WO2000018869A1 - Compositions detergentes solides - Google Patents

Compositions detergentes solides Download PDF

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Publication number
WO2000018869A1
WO2000018869A1 PCT/US1998/020221 US9820221W WO0018869A1 WO 2000018869 A1 WO2000018869 A1 WO 2000018869A1 US 9820221 W US9820221 W US 9820221W WO 0018869 A1 WO0018869 A1 WO 0018869A1
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WIPO (PCT)
Prior art keywords
alkyl
acid
preferred
weight
composition
Prior art date
Application number
PCT/US1998/020221
Other languages
English (en)
Inventor
Richard Timothy Hartshorn
Zayeed Alam
Kevin Norwood
Original Assignee
The Procter & Gamble Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=22267948&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2000018869(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Priority to MXPA01003081 priority Critical patent/MXPA01003081A/es
Priority to BRPI9816031-1A priority patent/BR9816031B1/pt
Priority to AU95108/98A priority patent/AU9510898A/en
Priority to JP2000572317A priority patent/JP2002525419A/ja
Priority to AT98948561T priority patent/ATE357500T1/de
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to PCT/US1998/020221 priority patent/WO2000018869A1/fr
Priority to CN98814316.XA priority patent/CN1322242A/zh
Priority to CA002344434A priority patent/CA2344434C/fr
Priority to DE69837403T priority patent/DE69837403T2/de
Priority to US09/787,454 priority patent/US6964945B1/en
Priority to EP98948561A priority patent/EP1115831B1/fr
Priority to MXPA01003097 priority patent/MX227672B/es
Priority to ES98948561T priority patent/ES2283074T3/es
Priority to PCT/US1998/021022 priority patent/WO2000018870A1/fr
Priority to CNB988143275A priority patent/CN1168815C/zh
Priority to EP98950950A priority patent/EP1115832A1/fr
Priority to BRPI9816029-0A priority patent/BR9816029B1/pt
Priority to AU96862/98A priority patent/AU9686298A/en
Priority to CA002343895A priority patent/CA2343895C/fr
Priority to US09/787,455 priority patent/US6630439B1/en
Priority to JP2000572318A priority patent/JP2003522213A/ja
Priority to JP2000572306A priority patent/JP2002525417A/ja
Priority to EP99949767A priority patent/EP1115819B1/fr
Priority to DE69923196T priority patent/DE69923196T2/de
Priority to BRPI9914050-0A priority patent/BR9914050B1/pt
Priority to ES99949767T priority patent/ES2237161T3/es
Priority to IN197DE2001 priority patent/IN243977B/en
Priority to AT99949767T priority patent/ATE286960T1/de
Priority to AU62570/99A priority patent/AU6257099A/en
Priority to US09/787,451 priority patent/US6635610B1/en
Priority to CA002344997A priority patent/CA2344997C/fr
Priority to PCT/US1999/021843 priority patent/WO2000018856A1/fr
Priority to CN99813557A priority patent/CN1328597A/zh
Priority to ZA9906130A priority patent/ZA996130B/xx
Priority to PH11999002387A priority patent/PH11999002387B1/en
Priority to ARP990104819A priority patent/AR020515A1/es
Priority to ARP990104820A priority patent/AR028137A1/es
Priority to ARP990104818A priority patent/AR026850A1/es
Publication of WO2000018869A1 publication Critical patent/WO2000018869A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/37—Mixtures of compounds all of which are anionic
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/128—Aluminium silicates, e.g. zeolites
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/143—Sulfonic acid esters
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers

Definitions

  • the invention relates to solid detergent compositions comprising aluminosilicate builder and surfactants comprised in two or more components which have an improved cleaning performance, an improved delivery to the wash and a reduced residue formation on the fabrics.
  • aluminosilicates are inexpensive builders, which have as an additional benefit that they are easy to process. They are in fact useful process aids because they are very good structurants, binders or carrier materials for other detergent ingredients. Therefore, most detergents comprise a base powder, made by spray-drying a slurry of aluminosilicate and surfactant or by agglomerating aluminosilicate and surfactant. Furthermore, aluminosilicates are useful as dusting agent, to reduce the stickiness or caking of the product.
  • the inventors have now su ⁇ risingly found that this problems in particular arises when the surfactants and the aluminosilicates in the detergent are in close contact with one another, for example when they are in the detergent in an intimately mixture.
  • This is for example the case in most known and used base powders, which are agglomerates or spray-dried powders containing.
  • the inventors have now found that the residue formation problem but also the gelling problem or dissolution or dispensing problem mainly arises in most known products, when about all the anionic surfactants and aluminosilicates are intimately mixed with one another. When the degree of intimate mixing is reduced or even avoided completely, they have found that these problems are reduced or even solved completely.
  • the inventors have found a solution which still allows the inco ⁇ oration of aluminosilicates and surfactants in detergent, but in a different manner: the invention provides thereto detergents comprising at least two components comprising the surfactants and the aluminosilicate in such a manner that a limited degree of intimate mixing occurs.
  • the detergents of the invention have a reduced fabric residue, in particular of insoluble detergent ingredients, gelling, an improved dispensing and dissolution. It has been found that these benefits are obtained by any convention way of introducing detergent to the wash, including by use of a dispensing drawer, a dispensing device or by addition of the detergent in the washing prior to addition of the wash load or addition of the detergent on top of the wash load.
  • compositions may comprise an effervescence system to further aid the dispensing or dissolution or foaming.
  • the invention provides a detergent composition comprising an aluminosilicate builder and an anionic surfactant and comprising (n) components (i), n being at least 2, whereby the level of aluminosilicate builder in said components together is at least 5% by weight of the composition and the level of the anionic surfactant in said components together is at least 5% by weight of the composition, and whereby the degree of mixture (M) of the anionic surfactant and the aluminosilicate builder is from 0 to 0.7, M being
  • ⁇ is the fraction of the anionic surfactant of the composition comprised in component (i); ⁇ is the fraction of the aluminosilicate of the composition comprised in component (i).
  • composition is in particular in granular form, in the form of an extrudate, marumerate or pastille, or in the form of an tablet.
  • the invention also relates to the use in a detergent composition of at least two components which comprise together an aluminosilicate at a level of at least 5% by weight of the composition and an anionic surfactant at a level of at least 5% by weight of the composition or mixtures thereof, whereby the degree of mixture (M) of the anionic surfactant and the aluminosilicate builder is from 0 to 0.7 for improvement of the delivery of the detergent to the washing water, M being as defined above.
  • the detergent compositions have an improved delivery to the washing water.
  • the compositions provide a reduction of fabric residues, in particular of water-insoluble detergent ingredients such as the aluminosilicate, an improvement of the dispensing of the detergent composition, an improvement in the dissolution of the detergent, a reduction in gelling of the detergent and / or a reduction of lump formation of the detergent on the fabrics and for bleach-containing compositions, an reduced risk of fabric damage.
  • the detergent composition herein comprise at least two components which comprise an anionic surfactant or an aluminosilicate or mixtures thereof, whereby if mixtures of aluminosilicate and the surfactant are present in one or more of the components, the degree of mixture M is less than 0.7, as defined by the formula.
  • each component comprises part or all of the aluminosilicate, all or part of the anionic surfactant or mixtures thereof, provided that M is from 0 to 0.7.
  • the components of the detergent composition of the invention comprise each at least two ingredients, including the anionic surfactant and/ or the aluminosilicate, which are intimately mixed. This means for the pu ⁇ ose of the invention that the two or more ingredients the component are substantially homogeneously divided in the component.
  • a component is such that when it comprises an anionic surfactant, the level of the anionic surfactant is less than 95%), preferably less than 85% or even less than 80% by weight of the component, whereby it may be preferred that the level of the anionic surfactant is at least 5%, preferably at least 10% more preferably at least 20% or even at least 30%) or even 35% by weight of the component.
  • a component is such that when it comprises an aluminosilicate, the level of the aluminosilicate is less than 95%), preferably less than 85% or even less than 80% by weight of the component, whereby it may be preferred that the level of the aluminosilicate is at least 5%>, preferably at least 10%> by weight of the component.
  • the detergent composition herein may also comprise additional intimately mixtures which are free of anionic surfactant and free of aluminosilicate.
  • the detergent composition may comprise additional ingredients which are not in an intimate mixture with another ingredient and thus not comprised in a component of the composition, as defined herein.
  • the composition may comprise a detergent ingredient sprayed onto the components herein or dry-added to the components herein.
  • the components together comprise the aluminosilicate builder at a level of least 5%> by weight of the composition of and the anionic surfactant at a level of at least 5%> by weight of the composition.
  • the components comprise the aluminosilicate at a level of at least 1%, or more preferably at least 10%> or even 15%> by weight of the composition.
  • the compositions of the invention can even comprise higher levels of aluminosilicate, such as more than 20%> or even more than 25%>, whilst still providing an improved delivery of the detergent to the wash.
  • At least 7%> or more preferably at least 10%> or even at least 12%> by weight of the composition of anionic surfactant is present in the components.
  • levels of anionic surfactants may be preferred to have levels of anionic surfactants of 18%) by weight of the composition or more.
  • the detergent composition comprises additional dry-added aluminosilicate, in particular to dust the detergent components to reduce the risk of caking and/ or to provide whiteness to the product.
  • M is less than 0.65, or even less than 0.45 or even 0.4 or even 0.35. It may be preferred that M is 0, and that thus no components are present in the detergent composition which comprise both aluminosilicate and anionic surfactants. Whether this is preferred will for example depend the levels of aluminosilicate and anionic surfactant in the detergent, on the other ingredients present in the formulation and the amount of components present in the formulation.
  • the components herein preferably are particles, having a particle size of at least 50 microns, preferably the particles have an weight average particle size of more than 150 or more than 250 microns or even more than 350 microns, as measured by sieving the composition on sieves of different mesh size, and calculating the fraction which remain on the sieve and the fraction which passes through the sieve.
  • At least one component is made by a spray-drying process, as known in the art, and at least one component is made by an agglomeration process, as known in the art.
  • the density of the components is from 250 g/litre to 1500 g/litre, more preferably at least one of the components, preferably all of the components, has a density from 400 g/litre to 1200gr/litre, more preferably from 500 g/litre to 900g/litre.
  • a highly preferred additional ingredient of the detergent compositions herein may be oxygen based bleach, preferably containing an hydrogen peroxide source, preferably a perhydrogen compound and a bleach activator, described herein after. It has been found that the improved product delivery to the wash results in an improved delivery of the bleach system therein, which reduces the risk of deposition of bleach on the fabric and the risk of patchy fabric damage.
  • Another preferred additional ingredient is one or more additional builder materials, such as one or more monomeric, oligomeric or polymeric carboxylate builders and/ or crystalline layered silicate builder material, described herein after.
  • additional builder materials such as one or more monomeric, oligomeric or polymeric carboxylate builders and/ or crystalline layered silicate builder material, described herein after.
  • the detergent composition may be substantially free of specific spray-on nonionic alkoxylated alcohol surfactants, which have been found to cause gelling or dispensing or dissolution problems. It may then be preferred that the composition comprises other nonionic surfactants, preferably nonionic surfactants which are solid at room temperature.
  • the omission of sprayed-on nonionic alkoxylated alcohols allows the reduction or omission of powdered materials normally required to dust the detergent particles containing these liquid nonionic surfactants, such as fine aluminosilicates. This not only reduces the process complexity, but moreover reduces the degree of mixing or contact of the s and surfactants.
  • the inventors have found that in certain embodiments of the invention it may be beneficial to reduce the degree of mixing between the aluminosilicate and one or more of the organic polymeric compounds, when present, for example flocculation polymers and polycarboxylate polymers, as described herein.
  • the degree of mixture of the aluminosilicate and one or more of these polymers can be determined by the formula above, wherein ⁇ would indicate the weight fraction of the specific polymer in a certain component. It has been found that this may reduce the fabric residue formation on the fabrics, in particular of water-insoluble components, such as the aluminosilicate.
