EP1712611B1 - Waschmittelzusammensetzungen - Google Patents

Waschmittelzusammensetzungen Download PDF

Info

Publication number
EP1712611B1
EP1712611B1 EP06110296.8A EP06110296A EP1712611B1 EP 1712611 B1 EP1712611 B1 EP 1712611B1 EP 06110296 A EP06110296 A EP 06110296A EP 1712611 B1 EP1712611 B1 EP 1712611B1
Authority
EP
European Patent Office
Prior art keywords
detergent composition
surfactant
composition according
preferred
detersive surfactant
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.)
Revoked
Application number
EP06110296.8A
Other languages
English (en)
French (fr)
Other versions
EP1712611A1 (de
Inventor
Neil Joseph Lant
Steven George Patterson
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.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=36968364&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP1712611(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Priority claimed from EP05250995A external-priority patent/EP1693439A1/de
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to PL06110296T priority Critical patent/PL1712611T3/pl
Priority to EP06110296.8A priority patent/EP1712611B1/de
Publication of EP1712611A1 publication Critical patent/EP1712611A1/de
Application granted granted Critical
Publication of EP1712611B1 publication Critical patent/EP1712611B1/de
Revoked legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/38Products with no well-defined composition, e.g. natural products
    • C11D3/386Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38627Preparations containing enzymes, e.g. protease or amylase containing lipase
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/04Water-soluble compounds
    • C11D3/06Phosphates, including polyphosphates
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/12Water-insoluble compounds
    • C11D3/124Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246Silicates, e.g. diatomaceous earth
    • C11D3/128Aluminium silicates, e.g. zeolites
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/38Products with no well-defined composition, e.g. natural products
    • C11D3/386Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38636Preparations containing enzymes, e.g. protease or amylase containing enzymes other than protease, amylase, lipase, cellulase, oxidase or reductase

