Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/34—Organic compounds containing sulfur
  • C11D3/3418—Toluene -, xylene -, cumene -, benzene - or naphthalene sulfonates or sulfates
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/38—Cationic compounds
  • C11D1/42—Amino alcohols or amino ethers
  • C11D1/44—Ethers of polyoxyalkylenes with amino alcohols; Condensation products of epoxyalkanes with amines
• • 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
  • C11D1/75—Amino oxides
• • 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
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3723—Polyamines or polyalkyleneimines
• • 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
  • 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

• EP-A-598170 discloses a particular type of cleaning compositions which are aqueous emulsions of a nonionic surfactant system further comprising hydrogen peroxide or water-soluble source thereof and a liquid bleach activator, or any other hydrophobic ingredient which needs to be separated from said hydrogen peroxide.
• a drawback associated with such emulsions or microemulsions comprising a peroxygen bleach and a bleach activator is that they do not deliver effective performance which satisfactorily meet consumer's needs on all types of stains including greasy stains, enzymatic stains, mud/clay stains as well as bleachable stains. Indeed, there is still some room to further improve the stain removal performance as well as the bleaching performance of such bleach-containing compositions when pretreating a fabric therewith.
• an advantage of the liquid compositions of the present invention formulated either as an emulsion or a microemulsion is that they deliver improved stain removal performance and improved bleaching performance while delivering acceptable viscosity, without the need to add viscosity control agents.
• the present invention allows to formulate emulsions or microemulsions with improved overall stain removal/bleaching performance and desirable physical characteristics at reduced costs, i.e., without adding any viscosity control agent that would raise the cost formula and bulk to the compositions without contributing to the bleaching/cleaning performance of said compositions.
• compositions according to the present invention which are formulated as emulsions or microemulsions is that they provide also excellent cleaning and/or bleaching performance when used in applications other than laundry pretreaters, such as in other laundry applications, as laundry detergents or laundry additives.
• US application number 08/663501 discloses pretreater compositions with particular chelants, a peroxygen bleach, and optional ingredients like bleach activators, polymeric soil releasing agents like sulfonated poly-ethoxy/propoxy end-capped ester oligomer. However, no ethoxylated amines, ethoxylated polyamines, or ethoxylated amine polymers are disclosed.
• EP-A-271 312 discloses laundry compositions comprising a peroxyacid bleach and a soil release agent like particular alkyl and hydroxyalkyl ethers of cellulose, polymers comprising ethylene terephthalate and polyethylene oxide terephthalate. No ethoxylated amines, ethoxylated polyamines or ethoxylated amine polymers are disclosed.
• WO96/12004 discloses laundry compositions comprising a lipophilic enzyme and a primary and/or tertiary amine. These compositions provide enhanced cleaning of greasy/oily soils and stains, particularly when used in pretreatment laundering process for cleaning fabrics stained with greasy soils.
• the compositions exemplified comprise tetraethylenepentamine ethoxylated (15-18) but no bleach.
• the present invention is based on the finding that by adding a soil dispersing agent, as described herein, in a liquid composition comprising a peroxygen bleach, improved stain removal performance is obtained with said composition when used to pretreat a soiled fabric before said fabric is washed, as compared to the stain removal performance delivered with the same composition without said soil dispersing agent.
• bleachable stains examples include tea, coffee, wine and the like.
• enzymatic stains examples include grass, chocolate and blood.
• the stain removal performance of a given composition on a soiled fabric under pretreatment conditions may be evaluated by the following test method.
• a composition according to the present invention is first applied to the stained portion of said fabric, left to act from about 1 to about 10 minutes, typically 5 minutes, and said pretreated fabric is then washed according to common washing conditions with a conventional detergent composition, at a temperature of from 30°C to 70°C for a period of time sufficient to bleach said fabric.
• the stain removal performance may then be evaluated by comparing side by side the soiled fabric pretreated with the composition according to the present invention with those pretreated with the reference, e.g., the same composition without such a soil dispersing agent according to the present invention.
• a visual grading scale may be used to assign differences in panel score units (psu), in a range from 0 to 4.
