WO2013092051A1 - Liquid detergents comprising lipase and bleach catalyst - Google Patents
Liquid detergents comprising lipase and bleach catalyst Download PDFInfo
- Publication number
- WO2013092051A1 WO2013092051A1 PCT/EP2012/072973 EP2012072973W WO2013092051A1 WO 2013092051 A1 WO2013092051 A1 WO 2013092051A1 EP 2012072973 W EP2012072973 W EP 2012072973W WO 2013092051 A1 WO2013092051 A1 WO 2013092051A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- composition
- alkyl
- catalyst
- lipase
- hydrogen
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 71
- 108090001060 Lipase Proteins 0.000 title claims abstract description 60
- 102000004882 Lipase Human genes 0.000 title claims abstract description 60
- 239000004367 Lipase Substances 0.000 title claims abstract description 47
- 235000019421 lipase Nutrition 0.000 title claims abstract description 47
- 239000007788 liquid Substances 0.000 title claims abstract description 33
- 239000003599 detergent Substances 0.000 title claims abstract description 21
- 239000007844 bleaching agent Substances 0.000 title claims description 24
- 239000000203 mixture Substances 0.000 claims abstract description 86
- 239000004094 surface-active agent Substances 0.000 claims abstract description 22
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 17
- 239000001257 hydrogen Substances 0.000 claims abstract description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 17
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000003446 ligand Substances 0.000 claims abstract description 12
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 10
- 150000003624 transition metals Chemical class 0.000 claims abstract description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 9
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 6
- 125000006514 pyridin-2-ylmethyl group Chemical group [H]C1=C([H])C([H])=C([H])C(=N1)C([H])([H])* 0.000 claims abstract description 6
- 125000000041 C6-C10 aryl group Chemical group 0.000 claims abstract description 5
- 229920000642 polymer Polymers 0.000 claims description 20
- -1 pyridin-2-yl methyl Chemical group 0.000 claims description 17
- 150000001412 amines Chemical class 0.000 claims description 16
- 238000004061 bleaching Methods 0.000 claims description 15
- 239000002689 soil Substances 0.000 claims description 15
- 229920002873 Polyethylenimine Polymers 0.000 claims description 13
- 239000004744 fabric Substances 0.000 claims description 13
- 102000004190 Enzymes Human genes 0.000 claims description 12
- 108090000790 Enzymes Proteins 0.000 claims description 12
- 229940088598 enzyme Drugs 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 229920000742 Cotton Polymers 0.000 claims description 9
- 229930153442 Curcuminoid Natural products 0.000 claims description 8
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- 239000004365 Protease Substances 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- 125000000129 anionic group Chemical group 0.000 claims description 4
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 4
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- 150000004996 alkyl benzenes Chemical class 0.000 claims description 3
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- HPGJIECPABCUFL-UHFFFAOYSA-N 6-chloro-9,9-dihydroxy-2,3,4-trimethyl-2,4-dipyridin-2-yl-7-(pyridin-2-ylmethyl)-3,7-diazabicyclo[3.3.1]nonane-1,5-dicarboxylic acid hydrochloride Chemical compound Cl.OC1(O)C2(C(O)=O)CN(CC=3N=CC=CC=3)C(Cl)C1(C(O)=O)C(C=1N=CC=CC=1)(C)N(C)C2(C)C1=CC=CC=N1 HPGJIECPABCUFL-UHFFFAOYSA-N 0.000 description 2
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- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- BZDOEVMUXJTHPS-UHFFFAOYSA-N n,n-bis(2-hydroxyethyl)hexadecan-1-amine oxide Chemical compound CCCCCCCCCCCCCCCC[N+]([O-])(CCO)CCO BZDOEVMUXJTHPS-UHFFFAOYSA-N 0.000 description 1
- CBLJNXZOFGRDAC-UHFFFAOYSA-N n,n-bis(2-hydroxyethyl)octadecan-1-amine oxide Chemical compound CCCCCCCCCCCCCCCCCC[N+]([O-])(CCO)CCO CBLJNXZOFGRDAC-UHFFFAOYSA-N 0.000 description 1
- IBOBFGGLRNWLIL-UHFFFAOYSA-N n,n-dimethylhexadecan-1-amine oxide Chemical compound CCCCCCCCCCCCCCCC[N+](C)(C)[O-] IBOBFGGLRNWLIL-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229920000847 nonoxynol Polymers 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 150000004967 organic peroxy acids Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 229940068984 polyvinyl alcohol Drugs 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 229920006261 self reinforced polyphenylene Polymers 0.000 description 1
