EP0755430A1 - Detergents with reduced peroxygen bleach levels containing a chelant and enzymes - Google Patents
Detergents with reduced peroxygen bleach levels containing a chelant and enzymesInfo
- Publication number
- EP0755430A1 EP0755430A1 EP95915372A EP95915372A EP0755430A1 EP 0755430 A1 EP0755430 A1 EP 0755430A1 EP 95915372 A EP95915372 A EP 95915372A EP 95915372 A EP95915372 A EP 95915372A EP 0755430 A1 EP0755430 A1 EP 0755430A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- bleach
- detergent composition
- weight
- composition according
- chelant
- 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.)
- Ceased
Links
Classifications
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- 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
- C11D3/364—Organic compounds containing phosphorus containing nitrogen
-
- 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
- C11D3/26—Organic compounds containing nitrogen
- C11D3/33—Amino carboxylic acids
-
- 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
- C11D3/16—Organic compounds
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
- C11D3/38627—Preparations containing enzymes, e.g. protease or amylase containing lipase
-
- 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
- C11D3/38645—Preparations containing enzymes, e.g. protease or amylase containing cellulase
-
- 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
- C11D3/3932—Inorganic compounds or complexes
Definitions
- the present invention relates to bleach-containing detergent compositions.
- the invention relates to detergent compositions which provide effective bleaching performance using lower levels of bleach and bleach activator.
- bleach to detergents is often desirable because of the performance benefits bleach can provide.
- laundry detergents containing bleach provide improved stain removal, dingy clean-up and whiteness maintenance.
- One aspect of the present invention is the establishment of a Biological Bleach Index ("BBI") by which bleach-containing detergent compositions, including those formulated for use in laundry and automatic dishwashing methods, are provided which contain lower levels of bleach and bleach activator along with particular levels of chelants and enzymes.
- BBI Biological Bleach Index
- [C] [chelant level (weight percent) x (number of chelating groups in the chelant)] ⁇ (molecular weight of the chelant) x 1000
- [E] weight percent of enzymes selected from the group consisting of proteases, amylases, lipases, cellulases and mixtures thereof, in the detergent composition assuming standard activities of protease 13 KNPU, amylase 300 KNU, lipase 165 KLU, and cellulase 2000 Cevu
- [BA] [(weight percent of bleach activator) x (a factor of 6 for BOBS, a factor of 6 for cationic activators, a factor of 550 for dinuclear manganese complex activators, and a factor of 4 for all other bleach activators)] ⁇ (molecular weight of the bleach activator) x 1000
- [PB] (weight percent of peroxygen bleach) x (percent available oxygen from the peroxygen bleach) ⁇
- bleach-containing detergent compositions which contain lower levels of bleach and bleach activator and higher levels of chelant and preferably higher levels of enzymes.
- amount of chelant increase is represented by the equation [Y]f > 2/a [Y] 0
- amount of enzyme increase is represented by the equation [Z]f >_1/a [Z] 0 . This is described in more detail hereinbelow.
- one aspect of the present invention relates to the establishment of a Biological Bleach Index ("BBI") which defines a formula which relates the lower levels of perborate bleach and bleach activator with particular required levels of chelant and enzymes.
- the Biological Bleach Index defines a particular relationship between the level of chelant, the level of enzymes, the level of peroxygen bleach and the level of bleach activator.
- detergent compositions can be provided containing lower levels of peroxygen bleach and bleach activator, but which still provide the benefits of bleach- containing laundry detergents.
- Detergent compositions according to the invention have a Biological Bleach Index of greater than 65, preferably greater than 75, and more preferably greater than 80.
- [C] is defined by [chelant level (weight percent) x (number of chelating groups in the chelant)] ⁇ (molecular weight of the chelant) x 1000.
- the number of chelating groups in the chelant are factored into the formula as a way to factor in the chelating efficiency of the chelant (i.e., the chelating efficiency is believed to be influenced by the number of these chelating groups).
- 'chelating groups' herein it is meant functional groups having chelating capacity including for example, phosphonate and carboxylate groups. It is noted that such chelating groups often comprise, in solution, anionically charged oxygen.
- EDTA has four chelating (carboxylate) groups.
- [E] is defined as the weight percent of the total enzymes present in the detergent composition assuming standard activities of protease 13 KNPU, amylase 300 KNU, lipase 165 KLU, and cellulase 2000 Cevu. If the actual activities of these enzymes in the detergent compositions are different from their standards activities, the factor [E] is adjusted accordingly. For example, if protease is used having an activity of 26 KNPU instead of the standard 13 KNPU, the factor [E] is multiplied by 2 to compensate for the extra ' activity of the enzyme. The same applies for the amylases, lipases and cellulases.
- KNPU denotes kilo Novo protease units
- KNU are kilo Novo units used for measuring amylase activity
- KLU are standard kilo units defined by Novo for measuring lipase activity
- CEVU are standard units for measuring cellulase activity.
- the factor [BA] in the formula defines the level of bleach activator as adjusted by a factor indicating its peractivity.
- a factor of 6 is assigned for BOBS and for cationic activators, a factor of 550 for dinuclear manganese complex activators, and a factor of 4 is assigned to all other bleach activators.
- the peroxygen bleach level is adjusted by the weight percent available oxygen from the peroxygen bleach.
- the weight percent "available oxygen” or percent “active oxygen” of peroxygen bleach compounds is well understood by persons skilled in the art. For example, percarbonates have a percent available oxygen of 13.5%, perborate monohydrates have a percent available oxygen of 5.5%, and perborate tetrahydrates have a percent available oxygen of 10.5%.
