EP0819164A1 - Composition detergente comportant une source de peroxyde d'hydrogene et une protease - Google Patents

Composition detergente comportant une source de peroxyde d'hydrogene et une protease

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Publication number
EP0819164A1
EP0819164A1 EP96906561A EP96906561A EP0819164A1 EP 0819164 A1 EP0819164 A1 EP 0819164A1 EP 96906561 A EP96906561 A EP 96906561A EP 96906561 A EP96906561 A EP 96906561A EP 0819164 A1 EP0819164 A1 EP 0819164A1
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EP
European Patent Office
Prior art keywords
weight
detergent composition
composition according
acid
enzyme
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP96906561A
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German (de)
English (en)
Other versions
EP0819164A4 (fr
EP0819164B2 (fr
EP0819164B1 (fr
Inventor
Gerard Marcel Baillely
Richard Timothy Hartshorn
Christian Leo Marie Vermote
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Procter and Gamble Co
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Procter and Gamble Co
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Priority claimed from GBGB9504978.9A external-priority patent/GB9504978D0/en
Priority claimed from GBGB9515580.0A external-priority patent/GB9515580D0/en
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to DE69634977T priority Critical patent/DE69634977T3/de
Publication of EP0819164A1 publication Critical patent/EP0819164A1/fr
Publication of EP0819164A4 publication Critical patent/EP0819164A4/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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/10—Carbonates ; Bicarbonates
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/08—Silicates
    • 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
    • C11D3/36—Organic compounds containing phosphorus
    • C11D3/361—Phosphonates, phosphinates or phosphonites
    • 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
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • 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
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C11D3/391—Oxygen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C11D3/3917—Nitrogen-containing compounds

Definitions

  • Detergent Composition Comprising Source of Hydrogen Peroxide and Protease Enzyme
  • the present invention relates to non-phosphate builder-containing detergent compositions. More particularly, the invention relates to non-phosphate detergent compositions, comprising a surfactant, a source of hydrogen peroxide, an organic peroxyacid precursor, a proteolytic enzyme and an alkalinity source, which provide effective soil/stain removal.
  • Oxygen bleaches are known to effectively decolourise pigments from soiled/stained substrates.
  • Enzymes are also known as effective soil/stain removal agents, for example, in the removal of proteinaceous stains/soils such as blood, egg, chocolate, gravy and the like.
  • Phosphorus containing compounds such as sodium tripolyphosphate have effective builder properties; however environmental concerns have made the use of phosphorus containing compounds less attractive in detergent compositions.
  • a problem encountered with the use of high levels of oxygen bleaches is the propensity of these oxygen bleaches to lead to stain fixing and/or darkening. Furthermore, high levels of oxygen bleaches increase the cost of the detergents to the consumer. On the other hand low levels of oxygen bleaches can lead to poor stain/soil removal performance, especially when used in a non-phosphate builder containing composition.
  • a problem encountered with the use of peroxyacids in machine dishwashing methods is the tarnishing/corrosion of any silverware components of the washload.
  • Oxygen bleaches tend to give rise to more of a problem of tarnishing than chlorine bleaches.
  • the level of tarnishing observed can range from slight discoloration of the silverware to the formation of a dense black coating on the surface of the silverware.
  • a problem encountered with the use of enzymes as components of detergents is that enzyme activity in the wash may be affected by the presence of other detergent components in the wash solution.
  • GB Patent Application No 9407533.0 discloses that enzymes may be degraded by bleach components.
  • the detergent formulator thus faces the challenge of formulating an environmentally friendly product which maximises soil/stain removal without fixing and/or darkening stains/soils, which avoids degradation of the detergent components and which is also inexpensive.
  • Pending GB Patent Application No 9407536.3 that forms part of the state of the art under Article 54(3) EPC discloses the use of a bleach containing detergent composition which contains low levels of bleach and bleach activator with higher levels of chelant and enzyme and defines a specific Biological Bleach Index which provides stain removal performance. Specific kinetics of bleach delivery are not disclosed, nor are the means to achieve such kinetics.
  • Pending GB Patent Application No 9407533.0 that forms part of the state of the art under Article 54(3) EPC discloses the use of an enzyme together with a source of peroxyacid bleach, wherein a means is provided for delaying the release to the wash solution of said peroxyacid bleach relative to the release of said enzyme.
  • the delayed release is provided by coating the source of peroxyacid bleach. The coating may occur on the hydrogen peroxide source itself and or the peroxyacid bleach precursor itself. Specific ratios of hydrogen peroxide: precursor: protease are not disclosed.
  • non-phosphate builder- containing detergent composition containing a source of hydrogen peroxide, an organic peroxyacid bleach precursor and a proteolytic enzyme, defined in term of an Hydrogen peroxide Precursor Proteolytic enzyme (HPP) index which relates to the ratios of Hydrogen peroxide, precursor and proteolytic enzyme, together with a high level of an alkalinity source, is employed an enhanced stain/soil removal may be obtained.
  • HPP Hydrogen peroxide Precursor Proteolytic enzyme
  • the total available oxygen (Av ⁇ 2) content in the composition should preferably be less than 1.5% by weight of the composition.
  • Such compounds may be selected from amylases, water-soluble organic polymeric polycarboxylic compounds, chelants and mixtures thereof It is therefore an object of the present invention to provide compositions suitable for use in laundry and machine dishwashing methods having enhanced stain removal.
  • compositions for use in laundry and machine dishwashing methods wherein said compositions show less propensity to cause stains fixing and/or darkening as well as detergent components degradation.
  • non-phosphate builder- containing detergent composition comprising a surfactant, and a)- at least 0.5% by weight of a source of hydrogen peroxide, b)- from 0.01% to 10% by weight of an organic peroxyacid bleach precursor, c)- from 0.001 % to 5% by weight of a proteolytic enzyme, and d)- an alkalinity source having the capacity to deliver alkalinity to a wash solution as measured by the alkalinity release test described herein, such that the % weight NaOH equivalent of the composition is greater than 10.6% by weight of the composition, and
  • the detergent composition has an Hydrogen peroxide Precursor Proteolytic enzyme (HPP) Index of at least 0.35 as defined by the formula
  • the %weight of proteolytic enzyme in the formulation is based on an enzyme activity of 13 knpu g of the enzyme particle, and wherein the %Av ⁇ 2 is the total amount of available oxygen present in the composition.
  • the level of proteolytic enzyme is defined as the actual level of the prill/granulate on a 13 knpu/g Savinase particle.
  • Non limiting examples of enzymes other than Savinase which can also be used for the purpose of the invention include enzyme of the Bacillus Lentus type backbone such as Maxacal, Opticlean, Durazym and Properase, enzyme of the Bacillus Licheniformis type backbone such as Alcalase and
  • Maxatase and enzyme of the Bacillus Amyloliquefaciens type backbone such as Primase.
  • the amount of protease will be reduced by a factor 2 to compensate for the extra activity of the protease.
  • proteases which are in other units of activity should be converted according to the following steps:
  • total amount of available oxygen present in the composition includes available oxygen provided by the source of hydrogen peroxide with or without peroxyacid bleach precursors.
  • the total available oxygen (Av ⁇ 2) content in the composition is less than 1.5% by weight.
  • Alkalinity is the combining power of a base measured by the maximum number of equivalents of an acid with which it can react to form a salt. In solution, it represents the carbonates and silicates in the water and is determined by titration with standard datum points.
  • alkalinity is defined as the weight equivalent of sodium hydroxide (NaOH) needed to be delivered into the wash to neutralise an equivalent amount of hydrochloric acid.
  • the present invention relates to the discovery of a Hydrogen peroxide Precursor Proteolytic enzyme (HPP) Index which defines a formula which relates specific ratios of hydrogen peroxide: precursor: proteolytic enzyme.
  • HPP Hydrogen peroxide Precursor Proteolytic enzyme
  • non-phosphate builder-containing detergent composition having a Hydrogen peroxide Precursor Proteolytic enzyme (HPP) Index of at least 0.35 as defined by the formula
  • the %weight of proteolytic enzyme in the formulation is based on an enzyme activity of 13 knpu/g of the enzyme particle, and wherein the %A ⁇ 2 is the total amount of available oxygen present in the composition.
  • HPP Index is of at least 0.40 and most preferably 0.50.
  • the total available oxygen (Av ⁇ 2) content in the composition is less than 1.5% by weight.
  • An essential component of the detergent composition is a source of hydrogen peroxide.
  • the source of hydrogen peroxide is normally incorporated at a level of at least 0.5% by weight, more preferably from 4% to 15% by weight and most preferably from 4% to 10% by weight of the composition.
  • Said source of hydrogen peroxide is a slow releasing source.
  • the slow release of hydrogen peroxide source relative to that of the protease is such that the time to achieve a concentration that is 50% of the ultimate concentration of said enzyme is less than 120 seconds, preferably less than 90 seconds, more preferably less than 60 seconds, and the time to achieve a concentration that is 50% of the ultimate concentration of said hydrogen peroxide source is more than 180 seconds, preferably from 180 to 480 seconds, more preferably from 240 to 360 seconds.
  • the time to achieve a concentration that is 50% of the ultimate concentration of said enzyme is at least 100 seconds less than the time to achieve a concentration that is 50% of the ultimate concentration for the hydrogen peroxide source.
  • a preferred source of hydrogen peroxide is an inorganic perhydrate.
  • a preferred perhydrate is perborate tetrahydrate of nominal formula NaB ⁇ 2H2 ⁇ 2-3H2 O.
  • the inorganic perhydrate will normally be in the form of the sodium salt.