• the present invention encompasses a process of bleaching a fabric with a liquid composition comprising from 0.01 % to 15% by weight of the total composition of a peroxygen bleach and a soil dispersing agent, as defined herein, said process comprises the steps of applying said composition in its neat form onto at least a portion of said fabric, optionally allowing said composition to remain in contact with said fabric preferably without leaving said composition to dry onto said fabric, before said fabric is washed.
• Said composition may remain in contact with said fabric, typically for a period of 1 minute to several hours, preferably 1 minute to 1 hour, more preferably 1 minute to 30 minutes, and most preferably 2 to 10 minutes.
• said composition may be rubbed and/or brushed more or less intensively, for example, by means of a sponge or a brush or simply by rubbing two pieces of fabric each against the other.
• liquid compositions are applied directly onto the fabrics to be pre-treated without undergoing any dilution, e.g., the liquid compositions according to the present invention are applied as described herein.
• the liquid compositions used in said process should preferably not be left to dry onto the fabrics. Indeed, it has been found that water evaporation contributes to increase the concentration of free radicals onto the surface of the fabrics and, consequently, the rate of chain reaction. It is also speculated that an auto-oxidation reaction occurs upon evaporation of water when the liquid compositions are left to dry onto the fabrics. Said reaction of auto-oxidation contributes to generate peroxy-radicals which may cause color damage and/or fabric damage. Thus, not leaving the liquid bleaching compositions used according to the present invention to dry onto the fabrics, in the process of bleaching fabrics according to the present invention would result in a safer pretreating operation with liquid bleaching compositions.
• compositions to be used according to the present invention comprise a peroxygen bleach or mixtures thereof.
• the peroxygen bleach to be used herein is any peroxygen bleach, known to those skilled in the art.
• Such peroxygen bleach includes hydrogen peroxide, or a water-soluble source thereof, or mixtures thereof. Indeed, the presence of the peroxygen bleach contributes to the excellent cleaning and bleaching benefits of the compositions used according to the present invention.
• a hydrogen peroxide source refers to any compound which produces perhydroxyl ions when said compound is in contact with water.
• Suitable water-soluble sources of hydrogen peroxide for use herein include percarbonates, persilicate, persulphate such as monopersulfate, perborates, peroxyacids such as diperoxydodecandioic acid (DPDA), magnesium perphtalic acid, perlauric acid, perbenzoic and alkylperbenzoic acids, hydroperoxides, diacyl peroxides and mixtures thereof.
• Preferred peroxygen bleaches used herein are hydrogen peroxide, hydroperoxide and/or aliphatic diacyl peroxide.
• compositions used according to the present invention comprise from 0.01% to 15% by weight of the total composition of such a peroxygen bleach or mixtures thereof, preferably from 0.1% to 12%, more preferably from 0.5% to 10% and most preferably from 2% to 8%.
• R 1 can be branched or most preferably linear alkylene, hydroxyalkylene, alkenylene, alkarylene or oxyalkylene.
• R 1 is preferably C 2 -C 6 alkylene for the ethoxylated diamines and amine polymers.
• the minimum degree of ethoxylation required for suitable soil removal/anti-redeposition properties decreases on going from C 2 -C 3 alkylene (ethylene, propylene) to hexamethylene.
• each R 2 is preferably the moiety _L_X.
• hydrophilic chain L usually consists entirely of the polyoxyalkylene moiety _[(R 5 O) m (CH 2 CH 2- O) n ]_.
• the moieties _(R 5 O) m _ and _(CH 2 CH 2 O) n _ of the polyoxyalkylene moiety can be mixed together or preferably form blocks of _(R 5 O) m _ and _(CH 2 CH 2 O) n _ moieties.
• R 5 is preferably C 3 H 6 (propylene).
• m is preferably from 0 to 5.
• m is most preferably 0, i.e. the polyoxyalkylene moiety consists entirely of the moiety _(CH 2 CH 2 O) n _.
• the moiety _(CH 2 CH 2 O) n _ preferably comprises at least 85% by weight of the polyoxyalkylene moiety and most preferably 100% by weight (m is O).
• X can be any compatible nonionic group, anionic group or mixture thereof.
