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EP2162522A1 - Granular enzymatic detergent compositions - Google Patents

Granular enzymatic detergent compositions

Info

Publication number
EP2162522A1
EP2162522A1 EP08760075A EP08760075A EP2162522A1 EP 2162522 A1 EP2162522 A1 EP 2162522A1 EP 08760075 A EP08760075 A EP 08760075A EP 08760075 A EP08760075 A EP 08760075A EP 2162522 A1 EP2162522 A1 EP 2162522A1
Authority
EP
European Patent Office
Prior art keywords
detergent composition
composition according
weight
sodium
thiosulphate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP08760075A
Other languages
German (de)
French (fr)
Other versions
EP2162522B1 (en
Inventor
Olaf C P Beers
Willem Oldenburg
Ronaldus T L Van Vliet
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Unilever PLC
Unilever NV
Original Assignee
Unilever PLC
Unilever NV
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.)
Filing date
Publication date
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Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Priority to EP08760075.5A priority Critical patent/EP2162522B1/en
Publication of EP2162522A1 publication Critical patent/EP2162522A1/en
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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
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/28—Sulfonation products derived from fatty acids or their derivatives, e.g. esters, amides
    • 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
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38672—Granulated or coated enzymes

Definitions

  • the present invention relates to granular detergent compositions, more in particular to granular detergent compositions comprising alkyl ester, in particular methyl ester fatty acid sulphonate surfactant and enzyme granules,
  • Laundry detergent compositions have for many years contained anionic sulphonate or sulphate surfactant, for example, linear alkylbenzene sulphonate (LAS) or primary alkyl sulphate (PAS) , together with ethoxylated alcohol nonionic surfactants.
  • anionic sulphonate or sulphate surfactant for example, linear alkylbenzene sulphonate (LAS) or primary alkyl sulphate (PAS)
  • ethoxylated alcohol nonionic surfactants used in laundry detergent compositions include typically ethoxylated Cio ⁇ Ci6 alcohols having an average degree of ethoxylation of 3 to 9.
  • MES methyl ester fatty acid sulphonate
  • the IUPAC name for e.g. a so-called C16 MES is Hexadecanoic acid, 2-sulfo-, 1-methylester, sodium salt (C17H33NaO5S) - -
  • Methyl ester sulphonate can be obtained by sulphonation of various renewable oleo-based methyl ester feedstocks derived from eg. coconut (C12-14), palm kernel (C8-18), palm stearin C16-18) or tallow (C16-18).
  • MES is of special interest due to good biodegradability, detergency and calcium hardness tolerance.
  • EP-A-I 634 941 (Lion) or WO-A-01/90284 (Huish) disclose high bulk density granular detergents containing surfactants (including ⁇ -sulpho-fatty acid esters), (bi) carbonate, zeolite and a polymer containing of monoethylenic unsaturated mono- and di-carboxylic acid units.
  • surfactants including ⁇ -sulpho-fatty acid esters
  • carbonate zeolite
  • zeolite a polymer containing of monoethylenic unsaturated mono- and di-carboxylic acid units.
  • the granular detergent composition according to the invention comprising 1 to 30% by weight of an alkyl ester fatty acid sulphonate surfactant and enzyme granules, wherein said composition is substantially free of thiosulphate .
  • a granular detergent composition comprising 1 to 30% by weight of an alkyl ester fatty acid sulphonate surfactant and 0.1 to 10% by weight enzyme granules, wherein said composition is substantially free of thiosulphate.
  • a detergent tablet obtained by compressing the granular detergent composition according to the invention.
  • a process for laundering textile fabrics by machine or hand characterised in that it comprises the step of immersing the fabrics in a wash liquor comprising water in which a granular detergent composition or detergent tablet according to the invention is dissolved or dispersed.
  • a process for manufacturing a granular detergent composition or tablet according to the invention is provided.
  • the granular detergent composition of the invention comprises 1 to 30% by weight of an alkyl ester fatty acid sulphonate surfactant, preferably methyl ester fatty acid sulphonate surfactant, and enzyme granules.
  • an alkyl ester fatty acid sulphonate surfactant preferably methyl ester fatty acid sulphonate surfactant
  • enzyme granules Preferably, the amount of ⁇ -sulpho-fatty acid esters is 1 to 15% by weight, more preferably 3 to 8% by weight.
  • ⁇ -sulfofatty acid esters can be prepared from a variety of sources, including beef tallow, palm kernel oil, palm kernel (olein) oil, palm kernel (stearin) oil, coconut oil, soybean oil, canola oil, cohune - -
  • Suitable fatty acids to make ⁇ -sulfofatty acid esters include, but are not limited to, caprylic (Cs) , capric ( (Cio) , lauric (C12) , myristic (Ci 4 ) , myristoleic (Ci 4 ) , palmitic (Ci ⁇ ) , palmitoleic (Ci ⁇ ) , stearic (Cis) , oleic (Cis) , linoleic (Cis) , linolenic (Cis) , ricinoleic (Cis) , arachidic (C20) , gadolic (C20) , behenic (C22) t and erucic (C22) fatty acids.
