EP0816483A1 - Granular bleaching compositions - Google Patents
Granular bleaching compositions Download PDFInfo
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- EP0816483A1 EP0816483A1 EP96870084A EP96870084A EP0816483A1 EP 0816483 A1 EP0816483 A1 EP 0816483A1 EP 96870084 A EP96870084 A EP 96870084A EP 96870084 A EP96870084 A EP 96870084A EP 0816483 A1 EP0816483 A1 EP 0816483A1
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- Prior art keywords
- precursor
- bleach
- composition according
- bleach precursor
- composition
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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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
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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
- C11D3/39—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
Definitions
- the present invention relates to a granular bleaching composition containing a hydrogen peroxide source and a peroxyacid bleach precursor, wherein the bleach precursor exhibits an effective perhydrolysis rate.
- bleach components such as oxygen bleaches, including hydrogen peroxide and organic peroxyacids.
- the organic peroxyacids are often obtained by the in situ perhydrolysis reaction between hydrogen peroxide and an organic peroxyacid bleach precursor.
- these bleach precursors those having a Krafft point of at least 10°C have been seen most useful in the removal of such coloured soils/stains.
- Suitable examples of bleach precursors having a Krafft point of at least 10°C are the amide substituted peroxyacid precursor compounds such as (6-octanamido-caproyl) oxy benzene sulfonate, (6-nonanamidocaproyl) oxy benzene sulfonate and (6-decanamido-caproyl) oxy benzene sulfonate as described in EP-A-0170386.
- the formulator of a granular bleaching composition is faced with the challenge of formulating a granular bleaching composition which provides effective perhydrolysis of the precursor.
- An advantage of the invention is that it provides bleach precursors containing bleaching compositions with an effective rate of perhydrolysis.
- Another advantage of the invention is that it provides compositions which enable the use of divalent and/or trivalent metal salts.
- a further advantage of the invention is that it provides compositions with improved resistance to the catalase.
- the present invention is a granular bleaching composition
- a granular bleaching composition comprising an alcohol alkoxylate nonionic surfactant, a hydrogen peroxide source and a bleach precursor having a Krafft point of at least 10°C, said alcohol alkoxylate nonionic surfactant and said precursor being present in a molar ratio of nonionic surfactant to bleach precursor of at least 3:1.
- a method of washing laundry comprises the step of contacting the fabrics with an aqueous liquor of a granular bleaching composition comprising an alcohol alkoxylate nonionic surfactant, a hydrogen peroxide source and a bleach precursor having a Krafft point of at least 10°C, said surfactant and said precursor being present in a molar ratio of nonionic surfactant to bleach precursor of at least 3:1.
- a granular bleaching composition comprising an alcohol alkoxylate nonionic surfactant, a hydrogen peroxide source and a bleach precursor having a Krafft point of at least 10°C, said surfactant and said precursor being present in a molar ratio of nonionic surfactant to bleach precursor of at least 3:1.
- An essential component of the invention is an alcohol alkoxylate nonionic surfactant. Not to be bound by theory, it is believed that such type of surfactant helps to dissolve the bleach precursors having a Krafft point of at least 10°C by forming mixed micelles, thereby preventing to some extent the precipitation of said bleach precursor in presence of hardness.
- the comicellisation is also believed to speed up the perhydrolysis by making the precursor molecule more accessible to the hydrogen peroxide.
- Typical levels of such nonionic surfactant are from 0.1% to 20% by weight, preferably 3% to 10% by weight and more preferably from 4% to 8% by weight of the composition.
- Suitable alcohol alkoxylate nonionic surfactants are the class of compounds which may be broadly defined as compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be branched or linear aliphatic (e.g. Guerbet or secondary alcohols) or alkyl aromatic in nature.
- the length of the hydrophilic or polyoxyalkylene radical 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.
- the nonionic surfactant may be included within the bleaching composition of the invention by any means as long as the molar ratio requirement within the composition, as defined herein after, is fulfilled. It may be processed together with the bleach precursor having a Krafft point of at least 10°C so as to form an agglomerate, or provide a coating. It may also be included as a separate component from the bleach into the detergent composition. Mixtures of any of these processes can be used.
- An essential component of the invention is a hydrogen peroxide source.
- Preferred sources of hydrogen peroxide include perhydrate bleaches.
- the perhydrate is typically an inorganic perhydrate bleach, normally in the form of the sodium salt, as the source of alkaline hydrogen peroxide in the wash liquor.
- This perhydrate is normally incorporated at a level of from 0.1% to 60%, preferably from 3% to 40% by weight, more preferably from 5% to 35% by weight and most preferably from 8% to 30% by weight of the composition.
- the perhydrate may be any of the alkalimetal inorganic salts such as perborate monohydrate or tetrahydrate, percarbonate, perphosphate and persilicate salts but is conventionally an alkali metal perborate or percarbonate.
- Sodium percarbonate which is the preferred perhydrate, is an addition compound having a formula corresponding to 2Na2CO3.3H2O2, and is available commercially as a crystalline solid. Most commercially available material includes a low level of a heavy metal sequestrant such as EDTA, 1-hydroxyethylidene 1, 1-diphosphonic acid (HEDP) or an amino-phosphonate, that is incorporated during the manufacturing process.
- a heavy metal sequestrant such as EDTA, 1-hydroxyethylidene 1, 1-diphosphonic acid (HEDP) or an amino-phosphonate
- the percarbonate can be incorporated into bleaching compositions without additional protection, but preferred executions of such compositions utilise a coated form of the material.
- a variety of coatings can be used including borate, boric acid and citrate or sodium silicate of SiO2:Na2O ratio from 1.6:1 to 3.4:1, preferably 2.8:1, applied as an aqueous solution to give a level of from 2% to 10%, (normally from 3% to 5%) of silicate solids by weight of the percarbonate.
- the most preferred coating is a mixture of sodium carbonate and sulphate or sodium chloride.
- the particle size range of the crystalline percarbonate is from 350 micrometers to 1500 micrometers with a mean of approximately 500-1000 micrometers.
- the other essential component of the invention is a bleach precursor having a Krafft point of at least 10°C, preferably at least 50°C, more preferably of at least 60°C.
- Krafft point is meant the temperature above which a solution of 10% by weight of said bleach precursor in deionised water becomes perfectly clear transparent.
- clear transparent is meant a substance which permits the passage of rays of the visible spectrum.
- the bleach precursors suitable for use herein are preferably of the anionic type.
- Suitable anionic bleach precursors for the purpose of the invention comprise at least one acyl group forming the peroxyacid moiety bonded to a leaving group through an -O- or-N- linkage.
- Suitable anionic peroxyacid bleach precursors for the purpose of the invention are the amide substituted compounds of the following general formulae: R1N(R5)C(O)R2C(O)L or R1C(O)N(R5)R2C(O)L wherein R1 is an alkyl, alkylene, aryl or alkaryl group with from 1 to 14 carbon atoms, R2 is an alkylene, arylene, and alkarylene group containing from 1 to 14 carbon atoms, and R5 is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms and L can be essentially any leaving group. R1 preferably contains from 6 to 12 carbon atoms.
- R2 preferably contains from 4 to 8 carbon atoms.
- R1 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.
- R2 can include alkyl, aryl, wherein said R2 may also contain halogen, nitrogen, sulphur and other typical substituent groups or organic compounds.
- R5 is preferably H or methyl.
- R1 and R5 should not contain more than 18 carbon atoms total. Amide substituted bleach activator compounds of this type are described in EP-A-0170386.
- 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: and mixtures thereof, wherein R1 is an alkyl, aryl, or alkaryl group containing from 1 to 14 carbon atoms, R3 is an alkyl chain containing from 1 to 8 carbon atoms, R4 is H or R3, and Y is H or a solubilizing group. Any of R1, R3 and R4 may be substituted by essentially any functional group including, for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl ammonium groups
- the preferred solubilizing groups are -SO3-M+, -CO2-M+, -SO4-M+, -N+(R3)4X- and O ⁇ --N(R3)3 and most preferably -SO3-M+ and -CO2-M+ wherein R3 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, methylsulfate or acetate anion.
- bleach precursors of the above formulae include amide substituted peroxyacid precursor compounds selected from (6-octanamido-caproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)oxy benzene sulfonate, (6-decanamido-caproyl)oxybenzenesulfonate, and mixtures thereof as described in EP-A-0170386.
- anionic bleach precursors having a Krafft point of at least 10°C could be used instead of or in combination of the above mentioned anionic bleach precursors.
- Such precursors are the above mentioned anionic bleach precursor present as a divalent and/or trivalent metal salt. This finding is especially surprising as such bleach precursor salts have a low solubility.
- Typical examples of such low solubility bleach precursors include Mg [(6-octanamido-caproyl)oxybenzenesulfonate] 2 , Mg [(6-nonanamido caproyl) oxy benzenesulfonate] 2 , Mg [(6-decanamido-caproyl)oxybenzene sulfonate] 2 , Ca [(6-octanamido-caproyl)oxybenzenesulfonate] 2 , Ca [(6-nonanamido-caproyl) oxy benzenesulfonate] 2 , Ca [(6-decanamido-caproyl)oxy benzenesulfonate] 2 , and mixtures thereof. It is therefore an advantage of the invention that it allows the use of anionic bleach precursors present as divalent and/or trivalent metal salts.
- peroxyacid bleach precursors are the amide-substituted peroxyacid precursor compounds selected from (6-octanamido-caproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)oxy benzene sulfonate, (6-decanamido-caproyl)oxybenzenesulfonate, and mixtures thereof.
- Typical levels of the peroxyacid bleach precursors having a Krafft point of at least 10°C within the bleaching compositions are from 0.1% to 25%, preferably from 1% to 20% and most preferably 3 to 15% by weight of the composition.
- nonionic surfactant and the precursor be present in a molar ratio of at least 3:1, preferably above 4:1.
- Optional bleach co-precursors may be used in addition to the bleach precursor having a Krafft point of at least 10°C so as to provide a bleaching composition with a broader spectrum of soil removal.