  • the source of hydrogen peroxide consists of at least 90% by weight of a perborate tetrahydrate.
  • perhydrate compounds may be used in addition or in place of the perborate tetrahydrate together with appropriate means, such as coating or coagglomeration, to obtain a slow release of hydrogen peroxide.
  • Such compounds can include perborate monohydrate, percarbonate, perphosphate, persilicate salts and mixtures thereof.
  • a preferred perhydrate is percarbonate.
  • Coarse percarbonate materials of average particle size greater than 600 micrometers and preferably greater than 750 micrometers, may be used.
  • these percarbonate materials are coated with substances which are sparingly soluble in water.
  • Water insoluble coating materials may be selected from fatty acid, polymers, hydrophobic silicas, waxes and magnesium silicates and mixtures thereof.
  • Percarbonate materials which are exclusively coated with water-soluble substances such as citrates, borosilicates, borate derivatives, sodium carbonate or sodium/magnesium sulphate are not preferred.
  • the source of hydrogen peroxide consists of at least 90% by weight of a percarbonate having a particle size of at least 600 micrometers and coated with water-insoluble materials.
  • the level of total available oxygen (Av ⁇ 2) in the composition is less than 1.5% by weight.
  • a method for determining Av ⁇ 2 levels is disclosed in European Patent Application No.93870004.4.
  • Peroxyacid bleach precursors are compounds which react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid.
  • peroxyacid bleach precursors may be represented as
  • L is a leaving group and X is essentially any functionality, such that on perhydrolysis the structure of the peroxyacid produced is
  • Peroxyacid bleach precursor compounds are preferably incorporated at a level of from 0.01% to 10% by weight, more preferably from 3% to 10% by weight, most preferably from 5% to 9% by weight of the precursor composition.
  • L group The leaving group, hereinafter L group, must be sufficiently reactive for the perhydrolysis reaction to occur within the optimum time frame (e.g., a wash cycle). However, if L is too reactive, this activator will be difficult to stabilize for use in a bleaching composition.
  • Preferred L groups are selected from the group consisting of:
  • R1 is an alkyl, aryl, or alkaryl group containing from 1 to 14 carbon atoms
  • R 3 is an alkyl chain containing from 1 to 8 carbon atoms
  • R 4 is H or R 3
  • Y is H or a solubilizing group.
  • Any of Rl , R 3 and R 4 may be substituted by essentially any functional group including, for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl ammmonium groups
  • the preferred solubilizing groups are -S ⁇ 3"M + , -C ⁇ 2"M + , -S ⁇ 4"M + , -N + (R 3 )4X- and 0 ⁇ -N(R 3 )3 and most preferably -SO3"M + and -C ⁇ 2 _ M + wherein R 3 is an alkyl chain containing from 1 to 4 carbon atoms, M is a cation which provides solubility to the bleach activator and X is an anion which provides solubility to the bleach activator.
  • M is an alkali metal, ammonium or substituted ammonium cation, with sodium and potassium being most preferred, and X is a halide, hydroxide, methyisulfate or acetate anion.
  • Suitable peroxyacid bleach precursor materials are compounds which comprise at least one acyl group forming the peroxyacid moiety bonded to a leaving group through an -O- or-N- linkage.
  • a preferred class of bleach precursor is the class of N-acylated precursors of which TAED is the preferred one.
  • Peroxyacid precursor compositions containing mixtures of any of the precursors hereinafter disclosed are also contemplated by the present invention.
  • Perbenzoic acid precursor compounds provide perbenzoic acid on perhydrolysis.
  • Suitable O-acylated perbenzoic acid precursor compounds include the substituted and unsubstituted benzoyl oxybenzene sulfonates, including for example benzoyl oxybenzene sulfonate:
  • benzoylation products of sorbitol, glucose, and all saccharides with benzoylating agents including for example:
  • Perbenzoic acid precursor compounds of the imide type include N-benzoyl succinimide, tetrabenzoyi ethylene diamine and the N-benzoyl substituted ureas.
  • Suitable imidazole type perbenzoic acid precursors include N- benzoyl imidazole and N-benzoyl benzimidazole and other useful N-acyl group-containing perbenzoic acid precursors include N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic acid.
  • perbenzoic acid precursors include the benzoyl diacyl peroxides, the benzoyl tetraacyl peroxides, and the compound having the formula:
  • Phthalic anhydride is another suitable perbenzoic acid precursor compound herein:
  • Suitable N-acylated precursor compounds of the lactam class are disclosed generally in GB-A-855735. Whilst the broadest aspect of the invention contemplates the use of any lactam useful as a peroxyacid precursor, preferred materials comprise the caprolactams and valerolactams.
  • Suitable caproiactam bleach precursors are of the formula:
  • P ⁇ is H or an alkyl, aryl, alkoxyaryl or alkaryl group containing from 1 to 12 carbon atoms, preferably from 6 to 12 carbon atoms.
  • Suitable valero lactams have the formula:
  • R ⁇ is H or an alkyl, aryl, alkoxyaryl or alkaryl group containing from 1 to 12 carbon atoms, preferably from 6 to 12 carbon atoms.
  • R ⁇ is selected from phenyl, heptyl, octyl, nonyl, 2,4,4-trimethylpentyl, decenyl and mixtures thereof.
  • T e most preferred materials are those which are normally solid at ⁇ 30°C, particularly the phenyl derivatives, ie. benzoyl valerolactam, benzoyl caproiactam and their substituted benzoyl analogues such as chloro, amino alkyl, alkyl, aryl and alkyloxy derivatives.
  • phenyl derivatives ie. benzoyl valerolactam, benzoyl caproiactam and their substituted benzoyl analogues such as chloro, amino alkyl, alkyl, aryl and alkyloxy derivatives.
  • Precursor compounds wherein R 6 comprises from 1 to 6 carbon atoms provide hydrophilic bleaching species which are particularly efficient for bleaching beverage stains.
  • Mixtures of 'hydrophobic' and 'hydrophilic' caprolactams and valero lactams, typically at weight ratios of 1 :5 to 5:1 , preferably 1 :1 can be used herein for mixed stain removal benefits.
  • Perbenzoic acid derivative precursors provide substituted perbenzoic acids on perhydrolysis.
  • Suitable substituted perbenzoic acid derivative precursors include any of the herein disclosed perbenzoic precursors in which the benzoyl group is substituted by essentially any non-positively charged (ie; non-cationic) functional group including, for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl and amide groups.
  • a preferred class of substituted perbenzoic acid precursor compounds are the amide substituted compounds of the following general formulae:
  • R1 is an aryl or alkaryl group with from 1 to 14 carbon atoms
  • R 2 is an arylene, or alkarylene group containing from 1 to 14 carbon atoms
  • R 5 is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms and L can be essentially any leaving group.
  • R 1 preferably contains from 6 to 12 carbon atoms.
  • R 2 preferably contains from 4 to 8 carbon atoms.
  • R 1 may be aryl, substituted aryl or alkylaryl containing branching, substitution, or both and may be sourced from either synthetic sources or natural sources including for example, tallow fat. Analogous structural variations are permissible for R 2 .
  • substitution can include alkyl, aryl, halogen, nitrogen, sulphur and other typical substituent groups or organic compounds.
  • R is preferably H or methyl.
  • R 1 and R ⁇ should not contain more than 18 carbon atoms in total.
  • Amide substituted bleach activator compounds of this type are described in EP-A-0170386. Cationic peroxyacid precursors
  • Cationic peroxyacid precursor compounds produce cationic peroxyacids on perhydrolysis.
  • cationic peroxyacid precursors are formed by substituting the peroxyacid part of a suitable peroxyacid precursor compound with a positively charged functional group, such as an ammonium or alkyl ammmonium group, preferably an ethyl or methyl ammonium group.
  • Cationic peroxyacid precursors are typically present in the solid detergent compositions as a salt with a suitable anion, such as a halide ion.
  • the peroxyacid precursor compound to be so cationically substituted may be a perbenzoic acid, or substituted derivative thereof, precursor compound as described hereinbefore.
  • the peroxyacid precursor compound may be an alkyl percarboxylic acid precursor compound or an amide substituted alkyl peroxyacid precursor as described hereinafter
  • Cationic peroxyacid precursors are described in U.S. Patents 4,904,406; 4,751 ,015; 4,988,451; 4,397,757; 5,269,962; 5,127,852; 5,093,022; 5,106,528; U.K. 1 ,382,594; EP 475,512, 458,396 and 284,292; and in JP 87-318,332.
  • Suitable cationic peroxyacid precursors include any of the ammonium or alkyl ammonium substituted alkyl or benzoyl oxybenzene sulfonates, N- acylated caprolactams, and monobenzoyltetraacety! glucose benzoyl peroxides.
  • a preferred cationically substituted benzoyl oxybenzene sulfonate is the 4- (trimethyl ammonium) methyl derivative of benzoyl oxybenzene sulfonate:
  • a preferred cationically substituted alkyl oxybenzene sulfonate has the formula:
  • Preferred cationic peroxyacid precursors of the N-acylated caproiactam class include the trialkyl ammonium methylene benzoyl caprolactams, particularly trimethyl ammonium methylene benzoyl caproiactam:
  • N-acylated caproiactam class include the trialkyl ammonium methylene alkyl caprolactams:
  • n is from 0 to 12.
  • Another preferred cationic peroxyacid precursor is 2-(N,N,N-trimethyl ammonium) ethyl sodium 4-sulphophenyl carbonate chloride.