Definitions

  • the present invention relates to laundry detergent compositions and in particular to detergents comprising lipolytic or lipase enzymes.
  • lipase enzymes such as Lipolase (trade name, Novozymes) worked particularly effectively at the lower moisture levels of the drying phase of the wash process. These enzymes tended to produce significant cleaning only in the second wash step because the active site of the enzyme was occupied by water during the washing process, so that fat breakdown was significant only on soils remaining on laundered clothes during the drying stage, the broken down fats then being removed in the next washing step.
  • lipases have been developed that also work effectively during the wash phase of the cleaning process, so that as well as cleaning in the second washing step, a significant improvement in cleaning effect due to lipase enzyme can be found in the first wash-cycle.
  • Such enzymes are as described in WO00/60063 and Research Disclsoure IP6553D. Such enzymes are referred to below as first wash lipases.
  • first wash lipases examples include certain variants of lipolase (wild-type Humicola lanuginosa) which should comprise one or more substitutions with positive amino acids near the N-terminal in the three-dimensional structure.
  • the variants should further comprise a peptide addition at the C-terminal and/or should meet certain limitations on electrically charged amino acids at positions 90-101 and 210, see also WO 03/097780 .
  • the problem facing the present inventors was how to maximise performance from this new generation of enzymes.
  • the present inventors found that whilst a small benefit could be achieved formulating such enzymes according to present day detergent formulations by simply replacing existing lipase enzymes with the new generation of enzymes, a considerable improvement in performance was found by formulating the detergent compositions in a different way and even reducing the levels of some conventional detergent ingredients.
  • the use of lipase enzymes in some conditions can generate malodours as the fatty soils are broken down to tri-glycerides.
  • the present invention aims to alleviate that problem.
  • a detergent composition comprising a lipase enzyme producing First Wash lard removal performance better than that produced by WT Lipolase (tradename from Novozymes) using the Lard First Wash Test described below, and the detergent composition having a reserve alkalinity greater than 7.5 and comprising up to 15 wt% aluminosilicate builder and/or phosphate builder.
  • WT Lipolase from Novozymes is described in US 5 869 438 , seq#2.
  • the detergent compositions of the invention comprise less than 15 wt% builders selected from aluminosilicate (zeolite) builder and/or phosphate builder. In a further preferred aspect of the invention, the compositions comprise less than 10 wt% zeolite and/or phosphate builder, or even less than 5 wt% or 4 wt % zeolite and/or phosphate builder.
  • zeolite aluminosilicate
  • the present inventors have found that when a first wash lipase is used in conjunction with high reserve alkalinity and low levels of builder, the problems of malodour formation are reduced or eliminated. Without wishing to be bound by theory the inventors work suggests that this is because the alkalinity in the wash neutralises the malodorous fatty acids produced by break-down of fatty soils by the lipase enzymes and then after neutralisation, calcium salts of the fatty acids form having a significantly lower vapour pressure than the protonated fatty acids released by the enzymes.
  • compositions show unexpectedly good performance. Without wishing to be bound by theory it is believed that this is due to fatty acids released by the lipase during lipolysis of fatty soils acting to (i) destabilize these stains via a hardness sequestration effect and (ii) reduce the wash pH slightly resulting in lightening of pH-sensitive stains.
  • the reference lipase used in this invention is the wild type lipase derived from Humicola lanuginosa strain DSM 4109. It is described in EP258068 and EP305216 and has the amino acid sequence shown in positions 1-269 of SEQ ID NO: 2 of US5869438 (attached hereto). In this specification, the reference lipase is also referred to as Lipolase.
  • the lipase of the invention comprises one or more (e.g. 2-4, particularly two) substitutions of an electrically neutral or negatively charged amino acid near E1 or Q249 with a positively charged amino acid, preferably R.
  • substitution is at the surface of the three-dimensional structure within 15 ⁇ of E1 or Q249 at any ofpositions 1-11, 90, 95, 169, 171-175, 192-211, 213-226, 228-258, 260-262.
  • substitution may be within 10 ⁇ of E1 or Q249, e.g. at any of positions 1-7, 10, 175, 195, 197-202, 204-206, 209, 215, 219-224, 230-239, 242-254.
  • substitution may be within 15 ⁇ of E1, e.g. at any of positions 1-11, 169, 171, 192-199, 217-225, 228-240, 243-247, 249, 261-262.
  • substitution is most preferably within 10 ⁇ of E1, e.g. at any of positions 1-7, 10, 219-224 and 230-239.
  • substitutions are S3R, S224R, P229R, T231R, N233R, D234R and T244R.
  • the lipase may comprise a peptide addition attached to C-terminal L269.
  • the peptide addition improves the first-wash performance in a variety of detergents.
  • the peptide addition preferably consists of 1-5 amino acids, e.g. 2, 3 or 4 amino acids.
  • the amino acids of the peptide addition will be numbered 270, 271, etc.
  • the peptide addition may consist of electrically neutral (e.g. hydrophobic) amino acids, e.g. PGL or PG.
  • the lipase peptide addition consists of neutral (e.g. hydrophobic) amino acids and the amino acid C, and the lipase comprises substitution of an amino acid with C at a suitable location so as to form a disulfide bridge with the C of the peptide addition. Examples are:
  • the lipase used in the invention preferably meets certain limitations on electrically charged amino acids at positions 90-101 and 210.
  • amino acid 210 may be negative.
  • E210 may be unchanged or it may have the substitution E210D/C/Y, particularly E210D.
  • the lipase may comprise a negatively charged amino acid at any of positions 90-101 (particularly 94-101), e.g. at position D96 and/or E99.
  • the lipase may comprise a neutral or negative amino acid at position N94, i.e. N94 (neutral or negative), e.g. N94N/D/E.
  • the lipase may have a negative or neutral net electric charge in the region 90-101 (particularly 94-101), i.e. the number of negative amino acids is equal to or greater than the number of positive amino acids.
  • the region may be unchanged from Lipolase, having two negative amino acids (D96 and E99) and one positive (K98), and having a neutral amino acid at position 94 (N94), or the region may be modified by one or more substitutions.
  • N94, N96 and E99 may have a negative or unchanged electric charge.
  • all three amino acids may be unchanged or may be changed by a conservative or negative substitution, i.e. N94 (neutral or negative), D(negative) and E99(negative).
  • N94D/E and D96E are examples of the three amino acids.
  • one of the three may be substituted so as to increase the electric charge, i.e. N94 (positive), D96 (neutral or positive) or E99 (neutral or positive).
  • Examples are N94K/R, D96I/L/N/S/W or E99N/Q/K/R/H.
  • the substitution of a neutral with a negative amino acid may improve the performance in an anionic detergent.
  • the substitution of a neutral amino acid with a positive amino acid may provide a variant lipase with good performance both in an anionic detergent and in an anionic/non-ionic detergent (a detergent with e.g. 40-70 % anionic out of total surfactant).
  • a substitution Q249R/K/H and/or a substitution of R209 with a neutral or negative amino acid e.g. R209P/S
  • the lipase may optionally comprise the substitution G91A.
  • the lipase may optionally comprise substitutions of one or more additional amino acids.
  • substitutions may, e.g. be made according to principles known in the art, e.g. substitutions described in WO92/05249 , WO94/25577 , WO95/22615 , WO97/04079 and WO97/07202 .
  • Specific examples of suitable combinations of substitutions are given in the table bridging pages 4 and 5 of WO00/60063 . Nomenclature for amino acid modifications is as described in WO00/60063 .
  • the preferred lipase enzymes are described in WO00/60063 , the most preferred being Lipex (registered tradename of Novozymes), a variant of the Humicola lanuginosa (Thermomyces lanuginosus) lipase (Lipolase registered tradename of Novozymes) with the mutations T231R and N233R.
  • the lipase enzyme incorporated into the detergent compositions of the present invention is generally present in an amount of 10 to 20000 LU/g of the detergent composition, or even 100 to 10000 LU/g.
  • the LU unit for lipase activity is defined in WO99/42566 .
  • the lipase dosage in the wash solution is typically from 0.01 to 5 mg/l active lipase protein, more typically from 0.1 to 2mg/l as enzyme protein.
  • the lipase enzyme may be incorporated into the detergent composition in any convenient form, generally in the form of a non-dusting granulate, a stabilised liquid or a protected, for example, coated enzyme particle.
  • the percentage of lard removed is determined as:
  • the reflectance (which may also be termed remission) is measured on an Elrepho 2000 apparatus from Datacolor which illuminates the sample with 2 xenon blitz lamps and measures the amount of reflected light so that entirely white corresponds to a 100% reflectance and entirely black a 0% reflectance. Comparing the results for lard removal due to the presence of enzyme, lipase enzymes giving better performance than WT LipolaseTM are suitable for use in the compositions of the present invention.
  • the RA of the detergent compositions of the invention will be greater than 7.5 and preferably greater than 8.
  • the RA may be greater than 9 or even greater than 9.5 or 10 or higher.
  • the RA may be up to 20 or higher.
  • Adequate reserve alkalinity may be provided, for example, by one or more of alkali metal silicates (excluding crystalline layered silicate), typically amorphous silicate salts, generally 1.2 to 2.2 ratio sodium salts, alkali metal typically sodium carbonate, bicarbonate and/or sesquicarbonates.
  • alkali metal silicates excluding crystalline layered silicate
  • typically amorphous silicate salts generally 1.2 to 2.2 ratio sodium salts
  • alkali metal typically sodium carbonate, bicarbonate and/or sesquicarbonates.
  • STPP and persalts such as perborates and percarbonates also contribute to alkalinity. Buffering is necessary to maintain an alkaline pH during the wash process counteracting the acidity of soils, especially fatty acids liberated by the lipase enzyme.
  • the detergent composition preferably comprises from 0 wt% to 50 wt% silicate salt, more usually 5 to 30 wt% silicate salt, or 7 to 20 wt% silicate salt, usually sodium silicate.
  • the detergent compositions of the invention may comprise a carbonate salt, typically from 1 wt% to 70 wt%, or from 5 wt% to 50 wt% or from 10 wt% to 30 wt% carbonate salt.
  • Preferred carbonate salts are sodium carbonate and/or sodium bicarbonate and/or sodium sesquicarbonate.
  • the carbonate salt may be incorporated into the detergent composition wholly or partially via a mixed salt such as Burkeite.