- 239000004289 sodium hydrogen sulphite Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229940075554 sorbate Drugs 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 235000010199 sorbic acid Nutrition 0.000 description 1
- 229940075582 sorbic acid Drugs 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- UJMBCXLDXJUMFB-GLCFPVLVSA-K tartrazine Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)C1=NN(C=2C=CC(=CC=2)S([O-])(=O)=O)C(=O)C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 UJMBCXLDXJUMFB-GLCFPVLVSA-K 0.000 description 1
- 235000012756 tartrazine Nutrition 0.000 description 1
- 239000004149 tartrazine Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 235000010384 tocopherol Nutrition 0.000 description 1
- 229930003799 tocopherol Natural products 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 229940116269 uric acid Drugs 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- GVJHHUAWPYXKBD-IEOSBIPESA-N α-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-IEOSBIPESA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/168—Organometallic compounds or orgometallic complexes
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
- C11D3/38627—Preparations containing enzymes, e.g. protease or amylase containing lipase
Definitions
- This invention relates to a liquid detergent composition
- a liquid detergent composition comprising anionic surfactant, lipase enzyme and a bleach catalyst and to the use of the composition for the removal of curcuminoid stains from surfaces, for example from fabrics.
- WO09153184 suggests that an improved laundry detergent liquid concentrate may be obtained by replacing surfactant with a mixture of more weight efficient ingredients selected from polymers and enzymes.
- a preferred composition uses lipase enzyme in combination with EPEI and a polyester soil release polymers to achieve excellent oily soil and particulate detergency at significantly lower in-wash surfactant levels than would normally be delivered from such a high performance laundry liquid.
- a bleach catalyst may be included. A long list of such catalysts is given.
- the non-bridged air bleaching catalyst preferred in WO2002/048307 (Unilever) is specifically mentioned as being preferred for use in WO09153184.
- Air bleaching catalysts as described and claimed in WO2002/048301 are referenced on page 48 lines 1 -2 of WO09153184 where it says "suitable bispidon catalyst materials and their action are described in WO02/48301 ".
- the combination of a specific amount of the selected air bleaching catalyst with a specific amount of lipase is not exemplified in WO09153184.
- WO 2002/48301 (Unilever) disclosed a group of bridged ligand air bleaching catalysts that included N2Py3o on page 30. There is no disclosure of this catalyst in combination with lipase, nor any suggestion that the combination would have synergistic effects on the air bleaching of curcuminoid (yellow and green curry) stains.
- WO01 /00768 Lipases are said to be preferred enzymes.
- WO 2005/033256 Unilever.
- WO 2004/1 1 1 173 Unilever that discloses liquids containing the bleach catalyst of interest but fails to disclose the amount or type of enzyme in its liquid detergent example.
- WO 2004/1 1 1 174 discloses the use of anti-oxidant to protect the catalyst in liquids during storage.
- the example showing improved perfume stability uses a bridged bleach catalyst of the correct type, but no lipase is present.
- WO 2002/50229 discloses to air bleach with a combination of metal catalyst and an air bleaching facilitator (unsaturated soap).
- the presently claimed catalyst is not exemplified or used with lipase.
- US2003/166485 discloses a combination of a lipase, lipogenase and bleach catalyst used in air bleaching mode.
- the examples show the effect with a non- bridged ligand type of catalyst (MeN4Py)FeCI CI.
- the examples without any lipogenase show some benefit of the combination of a lipase with this non bridged bleach catalyst compared to use of the lipase alone or the catalyst alone.