  • the degree of mixing between amo ⁇ hous silicate and an anionic surfactant is reduced, when an amo ⁇ hous silicate is present, in particular in mixtures containing anionic surfactant which are to be spray-dried, it may be beneficial to reduce the amount of silicate present, for example to levels of less than 3% by weight of the mixture, or even less than 2%, or even less thanl% or even 0%> by weight of the mixture.
  • Suitable aluminosilicates herein are zeolites which have the unit cell formula Na z [(AlO2) z (SiO2)y]- H2O wherein z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276, more preferably from 10 to 264.
  • the aluminosilicates are in preferably in hydrated form and are preferably crystalline, containing from 10% to 28%>, more preferably from 18% to 22% water in bound form. However, it may be useful to inco ⁇ orate overdried aluminosilictaes.
  • the aluminosilicates can be naturally occurring materials, but are preferably synthetically derived. Synthetic crystalline aluminosilicate ion exchange materials are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS and mixtures thereof. Zeolite A has the formula
  • Zeolite X has the formula Nagg [(Al ⁇ 2)86(Si ⁇ 2)l06]- 276 H 2 O.
  • anionic surfactant can be inco ⁇ orated in the compositions of the invention.
  • the anionic surfactant herein preferably comprises at least a sulphate surfactant and/ or a sulphonate surfactant or mixtures thereof. It may be preferred that the anionic surfactant comprises only alkyl sulphonate surfactant or optionally combined with fatty acids or soap salts thereof. Alternatively, it may be preferred that the composition comprises only akly sulphate surfactant, but hereby it is preferred that at least a mid-chain branched alkyl surfactant is present or at least two alkyl surfactants are present.
  • compositions herein comprise a particulate component, as descriebd above, preferably in the form of a flake of an alkyl sulfate or sulphonate surfactant, preferably an alkyl benzene sulphonate, present at a concentration of from 85% to 95%> of the particle or flake, the balance being an sulfate salt and moisture, the particle or flake being admixed to the other detergent component(s) or ingredients.
  • a particulate component preferably in the form of a flake of an alkyl sulfate or sulphonate surfactant, preferably an alkyl benzene sulphonate, present at a concentration of from 85% to 95%> of the particle or flake, the balance being an sulfate salt and moisture, the particle or flake being admixed to the other detergent component(s) or ingredients.
  • anionic surfactants include the isethionates such as the acyl isethionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated C, ⁇ -C, R monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C fi -C 1 4 diesters), N-acyl sarcosinates.
  • Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tallow oil.
  • anionic sulphonate surfactants in accordance with the invention include the salts of C5-C20 linear or branched alkylbenzene sulphonates, alkyl ester sulphonates, C6-C22 primary or secondary alkane sulphonates, Cg-C24 olefin sulphonates, sulphonated polycarboxylic acids, and any mixtures thereof.
  • Preferred salts are sodium and potassium salts.
  • alkyl ester sulphonated surfactant are also suitable for the invention, preferably those of formula
  • R! is a C6-C22 hydrocarbyl
  • R 2 is a C1 -Cg alkyl
  • A is a C ⁇ -C22 alkylene
  • alkenylene x is 0 or 1
  • M is a cation.
  • the counterion M is preferably sodium, potassium or ammonium.
  • the alkyl ester sulphonated surfactant is preferably a -sulpho alkyl ester of the formula above, whereby thus x is 0.
  • R 1 is an alkyl or alkenyl group of from 10 to 22, preferably 16 C atoms and x is preferably 0.
  • R 2 is preferably ethyl or more preferably methyl.
  • Rl of the ester is derived from unsaturated fatty acids, with preferably 1, 2 or 3 double bonds. It can also be preferred that R 1 of the ester is derived from a natural occurring fatty acid, preferably palmic acid or stearic acid or mixtures thereof.
  • the anionic sulphate surfactant herein include the linear and branched primary and secondary alkyl sulphates and disulphates, alkyl ethoxysulphates having an average ethoxylation number of 3 or below, fatty oleoyl glycerol sulphates, alkyl phenol ethylene oxide ether sulphates, the C 5 -C 17 acyl-N-(C ⁇ -C4 alkyl) and -N-(C ⁇ -C hydroxyalkyl) glucamine sulphates, and sulphates of alkylpolysaccharides.
  • Primary alkyl sulphate surfactants are preferably selected from the linear and branched primary C ⁇ Q-CI g alkyl sulphates, more preferably the C1 1 -C ⁇ 5 linear or branched chain alkyl sulphates, or more preferably the C ⁇ 2-C14 linear chain alkyl sulphates.
  • Preferred secondary alkyl sulphate surfactant are of the formula
  • R 3 is a C 8 -C 20 hydrocycarbyl
  • R 4 is a hydrocycarbyl
  • M is a cation.
  • Alkyl ethoxy sulphate surfactants are preferably selected from the group consisting of the C10-C18 alkyl sulphates which have been ethoxylated with from 0.5 to 3 moles of ethylene oxide per molecule. More preferably, the alkyl ethoxy sulphate surfactant is a Ci 1 -C ⁇ g, most preferably C ⁇ ⁇ -C ⁇ 5 alkyl sulphate which has been ethoxylated with from 0.5 to 3, preferably from 1 to 3, moles of ethylene oxide per molecule.
  • a particularly preferred aspect of the invention employs mixtures of the preferred alkyl sulphate and alkyl ethoxysulphate surfactants.
  • Preferred salts are sodium and potassium salts.
  • Preferred mid-chain branched primary alkyl_sulfate surfactants for use herein are of the formula
  • These surfactants have a linear primary alkyl sulfate chain backbone (i.e., the longest linear carbon chain which includes the sulfated carbon atom) which preferably comprises from 12 to 19 carbon atoms and their branched primary alkyl moieties comprise preferably a total of at least 14 and preferably no more than 20, carbon atoms.
  • the average total number of carbon atoms for the branched primary alkyl moieties is preferably within the range of from greater than 14.5 to about 17.5.
  • the surfactant system preferably comprises at least one branched primary alkyl sulfate surfactant compound having a longest linear carbon chain of not less than 12 carbon atoms or not more than 19 carbon atoms, and the total number of carbon atoms including branching must be at least 14, and further the average total number of carbon atoms for the branched primary alkyl moiety is within the range of greater than 14.5 to about 17.5.
  • R, R1 , and R 2 are each independently selected from hydrogen and Ci -C3 alkyl group (preferably hydrogen or Ci -C2 alkyl, more preferably hydrogen or methyl, and most preferably methyl), provided R, R*, and R 2 are not all hydrogen. Further, when z is 1, at least R or R! is not hydrogen.
  • M is hydrogen or a salt forming cation depending upon the method of synthesis.
  • w is an integer from 0 to 13;
  • x is an integer from 0 to 13;
  • y is an integer from 0 to 13;
  • z is an integer of at least 1 ;
  • w + x + y + z is an integer from 8 to 14.
  • a preferred mid-chain branched primary alkyl sulfate surfactant is, a C16 total carbon primary alkyl sulfate surfactant having 13 carbon atoms in the backbone and having 1, 2, or 3 branching units (i.e., R, R* and/or R 2 ) of in total 3 carbon atoms, (whereby thus the total number of carbon atoms is at least 16).
  • Preferred branching units can be one propyl branching unit or three methyl branching units.
  • Another preferred surfactant are branched primary alkyl sulfates having the formula
  • dianionic surfactants are also useful anionic surfactants for the present invention, in particular those of formula
  • R is an, optionally substituted, alkyl, alkenyl, aryl, alkaryl, ether, ester, amine or amide group of chain length C ⁇ to C28 > preferably C3 to C24, most preferably C8 to C20 > or hydrogen;
  • a nad B are independently selected from alkylene, alkenylene, (poly) alkoxylene, hydroxyalkylene, arylalkylene or amido alkylene groups of chain length C ⁇ to C28 preferably C ⁇ to C5, most preferably C ⁇ or C2, or a covalent bond, and preferably
  • a and B in total contain at least 2 atoms; A, B, and R in total contain from 4 to about 31 carbon atoms; X and Y are anionic groups selected from the group comprising carboxylate, and preferably sulfate and sulfonate, z is 0 or preferably 1 ; and M is a cationic moiety, preferably a substituted or unsubstituted ammonium ion, or an alkali or alkaline earth metal ion.
  • the most preferred dianionic surfactant has the formula as above where R is an alkyl group of chain length from Ci 0 to Ci 8, A and B are independently C ⁇ or C2, both X and
  • Y are sulfate groups
  • M is a potassium, ammonium, or a sodium ion.
  • Preferred dianionic surfactants herein include:
  • R is a straight or branched chain alkyl or alkenyl group of chain length from about C4 to about Cj8; preferred R are selected from octanyl, nonanyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, and mixtures thereof; and
  • R is a straight or branched chain alkyl or alkenyl group of chain length from about C4 to about Ci g.
  • dianionic surfactants of the invention are alkoxylated dianionic surfactants.
  • the alkoxylated dianionic surfactants of the invention comprise a structural skeleton of at least five carbon atoms, to which two anionic substituent groups spaced at least three atoms apart are attached. At least one of said anionic substituent groups is an alkoxy- linked sulphate or sulphonate group.
  • Said structural skeleton can for example comprise any of the groups consisting of alkyl, substituted alkyl, alkenyl, aryl, alkaryl, ether, ester, amine and amide groups.
  • Preferred alkoxy moieties are ethoxy, propoxy, and combinations thereof.
  • the structural skeleton preferably comprises from 5 to 32, preferably 7 to 28, most preferably 12 to 24 atoms.
  • the structural skeleton comprises only carbon- containing groups and more preferably comprises only hydrocarbyl groups.
  • the structural skeleton comprises only straight or branched chain alkyl groups.
  • the structural skeleton is preferably branched. Preferably at least 10 %> by weight of the structural skeleton is branched and the branches are preferably from 1 to 5, more preferably from 1 to 3, most preferably from 1 to 2 atoms in length (not including the sulphate or sulphonate group attached to the branching).
  • a preferred alkoxylated dianionic surfactant has the formula
  • R is an, optionally substituted, alkyl, alkenyl, aryl, alkaryl, ether, ester, amine or amide group of chain length C ⁇ to C28 > preferably C3 to C24, most preferably C to C20, or hydrogen;