  • a highly preferred carbonate salt is sodium carbonate.
  • the composition may comprise from 5 wt% to 50 wt% sodium carbonate, or from 10 to 40 wt% or even 15 to 35 wt% sodium carbonate. It may also be desired for the composition to comprise from 1wt% to 20 wt% sodium bicarbonate, or even 2 to 10 or 8 wt%.
  • the weight ratio of sodium carbonate and/or sodium silicate to zeolite builder may be at least 5:1, preferably at least 10:1, or at least 15:1, or at least 20:1 or even at least 25:1
  • the carbonate salt, or at least part thereof is typically in particulate form, typically having a weight average particle size in the range of from 200 to 500 micrometers. However, it may be preferred for the carbonate salt, or at least part thereof, to be in micronised particulate form, typically having a weight average particle size in the range of from 4 to 40 micrometers; this is especially preferred when the carbonate salt, or at least part thereof, is in the form of a co-particulate admixture with a detersive surfactant, such as an alkoxylated anionic detersive surfactant.
  • a detersive surfactant such as an alkoxylated anionic detersive surfactant.
  • the levels of carbonate and/or silicate salts typically sodium carbonate and sodium silicate will be from 10 to 70 wt%, or from 10 or even 15 to 50 wt% based on the total weight of the composition.
  • laundry detergents comprise strong inorganic builder, with either phosphate builder typically sodium tripolyphosphate (STPP), or zeolite typically sodium aluminosilicate builder being used as the predominant strong builder.
  • phosphate builder typically sodium tripolyphosphate (STPP)
  • zeolite typically sodium aluminosilicate builder
  • the amount of strong builder selected from phosphate and/or zeolite builder is less than 15 wt% based on the total weight of the detergent composition, preferably below 10 wt%, or even below 8 or 5 or 4 or 3 or 2 wt% .
  • compositions of the invention may comprise from 0 wt% to less than 15wt% zeolite builder, and 0 wt% to less than 15 wt% phosphate builder, the total amount of phosphate and/or zeolite not exceeding 15 wt%, and preferably being below 10 wt% as described above.
  • the compositions of the invention comprise from 0 wt% to 8 wt%, or from 0 wt% to 5 or 4 wt%, or from 0 wt% to 3 or even less than 2 wt% zeolite builder. It may even be preferred for the composition to be essentially free from zeolite builder.
  • the composition comprises no deliberately added zeolite builder. This is especially preferred if it is desirable for the composition to be very highly soluble, to minimise the amount of water-insoluble residues (for example, which may deposit on fabric surfaces), and also when it is highly desirable to have transparent wash liquor.
  • Zeolite builders include zeolite A, zeolite X, zeolite P and zeolite MAP.
  • compositions of the invention may comprise from 0 wt% to less than 15wt% phosphate builder.
  • the composition preferably comprises from 0 wt% to 8 wt%, or from 0 wt% to 5 or 4 wt%, or from 0 wt% to 3 or even 2 wt% phosphate builder. It may even be preferred for the composition to be essentially free from phosphate builder. By essentially free from phosphate builder it is typically meant that the composition comprises no deliberately added phosphate builder. This is especially preferred if it is desirable for the composition to have a very good environmental profile.
  • Phosphate builders include sodium tripolyphosphate.
  • the total level of weak builders selected from layered silicate (SKS-6), citric acid, citrate salts and nitrilo triacetic acid or salt thereof is below 15 wt%, more preferably below 8 wt%, more preferably below 4 wt% or even below 3 or 2 wt% based on the total weight of the detergent composition.
  • the level of each of layered silicate, citric acid, citrate salts and nitrilo triacetic acid or salt thereof will be below 10 wt% or even below 5 wt% or wt% based on the total weight of the composition.
  • builders bring several benefits to the formulator, their main role is to sequester divalent metal ions (such as calcium and magnesium ions) from the wash solution that would otherwise interact negatively with the surfactant system. Builders are also effective at removing metal ions and inorganic soils from the fabric surface too, leading to improved removal of particulate and beverage stains. It would therefore be expected that reduction of their levels would negatively impact on cleaning performance and therefore, preparation of detergent compositions that are effective with the claimed reduced levels of phosphate and zeolite builders is surprising.
  • divalent metal ions such as calcium and magnesium ions
  • a highly preferred adjunct component of the compositions of the invention is a surfactant.
  • the detergent composition comprises one or more surfactants.
  • the detergent composition comprises (by weight of the composition) from 0% to 50%, preferably from 5% and more preferably from 10 or even 15 wt% to 40%, or to 30%, or to 20% one or more surfactants.
  • Preferred surfactants are anionic surfactants, non-ionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants, cationic surfactants and mixtures thereof.
  • Suitable anionic surfactants typically comprise one or more moieties selected from the group consisting of carbonate, phosphate, phosphonate, sulphate, sulphonate, carboxylate and mixtures thereof.
  • the anionic surfactant may be one or mixtures of more than one of C 8-18 alkyl sulphates and C 8-18 alkyl sulphonates.
  • Suitable anionic surfactants incorporated alone or in mixtures in the compositions of the invention are also the C 8-18 alkyl sulphates and/or C 8-18 alkyl sulphonates optionally condensed with from 1 to 9 moles of C 1-4 alkylene oxide per mole of C 8-18 alkyl sulphate and/or C 8-18 alkyl sulphonate.
  • the alkyl chain of the C 8-18 alkyl sulphates and/or C 8-18 alkyl sulphonates may be linear or branched, preferred branched alkyl chains comprise one or more branched moieties that are C 1-6 alkyl groups.
  • suitable anionic surfactants include the C 10 -C 20 primary, branched-chain, linear-chain and random-chain alkyl sulphates (AS), typically having the following formula: CH 3 (CH 2 ) x CH 2 -OSO 3 - M + wherein, M is hydrogen or a cation which provides charge neutrality, preferred cations are sodium and ammonium cations, wherein x is an integer of at least 7, preferably at least 9; C 10 -C 18 secondary (2,3) alkyl sulphates, typically having the following formulae: wherein, M is hydrogen or a cation which provides charge neutrality, preferred cations include sodium and ammonium cations, wherein x is an integer of at least 7, preferably at least 9, y is an integer of at least 8, preferably at least 9; C 10 -C 18 alkyl alkoxy carboxylates; mid-chain branched alkyl sulphates as described in more detail in US 6,020,303 and US 6,060,443
  • Preferred anionic surfactants are C 8-18 alkyl benzene sulphates and/or C 8-18 alkyl benzene sulphonates.
  • the alkyl chain of the C 8-18 alkyl benzene sulphates and/or C 8-18 alkyl benzene sulphonates may be linear or branched, preferred branched alkyl chains comprise one or more branched moieties that are C 1-6 alkyl groups.
  • Suitable anionic surfactants are selected from the group consisting of: C 8-18 alkenyl sulphates, C 8-18 alkenyl sulphonates, C 8-18 alkenyl benzene sulphates, C 8-18 alkenyl benzene sulphonates, C 8-18 alkyl di-methyl benzene sulphate, C 8-18 alkyl di-methyl benzene sulphonate, fatty acid ester sulphonates, di-alkyl sulphosuccinates, and combinations thereof.
  • esters of alpha-sulfonated fatty acids typically containing from 6 to 20 carbon atoms in the fatty acid group and from 1 to 10 carbon atoms in the ester group; 2-acyloxy-alkane-1-sulfonic acid and salts thereof, typically containing from about 2 to 9 carbon atoms in the acyl group and from about 9 to 23 carbon atoms in the alkane moiety; alpha-olefin sulfonates (AOS), typically containing from about 12 to 24 carbon atoms; and beta-alkoxy alkane sulfonates, typically containing from about 1 to 3 carbon atoms in the alkyl group and from about 8 to 20 carbon atoms in the alkane moiety.
  • AOS alpha-olefin sulfonates
  • beta-alkoxy alkane sulfonates typically containing from about 1 to 3 carbon atoms in the alkyl group and from about 8 to 20 carbon atoms in the alkane moiety.
  • fatty acid esters containing an alkyl group typically with from 10 to 20 carbon atoms.
  • C 1-4 most preferably methyl ester sulphonates.
  • Preferred are C 16-18 methyl ester sulphonates (MES).
  • the anionic surfactants may be present in the salt form.
  • the anionic surfactant(s) may be an alkali metal salt of any of the above.
  • Preferred alkali metals are sodium, potassium and mixtures thereof.
  • Preferred anionic detersive surfactants are selected from the group consisting of: linear or branched, substituted or unsubstituted, C 12-18 alkyl sulphates; linear or branched, substituted or unsubstituted, C 10-13 alkylbenzene sulphonates, preferably linear C 10-13 alkylbenzene sulphonates; and mixtures thereof. Highly preferred are linear C 10-13 alkylbenzene sulphonates.
  • linear C 10-13 alkylbenzene sulphonates that are obtainable, preferably obtained, by sulphonating commercially available linear alkyl benzenes (LAB);
  • suitable LAB include low 2-phenyl LAB, such as those supplied by Sasol under the tradename Isochem ® or those supplied by Petresa under the tradename Petrelab ® , other suitable LAB include high 2-phenyl LAB, such as those supplied by Sasol under the tradename Hyblene ® .
  • the anionic detersive surfactant may be structurally modified in such a manner as to cause the anionic detersive surfactant to be more calcium tolerant and less likely to precipitate out of the wash liquor in the presence of free calcium ions.
  • This structural modification could be the introduction of a methyl or ethyl moiety in the vicinity of the head group of the anionic detersive surfactant, as this can lead to a more calcium tolerant anionic detersive surfactant due to steric hindrance of the head group, which may reduce the affinity of the anionic detersive surfactant for complexing with free calcium cations in such a manner as to cause precipitation out of solution.
  • the composition may comprise an alkoxylated anionic surfactant. Where present such a surfactant will generally be present in amounts form 0.1 wt% to 40 wt%, generally 0.1 to 10 wt%based on the detergent composition as a whole. It may be preferred for the composition to comprise from 3wt% to 5wt% alkoxylated anionic detersive surfactant, or it may be preferred for the composition to comprise from 1wt% to 3wt% alkoxylated anionic detersive surfactant.
  • the alkoxylated anionic detersive surfactant is a linear or branched, substituted or unsubstituted C 12-18 alkyl alkoxylated sulphate having an average degree of alkoxylation of from 1 to 30, preferably from 1 to 10.
  • the alkoxylated anionic detersive surfactant is a linear or branched, substituted or unsubstituted C 12-18 alkyl ethoxylated sulphate having an average degree of ethoxylation of from 1 to 10.
  • the alkoxylated anionic detersive surfactant is a linear unsubstituted C 12-18 alkyl ethoxylated sulphate having an average degree of ethoxylation of from 3 to 7.