• Suitable nonionic groups include C 1 -C 4 alkyl or hydroxyalkyl ester or ether groups, preferably acetate or methyl ether, respectively; hydrogen (H); or mixtures thereof.
• the particularly preferred nonionic group is H.
• anionic groups PO 3 -2 and SO 3 - are suitable.
• the particularly preferred anionic group is SO 3 - . It has been found that the percentage of anionic groups relative to nonionic groups can be important to the soil removal/anti-redeposition properties provided by the ethoxylated amine.
• a mixture of from 0 to 30% anionic groups and from 70 to 100% nonionic groups provides preferred properties.
• a mixture of from 5 to 10% anionic groups and from 90 to 95% nonionic groups provides the most preferred properties.
• a mixture of from 0 to 80% anionic groups and from 20 to 100% nonionic groups provides suitable soil removal/anti-redeposition properties.
• Preferred ethoxylated mono- and diamines have the formula: wherein X and n are defined as before, a is 0 or 1 and b is from 0 to 4.
• n is at least 15, with a typical range of from 15 to 35.
• n is at least 12 with atypical range of from 12 to 42.
• R 3 (linear, branched, or cyclic) is preferably a substituted C 3 -C 6 alkyl, hydroxyalkyl or aryl group;
• a 1 is preferably n is preferably at least 12, with a typical range of from 12 to 42;
• p is preferably from 3 to 6.
• q is preferably 1 and R 4 is preferably C 2 -C 3 alkylene.
• R 3 is an alkyl, hydroxyalkyl, or alkenyl group, and when q is 0, R 1 is preferably a C 2 -C 3 oxyalkylene moiety; when q is 1, R 4 is preferably C 2 -C 3 alkylene.
• ethoxylated polyamines can be derived from polyamino amides such as:
• ethoxylated polyamines can also be derived from polyaminopropyleneoxide derivatives such as: wherein each c is a number from 2 to 20.
• Preferred ethoxylated amine polymers are the ethoxylated C 2 -C 3 polyalkyleneamines and polyalkyleneimines Particularly preferred ethoxylated polyalkyleneamines and polyalkyleneimines are the ethoxylated polyethyleneamines (PEA's) and polyethyleneimines (PEI's). These preferred compounds comprise units having the general formula: wherein X, w, x, y, z and n are defined as before.
• the PEAs used in preparing compounds of the present invention have the following general formula: wherein x + y + z is from 2 to 9, y + z is from 2 to 9 and w is 0 or 1 (molecular weight of from 100 to 400). Each hydrogen atom attached to each nitrogen atom represents an active site for subsequent ethoxylation.
• y + z is from 3 to 7 (molecular weight of from 140 to 310) and most prefarably from 3 to 4 (molecular weight of from 140 to 200).
• These PEA's can be obtained by reactions involving ammonia and ethylene dichloride, followed by fractional distillation.
• the common PEA's obtained are triethylenetetramine (TETA) and tetraethylenepentamine (TEPA).
• TETA triethylenetetramine
• TEPA tetraethylenepentamine
• the cogenerically derived mixture does not appear to separate by distillation and can include other materials such as cyclic amines and particularly piperazines.
• cyclic amines with side chains in which nitrogen atoms appear. See US Patent 2,792,372 to Dickson, issued May 14, 1957, which describes the preparation of PEAs.
• the PEIs used in preparing the compounds of the present invention have a molecular weight of at least 440 prior to ethoxylation, which represents at least 10 units.
• Preferred PEIs used in preparing these compounds have a molecular weight of from 600 to 1800.
• the polymer backbone of these PEIs can be represented by the general formula: wherein the sum of x, y, and z represents a number of sufficient magnitude to yield a polymer having the molecular weights previously specified. Although linear polymer backbones are possible, branch chains can also occur.
• the relative proportions of primary, secondary and tertiary amine groups present in the polymer can vary, depending on the manner of preparation. The distribution of amine groups is typically as follows:
• n is at least 3 for the ethoxylated PEIs.
• the minimum degree of ethoxylation required for suitable soil removal/anti-redeposition performance can increase as the molecular weight of the PEI increases, especially much beyond 1800.
• the degree of ethoxylation for preferred compounds increases as the molecular weight of the PEI increases.