- Suitable bleach co-precursors include the tetraacetyl ethylene diamine (TAED) bleach precursor.
- Still another class of bleach co-precursor is the class of precursors exhibiting surfactancy properties and having a Krafft point of less than 10°C.
- Suitable bleach co-precursors having a Krafft point of less than 10°C is the class of alkyl percarboxylic acid bleach precursors.
- Preferred alkyl percarboxylic acid precursors include the monovalent salts of nonanoyl oxy benzene sulphonate (NOBS described in US 4,412,934) and 3,5,5-tri-methyl hexanoyl oxybenzene sulfonate (ISONOBS described in EP120,591).
- Still another class of bleach precursors suitable as a co-precursor having a Krafft point of less than 10°C are the N-acylated precursor compounds of the lactam class disclosed generally in GB-A-955735.
- Preferred materials of this class comprise the caprolactams.
- Suitable caprolactam bleach precursors are of the formula: wherein R 1 is an alkyl, aryl, alkoxyaryl or alkaryl group containing from 6 to 12 carbon atoms.
- Preferred hydrophobic N-acyl caprolactam bleach precursor materials are selected from benzoyl caprolactam, octanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam and mixtures thereof. A most preferred is nonanoyl caprolactam.
- Suitable valero lactams have the formula: wherein R 1 is an alkyl, aryl, alkoxyaryl or alkaryl group containing from 6 to 12 carbon atoms. More preferably, R 1 is selected from phenyl, heptyl, octyl, nonyl, 2,4,4-trimethylpentyl, decenyl and mixtures thereof.
- Suitable bleach co-precursors having a Krafft point of less than 10°C are the cationic bleach precursors.
- Suitable cationic peroxyacid co-precursors include any of the ammonium or alkyl ammonium substituted alkyl or benzoyl oxybenzene sulfonates, N-acylated caprolactams, N-acylated valerolactams and monobenzoyltetraacetyl glucose benzoyl peroxides.
- TAED tetraacetyl ethylene diamine
- said co-precursors will normally be incorporated at a level of from 0.1% to 60%, preferably from 1% to 40% and most preferably 3 to 25% by weight of the bleaching composition.
- the bleaching composition of the invention may also comprise optional ingredients conventional to detergent compositions. Accordingly, the term bleaching composition and detergent composition will be used hereinafter synonymously. Typically, such optional ingredients include additional surfactants, builders, detergent adjunct materials and mixtures thereof.
- Optional surfactants may be used in addition to the alcohol alkoxylate nonionic surfactant.
- such optional surfactants include one or more surfactants selected from anionic, cationic, nonionic, ampholytic, amphoteric and zwitterionic surfactants and mixtures thereof.
- anionic, cationic, nonionic, ampholytic, and zwitterionic classes, and species of these surfactants is given in U.S.P. 3,929,678 issued to Laughlin and Heuring on December 30, 1975. Further examples are given in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch).
- a list of suitable cationic surfactants is given in U.S.P. 4,259,217 issued to Murphy on March 31, 1981.
- Non-limiting examples of surfactants useful herein include the conventional C 11 -C 18 alkyl benzene sulfonates ("LAS") and primary, branched-chain and random C 10 -C 20 alkyl sulfates (“AS”), the C 10 -C 18 secondary (2,3) alkyl sulfates of the formula CH 3 (CH 2 ) x (CHOSO 3 - M + )CH 3 and CH 3 (CH 2 ) y (CHOSO 3 - M + ) CH 2 CH 3 where x and (y + 1) are integers of at least 7, preferably at least 9, and M is a water-solubilizing cation, especially sodium, unsaturated sulfates such as oleyl sulfate, the C 10 -C 18 alkyl alkoxy sulfates (“AE x S”; especially EO 1-7 ethoxy sulfates), C 10 -C 18 alkyl alkoxy carboxylates (especially the EO 1-5 e
- the conventional amphoteric surfactants such as the C 12 -C 18 betaines and sulfobetaines ("sultaines"), C 10 -C 18 amine oxides, and the like, can also be included in the overall compositions.
- the C 10 -C 18 N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include the C 12 -C 18 N-methylglucamides. See WO 9,206,154.
- Other sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C 10 -C 18 N (3-methoxypropyl) glucamide.
- N-propyl through N-hexyl C 12 -C 18 glucamides can be used for low sudsing.
- C 10 -C 20 conventional soaps may also be used.
- the branched-chain C 10 -C 16 soaps may be used.
- Other suitable surfactants suitable for the purpose of the invention are the anionic alkali metal sarcosinates of formula: R-CON(R 1 )CH 2 COOM wherein R is a C 9 -C 17 linear or branched alkyl or alkenyl group, R 1 is a C 1 -C 4 alkyl group and M is an alkali metal ion.
- Preferred examples are the lauroyl, cocoyl (C 12 -C 14 ), myristyl and oleyl methyl sarcosinates in the form of their sodium salts.
- the total amount of optional surfactants will generally be up to 70%, typically 1 to 55% by weight of the bleaching composition.
- high levels of surfactants present in a total amount of at least 11% by weight, more preferably 20% by weight of the composition have been found to be beneficial to the cleaning performance of the composition.
- Detergent builders can also 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 5% to 80%, more preferably less than 25% by weight, of the detergent builder. Lower or higher levels of builder, however, are not meant to be excluded.
- Inorganic or phosphate-containing detergent 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-phosphates).
- Non-phosphate builders may also be used. These can include, but are not restricted to phytic acid, silicates, alkali metal carbonates (including bicarbonates and sesquicarbonates), sulphates, aluminosilicates, monomeric polycarboxylates.
- silicate builders are the crystalline layered silicates, such as the layered sodium silicates described in U.S. 4,664,839.
- NaSKS-6 is the trademark for a crystalline layered silicate marketed by Hoechst (commonly abbreviated herein as "SKS-6"). Unlike zeolite builders, the Na SKS-6 silicate builder does not contain aluminium.
- NaSKS-6 has the delta-Na 2 Si 2 O 5 morphology form of layered silicate.
- 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 O 2x+1 .yH 2 O 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.
- Various other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as the alpha, beta and gamma forms.
- delta-Na 2 Si 2 O 5 (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 beaches, and as a component of suds control systems.
- Aluminosilicate builders are of great importance in most currently marketed heavy duty granular detergent compositions.
- Aluminosilicate builders include those having the empirical formula: Na z [(AlO 2 ) z (SiO 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.
- 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. 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 12 [(AlO 2 ) 12 (SiO 2 ) 12 ].xH 2 O 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.
- Suitable organic detergent builders 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 carboxylates.
- 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. 3,128,287 and U.S. 3,635,830. See also "TMS/TDS" builders of U.S. 4,663,071.
- Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S. 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, and carboxymethyloxysuccinic 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 which can 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 C 5 -C 20 alkyl and alkenyl succinic acids and salts thereof.
- a particularly preferred compound of this type is dodecenylsuccinic acid.
- succinate builders include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like. Laurylsuccinates are the preferred builders of this group, and are described in EP 0,200,263.
- Other suitable polycarboxylates are disclosed in U.S. 4,144,226 and in U.S. 3,308,067. See also U.S. 3,723,322.
- Fatty acids e.g., C 12 -C 18 monocarboxylic acids
- the aforesaid builders especially citrate and/or the succinate builders, to provide additional builder activity.
- 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 composition (e.g. colorants, dyes, etc.).
- other detergent adjunct materials e.g. colorants, dyes, etc.
- the following are illustrative examples of such adjunct materials.
- the enzymes to be incorporated include proteases, amylases, lipases, cellulases, and peroxidases, as well as mixtures thereof. Other types of enzymes may also be included. They may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. However, their choice is governed by several factors such as pH-activity and/or stability optima, thermostability and stability versus active detergents and builders. In this respect bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases.
- Enzymes are normally incorporated at levels sufficient to provide up to 5 mg by weight, more typically 0.01 mg to 3 mg, of active enzyme per gram of the composition. Stated otherwise, the compositions herein will typically comprise from 0.001% to 5%, preferably 0.01%-1% by weight of a commercial enzyme preparation.
- proteases are the subtilisins which are obtained from particular strains of B. subtilis and B. licheniforms. Another suitable protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold by Novo Industries A/S under the registered trade name ESPERASE. The preparation of this enzyme and analogous enzymes is described in GB 1,243,784 of Novo.
- proteases suitable for removing protein-based stains that are commercially available include those sold under the tradenames ALCALASE and SAVINASE by Novo Industries A/S (Denmark) and MAXATASE by International Bio-Synthetics, Inc. (The Netherlands).
- Other proteases include Protease A (see EP 130,756) and Protease B (see EP257189).
- Amylases include, for example, ⁇ -amylases described in GB 1,296,839 (Novo), RAPIDASE, International Bio-Synthetics, Inc. and TERMAMYL, Novo Industries. Fungamyl (Novo) is especially useful.
- 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. 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 Corp., 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.
- 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 WO 89/099813.
- Enzymes for use in detergents can be stabilized by various techniques. Enzyme stabilisation techniques are disclosed and exemplified in U.S. 3,600,319 and EP 0,199,405. Enzyme stabilisation systems are also described, for example, in U.S. 3,519,570.
- Polymeric dispersing agents can be utilized at levels from 0.5% to 8%, by weight, in the compositions herein, especially in the presence of zeolite and/or layered silicate builders.
- Suitable polymeric dispersing agents include polymeric polycarboxylates and polyethylene glycols, although others known in the art can also be used.
- 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 polyacrylates 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/maleate copolymers of this type are known materials which are described in EP 66915 as well as in EP 193,360, 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 use herein 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.
- a further example of polymeric polycarboxylic compounds which may be used herein include the maleic/acrylic/vinyl alcohol terpolymers. Such materials are also disclosed in EP 193,360, including, for example, the 45/45/10 terpolymer of acrylic/maleic/vinyl alcohol.