  • the alkoxylated anionic detersive surfactant may also increase the non-alkoxylated anionic detersive surfactant activity by making the non-alkoxylated anionic detersive surfactant less likely to precipitate out of solution in the presence of free calcium cations.
  • the weight ratio of non-alkoxylated anionic detersive surfactant to alkoxylated anionic detersive surfactant is less than 5:1, or less than 3:1, or less than 1.7:1, or even less than 1.5:1. This ratio gives optimal whiteness maintenance performance combined with a good hardness tolerency profile and a good sudsing profile.
  • the weight ratio of non-alkoxylated anionic detersive surfactant to alkoxylated anionic detersive surfactant is greater than 5:1, or greater than 6:1, or greater than 7:1, or even greater than 10:1. This ratio gives optimal greasy soil cleaning performance combined with a good hardness tolerency profile, and a good sudsing profile.
  • Suitable alkoxylated anionic detersive surfactants are: Texapan LEST TM by Cognis; Cosmacol AES TM by Sasol; BES151 TM by Stephan; Empicol ESC70/U TM ; and mixtures thereof.
  • compositions of the invention may comprise non-ionic surfactant. Where present it is generally present in amounts of from 0.5wt% to 20, more typically 0.5 to 10 wt% based on the total weight of the composition.
  • the composition may comprise from 1wt% to 7wt% or from 2wt% to 4wt% non-ionic detersive surfactant.
  • non-ionic detersive surfactant helps to provide a good overall cleaning profile, especially when laundering at high temperatures such as 60°C or higher.
  • the non-ionic detersive surfactant could be an alkyl polyglucoside and/or an alkyl alkoxylated alcohol.
  • the non-ionic detersive surfactant is a linear or branched, substituted or unsubstituted C 8-18 alkyl ethoxylated alcohol having an average degree of ethoxylation of from 1 to 50, more preferably from 3 to 40.
  • Non-ionic surfactants having a degree of ethoxylation from 3 to 9 may be especially useful either.
  • Nonionic surfactants having an HLB value of from 13 to 25, such as C 8-18 alkyl ethoxylated alcohols having an average degree of ethoxylation from 15 to 50, or even from 20 to 50 may also be preferred non-ionic surfactants in the compositions of the invention.
  • these latter non-ionic surfactants are Lutensol AO30 and similar materials disclosed in WO04/041982 . These may be beneficial as they have good lime soap dispersant properties.
  • the non-ionic detersive surfactant not only provides additional soil cleaning performance but may also increase the anionic detersive surfactant activity by making the anionic detersive surfactant less likely to precipitate out of solution in the presence of free calcium cations.
  • the weight ratio of non-alkoxylated anionic detersive surfactant to non-ionic detersive surfactant is in the range of less than 8:1, or less than 7:1, or less than 6:1 or less than 5:1, preferably from 1:1 to 5:1, or from 2:1 to 5:1, or even from 3:1 to 4:1.
  • the detergent compositions are free of cationic surfactant.
  • the composition optionally may comprise from 0.1wt% to 10 or 5wt% cationic detersive surfactant.
  • the composition comprises from 0.5wt% to 3wt%, or from 1% to 3wt%, or even from 1wt% to 2wt% cationic detersive surfactant. This is the optimal level of cationic detersive surfactant to provide good cleaning.
  • Suitable cationic detersive surfactants are alkyl pyridinium compounds, alkyl quaternary ammonium compounds, alkyl quaternary phosphonium compounds, and alkyl ternary sulphonium compounds.
  • the cationic detersive surfactant can be selected from the group consisting of: alkoxylate quaternary ammonium (AQA) surfactants as described in more detail in US 6,136,769 ; dimethyl hydroxyethyl quaternary ammonium as described in more detail in US 6,004,922 ; polyamine cationic surfactants as described in more detail in WO 98/35002 , WO 98/35003 , WO 98/35004 , WO 98/35005 , and WO 98/35006 ; cationic ester surfactants as described in more detail in US 4,228,042 , US 4,239,660 , US 4,260,529 and US 6,022,844 ; amino surfactants as described in more detail in US 6,221,825 and WO 00/47708 , specifically amido propyldimethyl amine; and mixtures thereof.
  • AQA alkoxylate quaternary ammonium
  • Preferred cationic detersive surfactants are quaternary ammonium compounds having the general formula: (R)(R 1 )(R 2 )(R 3 )N + X - wherein, R is a linear or branched, substituted or unsubstituted C 6-18 alkyl or alkenyl moiety, R 1 and R 2 are independently selected from methyl or ethyl moieties, R 3 is a hydroxyl, hydroxymethyl or a hydroxyethyl moiety, X is an anion which provides charge neutrality, preferred anions include halides (such as chloride), sulphate and sulphonate.
  • Preferred cationic detersive surfactants are mono-C 8-18 alkyl mono-hydroxyethyl di-methyl quaternary ammonium chlorides. Highly preferred cationic detersive surfactants are mono-C 8-18 alkyl mono-hydroxyethyl di-methyl quaternary ammonium chloride, mono-C 10-12 alkyl mono-hydroxyethyl di-methyl quaternary ammonium chloride and mono-C 10 alkyl mono-hydroxyethyl di-methyl quaternary ammonium chloride.
  • Cationic surfactants such as Praepagen HY (tradename Clariant) may be useful and may also be useful as a suds booster.
  • the cationic detersive surfactant provides additional greasy soil cleaning performance.
  • the cationic detersive surfactant may increase the tendency of any non-alkoxylated anionic detersive surfactant to precipitate out of solution.
  • the cationic detersive surfactant and any non-alkoxylated anionic detersive surfactant are separated in the detergent composition of the invention, for example if cationic surfactant is present, preferably the cationic a dn any anionic surfactant, particularly non-alkoxylated anionic surfactant will be present in the composition in separate particles.
  • the weight ratio of non-alkoxylated anionic detersive surfactant to cationic detersive surfactant is in the range of from 5:1 to 25:1, more preferably from 5:1 to 20:1 or from 6:1 to 15:1, or from 7:1 to 10:1, or even from 8:1 to 9:1.
  • the detergent composition comprises from 1 to 50 wt% anionic surfactant, more typically from 2 to 40 wt%.
  • Alkyl benzene sulphonates are preferred anionic surfactants.
  • compositions of the present invention comprise at least two different surfactants in combination comprising at least one selected from a first group, the first group comprising alkyl benzene sulphonate and MES surfactant; and at least one selected from a second group, the second group comprising alkoxylated anionic surfactant, MES and alkoxylated non-ionic surfactant and alpha olefin sulfonates (AOS).
  • a particularly preferred combination comprises alkyl benzene sulphonate, preferably LAS in combination with MES.
  • a further particularly preferred combination comprises alkyl benzene sulphonate, preferably LAS with an alkoxylated anionic surfactant, preferably C 8 - 18 alkyl alkoxylated sulphate having an average degree of alkoxylation of from 1 to 10.
  • a third particularly preferred combination comprises alkyl benzene sulphonate, preferably LAS in combination with an alkoxylated non-ionic surfactant, preferably C 8-18 alkyl ethoxylated alcohol having a degree of alkoxylation of from 15 to 50, preferably from 20 to 40.
  • the weight ratio of the surfactant from the first group to the weight ratio of the surfactant from the second group is typically 1:5 to 100:1, preferably 1:2 to 100:1 or 1:1 to 50:1 or even to 20:1 or 10:1.
  • the levels of the surfactants are as described above under the specific classes of surfactants. Presence of AE3S and/or MES in the system is preferred on account of their exceptional hardness-tolerance and ability to disperse lime soaps which are formed during the wash by lipase.
  • the surfactant in the detergent compositions of the invention comprises at least three surfactants, at least one from each of the first and second groups defined above and in addition a third surfactant, preferably also from the first or second groups defined above.
  • the detergent compositions of the invention may surprisingly contain relatively low levels of surfactant and yet still perform good cleaning, on account of the soil removal functionality delivered by the lipase, so that the overall level of surfactant may be below 12 wt%, or 10 wt% or 8 wt% based on total weight of the composition
  • compositions of the invention may comprise at least 0.1 wt%, or at least 0.5 wt%, or at least 2 or 3 wt%, or even at least 5 wt% polymeric polycarboxylates up to levels of 30 wt% or 20 wt% or 10 wt%.
  • Preferred polymeric polycarboxylates include: polyacrylates, preferably having a weight average molecular weight of from 1,000Da to 20,000Da; co-polymers of maleic acid and acrylic acid, preferably having a molar ratio of maleic acid monomers to acrylic acid monomers of from 1:1 to 1:10 and a weight average molecular weight of from 10,000Da to 200,000Da, or preferably having a molar ratio of maleic acid monomers to acrylic acid monomers of from 0.3:1 to 3:1 and a weight average molecular weight of from 1,000Da to 50,000Da.
  • Suitable polycarboxylates are the Sokalan CP, PA and HP ranges (BASF) such as Sokalan CP5, PA40 and HP22, and the Alcosperse range of polymers (Alco) such as Alcosperse 725, 747, 408, 412 and 420.
  • Sokalan CP Sokalan CP5
  • PA40 and HP22 PA40 and HP22
  • Alcosperse range of polymers Alcosperse 725, 747, 408, 412 and 420.
  • the composition comprises at least 1wt%, or at least 2wt%, or at least 3wt% soil dispersants.
  • the detergent composition also comprises a suds booster, typically in amounts from 0.01 to 10 wt%, preferably in amounts from 0.02 to 5 wt% based on the total weight of the composition.
  • Suitable suds boosters include fatty acid amides, fatty acid alkalonamides, betaines, sulfobetaines and amine oxides. Particularly preferred materials are cocamidopropyl betaine, cocomonoethanolamide and amine oxide.
  • a suitable amine oxide is Admox 12, supplied by Albemarle.
  • the detergent compositions of the invention may additionally comprise anti-redeposition polymers such as the polymeric polycarboxylates described above.
  • anti-redeposition polymers such as the polymeric polycarboxylates described above.
  • cellulose ethers such as carboxymethyl cellulose (CMC) will be useful.
  • a suitable CMC is Tylose CR1500 G2, sold by Clariant.
  • Suitable polymers are also sold by Andercol, Colombia under the Textilan brand name.
  • additives with lime soap dispersancy functionality such as the aforementioned MES, AES, highly ethoxylated nonionic surfactant or polymers showing excellent lime soap dispersancy such as Acusol 460N (Rohm & Haas). Lists of suitable lime soap dispersants are given in the following references and documents cited therein.
  • a soil release polymer has been found to be especially beneficial in further strengthening the stain removal and cleaning benefits of the development, especially on synthetic fibres.
  • Modified cellulose ethers such as methyl hydroxyethyl cellulose (MHEC), for example as sold by Clariant as Tylose MH50 G4 and Tylose MH300 G4, are preferred.
  • Polyester-based Soil Release Polymers are especially preferred as they can also be effective as lime soap dispersants. Examples of suitable materials are Repel-o-Tex PF (supplied by Rhodia), Texcare SRA100 (supplied by Clariant) and Sokalan SR100 (BASF)