- a detergent liquid comprising:
- a transition metal catalyst b) 0.05 to 0.3 wt% of a transition metal catalyst, the catalyst being a ligand of the formula (I) complexed with a transition metal, selected from Fe(ll) and Fe(lll),
- R1 and R2 are independently selected from:
- the catalyst is ([Fe(N2py3o)CI]CI) with structure (II):
- the composition further comprises ethoxylated polyethyleneimine (EPEI).
- EPEI ethoxylated polyethyleneimine
- SRP polyester soil release polymer
- the in-bottle pH of the composition is acidic and lies in the range 6 to less than 7, preferably 6.1 to 6.9 and more preferably 6.3 to 6.7.
- the bleach catalyst may be encapsulated.
- the composition preferably comprises at least two further enzymes selected from protease, mannanase, amylase, cellulase and pectate lyase. Most preferably the composition comprises protease.
- the composition may be a laundry detergent. In which case, the anionic surfactant preferably comprises linear alkyl benzene sulphonate.
- composition surfactant system may further comprise one or more of ethoxylated nonionic surfactant, amphoteric surfactant and ethoxylated anionic surfactant.
- the amphoteric surfactant may be selected from carbobetaine and amine oxide and mixtures thereof.
- the composition may be aqueous with a water content of greater than 20 wt%.
- it may be non aqueous with a water content of less than 15 wt%, preferably less than 10 wt%.
- Such a non aqueous composition may conveniently be contained in a water soluble sachet that can be added to water by a consumer.
- the sachet is desirably made from a conventional water soluble film, for example a poly vinyl alcohol as is known in the art.
- a method of air bleaching a surface on which there is a curcuminoid stain comprising treating the surface with a composition according to the invention any preceding claim and then exposing the surface to atmospheric air, preferably the exposure to air has a duration of at least 1 hour.
- the composition may be applied to the surface in undiluted, from the bottle, form. Consumers prefer many types of cleaning composition to be offered as a liquid, hard surface cleaners and fabric washing liquids being leading examples.
- the method may be performed by taking an aliquot of the
- composition and diluting it by at least 600 times its own weight of water to form a wash liquor and then contacting the surface with the wash liquor so formed.
- the surface is cloth fabric and most preferably it is cotton.
- the method involving dilution may take place in a front loading automatic washing machine.
- the preferred catalyst used in this invention is given a shorthand code of
- a particular type of air bleaching catalyst as described in WO02/48301 has a surprisingly strong synergistic effect with lipase in terms of the visual removal of yellow curry (curcuminoid) stains when a washed stain is dried in contact with a liquid comprising the catalyst and the lipase (air bleaching effect).
- the effect is particularly strong when high levels of the catalyst (and lipase) and low levels of surfactant are used. This may be due to the higher efficacy of the lipase when anionic surfactant is reduced.
- the lipase catalyst synergy is therefore particularly suited to the low surfactant compositions of the type described in WO091 53184. Lipase enzyme
- the amount of lipase should be at least 1 wt% to obtain the synergistic effect. 1 wt% is equivalent to 1000 LU per gram of the detergent composition. Preferably the lipase is 2000-20,000 LU per gram of the detergent composition.
- Suitable lipase enzyme is obtainable from Humicola lanuginosa, Pseudomonas
- lipase enzymes include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Most preferred lipases are obtainable from Humicola lanuginose.
- the detergent compositions preferably comprise 2500-4,000 LU per gram of the detergent composition, of lipase enzyme. In this specification LU or lipase units are defined as they are in EP-A-258 068 (Novo Nordisk).
- a further method of assessing the enzymatic activity is by measuring the reflectance at 460 nm according to standard techniques.
- lipases examples include lipases from Humicola which comprise a polypeptide having an amino acid sequence which has at least 90% sequence identity with the wild-type lipase derived from Humicola lanuginose, most preferably strain DSM 4109.
- the amount in the composition is higher than typically found in liquid detergents. This can be seen by the ratio of non-soap surfactant to lipase enzyme, in particular.
- a particularly preferred lipase enzyme is available under the trademark LipocleanTM from Novozymes.