  • ⁇ -Sulfofatty acid esters prepared from one or more of these sources are examples of these sources.
  • Samples of alkyl ester fatty acid sulphonate surfactant prepared in dry powder form via above mentioned production processes typically contain about 75-85 % by weight of the desired surfactant.
  • the other components in a typical production sample there is one of specific relevance for the present invention, which is sodium methylsulphate, typically present at (but not restricted to) a level of about 1-10 % based on the weight of the MES as such.
  • the composition may also comprise one or more other surfactants.
  • the other surfactant is present in an amount of from 5 to 40 wt.%, preferably from 7 to 30 wt.%, based on the weight of the total composition.
  • alkylbenzene sulphonates examples include alkylbenzene sulphonates, branched or linear alkyl benzene sulphonates, primary and secondary alcohol sulphates, particularly C8 ⁇ Ci6 primary alcohol sulphates; alkyl ether sulphates, olefin sulphonates, including alpha olefin sulphonates, alkane sulphonates, alkyl xylene sulphonates, dialkyl sulphosuccinates, and alkyl carboxylates . These may be present as sodium, potassium, calcium or magnesium salts or mixtures of these. Sodium salts are generally preferred.
  • the other surfactant is preferably a sulphonate or sulphate anionic surfactant or a combination thereof. More preferably, the anionic surfactant is linear alkylbenzene sulphonate or primary alkyl sulphate. Most preferably the other surfactant is linear alkylbenzene sulphonate.
  • the linear alkyl benzene sulphonate may be present as sodium, potassium, or alkaline earth metal salts, or mixtures of these salts. Sodium salts are generally preferred.
  • the other surfactant may also comprise a nonionic surfactant, preferably an ethoxylated alcohol nonionic surfactant with an average degree of ethoxylation ranging from about 3 to 9, preferably from about 3 to 7.
  • the alcohol may be derived from natural or synthetic feedstock. Preferred alcohol feedstocks are coconut and palm kernel, predominantly C 12 -C 14 , and oxo C 12 -C 15 alcohols.
  • the nonionic surfactant is suitably present in an amount of from 1 to 20 wt %, preferably from 1 to 10, more preferably from 2 to 6 wt %, most preferably from 3 to 5 wt %, based on the weight of the total composition.
  • Additional surfactants or detergent active compounds may comprise other nonionics such as alkylpolyglucosides, polyhydroxyamides (glucamide) , methyl ester ethoxylates and glycerol monoethers .
  • cationic, amphoteric surfactants and/or zwitterionic surfactants may be present.
  • Preferred cationic surfactants are quaternary ammonium salts of the general formula R 1 R 2 R3R 4 N + X-, for example where Ri is a C 12 - Ci 4 alkyl group, R 2 and R3 are methyl groups, R 4 is a
  • 2-hydroxyethyl group, and X- is a chloride ion.
  • This material is available commercially as Praepagen (Trade Mark) HY from Clariant GmbH, in the form of a 40 wt% aqueous solution .
  • Preferred amphoteric surfactants are amine oxides, for example coco dimethyl amine oxide.
  • Preferred zwitterionic surfactants are betaines, and especially amidobetaines .
  • Preferred betaines are C8 to C18 alkyl amidoalkyl betaines, for example coco amido betaine. These may be included as co- surfactants, preferably present in an amount of from 0 to 10 wt %, more preferably 1 to 5 wt %, based on the weight of the total composition.
  • the detergent compositions of the present invention comprise one or more other enzymes, which provide cleaning performance, fabric care and/or sanitation benefits.
  • Suitable enzymes for incorporation in detergent compositions preferably include protease, lipase, amylase, cellulase, mannanase and oxidase, peroxidise, oxidoreductase, beta- glucanase, pectinase and/or pectate lyase. Most preferably, the compositions contain a proteolytic enzyme or protease. - -
  • composition may contain additional enzymes as found in WO-A-01/007681 page 15, line 25 to pagel9, line 29 as well as those found in WO-A-02/02726 page 16 line 21 to page 19 line 16 and those found in WO-A-02/02726 page 33 line 28 to page 39 line 34, the contents of which are herein incorporated by reference. It also may contain maltogenic ⁇ -amylases as described in WO-A-02/02726 page 5, line 14 to page 11 line 29. Commercially available maltogenic ⁇ -amylases are NovamylTM and MaltogenaseTM from Novozymes.