  • the formulations may contain one or more other enzymes in addition to the first wash lipase, for example protease, amylase, cellulase (especially endoglucanase), pectate lyase and/or mannanase.
  • the present invention relates to granular compositions. Where the detergent compositions of the invention are solid, conventionally, surfactants are incorporated into agglomerates, extrudates or spray dried particles along with solid materials, usually builders, and these may be admixed to produce a fully formulated detergent composition according to the invention.
  • the detergent compositions of the present invention are preferably those having an overall bulk density of from 350 to 1200 g/l, more preferably 450 to 1000g/l or even 500 to 900g/l.
  • the detergent particles of the detergent composition in a granular form have a size average particle size of from 200 ⁇ m to 2000 ⁇ m, preferably from 350 ⁇ m to 600 ⁇ m.
  • the detergent compositions of the invention will comprise a mixture of detergent particles including combinations of agglomerates, spray-dried powders and/or dry added materials such as bleaching agents, enzymes etc.
  • the detergent compositions of the invention comprise an anionic surfactant from the list above which is a non-alkoxylated anionic detersive surfactant and this is preferably incorporated into the detergent composition in particulate form, such as via an agglomerate, a spray-dried powder, an extrudate, a bead, a noodle, a needle or a flake. Spray-dried particles are preferred.
  • the agglomerate preferably comprises at least 20%, by weight of the agglomerate, of a non-alkoxylated anionic detersive surfactant, more preferably from 25wt% to 65wt%, by weight of the agglomerate, of a non-alkoxylated anionic detersive surfactant. It may be preferred for part of the non-alkoxylated anionic detersive surfactant to be in the form of a spray-dried powder (e.g. a blown powder), and for part of the non-alkoxylated anionic detersive surfactant to be in the form of a non-spray-dried powder (e.g.
  • agglomerate, or an extrudate, or a flake such as a linear alkyl benzene sulphonate flake; suitable linear alkyl benzene sulphonate flakes are supplied by Pilot Chemical under the tradename F90 ® , or by Stepan under the tradename Nacconol 90G ® ). This is especially preferred when it is desirable to incorporate high levels of non-alkoxylated anionic detersive surfactant in the composition.
  • Any alkoxylated anionic detersive surfactant may be incorporated into the detergent compositons of the invention via a spray-dried particle of a non-spray-dried powder such as an extrudate, agglomerate, preferably an agglomerate.
  • a spray-dried particle of a non-spray-dried powder such as an extrudate, agglomerate, preferably an agglomerate.
  • Non- spray dried particles are preferred when it is desirable to incorporate high levels of alkoxylated anionic detersive surfactant in the composition
  • any non-ionic detersive surfactant, or at least part thereof can be incorporated into the composition in the form of a liquid spray-on, wherein the non-ionic detersive surfactant, or at least part thereof, in liquid form (e.g. in the form of a hot-melt) is sprayed onto the remainder of the composition.
  • the non-ionic detersive surfactant, or at least part thereof may be in included into a particulate for incorporation into the detergent composition of the invention and the non-ionic detersive surfactant, or at least part thereof, may be dry-added to the remainder of the composition.
  • the non-ionic surfactant, or at least part thereof may be in the form of a co-particulate admixture with a solid carrier material such as carbonate salt, sulphate salt, burkeite, silica or any mixture thereof.
  • Any non-ionic detersive surfactant, or at least part thereof, may be in a co-particulate admixture with either an alkoxylated anionic detersive surfactant, a non-alkoxylated anionic detersive surfactant or a cationic detersive surfactant.
  • the non-ionic detersive surfactant, or at least part thereof, may be agglomerated or extruded with either an alkoxylated anionic detersive surfactant, a non-alkoxylated anionic detersive surfactant or a cationic detersive surfactant.
  • the cationic detersive surfactant if present may be incorporated into the composition by incorporation in a particulate, such as a spray-dried powder, an agglomerate, an extrudate, a flake, a noodle, a needle, or any combination thereof.
  • a particulate such as a spray-dried powder, an agglomerate, an extrudate, a flake, a noodle, a needle, or any combination thereof.
  • the cationic detersive surfactant, or at least part thereof is in the form of a spray-dried powder or an agglomerate.
  • a detergent composition comprising granular components, and comprising at least two separate surfactant components or even at least three separate surfactant components: a first, a second and an optional third surfactant component.
  • These separate surfactant components may be present in separate particulates so that at least two surfactant components are separate from one another in the detergent composition.
  • the composition preferably comprises at least two separate surfactant components, each in particulate form. It may be preferred for the composition to comprise at least three separate surfactant components, each in particulate form.
  • the first surfactant component predominantly comprises an alkoxylated detersive surfactant.
  • predominantly comprises it is meant that the first surfactant component comprises greater than 50%, by weight of the first surfactant component, of an alkoxylated anionic detersive surfactant, preferably greater than 60%, or greater than 70%, or greater than 80%, or greater than 90% or even essentially 100%, by weight of the first surfactant component, of an alkoxylated anionic detersive surfactant.
  • the first surfactant component comprises less than 10%, by weight of the first surfactant component, of a non-alkoxylated anionic detersive surfactant, preferably less than 5%, or less than 2%, or even 0%, by weight of the first surfactant component, of a non-alkoxylated anionic detersive surfactant.
  • the first surfactant component is essentially free from non-alkoxylated anionic detersive surfactant.
  • essentially free from non-alkoxylated anionic detersive surfactant it is typically meant that the first surfactant component comprises no deliberately added non-alkoxylated anionic detersive surfactant. This is especially preferred in order to ensure that the composition has good dispensing and dissolution profiles, and also to ensure that the composition provides a clear wash liquor upon dissolution in water.
  • the first surfactant component comprises less than 10%, by weight of the first surfactant component, of a cationic detersive surfactant, preferably less than 5%, or less than 2%, or even 0%, by weight of the first surfactant component, of a cationic detersive surfactant.
  • the first surfactant component is essentially free from cationic detersive surfactant.
  • essentially free from cationic detersive surfactant it is typically meant that the first surfactant component comprises no deliberately added cationic detersive surfactant. This is especially preferred in order to reduce the degree of surfactant gelling in the wash liquor.
  • the first surfactant component is preferably in the form of a spray-dried powder, an agglomerate, an extrudate or a flake. If the first surfactant component is in the form of an agglomerate particle or an extrudate particle, then preferably the particle comprises from 20% to 65%, by weight of the particle, of an alkoxylated anionic detersive surfactant. If the first surfactant component is in spray-dried particle form, then preferably the particle comprises from 10wt% to 30wt%, by weight of the particle, of an alkoxylated anionic detersive surfactant.
  • the first surfactant component may be in the form of a co-particulate admixture with a solid carrier material.
  • the solid carrier material can be a sulphate salt and/or a carbonate salt, preferably sodium sulphate and/or sodium carbonate.
  • the second surfactant component predominantly comprises a non-alkoxylated detersive surfactant.
  • the second surfactant component comprises greater than 50%, by weight of the second surfactant component, of a non-alkoxylated anionic detersive surfactant, preferably greater than 60%, or greater than 70%, or greater than 80%, or greater than 90% or even essentially 100%, by weight of the second surfactant component, of a non-alkoxylated anionic detersive surfactant.
  • the second surfactant component comprises less than 10%, by weight of the second surfactant component, of an alkoxylated anionic detersive surfactant, preferably less than 5%, or less than 2%, or even 0%, by weight of the second surfactant component, of an alkoxylated anionic detersive surfactant.
  • the second surfactant component comprises less than 10%, by weight of the second surfactant component, of a cationic detersive surfactant, preferably less than 5%, or less than 2%, or even 0%, by weight of the second surfactant component, of a cationic detersive surfactant.
  • the second surfactant component is essentially free from alkoxylated anionic detersive surfactant.
  • alkoxylated anionic detersive surfactant it is typically meant that the second surfactant component comprises no deliberately added alkoxylated anionic detersive surfactant.
  • the second surfactant component is essentially free from cationic detersive surfactant.
  • essentially free from cationic detersive surfactant it is typically meant that the second surfactant component comprises no deliberately added cationic detersive surfactant. This is especially preferred in order to ensure that the composition has good dispensing and dissolution profiles, and also to ensure that the composition provides a clear wash liquor upon dissolution in water.
  • the second surfactant component may be in the form of a spray-dried powder, a flash-dried powder, an agglomerate or an extrudate. If the second surfactant component is in the form of an agglomerate particle, then preferably the particle from 5% to 50%, by weight of the particle, of a non-alkoxylated anionic detersive surfactant, or from 5wt% to 25wt% non-alkoxylated anionic detersive surfactant.
  • the second surfactant component may be in form of a co-particulate admixture with a solid carrier material.
  • the solid carrier material can be a sulphate salt and/or a carbonate salt, preferably sodium sulphate and/or sodium carbonate.
  • the detergent compositions of the invention may be substantially free of cationic surfactant, if present, the cationic surfactant may be present in a third surfactant component or may be incorporated into a spray-dried particle with at least some anionic surfactant. If present in a third component, it may be beneficial to have the third surfactant component predominantly comprising a cationic detersive surfactant. By predominantly comprises, it is meant the third surfactant component comprises greater than 50%, by weight of the third surfactant component, of a cationic detersive surfactant, preferably greater than 60%, or greater than 70%, or greater than 80%, or greater than 90% or even essentially 100%, by weight of the third surfactant component, of a cationic detersive surfactant.