- lipases examples include lipases from Humicola (synonym Thermomyces), e.g. from H. lanuginosa ( ⁇ . lanuginosus) as described in EP 258 068 and EP 305 216 or from H. insolens as described in WO 96/13580, a Pseudomonas lipase, e.g. from P. alcaligenes or P. pseudoalcaligenes (EP 218 272), P. cepacia (EP 331 376), P. stutzeri (GB 1 ,372,034), P. fluorescens, Pseudomonas sp.
- Humicola semomyces
- H. lanuginosa ⁇ . lanuginosus
- EP 258 068 and EP 305 216 or from H. insolens as described in WO 96/13580
- Pseudomonas lipase e.g. from P. al
- strain SD 705 (WO 95/06720 and WO 96/27002), P. wisconsinensis (WO 96/12012), a Sac/V/us lipase, e.g. from B. subtilis (Dartois et al. (1993), Biochemica et Biophysica Acta, 1 131 , 253-360), B. stearothermophilus (JP 64/744992) or B. pumilus (WO
- the preferred lipases have a high degree of homology with the wild- type lipase derived from Humicola lanuginose.
- lipase variants such as those described in WO 92/05249, WO 94/01541 , EP 407 225, EP 260 105, WO 95/35381 , WO 96/00292, WO 95/30744, WO 94/25578, WO 95/14783, WO 95/22615, WO 97/04079 and WO 97/07202.
- LipolaseTM and Lipolase UltraTM LipexTM and LipocleanTM (Novozymes A/S).
- lipase In addition to lipase one or more other enzymes may be present.
- compositions of the invention has a beneficial effect on the turnover of certain enzymes, particularly lipase enzymes and preferably lipases from Humicola.
- Suitable enzymes for the compositions of the invention can be found in the enzyme classes of the esterases and lipases, (EC 3.1 .1 . * , wherein the asterisk denotes any number). Cutinases differ from classical lipases in that they do not possess a helical lid covering the catalytic binding site. Cutinases belong to a different subclass of enzymes (EC 3.1 .1 .50) and are regarded to be outside the scope of the present invention.
- the enzyme to be used in the detergent compositions according to the invention can be produced by cloning the gene for the enzyme into a suitable production organism, such as Bacilli, or Pseudomonaceae, yeasts, such as Saccharomyces, Kluyveromyces, Hansenula or Pichia, or fungi like Aspergillus.
- a suitable production organism such as Bacilli, or Pseudomonaceae, yeasts, such as Saccharomyces, Kluyveromyces, Hansenula or Pichia, or fungi like Aspergillus.
- the preferred production organism is Aspergillus with especial preference for Aspergillus oryzae.
- the lipase enzyme can be stabilised for use in a liquid detergent by various techniques as for example disclosed in US-A-4 261 868 and US-A-4 318 818.
- the selected bleach catalyst is a cross-bridged polydentate N-donor ligand capable of forming a complex with a transition metal, wherein said complex is capable of catalysing the bleaching of stains on fabrics by means of atmospheric oxygen.
- the bleach catalyst is a very specific complex of Iron and a multicyclic organic ligand as described already in W021002/48301 .
- the preferred material is [Fe(N2py3o)CI]CI - see WO02248301 . Its structure (II) is:
- the bridged ligand catalysts are more stable under acidic conditions and the detergent liquids are therefore preferably acidic.
- Such liquids are compatible with SRPs that suffer from hydrolysis when included in alkaline liquids (especially if TEA is present).
- Texcare SRN170 has been found to be susceptible to alkaline hydrolysis in laundry liquids.
- the composition preferably comprises from 0.005 to 2 wt% of anti-oxidant. More preferably, the anti-oxidant is present at a concentration in the range of 0.01 to 0.08 wt%.
- Anti-oxidants are substances as described in Kirk-Othmer (Vol 3, pg 424) and in Uhlmans Encyclopaedia (Vol 3, pg 91 ).
- One class of anti-oxidants used in the present invention is alkylated phenols.
- hindered phenolic compounds of alkylated phenols according to this formula.
- a particularly preferred hindered phenolic compound of this type is 2,6-di- tert-butyl-hydroxy- toluene (BHT).