  • composition may also contain a lipase variant of the Humicola lanuginosa lipase with substitutions T231R + N233R, commercially available as LipexTM from Novozymes or another variant as described in WO-A-00/60063.
  • composition may also contain other commercial enzymes not described in any of the previous specifications such as the new enzymes from Novozymes: MannawayTM, NatalaseTM, RenozymeTM, OvozymeTM, CelluCleanTM, PolarzymeTM, StainzymeTM, CoronaseTM, PectaawayTM, PectawashTM, Termamyl UltraTM. And the new enzymes from Genencor: FN-3, FN-4, Purafect PrimeTM, ProperaseTM. - -
  • detergency enzymes are employed in granular form in amounts of from about 0.1 to about 10.0 wt %, preferably from about 0.2 to about 3% by weight, more preferably from about 0.2 to about 1% by weight.
  • the detergent compositions are substantially free of thiosulphate . Since enzyme granules sometimes contain thiosulphate, it was found to be important to use thiosulphate free enzyme granules. Preferably enzyme granules contain less than 3% by weight, more preferably less than 1% by weight, most preferably less than 0.1% by weight of thiosulphate. The amount of thiosulphate in the compositions can be determined using standard analytical techniques. Thiosulphate in the context of this invention means any salt thereof, such as alkalimetal, especially sodium, but also ammonium, Monoethanolamine or Triethanolamine salts.
  • compositions of the invention may contain a detergency builder.
  • the builder is present in an amount of from 1 to less than 80 wt % based on the weight of the total composition. More preferably the amount of builder is from 1 to 60 wt %.
  • Builders are well-known to those skilled in the art. Many suitable builder compounds are available. Examples are zeolites, sodium tripolyphosphate, layered silicate, sodium carbonate, sodium bicarbonate, burkeite, sodium silicate and mixtures thereof. - -
  • compositions may optionally contain other active ingredients to enhance performance and properties.
  • compositions of the invention may contain from 0 to 85 wt % of an inorganic non-builder salt, such as sodium sulphate, sodium sesquicarbonate, sodium chloride, calcium chloride, magnesium chloride and calcite, preferably from 0 to 60 wt %, preferably from 0 to 40 wt %, based on the weight of the total composition.
  • an inorganic non-builder salt such as sodium sulphate, sodium sesquicarbonate, sodium chloride, calcium chloride, magnesium chloride and calcite
  • compositions of the invention may contain a polycarboxylate polymer.
  • polycarboxylate polymer include homopolymers and copolymers of acrylic acid, maleic acid and acrylic/maleic acids.
  • the publication ⁇ Polymeric Dispersing Agents, Sokalan' a printed publication of BASF Aktiengesellschaft, D-6700 Ludwigshaven, Germany describes organic polymers which are useful.
  • the polycarboxylate polymer is selected from the group consisting of sodium polyacrylate, sodium acrylate maleate and mixtures thereof.
  • suitable polymers include Sokalan CP5, ex BASF polyacrylate, namely maleic acid-acrylic acid copolymer, with a sodium salt.
  • the detergent compositions of the invention may comprise one or more optional ingredients selected from soap, peroxyacid and persalt bleaches, bleach activators, air bleach catalysts, sequestrants, cellulose ethers and esters, cellulosic polymers, other antiredeposition agents, sodium bicarbonate, other inorganic salts, fluorescers, photobleaches, polyvinyl pyrrolidone, other dye transfer inhibiting polymers, foam controllers, foam boosters, - -
  • citric acid soil release polymers, silicone, fabric conditioning compounds, coloured speckles such as blue speckles, and perfume. This list is not intended to be exhaustive .
  • compositions of the invention are granular detergent compositions, preferably in powder form, having a mean particle size between 200 and 800 micrometer. Alternatively, the compositions may be in tablet form.
  • the compositions can be formulated for use as hand wash or machine wash detergents .
  • compositions of the invention may be prepared by any suitable process. Powders of low to moderate bulk density may be prepared by spray-drying a slurry, and optionally postdosing (dry-mixing) further ingredients. “Concentrated” or “compact” powders may be prepared by mixing and granulating processes, for example, using a highspeed mixer/granulator, or other non-tower processes.
  • Tablets may be prepared by compacting powders, especially "concentrated" powders.
  • the choice of processing route may be in part dictated by the stability or heat-sensitivity of the surfactants involved, and the form in which they are available. In all cases, all ingredients may be added separately.
  • Sodium LAS sodium C10-C13 alkylbenzene sulphonate (anionic surfactant)
  • Nonionic 7EO C13-C15 fatty alcohol ethoxylated with an average of 7 ethyleneoxide units per mole (nonionic surfactant)
  • Zeolite 4A sodium alumino silicate with Si:Al ratio 1 (ion- exchange builder)
  • Polymer acrylic acid/maleic acid type of polymer (anti- redeposition, anti-ashing or co-builder)
  • SCMC sodium carboxy methyl cellulose (anti-redeposition polymer)
  • Polarzyme 12.0 T protease enzyme granule from Novozymes; granule contains sodium thiosulphate as stabilizer.