  • the third surfactant component comprises less than 10%, by weight of the third surfactant component, of an alkoxylated anionic detersive surfactant, preferably less than 5%, or less than 2%, or even essentially 0%, by weight of the third surfactant component, of an alkoxylated anionic detersive surfactant.
  • the third surfactant component comprises less than 10%, by weight of the third surfactant component, of a non-alkoxylated anionic detersive surfactant, preferably less than 5%, or less than 2%, or even 0%, by weight of the third surfactant component, of a non-alkoxylated anionic detersive surfactant.
  • the third surfactant component is essentially free from alkoxylated anionic detersive surfactant.
  • alkoxylated anionic detersive surfactant it is typically meant that the third surfactant component comprises no deliberately added alkoxylated anionic detersive surfactant.
  • the third surfactant component is essentially free from non-alkoxylated anionic detersive surfactant.
  • non-alkoxylated anionic detersive surfactant By essentially free from non-alkoxylated anionic detersive surfactant it is typically meant that the third surfactant component comprises no deliberately added non-alkoxylated anionic detersive surfactant. This is especially preferred in order to ensure that the composition has good dispensing and dissolution profiles, and also to ensure that the composition provides a clear wash liquor upon dissolution in water.
  • the third surfactant component is preferably in the form of a spray-dried powder, a flash-dried powder, an agglomerate or an extrudate. If the third surfactant component is in the form of an agglomerate particle, then preferably the particle comprises from 5% to 50%, by weight of the particle, of cationic detersive surfactant, or from 5wt% to 25wt% cationic detersive surfactant.
  • the third surfactant component may be in form of a co-particulate admixture with a solid carrier material.
  • the solid carrier material can be a sulphate salt and/or a carbonate salt, preferably sodium sulphate and/or sodium carbonate.
  • the detergent ingredients can include one or more other detersive adjuncts or other materials for assisting or enhancing cleaning performance, treatment of the substrate to be cleaned, or to modify the aesthetics of the detergent composition.
  • Usual detersive adjuncts of detergent compositions include the ingredients set forth in U.S. Pat. No. 3,936,537, Baskerville et al. and in Great Britain Patent Application No. 9705617.0, Trinh et al., published September 24, 1997 .
  • adjuncts are included in detergent compositions at their conventional art-established levels of use, generally from 0 wt% to about 80 wt% of the detergent ingredients, preferably from about 0.5 wt% to about 20wt % and can include color speckles, suds boosters, suds suppressors, anti-tarnish and/or anticorrosion agents, soil-suspending agents, soil release agents, dyes, fillers, optical brighteners, germicides, alkalinity sources, hydrotropes, antioxidants, enzymes, enzyme stabilizing agents, solvents, solubilizing agents, chelating agents, clay soil removal/anti-redeposition agents, polymeric dispersing agents, processing aids, fabric softening components, static control agents, bleaching agents, bleaching activators, bleach stabilizers, dye-transfer inhibitors, flocculants, fabric softeners, suds supressors, fabric integrity agents, perfumes, whitening agents, photobleach, alkali metal sulphate salts, sulphamic acid, sodium
  • Preferred zwitterionic surfactants comprise one or more quaternized nitrogen atoms and one or more moieties selected from the group consisting of: carbonate, phosphate, sulphate, sulphonate, and combinations thereof.
  • Preferred zwitterionic surfactants are alkyl betaines.
  • Other preferred zwitterionic surfactants are alkyl amine oxides.
  • Catanionic surfactants which are complexes comprising a cationic surfactant and an anionic surfactant may also be included. Typically, the molar ratio of the cationic surfactant to anionic surfactant in the complex is greater than 1:1, so that the complex has a net positive charge.
  • a preferred adjunct component is a bleaching agent.
  • the detergent composition comprises one or more bleaching agents.
  • the composition comprises (by weight of the composition) from 1% to 50% of one or more bleaching agent.
  • Preferred bleaching agents are selected from the group consisting of sources of peroxide, sources of peracid, bleach boosters, bleach catalysts, photo-bleaches, and combinations thereof.
  • Preferred sources of peroxide are selected from the group consisting of: perborate monohydrate, perborate tetra-hydrate, percarbonate, salts thereof, and combinations thereof.
  • Preferred sources of peracid are selected from the group consisting of bleach activator typically with a peroxide source such as perborate or percarbonate, preformed peracids, and combinations thereof.
  • Preferred bleach activators are selected from the group consisting of: oxy-benzene-sulphonate bleach activators, lactam bleach activators, imide bleach activators, and combinations thereof.
  • a preferred source of peracid is tetra-acetyl ethylene diamine (TAED)and peroxide source such as percarbonate.
  • Preferred oxy-benzene-sulphonate bleach activators are selected from the group consisting of: nonanoyl-oxy-benzene-sulponate, 6-nonamido-caproyl-oxy-benzene-sulphonate, salts thereof, and combinations thereof.
  • Preferred lactam bleach activators are acyl-caprolactams and/or acyl-valerolactams.
  • a preferred imide bleach activator is N-nonanoyl-N-methyl-acetamide.
  • Preferred preformed peracids are selected from the group consisting of N,N-pthaloyl-amino-peroxycaproic acid, nonyl-amido-peroxyadipic acid, salts thereof, and combinations thereof.
  • the STW-composition comprises one or more sources of peroxide and one or more sources of peracid.
  • Preferred bleach catalysts comprise one or more transition metal ions.
  • Other preferred bleaching agents are di-acyl peroxides.
  • Preferred bleach boosters are selected from the group consisting of: zwitterionic imines, anionic imine polyions, quaternary oxaziridinium salts, and combinations thereof.
  • Highly preferred bleach boosters are selected from the group consisting of aryliminium zwitterions, aryliminium polyions, and combinations thereof. Suitable bleach boosters are described in US360568 , US5360569 and US5370826 .
  • a preferred adjunct component is an anti-redeposition agent.
  • the detergent composition comprises one or more anti-redeposition agents.
  • Preferred anti-redeposition agents are cellulosic polymeric components, most preferably carboxymethyl celluloses.
  • a preferred adjunct component is a chelant.
  • the detergent composition comprises one or more chelants.
  • the detergent composition comprises (by weight of the composition) from 0.01 % to 10% chelant, or 0.01 to 5 wt% or 4 wt% or 2 wt%.
  • Preferred chelants are selected from the group consisting of: hydroxyethane-dimethylene-phosphonic acid, ethylene diamine tetra(methylene phosphonic) acid, diethylene triamine pentacetate, ethylene diamine tetraacetate, diethylene triamine penta(methyl phosphonic) acid, ethylene diamine disuccinic acid, and combinations thereof.
  • a preferred adjunct component is a dye transfer inhibitor.
  • the detergent composition comprises one or more dye transfer inhibitors.
  • dye transfer inhibitors are polymeric components that trap dye molecules and retain the dye molecules by suspending them in the wash liquor.
  • Preferred dye transfer inhibitors are selected from the group consisting of polyvinylpyrrolidones, polyvinylpyridine N-oxides, polyvinylpyrrolidone-polyvinylimidazole copolymers, and combinations thereof.
  • Preferred adjunct components include other enzymes.
  • the detergent composition comprises one or more additional enzymes.
  • Preferred enzymes are selected from then group consisting of: amylases, arabinosidases, carbohydrases, cellulases, chondroitinases, cutinases, dextranases, esterases, B-glucanases, gluco-amylases, hyaluronidases, keratanases, laccases, ligninases, lipoxygenases, malanases, mannanases, oxidases, pectinases, pentosanases, peroxidases, phenoloxidases, phospholipases, proteases, pullulanases, reductases, tannases, transferases, xylanases, xyloglucanases, and combinations thereof.
  • Preferred additional enzymes are selected from the group consisting of amylases, carbohydrases, cellulases
  • a preferred adjunct component is a fabric integrity agent.
  • the detergent composition comprises one or more fabric integrity agents.
  • fabric integrity agents are polymeric components that deposit on the fabric surface and prevent fabric damage during the laundering process.
  • Preferred fabric integrity agents are hydrophobically modified celluloses. These hydrophobically modified celluloses reduce fabric abrasion, enhance fibre-fibre interactions and reduce dye loss from the fabric.
  • a preferred hydrophobically modified cellulose is described in WO99/14245 .
  • Other preferred fabric integrity agents are polymeric components and/or oligomeric components that are obtainable, preferably obtained, by a process comprising the step of condensing imidazole and epichlorhydrin.
  • a preferred adjunct component is a salt.
  • the detergent composition comprises one or more salts.
  • the salts can act as alkalinity agents, buffers, builders, co-builders, encrustation inhibitors, fillers, pH regulators, stability agents, and combinations thereof.
  • the detergent composition comprises (by weight of the composition) from 5% to 60% salt.
  • Preferred salts are alkali metal salts of aluminate, carbonate, chloride, bicarbonate, nitrate, phosphate, silicate, sulphate, and combinations thereof.
  • Other preferred salts are alkaline earth metal salts of aluminate, carbonate, chloride, bicarbonate, nitrate, phosphate, silicate, sulphate, and combinations thereof.
  • Especially preferred salts are sodium sulphate, sodium carbonate, sodium bicarbonate, sodium silicate, sodium sulphate, and combinations thereof.
  • the alkali metal salts and/or alkaline earth metal salts may be anhydrous.
  • a preferred adjunct component is a soil release agent.
  • the detergent composition comprises one or more soil release agents.
  • soil release agents are polymeric compounds that modify the fabric surface and prevent the redeposition of soil on the fabric.
  • Preferred soil release agents are copolymers, preferably block copolymers, comprising one or more terephthalate unit.
  • Preferred soil release agents are copolymers that are synthesised from dimethylterephthalate, 1,2-propyl glycol and methyl capped polyethyleneglycol.
  • Other preferred soil release agents are anionically end capped polyesters.
  • the detergent compositions of the invention may comprise softening agents for softening through the wash such as clay optionally also with flocculant and enzymes.
  • the invention also includes methods of washing textiles comprising contacting textiles with an aqueous solution comprising the detergent composition of the invention.
  • the invention may be particularly beneficial at low water temperatures such as below 30°C or below 25 or 20°C.
  • the aqueous wash liquor will comprise at least 100 ppm, or at least 500ppm of the detergent composition