- polymeric polycarboxylic compounds which may be used herein include the biodegradable polyaspartic acid and polyglutamic acid compounds.
- Granular bleaching compositions which contain these compounds typically contain from 0.01% to 10.0% by weight of the water-soluble ethoxylates amines.
- the most preferred soil release and anti-redeposition agent is ethoxylated tetraethylenepentamine. Exemplary ethoxylated amines are further described in U.S. 4,597,898.
- Another group of preferred clay soil removal-antiredeposition agents are the cationic compounds disclosed in EP 111,965.
- Other clay soil removal/antiredeposition agents which can be used include the ethoxylated amine polymers disclosed in EP 111,984; the zwitterionic polymers disclosed in EP 112,592; and the amine oxides disclosed in U.S. 4,548,744 and the carboxy methyl cellulose (CMC) materials. These materials are well known in the art.
- Polymeric soil release agents are characterised 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 C 4 -C 6 alkylene hydrophobe segments include, but are not limited to, end-caps of polymeric soil release agents such as MO 3 S(CH 2 ) n OCH 2 CH 2 O-, where M is sodium and n is an integer from 4-6, as disclosed in U.S. 4,721,580.
- 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) and carboxy alkyl of cellulose such as Metolose (Shin Etsu). Cellulosic soil release agents for use herein also include those selected from C 1 -C 4 alkyl and C 4 hydroxyalkyl cellulose; see U.S. 4,000,093.
- Soil release agents characterised by poly(vinyl ester) hydrophobe segments include graft copolymers of poly(vinyl ester), e.g., C 1 -C 6 vinyl esters, preferably poly(vinyl acetate) grafted onto polyalkylene oxide backbones, such as polyethylene oxide backbones (see EP 0 219 048).
- 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. 3,959,230 and U.S. 3,893,929.
- Another preferred polymeric soil release agent is a polyester with repeat units of ethylene terephthalate units which 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. 4,702,857.
- Another preferred polymeric soil release agent is a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and terminal moieties covalently attached to the backbone.
- These soil release agents are described in U.S. 4,968,451.
- Other suitable polymeric soil release agents include the terephthalate polyesters of U.S. 4,711,730, the anionic end-capped oligomeric esters of U.S. 4,721,580 and the block polyester oligomeric compounds of U.S. 4,702,857.
- 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 xylene sulfonate, cumene sulfonate, toluene sulfonate and mixtures thereof.
- a crystalline-reducing stabilizer preferably selected from xylene sulfonate, cumene sulfonate, toluene sulfonate and mixtures thereof.
- Preferred polymeric soil release agents also include the soil release agents of U.S. 4,877,896, which discloses anionic, especially sulfoaroyl, end-capped terephthalate esters.
- soil release agents will generally comprise from 0.01% to 10.0%, by weight, of the compositions herein, typically from 0.1% to 5%, preferably from 0.2% to 3.0%.
- dye transfer inhibiting agents include polyvinyl pyrrolidone 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%.
- the polyamine N-oxide polymers preferred for use herein contain units having the following structural formula: R-A x -P; wherein P is a polymerizable unit to which an N-O group can be attached or the N-O group can form part of the polymerizable unit or the N-O group can be attached to both units;
- x is 0 or 1; and
- R is aliphatic, ethoxylated aliphatics, aromatics, heterocyclic or alicyclic groups or any combination thereof to which the nitrogen of the N-O group can be attached or the N-O group is part of these groups.
- Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof.
- the N-O group can be represented by the following general structures: wherein R 1 , R 2 , R 3 are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof; x, y and z are 0 or 1; and the nitrogen of the N-O group can be attached or form part of any of the aforementioned groups.
- the amine oxide unit of the polyamine N-oxides has a pKa ⁇ 10, preferably pKa ⁇ 7, more preferred pKa ⁇ 6.
- 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, polyalkylenes, 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 bleaching 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 action. If used, the compositions herein will preferably comprise from 0.01% to 1.2% by weight of such optical brighteners.
- the hydrophilic optical brighteners useful in the present invention are those having the structural formula: wherein R 1 is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R 2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphilino, chloro and amino; and M is a salt-forming cation such as sodium or potassium.
- R 1 is anilino
- R 2 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 Corporation.
- R 1 is anilino
- R 2 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 1 is anilino
- R 2 is morphilino
- M is a cation such as sodium
- the brightener is 4,4'-bis[(4-anilino-6-morphilino-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 Corporation.
- 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 compositions herein.
- Commercial optical brighteners which may be useful 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 heterocycles, and other miscellaneous agents. Examples of such brighteners are disclosed in "The Production and Application of Fluorescent Brightening Agents", M. Zahradnik, Published by John Wiley & Sons, New York (1982). Further optical brightener which may also be used include naphthalimide, benzoxazole, benzofuran, benzimidazole and any mixtures thereof.
- optical brighteners which are useful in the present compositions are those identified in U.S. 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; Artic White CC and Artic White CWD; the 2-(4-styryl-phenyl)-2H-naptho[1,2-d]triazoles; 4,4'-bis(1,2,3-triazol-2-yl)-stilbenes; 4,4'-bis(styryl)bisphenyls; and the aminocoumarins.
- these brighteners include 4-methyl-7-diethyl- amino coumarin; 1,2-bis(-benzimidazol-2-yl)ethylene; 1,3-diphenyl-pyrazolines; 2,5-bis(benzoxazol-2-yl)thiophene; 2-styryl-naptho-[1,2-d]oxazole; and 2-(stilbene-4-yl)-2H-naphtho[1,2-d]triazole. See also U.S. 3,646,015.
- 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., 979).
- One category of suds suppressor of particular interest encompasses monocarboxylic fatty acid and soluble salts therein. See U.S. 2,954,347.
- 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.
- compositions herein may also contain non-surfactant suds suppressors.
- non-surfactant suds suppressors include, for example: high molecular weight hydrocarbons such as paraffin, fatty acid esters (e.g., fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C 18 -C 40 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 dialkali metal (e.g., K, Na, and Li) phosphates and phosphate esters.
- the hydrocarbons such as paraffin and haloparaffin can be utilized in liquid form. It is also known to utilize waxy hydrocarbons, preferably having a melting point below 100°C.
- hydrocarbons constitute a preferred category of suds suppressor for detergent compositions.
- Hydrocarbon suds suppressors are described, for example, in U.S. 4,265,779.
- the hydrocarbons thus, include aliphatic, alicyclic, 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-surfactant 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, disclosed in U.S. 4,265,779 and EP 354016.
- Other silicone suds suppressors are disclosed in U.S. 3,455,839 which relates to compositions and processes for defoaming aqueous solutions by incorporating therein small amounts of polydimethylsiloxane fluids.
- 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. 3,933,672 and in U.S. 4,652,392.
- An exemplary silicone based suds suppressor for use herein is a suds suppressing amount of a suds controlling agent consisting essentially of:
- 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.
- 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/polypropylene 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 6 -C 16 alkyl alcohols having a C 1 -C 16 chain.
- 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 select 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 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 composition, although higher amounts may be used. This upper limit is practical in nature, due primarily to concern with keeping costs minimized and effectiveness of lower amounts for effectively 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 adjunct 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.
- Various through-the-wash fabric softeners especially the impalpable smectite clays of U.S. 4,062,647, as well as other softener clays known in the art, can optionally be used typically at levels of from 0.5% to 10%, preferably from 0.5% to 2% 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. 4,375,416 and U.S. 4,291,071.
- compositions herein A wide variety of other functional ingredients useful in detergent compositions can be included in the compositions herein, including other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, solid fillers for bar compositions.
- the compositions herein will preferably be formulated such that, during use in aqueous cleaning operations, the wash water will have a pH of between 6.5 and 11, preferably between 7.5 and 10.5. Laundry products are typically at pH 9-11. Techniques for controlling pH at recommended usage levels include the use of buffers, alkalis, acids, etc., and are well known to those skilled in the art.
- the mean particle size of the components of granular compositions in accordance with the invention should be such that no more than 5% of particles are greater than 1.4mm in diameter and not more than 5% of particles are less than 0.15mm in diameter.
- mean particle size is determined by sieving a sample of the composition into a number of fractions (typically 5 fractions) on a series of Tyler sieves. The weight fractions 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 is particularly 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 400 g/litre, more preferably from 650 g/litre to 1200 g/litre, most preferably from 800g/litre to 1000g/litre.
- 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.
- a method of washing laundry comprises the step of contacting the fabrics with an aqueous liquor of the above defined granular detergent composition.
- effective perhydrolysis is meant that the use of a composition comprising an alcohol alkoxylate nonionic surfactant and a bleach precursor having a Krafft point of at least 10°C as described above exhibits a better bleach precursor perhydrolysis than the use of the same composition without the alcohol alkoxylate nonionic surfactant or than the same composition without the molar ratio requirement.
- compositions of the invention have the following meanings:
- formulation A is a phosphorus-containing detergent composition
- formulation B is a zeolite-containing detergent composition
- formulation C is a compact detergent composition:
- a B C Blown Powder STPP 24 - 24.0 Zeolite A - 24.0 - Sulphate 9.0 6.0 13.0 MA/AA 2.0 4.0 2.0 LAS 6.0 8.0 11.0 TAS 2.0 - - Silicate 7.0 3.0 3.0
- CMC 1.0 1.0 0.5 Brightener 2 0.2 0.2 0.2 Soap 1.0 1.0 1.0 DTPMP 0.4 0.4 0.2 Spray On C45E7 2.5 2.5 2.0 C25E3 2.5 2.5 2.0 Silicone antifoam 0.3 0.3 0.3 Perfume 0.3 0.3 0.3 Dry additives Carbonate 6.0 13.0 15.0 PB4 18.0 18.0 10.0 PB1 4.0 - TAED 3.0 3.0 1.0 Photoactivated bleach 0.02 0.02 0.02 Savinase 1.0 1.0 1.0 Lipolase 0.4 0.4 0.4 .