- [C] is the millimols chelant/100g of detergent corrected for the number of chelating groups
- [E] is the total enzyme level corrected for the activity level of the enzymes
- [BA] is the millimols bleach activator/1 OOg of detergent corrected for activity
- [PB] is the weight percent of available oxygen from the peroxygen bleach.
- bleach- containing detergent compositions which are defined by a reduction in the level of bleaching agent and an increase in the level of chelants and/or enzymes.
- a bleach-containing detergent composition comprising from 5% to 95% by weight detergent surfactant, from 0% to 80% by weight detergency builder, bleaching agent, and chelant and/or enzymes, wherein the levels of ingredients are defined as follows.
- [X] is the sum of bleaching agents by weight % levels in the product, considering 100% activity, for the bleaching agents.
- the bleaching agents are either a peroxygen bleach and a bleach activator, an organic peroxy acid, or mixtures thereof.
- the bleach reduction may come from decreasing the peroxygen bleach and/or bleach activator level in the detergent.
- [Y] is the sum of chelant(s) by weight % in the product. Increases in chelant level may come from increasing the level of the type of chelant present in the high-bleach level product (if any), or by adding other type(s) of chelant(s) to the product, or both. If the product with high-bleach level of bleach; i.e., [X] 0 , does not contain any chelant then preferably: [Y]f>([X]o-[X]f)/3-
- [Z] is the sum of the total enzymes by weight % in the product, assuming enzymatic activities as: Proteases: 13 KNPU, Amylases: 300 KNU Lipolases: 165 KLU Cellulases: 2000 Cevu
- Other types of enzymes e.g., peroxidases or lignases, where present, are used at standard activities.
- Increases in enzyme levels may come from increases of all or some of the enzymes in the high-bleach formula, or from adding different enzymes, or both.
- An essential feature of the invention is an oxygen bleaching system.
- the bleaching system contains a peroxygen compound and an organic bleach activator compound.
- the production of the organic peroxyacid occurs by an in situ reaction of the activator with the hydrogen peroxide which is provided by the peroxygen compound.
- Preferred peroxygen compounds include inorganic perhydrate bleaches. Compositions containing mixtures of a peroxygen compound and bleach activator in combination with a preformed organic peroxyacid are also envisaged.
- Inorganic perhydrate salts are preferred peroxygen bleach compounds herein. These salts are normally incorporated in the form of the alkali metal, preferably sodium salt at a level of from 0.5% to 40% by weight, more preferably from 1 % to 30% by weight and most preferably from 1 % to 7% by weight of the compositions.
- inorganic perhydrate salts include perborate, particularly perborate monohydrate and perborate tetrahydrate, percarbonate, perphosphate, persulfate and persilicate salts.
- the inorganic perhydrate salts are normally the alkali metai salts.
- the inorganic perhydrate salt may be included as the crystalline solid without additional protection.
- the preferred executions of such granular compositions utilize a coated form of the material which provides better storage stability for the perhydrate salt in the granular product.
- Sodium perborate can be in the form of the monohydrate of nominal formula NaB ⁇ 2H2 ⁇ 2 or the tetrahydrate NaB ⁇ 2H2 ⁇ 2-3H2 ⁇ .
- Alkali metal percarbonates, particularly sodium percarbonate are preferred perhydrates for inclusion in compositions in accordance with the invention.
- Compositions containing percarbonate have been found to have a reduced tendency to form undesirable gels in the presence of surfactants and water than similar compositions which contain perborate. It is believed that this is because typically percarbonate has a lower surface area and lower porosity than perborate monohydrate. This low surface area and low porosity acts to prevent the co-gelling with fine particles of surfactant agglomerates and is therefore not detrimental to dispensing.
- Sodium percarbonate is an addition compound having a formula corresponding to 2Na2C ⁇ 3.3H2 ⁇ 2# and is available commercially as a crystalline solid.
- the percarbonate is most preferably incorporated into such compositions in a coated form which provides in product stability.
- a suitable coating material providing in product stability comprises mixed salt of a water soluble alkali metal sulphate and carbonate. Such coatings together with coating processes have previously been described in GB- 1 ,466,799, granted to Interox on 9th March 1977.
- the weight ratio of the mixed salt coating material to percarbonate lies in the range from 1 : 200 to 1 : 4, more preferably from 1 : 99 to 1 : 9, and most preferably from 1 : 49 to 1 : 19.
- the mixed salt is of sodium sulphate and sodium carbonate which has the general formula Na2SO n.Na2C ⁇ 3 wherein n is from 0.1 to 3, preferably n is from 0.3 to 1.0 and most preferably n is from 0.2 to 0.5.
- coatings which contain silicate (alone or with borate salts or boric acids or other inorganics), waxes, oils, fatty soaps can also be used advantageously within the present invention.
- Potassium peroxymonopersulfate is another inorganic perhydrate salt of use in the detergent compositions herein.
- Bleach activators are compounds which react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid. Generally bleach activators 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
- Bleach activator compounds are preferably incorporated at a level of from 0.01 % to 10% by weight, more preferably from 0.2% to 7% by weight, most preferably from 0.5% to 4% by weight of the detergent compositions.
- Suitable bleach activator compounds typically contain one or more N- or O- acyl groups, which activators can be selected from a wide range of classes. Suitable classes include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. Examples of useful materials within these classes are disclosed in GB-A-1586789. Suitable esters are disclosed in GB-A-836988, 864798, 1147871 , 2143231 and EP-A- 0170386.
