11 The Procter & Gamble Company Compositions comprenant des mélanges de sulfonates d'alkylphényle c10-c13
US9193937B2 (en) 2011-02-17 2015-11-24 The Procter & Gamble Company Mixtures of C10-C13 alkylphenyl sulfonates
WO2012112828A1 (fr) 2011-02-17 2012-08-23 The Procter & Gamble Company Sulfonates d'alkylphényle linéaires d'origine biologique
US9902627B2 (en) 2011-12-20 2018-02-27 Ecolab Usa Inc. Stable percarboxylic acid compositions and uses thereof
US9242879B2 (en) 2012-03-30 2016-01-26 Ecolab Usa Inc. Use of peracetic acid/hydrogen peroxide and peroxide-reducing agents for treatment of drilling fluids, frac fluids, flowback water and disposal water
US10023484B2 (en) 2012-03-30 2018-07-17 Ecolab Usa Inc. Use of peracetic acid/hydrogen peroxide and peroxide-reducing agents for treatment of drilling fluids, frac fluids, flowback water and disposal water
US9926214B2 (en) 2012-03-30 2018-03-27 Ecolab Usa Inc. Use of peracetic acid/hydrogen peroxide and peroxide-reducing agents for treatment of drilling fluids, frac fluids, flowback water and disposal water
US10017403B2 (en) 2012-03-30 2018-07-10 Ecolab Usa Inc. Use of peracetic acid/hydrogen peroxide and peroxide-reducing enzymes for treatment of drilling fluids, frac fluids, flowback water and disposal water
US11939241B2 (en) 2012-10-05 2024-03-26 Ecolab Usa Inc. Stable percarboxylic acid compositions and uses thereof
US11180385B2 (en) 2012-10-05 2021-11-23 Ecolab USA, Inc. Stable percarboxylic acid compositions and uses thereof
US11026421B2 (en) 2013-03-05 2021-06-08 Ecolab Usa Inc. Efficient stabilizer in controlling self accelerated decomposition temperature of peroxycarboxylic acid compositions with mineral acids
US10165774B2 (en) 2013-03-05 2019-01-01 Ecolab Usa Inc. Defoamer useful in a peracid composition with anionic surfactants
US9585397B2 (en) 2013-03-05 2017-03-07 Ecolab Usa Inc. Peroxycarboxylic acid compositions suitable for inline optical or conductivity monitoring
US9288992B2 (en) 2013-03-05 2016-03-22 Ecolab USA, Inc. Efficient stabilizer in controlling self accelerated decomposition temperature of peroxycarboxylic acid compositions with mineral acids
US11206826B2 (en) 2013-03-05 2021-12-28 Ecolab Usa Inc. Defoamer useful in a peracid composition with anionic surfactants
US10893674B2 (en) 2013-03-05 2021-01-19 Ecolab Usa Inc. Efficient stabilizer in controlling self accelerated decomposition temperature of peroxycarboxylic acid compositions with mineral acids
RU2683035C1 (ru) * 2015-06-05 2019-03-26 Дзе Проктер Энд Гэмбл Компани Уплотненная композиция жидкого моющего средства для стирки
CN107683324A (zh) * 2015-06-05 2018-02-09 宝洁公司 致密液体衣物洗涤剂组合物
US10711225B2 (en) 2015-06-05 2020-07-14 The Procter & Gamble Company Compacted liquid laundry detergent composition
US10683474B2 (en) 2015-06-05 2020-06-16 The Procter & Gamble Company Compacted liquid laundry detergent composition
US10655093B2 (en) 2015-06-05 2020-05-19 The Procter & Gamble Company Compacted liquid laundry detergent composition
EP3101106A1 (fr) * 2015-06-05 2016-12-07 The Procter and Gamble Company Composition de detergent liquide compacte pour blanchisserie
WO2016196699A1 (fr) * 2015-06-05 2016-12-08 The Procter & Gamble Company Composition de détergent à lessive liquide compactée
US12096768B2 (en) 2019-08-07 2024-09-24 Ecolab Usa Inc. Polymeric and solid-supported chelators for stabilization of peracid-containing compositions

Also Published As

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EP0784669A1 (fr) 1997-07-23
CA2199816A1 (fr) 1996-04-04
JPH10506930A (ja) 1998-07-07
PE18896A1 (es) 1996-05-23
AU3584195A (en) 1996-04-19
TR199501168A2 (tr) 1996-06-21
TW311932B (fr) 1997-08-01

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