  • a and B are independently selected from, optionally substituted, alkyl and alkenyl group of chain length C ⁇ to C28 > preferably C ⁇ to C5, most preferably C ⁇ or C2, or a covalent bond;
  • EO/PO are alkoxy moieties selected from ethoxy, propoxy, and mixed ethoxy/propoxy groups, wherein n and m are independently within the range of from about 0 to about 10, with at least m or n being at least 1 ;
  • a and B in total contain at least 2 atoms;
  • A, B, and R in total contain from 4 to about 31 carbon atoms;
  • X and Y are anionic groups selected from the group consisting of sulphate and sulphonate,
  • the most preferred alkoxylated dianionic surfactant has the formula as above where R is an alkyl group of chain length from Ci Q to Ci g, A and B are independently C ⁇ or C , n and m are both 1 , both X and Y are sulfate groups, and M is a potassium, ammonium, or a sodium ion.
  • Preferred alkoxylated dianionic surfactants herein include: ethoxylated and/or propoxylated disulphate compounds, preferably C10-C24 straight or branched chain alkyl or alkenyl ethoxylated and/or propoxylated disulphates, more preferably having the formulae:
  • R is a straight or branched chain alkyl or alkenyl group of chain length from about C6 to about C ⁇ g;
  • EO/PO are alkoxy moieties selected from ethoxy, propoxy, and mixed ethoxy/propoxy groups; and
  • n and m are independently within the range of from about 0 to about 10 (preferably from about 0 to about 5), with at least m or n being 1.
  • Suitable anionic carboxylate surfactants include the alkyl ethoxy carboxylates, the alkyl polyethoxy polycarboxylate surfactants and the soaps ('alkyl carboxyls'), especially certain secondary soaps as described herein.
  • Suitable alkyl ethoxy carboxylates include those with the formula RO(CH2CH2 ⁇ ) x CH2C00"M + wherein R is a C to C ⁇ 8 alkyl group, x ranges from O to 10, and the ethoxylate distribution is such that, on a weight basis, the amount of material where x is 0 is less than 20 % and M is a cation.
  • Suitable alkyl polyethoxy polycarboxylate surfactants include those having the formula RO-(CHR ⁇ -CHR2-O)-R3 wherein R is a Cg to C ⁇ g alkyl group, x is from 1 to 25, R ⁇ and R2 are selected from the group consisting of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid radical, and mixtures thereof, and R3 is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having between 1 and 8 carbon atoms, and mixtures thereof.
  • Suitable soap surfactants include the secondary soap surfactants which contain a carboxyl unit connected to a secondary carbon.
  • Preferred secondary soap surfactants for use herein are water-soluble members selected from the group consisting of the water-soluble salts of 2-methyl-l-undecanoic acid, 2-ethyl-l-decanoic acid, 2-propyl-l-nonanoic acid, 2- butyl-1-octanoic acid and 2-pentyl-l-heptanoic acid.
  • Certain soaps may also be included as suds suppressors.
  • alkali metal sarcosinates of formula R-CON (R 1 ) CH2 COOM, wherein R is a C5-C17 linear or branched alkyl or alkenyl group, R! is a Ci -C4 alkyl group and M is an alkali metal ion.
  • R is a C5-C17 linear or branched alkyl or alkenyl group
  • R! is a Ci -C4 alkyl group
  • M is an alkali metal ion.
  • a preferred effervescence system comprises an acid source, capable of reacting with an alkali source in the presence of water to produce a gas.
  • the acid source is preferably present at a level of from 0.5% o 35
  • the acid source or part thereof and the alkali source or part thereof are comprised in an intimate mixture, for example in the form of a compacted particle.
  • the molecular ratio of the acid source to the alkali source is preferably from 50:1 to 1 :50, more preferably from 20: 1 to 1 :20 more preferably from 10:1 to 1 :10, whereby when an intimate mixture of the acid source and the alkali source is present, this ratio is more preferably from 5:1 to 1 :3, more preferably from 3:1 to 1 :2, more preferably from 2:1 to 1 :2.
  • the acid source component may be any organic, mineral or inorganic acid, or a derivative thereof, or a mixture thereof.
  • the acid source component comprises an organic acid.
  • the acid compound is preferably substantially anhydrous or non-hygroscopic and the acid is preferably water-soluble. It may be preferred that the acid source is overdried.
  • Suitable acids source components include citric, malic, maleic, fumaric, aspartic, glutaric, tartaric succinic or adipic acid, monosodium phosphate, boric acid, or derivative thereof. Citric acid, maleic or malic acid are especially preferred.
  • the acid source provides acidic compounds which have an average particle size in the range of from about 75 microns to 1180 microns, more preferably from 150 microns to about 710 microns, calculated by sieving a sample of the source of acidity on a series of Tyler sieves.
  • the effervescence system preferably comprises an alkali source, however, for the pu ⁇ ose of the invention, it should be understood that the alkali source may be part of the effervescence particle or can be part of the cleaning composition comprising the particle, or can be present in the washing liquor, whereto the particle or the cleaning composition is added.
  • any alkali source which has the capacity to react with the acid source to produce a gas may be present in the particle, which may be any gas known in the art, including nitrogen ogygen and carbondioxide gas. Preferred can be perhydrate bleaches, including perborate, and silicate material.
  • the alkali source is preferably substantially anhydrous or non- hydroscopic. It may be preferred that the alkali source is overdried.
  • this gas is carbon dioxide
  • the alkali source is a preferably a source of carbonate, which can be any source of carbonate known in the art.
  • the carbonate source is a carbonate salt.
  • preferred carbonates are the alkaline earth and alkali metal carbonates, including sodium or potassium carbonate, bicarbonate and sesqui-carbonate and any mixtures thereof with ultra-fine calcium carbonate such as are disclosed in German Patent Application No. 2,321,001 published on November 15, 1973.
  • Alkali metal percarbonate salts are also suitable sources of carbonate species, which may be present combined with one or more other carbonate sources.
  • the carbonate and bicarbonate preferably have an amo ⁇ hous structure.
  • the carbonate and/ or bicarbonates may be coated with coating materials.
  • the particles of carbonate and bicarbonate can have a mean particle size of 75 microns or preferably 150 ⁇ m or greater, more preferably of 250 ⁇ m or greater, preferably 500 ⁇ m or greater.
  • the carbonate salt is such that fewer than 20%) (by weight) of the particles have a particle size below 500 ⁇ m, calculated by sieving a sample of the carbonate or bicarbonate on a series of Tyler sieves.
  • the fewer than 60%> or even 25%) of the particles have a particle size below 150 ⁇ m, whilst fewer than 5% has a particle size of more than 1.18 mm, more preferably fewer than 20%> have a particle size of more than 212 ⁇ m, calculated by sieving a sample of the carbonate or bicarbonate on a series of Tyler sieves.
  • compositions herein may contain additional detergent components.
  • additional detergent components The precise nature of these additional components, and levels of inco ⁇ oration thereof will depend on the physical form of the compositions comprising the builder component and the precise nature of the washing operation for which it is to be used.
  • Additional ingredients include additional builders, additional surfactants, bleach, enzymes, suds suppressors, lime soap, dispersants, soil suspension and anti-redeposition agents soil releasing agents, perfumes, brightners, photobleaching agents and additional corrosion inhibitors.
  • the composition preferably comprises one or more water-soluble or partially water- soluble builders.
  • crystalline layered silicates an organic carboxylates or carboxylic acids.
  • the preferred crystalline layered silicate herein have the general formula
  • M is sodium or hydrogen
  • x is a number from 1.9 to 4 and y is a number from 0 to 20.
  • Crystalline layered sodium silicates of this type are disclosed in EP-A-0164514 and methods for their preparation are disclosed in DE-A-3417649 and DE-A-3742043.
  • x in the general formula above has a value of 2, 3 or 4 and is preferably 2.
  • M is preferably H, K or Na or mixtures thereof, preferably Na.
  • the most preferred material is ⁇ -Na2Si2 ⁇ 5 ⁇ . Na2Si2 ⁇ 5 or ⁇ -Na2Si2 ⁇ 5, or mixtures thereof, preferably being at least 15% -Na2S-2 ⁇ 5 for example available from Clariant as NaSKS-6.
  • the crystalline layered silicate material in particular of the formula Na2S-2 ⁇ 5 may optionally comprise other elements such as B, P, S, for example obtained by processes as described in EP 578986-B.
  • the crystalline layered silicate may be in an intimate mixture with other materials, including one or more of surfactants of the surfactant system herein.
  • Preferred other materials are other water-soluble builders, including (poly) carboxylic acids and salts thereof, including polymeric compounds such as acrylic and/ or maleic acid polymers, inorganic acids or salts, including carbonates and sulphates, or small levels of other silicate material, including amo ⁇ hous silicate, meta silicates, and aluminosilicates, as described herein.
  • Suitable water-soluble builder compounds include the water soluble monomeric polycarboxylates, or their acid forms, homo or copolymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxylic radicals separated from each other by not more that two carbon atoms and mixtures of any of the foregoing.
  • the carboxylate or polycarboxylate builder can be momomeric or oligomeric in type although monomeric polycarboxylates are generally preferred for reasons of cost and performance.
  • polymeric polycarboxyltes may be present, including homo and copolymers of maleic acid and acrylic acid and their salts.
  • Suitable carboxylates containing one carboxy group include the water soluble salts of lactic acid, glycolic acid and ether derivatives thereof.
  • Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates and the sulfinyl carboxylates.
  • Polycarboxylates containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No.
  • Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed in British Patent No. 1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1, 3, 3 -propane tetracarboxylates and 1,1, 2, 3 -propane tetracarboxylates.
  • Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448, and the sulfonated pyrolysed citrates described in British Patent No. 1,439,000.
  • Preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.
  • Most preferred may be citric acid, malic acid, and fumaric acid, or their salts or mixtures thereof.