  • Savinase 24.0 GTT (12.0 or 24.0 T): protease enzyme granule from Novozymes; granule contains sodium thiosulphate as stabilizer.
  • Stainzyme 12.0 T amylase enzyme granule from Novozymes; granule contains sodium thiosulphate as stabilizer.
  • Termamyl 60 T amylase enzyme granule from Novozymes; granule contains sodium thiosulphate as stabilizer.
  • Properase 100OM protease enzyme granule from Genencor; granule is free of sodium thiosulphate.
  • Purafect 3450M protease enzyme granule from Genencor; granule is free of sodium thiosulphate.
  • Lipex 100 T lipase enzyme granule from Novozymes; granule is free of sodium thiosulphate. - -
  • Savinase pure pure protease enzyme powder from Novozymes; without coating and sodium thiosulphate .
  • Dummy granule granule from Novozymes without enzymes and sodium thiosulphate.
  • BSA Bovine Serum Albumin
  • model protein model protein
  • the malodour molecule generated during storage has been identified via GC/MS headspace analyses to be a dimethyl- sulfide (abbr. DMS), predominantly dimethyl-disulfide, dimethyl-trisulfide and dimethyl-tetrasulfide .
  • DMS dimethyl- sulfide
  • the severity of malodour due to dimethylsulfides can be best assessed olfactively using following intensity scale:
  • Malodour is due to an interaction of MES/MS and thiosulphate (which is present within enzyme-granules of Novozymes) , since - i

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Abstract

Potential malodour problems are avoided by using a granular detergent composition comprising 1 to 30% by weight of an alkyl ester fatty acid sulphonate surfactant and enzyme granules, wherein said composition is substantially free of thiosulphate.

Description

- -
GRANULAR ENZYMATIC DETERGENT COMPOSITIONS
TECHNICAL FIELD
The present invention relates to granular detergent compositions, more in particular to granular detergent compositions comprising alkyl ester, in particular methyl ester fatty acid sulphonate surfactant and enzyme granules,
BACKGROUND OF THE INVENTION
Laundry detergent compositions have for many years contained anionic sulphonate or sulphate surfactant, for example, linear alkylbenzene sulphonate (LAS) or primary alkyl sulphate (PAS) , together with ethoxylated alcohol nonionic surfactants. Conventional ethoxylated alcohol nonionic surfactants used in laundry detergent compositions include typically ethoxylated Cio~Ci6 alcohols having an average degree of ethoxylation of 3 to 9.
More recently, granular detergent compositions have been proposed wherein part or all of the linear alkylbenzene sulphonate has been replaced with methyl ester fatty acid sulphonate (MES), having the formula:
where Ak = predominantly linear C14-16 alkyl chain.
The IUPAC name for e.g. a so-called C16 MES is Hexadecanoic acid, 2-sulfo-, 1-methylester, sodium salt (C17H33NaO5S) - -
Methyl ester sulphonate can be obtained by sulphonation of various renewable oleo-based methyl ester feedstocks derived from eg. coconut (C12-14), palm kernel (C8-18), palm stearin C16-18) or tallow (C16-18). Besides the renewable origin, MES is of special interest due to good biodegradability, detergency and calcium hardness tolerance.
EP-A-I 634 941 (Lion) or WO-A-01/90284 (Huish) disclose high bulk density granular detergents containing surfactants (including α-sulpho-fatty acid esters), (bi) carbonate, zeolite and a polymer containing of monoethylenic unsaturated mono- and di-carboxylic acid units.
While the (partial) replacement of LAS by methyl ester fatty acid sulphonate (MES) might seem to be straightforward, the present inventors were unexpectedly confronted with a malodour problem which occurred upon storage.
It has now surprisingly been found that this malodour problem may be avoided by the granular detergent composition according to the invention comprising 1 to 30% by weight of an alkyl ester fatty acid sulphonate surfactant and enzyme granules, wherein said composition is substantially free of thiosulphate .
DEFINITION OF THE INVENTION
According to a first aspect of the invention, there is provided a granular detergent composition comprising 1 to 30% by weight of an alkyl ester fatty acid sulphonate surfactant and 0.1 to 10% by weight enzyme granules, wherein said composition is substantially free of thiosulphate. - -
According to a second aspect of the invention, there is provided a detergent tablet obtained by compressing the granular detergent composition according to the invention.
According to a third aspect of the invention, there is provided a process for laundering textile fabrics by machine or hand, characterised in that it comprises the step of immersing the fabrics in a wash liquor comprising water in which a granular detergent composition or detergent tablet according to the invention is dissolved or dispersed.