- the antioxidant used in the composition of the invention may be selected from the group consisting of a-, y-, 8-tocopherol, ethoxyquin, 2,2,4- trimethyl-1 ,2- dihydroquinoline, 2,6-di-tert-butyl hydroquinone, tert-butyl- hydroxy anisole, lignosulphonic acid and salts thereof, and mixtures thereof.
- Ethoxyquin (1 ,2-dihydro-6- ethoxy-2,2,4-trimethylchinolin) is marketed under the name
- antioxidants 6 hydroxy-2, 5, 7, 8-tetra-methylchroman-2-carboxylic acid (TroloxTM) and 1 , 2- benzisothiazoline-3-one (Proxel GXL).
- a further class of anti-oxidants which may be suitable for use in the present invention is a benzofuran or benzopyran derivative.
- Anti-oxidants such as tocopherol sorbate, butylated hydroxy benzoic acids and their salts, gallic acid and its alkyl esters, uric acid and its salts and alkyl esters, sorbic acid and its salts, and dihydroxy fumaric acid and its salts may also be used..
- anti-oxidants for use in the present invention are 2,6-di-tert- butyl-hydroxy-toluene (BHT), ⁇ , ⁇ , ⁇ , ⁇ ⁇ tocopherol and mixtures thereof, 6-hydroxy- 2, 5, 7, 8-tetra-methylchroman-2- carboxylic acid (TroloxTM), 1 , 2- benzisothiazoline-3-one (Proxel GXL) and mixtures thereof.
- the most preferred anti-oxidants are 2,6-di-tert-butyl-hydroxy-toluene (BHT, 1 , 2 benzisothiazoline-3- one (Proxel GXL TM) and mixtures thereof.
- Surfactants assist in removing soil from the textile materials and also assist in maintaining removed soil in solution or suspension in the wash liquor. Blends of anionic and nonionic surfactants are a preferred feature of the present invention.
- the amount of anionic surfactant is at least 5 wt% and preferably at least 10 wt%. Preferably, anionic surfactant forms the majority of the surfactant (a).
- anionic surfactants are alkylbenzene sulphonates, particularly linear alkylbenzene sulphonates having an alkyi chain length of C 8 -C-
- the counter ion for anionic surfactants is generally an alkali metal, typically sodium, although other counter-ions such as MEA, TEA or ammonium can be used.
- Preferred linear alkyi benzene sulphonate surfactants are Detal LAS with an alkyi chain length of from 8 to 15, more preferably 12 to 14.
- composition comprises an alkyi polyethoxylate sulphate anionic surfactant of the formula (I):
- R is an alkyi chain having from 10 to 22 carbon atoms, saturated or unsaturated
- M is a cation which makes the compound water-soluble, especially an alkali metal, ammonium or substituted ammonium cation, and x averages from 1 to 15.
- R is an alkyi chain having from 12 to 16 carbon atoms
- M is Sodium and x averages from 1 to 3, preferably x is 3;
- SLES sodium lauryl ether sulphate It is the sodium salt of lauryl ether sulphonic acid in which the predominantly C12 lauryl alkyi group has been ethoxylated with an average of 3 moles of ethylene oxide per mole.
- Nonionic surfactants include primary and secondary alcohol ethoxylates, especially C 8 -C 2 o aliphatic alcohol ethoxylated with an average of from 1 to 20 moles of ethylene oxide per mole of alcohol, and more especially the C-
- Non-ethoxylated nonionic surfactants include alkyl polyglycosides, glycerol monoethers and polyhydroxy amides (glucamide). Mixtures of nonionic surfactant may be used.
- the composition contains from 0.2 wt% to 40 wt%, preferably 1 wt% to 20 wt%, more preferably 5 to 15 wt% of a non-ionic surfactant, such as alcohol ethoxylate, nonylphenol ethoxylate, alkylpolyglycoside, alkyldimethylamineoxide, ethoxylated fatty acid monoethanolamide, fatty acid monoethanolamide, polyhydroxy alkyl fatty acid amide, or N-acyl N-alkyl derivatives of glucosamine (“glucamides").