• n is preferably at least 12, with a typical range of from 12 to 42.
• n is preferably at least 24, with a typical range of from 24 to 42.
• a soil dispersing agent in a liquid composition comprising a peroxygen bleach, a surfactant and being formulated either as an emulsion or a microemulsion, that not only improved stain removal performance is obtained especially under pretreatment conditions, on various stains including greasy stains, enzymatic stains, clay/mud stains as well as improved bleaching performance but also desirable viscosity is achieved.
• the soil dispersing agents according to the present invention are easily processed in a composition being formulated either as an emulsion or a microemulsion, while providing the appropriate viscosity, i.e., the viscosity of said composition is reduced, whatever the viscosity was before the addition of said soil dispersing agents into said composition comprising a peroxygen bleach and a surfactant.
• a surfactant system is used in the compositions according to the present invention comprising at least one hydrophilic surfactant and at least one hydrophobic surfactant.
• Said two surfactants in order to form emulsions or microemulsions which are stable preferably have different HLB values (hydrophilic lipophilic balance) and typically the difference in value of the HLBs of said two surfactants is at least 1, preferably at least 2 and most preferably at least 3.
• hydrophilic surfactant it is meant herein a surfactant having an HLB above 10 or mixtures thereof, preferably above 10.5, and more preferably above 11.
• nonionic surfactants particularly preferred surfactants to be used in the compositions according to the present invention are nonionic surfactants.
• suitable nonionic surfactants for use herein include alkoxylated fatty alcohols preferably, fatty alcohol ethoxylates and/or propoxylates.
• alkoxylated fatty alcohols preferably, fatty alcohol ethoxylates and/or propoxylates.
• a great variety of such alkoxylated fatty alcohols are commercially available which have very different HLB values (hydrophilic / lipophilic balance).
• HLB values of such alkoxylated nonionic surfactants depend essentially on the chain length of the fatty alcohol, the nature of the alkoxylation and the degree of alkoxylation.
• Preferred hydrophobic nonionic surfactants to be used in the compositions according to the present invention are surfactants having an HLB up to 10 and being according to the formula RO-(C 2 H 4 O) n (C 3 H 6 O) m H, wherein R is a C 6 to C 22 alkyl chain or a C 6 to C 28 alkyl benzene chain, and wherein n+m is from 0.5 to 5 and n is from 0 to 5 and m is from 0 to 5 and preferably n+m is from 0.5 to 4.5 and, n and m are from 0 to 4.5.
• the preferred R chains for use herein are the C 8 to C 22 alkyl chains.
• Suitable polyhydroxy fatty acid amide surfactants to be used herein may be commercially available under the trade name HOE® from Hoechst.
• acyl sarcosinate or mixtures thereof, in its acid and/or salt form preferably long chain acyl sarcosinates having the following formula: wherein M is hydrogen or a cationic moiety and wherein R is an alkyl group of from 11 to 15 carbon atoms, preferably of from 11 to 13 carbon atoms.
• M are hydrogen and alkali metal salts, especially sodium and potassium.
• Said acyl sarcosinate surfactants are derived from natural fatty acids and the amino-acid sarcosine (N-methyl glycine). They are suitable to be used as aqueous solution of their salt or in their acidic form as powder. Being derivatives of natural fatty acids, said acyl sarcosinates are rapidly and completely biodegradable and have good skin compatibility.
• compositions of the present invention formulated either as an emulsion or microemulsion are typically aqueous and are formulated in the acidic pH range up to 6, preferably at a pH of from 1 to 5, more preferably of from 2 to 5 and most preferably from 3 to 5. Formulating the compositions of the present invention in the acidic pH range contributes to the stability of said compositions.
• the pH of the compositions of the present invention can be adjusted by using organic or inorganic acids.
• Suitable-hydrophobic solvents to be used herein include terpenes like mono-and bicyclic monoterpenes, especially those of the hydrocarbon class, which include the terpinenes, terpinolenes, limonenes and pinenes and mixtures thereof. Highly preferred materials of this type are d-limonene, dipentene, alpha-pinene and/or beta-pinene.