- D E Agglomerate C45AS 11.0 14.0 Zeolite A 15.0 6.0 Carbonate 4.0 8.0 MA/AA 4.0 2.0 CMC 0.5 0.5 DTPMP 0.4 0.4 Spray On C25E5 5.0 5.0 Perfume 0.5 0.5 Dry Additives HEDP 0.5 0.3 NaSKS 6 13.0 10.0 Citrate 3.0 1.0 TAED 3.0 3.5 NACA-OBS 1.6 1.4 Percarbonate 20.0 20.0 SRP 0.3 0.3 Savinase 1.4 1.4 Lipolase 0.4 0.4 Carezyme 0.6 0.6 Termamyl 0.6 0.6 Silicone antifoam particle 5.0 5.0 Brightener 1 0.2 0.2 Brightener 2 0.2 - Balance (Moisture and Miscellaneous) 100 100 Density (g/litre) 850 850 850
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Abstract
The present invention relates to granular bleaching compositions comprising
an alcohol alkoxylate nonionic surfactant, a hydrogen peroxide source and a
bleach precursor having a Krafft point of at least 10°C, whereby the bleach
precursor exhibits an effective perhydrolysis rate.
Description
The present invention relates to a granular bleaching composition containing a
hydrogen peroxide source and a peroxyacid bleach precursor, wherein the
bleach precursor exhibits an effective perhydrolysis rate.
The satisfactory removal of coloured naturally derived soils/stains such as
blood, egg, chocolate, gravy from soiled/stained substrates is a particular
challenge to the formulator of a bleaching composition for use in a washing
method such as a laundry or machine dishwashing method.
Traditionally, the removal of such coloured soils/stains has been enabled by
the use of bleach components such as oxygen bleaches, including hydrogen
peroxide and organic peroxyacids. The organic peroxyacids are often obtained
by the in situ perhydrolysis reaction between hydrogen peroxide and an organic
peroxyacid bleach precursor. Of these bleach precursors, those having a Krafft
point of at least 10°C have been seen most useful in the removal of such
coloured soils/stains. Suitable examples of bleach precursors having a Krafft
point of at least 10°C are the amide substituted peroxyacid precursor
compounds such as (6-octanamido-caproyl) oxy benzene sulfonate, (6-nonanamidocaproyl)
oxy benzene sulfonate and (6-decanamido-caproyl) oxy
benzene sulfonate as described in EP-A-0170386.
However, a problem encountered with the use of bleach precursors having a
Krafft point of at least 10°C is their low perhydrolysis rate. Not to be bound by
theory, it is believed that the low perhydrolysis rate is associated to the low
dissolution rate of the precursor. As a result, the cleaning performance is
reduced. The potential for such a problem is now even more acute with the
move in consumer washing habits towards lower washing temperature.
Problems can also, in particular, be encountered when said bleach precursors
are used under high water hardness conditions, resulting upon dissolution in
the formation of calcium salts of bleach precursor with low solubility. Such a
problem of reduced perhydrolysis is further increased where the bleach
precursor is present in a form that exhibits a low rate of dissolution, e.g as
divalent and/or trivalent metal salt, thus affecting the perhydrolysis rate.
A further problem, associated with the bleach precursors having slow
perhydrolysis rate, appears when the soiled fabrics also comprise a catalase
enzyme. Hence, due to the slow perhydrolysis of the precursor, the catalase
will destroy the hydrogen peroxide component before the bleach activator is
properly perhydrolysed. As a result, the concentration of peracid present in the
wash is reduced and so is the bleaching performance.
Accordingly, the formulator of a granular bleaching composition is faced with
the challenge of formulating a granular bleaching composition which provides
effective perhydrolysis of the precursor.
To solve this problem of low perhydrolysis rate, the use of a dispensing means
to deliver the detergent product directly to the wash solution has been
proposed as described in co-pending application PCT/US95/14077.
Notwithstanding the advances in the art, there is still a need for alternative
compositions which provide effective dissolution of the bleach precursors
having a Krafft point of at least 10°C.
The Applicant has now found that the use of high levels of alcohol alkoxylate
nonionic surfactants relative to the levels of bleach precursors having a Krafft
point of at least 10°C, within a granular bleaching composition or within the
aqueous wash liquor, also fulfills such a need.
An advantage of the invention is that it provides bleach precursors containing
bleaching compositions with an effective rate of perhydrolysis.
Another advantage of the invention is that it provides compositions which
enable the use of divalent and/or trivalent metal salts.
A further advantage of the invention is that it provides compositions with
improved resistance to the catalase.
The present invention is a granular bleaching composition comprising an
alcohol alkoxylate nonionic surfactant, a hydrogen peroxide source and a
bleach precursor having a Krafft point of at least 10°C, said alcohol alkoxylate
nonionic surfactant and said precursor being present in a molar ratio of
nonionic surfactant to bleach precursor of at least 3:1.
In another aspect of the invention a method of washing laundry is provided
which comprises the step of contacting the fabrics with an aqueous liquor of a
granular bleaching composition comprising an alcohol alkoxylate nonionic
surfactant, a hydrogen peroxide source and a bleach precursor having a Krafft
point of at least 10°C, said surfactant and said precursor being present in a
molar ratio of nonionic surfactant to bleach precursor of at least 3:1. By the
present method, effective perhydrolysis of the bleach precursor is obtained.
An essential component of the invention is an alcohol alkoxylate nonionic
surfactant. Not to be bound by theory, it is believed that such type of surfactant
helps to dissolve the bleach precursors having a Krafft point of at least 10°C by
forming mixed micelles, thereby preventing to some extent the precipitation of
said bleach precursor in presence of hardness. The comicellisation is also
believed to speed up the perhydrolysis by making the precursor molecule more
accessible to the hydrogen peroxide.
Typical levels of such nonionic surfactant are from 0.1% to 20% by weight,
preferably 3% to 10% by weight and more preferably from 4% to 8% by weight
of the composition.
Suitable alcohol alkoxylate nonionic surfactants are the class of compounds
which may be broadly defined as compounds produced by the condensation of
alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic
compound, which may be branched or linear aliphatic (e.g. Guerbet or
secondary alcohols) or alkyl aromatic in nature. The length of the hydrophilic or
polyoxyalkylene radical 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.
Suitable exemplary classes of such alcohol alkoxylate nonionic surfactant are
listed below:
Mixtures of any of the above mentioned nonionic alkoxylated surfactants may
be used.
The nonionic surfactant may be included within the bleaching composition of
the invention by any means as long as the molar ratio requirement within the
composition, as defined herein after, is fulfilled. It may be processed together
with the bleach precursor having a Krafft point of at least 10°C so as to form an
agglomerate, or provide a coating. It may also be included as a separate
component from the bleach into the detergent composition. Mixtures of any of
these processes can be used.
An essential component of the invention is a hydrogen peroxide source.
Preferred sources of hydrogen peroxide include perhydrate bleaches. The
perhydrate is typically an inorganic perhydrate bleach, normally in the form of
the sodium salt, as the source of alkaline hydrogen peroxide in the wash liquor.
This perhydrate is normally incorporated at a level of from 0.1% to 60%,
preferably from 3% to 40% by weight, more preferably from 5% to 35% by
weight and most preferably from 8% to 30% by weight of the composition.
The perhydrate may be any of the alkalimetal inorganic salts such as perborate
monohydrate or tetrahydrate, percarbonate, perphosphate and persilicate salts
but is conventionally an alkali metal perborate or percarbonate.
Sodium percarbonate, which is the preferred perhydrate, is an addition
compound having a formula corresponding to 2Na2CO3.3H2O2, and is
available commercially as a crystalline solid. Most commercially available
material includes a low level of a heavy metal sequestrant such as EDTA, 1-hydroxyethylidene
1, 1-diphosphonic acid (HEDP) or an amino-phosphonate,
that is incorporated during the manufacturing process. For the purposes of the
bleaching composition aspect of the present invention, the percarbonate can
be incorporated into bleaching compositions without additional protection, but
preferred executions of such compositions utilise a coated form of the material.
A variety of coatings can be used including borate, boric acid and citrate or
sodium silicate of SiO2:Na2O ratio from 1.6:1 to 3.4:1, preferably 2.8:1, applied
as an aqueous solution to give a level of from 2% to 10%, (normally from 3% to
5%) of silicate solids by weight of the percarbonate. However, the most
preferred coating is a mixture of sodium carbonate and sulphate or sodium
chloride.
The particle size range of the crystalline percarbonate is from 350 micrometers
to 1500 micrometers with a mean of approximately 500-1000 micrometers.
The other essential component of the invention is a bleach precursor having a
Krafft point of at least 10°C, preferably at least 50°C, more preferably of at least
60°C. By Krafft point is meant the temperature above which a solution of 10%
by weight of said bleach precursor in deionised water becomes perfectly clear
transparent. By " clear transparent" is meant a substance which permits the
passage of rays of the visible spectrum. The bleach precursors suitable for use
herein are preferably of the anionic type.
Suitable anionic bleach precursors for the purpose of the invention comprise at
least one acyl group forming the peroxyacid moiety bonded to a leaving group
through an -O- or-N- linkage.
Suitable anionic peroxyacid bleach precursors for the purpose of the invention
are the amide substituted compounds of the following general formulae:
R1N(R5)C(O)R2C(O)L or R1C(O)N(R5)R2C(O)L
wherein R1 is an alkyl, alkylene, aryl or alkaryl group with from 1 to 14 carbon
atoms, R2 is an alkylene, arylene, and alkarylene group containing from 1 to 14
carbon atoms, and R5 is H or an alkyl, aryl, or alkaryl group containing 1 to 10
carbon atoms and L can be essentially any leaving group. R1 preferably
contains from 6 to 12 carbon atoms. R2 preferably contains from 4 to 8 carbon
atoms. R1 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. R2 can include alkyl,
aryl, wherein said R2 may also contain halogen, nitrogen, sulphur and other
typical substituent groups or organic compounds. R5 is preferably H or methyl.
R1 and R5 should not contain more than 18 carbon atoms total. Amide
substituted bleach activator compounds of this type are described in EP-A-0170386.