- the bleach activator is preferably selected from the group consisting of tetraacetylethylenediamine ("TAED”), sodium nonanoyloxybenzene sulfonate (“NOBS”), sodium benzoyloxybenzene sulfonate (“BOBS”), benzoyl caproiactam, (6-Nonanamidocaproyl)oxybenzene sulfonate (“NACA-OBS”), quaternary ammonium- and phosphonium-substituted bleach activators, cationic nitriles, dinuclear manganese (III) or (IV) complexes, and mixtures thereof. Most preferred is tetraacetylethylenediamine.
- TAED tetraacetylethylenediamine
- NOBS sodium nonanoyloxybenzene sulfonate
- BOBS sodium benzoyloxybenzene sulfonate
- NACA-OBS (6-Nonanamidoca
- 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.
- L is a leaving group where the conjugate acid of the anion formed on L has a pKa of from 4 to 13.
- Preferred L groups are selected from the group consisting of:
- R is an alkyl, aryl, or alkaryl group
- R is an alkyl chain containing from 1 to 14 carbon atoms
- R is H or R
- Y is H or a solubilizing group.
- R , R and R 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 -SO 3 " M + , -CO 2 " M , -SO M , -N + (R 3 ) 4 X " and O ⁇ --N(R 3 ) 3 and most preferably -SO 3 " M + and -CO 2 " M + wherein R 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 I I
- X is a halide, hydroxide, methylsulfate or acetate anion.
- Perbenzoic acid activator compounds provide perbenzoic acid on perhydrolysis.
- Suitable O-acylated perbenzoic acid activator compounds include the substituted and unsubstituted benzoyi oxybenzene sulfonates, including for example benzoyi oxybenzene sulfonate:
- benzo ⁇ lation products of sorbitol, glucose, and all saccharides with benzoylating agents including for example:
- Perbenzoic acid activator compounds of the imide type include N-benzoyl succinimide, tetrabenzoyi ethylene diamine and the N-benzoyl substituted ureas.
- Suitable imidazole type perbenzoic acid activators include N-benzoyl imidazole and N-benzoyl benzimidazole and other useful N-acyl group- containing perbenzoic acid activators include N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyi pyroglutamic acid.
- Other perbenzoic acid activators include the benzoyi diacyl peroxides, the benzoyi tetraacyl peroxides, and the compound having the formula:
- Phthalic anhydride is another suitable perbenzoic acid activator compound herein:
- Suitable N-acylated lactam perbenzoic acid activators have the formula:
- n is from 0 to 8, preferably from 0 to 2, and R is a benzoyi group.
- Perbenzoic acid derivative activators provide substituted perbenzoic acids on perhydrolysis.
- Suitable substituted perbenzoic acid derivative activators include any of the herein disclosed perbenzoic activators in which the benzoyi 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 activator compounds are the amide substituted compounds of the following general formulae:
- R 1 is an aryl or alkaryl group with from 1 to 14 carbon atoms
- R ⁇ is an arylene, or alkarylene group containing from 1 to 14 carbon atoms
- R5 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 ⁇ 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 R2.
- 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 bleach activator compounds produce cationic peroxyacids on perhydrolysis.
- cationic bleach activators are formed by substituting the peroxyacid part of a suitable bleach activator compound with a positively charged functional group, such as an ammonium or alkyl ammmonium group, preferably an ethyl or methyl ammonium group.
- Cationic bleach activators are typically present in the solid detergent compositions as a salt with a suitable anion, such as a halide ion.
- the bleach activator compound to be so cationically substituted may be a perbenzoic acid, or substituted derivative thereof, activator compound as described hereinbefore.
- the bleach activator compound may Y ⁇
- alkyl percarboxylic acid activator compound or an amide substituted alkyl bleach activator as described hereinafter
- Cationic bleach activators 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 bleach activators include any of the ammonium or alkyl ammonium substituted alkyl or benzoyi oxybenzene sulfonates, N-acylated caproiactams, and monobenzoyltetraacetyl glucose benzoyi peroxides.
- a preferred cationically substituted benzoyi oxybenzene sulfonate is the 4- (trimeth ⁇ l ammonium) methyl derivative of benzoyi oxybenzene sulfonate:
- a preferred cationically substituted alkyl oxybenzene sulfonate has the formula:
- Preferred cationic bleach activators of the N-acylated caprolactam class include the trialkyi ammonium methylene benzoyi caproiactams, particularly trimethyl ammonium methylene benzoyi caprolactam: IS
- N-acylated caprolactam class include the trialkyi ammonium methylene alkyl caproiactams:
- n is from 0 to 12.
- Another preferred cationic bleach activator is 2-(N,N,N-trimethyl ammonium) ethyl sodium 4-sulphophenyl carbonate chloride.
- Alkyl percarboxylic acid bleach activators form percarboxylic acids on perhydrolysis.
- Preferred activators of this type provide peracetic acid on perhydrolysis.
- Preferred alkyl percarboxylic activator compounds of the imide type include the N-,N,N1 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. Tetraacetylethylenediamine (TAED) is particularly preferred.
- TAED Tetraacetylethylenediamine
- alkyl percarboxylic acid activators include sodium 3,5,5-tri- methyl hexanoyioxybenzene sulfonate (iso-NOBS), sodium nonanoyloxybenzene sulfonate (NOBS), sodium acetoxybenzene sulfonate (ABS) and pentaacetyl glucose.