According to a fourth aspect of the invention, there is provided a process for manufacturing a granular detergent composition or tablet according to the invention.
DETAILED DESCRIPTION OF THE INVENTION
The granular detergent composition of the invention comprises 1 to 30% by weight of an alkyl ester fatty acid sulphonate surfactant, preferably methyl ester fatty acid sulphonate surfactant, and enzyme granules. Preferably, the amount of α-sulpho-fatty acid esters is 1 to 15% by weight, more preferably 3 to 8% by weight.
Methods of preparing α-sulfofatty acid esters are known to skilled artisan. (See, e.g., US-A-5 587 500; US-A-5 384 422; US-A-5 382 677; US-A-5 329 030; US-A-4 816 188; and US-A- 4 671 900; and The Journal of American Oil Chemists Society 52:323-29 (1975) the disclosures of which are incorporated herein by reference) . α-Sulfofatty acid esters can be prepared from a variety of sources, including beef tallow, palm kernel oil, palm kernel (olein) oil, palm kernel (stearin) oil, coconut oil, soybean oil, canola oil, cohune - -
oil, coco butter, palm oil, white grease, cottonseed oil, corn oil, rape seed oil, soybean oil, yellow grease, mixtures thereof or fractions thereof. Suitable fatty acids to make α-sulfofatty acid esters include, but are not limited to, caprylic (Cs) , capric ( (Cio) , lauric (C12) , myristic (Ci4) , myristoleic (Ci4) , palmitic (Ciε) , palmitoleic (Ciε) , stearic (Cis) , oleic (Cis) , linoleic (Cis) , linolenic (Cis) , ricinoleic (Cis) , arachidic (C20) , gadolic (C20) , behenic (C22) t and erucic (C22) fatty acids. α-Sulfofatty acid esters prepared from one or more of these sources are within the scope of the present invention.
Samples of alkyl ester fatty acid sulphonate surfactant prepared in dry powder form via above mentioned production processes typically contain about 75-85 % by weight of the desired surfactant. Amongst the other components in a typical production sample there is one of specific relevance for the present invention, which is sodium methylsulphate, typically present at (but not restricted to) a level of about 1-10 % based on the weight of the MES as such.
The composition may also comprise one or more other surfactants. The other surfactant is present in an amount of from 5 to 40 wt.%, preferably from 7 to 30 wt.%, based on the weight of the total composition.
Surfactants are well-known to those skilled in the art. Many suitable detergent-active compounds are available and are fully described in the literature, for example, in "Surface-Active Agents and Detergents", Volumes I and II, by Schwartz, Perry and Berch. - -
Examples include alkylbenzene sulphonates, branched or linear alkyl benzene sulphonates, primary and secondary alcohol sulphates, particularly C8~Ci6 primary alcohol sulphates; alkyl ether sulphates, olefin sulphonates, including alpha olefin sulphonates, alkane sulphonates, alkyl xylene sulphonates, dialkyl sulphosuccinates, and alkyl carboxylates . These may be present as sodium, potassium, calcium or magnesium salts or mixtures of these. Sodium salts are generally preferred.
The other surfactant is preferably a sulphonate or sulphate anionic surfactant or a combination thereof. More preferably, the anionic surfactant is linear alkylbenzene sulphonate or primary alkyl sulphate. Most preferably the other surfactant is linear alkylbenzene sulphonate. The linear alkyl benzene sulphonate may be present as sodium, potassium, or alkaline earth metal salts, or mixtures of these salts. Sodium salts are generally preferred.
The other surfactant may also comprise a nonionic surfactant, preferably an ethoxylated alcohol nonionic surfactant with an average degree of ethoxylation ranging from about 3 to 9, preferably from about 3 to 7. The alcohol may be derived from natural or synthetic feedstock. Preferred alcohol feedstocks are coconut and palm kernel, predominantly C12-C14, and oxo C12-C15 alcohols.
The nonionic surfactant is suitably present in an amount of from 1 to 20 wt %, preferably from 1 to 10, more preferably from 2 to 6 wt %, most preferably from 3 to 5 wt %, based on the weight of the total composition. - -
Additional surfactants or detergent active compounds may comprise other nonionics such as alkylpolyglucosides, polyhydroxyamides (glucamide) , methyl ester ethoxylates and glycerol monoethers . Also cationic, amphoteric surfactants and/or zwitterionic surfactants may be present. Preferred cationic surfactants are quaternary ammonium salts of the general formula R1R2R3R4N+ X-, for example where Ri is a C12- Ci4 alkyl group, R2 and R3 are methyl groups, R4 is a
2-hydroxyethyl group, and X- is a chloride ion. This material is available commercially as Praepagen (Trade Mark) HY from Clariant GmbH, in the form of a 40 wt% aqueous solution .