  • precursor compounds of the benzoxazin-type as disclosed for example in EP-A-332,294 and EP-A-482,807, particularly those having the formula:
  • R 1 is H, alkyl, alkaryl, aryl, arylalkyi
  • R 2 , R 3 , R 4 , and R5 may be the same or different substituents selected from H, halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxyl, amino, alkyl amino, COOR 6 (wherein R 6 is H or an alkyl group) and carbonyl functions.
  • An especially preferred precursor of the benzoxazin-type is:
  • Preferred precursors of this type provide peracetic ac on perhydrolysis. 17
  • Preferred alkyl percarboxylic precursor compounds of the imide type include the N,N-N',N' tetra acetylated alkylene diamines wherein the alkylene group contains from 1 to 6 carbon atoms, particularly those compounds in which the alkylene group contains 1 , 2 and 6 carbon atoms. Tetraacetyl ethylene diamine (TAED) is particularly preferred.
  • TAED Tetraacetyl ethylene diamine
  • alkyl percarboxylic acid precursors include sodium 3,5,5-tri- methyl hexanoyloxybenzene sulfonate (ISONOBS), sodium nonanoyloxybenzene sulfonate (NOBS), sodium acetoxybenzene sulfonate (ABS) and pentaacetyl glucose.
  • ISONOBS sodium 3,5,5-tri- methyl hexanoyloxybenzene sulfonate
  • NOBS sodium nonanoyloxybenzene sulfonate
  • ABS sodium acetoxybenzene sulfonate
  • pentaacetyl glucose pentaacetyl glucose
  • Amide substituted alkyl peroxyacid precursor compounds are also suitable, including those of the following general formulae:
  • R1 is an alkyl group with from 1 to 14 carbon atoms
  • R 2 is an alkylene group containing from 1 to 14 carbon atoms
  • R 5 is H or an alkyl group containing 1 to 10 carbon atoms and L can be essentially any leaving group.
  • R " - preferably contains from 6 to 12 carbon atoms.
  • R 2 preferably contains from 4 to 8 carbon atoms.
  • R 1 may be straight chain or branched alkyl containing branching, substitution, or both and may be sourced from either synthetic sources or natural sources including for example, tallow fat. Analogous structural variations are permissible for R 2 .
  • the substitution can include alkyl, halogen, nitrogen, sulphur and other typical substituent groups or organic compounds.
  • R 5 is preferably H or methyl.
  • R 1 and R 5 should not contain more than 18 carbon atoms in total. Amide substituted bleach activator compounds of this type are described in EP-A-0170386.
  • Preferred amide substituted alkyl peroxyacid precursor compounds are (6-octanamido-caproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)oxy benzene sulfonate and (6-decanamido-caproyl)oxybenzene sulfonate and mixture thereof.
  • More preferred peroxyacid bleach precursors compounds for use in the invention are selected from N.N-N'.N' tetra acetyl ethylene diamine, 3,5,5-tri- methyl h ⁇ xanoyl oxybenzene sulfonate, nonanoyl oxybenzene sulfonate, amide substituted perbenzoic acid precursor compounds, amide substituted alkyl peroxyacid precursors and mixtures thereof.
  • a most preferred peroxyacid bleach precursor is N.N-N'.N' tetra acetyl ethylene diamine.
  • TAED When used TAED will preferably be at a level of from 0.5% to 2.5% by weight.
  • Bleaching agents other than oxygen bleaching agents are also known in the art and can optionally be utilized herein.
  • One type of non-oxygen bleaching agent of particular interest includes photoactivated bleaching agents such as the suifonated zinc and/or aluminum phthalocyanines. See U.S. Patent 4,033,718, issued July 5, 1977 to Hoicombe et al. If used, detergent compositions will typically contain from 0.025% to 1.25%, by weight, of such bleaches, especially sulfonate zinc phthalocyanine.
  • An essential component of the detergent composition is an enzyme showing proteolytic activity.
  • the level of proteolytic enzyme in the formulation is based on an enzyme activity of 13 knpu/g of the enzyme particle.
  • compositions herein will typically comprise from 0.001 % to 5% active protease by weight of the composition.
  • Non limiting examples of enzymes other than Savinase which can also be used for the purpose of the invention include enzyme of the Bacillus Lentus type backbone such as Maxacal, Opticlean, Durazym and Properase, enzyme of the Bacillus Licheniformis type backbone such as Alcalase and Maxatase and enzyme of the Bacillus Amyloliquefaciens type backbone such as Primase. Of these, Maxacal is a preferred one.
  • protease enzymes include those sold under the tradenames Alcalase, Savinase, Primase, Durazym, and Esperase by Novo Industries A/S (Denmark), those sold under the tradename Maxatase, Maxacal and Maxapem by Gist-Brocades, those sold by Genencor International, and those sold under the tradename Opticlean and Optimase by Solvay Enzymes. Mixture of the herein before described proteases may be used. A most preferred protease is Savinase.
  • An essential component of the detergent composition is an alkalinity source.
  • alkalinity is defined as the weight equivalent of sodium hydroxide (NaOH) needed to be delivered into the wash to neutralise an equivalent amount of hydrochloric acid.
  • a 1g sample of detergent composition is added to 100 ml of distilled water at a temperature of 30°C with stirring at 150 rpm using a magnetic stirrer of size 2cm, thus providing a 1% detergent solution, as would be a typical concentration of a laundry wash solution.
  • the solution is titrated against a standard HCI solution using any suitable titration method.
  • Commonly known acid-base titration methods employing colorimetric end-point determination methods, for example using chemical end-point indicators are particularly suitable.
  • the number of moles of HCI which the detergent solution is capable of neutralising is obtained.
  • 'neutralising' in this context is defined to mean titrating to pH 7. This number will be equivalent to the number of moles of alkalinity, expressed as NaOH equivalent, present in the detergent solution.
  • the % weight equivalent NaOH present in the sample of the detergent composition may be calculated as:
  • compositional make up of a detergent product is known, it is possible to calculate the theoretical maximum alkalinity, expressed as % weight equivalent of NaOH, which the product could provide to a solution as the sum over each alkaline species of:
  • n is the formal negative charge carried by the alkaline species.
  • a composition containing 15% sodium carbonate is equivalent to a theoretical maximum of 11.32% NaOH, obtained as (15 x 40 x 2)/106, since this amount of NaOH in the composition would theoretically neutralise the same amount of acid as the 15% sodium carbonate alkaline component.
  • the alkalinity source is present in the detergent composition such that the capacity to deliver alkalinity to a wash solution measured by the given test method is such that the % weight NaOH equivalent of the composition is greater than 10.6%, preferably at least 14.6% by weight of the composition.
  • the alkalinity source is preferably selected from alkali metal carbonate, alkali metal silicate and mixture thereof.
  • Suitable alkali metal carbonates include the alkaline earth and alkali metal carbonates, including sodium carbonate and sesqui-carbonate and mixtures thereof with ultra-fine calcium carbonate as disclosed in German Patent Application No. 2,321 ,001 published on November 15, 1973.
  • Suitable silicates include the alkali metal silicate Si ⁇ 2:Na2 ⁇ with a ratio of from 1.0 to 2.8 and 1.6:1 ratio being more preferred.
  • the silicates may be in the form of either the anhydrous salt or a hydrated salt.
  • Sodium silicate with an Si ⁇ 2:Na2 ⁇ ratio of 1.6:1 is the most preferred silicate.
  • Such compounds include the crystalline layered silicate and/or aluminosilicate compounds as described herein after, but also the bicarbonates, hydroxides, borates and phosphates.
  • the detergent composition of the invention will, of course contain one or more surfactants and additional compounds for enhancing the soil removal performance.
  • Such compounds include the water-soluble organic polymeric polycarboxylic compounds, chelants, amylases, builders and conventional detersive adjuncts.
  • the total amount of surfactants will be generally up to 70%, typically 1 to 55%, preferably 1 to 30%, more preferably 5 to 25% and especially 10 to 20% by weight of the total composition.
  • Nonlimiting examples of surfactants useful herein include the conventional C 11-C-
  • the conventional nonionic and amphoteric surfactants such as the C12-C18 a,k yl ⁇ thoxylates ("AE"), including the so-called narrow peaked alkyl ethoxylates and C6-C12 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), C12-C18 betaines and sulfobetaines ("sultaines”), C10-C18 amine oxides, and the like, can also be included in the overall compositions.
  • the C10-C18 N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include the C-12- 18 N-methylglucamides. See WO 9,206,154.
  • sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C10-C18 N-(3- methoxypropyl) glucamide.
  • the N-propyl through N-hexyl C12-C18 glucamides can be used for low sudsing.
  • C10-C20 conventional soaps may also be used. If high sudsing is desired, the branched-chain C10-C16 soaps may be used.
  • Suitable surfactants suitable for the purpose of the invention are the anionic alkali metal sarcosinates of formula:
  • R-CON(Rl )CH 2 COOM wherein R is a C9-C17 linear or branched alkyl or alkenyl group, R ⁇
  • R is a C9-C17 linear or branched alkyl or alkenyl group
  • is a C - C4 alkyl group
  • M is an alkali metal ion.
  • Preferred examples are the lauroyl, cocoyl (C12-C14). myristyl and oleyl methyl sarcosinates in the form of their sodium salts.
  • Still another class of surfactant which may be suitable for the purpose of the invention are the cationic surfactant.
  • Suitable cationic surfactants include the quaternary ammonium surfactants selected from mono Ce-C-
  • Water-soluble organic polymeric polvcarboxylic compounds are the water-soluble organic polymeric polycarboxylic compounds. Preferably these compounds are homo- or co-polymeric polycarboxylic compounds and most preferably co-polymeric polycarboxylic compounds in which the acid monomer of said polycarboxylic compound comprises at least two carboxyl groups separated by not more than two carbon atoms. Salts of these polycarboxylic compounds are also considered herein.