• Other hydrophobic solvents include all type of paraffins, both linear and not, containing from 2 to 20 carbons, preferably from 4 to 10, more preferably from 6 to 8. Preferred herein is octane.
• Another hydrophobic solvent suitable to be used herein is benzyl alcohol. Particularly preferred hydrophobic solvents to be used herein include d-limonene, dipentene, alpha-pinene, beta-pinene, octane, benzyl alcohol, or mixtures thereof.
• Another preferred polymeric soil release agent is a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and terminal moieties covalently attached to the backbone.
• These soil release agents are described fully in U.S. Patent 4,968,451, issued November 6, 1990 to J.J. Scheibel and E. P. Gosselink.
• Other suitable polymeric soil release agents include the terephthalate polyesters of U.S. Patent 4,711,730, issued December 8, 1987 to Gosselink et al, the anionic end-capped oligomeric esters of U.S. Patent 4,721,580, issued January 26, 1988 to Gosselink, and the block polyester oligomeric compounds of U.S. Patent 4,702,857, issued October 27, 1987 to Gosselink.
• soil release agents will generally comprise from about 0.01% to about 10.0%, by weight, of the detergent compositions herein, typically from about 0.1% to about 5%, preferably from about 0.2% to about 3.0%.
• Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof.
• the N-O group can be represented by the following general structures: wherein R 1 , R 2 , R 3 are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof; x, y and z are 0 or 1; and the nitrogen of the N-O group can be attached or form part of any of the aforementioned groups.
• the amine oxide unit of the polyamine N-oxides has a pKa ⁇ 10, preferably pKa ⁇ 7, more preferred pKa ⁇ 6.
• compositions may also employ a polyvinylpyrrolidone ("PVP") having an average molecular weight of from about 5,000 to about 400,000, preferably from about 5,000 to about 200,000, and more preferably from about 5,000 to about 50,000.
• PVP's are known to persons skilled in the detergent field; see, for example, EP-A-262,897 and EP-A-256,696, incorporated herein by reference.
• Compositions containing PVP can also contain polyethylene glycol (“PEG”) having an average molecular weight from about 500 to about 100,000, preferably from about 1,000 to about 10,000.
• PEG polyethylene glycol
• the ratio of PEG to PVP on a ppm basis delivered in wash solutions is from about 2:1 to about 50:1, and more preferably from about 3:1 to about 10:1.
• optical brighteners which are useful in the present compositions are those identified in U.S. Patent 4,790,856, issued to Wixon on December 13, 1988. These brighteners include the PHORWHITE series of brighteners from Verona. Other brighteners disclosed in this reference include: Tinopal UNPA, Tinopal CBS and Tinopal 5BM; available from Ciba-Geigy; Artic White CC and Artic White CWD, available from Hilton-Davis, located in Italy; the 2-(4-styryl-phenyl)-2H-naphthol[1,2-d]triazoles; 4,4'-bis-(1,2,3-triazol-2-yl)stil- benes; 4,4'-bis(styryl)bisphenyls; and the aminocoumarins.
• these brighteners include 4-methyl-7-diethyl- amino coumarin; 1,2-bis(-benzimidazol-2-yl)ethylene; 2,5-bis(benzoxazol-2-yl)thiophene; 2-styrylnapth-[1,2-d]oxazole; and 2-(stilbene-4-yl)-2H-naphtho- [1,2-d]triazole. See also U.S. Patent 3,646,015, issued February 29, 1972 to Hamilton. Anionic brighteners are typically preferred herein.
• compositions of the present invention suitable for pretreating fabrics can be packaged in a variety of containers including conventional bottles, bottles equipped with roll-on, sponge, brusher or sprayers.

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• 1996
  • 1996-09-13 EP EP96870116A patent/EP0794245B1/fr not_active Expired - Lifetime
  • 1996-09-13 ES ES96870116T patent/ES2202424T3/es not_active Expired - Lifetime
  • 1996-09-13 DE DE69629006T patent/DE69629006T2/de not_active Expired - Fee Related
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• 1997
  • 1997-02-26 BR BR9708168A patent/BR9708168A/pt not_active IP Right Cessation
  • 1997-02-26 WO PCT/US1997/003238 patent/WO1997032962A1/fr not_active Application Discontinuation
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