- iso-NOBS sodium 3,5,5-tri- methyl hexanoyioxybenzene sulfonate
- NOBS nonanoyloxybenzene sulfonate
- ABS sodium acetoxybenzene sulfonate
- pentaacetyl glucose pentaacetyl glucose
- Amide substituted alkyl peroxyacid bleach activator compounds are also suitable, including those of the following general formulae:
- R 1 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 ⁇ is H or an alkyl 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 ⁇ 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 substituenrgroups 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.
- activator 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- is H, alkyl, alkaryl, aryl, arylalkyi, and wherein R 2 _ 3.
- R4, and Rc may be the same or different substituents selected from H, halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxyl, amino, alkyl amino, COORg (wherein Rg is H or an alkyl group) and carbonyl functions.
- An especially preferred activator of the benzoxazin-type is:
- bleach activators are a dinuclear manganese (III) or manganese (IV) complex as described, for example, in US Patent Application Nos. 5,246,621 and 5,244,594.
- Preferred activators of this class are those referred to as having the following formulae:
- the bleaching system may contain a preformed organic peroxyacid , typically at a level of from 0.1 % to 20% by weight, more preferably from 0.2% to 10% by weight, most preferably from 0.3% to 5% by weight of the composition.
- a preferred class of organic peroxyacid compounds are the amide substituted compounds of the following general formulae:
- R 1 is an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms
- R 2 is an alkylene, arylene, and alkarylene group containing from 1 to 14 carbon atoms
- R > is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms.
- R1 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, 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 R2.
- substitution can include alkyl, aryl, halogen, nitrogen, sulphur and other typical substituent groups or organic compounds.
- R ⁇ is preferably H or methyl.
- R ⁇ and R ⁇ should not contain more than 18 carbon atoms in total. Amide substituted organic peroxyacid compounds of this type are described in EP-A- 0170386.
- organic peroxyacids include diacyl and tetraacylperoxides, especially diperox ⁇ dodecanedioc acid, diperox ⁇ tetradecanedioc acid and diperoxyhexadecanedioc acid.
- diacyl and tetraacylperoxides especially diperox ⁇ dodecanedioc acid, diperox ⁇ tetradecanedioc acid and diperoxyhexadecanedioc acid.
- Mono- and diperazelaic acid, mono- and diperbrassylic acid and N-phthaloylaminoperoxicaproic acid are also suitable herein.
- Suitable chelants have the ability to sequester heavy metal ions (such as Mn ++ , Fe ++ and Cu ++ ) in solution.
- Such chelants include amino carboxylates, amino phosphonates, and polyfunctionally-substituted aromatic chelants.
- Amino carboxylates useful as chelating agents in compositions of the invention can have one or more, preferably at least two, units of the substructure
- M is hydrogen, alkali metal, ammonium or substituted ammonium (e.g. ethanolamine) and x is from 1 to 3, preferably 1.
- these amino carboxylates do not contain alkyl or alkenyl groups with more than 6 carbon atoms.
- Operable amino carboxylates include ethylenediaminetetraacetates, N- hydroxyethylethylenediaminetriacetates, nitrilotriacetates, ethylenediamine disuccinates, ethylenediamine-N, N'-diglutamates, 2-hydroxypropylenediamine- N,N'-disuccinates, ethylenediamine tetraproprionates, triethylenetetraaminehexaacetates, diethylenetriaminepentaacetates, and ethanoldiglycines, alkali metal, ammonium, and substituted ammonium salts thereof and mixtures thereof.
- Amino 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.
- M is hydrogen, alkali metal, ammonium or substituted ammonium and x is from 1 to 3, preferably 1 , are useful and include ethylenediamine tetramethylenephosphonates, hexamethylenediamine tetramethylenephosphonates, aminotetramethylenephosphonates, nitrilo trimethylenephosphonates and diethylenethamine pentamethylenephosphonates.
- these amino phosphonates do not contain alkyl or alkenyl groups with more than 6 carbon atoms.
- Alkylene groups can be shared by substructures.
- Polyfunctionally-substituted aromatic chelating agents are also useful in the compositions herein. These materials can comprise compounds having the general formula 2 ⁇
- R comprises -SO3H or -COOH chelating groups or soluble salts thereof and mixtures thereof.
- Alkaline detergent compositions can contain these materials in the form of alkali metal, ammonium or substituted ammonium (e.g. mono- or triethanol-amine) salts.
- Suitable chelants include hydroxy-1,1-ethylidene diphosphonic acid and derivatives; ethylenediamine disuccinate; tri-sodium salt of S,S, ethylene diamine disuccinate; iminodiacetic acid-N-2-hydroxypropyl sulphonic acid and aspartic acid-N-carboxymethyl-N-2-hydroxypropyl-3-sulphonic acid (see EP 516,102 by Dow Chemicals); beta alanine N,N-diacetic acid, aspartic acid N,N- diacetic acid, aspartic acid N-monoacetic acid and iminodisuccinic acid (see EP 509,382 by Grace Co.); alkyl iminodiacetic acid (see EP 526,959 by Grace Co.); iso serine diacetic acid (BASF); 2-phosphonobutane-1 ,2,4-tricarboxylic acid (Bayer); dipicolinic acid; protein derived from collagen, keratin or casein (see EP
- Preferred chelants according to the present invention are selected from the group consisting of diethylenetriamine pentamethylenephosphonates, ethylenediamine tetramethylenephosphonates, diethylenetriamine pentaacetates, ethylenediamine disuccinates, ethylenediamine tetraacetates, and mixtures thereof.