  • Polymeric polycarboxylate compounds can advantageously be utilized at levels from 0.1% to 7%, preferably less than 3% and more preferably less than 1 % by weight, in the compositions herein, especially in the presence of zeolite and/or layered silicate builders and diphosphonate chelants.
  • 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 are selected from acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid.
  • the presence in the polymeric polycarboxylates herein of monomeric segments, containing no carboxylate radicals such as vinylmethyl ether, styrene, ethylene, etc. is suitable provided that such segments do not constitute more than 40% by weight.
  • Polymeric polycarboxylate materials can also optionally include further monomeric units such as nonionic spacing units.
  • suitable nonionic spacing units may include vinyl alcohol or vinyl acetate.
  • Particularly preferred polymeric polycarboxylates are co-polymers derived from monomers of acrylic acid and maleic acid.
  • the average molecular weight of such polymers in the acid form preferably ranges from 2,000 to 10,000, more preferably from 4,000 to 7,000 and most preferably from 4,000 to 5,000.
  • Water-soluble salts of such acrylic/maleic acid polymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble polymers of this type are known materials. Use of polyacryiates of this type in detergent compositions has been disclosed, for example, in Diehl, U.S. Patent 3,308,067, issued march 7, 1967.
  • the ratio of acrylate to maleate segments in such copolymers will generally range from 30:1 to 1:1 , more preferably from 10:1 to 2:1.
  • Soluble acrylate/maleat ⁇ copolymers of this type are known materials which are described in European Patent Application No. 66915, published December 15, 1982, as well as in EP 193,360, published September 3, 1986, which also describes such polymers comprising hydroxypropylacrylate.
  • acrylic/maleic-based copolymers the water-soluble salts of copolymers of acrylic acid and maleic acid are preferred.
  • polymeric polycarboxylic acid compounds suitable for the pu ⁇ ose of the invention are the homo-polymeric polycarboxylic acid compounds derived from acrylic acid.
  • the average molecular weight of such homo-polymers in the acid form preferably ranges from 2,000 to 100,000, more preferably from 3,000 to 75,000, most preferably from 4,000 to 65,000.
  • polymeric polycarboxylic compounds suitable for the purpose of the invention include the maleic/acrylic/vinyl alcohol terpolymers Such materials are also disclosed in EP 193,360, including, for example, the 45/45/10 t ⁇ olymer of acrylic/maleic/vinyl alcohol.
  • polymeric polycarboxylic compounds suitable for the purpose of the invention include the biodegradable polyaspartic acid and polyglutamic acid compounds.
  • Chelating agents generally comprise from 0.1% to 10% by weight of the compositions herein. More preferably, if utilized, the chelating agents will comprise from 0.1% to 3.0% by weight of such compositions.
  • a chelating agent can be selected from amino carboxylate, organic phosphonate, polyfunctionally-substituted aromatic compound, nitriloacetic acid and mixture thereof. Without intending to be bound by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove transition metal ions such as iron and manganese ions from washing solutions by formation of soluble chelates.
  • Amino carboxylates useful as optional chelating agents include ethylenediaminetetracetates, ethylenediamine disuccinate, N- hydroxyethylethylenediaminetriacetat ⁇ s, 2-hydroxypropylene diamine disuccinate, nitrilotriaceta.es, ethylenediamine tetraproprionates, triethylenetetraaminehexacetates, ethylene triamine pentaacetate, diethylenetriaminepentaacetates, and ethanoldiglycines, alkali metal, ammonium, and substituted ammonium salts therein and mixtures therein.
  • Preferred amino carboxylates chelants for use herein are ethylenediamine disuccinate ("EDDS"), especially the [S,S] isomer as described in U.S. Patent 4,704,233, ethylenediamine-N.N'-diglutamate (EDDG) and 2- hydroxypropylene-diamine-N.N'-disuccinate (HPDDS) compounds.
  • EDDS ethylenediamine disuccinate
  • a most preferred amino carboxylate chelant is ethylenediamine disuccinate.
  • Organic phosphonates are also suitable for use as chelating agents in the compositions of the invention when at least low levels of total phosphorus are permitted in detergent compositions, and include ethylenediaminetetrakis (methylenephosphonates) available under the trademark DEQUEST from Monsanto, diethylene triamine penta (methylene phosphonate), ethylene diamine tri (methylene phosphonate), hexamethylene diamine tetra (methylene phosphonate), ⁇ -hydroxy-2 phenyl ethyl diphosphonate, methylene diphosphonate, hydroxy 1,1-hexylidene, vinylidene 1,1 diphosphonate, 1,2 dihydroxyethane 1,1 diphosphonate and hydroxy-ethylene 1,1 diphosphonate.
  • methylenephosphonates ethylenediaminetetrakis
  • these amino phosphonates do not contain alkyl or alkenyl groups with more than 6 carbon atoms.
  • Preferred chelants are the diphosphonate derivatives selected from ⁇ - hydroxy-2 phenyl ethyl diphosphonate, methylene diphosphonate, hydroxy 1,1-hexylidene, vinylidene 1,1 diphosphonate, 1,2 dihydroxyethane 1 ,1 diphosphonate and hydroxy-ethylene 1,1 diphosphonate.
  • a most preferred is hydroxy-ethylene 1,1 diphosphonate.
  • Polyfunctionally-substituted aromatic chelating agents are also useful in the compositions herein. See U.S. Patent 3,812,044.
  • Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1 ,2-dihydroxy- 3,5-disulfobenzene.
  • Preferred amylases include, for example, ⁇ -amylases obtained from a special strain of B licheniformis, described in more detail in GB-1 ,269,839 (Novo).
  • Preferred commercially available amylases include for example, those sold under the tradename Rapidase by Gist-Brocades, and those sold under the tradename Termamyl and BAN by Novo Industries A/S.
  • Amylase enzyme may be inco ⁇ orated into the composition in accordance with the invention at a level of from 0.001 % to 5% active enzyme by weight of the composition. Builders
  • Detergent builders can optionally be included in the compositions herein to assist in controlling mineral hardness. Inorganic as well as organic builders can be used. Builders are typically used in fabric laundering compositions to assist in the removal of particulate soils.
  • the level of builder can vary widely depending upon the end use of the composition and its desired physical form. When present, the compositions will typically comprise at least 1% builder. Granular formulations typically comprise from 10% to 80%, more typically from 15% to 50% by weight, of the detergent builder. Lower or higher levels of builder, however, are not meant to be excluded.
  • silicates can include, but are not restricted to phytic acid, silicates, alkali metal carbonates (including bicarbonates and sesquicarbonates), sulphates, aluminosilicates, monomeric polycarboxylates, homo or copolymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxylic radicals separated from each other by not more than two carbon atoms.
  • silicate builders are the crystalline layered silicates, such as the layered sodium silicates described in U.S. Patent 4,664,839.
  • NaSKS-6 is the trademark for a crystalline layered silicate marketed by Hoechst (commonly abbreviated herein as "SKS-6").
  • Na SKS-6 silicate builder does not contain aluminum.
  • NaSKS-6 has the delta-Na2Si2 ⁇ 5 mo ⁇ hology form of layered silicate. It can be prepared by methods such as those described in German DE-A- 3,417,649 and DE-A-3,742,043.
  • SKS-6 is a highly preferred layered silicate for use herein, but other such layered silicates, such as those having the general formula NaMSi x ⁇ 2 ⁇ + ⁇ .yH2 ⁇ wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0 can be used herein.
  • layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11 , as the alpha, beta and gamma forms.
  • the delta-Na2Si2 ⁇ s (NaSKS-6 form) is most preferred for use herein.
  • Other silicates may also be useful such as for example magnesium silicate, which can serve as a crispening agent in granular formulations, as a stabilising agent for oxygen bleaches, and as a component of suds control systems.
  • Aluminosilicat ⁇ builders are especially useful in the present invention.
  • Aluminosilicate builders are of great importance in most currently marketed heavy duty granular detergent compositions, and can also be a significant builder ingredient in liquid detergent formulations.
  • Aluminosilicate builders include those having the empirical formula:
  • aluminosilicate ion exchange materials are commercially available. These aluminosilicates can be crystalline or amorphous in structure and can be naturally-occurring aluminosilicates or synthetically derived. A method for producing aluminosilicate ion exchange materials is disclosed in U.S. Patent 3,985,669. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X.
  • the crystalline aluminosilicate ion exchange material has the formula: Na 1 2[(AI0 2 )i2(Si ⁇ 2)i2].xH 2 0 wherein x is from 20 to 30, especially 27.
  • This material is known as Zeolite A.
  • the aluminosilicate has a particle size of 0.1-10 microns in diameter.
  • Organic detergent builders suitable for the pu ⁇ oses of the present invention include, but are not restricted to, a wide variety of polycarboxylate compounds.
  • polycarboxylate refers to compounds having a plurality of carboxylate groups, preferably at least 3 c-arboxyla.es.
  • Polycarboxylate builder can generally be added to the composition in acid form, but can also be added in the form of a neutralised salt. When utilized in salt form, alkali metals, such as sodium, potassium, and lithium, or alkanolammonium salts are preferred.
  • polycarboxylate builders include a variety of categories of useful materials.
  • One important category of polycarboxylate builders encompasses the ether polycarboxylates, including oxydisuccinate, as disclosed in U.S. Patent 3,128,287 and U.S. Patent 3,635,830. See also "TMS/TDS" builders of U.S. Patent 4,663,071.
  • Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S. Patents 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.
  • ether hydroxypolycarboxylates copolymers of maleic anhydride with ethylene or vinyl methyl ether, or acrylic acid, 1, 3, 5-trihydroxy benzene-2, 4, 6- trisulphonic acid, and carboxymethyloxysuccinic acid
  • acrylic acid 1, 3, 5-trihydroxy benzene-2, 4, 6- trisulphonic acid
  • carboxymethyloxysuccinic acid the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid, as well as polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.
  • Citrate builders e.g., citric acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders of particular importance for heavy duty liquid detergent formulations due to their availability from renewable resources and their biodegradability. Citrates can also be used in granular compositions, especially in combination with zeolite and/or layered silicate builders. Oxydisuccinates are also especially useful in such compositions and combinations.
  • succinic acid builders include the C5-C20 alkyl and alkenyl succinic acids and salts thereof.
  • a particularly preferred compound of this type is dodecenyisuccinic acid.
  • succinate builders include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dod ⁇ cenylsuccinate (preferred), 2-pentadecenylsucci- nate, and the like. Laurylsuccinates are the preferred builders of this group, and are described in EP 0,200,263.
  • Fatty acids e.g., C12-C18 rnonocarboxylic acids
  • Such use of fatty acids will generally result in a diminution of sudsing, which should be taken into account by the formulator.
  • compositions herein can optionally include one or more other detergent adjunct materials or other materials for assisting or enhancing cleaning performance, treatment of the substrate to be cleaned, or to modify the aesthetics of the detergent composition (e.g., perfumes, colorants, dyes, etc.).
  • other detergent adjunct materials e.g., perfumes, colorants, dyes, etc.
  • the following are illustrative examples of such adjunct materials.
  • enzymes than proteases and amylases may be used. These include cellulases, Upases, peroxidase, endoglucanase and mixtures thereof.
  • These enzymes may be incorporated into the composition in accordance with the invention at a level of from 0.001 % to 5% active enzyme by weight of the composition.
  • the cellulases usable in the present invention include both bacterial or fungal cellulase. Preferably, they will have a pH optimum of between 5 and 9.5. Suitable cellulases are disclosed in U.S. Patent 4,435,307, which discloses fungal cellulase produced from Humicola insolens and Humicola strain DSM1800 or a cellulase 212-producing fungus belonging to the genus Aeromonas, and cellulase extracted from the hepatopancreas of a marine mollusk (Dolabella Auricula Solander). Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832. ENDO A, CAREZYME both from Novo Industries A/S are especially useful.
  • Suitable lipase enzymes for detergent usage include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in GB 1 ,372,034. See also lipases in Japanese Patent Application 53,20487, laid open to public inspection on February 24, 1978. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano,” hereinafter referred to as "Amano-P.” Other commercial lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var.
  • lipolyticum NRRLB 3673 commercially available from Toyo Jozo Co., Tagata, Japan; and further Chromobacter viscosum lipases from U.S. Biochemical Co ⁇ ., U.S.A. and Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli.
  • the LIPOLASE enzyme derived from Humicola lanuginosa and commercially available from Novo is a preferred lipase for use herein.
  • Peroxidase enzymes are used in combination with oxygen sources, e.g., percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for "solution bleaching," i.e. to prevent transfer of dyes or pigments removed from substrates during wash operations to other substrates in the wash solution.
  • Peroxidase enzymes are known in the art, and include, for example, horseradish peroxidase, ligninase, and haloperoxidase such as chloro- and bromo-peroxidase.
  • Peroxidase-containing detergent compositions are disclosed, for example, in EP-A-0,424,398.
  • a wide range of enzyme materials and means for their inco ⁇ oration into synthetic detergent compositions are also disclosed in U.S. Patent 3,553,139. Enzymes are further disclosed in U.S. Patent 4,101 ,457 and in U.S. Patent 4,507,219. Enzyme materials useful for liquid detergent formulations, and their incorporation into such formulations, are disclosed in U.S. Patent 4,261 ,868. Enzymes for use in detergents can be stabilized by various techniques. Enzyme stabilisation techniques are disclosed and exemplified in U.S. Patent 3,600,319 and EP 0 199 405. Enzyme stabilisation systems are also described, for example, in U.S. Patent 3,519,570.
  • Enzvme Stabilizers The enzymes employed herein are stabilized by the presence of water-soluble sources of calcium and/or magnesium ions in the finished compositions which provide such ions to the enzymes. (Calcium ions are generally somewhat more effective than magnesium ions and are preferred herein if only one type of cation is being used.) Additional stability can be provided by the presence of various other art-disclosed stabilizers, especially borate species: see Severson, U.S. 4,537,706. Typical detergents, especially liquids, will comprise from 1 to 30, preferably from 2 to 20, more preferably from 5 to 15, and most preferably from 8 to 12, miliimoles of calcium ion per liter of finished composition.
  • the level of calcium or magnesium ions should be selected so that there is always some minimum level available for the enzyme, after allowing for complexation with builders, fatty acids, etc., in the composition.
  • Any water-soluble calcium or magnesium salt can be used as the source of calcium or magnesium ions, including, but not limited to, calcium chloride, calcium sulfate, calcium malate, calcium maleate, calcium hydroxide, calcium formate, and calcium acetate, and the corresponding magnesium salts.
  • a small amount of calcium ion generally from 0.05 to 0.4 miliimoles per liter, is often also present in the composition due to calcium in the enzyme slurry and formula water.
  • the formulation may include a sufficient quantity of a water-soluble calcium ion source to provide such amounts in the laundry liquor. In the alternative, natural water hardness may suffice.
  • compositions herein may also optionally, but preferably, contain various additional stabilizers, especially borate-type stabilizers.
  • additional stabilizers especially borate-type stabilizers.
  • such stabilizers will be used at levels in the compositions from 0.25% to 10%, preferably from 0.5% to 5%, more preferably from 0.75% to 3%, by weight of boric acid or other borate compound capable of forming boric acid in the composition (calculated on the basis of boric acid).
  • Boric acid is preferred, although other compounds such as boric oxide, borax and other alkali metal borates (e.g., sodium ortho-, meta- and pyroborate, and sodium pentaborate) are suitable.
  • Substituted boric acids e.g., phenylboronic acid, butane boronic acid, and p-bromo phenylboronic acid
  • Polymeric Dispersing Agents can be utilized at levels from 0.1% to 7%, by weight, in the compositions herein.
  • a polymeric material which can be included is polyethylene glycol (PEG).
  • PEG can exhibit dispersing agent performance as well as act as a clay soil removal-antiredeposition agent.
  • Typical molecular weight ranges for these purposes range from 500 to 100,000, preferably from 1 ,000 to 50,000, more preferably from 1 ,500 to 10,000.
  • Polyaspartate and polyglutamate dispersing agents may also be used, especially in conjunction with zeolite builders.
  • Dispersing agents such as polyaspartate preferably have a molecular weight (avg.) of 10,000.
  • compositions of the present invention can also optionally contain water-soluble ethoxylated amines having clay soil removal and antiredeposition properties.
  • Granular detergent compositions which contain these compounds typically contain from 0.01% to 10.0% by weight of the water-soluble ethoxylates amines; liquid detergent compositions typically contain 0.01% to 5%.
  • the most preferred soil release and anti-redeposition agent is ethoxylated tetraethylenepentamine. Exemplary ethoxylated amines are further described in U.S. Patent 4,597,898, VanderMeer, issued July 1 , 1986.
  • Another group of preferred clay soil removal-antiredeposition agents are the cationic compounds disclosed in European Patent Application 111,965, Oh and Gosselink, published June 27, 1984.
  • Other clay soil removal/antiredeposition agents which can be used include the ethoxylated amine polymers disclosed in European Patent Application 111 ,984, Gosselink, published June 27, 1984; the zwitterionic polymers disclosed in European Patent Application 112,592, Gosselink, published July 4, 1984; and the amine oxides disclosed in U.S.
  • CMC carboxy methyl cellulose
  • Polymeric Soil Release Aoent Any polymeric soil release agent known to those skilled in the art can optionally be employed in the compositions and processes of this invention.
  • Polymeric soil release agents are characterized by having both hydrophilic segments, to hydrophilize the surface of hydrophobic fibers, such as polyester and nylon, and hydrophobic segments, to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles and, thus, serve as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to treatment with the soil release agent to be more easily cleaned in later washing procedures.
  • the polymeric soil release agents useful herein especially include those soil release agents having: (a) one or more nonionic hydrophile components consisting essentially of (i) polyoxyethylene segments with a degree of polymerization of at least 2, or (ii) oxypropylene or polyoxypropylene segments with a degree of polymerization of from 2 to 10, wherein said hydrophile segment does not encompass any oxypropylene unit unless it is bonded to adjacent moieties at each end by ether linkages, or (iii) a mixture of oxyalkylene units comprising oxyethylene and from 1 to 30 oxypropylene units wherein said mixture contains a sufficient amount of oxyethylene units such that the hydrophile component has hydrophilicity great enough to increase the hydrophilicity of conventional polyester synthetic fiber surfaces upon deposit of the soil release agent on such surface, said hydrophile segments preferably comprising at least 25% oxyethylene units and more preferably, especially for such components having 20 to 30 oxypropylene units, at least 50% oxyethylene units; or (b) one
  • the polyoxyethylene segments of (a)(i) will have a degree of polymerization of from 200, although higher levels can be used, preferably from 3 to 150, more preferably from 6 to 100.