- a non-ionic surfactant such as alcohol ethoxylate, nonylphenol ethoxylate, alkylpolyglycoside, alkyldimethylamineoxide, ethoxylated fatty acid monoethanolamide, fatty acid monoethanolamide, polyhydroxy alkyl fatty acid amide, or N-acyl N-alkyl derivatives of glucosamine (“glucamides”).
- Nonionic surfactants that may be used include the primary and secondary alcohol ethoxylates, especially the C-8-C20 aliphatic alcohols ethoxylated with an average of from 1 to 35 moles of ethylene oxide per mole of alcohol, and more especially the C-10-C-15 primary and secondary aliphatic alcohols ethoxylated with an average of from 1 to 10 moles of ethylene oxide per mole of alcohol.
- the composition may comprise up to 10 wt% of a carbobetaine or an amine oxide or mixtures thereof.
- the amine oxide has the formula:
- R 1 is a long chain moiety each CH 2 R 2 are short chain moieties.
- R 2 is preferably selected from hydrogen, methyl and -CH 2 OH.
- R 1 is a primary or branched hydrocarbyl moiety which can be saturated or unsaturated, preferably, R 1 is a primary alkyl moiety.
- R 1 is a hydrocarbyl moiety having chain length of from about 8 to about 18.
- Preferred amine oxides have R 1 is C 8 -Ci 8 alkyl, and R 2 is H. These amine oxides are illustrated by C12-14 alkyldimethyl amine oxide, hexadecyl dimethylamine oxide, octadecylamine oxide.
- a preferred amine oxide material is Lauryl dimethylamine oxide, also known as dodecyldimethylamine oxide or DDAO. Such an amine oxide material is commercially available from Huntsman under the trade name Empigen® OB. Amine oxides suitable for use herein are also available from Akzo Chemie and Ethyl Corp. See McCutcheon's compilation and Kirk-Othmer review article for alternate amine oxide manufacturers.
- R 2 is H
- R 2 may be CH 2 OH, such as: hexadecylbis(2- hydroxyethyl)amine oxide, tallowbis(2-hydroxyethyl)amine oxide, stearylbis(2- hydroxyethyl)amine oxide and oleylbis(2- hydroxyethyl)amine oxide.
- Preferred amine oxides have the formula:
- a preferred zwitterionic carbobetaine material is available from Huntsman under the name Empigen® BB. Betaines, improve particulate soil detergency in the compositions of the invention. Additional surfactants
- surfactants than the preferred LAS, SLES, nonionic and amine oxide/ carbobetaine may be added to the mixture of detersive surfactants.
- cationic surfactants are preferably substantially absent.
- alkyl sulphate surfactant may be used, especially the non-ethoxylated C12-15 primary and secondary alkyl sulphates.
- compositions are as described in WO09153184.
- EPEI and polyester soil release polymer are most preferred components of the detergent liquids and are advantageously used in combination and at high levels.
- a particularly preferred class of polymer for use in the present invention is polyethylene imine, preferably modified polyethylene imine.
- Polyethylene imines are materials composed of ethylene imine units -CH2CH2NH- and, where branched, the hydrogen on the nitrogen is replaced by another chain of ethylene imine units.
- These polyethyleneimines can be prepared, for example, by polymerizing ethyleneimine in the presence of a catalyst such as carbon dioxide, sodium bisulphite, sulphuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, and the like. Specific methods for preparing these polyamine backbones are disclosed in U.S. Pat. No. 2,182,306, Ulrich et al., issued Dec. 5, 1939; U.S. Pat. No.
- the EPEI comprises a polyethyleneimine backbone of about 300 to about 10000 weight average molecular weight; wherein the modification of the polyethyleneimine backbone is intended to leave the polymer without
- Such nonionic EPEI may be represented as PEI(X)YEO where X represents the molecular weight of the unmodified PEI and Y represents the average moles of ethoxylation per nitrogen atom in the polyethyleneimine backbone.
- the ethoxylation may range from 9 to 40 ethoxy moieties per modification, preferably it is in the range of 16 to 26, most preferably 18 to 22.
- the polyethyleneimine polymer is present in the composition preferably at a level of between 0.01 and 25 wt%, but more preferably at a level of at least 2 wt% and/or less than 9.5 wt%, most preferably from 3 to 9 wt% and with a ratio of non- soap surfactant to EPEI of from 2:1 to 7:1 , preferably from 3:1 to 6:1 , or even to 5:1 .