- the amount of chelant used in the present detergent compositions is typically from 0.1 % to 10% by weight, preferably from 0.2% to 7%, more preferably from 0.4% to 3%, and most preferably from 1 % to 1.8%.
- the enzymes suitable for use in the present invention are proteases, amylases, lipases, cellulases, or mixtures thereof, and optionally other enzyme types. Preferred are proteases and amylases.
- proteases are the subtilisins which are obtained from particular strains of B.subtilis. B.lentus and B.licheniformis.
- Another suitable protease is a modified bacterial serine protease enzyme obtained from Bacillus subtilis or Bacillus licheniformis. having maximum activity throughout the pH range of 8-12, developed and sold by Novo Industries A/S (Denmark) under the registered tradename ESPERASE. The preparation of this enzyme and analogous enzymes is described in British Patent Specification No. 1 ,243,784 of " Novo.
- Proteolytic enzymes suitable for removing protein-based stains include those sold under the tradenames ALCALASE and SAVINASE by Novo Industries A/S and MAXATASE by International Bio- Synthetics, Inc. (The Netherlands).
- Other proteases include Protease A (see European Patent Application 130,756, published January 9, 1985) and Protease B (see European Patent Application Serial No. 87303761.8, filed April 28, 1987, and European Patent Application 130,756, Bott et al., published January 9, 1985). Most preferred is what is called herein "Protease C", which is a variant of an alkaline serine protease from Bacillus, particularly Bacillus lentus.
- Protease C is described in EP 90915958:4, U.S. Patent No. 5,185,250 and U.S. Patent No. 5,204,015, which are incorporated herein by reference. Genetically modified variants, particularly of Protease C, are also included herein.
- Amylases include, for example, a-amylases described in British Patent Specification No. 1,296,839 (Novo); RAPIDASE, International Bio-Synthetics, Inc.; and TERMAMYL and BAN (bacterial a-amylase), Novo Industries.
- 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, Barbesgoard et al, issued March 6, 1984, 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.
- 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 British Patent 1 ,372,034. See also lipases in Japanese Patent Application 53-20487, laid open to public inspection on February 28, 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 Corp. U.S.A. and Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli.
- the LIPOLASE enzyme derived from the fungus Humicola lanuginosa and expressed in Aspergillus orvzae as host and commercially available from Novo (see also E.P. Patent 341,947) is a preferred lipase for use herein.
- 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 PCT International Application WO 89/099813, published October 19, 1989, by O. Kirk, assigned to Novo Industries A/S.
- the detergent compositions of the invention preferably contain from 0.05% to 5% by weight enzymes, more preferably from 0.1 % to 3%, more preferably from 0.2% to 2%, and most preferably from 0.5% to 1.5%.
- Detergent surfactants useful herein are listed in U.S. Patents 3,664,961 , Norris, issued May 23, 1972, and 3,919,678, Laughlin et al., issued December 30, 1975, both incorporated herein by reference. The following are representative examples of detergent surfactants useful in the present compositions.
- Water-soluble salts of the higher fatty acids are useful anionic surfactants in the compositions herein.
- Soaps can be made by direct saponification of fats and oils or by the neutralization of free fatty acids.
- Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap.
- Useful anionic surfactants also include the water-soluble salts, preferably the alkali metal, ammonium and alkylolammonium salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from 10 to 20 carbon atoms and a sulfonic acid or sulfuric acid ester group.
- alkyl is the alkyl portion of acyl groups.
- this group of synthetic surfactants are the sodium and potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols (C ⁇ -Ci ⁇ carbon atoms) such as those produced by reducing the glycerides of tallow or coconut oil; and the sodium and potassium alkylbenzene sulfonates in which the alkyl group contains from 9 to 15 carbon atoms, in straight chain or branched chain configuration, e.g., those of the type described in U.S. Patents 2,220,099 and 2,477,383.
- linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from 11 to 13, C-
- anionic surfactants herein are the sodium alkyl glyceryl ether sulfonates, especially those ethers of higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfonates and sulfates; sodium or potassium salts of alkyl phenol ethylene oxide ether sulfates containing from 1 to 10 units of ethylene oxide per molecule and wherein the alkyl groups contain from 8 to 12 carbon atoms; and sodium or potassium salts of alkyl ethylene oxide ether sulfates containing 1 to 10 units of ethylene oxide per molecule and wherein the alkyl group contains from 10 to 20 carbon atoms.
- Other useful anionic surfactants herein include the water-soluble salts of esters of alpha-sulfonated fatty acids containing from 6 to 20 carbon atoms in the fatty acid group and from 1 to 10 carbon atoms in the ester group; water- soluble salts of 2-acyloxyalkane-1 -sulfonic acids containing from 2 to 9 carbon atoms in the acyl group and from 9 to 23 carbon atoms in the alkane moiety; water-soluble salts of olefin and paraffin sulfonates containing from 12 to 20 carbon atoms; and beta-alkyloxy alkane sulfonates containing from 1 to 3 carbon atoms in the alkyl group and from 8 to 20 carbon atoms in the alkane moiety.
- Water-soluble nonionic surfactants are also useful in the compositions of the invention.
- Such nonionic materials include compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature.