  • the parent acids of the monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts are also contemplated as useful builder components.
  • any alkoxylated nonionic surfactants are suitable herein.
  • the ethoxylated and propoxylated nonionic surfactants are preferred.
  • Preferred alkoxylated surfactants can be selected from the classes of the nonionic condensates of alkyl phenols, nonionic ethoxylated alcohols, nonionic ethoxylated/propoxylated fatty alcohols, nonionic ethoxylate/propoxylate condensates with propylene glycol, and the nonionic ethoxylate condensation products with propylene oxide/ethylene diamine adducts.
  • the condensation products of aliphatic alcohols with from 1 to 25 moles of alkylene oxide, particularly ethylene oxide and/or propylene oxide, are suitable for use herein.
  • the alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from 6 to 22 carbon atoms.
  • Particularly preferred are the condensation products of alcohols having an alkyl group containing from 8 to 20 carbon atoms with from 2 to 10 moles of ethylene oxide per mole of alcohol.
  • Polyhydroxy fatty acid amides suitable for use herein are those having the structural formula R ⁇ CONR ⁇ Z wherein : Rl is H, Ci -C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, ethoxy, propoxy, or a mixture thereof, preferable C1-C4 alkyl, more preferably C ⁇ or C2 alkyl, most preferably C ⁇ alkyl (i.e., methyl); and R2 is a C5-C31 hydrocarbyl, preferably straight-chain C5-C19 alkyl or alkenyl, more preferably straight-chain C9-C17 alkyl or alkenyl, most preferably straight-chain Ci 1 -Ci 7 alkyl or alkenyl, or mixture thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof.
  • Nonionic Fatty Acid Amide Surfactant Suitable fatty acid amide surfactants include those having the formula: R ⁇ CON(R ⁇ )2 wherein R ⁇ is an alkyl group containing from 7 to 21, preferably from 9 to 17 carbon atoms and each R is selected from the group consisting of hydrogen, C1 -C4 alkyl, Cj-
  • Suitable alkylpolysaccharides for use herein are disclosed in U.S. Patent 4,565,647, Llenado, issued January 21, 1986, having a hydrophobic group containing from 6 to 30 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group containing from 1.3 to 10 saccharide units.
  • Preferred alkylpolyglycosides have the formula:
  • R 2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from 10 to 18 carbon atoms; n is 2 or 3; t is from 0 to 10, and x is from 1.3 to 8.
  • the glycosyl is preferably derived from glucose.
  • Suitable amphoteric surfactants for use herein include the amine oxide surfactants and the alkyl amphocarboxylic acids.
  • Suitable amine oxides include those compounds having the formula R (OR4) X NO(R5) 2 wherein R ⁇ is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containing from 8 to 26 carbon atoms; R ⁇ is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms, or mixtures thereof; x is from 0 to 5, preferably from 0 to 3; and each R ⁇ is an alkyl or hydroxyalkyl group containing from 1 to 3, or a polyethylene oxide group containing from 1 to 3 ethylene oxide groups.
  • Preferred are Ci Q-CJ alkyl dimethylamine oxide, and Ci Q-18 acylamido alkyl dimethylamine oxide.
  • a suitable example of an alkyl aphodicarboxylic acid is Miranol(TM) C2M Cone, manufactured by Miranol, Inc., Dayton, NJ.
  • Zwitterionic surfactants can also be inco ⁇ orated into the detergent compositions in accord with the invention. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Betaine and sultaine surfactants are exemplary zwitterionic surfactants for use herein.
  • Suitable betaines are those compounds having the formula R(R')2N + R2C00" wherein R is a Cg-Ci 8 hydrocarbyl group, each R* is typically C1 -C3 alkyl, and R2 is a C1 -C5 hydrocarbyl group.
  • Preferred betaines are C ⁇ 2 _ ⁇ 8 dimethyl-ammonio hexanoate and the Ci 0-18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines.
  • Complex betaine surfactants are also suitable for use herein.
  • Suitable cationic surfactants to be used in the detergent herein include the quaternary ammonium surfactants.
  • the quaternary ammonium surfactant is a mono Cg-
  • C1 g preferably Cg-Ci Q N-alkyl or alkenyl ammonium surfactants wherein the remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.
  • Preferred are also the mono-alkoxylated and bis-alkoxylated amine surfactants.
  • cationic ester surfactants Another suitable group of cationic surfactants which can be used in the detergent compositions or components thereof herein are cationic ester surfactants.
  • the cationic ester surfactant is a, preferably water dispersible, compound having surfactant properties comprising at least one ester (i.e. -COO-) linkage and at least one cationically charged group.
  • Suitable cationic ester surfactants including choline ester surfactants, have for example been disclosed in US Patents No.s 4228042, 4239660 and 4260529.
  • ester linkage and cationically charged group are separated from each other in the surfactant molecule by a spacer group consisting of a chain comprising at least three atoms (i.e. of three atoms chain length), preferably from three to eight atoms, more preferably from three to five atoms, most preferably three atoms.
  • the atoms forming the spacer group chain are selected from the group consisting of carbon, nitrogen and oxygen atoms and any mixtures thereof, with the proviso that any nitrogen or oxygen atom in said chain connects only with carbon atoms in the chain.
  • spacer groups having, for example, -O-O- (i.e.
  • spacer groups having, for example -CH 2 -O- CH2- and -CH2-NH-CH2- linkages are included.
  • the spacer group chain comprises only carbon atoms, most preferably the chain is a hydrocarbyl chain.
  • cationic mono-alkoxylated amine surfactant preferably of the general formula I:
  • R! is an alkyl or alkenyl moiety containing from about 6 to about 18 carbon atoms, preferably 6 to about 16 carbon atoms, most preferably from about 6 to about 14 carbon atoms;
  • R2 and R ⁇ are each independently alkyl groups containing from one to about three carbon atoms, preferably methyl, most preferably both R2 and R ⁇ are methyl groups;
  • R ⁇ is selected from hydrogen (preferred), methyl and ethyl;
  • X" is an anion such as chloride, bromide, methylsulfate, sulfate, or the like, to provide electrical neutrality;
  • A is a alkoxy group, especially a ethoxy, propoxy or butoxy group; and
  • p is from 0 to about 30, preferably 2 to about 15, most preferably 2 to about 8.
  • Particularly preferred ApR ⁇ groups are — CH 2 CH 2 OH, — CH 2 CH 2 CH2OH, — CH 2 CH(CH 3 )OH and —
  • R 1 groups are linear alkyl groups. Linear R* groups having from 8 to 14 carbon atoms are preferred.
  • Another highly preferred cationic mono-alkoxylated amine surfactants for use herein are of the formula
  • R* is Ci Q-CI 8 hydrocarbyl and mixtures thereof, especially CJ Q-CH alkyl, preferably C ⁇ Q and C ⁇ 2 alkyl, and X is any convenient anion to provide charge balance, preferably chloride or bromide.
  • the levels of the cationic mono-alkoxylated amine surfactants used in detergent compositions of the invention is preferably from 0.1 %> to 20%>, more preferably from 0.2%) to 7%>, most preferably from 0.3%) to 3.0%> by weight of the composition.
  • the cationic bis-alkoxylated amine surfactant preferably has the general formula II:
  • R! is an alkyl or alkenyl moiety containing from about 8 to about 18 carbon atoms, preferably 10 to about 16 carbon atoms, most preferably from about 10 to about 14 carbon atoms;
  • R2 is an alkyl group containing from one to three carbon atoms, preferably methyl;
  • R ⁇ and R ⁇ can vary independently and are selected from hydrogen (preferred), methyl and ethyl,
  • X" is an anion such as chloride, bromide, methylsulfate, sulfate, or the like, sufficient to provide electrical neutrality.
  • a and A' can vary independently and are each selected from Ci -C4 alkoxy, especially ethoxy, (i.e., -CH2CH2O-), propoxy, butoxy and mixtures thereof; p is from 1 to about 30, preferably 1 to about 4 and q is from 1 to about 30, preferably 1 to about 4, and most preferably both p and q are 1.
  • RI is CJ Q-CI S hydrocarbyl and mixtures thereof, preferably Ci Q, C ⁇ 2 > C14 alkyl and mixtures thereof.
  • X is any convenient anion to provide charge balance, preferably chloride.
  • cationic bis-alkoxylated amine surfactants useful herein include compounds of the formula:
  • R is CI Q-CI hydrocarbyl, preferably Ci 0-C14 alkyl, independently p is 1 to about 3 and q is 1 to about 3, R2 is Ci -C3 alkyl, preferably methyl, and X is an anion, especially chloride or bromide.
  • compositions herein is an oxygen bleach, preferably comprising a hydrogen peroxide source and a bleach precursor or activator.
  • a prferred source of hydrogen peroxide is a perhydrate bleach, such as metal perborates, more preferably metal percarbonates, particularly the sodium salts.
  • Perborate can be mono or tetra hydrated.
  • Sodium percarbonate has the formula corresponding to 2Na2C ⁇ 3-3H2 ⁇ 2, and is available commercially as a crystalline solid.
  • percarbonate salts are preferably coated.
  • Suitable coating agent are known in the art, and include silicates, magnesium salts and carbonates salts.
  • Potassium peroxymonopersulfate, sodium per is another optional inorganic perhydrate salt of use in the detergent compositions herein.
  • a preferred feature of the composition herein is an organic peroxyacid bleaching system.
  • the bleaching system contains a hydrogen peroxide source and an organic peroxyacid bleach precursor compound.
  • the production of the organic peroxyacid occurs by an in situ reaction of the precursor with a source of hydrogen peroxide.
  • Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches, such as the perborate bleach of the claimed invention.
  • a preformed organic peroxyacid is inco ⁇ orated directly into the composition.
  • Compositions containing mixtures of a hydrogen peroxide source and organic peroxyacid precursor in combination with a preformed organic peroxyacid are also envisaged.
  • Peroxyacid bleach precursors are compounds which react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid.
  • peroxyacid bleach precursors may be represented as
  • L is a leaving group and X is essentially any functionality, such that on perhydroloysis the structure of the peroxyacid produced is
  • Peroxyacid bleach precursor compounds are preferably inco ⁇ orated at a level of from 0.5%) to 20%) by weight, more preferably from 1%> to 15%> by weight, most preferably from 1.5% to 10%> by weight of the detergent compositions.
  • Suitable peroxyacid bleach precursor compounds typically contain one or more N- or O- acyl groups, which precursors can be selected from a wide range of classes.
  • Suitable classes include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. Examples of useful materials within these classes are disclosed in GB-A- 1586789. Suitable esters are disclosed in GB-A-836988, 864798, 1147871, 2143231 and EP-A-0170386. Leaving Groups