Preferred amphoteric surfactants are amine oxides, for example coco dimethyl amine oxide. Preferred zwitterionic surfactants are betaines, and especially amidobetaines . Preferred betaines are C8 to C18 alkyl amidoalkyl betaines, for example coco amido betaine. These may be included as co- surfactants, preferably present in an amount of from 0 to 10 wt %, more preferably 1 to 5 wt %, based on the weight of the total composition.
Enzymes
The detergent compositions of the present invention comprise one or more other enzymes, which provide cleaning performance, fabric care and/or sanitation benefits.
Suitable enzymes for incorporation in detergent compositions preferably include protease, lipase, amylase, cellulase, mannanase and oxidase, peroxidise, oxidoreductase, beta- glucanase, pectinase and/or pectate lyase. Most preferably, the compositions contain a proteolytic enzyme or protease. - -
Suitable members of these enzyme classes are described in Enzyme nomenclature 1992: recommendations of the Nomenclature Committee of the International Union of Biochemistry and Molecular Biology on the nomenclature and classification of enzymes, 1992, ISBN 0-12-227165-3, Academic Press. The most recent information on the nomenclature of enzymes is available on the Internet through the ExPaSy Molecular Biology Server (http://us.expasy.org/)
The composition may contain additional enzymes as found in WO-A-01/007681 page 15, line 25 to pagel9, line 29 as well as those found in WO-A-02/02726 page 16 line 21 to page 19 line 16 and those found in WO-A-02/02726 page 33 line 28 to page 39 line 34, the contents of which are herein incorporated by reference. It also may contain maltogenic α-amylases as described in WO-A-02/02726 page 5, line 14 to page 11 line 29. Commercially available maltogenic α-amylases are Novamyl™ and Maltogenase™ from Novozymes.
The composition may also contain a lipase variant of the Humicola lanuginosa lipase with substitutions T231R + N233R, commercially available as Lipex™ from Novozymes or another variant as described in WO-A-00/60063.
The composition may also contain other commercial enzymes not described in any of the previous specifications such as the new enzymes from Novozymes: Mannaway™, Natalase™, Renozyme™, Ovozyme™, CelluClean™, Polarzyme™, Stainzyme™, Coronase™, Pectaaway™, Pectawash™, Termamyl Ultra™. And the new enzymes from Genencor: FN-3, FN-4, Purafect Prime™, Properase™. - -
In the granular or particulate detergent compositions, detergency enzymes are employed in granular form in amounts of from about 0.1 to about 10.0 wt %, preferably from about 0.2 to about 3% by weight, more preferably from about 0.2 to about 1% by weight.
It was found to be important that the detergent compositions are substantially free of thiosulphate . Since enzyme granules sometimes contain thiosulphate, it was found to be important to use thiosulphate free enzyme granules. Preferably enzyme granules contain less than 3% by weight, more preferably less than 1% by weight, most preferably less than 0.1% by weight of thiosulphate. The amount of thiosulphate in the compositions can be determined using standard analytical techniques. Thiosulphate in the context of this invention means any salt thereof, such as alkalimetal, especially sodium, but also ammonium, Monoethanolamine or Triethanolamine salts.
The detergency builder
The compositions of the invention may contain a detergency builder. Preferably the builder is present in an amount of from 1 to less than 80 wt % based on the weight of the total composition. More preferably the amount of builder is from 1 to 60 wt %. Builders are well-known to those skilled in the art. Many suitable builder compounds are available. Examples are zeolites, sodium tripolyphosphate, layered silicate, sodium carbonate, sodium bicarbonate, burkeite, sodium silicate and mixtures thereof. - -
Other optional detergent ingredients
As well as the surfactants, builders and enzymes discussed above, the compositions may optionally contain other active ingredients to enhance performance and properties.
The compositions of the invention may contain from 0 to 85 wt % of an inorganic non-builder salt, such as sodium sulphate, sodium sesquicarbonate, sodium chloride, calcium chloride, magnesium chloride and calcite, preferably from 0 to 60 wt %, preferably from 0 to 40 wt %, based on the weight of the total composition.
The compositions of the invention may contain a polycarboxylate polymer. These include homopolymers and copolymers of acrylic acid, maleic acid and acrylic/maleic acids. The publication λPolymeric Dispersing Agents, Sokalan' , a printed publication of BASF Aktiengesellschaft, D-6700 Ludwigshaven, Germany describes organic polymers which are useful. Preferably, the polycarboxylate polymer is selected from the group consisting of sodium polyacrylate, sodium acrylate maleate and mixtures thereof. Examples of suitable polymers include Sokalan CP5, ex BASF polyacrylate, namely maleic acid-acrylic acid copolymer, with a sodium salt.