- the length of the polyoxyalkylene group which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
- adjunct nonionic surfactants especially useful herein comprises the polyhydroxy fatty acid amides of the formula:
- R-! is H, C-j-Cs hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl, or a mixture thereof, preferably C-1-C4 alkyl, more preferably C-j or C2 alkyl, most preferably C-j alkyl (i.e., methyl); and R 2 is a C5-C32 hydrocarbyl moiety, preferably straight chain C7-C-19 alkyl or alkenyl, more preferably straight chain C9-C17 alkyl or alkenyl, most preferably straight chain C11-C-19 alkyl or alkenyl, or mixture thereof; and Z is a polyhydroxyhydrocarbyl moiety having a linear hydrocarbyl chain with at least 2 (in the case of glyceraldehyde) or at least 3 hydroxyls (in the case of other reducing sugars) directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof.
- Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z is a glycityl moiety.
- Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose, as well as glyceraldehyde.
- high dextrose corn syrup, high fructose corn syrup, and high maltose corn syrup can be utilized as well as the individual sugars listed above. These corn syrups may yield a mix of sugar components for Z. It should be understood that it is by no means intended to exclude other suitable raw materials.
- Z preferably will be selected from the group consisting of -CH2-(CHOH) n -CH2 ⁇ H,-CH(CH2 ⁇ H)-(CHOH) n . 1 -CH 2 OH ; and -CH 2 - (CHOH)2(CHOR')(CHOH)-CH2 ⁇ H, where n is an integer from 1 to 5, inclusive, and R' is H or a cyclic mono- or poly- saccharide, and alkoxylated derivatives thereof. Most preferred are glycityls wherein n is 4, particularly -CH2- (CHOH)4CH 2 OH.
- R1 can be, for example, N-methyl, N-ethyl, N- propyl, N-isopropyl, N-butyl, N-isobutyl, N-2-hydroxy ethyl, or N-2-hydroxy propyl.
- R 1 is preferably methyl or hydroxyalkyl.
- R 1 is preferably C2-C8 alkyl, especially n-propyl, iso-propyl, n-butyl, isobutyl, pentyl, hexyl and 2-ethyl hexyl.
- R 2 -CO-N ⁇ can be, for example, cocamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, tallowamide, etc.
- nonionic surfactants include the polyethylene oxide condensates of alkyl phenols, e.g., the condensation products of alkyl phenols having an alkyl group containing from 6 to 15 carbon atoms, in either a straight chain or branched configuration, w'th from 3 to 12 moles of ethylene oxide per mole of alkyl phenol.
- Preferred nonionics are the water-soluble and water-dispersible condensation products of the aliphatic alcohols containing from 8 to 22 carbon atoms, in either straight chain or branched configuration, with from 3 to 12 moles of ethylene oxide per mole of alcohol.
- Particularly preferred are the condensation products of alcohols having an alkyl group containing from 9 to 15 carbon atoms with from 4 to 8 moles of ethylene oxide per mole of alcohol.
- Semi-polar nonionic surfactants include water-soluble amine oxides containing one alkyl moiety of from 10 to 18 carbon atoms and two moieties selected from the group of alkyl and hydroxyalkyl moieties of from 1 to 3 carbon atoms; water-soluble phosphine oxides containing one alkyl moiety of 10 to 18 carbon atoms and two moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from 1 to 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of from 10 to 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from 1 to 3 carbon atoms.
- Ampholytic surfactants include derivatives of aliphatic or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic moiety can be straight chain or branched and wherein one of the aliphatic substituents contains from 8 to 18 carbon atoms and at least one aliphatic substituent contains an anionic water-solubilizing group.
- Zwitterionic surfactants include derivatives of aliphatic, quaternary, ammonium, phosphonium and sulfonium compounds in which one of the aliphatic substituents contains from 8 to 18 carbon atoms.
- the detergent compositions of the invention contain from 5% to 95% by weight detergent surfactant, preferably from 5% to 50%, and most preferably from 10% to 30%. 2G>
- the detersive surfactants used in the present detergent compositions are preferably a mixture of anionic and nonionic surfactants.
- Optional Detergency Builder a mixture of anionic and nonionic surfactants.
- Optional detergent ingredients employed in the present invention are inorganic and/or organic detersive builders.
- Inorganic detersive builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta-phopshates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates, and aluminosilicates.
- non ⁇ ho p ate builders are required in some locales.
- silicate builder examples include the alkali metal silicates, particularly those having a Si ⁇ 2:Na2 ⁇ ratio in the range 1.6:1 to 3.2:1 and layered silicates, such as the layered sodium silicates described in U. S. Patent 4,664,839, issued May 12, 1987 to H. P. Rieck, available from Hoechst under the trademark "SKS"; SKS-6 is an especially preferred layered silicate builder.
- Carbonate builders especially a finely ground calcium carbonate with surface area greater than 10 m 2 /g, are preferred builders that can be used in granular compositions.
- the density of such alkali metal carbonate built detergents can be in the range of 450-850 g/l with the moisture content preferably below 4%.
- Examples of carbonate builders are the alkaline earth and alkali metal carbonates as disclosed in German Patent Application No. 2,321 ,001 published on November 15, 1973.
- Aluminosiiicate builders are especially useful in the present invention.
- Preferred aluminosilicates are zeolite builders which have the formula: Na 2 [(Al ⁇ 2) z (Si ⁇ 2)y] xH 2 O wherein z and y are integers of at least 6, the molar ratio of z to y is in the range from 1.0 to 0.5, and x is an integer from 15 to 264.
- Useful aluminosiiicate ion exchange materials are commercially available. These aluminosilicates can be crystalline or amorphous in structure and can be naturally-occurring aluminoosilicates or synthetically derived.
- aluminosiiicate ion exchange materials are disclosed in U.S. Patent 3,985,669, Krummel, et al., issued October 12, 1976, and U.S. Patent 4,605,509, Corkill, et al., issued August 12, 1986.