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:
and mixtures thereof, wherein R1 is an alkyl, aryl, or alkaryl group containing
from 1 to 14 carbon atoms, R3 is an alkyl chain containing from 1 to 8 carbon
atoms, R4 is H or R3, and Y is H or a solubilizing group. Any of R1, R3 and R4
may be substituted by essentially any functional group including, for example
alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl
ammonium groups
The preferred solubilizing groups are -SO3-M+, -CO2-M+, -SO4-M+,
-N+(R3)4X- and O<--N(R3)3 and most preferably -SO3-M+ and -CO2-M+
wherein R3 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. Preferably, M is an alkali metal,
ammonium or substituted ammonium cation, with sodium and potassium being
most preferred, and X is a halide, hydroxide, methylsulfate or acetate anion.
Preferred examples of bleach precursors of the above formulae include amide
substituted peroxyacid precursor compounds selected from (6-octanamido-caproyl)oxybenzenesulfonate,
(6-nonanamidocaproyl)oxy benzene sulfonate,
(6-decanamido-caproyl)oxybenzenesulfonate, and mixtures thereof as
described in EP-A-0170386.
The Applicant also found that further anionic bleach precursors having a Krafft
point of at least 10°C could be used instead of or in combination of the above
mentioned anionic bleach precursors. Such precursors are the above
mentioned anionic bleach precursor present as a divalent and/or trivalent metal
salt. This finding is especially surprising as such bleach precursor salts have a
low solubility. Typical examples of such low solubility bleach precursors include
Mg [(6-octanamido-caproyl)oxybenzenesulfonate]2, Mg [(6-nonanamido
caproyl) oxy benzenesulfonate]2, Mg [(6-decanamido-caproyl)oxybenzene
sulfonate]2, Ca [(6-octanamido-caproyl)oxybenzenesulfonate]2, Ca [(6-nonanamido-caproyl)
oxy benzenesulfonate]2, Ca [(6-decanamido-caproyl)oxy
benzenesulfonate]2, and mixtures thereof. It is therefore an advantage of the
invention that it allows the use of anionic bleach precursors present as divalent
and/or trivalent metal salts.
Mixtures of any of the peroxyacid bleach precursor, hereinbefore described,
may also be used.
Preferred among the above-mentioned peroxyacid bleach precursors are the
amide-substituted peroxyacid precursor compounds selected from (6-octanamido-caproyl)oxybenzenesulfonate,
(6-nonanamidocaproyl)oxy benzene
sulfonate, (6-decanamido-caproyl)oxybenzenesulfonate, and mixtures thereof.
Typical levels of the peroxyacid bleach precursors having a Krafft point of at
least 10°C within the bleaching compositions are from 0.1% to 25%, preferably
from 1% to 20% and most preferably 3 to 15% by weight of the composition.
It is also an essential requirement of the bleaching composition of the invention
that the nonionic surfactant and the precursor be present in a molar ratio of at
least 3:1, preferably above 4:1.
Optional bleach co-precursors may be used in addition to the bleach precursor
having a Krafft point of at least 10°C so as to provide a bleaching composition
with a broader spectrum of soil removal.
Suitable bleach co-precursors include the tetraacetyl ethylene diamine (TAED)
bleach precursor.
Still another class of bleach co-precursor is the class of precursors exhibiting
surfactancy properties and having a Krafft point of less than 10°C.
Suitable bleach co-precursors having a Krafft point of less than 10°C is the
class of alkyl percarboxylic acid bleach precursors. Preferred alkyl
percarboxylic acid precursors include the monovalent salts of nonanoyl oxy
benzene sulphonate (NOBS described in US 4,412,934) and 3,5,5-tri-methyl
hexanoyl oxybenzene sulfonate (ISONOBS described in EP120,591).
Still another class of bleach precursors suitable as a co-precursor having a
Krafft point of less than 10°C are the N-acylated precursor compounds of the
lactam class disclosed generally in GB-A-955735. Preferred materials of this
class comprise the caprolactams.
Suitable caprolactam bleach precursors are of the formula:
wherein R1 is an alkyl, aryl, alkoxyaryl or alkaryl group containing from 6 to 12
carbon atoms. Preferred hydrophobic N-acyl caprolactam bleach precursor
materials are selected from benzoyl caprolactam, octanoyl caprolactam,
nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, 3,5,5-trimethylhexanoyl
caprolactam and mixtures thereof. A most preferred is
nonanoyl caprolactam.
Suitable valero lactams have the formula:
wherein R1 is an alkyl, aryl, alkoxyaryl or alkaryl group containing from 6 to 12
carbon atoms. More preferably, R1 is selected from phenyl, heptyl, octyl, nonyl,
2,4,4-trimethylpentyl, decenyl and mixtures thereof.
Other suitable bleach co-precursors having a Krafft point of less than 10°C are
the cationic bleach precursors. Suitable cationic peroxyacid co-precursors
include any of the ammonium or alkyl ammonium substituted alkyl or benzoyl
oxybenzene sulfonates, N-acylated caprolactams, N-acylated valerolactams
and monobenzoyltetraacetyl glucose benzoyl peroxides. Preferred cationic
bleach precursors are derived from the valerolactam and acyl caprolactam
compounds, of formula:
wherein x is 0 or 1, substituents R, R' and R'' are each C1-C10 alkyl or C2-C4
hydroxy alkyl groups, or [(CyH2y)O]n-R''' wherein y=2-4, n=1-20 and R''' is a
C1-C4 alkyl group or hydrogen and X is an anion.
Highly preferred among these additional bleach co-precursors is the tetraacetyl
ethylene diamine (TAED) bleach precursor.
When present, said co-precursors will normally be incorporated at a level of
from 0.1% to 60%, preferably from 1% to 40% and most preferably 3 to 25% by
weight of the bleaching composition.
The bleaching composition of the invention, may also comprise optional
ingredients conventional to detergent compositions. Accordingly, the term
bleaching composition and detergent composition will be used hereinafter
synonymously. Typically, such optional ingredients include additional
surfactants, builders, detergent adjunct materials and mixtures thereof.
Optional surfactants may be used in addition to the alcohol alkoxylate nonionic
surfactant. Typically, such optional surfactants include one or more surfactants
selected from anionic, cationic, nonionic, ampholytic, amphoteric and
zwitterionic surfactants and mixtures thereof. A typical listing of anionic,
nonionic, ampholytic, and zwitterionic classes, and species of these
surfactants, is given in U.S.P. 3,929,678 issued to Laughlin and Heuring on
December 30, 1975. Further examples are given in "Surface Active Agents and
Detergents" (Vol. I and II by Schwartz, Perry and Berch). A list of suitable
cationic surfactants is given in U.S.P. 4,259,217 issued to Murphy on March 31,
1981.
Non-limiting examples of surfactants useful herein include the conventional
C11-C18 alkyl benzene sulfonates ("LAS") and primary, branched-chain and
random C10-C20 alkyl sulfates ("AS"), the C10-C18 secondary (2,3) alkyl
sulfates of the formula CH3(CH2)x(CHOSO3 -M+)CH3 and CH3
(CH2)y(CHOSO3 -M+) CH2CH3 where x and (y + 1) are integers of at least 7,
preferably at least 9, and M is a water-solubilizing cation, especially sodium,
unsaturated sulfates such as oleyl sulfate, the C10-C18 alkyl alkoxy sulfates
("AExS"; especially EO 1-7 ethoxy sulfates), C10-C18 alkyl alkoxy carboxylates
(especially the EO 1-5 ethoxycarboxylates), the C10-18 glycerol ethers, the
C10-C18 alkyl polyglycosides and their corresponding sulfated polyglycosides,
and C12-C18 alpha-sulfonated fatty acid esters. If desired, the conventional
amphoteric surfactants such as the 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 C12-C18 N-methylglucamides. See
WO 9,206,154. Other 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.
Other suitable surfactants suitable for the purpose of the invention are the
anionic alkali metal sarcosinates of formula:
R-CON(R1)CH2COOM
wherein R is a C9-C17 linear or branched alkyl or alkenyl group, R1 is a C1-C4
alkyl group and 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.
Mixtures of anionic and nonionic surfactants are especially useful. Other
conventional useful surfactants are listed in standard texts.
The total amount of optional surfactants will generally be up to 70%, typically 1
to 55% by weight of the bleaching composition. Preferably, high levels of
surfactants present in a total amount of at least 11% by weight, more preferably
20% by weight of the composition have been found to be beneficial to the
cleaning performance of the composition. Most preferably, a better cleaning
performance is observed where at least one of the surfactant components is an
anionic surfactant.
Detergent builders can also 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 5% to 80%, more preferably less than 25% by weight, of the detergent
builder. Lower or higher levels of builder, however, are not meant to be
excluded.
Inorganic or phosphate-containing detergent 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-phosphates).
Non-phosphate builders may also be used. These can include, but are not
restricted to phytic acid, silicates, alkali metal carbonates (including
bicarbonates and sesquicarbonates), sulphates, aluminosilicates, monomeric
polycarboxylates. Examples of silicate builders are the crystalline layered
silicates, such as the layered sodium silicates described in U.S. 4,664,839.
NaSKS-6 is the trademark for a crystalline layered silicate marketed by
Hoechst (commonly abbreviated herein as "SKS-6"). Unlike zeolite builders, the
Na SKS-6 silicate builder does not contain aluminium. NaSKS-6 has the delta-Na2Si2O5
morphology form of layered silicate. It can be prepared by methods
such as those described in 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 NaMSixO2x+1.yH2O 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. Various other layered
silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as the
alpha, beta and gamma forms. As noted above, the delta-Na2Si2O5 (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 beaches, and as a
component of suds control systems.
Aluminosilicate builders are of great importance in most currently marketed
heavy duty granular detergent compositions. Aluminosilicate builders include
those having the empirical formula:
Naz[(AlO2)z(SiO2)y].xH2O
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 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.