The detergent compositions of the invention may comprise one or more optional ingredients selected from soap, peroxyacid and persalt bleaches, bleach activators, air bleach catalysts, sequestrants, cellulose ethers and esters, cellulosic polymers, other antiredeposition agents, sodium bicarbonate, other inorganic salts, fluorescers, photobleaches, polyvinyl pyrrolidone, other dye transfer inhibiting polymers, foam controllers, foam boosters, - -
citric acid, soil release polymers, silicone, fabric conditioning compounds, coloured speckles such as blue speckles, and perfume. This list is not intended to be exhaustive .
Form of the composition
The compositions of the invention are granular detergent compositions, preferably in powder form, having a mean particle size between 200 and 800 micrometer. Alternatively, the compositions may be in tablet form. The compositions can be formulated for use as hand wash or machine wash detergents .
Preparation of the compositions The granular compositions of the invention may be prepared by any suitable process. Powders of low to moderate bulk density may be prepared by spray-drying a slurry, and optionally postdosing (dry-mixing) further ingredients. "Concentrated" or "compact" powders may be prepared by mixing and granulating processes, for example, using a highspeed mixer/granulator, or other non-tower processes.
Tablets may be prepared by compacting powders, especially "concentrated" powders. The choice of processing route may be in part dictated by the stability or heat-sensitivity of the surfactants involved, and the form in which they are available. In all cases, all ingredients may be added separately.
The invention will now be further illustrated by the following, non-limiting Examples, in which parts and percentages are by weight, unless indicated otherwise. In the - -
examples, the following abbreviations are used and the compounds have the indicated functions:
Sodium LAS: sodium C10-C13 alkylbenzene sulphonate (anionic surfactant)
Nonionic 7EO: C13-C15 fatty alcohol ethoxylated with an average of 7 ethyleneoxide units per mole (nonionic surfactant)
MES: sodium C16-C18 methyl ester sulphonate (ca. 80-90% pure, having an average molecular weight of sodium salt = 370 - 390 g/mol) (anionic surfactant)
STP: Sodium Tri Polyphosphate (complexing builder)
Zeolite 4A: sodium alumino silicate with Si:Al ratio 1 (ion- exchange builder)
Sodium carbonate (precipitating builder and buffer)
Calcite (filler)
Sodium disilicate (builder and buffer; alkaline silicate)
Polymer: acrylic acid/maleic acid type of polymer (anti- redeposition, anti-ashing or co-builder)
SCMC: sodium carboxy methyl cellulose (anti-redeposition polymer)
Fluorescer (optical brightener)
Sodium sulphate (filler salt) - -
Sodium chloride (filler salt)
Speckles: visual cue.
Sodium perborate mono hydrate; (hydrogen peroxide) bleach.
MS: Sodium methyl sulphate, chemical from Aldrich.
Sodium thiosulphate : chemical from BDH Prolabo.
Polarzyme 12.0 T: protease enzyme granule from Novozymes; granule contains sodium thiosulphate as stabilizer.
Savinase 24.0 GTT (12.0 or 24.0 T): protease enzyme granule from Novozymes; granule contains sodium thiosulphate as stabilizer.
Stainzyme 12.0 T: amylase enzyme granule from Novozymes; granule contains sodium thiosulphate as stabilizer.
Termamyl 60 T: amylase enzyme granule from Novozymes; granule contains sodium thiosulphate as stabilizer.
Properase 100OM: protease enzyme granule from Genencor; granule is free of sodium thiosulphate.
Purafect 3450M: protease enzyme granule from Genencor; granule is free of sodium thiosulphate.
Lipex 100 T: lipase enzyme granule from Novozymes; granule is free of sodium thiosulphate. - -
Savinase pure: pure protease enzyme powder from Novozymes; without coating and sodium thiosulphate .
Dummy granule: granule from Novozymes without enzymes and sodium thiosulphate.
BSA: Bovine Serum Albumin; model protein.
Example 1
The following tables show the composition of the formulations used in examples 3-5:
100.0 100.0 100.0 100.0 - -
100.0 100.0 100.0 100.0 100.0 100.0 100.0
100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 - -
100.0 100.0
Example 2
The malodour molecule generated during storage has been identified via GC/MS headspace analyses to be a dimethyl- sulfide (abbr. DMS), predominantly dimethyl-disulfide, dimethyl-trisulfide and dimethyl-tetrasulfide . The severity of malodour due to dimethylsulfides can be best assessed olfactively using following intensity scale:
Samples of various products have been stored for 8 weeks in closed glass jars at Room Temperature, 37°C/70%RH, and 45°C. - -
At 37°C/70%RH the products are also stored in closed carton packs .
Example 3
MES in combination with thiosulphate-containing proteases in various products.