- Preferred synthetic crystalline aluminosiiicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B) (including those disclosed in EPO 384,070), and Zeolite X.
- the aluminosiiicate has a particle size of 0.1-10 microns in diameter.
- Organic detersive builders suitable for the purposes of the present invention include, but are not restricted to, a wide variety of polycarboxylate compounds, such as ether polycarboxylates, including oxydisuccinate, as disclosed in Berg, U.S. Patent 3,128,287, issued April 7, 1964, and Lamberti et al., U.S. Patent 3,635,830, issued January 18, 1972. See also "TMS/TDS" builders of U.S. Patent 4,663,071 , issued to Bush et al., on May 5, 1987.
- Suitable ether polycarboyxlates 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 hydroxy- polycarboxylates copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1 ,3,5-trihydroxy benzene-2,4,6-trisulphonic acid, and carboxymethyl- oxysuccinic acid
- various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid
- 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 preferred polycarboxylate builders that can also be used in granular compositions, especially in combination with zeolite and/or layered silicate builders.
- detergent compositions of the present invention are the 3,3-dicarboxy-4-oxa-1 ,6-hexanedioates and the related compounds disclosed in U.S. Patent 4,566,984, Bush, issued January 28, 1986.
- the various alkali metal phosphates such as the well-known sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate can be used.
- Phosphonate builders such as ethane-1-hydroxy-1 ,1-diphosphonate and other known phosphates (see, for example, U.S. Patents 3,159,581 ; 3,213,030; 3,422,021; 3,400,148 and 3,422,137) can also be used.
- detergent builders are used in the present detergent compositions, they are used at levels from 1 % to 80% by weight, preferably from 5% to 60% by weight, and more preferably from 10% to 50% by weight.
- the detergent ingredients can include one or more other detersive adjuncts 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.
- Usual detersive adjuncts of detergent compositions include the ingredients set forth in U.S. Patent No. 3,936,537, Baskerville et al., incorporated herein by reference.
- adjuncts which can be included in detergent compositions employed in the present invention, in their conventional art-established levels for use (generally from 0% to 30% of the detergent ingredients, preferably from 0.5% to 20%), include colored speckles, suds boosters, suds suppressors, antitamish and/or anticorrosion agents, soil- suspending agents, soil release agents, dyes, fillers, optical brighteners, germicides, alkalinity sources, hydrotropes, antioxidants, perfumes, solvents, solubilizing agents, clay soil removal/anti-redeposition agents, polymeric dispersing agents, processing aids, fabric softening components, static control agents, etc.
- the present detergent compositions can be in any of the different physical forms known to persons skilled in the art, for example granules/powders, liquids, bars, gels or pastes.
- the detergents can be laundry detergents, including those - suitable for use in machine laundering, or hand laundering methods or both, dishwashing detergents including automatic dishwashing detergents, hardsurface cleaners, or other known detergents, preferably laundry detergents.
- Comparative A and “Comparative B” are used in detergent compositions outside the scope of the present invention, while “Example 1” is used in a detergent made according to this invention.
- Example 1 is used in a detergent made according to this invention.
- the whiteness performances of Comparative A and B are poor in comparison with Example 1.
- Example 1 has less color fading than Comparative A because it uses a lower level of TAED.
- compositions Comaparative A and B and Example 1
- Example 1 The performance of the three compositions was compared in full scale six cycle washing machine tests using Miele 701 washing machines.
- Each full wash-cycle comprised only a main-wash cycle.
- Each laundry load comprised four 15 cm x 30 cm pieces of each of clean white terry towel, knitted cotton and cotton fabrics. Before the commencement of the first full wash cycle the laundry load together with a stained fabric strip as sold by the EMPA Institute, Switzerland under the tradename 'combined EMPA wash test strip no.
- 103' comprising a strip of 8 cotton test swatches, each of size 12cm x 12cm being cotton, bleached without optical brightener, cotton EMPA standard soiling, cotton soiled with blood, cotton soiled with cocoa, cotton soiled with blood/milk/carbon black, cotton dyed with sulphur black, cotton raw and cotton soiled with red wine together with a dispensing device of the "granulette" type containing 75 g of the detergent product was placed in the drum of the washing machine. For each of the subsequent five full wash cycles the same amount of detergent product and stained fabric strip was used. At the end of the sixth full wash cycle the laundry load was removed from the machine, dried in air and then an assessment of the whiteness/dinginess of the three types of fabric was made.
- the laundry load comprised a single 43 cm x 43 cm purple wool (bleach sensitive) fabric swatch and a ballast load of 2 white sheets.
- the laundry load together with a dispensing device of the "granulette" type containing 75 g of the detergent product was placed in the drum of the washing machine.
- the purple wool swatch was positioned such as to be adjacent to the dispensing 'mouth' of the granulette.