Landscapes

  • 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)

Claims (18)

  1. Granulöse Wäschewaschmittelzusammensetzung, die eine Lipase umfasst, die ein Polypeptid mit einer Aminosäure-Sequenz ist, die: (a) eine wenigstens 90-%ige Identität mit der Wildtyp-Lipase aufweist, die vom Humicola lanuginosa-Stamm DSM 4109 abgeleitet ist; (b) im Gegensatz zur Wildtyp-Lipase eine Substitution einer elektrisch neutralen oder negativ geladenen Aminosäure an der Oberfläche der räumlichen Struktur innerhalb von 15 Angström von E1 oder Q249 an einer der Positionen 1-11, 90, 95, 169, 171-175, 192-211, 213-226, 228-258, 260-262 mit einer positiv geladenen Aminosäure umfasst, und (c) die Hinzufügung eines Peptids an der C-Endgruppe umfasst; und/oder (d) die Hinzufügung eines Peptids an der N-Endgruppe umfasst, und/oder die folgenden Beschränkungen erfüllt: i) umfasst eine negativ geladene Aminosäure an der Position E210 der Wildtyp-Lipase; ii) eine negativ geladene Aminosäure in der Region umfasst, die den Positionen 90-101 der Wildtyp-Lipase entspricht; und iii) eine neutrale oder negative Aminosäure an einer Position umfasst, die N94 der Wildtyp-Lipase entspricht und/oder eine negative oder neutrale elektrische Nettoladung in dem Bereich aufweist, der den Positionen 90-101 der Wildtyp-Lipase entspricht; wobei die Zusammensetzung eine Reservealkalinität, wie hierin definiert, von mehr als 7,5 aufweist und die Waschmittelzusammensetzung eine Gesamtmenge von bis zu 15 Gew.-% Alumosilikat- (wasserfreie Basis) und/oder Phosphat-Builder (wasserfreie Basis) umfasst.
  2. Waschmittelzusammensetzung nach Anspruch 1 mit einer Reservealkalinität von mehr als 8 oder mehr als 9.
  3. Waschmittelzusammensetzung nach Anspruch 1 oder Anspruch 2, umfassend weniger als 8 Gew.-% Alumosilikat- und/oder Phosphat-Builder.
  4. Waschmittelzusammensetzung nach Anspruch 1, umfassend bis zu 5 Gew.-% Alumosilicat (wasserfreie Basis).
  5. Waschmittelzusammensetzung nach Anspruch 4, umfassend bis zu 4 Gew.-% Alumosilicat (wasserfreie Basis).
  6. Waschmittelzusammensetzung nach einem der vorstehenden Ansprüche mit einer Reservealkalität von mehr als 10.
  7. Waschmittelzusammensetzung nach einem der vorstehenden Ansprüche, wobei die Gesamtkonzentration schwacher Builder, ausgewählt aus Schichtsilicaten (SKS-6), Citronensäure, Citratsalzen und Nitrilotriessigsäure oder Salz davon, unter 15 Gew.-%, vorzugsweise unter 8 Gew.-% liegt.
  8. Waschmittelzusammensetzung nach einem der vorstehenden Ansprüche, umfassend nichtionisches Tensid in Mengen bis zu 20 Gew.-%.
  9. Waschmittelzusammensetzung nach Anspruch 8, umfassend nichtionisches Tensid in Mengen von 0,5 bis 20 Gew.-%.
  10. Waschmittelzusammensetzung nach Anspruch 9, umfassend nichtionisches Tensid in Mengen von 0,5 bis 10 Gew.-%.
  11. Waschmittelzusammensetzung nach einem der vorstehenden Ansprüche, umfassend von 1 bis 50 Gew.-% ein oder mehrere Bleichmittel.
  12. Waschmittelzusammensetzung nach einem der vorstehenden Ansprüche, umfassend von 0,1 Gew.-% bis 30 Gew.-% polymere Polycarboxylate, ausgewählt aus Polyacrylaten und Copolymeren von Maleinsäure und Acrylsäure.
  13. Waschmittelzusammensetzung nach einem der vorstehenden Ansprüche, umfassend anionisches Tensid.
  14. Waschmittelzusammensetzung nach einem der vorstehenden Ansprüche, umfassend von 0,1 bis 40 Gew.-% alkoxyliertes Alkylsulfattensid und/oder von 0,1 bis 40 Gew.-% C1-4-Alkylestersulfonat, vorzugsweise Methylestersulfonat (MES), vorzugsweise in Kombination mit Alkylbenzolsulfonattensid in einer Menge von 5 bis 40 Gew.-%.
  15. Waschmittelzusammensetzung nach einem der vorstehenden Ansprüche, die einen Schaumverstärker in einer Menge von 0,05 bis 2 Gew.-% umfasst, vorzugsweise ausgewählt aus Fettsäureamiden, Fettsäurealkanolamiden, Betainen, Sulfobetainen und Aminoxiden oder Mischungen davon.
  16. Waschmittelzusammensetzung nach einem der vorstehenden Ansprüche, die zu 0,05 bis 5, vorzugsweise zu 0,1 bis 1 Gew.-% Schmutzabweisungspolymer umfasst, vorzugsweise ausgewählt aus modifizierten Celluloseethern wie Methylhydroxyethylcellulose (MHEC) oder Schmutzabweisungspolymeren auf Polyesterbasis oder Mischungen davon.
  17. Waschverfahren, das das Waschen von Textilwaren in einer wässrigen Lösung umfasst, die die Waschmittelzusammensetzung nach einem der vorstehenden Ansprüche umfasst.
  18. Waschverfahren nach Anspruch 17, bei dem die wässrige Lösung bei einer Temperatur von unter 30 °C vorliegt.
EP06110296.8A 2005-02-22 2006-02-22 Waschmittelzusammensetzungen Revoked EP1712611B1 (de)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PL06110296T PL1712611T3 (pl) 2005-02-22 2006-02-22 Kompozycje detergentu
EP06110296.8A EP1712611B1 (de) 2005-02-22 2006-02-22 Waschmittelzusammensetzungen