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. In an especially preferred embodiment, the
crystalline aluminosilicate ion exchange material has the formula:
Na12[(AlO2)12(SiO2)12].xH2O
wherein x is from 20 to 30, especially 27. This material is known as Zeolite A.
Dehydrated zeolites (x = 0 - 10) may also be used herein. Preferably, the
aluminosilicate has a particle size of 0.1-10 microns in diameter.
Suitable organic detergent builders include, but are not restricted to, a wide
variety of polycarboxylate compounds. As used herein, "polycarboxylate" refers
to compounds having a plurality of carboxylate groups, preferably at least 3
carboxylates. 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.
Included among the polycarboxylate builders are a variety of categories of
useful materials. One important category of polycarboxylate builders
encompasses the ether polycarboxylates, including oxydisuccinate, as
disclosed in U.S. 3,128,287 and U.S. 3,635,830. See also "TMS/TDS" builders
of U.S. 4,663,071. Suitable ether polycarboxylates also include cyclic
compounds, particularly alicyclic compounds, such as those described in U.S.
3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.
Other useful detergency builders include the 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, 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 which can 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.
Also suitable in the compositions of the invention are the 3,3-dicarboxy-4-oxa-1,6-hexanedioates
and the related compounds disclosed in U.S. 4,566,984.
Useful succinic acid builders include the C5-C20 alkyl and alkenyl succinic
acids and salts thereof. A particularly preferred compound of this type is dodecenylsuccinic
acid. Specific examples of succinate builders include:
laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate
(preferred), 2-pentadecenylsuccinate, and the like. Laurylsuccinates are the
preferred builders of this group, and are described in EP 0,200,263.
Other suitable polycarboxylates are disclosed in U.S. 4,144,226 and in U.S.
3,308,067. See also U.S. 3,723,322.
Fatty acids, e.g., C12-C18 monocarboxylic acids, can also be incorporated into
the compositions alone, or in combination with the aforesaid builders,
especially citrate and/or the succinate builders, to provide additional builder
activity. Such use of fatty acids will generally result in a diminution of sudsing,
which should be taken into account by the formulator.
The 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 composition (e.g. colorants, dyes, etc.). The following are
illustrative examples of such adjunct materials.
The enzymes to be incorporated include proteases, amylases, lipases,
cellulases, and peroxidases, as well as mixtures thereof. Other types of
enzymes may also be included. They may be of any suitable origin, such as
vegetable, animal, bacterial, fungal and yeast origin. However, their choice is
governed by several factors such as pH-activity and/or stability optima,
thermostability and stability versus active detergents and builders. In this
respect bacterial or fungal enzymes are preferred, such as bacterial amylases
and proteases, and fungal cellulases.
Enzymes are normally incorporated at levels sufficient to provide up to 5 mg by
weight, more typically 0.01 mg to 3 mg, of active enzyme per gram of the
composition. Stated otherwise, the compositions herein will typically comprise
from 0.001% to 5%, preferably 0.01%-1% by weight of a commercial enzyme
preparation.
Suitable examples of proteases are the subtilisins which are obtained from
particular strains of B. subtilis and B. licheniforms. Another suitable protease is
obtained from a strain of Bacillus, having maximum activity throughout the pH
range of 8-12, developed and sold by Novo Industries A/S under the registered
trade name ESPERASE. The preparation of this enzyme and analogous
enzymes is described in GB 1,243,784 of Novo. Proteolytic enzymes suitable
for removing protein-based stains that are commercially available include those
sold under the tradenames ALCALASE and SAVINASE by Novo Industries A/S
(Denmark) and MAXATASE by International Bio-Synthetics, Inc. (The
Netherlands). Other proteases include Protease A (see EP 130,756) and
Protease B (see EP257189).
Amylases include, for example, α-amylases described in GB 1,296,839 (Novo),
RAPIDASE, International Bio-Synthetics, Inc. and TERMAMYL, Novo
Industries. Fungamyl (Novo) is especially useful.
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. 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 Corp., 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 (see also EP 341,947) 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 WO 89/099813.
A wide range of enzyme materials and means for their incorporation into
synthetic detergent compositions are also disclosed in U.S. 3,553,139.
Enzymes are further disclosed in U.S. 4,101,457 and in U.S. 4,507,219.
Enzymes for use in detergents can be stabilized by various techniques.
Enzyme stabilisation techniques are disclosed and exemplified in U.S.
3,600,319 and EP 0,199,405. Enzyme stabilisation systems are also described,
for example, in U.S. 3,519,570.
Polymeric dispersing agents can be utilized at levels from 0.5% to 8%, by
weight, in the compositions herein, especially in the presence of zeolite and/or
layered silicate builders. Suitable polymeric dispersing agents include
polymeric polycarboxylates and polyethylene glycols, although others known in
the art can also be used.
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. For example, 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 polyacrylates 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/maleate copolymers of this type are known materials
which are described in EP 66915 as well as in EP 193,360, which also
describes such polymers comprising hydroxypropylacrylate. Of these
acrylic/maleic-based copolymers, the water-soluble salts of copolymers of
acrylic acid and maleic acid are preferred.
Another class of polymeric polycarboxylic acid compounds suitable for use
herein 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.
A further example of polymeric polycarboxylic compounds which may be used herein include the maleic/acrylic/vinyl alcohol terpolymers. Such materials are also disclosed in EP 193,360, including, for example, the 45/45/10 terpolymer of acrylic/maleic/vinyl alcohol.
A further example of polymeric polycarboxylic compounds which may be used herein include the maleic/acrylic/vinyl alcohol terpolymers. Such materials are also disclosed in EP 193,360, including, for example, the 45/45/10 terpolymer of acrylic/maleic/vinyl alcohol.
Another example of polymeric polycarboxylic compounds which may be used
herein include the biodegradable polyaspartic acid and polyglutamic acid
compounds.
Granular bleaching compositions which contain these compounds typically
contain from 0.01% to 10.0% by weight of the water-soluble ethoxylates
amines.
The most preferred soil release and anti-redeposition agent is ethoxylated
tetraethylenepentamine. Exemplary ethoxylated amines are further described in
U.S. 4,597,898. Another group of preferred clay soil removal-antiredeposition
agents are the cationic compounds disclosed in EP 111,965. Other clay soil
removal/antiredeposition agents which can be used include the ethoxylated
amine polymers disclosed in EP 111,984; the zwitterionic polymers disclosed in
EP 112,592; and the amine oxides disclosed in U.S. 4,548,744 and the carboxy
methyl cellulose (CMC) materials. These materials are well known in the art.
Polymeric soil release agents are characterised 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 or more hydrophobe components comprising (i) C3
oxyalkylene terephthalate segments, wherein, if said hydrophobe components
also comprise oxyethylene terephthalate, the ratio of oxyethylene
terephthalate:C3 oxyalkylene terephthalate units is 2:1 or lower, (ii) C4-C6
alkylene or oxy C4-C6 alkylene segments, or mixtures therein, (iii) poly (vinyl
ester) segments, preferably polyvinyl acetate), having a degree of
polymerization of at least 2, or (iv) C1-C4 alkyl ether or C4 hydroxyalkyl ether
substituents, or mixtures therein, wherein said substituents are present in the
form of C1-C4 alkyl ether or C4 hydroxyalkyl ether cellulose derivatives, or
mixtures therein, and such cellulose derivatives are amphiphilic, whereby they
have a sufficient level of C1-C4 alkyl ether and/or C4 hydroxyalkyl ether units
to deposit upon conventional polyester synthetic fiber surfaces and retain a
sufficient level of hydroxyls, once adhered to such conventional synthetic fiber
surface, to increase fiber surface hydrophilicity, or a combination of (a) and (b).
Typically, 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 MO3S(CH2)nOCH2CH2O-, where M is sodium and n is
an integer from 4-6, as disclosed in U.S. 4,721,580.
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) and carboxy alkyl of cellulose such as Metolose (Shin
Etsu). Cellulosic soil release agents for use herein also include those selected
from C1-C4 alkyl and C4 hydroxyalkyl cellulose; see U.S. 4,000,093.
Soil release agents characterised by poly(vinyl ester) hydrophobe segments
include graft copolymers of poly(vinyl ester), e.g., C1-C6 vinyl esters,
preferably poly(vinyl acetate) grafted onto polyalkylene oxide backbones, such
as polyethylene oxide backbones (see EP 0 219 048). 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. 3,959,230 and U.S. 3,893,929.
Another preferred polymeric soil release agent is a polyester with repeat units
of ethylene terephthalate units which 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. Examples of this polymer include the commercially available
material ZELCON 5126 (from Dupont) and MILEASE T (from ICI). See also
U.S. 4,702,857.
Another preferred polymeric soil release agent is a sulfonated product of a
substantially linear ester oligomer comprised of an oligomeric ester backbone
of terephthaloyl and oxyalkyleneoxy repeat units and terminal moieties
covalently attached to the backbone. These soil release agents are described
in U.S. 4,968,451. Other suitable polymeric soil release agents include the
terephthalate polyesters of U.S. 4,711,730, the anionic end-capped oligomeric
esters of U.S. 4,721,580 and the block polyester oligomeric compounds of U.S.
4,702,857.
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 xylene sulfonate, cumene sulfonate, toluene sulfonate and mixtures
thereof.
Preferred polymeric soil release agents also include the soil release agents of
U.S. 4,877,896, which discloses anionic, especially sulfoaroyl, end-capped
terephthalate esters.
If utilized, soil release agents will generally comprise from 0.01% to 10.0%, by
weight, of the compositions herein, typically from 0.1% to 5%, preferably from
0.2% to 3.0%.
Generally, such dye transfer inhibiting agents include polyvinyl pyrrolidone
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%.