  • Suitable oxy C4-C6 alkylene hydrophobe segments include, but are not limited to, end-caps of polymeric soil release agents such as M ⁇ 3S(CH2) n OCH2CH2 ⁇ -, where M is sodium and n is an integer from 4-6, as disclosed in U.S. Patent 4,721 ,580, issued January 26, 1988 to Gosselink.
  • Polymeric soil release agents useful in the present invention also include cellulosic derivatives such as hydroxyether cellulosic polymers, copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, and the like. Such agents are commercially available and include hydroxyethers of cellulose such as METHOCEL (Dow). Cellulosic soil release agents for use herein also include those selected from the group consisting of C1-C4 alkyl and C4 hydroxyalkyl cellulose; see U.S. Patent 4,000,093, issued December 28, 1976 to Nicol, et al.
  • Soil release agents characterized by poly(vinyl ester) hydrophobe segments include graft copolymers of poly(vinyl ester), e.g., C-j-C ⁇ vinyl esters, preferably poly(vinyl acetate) grafted onto polyalkylene oxide backbones, such as polyethylene oxide backbones.
  • poly(vinyl ester) e.g., C-j-C ⁇ vinyl esters
  • poly(vinyl acetate) grafted onto polyalkylene oxide backbones such as polyethylene oxide backbones.
  • Commercially available soil release agents of this kind include the SOKALAN type of material, e.g., SOKALAN HP-22, available from BASF (West Germany).
  • One type of preferred soil release agent is a copolymer having random blocks of ethylene terephthalate and polyethylene oxide (PEO) terephthalate.
  • the molecular weight of this polymeric soil release agent is in the range of from 25,000 to 55,000. See U.S. Patent 3,959,230 to Hays, issued May 25, 1976 and U.S. Patent 3,893,929 to Basadur issued July 8, 1975.
  • Another preferred polymeric soil release agent is a polyester with repeat units of ethylene terephthalate units contains 10-15% by weight of ethylene terephthalate units together with 90-80% by weight of polyoxyethylene terephthalate units, derived from a polyoxyethylene glycol of average molecular weight 300-5,000.
  • this polymer include the commercially available material ZELCON 5126 (from Dupont) and MILEASE T (from ICI). See also U.S. Patent 4,702,857, issued October 27, 1987 to Gosselink.
  • Another preferred polymeric soil release agent is a suifonated 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.
  • Preferred polymeric soil release agents also include the soil release agents of U.S. Patent 4,877,896, issued October 31 , 1989 to Maldonado et al, which discloses anionic, especially sulfoarolyl, end-capped terephthalate esters.
  • soil release agents will generally comprise from 0.01 % to 10.0%, by weight, of the detergent compositions herein, typically from 0.1% to 5%, preferably from 0.2% to 3.0%.
  • Still another preferred soil release agent is an oligomer with repeat units of terephthaloyl units, sulfoisoterephthaloyl units, oxyethyleneoxy and oxy-1 ,2-propylene units.
  • the repeat units form the backbone of the oligomer and are preferably terminated with modified isethionate end-caps.
  • a particularly preferred soil release agent of this type comprises one sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy and oxy-1,2- propyleneoxy units in a ratio of from 1.7 to 1.8, and two end-cap units of sodium 2-(2-hydroxyethoxy)-ethanesulfonate.
  • Said soil release agent also comprises from 0.5% to 20%, by weight of the oligomer, of a crystalline- reducing stabilizer, preferably selected from the group consisting of xylene sulfonate, cumene sulfonate, toluene sulfonate, and mixtures thereof.
  • a crystalline- reducing stabilizer preferably selected from the group consisting of xylene sulfonate, cumene sulfonate, toluene sulfonate, and mixtures thereof.
  • compositions of the present invention may also include one or more materials effective for inhibiting the transfer of dyes from one fabric to another during the cleaning process.
  • dye transfer inhibiting agents include polyvinyl pyrrolidon ⁇ polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N- vinylimidazole, manganese phthalocyanine, peroxidases, and mixtures thereof. If used, these agents typically comprise from 0.01% to 10% by weight of the composition, preferably from 0.01% to 5%, and more preferably from 0.05% to 2%.
  • Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as py dine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof.
  • the N-0 group can be represented by the following general structures:
  • R 3 (R 3 )z 36 wherein R-j , R2, R3 are aliphatic, aromatic, heterocyclic or alicydic groups or combinations thereof; x, y and z are 0 or 1 ; and the nitrogen of the N-0 group can be attached or form part of any of the aforementioned groups.
  • the amine oxide unit of the polyamine N-oxides has a pKa ⁇ 10, preferably pKa ⁇ 7, more preferred pKa ⁇ 6.
  • Any polymer backbone can be used as long as the amine oxide polymer formed is water-soluble and has dye transfer inhibiting properties.
  • suitable polymeric backbones are polyvinyls, poly alky lenes, polyesters, polyethers, polyamide, polyimides, polyacrylates and mixtures thereof. These polymers include random or block copolymers where one monomer type is an amine N-oxide and the other monomer type is an N- oxide.
  • the amine N-oxide polymers typically have a ratio of amine to the amine N-oxide of 10:1 to 1:1 ,000,000. However, the number of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate copolymerization or by an appropriate degree of N-oxidation.
  • the polyamine oxides can be obtained in almost any degree of polymerization. Typically, the average molecular weight is within the range of 500 to 1 ,000,000; more preferred 1,000 to 500,000; most preferred 5,000 to 100,000. This preferred class of materials can be referred to as "PVNO".
  • poly(4-vinylpyridine-N-oxide) which as an average molecular weight of 50,000 and an amine to amine N-oxide ratio of 1 :4.
  • Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers are also preferred for use herein.
  • the PVPVI has an average molecular weight range from 5,000 to 1 ,000,000, more preferably from 5,000 to 200,000, and most preferably from 10,000 to 20,000. (The average molecular weight range is determined by light scattering as described in Barth, et al., Chemical Analysis. Vol 113.
  • the PVPVI copolymers typically have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1 :1 to 0.2:1 , more preferably from 0.8:1 to 0.3:1, most preferably from 0.6:1 to 0.4:1. These copolymers can be either linear or branched.
  • compositions also may employ a polyvinyl- pyrrolidone (“PVP”) having an average molecular weight of from 5,000 to 400,000, preferably from 5,000 to 200,000, and more preferably from 5,000 to 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.
  • Compositions containing PVP can also contain polyethylene glycol (“PEG”) having an average molecular weight from 500 to 100,000, preferably from 1 ,000 to 10,000.
  • PEG polyethylene glycol
  • the ratio of PEG to PVP on a ppm basis delivered in wash solutions is from 2:1 to 50:1 , and more preferably from 3:1 to 10:1.
  • the detergent compositions herein may also optionally contain from 0.005% to 5% by weight of certain types of hydrophilic optical brighteners which also provide a dye transfer inhibition adion. If used, the compositions herein will preferably comprise from 0.01 % to 1 % by weight of such optical brighteners.
  • hydrophilic optical brighteners useful in the present invention are those having the strudural formula:
  • R-j is seleded from anilino, N-2-bis-hydroxyethyl and NH-2- hydroxyethyl
  • R2 is seleded from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N- methylamino, mo ⁇ hilino, chloro and amino
  • M is a salt-forming cation such as sodium or potassium.
  • is anilino
  • R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium
  • the brightener is 4,4',-bis[(4-anilino-6-(N- 2-bis-hydroxyethyl)-s-triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal-UNPA-GX by Ciba-Geigy Co ⁇ oration. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein.
  • R-j is anilino
  • R2 is N-2-hydroxyethyl-N- 2-methylamino
  • M is a cation such as sodium
  • the brightener is 4,4'- bis[(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2- yl)amino]2,2'-stilbenedisulfonic acid disodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal 5BM-GX by Ciba-Geigy Corporation.
  • R-j is anilino
  • R2 is mo ⁇ hilino
  • M is a cation such as sodium
  • the brightener is 4,4'-bis[(4-anilino-6-mo ⁇ hilino-s- triazine-2-yl)amino]2,2'-stilbenedisulfonic acid, sodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal AMS-GX by Ciba Geigy Co ⁇ oration.
  • the specific optical brightener species seleded for use in the present invention provide especially effective dye transfer inhibition performance benefits when used in combination with the seleded polymeric dye transfer inhibiting agents hereinbefore described.
  • the combination of such seleded polymeric materials (e.g., PVNO and/or PVPVI) with such seleded optical brighteners (e.g., Tinopal UNPA-GX, Tinopal 5BM-GX and/or Tinopal AMS- GX) provides significantly better dye transfer inhibition in aqueous wash solutions than does either of these two detergent composition components when used alone. Without being bound by theory, it is believed that such brighteners work this way because they have high affinity for fabrics in the wash solution and therefore deposit relatively quick on these fabrics.
  • the extent to which brighteners deposit on fabrics in the wash solution can be defined by a parameter called the "exhaustion coefficient".
  • the exhaustion coefficient is in general as the ratio of a) the brightener material deposited on fabric to b) the initial brightener concentration in the wash liquor. Brighteners with relatively high exhaustion coefficients are the most suitable for inhibiting dye transfer in the context of the present invention.
  • optical brighteners or other brightening or whitening agents known in the art can be incorporated at levels typically from 0.005% to 5%, preferably from 0.01% to 1.2% and most preferably from 0.05% to 1.2%, by weight, into the detergent compositions herein.
  • Commercial optical brighteners which may be useful in the present invention can be classified into subgroups, which include, but are not necessarily limited to, derivatives of stilbene, pyrazoline, coumarin, carboxylic acid, methinecyanines, dibenzothiophene-5,5-dioxide, azoles, 5- and 6-membered-ring heterocycies, and other miscellaneous agents. Examples of such brighteners are disclosed in 'The Production and Application of Fluorescent Brightening Agents", M.