  • L group The leaving group, hereinafter L group, must be sufficiently reactive for the perhydrolysis reaction to occur within the optimum time frame (e.g., a wash cycle). However, if L is too reactive, this activator will be difficult to stabilize for use in a bleaching composition.
  • Preferred L groups are selected from the group consisting of:
  • R is an alkyl, aryl, or alkaryl group containing from 1 to
  • R 3 is an alkyl chain containing from 1 to 8 carbon atoms
  • R 4 is H or
  • R 3 , and Y is H or a solubilizing group.
  • Any of R 1 , R3 and R 4 may be substituted by essentially any functional group including, for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl ammmonium groups.
  • the preferred solubilizing groups are -SO., M , -CO-, M , -SO . M , -N (R ) ,X and
  • 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.
  • Alkyl percarboxylic acid bleach precursors form percarboxylic acids on perhydrolysis.
  • Preferred precursors of this type provide peracetic acid on perhydrolysis.
  • Preferred alkyl percarboxylic precursor compounds of the imide type include the N-
  • TAED Tetraacetyl ethylene diamine
  • the TAED is preferably not present in the agglomerated particle of the present invention, but preferably present in the detergent composition, comprising the particle.
  • alkyl percarboxylic acid precursors include sodium 3,5,5-tri-methyl hexanoyloxybenzene sulfonate (iso-NOBS), sodium nonanoyloxybenzene sulfonate (NOBS), sodium acetoxybenzene sulfonate (ABS) and pentaacetyl glucose.
  • Amide substituted alkyl peroxyacid precursor compounds are suitable herein, including those of the following general formulae:
  • R is an alkyl group with from 1 to 14 carbon atoms
  • R2 is an alkylene group containing from 1 to 14 carbon atoms
  • R ⁇ is H or an alkyl group containing 1 to 10 carbon atoms and L can be essentially any leaving group.
  • Amide substituted bleach activator compounds of this type are described in EP-A-0170386.
  • Perbenzoic acid precursor compounds provide perbenzoic acid on perhydrolysis.
  • Suitable O-acylated perbenzoic acid precursor compounds include the substituted and unsubstituted benzoyl oxybenzene sulfonates, and the benzoylation products of sorbitol, glucose, and all saccharides with benzoylating agents, and those of the imide type including N-benzoyl succinimide, tetrabenzoyl ethylene diamine and the N-benzoyl substituted ureas.
  • Suitable imidazole type perbenzoic acid precursors include N-benzoyl imidazole and N-benzoyl benzimidazole.
  • Other useful N-acyl group-containing perbenzoic acid precursors include N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic acid.
  • the detergent composition may contain, in addition to, or as an alternative to, an organic peroxyacid bleach precursor compound, a preformed organic peroxyacid , typically at a level of from 1%> to 15% by weight, more preferably from 1%> to 10%> by weight of the composition.
  • a preferred class of organic peroxyacid compounds are the amide substituted compounds of the following general formulae:
  • R is an alkyl, 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
  • R ⁇ is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms.
  • Amide substituted organic peroxyacid compounds of this type are described in EP-A-0170386.
  • organic peroxyacids include diacyl and tetraacylperoxides, especially diperoxydodecanedioc acid, diperoxytetradecanedioc acid and diperoxyhexadecanedioc acid.
  • diacyl and tetraacylperoxides especially diperoxydodecanedioc acid, diperoxytetradecanedioc acid and diperoxyhexadecanedioc acid.
  • Mono- and diperazelaic acid, mono- and diperbrassylic acid and N- phthaloylaminoperoxicaproic acid are also suitable herein.
  • Heavy Metal Ion Sequestrant are also useful additional ingredients herein.
  • heavy metal ion sequestrant it is meant herein components which act to sequester (chelate) heavy metal ions. These components may also have a limited calcium and magnesium chelation capacity, but preferentially they show selectivity to binding heavy metal ions such as iron, manganese and copper. The are thus not considered builders for the pu ⁇ ose of the invention.
  • Heavy metal ion sequestrants are generally present at a level of from 0.005%) to 10%>, preferably from 0.1% to 5%>, more preferably from 0.25%> to 7.5% and most preferably from 0.3%) to 2%> by weight of the compositions.
  • Suitable heavy metal ion sequestrants for use herein include organic phosphonates, such as the amino alkylene poly (alkylene phosphonates), alkali metal ethane 1 -hydroxy disphosphonates and nitrilo trimethylene phosphonates.
  • Preferred among the above species are diethylene triamine penta (methylene phosphonate), ethylene diamine tri (methylene phosphonate) hexamethylene diamine tetra (methylene phosphonate) and hydroxy-ethylene 1,1 diphosphonate, 1,1 hydroxyethane diphosphonic acid and 1,1 hydroxyethane dimethylene phosphonic acid.
  • Suitable heavy metal ion sequestrant for use herein include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminotetracetic acid, ethylenediamine disuccinic acid, ethylenediamine diglutaric acid, 2-hydroxypropylenediamine disuccinic acid or any salts thereof.
  • Suitable heavy metal ion sequestrants for use herein are iminodiacetic acid derivatives such as 2-hydroxyethyl diacetic acid or glyceryl imino diacetic acid, described in EP-A-317,542 and EP-A-399,133.
  • iminodiacetic acid-N-2-hydroxypropyl sulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropy 1-3 -sulfonic acid sequestrants described in EP-A-516,102 are also suitable herein.
  • EP-A-476,257 describes suitable amino based sequestrants.
  • EP-A-510,331 describes suitable sequestrants derived from collagen, keratin or casein.
  • EP-A- 528,859 describes a suitable alkyl iminodiacetic acid sequestrant. Dipicolinic acid and 2-phosphonobutane-l,2,4-tricarboxylic acid are alos suitable.
  • Glycinamide- N,N'-disuccinic acid (GADS), ethylenediamine-N-N'-diglutaric acid (EDDG) and 2- hydroxypropylenediamine-N-N'-disuccinic acid (HPDDS) are also suitable.
  • diethylenetriamine pentacetic acid ethylenediamine-N,N'- disuccinic acid (EDDS) and 1,1 hydroxyethane diphosphonic acid or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof.
  • EDDS ethylenediamine-N,N'- disuccinic acid
  • 1,1 hydroxyethane diphosphonic acid or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof.
  • Another preferred ingredient useful herein is one or more additional enzymes.
  • Preferred additional enzymatic materials include the commercially available lipases, cutinases, amylases, neutral and alkaline proteases, cellulases, endolases, esterases, pectinases, lactases and peroxidases conventionally inco ⁇ orated into detergent compositions. Suitable enzymes are discussed in US Patents 3,519,570 and 3,533,139.
  • Organic polymeric compounds are preferred additional components of the compositions herein.
  • organic polymeric compound it is meant herein essentially any polymeric organic compound commonly used as binder, dispersants, and anti-redeposition and soil suspension agents in detergent compositions, including any of the high molecular weight organic polymeric compounds described as clay flocculating agents herein, including quateraised ethoxylated (poly) amine clay-soil removal/ anti-redeposition agent.
  • Organic polymeric compound is typically inco ⁇ orated in the detergent compositions of the invention at a level of from 0.01% to 30%), preferably from 0.1%> to 15%, most preferably from 0.5%> to 10%> by weight of the compositions.
  • organic polymeric compounds include the water soluble organic homo- or co-polymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms.
  • Polymers of the latter type are disclosed in GB-A-1, 596,756.
  • salts are polyacrylates of MWt 1000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 2000 to 100,000, especially 40,000 to 80,000.
  • polyamino compounds are useful herein including those derived from aspartic acid such as those disclosed in EP-A-305282, EP-A-305283 and EP-A-351629.
  • Te ⁇ olymers containing monomer units selected from maleic acid, acrylic acid, polyaspartic acid and vinyl alcohol, particularly those having an average molecular weight of from 5,000 to 10,000, are also suitable herein.
  • organic polymeric compounds suitable for inco ⁇ oration in the detergent compositions herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose and hydroxyethylcellulose.
  • Further useful organic polymeric compounds are the polyethylene glycols, particularly those of molecular weight 1000-10000, more particularly 2000 to 8000 and most preferably about 4000.
  • Highly preferred polymeric components herein are cotton and non-cotton soil release polymer according to U.S. Patent 4,968,451, Scheibel et al., and U.S. Patent 5,415,807, Gosselink et al., and in particular according to US application no.60/051517.
  • Another organic compound which is a preferred clay dispersant anti-redeposition agent, for use herein, can be the ethoxylated cationic monoamines and diamines of the formula:
  • X is a nonionic group selected from the group consisting of H, C -C4 alkyl or hydroxyalkyl ester or ether groups, and mixtures thereof
  • a is from 0 to 20, preferably from 0 to 4 (e.g. ethylene, propylene, hexamethylene)
  • the detergent compositions of the invention when formulated for use in machine washing compositions, may comprise a suds suppressing system present at a level of from 0.01% to 15%, preferably from 0.02% to 10%, most preferably from 0.05% to 3% by weight of the composition.
  • Suitable suds suppressing systems for use herein may comprise essentially any known antifoam compound, including, for example silicone antifoam compounds and 2-alkyl alcanol antifoam compounds.
  • antifoam compound any compound or mixtures of compounds which act such as to depress the foaming or sudsing produced by a solution of a detergent composition, particularly in the presence of agitation of that solution.
  • Particularly preferred antifoam compounds for use herein are silicone antifoam compounds defined herein as any antifoam compound including a silicone component. Such silicone antifoam compounds also typically contain a silica component.
  • silicone antifoam compounds as used herein, and in general throughout the industry, encompasses a variety of relatively high molecular weight polymers containing siloxane units and hydrocarbyl group of various types.
  • Preferred silicone antifoam compounds are the siloxanes, particularly the polydimethylsiloxanes having trimethylsilyl end blocking units.
  • Suitable antifoam compounds include the monocarboxylic fatty acids and soluble salts thereof. These materials are described in US Patent 2,954,347, issued September 27, 1960 to Wayne St. John.