- a soil release polymer preferably of the PET POET type
- Acidic compositions according to the invention are particularly suited to the types of soil release polymers disclosed in WO09153184 since they tend to decompose when stored under alkaline conditions.
- an alkaline stable type of polyester soil release polymer may be used.
- Other polymer types may be used.
- Dye transfer inhibition polymers, anti redeposition polymers and cotton soil release polymers, especially those based on modified cellulosic materials may also be used in the compositions of the present invention.
- the Detergent liquids preferably do not contain any additional conventional bleach system.
- peroxy bleach compounds for example, inorganic persalts or organic peroxyacids, capable of yielding hydrogen peroxide in aqueous solution are absent.
- composition may comprise other ingredients as set forth in WO09153184.
- LAS acid is C12-14 linear alkylbenzene sulphonic acid.
- Fatty acid is saturated lauric fatty acid Prifac® 5908 ex Croda.
- SLES 3EO is sodium lauryl ether sulphate with 3 moles EO.
- Empigen® BB is an alkyl betaine ex Huntsman (Coco dimethyl
- carbobetaine an amphoteric surfactant.
- Nl 7EO is C12-15 alcohol ethoxylate 7EO nonionic
- Neodol® 25-7 (ex Shell Chemicals).
- MPG is mono propylene glycol.
- TEA triethanolamine.
- NaOH is 47% sodium hydroxide solution.
- EPEI is Sokalan HP20 - ethoxylated polyethylene imine cleaning polymer: PEI(600) 20EO ex BASF.
- SRP is polyester soil release polymer (Texcare SRN170 ex
- Perfume is free oil perfume.
- Demin water is demineralised water
- Protease enzyme is Relase Ultra 16 LEX ex Novozymes A/S
- Amylase enzyme is Stainzyme 12L 1 ex Novozymes A/S
- Mannanase enzyme is Mannaway 4L 1 ex Novozymes A/S
- Patent Blue V85 is a Colorant
- Acid Yellow 23 is a Colorant
- Bridged catalyst is BL1749 which has lUPAC name: lron(2+),
- Lipase enzyme is 100L Lipoclean from Novozymes A/S.
- Example 1 Synergistic effect of lipase and bleach catalyst on yellow curry stains
- Prototype fabric washing liquids were prepared according to the compositions given in table 1 . Knitted cotton fabric swatches stained with yellow curry supplied by Warwick Equest Ltd. - where the stain is applied to washed but otherwise untreated cotton - were washed at 25 °C for 30 minutes with unstained polyester and cotton ballast such that the liquor/cloth ratio was 25/1 , using 1 .3g fabric washing liquid with composition as shown in Table 1 in one litre of 26°FH (26 degrees French Hardness according to the Internationally recognised hardness scale where 1 degree French is defined as 10 milligrams of calcium carbonate per litre of water, equivalent to 10 ppm).
- the molecular weight of the bridged ligand catalyst with structure (II) according to the invention is 641 .85 and the molecular weight of the catalyst of structure (III) is 507.85. It would be expected that the prior art catalyst of structure (III) would be more effective on an equal weight basis if it was an alternative as suggested by US2003/166485. Testing was done using the concentrated liquid composition given in Table 3. The lipase used was Lipex 100L ex Novozymes and it was added over the side to each tergo pot, including the zero catalyst control
- test protocol was otherwise the same as for example 1 except that the test cloths were knitted cotton fabric swatches stained with Rogan Josh supplied by Warwick Equest Ltd. - where the stain is applied to washed but otherwise untreated cotton.
- the Rogan Josh used contained turmeric as one of the spices. Curcumin is a component of turmeric and is responsible for its yellow colour.
- Dequest 2010 is HEDP (1 -Hydroxyethylidene -1 ,1 ,-diphosphonic acid) ex Dequest AG.
- Endocellulase is Endolase® 5000L, an endocellulase enzyme promoted for its whitening benefits ex Novozymes.