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Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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GB9407536 | 1994-04-13 | ||
GB9407536A GB9407536D0 (en) | 1994-04-13 | 1994-04-13 | Detergents with reduced bleach levels |
PCT/US1995/002732 WO1995028463A1 (en) | 1994-04-13 | 1995-03-30 | Detergents with reduced peroxygen bleach levels containing a chelant and enzymes |
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EP0755430A1 true EP0755430A1 (en) | 1997-01-29 |
EP0755430A4 EP0755430A4 (en) | 1998-12-23 |
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EP95915372A Ceased EP0755430A4 (en) | 1994-04-13 | 1995-03-30 | Detergents with reduced peroxygen bleach levels containing a chelant and enzymes |
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EP (1) | EP0755430A4 (en) |
JP (1) | JPH09512290A (en) |
CN (1) | CN1150452A (en) |
AU (1) | AU2226995A (en) |
BR (1) | BR9507377A (en) |
CA (1) | CA2187307A1 (en) |
CZ (1) | CZ295896A3 (en) |
GB (1) | GB9407536D0 (en) |
HU (1) | HU219179B (en) |
MA (1) | MA23507A1 (en) |
PE (1) | PE796A1 (en) |
WO (1) | WO1995028463A1 (en) |
Families Citing this family (13)
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US5686015A (en) * | 1994-08-31 | 1997-11-11 | The Procter & Gamble Company | Quaternary substituted bleach activators |
AU4877296A (en) * | 1995-02-18 | 1996-09-11 | Albright & Wilson Uk Limited | Enzyme detergents |
DE19518039A1 (en) * | 1995-05-17 | 1996-11-21 | Basf Ag | Use of heterocyclic compounds as activators for inorganic per compounds |
GB2311078A (en) * | 1996-03-16 | 1997-09-17 | Procter & Gamble | Bleaching composition containing cellulolytic enzyme |
EP0927241A1 (en) * | 1996-08-26 | 1999-07-07 | The Procter & Gamble Company | Cellulase activity control by a terminator |
GB2329188A (en) * | 1997-09-11 | 1999-03-17 | Procter & Gamble | Detergent composition containing a stabilised percarboxylic bleaching system |
JPH11217590A (en) * | 1998-02-04 | 1999-08-10 | Kao Corp | Breaching and detergent composition |
DE19824705A1 (en) * | 1998-06-03 | 1999-12-09 | Henkel Kgaa | Detergents and cleaning agents containing amylase and protease |
DE19914811A1 (en) * | 1999-03-31 | 2000-10-05 | Henkel Kgaa | Detergent compositions containing a bleaching agent include a combination of a cyanomethyl ammonium salt bleach activator and an enzyme |
EP1187898A1 (en) * | 1999-05-19 | 2002-03-20 | Colgate-Palmolive Company | Laundry detergent composition containing high level of protease enzyme |
DE102007008655A1 (en) † | 2007-02-20 | 2008-08-21 | Henkel Ag & Co. Kgaa | Siderophore-metal complexes as bleach catalysts |
JP5535452B2 (en) * | 2008-06-09 | 2014-07-02 | 第一工業製薬株式会社 | Laundry method and laundry detergent used therefor |
CN112362864B (en) * | 2021-01-12 | 2021-04-30 | 广州科方生物技术股份有限公司 | Treating agent for reducing background luminescence value of immunodiagnostic reagent and preparation method thereof |
Citations (1)
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EP0283252A1 (en) * | 1987-03-17 | 1988-09-21 | The Procter & Gamble Company | Bleaching compositions |
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US4417994A (en) * | 1981-01-24 | 1983-11-29 | The Procter & Gamble Company | Particulate detergent additive compositions |
GB8321924D0 (en) * | 1983-08-15 | 1983-09-14 | Unilever Plc | Enzymatic machine-dishwashing compositions |
GB8321923D0 (en) * | 1983-08-15 | 1983-09-14 | Unilever Plc | Machine-dishwashing compositions |
US5292448A (en) * | 1988-05-10 | 1994-03-08 | Lever Brothers Company, Division Of Conopco, Inc. | Enzymatic detergent composition |
-
1994
- 1994-04-13 GB GB9407536A patent/GB9407536D0/en active Pending
-
1995
- 1995-03-30 AU AU22269/95A patent/AU2226995A/en not_active Abandoned
- 1995-03-30 CN CN95193548A patent/CN1150452A/en active Pending
- 1995-03-30 EP EP95915372A patent/EP0755430A4/en not_active Ceased
- 1995-03-30 CA CA002187307A patent/CA2187307A1/en not_active Abandoned
- 1995-03-30 JP JP7526954A patent/JPH09512290A/en active Pending
- 1995-03-30 BR BR9507377A patent/BR9507377A/en not_active Application Discontinuation
- 1995-03-30 HU HU9602814A patent/HU219179B/en not_active IP Right Cessation
- 1995-03-30 CZ CZ962958A patent/CZ295896A3/en unknown
- 1995-03-30 WO PCT/US1995/002732 patent/WO1995028463A1/en not_active Application Discontinuation
- 1995-04-12 MA MA23835A patent/MA23507A1/en unknown
- 1995-04-17 PE PE1995266502A patent/PE796A1/en not_active Application Discontinuation
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EP0283252A1 (en) * | 1987-03-17 | 1988-09-21 | The Procter & Gamble Company | Bleaching compositions |
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See also references of WO9528463A1 * |
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Publication number | Publication date |
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PE796A1 (en) | 1996-03-04 |
EP0755430A4 (en) | 1998-12-23 |
HUT76033A (en) | 1997-06-30 |
CA2187307A1 (en) | 1995-10-26 |
JPH09512290A (en) | 1997-12-09 |
MA23507A1 (en) | 1995-12-31 |
WO1995028463A1 (en) | 1995-10-26 |
HU219179B (en) | 2001-02-28 |
CZ295896A3 (en) | 1997-04-16 |
AU2226995A (en) | 1995-11-10 |
BR9507377A (en) | 1997-09-30 |
GB9407536D0 (en) | 1994-06-08 |
HU9602814D0 (en) | 1996-12-30 |
CN1150452A (en) | 1997-05-21 |
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