More specifically, the polyamine N-oxide polymers preferred for use herein
contain units having the following structural formula: R-Ax-P; wherein P is a
polymerizable unit to which an N-O group can be attached or the N-O group
can form part of the polymerizable unit or the N-O group can be attached to
both units; A is one of the following structures: -NC(O)-, -C(O)O-, -S-, -O-, -N=;
x is 0 or 1; and R is aliphatic, ethoxylated aliphatics, aromatics, heterocyclic or
alicyclic groups or any combination thereof to which the nitrogen of the N-O
group can be attached or the N-O group is part of these groups. Preferred
polyamine N-oxides are those wherein R is a heterocyclic group such as
pyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof.
The N-O group can be represented by the following general structures:
wherein R1, R2, R3 are aliphatic, aromatic, heterocyclic or alicyclic groups or
combinations thereof; x, y and z are 0 or 1; and the nitrogen of the N-O group
can be attached or form part of any of the aforementioned groups. The amine
oxide unit of the polyamine N-oxides has a pKa <10, preferably pKa <7, more
preferred pKa <6.
Any polymer backbone can be used as long as the amine oxide polymer formed
is water-soluble and has dye transfer inhibiting properties. Examples of suitable
polymeric backbones are polyvinyls, polyalkylenes, 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".
The most preferred polyamine N-oxide useful in the compositions herein is
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 (referred to as
a class as "PVPVI") are also preferred for use herein. Preferably 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. "Modern Methods of Polymer
Characterization".) 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.
The present invention 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. Preferably, 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 bleaching 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 action. If used, the compositions herein will
preferably comprise from 0.01% to 1.2% by weight of such optical brighteners.
The hydrophilic optical brighteners useful in the present invention are those
having the structural formula:
wherein R1 is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl;
R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino,
morphilino, chloro and amino; and M is a salt-forming cation such
as sodium or potassium.
When in the above formula, R1 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 Corporation.
When in the above formula, R1 is anilino, R2 is N-2-hydroxyethyl-N-2-methylamino
and 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.
When in the above formula, R1 is anilino, R2 is morphilino and M is a cation
such as sodium, the brightener is 4,4'-bis[(4-anilino-6-morphilino-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 Corporation.
Other conventional optical brightener types of compounds can optionally be
used in the present compositions to provide conventional fabric "brightness"
benefits, rather than a true dye transfer inhibiting effect. Such usage is
conventional and well-known to detergent formulations.
Conventional 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 compositions herein. Commercial optical brighteners which may
be useful 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
heterocycles, and other miscellaneous agents. Examples of
such brighteners are disclosed in "The Production and Application of
Fluorescent Brightening Agents", M. Zahradnik, Published by John Wiley &
Sons, New York (1982). Further optical brightener which may also be used
include naphthalimide, benzoxazole, benzofuran, benzimidazole and any
mixtures thereof.
Specific examples of optical brighteners which are useful in the present
compositions are those identified in U.S. 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; Artic White CC and Artic White CWD; the 2-(4-styryl-phenyl)-2H-naptho[1,2-d]triazoles;
4,4'-bis(1,2,3-triazol-2-yl)-stilbenes;
4,4'-bis(styryl)bisphenyls; and the aminocoumarins. Specific examples of these
brighteners include 4-methyl-7-diethyl- amino coumarin; 1,2-bis(-benzimidazol-2-yl)ethylene;
1,3-diphenyl-pyrazolines; 2,5-bis(benzoxazol-2-yl)thiophene; 2-styryl-naptho-[1,2-d]oxazole;
and 2-(stilbene-4-yl)-2H-naphtho[1,2-d]triazole.
See also U.S. 3,646,015.
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., 979). One category of suds suppressor of
particular interest encompasses monocarboxylic fatty acid and soluble salts
therein. See U.S. 2,954,347. 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 compositions herein may also contain non-surfactant suds suppressors.
These include, for example: high molecular weight hydrocarbons such as
paraffin, fatty acid esters (e.g., fatty acid triglycerides), fatty acid esters of
monovalent alcohols, aliphatic C18-C40 ketones (e.g., stearone), etc. Other
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 dialkali
metal (e.g., K, Na, and Li) phosphates and phosphate esters. The
hydrocarbons such as paraffin and haloparaffin can be utilized in liquid form. 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. 4,265,779. The hydrocarbons, thus, include
aliphatic, alicyclic, 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.
Another preferred category of non-surfactant 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, disclosed in U.S. 4,265,779 and EP 354016.
Other silicone suds suppressors are disclosed in U.S. 3,455,839 which relates
to compositions and processes for defoaming aqueous solutions by
incorporating therein small amounts of polydimethylsiloxane fluids.
Mixtures of 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. 3,933,672 and
in U.S. 4,652,392.
An exemplary silicone based suds suppressor for use herein is a suds
suppressing amount of a suds controlling agent consisting essentially of:
In the preferred silicone suds suppressor used herein, 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.
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/polypropylene 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.
Other 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 C6-C16 alkyl alcohols having a C1-C16 chain.
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.
For any detergent compositions to be used in automatic laundry washing
machines, suds should not form to the extent that they overflow the washing
machine. Suds suppressors, when utilized, are preferably present in a "suds
suppressing amount". By "suds suppressing amount" is meant that the
formulator of the composition can select 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.
The compositions herein will generally comprise from 0% to 5% of suds
suppressor. When utilized as suds suppressors, monocarboxylic fatty acids,
and salts therein, will be present typically in amounts up to 5%, by weight, of
the composition. Preferably, 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 composition, although higher amounts
may be used. This upper limit is practical in nature, due primarily to concern
with keeping costs minimized and effectiveness of lower amounts for effectively
controlling sudsing. Preferably from 0.01% to 1% of silicone suds suppressor is
used, more preferably from 0.25% to 0.5%. As used herein, these weight
percentage values include any silica that may be utilized in combination with
polyorganosiloxane, as well as any adjunct 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.
Various through-the-wash fabric softeners, especially the impalpable smectite
clays of U.S. 4,062,647, as well as other softener clays known in the art, can
optionally be used typically at levels of from 0.5% to 10%, preferably from 0.5%
to 2% 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. 4,375,416
and U.S. 4,291,071.
A wide variety of other functional ingredients useful in detergent compositions
can be included in the compositions herein, including other active ingredients,
carriers, hydrotropes, processing aids, dyes or pigments, solid fillers for bar
compositions. The compositions herein will preferably be formulated such that,
during use in aqueous cleaning operations, the wash water will have a pH of
between 6.5 and 11, preferably between 7.5 and 10.5. Laundry products are
typically at pH 9-11. Techniques for controlling pH at recommended usage
levels include the use of buffers, alkalis, acids, etc., and are well known to
those skilled in the art.
Preferably, the mean particle size of the components of granular compositions
in accordance with the invention should be such that no more than 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 determined by sieving a
sample of the composition into a number of fractions (typically 5 fractions) on a
series of Tyler sieves. The weight fractions 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 is particularly 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 400 g/litre, more
preferably from 650 g/litre to 1200 g/litre, most preferably from 800g/litre to
1000g/litre.
In general, 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.
In another aspect of the invention a method of washing laundry is provided
which comprises the step of contacting the fabrics with an aqueous liquor of the
above defined granular detergent composition. By the present method,
effective perhydrolysis of the bleach precursor is obtained.
By effective perhydrolysis is meant that the use of a composition comprising an
alcohol alkoxylate nonionic surfactant and a bleach precursor having a Krafft
point of at least 10°C as described above exhibits a better bleach precursor
perhydrolysis than the use of the same composition without the alcohol
alkoxylate nonionic surfactant or than the same composition without the molar
ratio requirement.
The invention is illustrated in the following non-limiting examples, in which all
percentages are on a weight basis unless otherwise stated.
In the compositions of the invention, the abbreviated component identifications
have the following meanings:
- LAS
- : Sodium linear C12 alkyl benzene sulphonate
- TAS
- : Sodium tallow alcohol sulphate
- C45AS
- : Sodium C14-C15 linear alkyl sulphate
- C45E7
- : A C14-15 predominantly linear primary alcohol condensed with an average of 7 moles of ethylene oxide
- C25 E3
- : A C12-15 branched primary alcohol condensed with an average of 3 moles of ethylene oxide
- C25E5
- : A C12-15 branched primary alcohol condensed with an average of 5 moles of ethylene oxide
- Soap
- : Sodium linear alkyl carboxylate derived from an 80/20 mixture of tallow and a coconut oils.
- STPP
- : Anhydrous sodium tripolyphosphate
- Zeolite A
- : Hydrated Sodium Aluminosilicate of formula
Na12(A102SiO2)12.27H2O
having a primary particle size in the range from 0.1 to 10 micrometers - NaSKS-6
- : Crystalline layered silicate of formula δ-Na2Si2O5
- Carbonate
- : Anhydrous sodium carbonate with a particle size between 200µm and 900µm
- Silicate
- : Amorphous Sodium Silicate (SiO2:Na2O; 2.0 ratio)
- Sulphate
- : Anhydrous sodium sulphate
- Citrate
- : Tri-sodium citrate dihydrate of activity 86.4% with a particle size distribution between 425µm and 850µm
- MA/AA
- : Copolymer of 1:4 maleic/acrylic acid, average molecular weight about 70,000. CMC : Sodium carboxymethyl cellulose
- Savinase
- : Proteolytic enzyme of activity 4KNPU/g
- Carezyme
- . Cellulytic enzyme of activity 1000 CEVU/g
- Termamyl
- : Amylolytic enzyme of activity 60KNU/g
- Lipolase
- : Lipolytic enzyme of activity 100kLU/g
all sold by NOVO Industries A/S and of activity mentioned above unless otherwise specified - PB4
- : Sodium perborate tetrahydrate of nominal formula NaBO2.3H2O.H2O2
- PB1
- : Anhydrous sodium perborate bleach of nominal formula NaBO2.H2O2
- Percarbonate
- : Sodium Percarbonate of nominal formula 2Na2CO3.3H2O2
- TAED
- : Tetraacetyl ethylene diamine
- NACA-OBS
- : (6-nonanamidocaproyl)oxy benzene sulfonate
- DTPMP
- : Diethylene triamine penta (methylene phosphonate), marketed by Monsanto under the Trade name Dequest 2060
- Photoactivated bleach
- : Sulphonated Zinc Phthalocyanin encapsulated in dextrin soluble polymer
- Brightener 1
- : Disodium 4,4'-bis(2-sulphostyryl)biphenyl
- Brightener 2
- : Disodium 4,4'-bis(4-anilino-6-morpholino-1.3.5-triazin-2-yl)amino) stilbene-2:2'-disulphonate.