  • the monocarboxylic fatty acids, and salts thereof, for use 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.
  • Suitable antifoam compounds include, for example, high molecular weight fatty esters (e.g. fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C 8-C40 ketones (e.g. stearone) 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, bis stearic acid amide and monostearyl di-alkali metal (e.g. sodium, potassium, lithium) phosphates and phosphate esters.
  • high molecular weight fatty esters e.g. fatty acid triglycerides
  • fatty acid esters of monovalent alcohols e.g. fatty acid esters of monovalent alcohols
  • a preferred suds suppressing system comprises:
  • antifoam compound preferably silicone antifoam compound, most preferably a silicone antifoam compound comprising in combination
  • silica at a level of from 1 % to 50%), preferably 5% to 25% by weight of the silicone/silica antifoam compound;
  • silica/silicone antifoam compound is inco ⁇ orated at a level of from 5% to 50%, preferably 10% to 40% by weight;
  • a dispersant compound most preferably comprising a silicone glycol rake copolymer with a polyoxyalkylene content of 72-78%) and an ethylene oxide to propylene oxide ratio of from 1 :0.9 to 1 : 1.1 , at a level of from 0.5%> to 10%>, preferably 1%> to 10% by weight;
  • a particularly preferred silicone glycol rake copolymer of this type is DCO544, commercially available from DOW Corning under the tradename DCO544;
  • an inert carrier fluid compound most preferably comprising a C ⁇ -C ⁇ 8 ethoxylated alcohol with a degree of ethoxylation of from 5 to 50, preferably 8 to 15, at a level of from 5% to 80%, preferably 10% to 70%, by weight;
  • a highly preferred particulate suds suppressing system is described in EP-A-0210731 and comprises a silicone antifoam compound and an organic carrier material having a melting point in the range 50°C to 85°C, wherein the organic carrier material comprises a monoester of glycerol and a fatty acid having a carbon chain containing from 12 to 20 carbon atoms.
  • EP-A-0210721 discloses other preferred particulate suds suppressing systems wherein the organic carrier material is a fatty acid or alcohol having a carbon chain containing from 12 to 20 carbon atoms, or a mixture thereof, with a melting point of from 45°C to 80°C.
  • the organic carrier material is a fatty acid or alcohol having a carbon chain containing from 12 to 20 carbon atoms, or a mixture thereof, with a melting point of from 45°C to 80°C.
  • suds suppressing systems comprise polydimethylsiloxane or mixtures of silicone, such as polydimethylsiloxane, aluminosilicate and polycarboxylic polymers, such as copolymers of laic and acrylic acid.
  • compositions herein may also comprise from 0.01%> to 10 %>, preferably from 0.05% to 0.5%) by weight of polymeric dye transfer inhibiting agents.
  • the polymeric dye transfer inhibiting agents are preferably selected from polyamine N- oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidonepolymers or combinations thereof, whereby these polymers can be cross-linked polymers.
  • compositions herein also optionally contain from about 0.005% to 5%> by weight of certain types of hydrophilic optical brighteners, as known in the art.
  • Polymeric Soil Release Agent
  • SRA Polymeric soil release agents, hereinafter "SRA" can optionally be employed in the present compositions. If utilized, SRA's will generally comprise from 0.01% to 10.0%, typically from 0.1 % to 5%, preferably from 0.2% to 3.0%> by weight, of the compositions.
  • Preferred SRA's typically have 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, thereby serving as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to treatment with the SRA to be more easily cleaned in later washing procedures.
  • Preferred SRA's include oligomeric terephthalate esters, typically prepared by processes involving at least one transesterification/oligomerization, often with a metal catalyst such as a titanium(IV) alkoxide.
  • esters may be made using additional monomers capable of being inco ⁇ orated into the ester structure through one, two, three, four or more positions, without, of course, forming a densely crosslinked overall structure.
  • Suitable SRA's include a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and allyl-derived sulfonated terminal moieties covalently attached to the backbone, for example as described in U.S. 4,968,451, November 6, 1990 to J.J. Scheibel and E.P. Gosselink.
  • ester oligomers can be prepared by: (a) ethoxylating allyl alcohol; (b) reacting the product of (a) with dimethyl terephthalate (“DMT”) and 1 ,2-propylene glycol (“PG”) in a two-stage transesterif ⁇ cation/oligomerization procedure; and (c) reacting the product of (b) with sodium metabisulfite in water.
  • DMT dimethyl terephthalate
  • PG ,2-propylene glycol
  • SRA's include the nonionic end- capped 1 ,2-propylene/polyoxyethylene terephthalate polyesters of U.S.
  • Gosselink et al. for example those produced by transesterification/oligomerization of poly(ethyleneglycol) methyl ether, DMT, PG and poly(ethyleneglycol) ("PEG").
  • SRA's include: the partly- and fully- anionic-end-capped oligomeric esters of U.S. 4,721,580, January 26, 1988 to Gosselink, such as oligomers from ethylene glycol ("EG"), PG, DMT and Na-3,6-dioxa-8- hydroxyoctanesulfonate; the nonionic-capped block polyester oligomeric compounds of U.S.
  • Gosselink for example produced from DMT, methyl (Me)-capped PEG and EG and/or PG, or a combination of DMT, EG and/or PG, Me-capped PEG and Na-dimethyl-5-sulfoisophthalate; and the anionic, especially sulfoaroyl, end-capped terephthalate esters of U.S.
  • SRA's also include: simple copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, see U.S. 3,959,230 to Hays, May 25, 1976 and U.S. 3,893,929 to Basadur, July 8, 1975; cellulosic derivatives such as the hydroxyether cellulosic polymers available as METHOCEL from Dow; the C1-C4 alkyl celluloses and C4 hydroxyalkyl celluloses, see U.S. 4,000,093,
  • methyl cellulose ethers having an average degree of substitution (methyl) per anhydroglucose unit from about 1.6 to about 2.3 and a solution viscosity of from about 80 to about 120 centipoise measured at 20°C as a 2%> aqueous solution.
  • Such materials are available as METOLOSE SMI 00 and METOLOSE SM200, which are the trade names of methyl cellulose ethers manufactured by Shin-etsu Kagaku Kogyo KK.
  • SRA's include: (I) nonionic terephthalates using diisocyanate coupling agents to link polymeric ester structures, see U.S. 4,201,824, Violland et al. and U.S. 4,240,918 Lagasse et al.; and (II) SRA's with carboxylate terminal groups made by adding trimellitic anhydride to known SRA's to convert terminal hydroxyl groups to trimellitate esters. With the proper selection of catalyst, the trimellitic anhydride forms linkages to the terminals of the polymer through an ester of the isolated carboxylic acid of trimellitic anhydride rather than by opening of the anhydride linkage.
  • Either nonionic or anionic SRA's may be used as starting materials as long as they have hydroxyl terminal groups which may be esterified. See U.S. 4,525,524 Tung et al..
  • Other classes include: (III) anionic terephthalate-based SRA's of the urethane-Iinked variety, see U.S. 4,201,824, Violland et al.;
  • compositions of the invention include perfumes, speckles, colours or dyes, filler salts, with sodium sulfate being a preferred filler salt.
  • encapsulated perfumes preferably comprising a starch encapsulte.
  • compositions of the invention it may be preferred that when dyes and/ or perfumes are sprayed onto the another component, the component does not comprise spray-on nonionic alkoxylated alcohol surfactant.
  • composition of the invention thereof can be made via a variety of methods involving the mixing of ingredients, including dry-mixing, compaction such as agglomerating, extrusion, tabletting, or spray-drying of the various compounds comprised in the detergent component, or mixtures of these techniques, whereby the components herein also can be made by for example compaction, including extrusion and agglomerating, or spray-drying.
  • compositions herein can take a variety of physical solid forms including forms such as tablet, flake, pastille and bar, and preferably the composition is in the form of granules or a tablet.
  • compositions in accord with the present invention can also be used in or in combination with bleach additive compositions, for example comprising chlorine bleach.
  • compositions preferably have a density of more than 350 gr/litre, more preferably more than 450 gr/litre or even more than 570 gr/litre.
  • Na ⁇ 2 (AlO 2 SiO 2 ) ⁇ .27H 2 O having a primary particle size in the range from 0.1 to 10 micrometers (weight expressed on an anhydrous basis)
  • NaSKS-6 (II) Crystalline layered silicate of formula ⁇ - Na 2 Si 2 O5 0 f weight average particle size of 18 microns and at least 90% by weight being of particle size of below 42.1 microns.
  • Citric acid Anhydrous citric acid
  • Silicate Amo ⁇ hous sodium silicate (SiO 2 :Na 2 O 2.0:1)
  • Protease Proteolytic enzyme having 3.3%> by weight of active enzyme, sold by NOVO Industries A/S under the tradename Savinase
  • Protease I Proteolytic enzyme, having 4%> by weight of active enzyme, as described in WO 95/10591, sold by Genencor
  • Alcalase Proteolytic enzyme having 5.3%> by weight of active enzyme, sold by NOVO Industries A/S
  • Amylase Amylolytic enzyme having 1.6% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Termamyl 120T
  • Amylase II Amylolytic enzyme as disclosed in PCT/ US9703635 Lipase Lipolytic enzyme, having 2.0%) by weight of active enzyme, sold by NOVO Industries A/S under the tradename Lipolase
  • Lipase (1) Lipolytic enzyme, having 2.0%) by weight of active enzyme, sold by NOVO Industries A/S under the tradename Lipolase Ultra
  • Endolase Endoglucanase enzyme having 1.5% by weight of active enzyme, sold by NOVO Industries A/S PB4 Sodium perborate tetrahydrate of nominal formula
  • NACA-OBS (6-nonamidocaproyl) oxybenzene sulfonate
  • DOBS Decanoyloxybenzene sulfonate in the form of the sodium salt
  • Photoactivated bleach Sulfonated zinc phthlocyanine or sulfonated alumino phthlocyanine encapsulated in or carried by a soluble polymer
  • Brightener 1 Disodium 4,4'-bis(2-sulphostyryl)biphenyl
  • Brightener 2 Disodium 4,4'-bis(4-anilino-6-mo ⁇ holino-l .3.5-triazin-2- yl)amino) stilbene-2 :2'-disulfonate
  • HEDP 1,1 -hydroxyethane diphosphonic acid PEGx Polyethylene glycol, with a molecular weight of x
  • PVPVI Copolymer of polyvinylpyrolidone and vinylimidazole with an average molecular weight of 20,000
  • SRP 1 Anionically end capped poly esters
  • SRP 2 Diethoxylated poly (1, 2 propylene terephtalate) short block polymer
  • Opacifier Water based monostyrene latex mixture, sold by BASF