  • optical brightener which may also be used in the present invention include naphthlimide, benzoxazole, benzofuran, benzimidazole and any mixtures thereof.
  • optical brighteners which are useful in the present compositions are those identified in U.S. Patent 4,790,856. 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; Artie White CC and Artie White CWD; the 2-(4-styryl-ph ⁇ nyl)-2H-naptho[1,2-d]triazoles; 4,4'-bis(1,2,3-triazol-2-yl)-stilbenes; 4,4'-bis(styryl)bisphenyls; and the aminocoumarins.
  • Suds Suppressors - Compounds for reducing or suppressing the formation of suds can be inco ⁇ orated into the compositions of the present invention. Suds suppression can be of particular importance in the so-called "high concentration cleaning process" and in front-loading European-style washing machines.
  • suds suppressors A wide variety of materials may be used as suds suppressors, and suds suppressors are well known to those skilled in the art. See, for example, Kirk Othmer Encyclopedia of Chemical Technology, Third Edition, Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979).
  • One category of suds suppressor of particular interest encompasses monocarboxylic fatty acid and soluble salts therein. See U.S. Patent 2,954,347, issued September 27, 1960 to Wayne St. John.
  • the monocarboxylic fatty acids and salts thereof used as suds suppressor typically have hydrocarbyl chains of 10 to 24 carbon atoms, preferably 12 to 18 carbon atoms.
  • Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts.
  • the detergent compositions herein may also contain non-surfactant suds suppressors.
  • non-surfactant suds suppressors include, for example: high molecular weight hydrocarbons such as paraffin, fatty add esters (e.g., fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C18-C40 ketones (e.g., stearone), etc.
  • suds inhibitors include N-alkylated amino triazines such as tri- to hexa-alkylmelamines or di- to tetra- alkyldiamine chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, and monostearyl phosphates such as monostearyl alcohol phosphate ester and monostearyl di-alkali metal (e.g., K, Na, and Li) phosphates and phosphate esters.
  • the hydrocarbons such as paraffin and haloparaffin can be utilized in liquid form.
  • the liquid hydrocarbons will be liquid at room temperature and atmospheric pressure, and will have a pour point in the range of -40 ⁇ C and 50 ⁇ C, and a minimum boiling point not less than 110°C (atmospheric pressure). It is also known to utilize waxy hydrocarbons, preferably having a melting point below 100 ⁇ C.
  • the hydrocarbons constitute a preferred category of suds suppressor for detergent compositions. Hydrocarbon suds suppressors are described, for example, in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al.
  • the hydrocarbons thus, include aliphatic, alicydic, aromatic, and heterocyclic saturated or unsaturated hydrocarbons having from 12 to 70 carbon atoms.
  • the term "paraffin,” as used in this suds suppressor discussion, is intended to include mixtures of true paraffins and cyclic hydrocarbons.
  • Non-surfadant suds suppressors comprises silicone suds suppressors.
  • This category includes the use of polyorganosiloxane oils, such as polydimethylsiloxane, dispersions or emulsions of polyorganosiloxane oils or resins, and combinations of polyorganosiloxane with silica particles wherein the polyorganosiloxane is chemisorbed or fused onto the silica.
  • Silicone suds suppressors are well known in the art and are, for example, disdosed in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al and European Patent Application No. 89307851.9, published February 7, 1990, by Starch, M. S.
  • silicone and silanated silica are described, for instance, in German Patent Application DOS 2,124,526.
  • Silicone defoamers and suds controlling agents in granular detergent compositions are disclosed in U.S. Patent 3,933,672, Bartolotta et al, and in U.S. Patent 4,652,392, Baginski et al, issued March 24, 1987.
  • An exemplary silicone based suds suppressor for use herein is a suds suppressing amount of a suds controlling agent consisting essentially of:
  • polydimethylsiloxane fluid having a viscosity of from 20 cs. to 1 ,500 cs. at 25 ⁇ C;
  • the solvent for a continuous phase is made up of certain polyethylene glycols or polyethylene-polypropylene glycol copolymers or mixtures thereof (preferred), or polypropylene glycol.
  • the primary silicone suds suppressor is branched/crosslinked and preferably not linear.
  • typical liquid laundry detergent compositions with controlled suds will optionally comprise from 0.001 to 1 , preferably from 0.01 to 0.7, most preferably from 0.05 to 0.5, weight % of said silicone suds suppressor, which comprises (1) a nonaqueous emulsion of a primary antifoam agent which is a mixture of (a) a polyorganosiloxane, (b) a resinous siloxane or a silicone resin-producing silicone compound, (c) a finely divided filler material, and (d) a catalyst to promote the readion of mixture components (a), (b) and (c), to form silanolates; (2) at least one nonionic silicone surfadant; and (3) polyethylene glycol or a copolymer of polyethylene-polypropylene glycol having a solubility in water at room temperature of more than 2 weight %; and without polypropylene glycol.
  • a primary antifoam agent which is a mixture of (a) a polyorganosiloxan
  • the silicone suds suppressor herein preferably comprises polyethylene glycol and a copolymer of polyethylene glycol/polypropylene glycol, all having an average molecular weight of less than 1,000, preferably between 100 and 800.
  • the polyethylene glycol and polyethylene/polypropylene copolymers herein have a solubility in water at room temperature of more than 2 weight %, preferably more than 5 weight %.
  • the preferred solvent herein is polyethylene glycol having an average molecular weight of less than 1,000, more preferably between 100 and 800, most preferably between 200 and 400, and a copolymer of polyethylene glycol/polypropyl ⁇ ne glycol, preferably PPG 200/PEG 300.
  • Preferred is a weight ratio of between 1 :1 and 1:10, most preferably between 1 :3 and 1 :6, of polyethylene glycol: copolymer of polyethylene- polypropylene glycol.
  • the preferred silicone suds suppressors used herein do not contain polypropylene glycol, particularly of 4,000 molecular weight. They also preferably do not contain block copolymers of ethylene oxide and propylene oxide, like PLURONIC L101.
  • suds suppressors useful herein comprise the secondary alcohols (e.g., 2-alkyl alkanols) and mixtures of such alcohols with silicone oils, such as the silicones disclosed in U.S. 4,798,679, 4,075,118 and EP 150,872.
  • the secondary alcohols include the C ⁇ -Ci ⁇ alkyl alcohols having a C-
  • a preferred alcohol is 2-butyl octanol, which is available from Condea under the trademark ISOFOL 12.
  • Mixtures of secondary alcohols are available under the trademark ISALCHEM 123 from Enichem.
  • Mixed suds suppressors typically comprise mixtures of alcohol + silicone at a weight ratio of 1 :5 to 5:1.
  • Suds suppressors when utilized, are preferably present in a "suds suppressing amount.
  • Suds suppressing amount is meant that the formulator of the composition can seled an amount of this suds controlling agent that will sufficiently control the suds to result in a low- sudsing laundry detergent for use in automatic laundry washing machines.
  • compositions herein will generally comprise from 0% to 5% of suds suppressor.
  • monocarboxylic fatty acids, and salts therein will be present typically in amounts up to 5%, by weight, of the detergent composition.
  • from 0.5% to 3% of fatty monocarboxylate suds suppressor is utilized.
  • Silicone suds suppressors are typically utilized in amounts up to 2.0%, by weight, of the detergent composition, although higher amounts may be used. This upper limit is pradical in nature, due primarily to concern with keeping costs minimized and effediveness of lower amounts for effedively controlling sudsing.
  • from 0.01% to 1% of silicone suds suppressor is used, more preferably from 0.25% to 0.5%.
  • these weight percentage values include any silica that may be utilized in combination with polyorganosiloxane, as well as any adjund materials that may be utilized.
  • Monostearyl phosphate suds suppressors are generally utilized in amounts ranging from 0.1% to 2%, by weight, of the composition.
  • Hydrocarbon suds suppressors are typically utilized in amounts ranging from 0.01% to 5.0%, although higher levels can be used.
  • the alcohol suds suppressors are typically used at 0.2%-3% by weight of the finished compositions.
  • Fabric Softeners Various through-the-wash fabric softeners, especially the impalpable smedite clays of U.S. Patent 4,062,647, Storm and Nirschl, issued December 13, 1977, as well as other softener clays known in the art, can optionally be used typically at levels of from 0.5% to 10% by weight in the present compositions to provide fabric softener benefits concurrently with fabric cleaning.
  • Clay softeners can be used in combination with amine and cationic softeners as disclosed, for example, in U.S. Patent 4,375,416, Crisp et al, March 1, 1983 and U.S. Patent 4,291,071 , Harris et al, issued September 22, 1981.
  • compositions herein A wide variety of other fundional ingredients useful in detergent compositions can be included in the compositions herein, including other adive ingredients, carriers, hydrotropes, processing aids, dyes or pigments, solvents for liquid formulations, solid fillers for bar compositions, etc.
  • suds boosters such as the C10-C16 alkanolamides can be incorporated into the compositions, typically at 1%-10% levels.
  • the C10-C14 monoethanol and diethanol amides illustrate a typical class of such suds boosters.
  • Use of such suds boosters with high sudsing adjund surfadants such as the amine oxides, betaines and sultaines noted above is also advantageous.
  • soluble magnesium salts such as MgCl2, MgS04, and tne ' ik ⁇ - an b ⁇ added at levels of, typically, 0.1%-2%, to provide additional suds and to enhance grease removal performance.
  • Liquid detergent compositions can contain water and other solvents as carriers.