- the stain removal data (expressed as ⁇ ( ⁇ E)) for each catalyst at different levels of inclusion is given in Table 4.
- the catalyst according to the invention provides superior air bleaching with lipase compared to the one in the prior art.
- Example 2 The comparative testing done in Example 2 was also carried out using Lipoclean as the Lipase enzyme, as was used for Example 1 . Again, the catalyst according to the invention outperformed that of the prior art when used with the lipase to air bleach yellow curry stains.
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP12788520.0A EP2809762B1 (en) | 2011-12-20 | 2012-11-19 | Liquid detergents comprising lipase and bleach catalyst |
ES12788520.0T ES2569052T3 (en) | 2011-12-20 | 2012-11-19 | Liquid detergents comprising lipase and bleaching catalyst |
BR112014014724A BR112014014724A8 (en) | 2011-12-20 | 2012-11-19 | detergent liquid composition, method of air bleaching a surface and use of the combination |
CN201280063097.XA CN103998593B (en) | 2011-12-20 | 2012-11-19 | Liquid detergents comprising lipase and bleach catalyst |
ZA2014/03702A ZA201403702B (en) | 2011-12-20 | 2014-05-21 | Liquid detergents comprising lipase and bleach catalyst |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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EP11194488.0 | 2011-12-20 | ||
EP11194488 | 2011-12-20 |
Publications (1)
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WO2013092051A1 true WO2013092051A1 (en) | 2013-06-27 |
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Application Number | Title | Priority Date | Filing Date |
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PCT/EP2012/072973 WO2013092051A1 (en) | 2011-12-20 | 2012-11-19 | Liquid detergents comprising lipase and bleach catalyst |
Country Status (6)
Country | Link |
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EP (1) | EP2809762B1 (en) |
CN (1) | CN103998593B (en) |
BR (1) | BR112014014724A8 (en) |
ES (1) | ES2569052T3 (en) |
WO (1) | WO2013092051A1 (en) |
ZA (1) | ZA201403702B (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2023116569A1 (en) * | 2021-12-21 | 2023-06-29 | Novozymes A/S | Composition comprising a lipase and a booster |
EP4299701A1 (en) * | 2022-06-27 | 2024-01-03 | The Procter & Gamble Company | A solid free-flowing particulate laundry detergent composition |
EP4299702A1 (en) * | 2022-06-27 | 2024-01-03 | The Procter & Gamble Company | A solid free-flowing particulate laundry detergent composition |
EP4299704A1 (en) * | 2022-06-27 | 2024-01-03 | The Procter & Gamble Company | A method of laundering and drying fabric |
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2023116569A1 (en) * | 2021-12-21 | 2023-06-29 | Novozymes A/S | Composition comprising a lipase and a booster |
EP4299701A1 (en) * | 2022-06-27 | 2024-01-03 | The Procter & Gamble Company | A solid free-flowing particulate laundry detergent composition |
EP4299702A1 (en) * | 2022-06-27 | 2024-01-03 | The Procter & Gamble Company | A solid free-flowing particulate laundry detergent composition |
EP4299704A1 (en) * | 2022-06-27 | 2024-01-03 | The Procter & Gamble Company | A method of laundering and drying fabric |
WO2024006654A1 (en) * | 2022-06-27 | 2024-01-04 | The Procter & Gamble Company | A solid free-flowing particulate laundry detergent composition |
WO2024006658A1 (en) * | 2022-06-27 | 2024-01-04 | The Procter & Gamble Company | A method of laundering and drying fabric |
WO2024006656A1 (en) * | 2022-06-27 | 2024-01-04 | The Procter & Gamble Company | A solid free-flowing particulate laundry detergent composition |
Also Published As
Publication number | Publication date |
---|---|
EP2809762A1 (en) | 2014-12-10 |
BR112014014724A2 (en) | 2017-06-13 |
CN103998593B (en) | 2017-05-03 |
ZA201403702B (en) | 2015-12-23 |
BR112014014724A8 (en) | 2017-07-04 |
CN103998593A (en) | 2014-08-20 |
EP2809762B1 (en) | 2016-03-23 |
ES2569052T3 (en) | 2016-05-06 |
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