- HEDP
- : 1,1-hydroxyethane diphosphonic acid
- SRP
- : Sulfobenzoyl end capped esters with oxyethylene oxy and terephtaloyl backbone
- Silicone antifoam
- : Polydimethyldiloxane 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.
The following detergent formulations, according to the present invention were
prepared, where formulation A is a phosphorus-containing detergent
composition, formulation B is a zeolite-containing detergent composition and
formulation C is a compact detergent composition:
A | B | C | |
Blown Powder | |||
STPP | 24 | - | 24.0 |
Zeolite A | - | 24.0 | - |
Sulphate | 9.0 | 6.0 | 13.0 |
MA/AA | 2.0 | 4.0 | 2.0 |
LAS | 6.0 | 8.0 | 11.0 |
TAS | 2.0 | - | - |
Silicate | 7.0 | 3.0 | 3.0 |
CMC | 1.0 | 1.0 | 0.5 |
Brightener 2 | 0.2 | 0.2 | 0.2 |
Soap | 1.0 | 1.0 | 1.0 |
DTPMP | 0.4 | 0.4 | 0.2 |
Spray On | |||
C45E7 | 2.5 | 2.5 | 2.0 |
C25E3 | 2.5 | 2.5 | 2.0 |
Silicone antifoam | 0.3 | 0.3 | 0.3 |
Perfume | 0.3 | 0.3 | 0.3 |
Dry additives | |||
Carbonate | 6.0 | 13.0 | 15.0 |
PB4 | 18.0 | 18.0 | 10.0 |
PB1 | 4.0 | 4.0 | - |
TAED | 3.0 | 3.0 | 1.0 |
Photoactivated bleach | 0.02 | 0.02 | 0.02 |
Savinase | 1.0 | 1.0 | 1.0 |
Lipolase | 0.4 | 0.4 | 0.4 |
Termamyl | 0.25 | 0.30 | 0.15 |
Sulphate | 3.0 | 3.0 | 5.0 |
NACA-OBS | 1.0 | 1.0 | 0.8 |
Balance (Moisture & Miscellaneous) | 100.0 | 100.0 | 100.0 |
Density (g/litre) | 630 | 670 | 670 |
The following high density detergent formulations D and E, according to the
present invention were prepared:
D | E | |
Agglomerate | ||
C45AS | 11.0 | 14.0 |
Zeolite A | 15.0 | 6.0 |
Carbonate | 4.0 | 8.0 |
MA/AA | 4.0 | 2.0 |
CMC | 0.5 | 0.5 |
DTPMP | 0.4 | 0.4 |
Spray On | ||
C25E5 | 5.0 | 5.0 |
Perfume | 0.5 | 0.5 |
Dry Additives | ||
HEDP | 0.5 | 0.3 |
NaSKS 6 | 13.0 | 10.0 |
Citrate | 3.0 | 1.0 |
TAED | 3.0 | 3.5 |
NACA-OBS | 1.6 | 1.4 |
Percarbonate | 20.0 | 20.0 |
SRP | 0.3 | 0.3 |
Savinase | 1.4 | 1.4 |
Lipolase | 0.4 | 0.4 |
Carezyme | 0.6 | 0.6 |
Termamyl | 0.6 | 0.6 |
Silicone antifoam particle | 5.0 | 5.0 |
Brightener 1 | 0.2 | 0.2 |
Brightener 2 | 0.2 | - |
Balance (Moisture and Miscellaneous) | 100 | 100 |
Density (g/litre) | 850 | 850 |
Claims (10)
- A granular bleaching composition comprising an alcohol alkoxylate nonionic surfactant, a hydrogen peroxide source and a bleach precursor having a Krafft point of at least 10°C, said surfactant and said precursor being present in a molar ratio of alcohol alkoxylate nonionic surfactant to bleach precursor of at least 3:1.
- A composition according to Claim 2, wherein said surfactant is selected from polyethylene, polypropylene, and polybutylene oxide condensates of alkyl phenols, condensation products of aliphatic alcohols with from 1 to 25 moles of ethylene oxide, condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol, condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine and mixtures thereof.
- A composition according to either one of Claim 1 or 2, wherein said bleach precursor has a Krafft point of at least 50°C, preferably 60°C.
- A composition according to any one of Claims 1-3, wherein said bleach precursor is an anionic bleach precursor.
- A composition according to Claim 4, wherein said bleach precursor is an anionic bleach precursor of the amido peroxy class.
- A composition according to Claim 5, wherein said bleach precursor is selected from the group consisting of monovalent, divalent, trivalent metal salts of amide substituted peroxyacid precursor compounds and mixtures thereof, preferably monovalent salt of amide substituted peroxyacid precursor compounds.
- A composition according to Claim 6, wherein said bleach precursor is selected from the group consisting of (6-octanamidocaproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)oxy benzene sulfonate, (6-decanamido-caproyl)oxybenzenesulfonate, and mixtures thereof.
- A composition according to any one of Claims 1-6, wherein said composition further comprises a bleach co-precursor.
- A composition according to Claim 8, wherein said bleach co-precursor is tetraacetyl ethylene diamine.
- A method of washing laundry which comprises the step of contacting the fabrics with an aqueous liquor of a composition as defined in any one of Claims 1-9.
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP96870084A EP0816483A1 (en) | 1996-06-27 | 1996-06-27 | Granular bleaching compositions |
JP10503478A JPH11514025A (en) | 1996-06-27 | 1997-06-23 | Granular bleaching composition |
PCT/US1997/010973 WO1997049791A1 (en) | 1996-06-27 | 1997-06-23 | Granular bleaching compositions |
BR9710008A BR9710008A (en) | 1996-06-27 | 1997-06-23 | Granular bleaching compositions |
ARP970102880A AR008050A1 (en) | 1996-06-27 | 1997-06-27 | COMPOSITION FOR CHEMICAL BLEACHING IN GRANULES AND WASHING METHOD WITH THE SAME. |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP96870084A EP0816483A1 (en) | 1996-06-27 | 1996-06-27 | Granular bleaching compositions |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0816483A1 true EP0816483A1 (en) | 1998-01-07 |
Family
ID=8226153
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP96870084A Withdrawn EP0816483A1 (en) | 1996-06-27 | 1996-06-27 | Granular bleaching compositions |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP0816483A1 (en) |
JP (1) | JPH11514025A (en) |
AR (1) | AR008050A1 (en) |
BR (1) | BR9710008A (en) |
WO (1) | WO1997049791A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2008017737A1 (en) | 2006-08-10 | 2008-02-14 | Brevetix | Sound-absorbing assembly |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2329747A1 (en) * | 1975-11-03 | 1977-05-27 | Unilever Nv | BLEACHING AIDS, THEIR PREPARATION AND THEIR USE IN WASHING COMPOSITIONS |
EP0006655A1 (en) * | 1978-06-26 | 1980-01-09 | THE PROCTER & GAMBLE COMPANY | Particulate detergent additive product |
EP0106634A1 (en) * | 1982-10-08 | 1984-04-25 | THE PROCTER & GAMBLE COMPANY | Bodies containing bleach activators |
EP0170386A2 (en) * | 1984-06-21 | 1986-02-05 | The Procter & Gamble Company | Bleaching compounds and compositions comprising fatty peroxy acids, salts thereof, and precursors therefor |
GB2178075A (en) * | 1985-07-19 | 1987-02-04 | Colgate Palmolive Co | Bleach active detergent additive composition |
EP0402971A2 (en) * | 1989-06-14 | 1990-12-19 | Unilever N.V. | Particulate detergent composition additive |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5445755A (en) * | 1994-05-31 | 1995-08-29 | The Procter & Gamble Company | Detergent compositions containing a peroxidase/accelerator system without linear alkylbenzenesulfonate |
-
1996
- 1996-06-27 EP EP96870084A patent/EP0816483A1/en not_active Withdrawn
-
1997
- 1997-06-23 WO PCT/US1997/010973 patent/WO1997049791A1/en active Application Filing
- 1997-06-23 JP JP10503478A patent/JPH11514025A/en active Pending
- 1997-06-23 BR BR9710008A patent/BR9710008A/en unknown
- 1997-06-27 AR ARP970102880A patent/AR008050A1/en unknown
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2329747A1 (en) * | 1975-11-03 | 1977-05-27 | Unilever Nv | BLEACHING AIDS, THEIR PREPARATION AND THEIR USE IN WASHING COMPOSITIONS |
EP0006655A1 (en) * | 1978-06-26 | 1980-01-09 | THE PROCTER & GAMBLE COMPANY | Particulate detergent additive product |
EP0106634A1 (en) * | 1982-10-08 | 1984-04-25 | THE PROCTER & GAMBLE COMPANY | Bodies containing bleach activators |
EP0170386A2 (en) * | 1984-06-21 | 1986-02-05 | The Procter & Gamble Company | Bleaching compounds and compositions comprising fatty peroxy acids, salts thereof, and precursors therefor |
GB2178075A (en) * | 1985-07-19 | 1987-02-04 | Colgate Palmolive Co | Bleach active detergent additive composition |
EP0402971A2 (en) * | 1989-06-14 | 1990-12-19 | Unilever N.V. | Particulate detergent composition additive |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2008017737A1 (en) | 2006-08-10 | 2008-02-14 | Brevetix | Sound-absorbing assembly |
Also Published As
Publication number | Publication date |
---|---|
BR9710008A (en) | 1999-08-10 |
AR008050A1 (en) | 1999-12-09 |
JPH11514025A (en) | 1999-11-30 |
WO1997049791A1 (en) | 1997-12-31 |
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