  • Low molecular weight primary or secondary alcohols exemplified by methanol, ethanol, propanol, and isopropanol are suitable.
  • Monohydric alcohols are preferred for solubilizing surfada ⁇ t, but polyols such as those containing from 2 to 6 carbon atoms and from 2 to 6 hydroxy groups (e.g., 1,3-propanediol, ethylene glycol, glycerine, and 1 ,2- propanediol) can also be used.
  • the compositions may contain from 5% to 90%, typically 10% to 50% of such carriers.
  • the detergent compositions herein will preferably be formulated such that, during use in aqueous deaning operations, the wash water will have a pH of between 6.5 and 11, preferably between 7.5 and 10.5.
  • Liquid dishwashing product formulations preferably have a pH between 6.8 and 9.0.
  • Laundry produds are typically at pH 9-11. Techniques for controlling pH at recommended usage levels indude the use of buffers, alkalis, acids, etc., and are well known to those skilled in the art.
  • the detergent compositions of the invention can be formulated in any desirable form such as powders, granulates, pastes, liquids, and gels.
  • the detergent compositions of the present invention may be formulated as liquid detergent compositions.
  • Such liquid detergent compositions typically comprise from 94% to 35% by weight, preferably from 90% to 40% by weight, most preferably from 80% to 50% by weight of a liquid carrier, e.g., water, preferably a mixture of water and organic solvent.
  • the detergent compositions of the present invention may also be in the form of gels.
  • Such compositions are typically formulated with polyakenyl polyether having a molecular weight of from about 750,000 to about
  • the detergent compositions of the invention may also be in the form of solids, such as powders and granules.
  • the mean particle size of the components of granular compositions in accordance with the invention should preferably be such that no more that 5% of particles are greater than 1 4mm in diameter and not more than 5% of particles are less than 0.15mm in diameter.
  • the term mean particle size as defined herein is calculated by sieving a sample of the composition into a number of fradions (typically 5 fradions) on a series of Tyler sieves. The weight fradions thereby obtained are plotted against the aperture size of the sieves. The mean particle size is taken to be the aperture size through which 50% by weight of the sample would pass.
  • the bulk density of granular detergent compositions in accordance with the present invention are also useful in concentrated granular detergent compositions that are characterised by a relatively high density in comparison with conventional laundry detergent compositions.
  • Such high density compositions typically have a bulk density of at least 600 g/l it re, more preferably from 650 g/litre to 1200 g/litre, most preferably from 800g/litre to 1000g/litre.
  • Bulk density is measured by means of a simple funnel and cup device consisting of a conical funnel moulded rigidly on a base and provided with a flap valve at its lower extremity to allow the contents of the funnel to be emptied into an axially aligned cylindrical cup disposed below the funnel.
  • the funnel is 130 mm high and has internal diameters of 130 mm and 40 mm at its respedive upper and lower extremities. It is mounted so that the lower extremity is 140 mm above the upper surface of the base.
  • the cup has an overall height of 90 mm, an internal height of 87 mm and an internal diameter of 84 mm. Its nominal volume is 500 ml.
  • the funnel is filled with powder by hand pouring, the flap valve is opened and powder allowed to overfill the cup.
  • the filled cup is removed from the frame and excess powder removed from the cup by passing a straight edged implement eg; a knife, across its upper edge.
  • the filled cup is then weighed and the value obtained for the weight of powder doubled to provide a bulk density in g/litre. Replicate measurements are made as required.
  • granular detergent compositions in accordance with the present invention can be made via a variety of methods including dry mixing, spray drying, agglomeration and granulation. 46
  • Nonionic (hydroxyethyl dimethyl) ammonium quaternary Silicate Amo ⁇ hous Sodium Silicate (Si ⁇ 2:Na2 ⁇ ; 1.6 ratio)
  • Carbonate Anhydrous sodium carbonate with a particle size between 200 ⁇ m and 900 ⁇ m
  • PB4 Sodium perborate tetrahydrate of nominal formula NaBO2.3H2O.H2O2
  • Brightener 1 Disodium 4,4'-bis(2-sulphostyryl)biphenyl
  • Brightener 2 Disodium 4,4'-bis(4-anilino-6-mo ⁇ holino-1.3.5- triazin-2-yl)amino) stilbene-2:2'-disulphonate.
  • Silicone antifoam Polydimethylsiloxane foam controller with
  • Siloxane-oxyalkylene copolymer as dispersing agent with a ratio of said foam controller to said dispersing agent of 10:1 to 100:1.
  • PVNO Polyvinylpyridine N-oxide PVPVI Copolymer of polyvinylpyrolidone and vinylimidazole
  • Example 1 The following formulations were prepared, where A and B are in accord with the invention and 1 and 5 are prior art compositions.
  • compositions A and B produce enhanced stain removal performance over the prior art Compositions 1 to 5.
  • Component C D 6 (% by weight)
  • compositions having an HPP Index over 0.35 produced enhanced soil removal performance. Said performance is further enhanced when the hydrogen peroxide consisted of at least 90% by weight of PB4.
  • Example 3 The following laundry detergent compositions E, F and 7 were prepared, where E and F are in accord with the invention and 7 is a prior art composition:
  • Component E F 7 (% by weight)
  • compositions E and F with HPP Index of 0.6 produce enhanced soil removal performance over the prior art reference composition 7 of HPP Index 0.05.

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Abstract

L'invention porte sur une composition détergente sans phosphates contenant des adjuvants, comprenant, un tensioactif et: (a) au moins 0,5 % en poids d'une source de peroxyde d'hydrogène, (b) 0,01 à 10 % en poids d'un peroxyacide organique précurseur de blanchiment, (c) 0,001 à 5 % en poids d'une enzyme protéolytique, (d) une source d'alcalinité capable de conférer une alcalinité à une solution de lavage mesurée par le test de libération d'alcalinité ci-décrit, de manière que le % en poids d'équivalent NaOH de la composition soit supérieur à 10,6 % en poids de ladite composition. La composition détergente doit présenter un indice HPP (d'enzyme protéolytique précurseur de peroxyde d'hydrogène) d'au moins 0,35, défini par la formule: HPP = % en poids précurseur x % en poids enzyme protéolytique/(%AvO2)2, dans laquelle le % en poids de l'enzyme protéolytique est basé sur une activité enzymatique de 13 knpu/g de particule d'enzyme, et dans laquelle le % d'AvO¿2? représente la quantité totale d'oxygène disponible présent dans la composition.
EP96906561A 1995-03-11 1996-02-20 Composition detergente comportant une source de peroxyde d'hydrogene et une protease Expired - Lifetime EP0819164B2 (fr)

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WO1994024240A1 (fr) † 1993-04-08 1994-10-27 The Procter & Gamble Company Tensioactifs de sulfates secondaires d'alkyle (2,3) se trouvant dans des compositions detergentes stables contenant des enzymes
EP0634479A1 (fr) † 1993-07-14 1995-01-18 The Procter & Gamble Company Compositions détergentes stables contenant des agents de blanchiment
WO1995002671A1 (fr) † 1993-07-14 1995-01-26 The Procter & Gamble Company Detergents granuleux contenant des granules blanchissantes stabilisees par un silicate insoluble dans l'eau
WO1995012652A1 (fr) * 1993-11-03 1995-05-11 The Procter & Gamble Company Compositions detergentes
EP0657527A1 (fr) * 1993-12-10 1995-06-14 The Procter & Gamble Company Stabilisation de substances sensibles à l'oxidation dans de compositions détergentes contenant un percarbonate
EP0755434A1 (fr) † 1994-04-13 1997-01-29 The Procter & Gamble Company Detergents contenant un adjuvant de lavage et une enzyme liberee avec un retard
EP0755432A1 (fr) † 1994-04-13 1997-01-29 The Procter & Gamble Company Detergents contenant une enzyme et un systeme de peroxyacide de blanchiment a liberation retardee
WO1996009273A1 (fr) * 1994-09-22 1996-03-28 The Procter & Gamble Company Compositions detergentes
EP0710714A2 (fr) † 1994-11-05 1996-05-08 The Procter & Gamble Company Compositions de blanchiment
EP0710713A2 (fr) † 1994-11-05 1996-05-08 The Procter & Gamble Company Compositions de blanchiment
EP0713910A2 (fr) * 1994-11-05 1996-05-29 The Procter & Gamble Company Compositions détergentes
EP0842246A1 (fr) † 1995-07-08 1998-05-20 The Procter & Gamble Company Composition detergente comprenant un tensioactif cationique du type ester et une protease

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Also Published As

Publication number Publication date
HUP9801417A2 (hu) 1998-12-28
CZ283897A3 (cs) 1998-02-18
AU4990196A (en) 1996-10-02
EP0819164A4 (fr) 2001-08-08
CA2214397A1 (fr) 1996-09-19
PE60696A1 (es) 1997-01-10
EP0819164B2 (fr) 2013-03-13
CO4700545A1 (es) 1998-12-29
DE69634977D1 (de) 2005-09-01
BR9607676A (pt) 1998-07-07
DE69634977T2 (de) 2006-05-24
ES2247603T3 (es) 2006-03-01
HUP9801417A3 (en) 1999-03-01
ES2247603T5 (es) 2013-07-08
ATE300603T1 (de) 2005-08-15
TR199700936T1 (xx) 1998-02-21
EP0819164B1 (fr) 2005-07-27
DE69634977T3 (de) 2013-07-25
WO1996028534A1 (fr) 1996-09-19
AR001203A1 (es) 1997-09-24
MX9706915A (es) 1997-11-29

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