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

Compositions détergentes solides qui contiennent un adjuvant aluminosilicate et un tensioactif anionique et comprennent (n) constituants (i), (n) étant égal à 2 au moins. Le niveau de l'adjuvant aluminosilicate par rapport au total desdits constituants est d'au moins 5 % en poids de la composition et le niveau du tensioactif anionique par rapport au total desdits constituants est d'au moins 5 % en poids de la composition, le degré de mélange (M) du tensioactif anionique et de l'adjuvant aluminosilicate étant de 0 à 0,7, tel que défini dans le descriptif.
PCT/US1998/020221 1998-06-21 1998-09-25 Compositions detergentes solides WO2000018869A1 (fr)

Priority Applications (38)

Application Number Priority Date Filing Date Title
ES98948561T ES2283074T3 (es) 1998-09-25 1998-09-25 Composiciones detergentes solidas.
CN98814316.XA CN1322242A (zh) 1998-09-25 1998-09-25 洗涤剂组合物
AU95108/98A AU9510898A (en) 1998-09-25 1998-09-25 Solid detergent compositions
JP2000572317A JP2002525419A (ja) 1998-09-25 1998-09-25 固体洗剤組成物
AT98948561T ATE357500T1 (de) 1998-09-25 1998-09-25 Feste reinigungszusammensetzungen
MXPA01003081 MXPA01003081A (es) 1998-09-25 1998-09-25 Composiciones detergentes soli
PCT/US1998/020221 WO2000018869A1 (fr) 1998-09-25 1998-09-25 Compositions detergentes solides
BRPI9816031-1A BR9816031B1 (pt) 1998-09-25 1998-09-25 composição detergente sólida compreendendo um builder de aluminossilicato e um tensoativo aniÈnico.
CA002344434A CA2344434C (fr) 1998-09-25 1998-09-25 Compositions detergentes solides
DE69837403T DE69837403T2 (de) 1998-09-25 1998-09-25 Feste reinigungszusammensetzungen
US09/787,454 US6964945B1 (en) 1998-09-25 1998-09-25 Solid detergent compositions
EP98948561A EP1115831B1 (fr) 1998-09-25 1998-09-25 Compositions detergentes solides
MXPA01003097 MX227672B (en) 1998-09-25 1998-09-25 Solid detergent compositions
JP2000572318A JP2003522213A (ja) 1998-09-25 1998-10-05 洗剤組成物
CA002343895A CA2343895C (fr) 1998-09-25 1998-10-05 Compositions detergentes
CNB988143275A CN1168815C (zh) 1998-09-25 1998-10-05 洗涤剂组合物
EP98950950A EP1115832A1 (fr) 1998-09-25 1998-10-05 Compositions detergentes
BRPI9816029-0A BR9816029B1 (pt) 1998-09-25 1998-10-05 composição detergente sólida.
AU96862/98A AU9686298A (en) 1998-09-25 1998-10-05 Detergent compositions
PCT/US1998/021022 WO2000018870A1 (fr) 1998-09-25 1998-10-05 Compositions detergentes
US09/787,455 US6630439B1 (en) 1998-09-25 1998-10-05 Solid detergent compositions comprising sesquicarbonate
CN99813557A CN1328597A (zh) 1998-09-25 1999-09-20 颗粒状洗涤剂
IN197DE2001 IN243977B (fr) 1998-09-25 1999-09-20
CA002344997A CA2344997C (fr) 1998-09-25 1999-09-20 Granules detergents
DE69923196T DE69923196T2 (de) 1998-09-25 1999-09-20 Waschmittelgranulate
BRPI9914050-0A BR9914050B1 (pt) 1998-09-25 1999-09-20 gránulo ou tablete de detergente que compreende um sistema tensoativo aniÈnico que compreende um tensoativo de sulfato aniÈnico e um tensoativo de sulfonato aniÈnico e outros ingredientes ativos detergentes, processo para a sua obtenção e composição detergente.
ES99949767T ES2237161T3 (es) 1998-09-25 1999-09-20 Granulos detergentes.
JP2000572306A JP2002525417A (ja) 1998-09-25 1999-09-20 洗剤顆粒
AT99949767T ATE286960T1 (de) 1998-09-25 1999-09-20 Waschmittelgranulate
AU62570/99A AU6257099A (en) 1998-09-25 1999-09-20 Detergent granules
US09/787,451 US6635610B1 (en) 1998-09-25 1999-09-20 Detergent granules
EP99949767A EP1115819B1 (fr) 1998-09-25 1999-09-20 Granules de detergent
PCT/US1999/021843 WO2000018856A1 (fr) 1998-09-25 1999-09-20 Granules detergents
ZA9906130A ZA996130B (en) 1998-09-25 1999-09-23 Detergent compositions.
PH11999002387A PH11999002387B1 (en) 1998-09-25 1999-09-24 Detergent granules
ARP990104819A AR020515A1 (es) 1998-09-25 1999-09-24 Composiciones detergentes.
ARP990104820A AR028137A1 (es) 1998-06-21 1999-09-24 Granulos de detergente
ARP990104818A AR026850A1 (es) 1998-09-25 1999-09-24 Composicion detergente que comprende mejorador de detergencia de aluminosilicato y surfactante anionico, en forma efervescente particulada o en tabletas yuso para mejorar suministro de detergente

Applications Claiming Priority (1)

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PCT/US1998/020221 WO2000018869A1 (fr) 1998-09-25 1998-09-25 Compositions detergentes solides

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US09/787,451 Continuation US6635610B1 (en) 1998-09-25 1999-09-20 Detergent granules

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AR (1) AR026850A1 (fr)
AT (1) ATE357500T1 (fr)
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CA (1) CA2344434C (fr)
DE (1) DE69837403T2 (fr)
ES (1) ES2283074T3 (fr)
MX (2) MXPA01003081A (fr)
WO (1) WO2000018869A1 (fr)
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Cited By (1)

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Publication number Priority date Publication date Assignee Title
WO2004053050A1 (fr) * 2002-12-07 2004-06-24 Unilever Plc Compositions detergentes

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JP5785747B2 (ja) * 2011-03-18 2015-09-30 ライオン株式会社 粒状洗剤組成物

Citations (1)

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Publication number Priority date Publication date Assignee Title
WO1997032952A1 (fr) * 1996-03-08 1997-09-12 The Procter & Gamble Company Preparation de particules de sulfate alkyle secondaire possedant une meilleure solubilite

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997032952A1 (fr) * 1996-03-08 1997-09-12 The Procter & Gamble Company Preparation de particules de sulfate alkyle secondaire possedant une meilleure solubilite

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004053050A1 (fr) * 2002-12-07 2004-06-24 Unilever Plc Compositions detergentes
US7208461B2 (en) 2002-12-07 2007-04-24 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Detergent compositions
CN1324122C (zh) * 2002-12-07 2007-07-04 荷兰联合利华有限公司 洗涤剂组合物

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CA2344434C (fr) 2005-10-18
MXPA01003081A (es) 2001-09-01
ATE357500T1 (de) 2007-04-15
EP1115831A1 (fr) 2001-07-18
ES2283074T3 (es) 2007-10-16
ZA996130B (en) 2000-03-27
DE69837403D1 (de) 2007-05-03
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