It can be concluded that malodour development increases with increasing level of enzymes for all formulations with the various builder types. - -
Example 4
MES or sodium methylsulphate in combination with thiosulphate-containing enzymes.
Malodour formation seems to be triggered by an interaction between enzymes and methylsulphate rather than MES itself (note: methylsulphate is one of the main by-products formed during MES production) .
Example 5
Comparison of protease enzymes with and without thiosulphate .
Malodour is due to an interaction of MES/MS and thiosulphate (which is present within enzyme-granules of Novozymes) , since - i
no malodour develops in the presence of thiosulphate-free enzymes from Genencor.
Example 6
Mixtures of MES or methylsulphate with various enzymes (1:1 mixtures of single ingredients) .
The 1:1 mixtures show again that malodour is due to an interaction of MES/MS and thiosulphate (which is present - -
within enzyme-granules of Novozyme) , since no malodour develops in the presence of thiosulphate-free enzymes from Genencor, pure Savinase, BSA, and the thiosulphate-free coating of Novozyme-granules . In addition, very severe malodour generates during storage of MES/MS with thiosulphate as such. Malodour is identified via GC/MS headspace analyses to be DMS.

Claims

- -CLAIMS
1. Granular detergent composition comprising 1 to 30% by weight of an alkyl ester fatty acid sulphonate surfactant and 0.1 to 10% by weight enzyme granules, wherein said composition is substantially free of thiosulphate .
2. A detergent composition according to claim 1, wherein the alkyl ester fatty acid sulphonate surfactant is methyl ester fatty acid sulphonate surfactant.
3. A detergent composition according to any one of the preceding claims, comprising methyl sulphate as a by- product of the production process of the methyl ester fatty acid sulphonate.
4. A detergent composition according to claim 3, containing 0.5 to 10% methyl sulphate, based on the amount of methyl ester fatty acid sulphonate.
5. A detergent composition according to any one of the preceding claims, wherein the enzyme is selected from the group consisting of protease, lipase, amylase, cellulase, mannanase and oxidoreductase .
6. A detergent composition according to any one of the preceding claims, wherein said composition contains less than 0.3% by weight of thiosulphate.
7. A detergent composition according to any one of the preceding claims, wherein the enzyme granules contain preferably less than 3% by weight, more preferably less - -
than 1% by weight, most preferably less than 0.1% by weight of thiosulphate .
8. A detergent composition according to any one of the preceding claims, further comprising linear alkyl benzene sulphonate.
9. A detergent composition according to any one of the preceding claims, comprising an ethoxylated alcohol nonionic surfactant.
10. A detergent composition according to claim 9, wherein the ethoxylated alcohol nonionic surfactant has an average degree of ethoxylation n of from 3 to 7.
11. A detergent composition according to any one of the preceding claims, comprising a builder in an amount of from 1 to 60%, preferably from 1 to 40% by weight.
12. A detergent composition according to claim 11, wherein said builder selected from the group consisting of zeolite, sodium tripolyphosphate, layered silicate, sodium carbonate, sodium bicarbonate, burkeite, sodium silicate and mixtures thereof.
13. A detergent composition according to any one of the preceding claims, comprising sodium sulphate in an amount of from 2 to 50%, preferably from 10 to 40% by weight .
14. A detergent composition according to claim 12, wherein the sodium silicate is present in an amount of from 1 - -
to 20% by weight.
15. A detergent composition according to any one of the preceding claims, further comprising a cationic surfactant in an amount of from 0.1 to 5% by weight.
16. A detergent composition according to any one of the preceding claims, further comprising a polycarboxylate polymer selected from the group consisting of sodium polyacrylate, sodium acrylate maleate and mixtures thereof .
17. A detergent composition according to any one of the preceding claims, characterised in that it further comprises one or more optional ingredients selected from soap, peroxyacid and persalt bleaches, bleach activators, air bleach catalyst, sequestrants, cellulose ethers and esters, cellulosic polymers, other antiredeposition agents, fluorescers, photobleaches, polyvinyl pyrrolidone, other dye transfer inhibiting polymers, foam controllers, foam boosters, colourants, citric acid, soil release polymers, fabric conditioning compounds, coloured speckles, and perfume.
18. A detergent tablet obtained by compressing the granular detergent composition according to any one of the preceding claims.
19. Process for laundering textile fabrics by machine or hand, characterised in that it comprises the step of immersing the fabrics in a wash liquor comprising water in which a granular detergent composition or detergent tablet as claimed in any preceding claim is dissolved - -
or dispersed.
20. Process for manufacturing a granular detergent composition or tablet according to any one of claims 1- 18.
EP08760075.5A 2007-06-22 2008-05-27 Granular enzymatic detergent compositions Active EP2162522B1 (en)

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