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP05250995A EP1693439A1 (de) 2005-02-22 2005-02-22 Waschmittelzusammensetzungen
EP06110296.8A EP1712611B1 (de) 2005-02-22 2006-02-22 Waschmittelzusammensetzungen

Publications (2)

Publication Number Publication Date
EP1712611A1 EP1712611A1 (de) 2006-10-18
EP1712611B1 true EP1712611B1 (de) 2014-10-22

Family

ID=36968364

Family Applications (1)

Application Number Title Priority Date Filing Date
EP06110296.8A Revoked EP1712611B1 (de) 2005-02-22 2006-02-22 Waschmittelzusammensetzungen

Country Status (2)

Country Link
EP (1) EP1712611B1 (de)
PL (1) PL1712611T3 (de)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3749759A1 (de) 2018-02-08 2020-12-16 Novozymes A/S Lipasevarianten und zusammensetzungen davon
WO2021001400A1 (en) 2019-07-02 2021-01-07 Novozymes A/S Lipase variants and compositions thereof

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0258068B1 (de) * 1986-08-29 1994-08-31 Novo Nordisk A/S Enzymhaltiger Reinigungsmittelzusatz
EP0305216B1 (de) * 1987-08-28 1995-08-02 Novo Nordisk A/S Rekombinante Humicola-Lipase und Verfahren zur Herstellung von rekombinanten Humicola-Lipasen
US5869438A (en) * 1990-09-13 1999-02-09 Novo Nordisk A/S Lipase variants
AU3247699A (en) * 1998-02-17 1999-09-06 Novo Nordisk A/S Lipase variant
US6939702B1 (en) * 1999-03-31 2005-09-06 Novozymes A/S Lipase variant

Also Published As

Publication number Publication date
PL1712611T3 (pl) 2015-03-31
EP1712611A1 (de) 2006-10-18

Similar Documents

Publication Publication Date Title
US8859480B2 (en) Detergent compositions
US9062279B2 (en) Laundry detergent compositions comprising lipolytic or lipase enzymes
EP1726636B1 (de) Waschmittelzusammensetzungen
AU2006218400A1 (en) Detergent compositions
EP1867707B1 (de) Waschmittelzusammensetzungen
EP1712610B1 (de) Waschmittelzusammensetzungen
EP1882731A1 (de) Waschmittelzusammensetzungen
US20070197423A1 (en) Detergent compositions
EP1712611B1 (de) Waschmittelzusammensetzungen
GB2287948A (en) Laundry detergent composition

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL BA HR MK YU

17P Request for examination filed

Effective date: 20070323

AKX Designation fees paid

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

17Q First examination report despatched

Effective date: 20070614

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20130513

RIN1 Information on inventor provided before grant (corrected)

Inventor name: LANT, NEIL JOSEPH

Inventor name: PATTERSON, STEVEN GEORGE

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

RIN1 Information on inventor provided before grant (corrected)

Inventor name: PATTERSON, STEVEN GEORGE

Inventor name: LANT, NEIL JOSEPH

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20140407

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 692672

Country of ref document: AT

Kind code of ref document: T

Effective date: 20141115

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602006043423

Country of ref document: DE

Effective date: 20141204

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2526198

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20150108

REG Reference to a national code

Ref country code: NL

Ref legal event code: T3

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

REG Reference to a national code

Ref country code: PL

Ref legal event code: T3

REG Reference to a national code

Ref country code: GR

Ref legal event code: EP

Ref document number: 20150400052

Country of ref document: GR

Effective date: 20150220

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20141022

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20141022

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150222

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150223

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20141022

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20141022

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20141022

REG Reference to a national code

Ref country code: HU

Ref legal event code: AG4A

Ref document number: E022821

Country of ref document: HU

REG Reference to a national code

Ref country code: DE

Ref legal event code: R026

Ref document number: 602006043423

Country of ref document: DE

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20141022

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20141022

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20141022

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20141022

26 Opposition filed

Opponent name: UNILEVER PLC / UNILEVER NV

Effective date: 20150710

26 Opposition filed

Opponent name: HENKEL AG & CO. KGAA

Effective date: 20150716

PLAX Notice of opposition and request to file observation + time limit sent

Free format text: ORIGINAL CODE: EPIDOSNOBS2

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150222

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20141022

REG Reference to a national code

Ref country code: RO

Ref legal event code: EPE

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 11

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20150222

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20141022

PLBB Reply of patent proprietor to notice(s) of opposition received

Free format text: ORIGINAL CODE: EPIDOSNOBS3

PLAB Opposition data, opponent's data or that of the opponent's representative modified

Free format text: ORIGINAL CODE: 0009299OPPO

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 12

PLAB Opposition data, opponent's data or that of the opponent's representative modified

Free format text: ORIGINAL CODE: 0009299OPPO

R26 Opposition filed (corrected)

Opponent name: UNILEVER PLC / UNILEVER NV

Effective date: 20150710

R26 Opposition filed (corrected)

Opponent name: UNILEVER PLC / UNILEVER NV

Effective date: 20150710

PLAB Opposition data, opponent's data or that of the opponent's representative modified

Free format text: ORIGINAL CODE: 0009299OPPO

R26 Opposition filed (corrected)

Opponent name: UNILEVER PLC / UNILEVER NV

Effective date: 20150710

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20141022

APBM Appeal reference recorded

Free format text: ORIGINAL CODE: EPIDOSNREFNO

APBP Date of receipt of notice of appeal recorded

Free format text: ORIGINAL CODE: EPIDOSNNOA2O

APAH Appeal reference modified

Free format text: ORIGINAL CODE: EPIDOSCREFNO

APAW Appeal reference deleted

Free format text: ORIGINAL CODE: EPIDOSDREFNO

APBM Appeal reference recorded

Free format text: ORIGINAL CODE: EPIDOSNREFNO

APBP Date of receipt of notice of appeal recorded

Free format text: ORIGINAL CODE: EPIDOSNNOA2O

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 13

PLAB Opposition data, opponent's data or that of the opponent's representative modified

Free format text: ORIGINAL CODE: 0009299OPPO

R26 Opposition filed (corrected)

Opponent name: HENKEL AG & CO. KGAA

Effective date: 20150716

PLAB Opposition data, opponent's data or that of the opponent's representative modified

Free format text: ORIGINAL CODE: 0009299OPPO

R26 Opposition filed (corrected)

Opponent name: UNILEVER PLC / UNILEVER NV

Effective date: 20150710

APAL Date of receipt of statement of grounds of an appeal modified

Free format text: ORIGINAL CODE: EPIDOSCNOA3O

APBQ Date of receipt of statement of grounds of appeal recorded

Free format text: ORIGINAL CODE: EPIDOSNNOA3O

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20210308

Year of fee payment: 16

REG Reference to a national code

Ref country code: DE

Ref legal event code: R103

Ref document number: 602006043423

Country of ref document: DE

Ref country code: DE

Ref legal event code: R064

Ref document number: 602006043423

Country of ref document: DE

APBU Appeal procedure closed

Free format text: ORIGINAL CODE: EPIDOSNNOA9O

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20211230

Year of fee payment: 17

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: HU

Payment date: 20220112

Year of fee payment: 17

Ref country code: DE

Payment date: 20211230

Year of fee payment: 17

Ref country code: CH

Payment date: 20220114

Year of fee payment: 17

Ref country code: AT

Payment date: 20220125

Year of fee payment: 17

RDAF Communication despatched that patent is revoked

Free format text: ORIGINAL CODE: EPIDOSNREV1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: PATENT REVOKED

RDAG Patent revoked

Free format text: ORIGINAL CODE: 0009271

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: TR

Payment date: 20220218

Year of fee payment: 17

Ref country code: RO

Payment date: 20220127

Year of fee payment: 17

Ref country code: PL

Payment date: 20220130

Year of fee payment: 17

Ref country code: NL

Payment date: 20220118

Year of fee payment: 17

Ref country code: IT

Payment date: 20220111

Year of fee payment: 17

Ref country code: GR

Payment date: 20220120

Year of fee payment: 17

Ref country code: FR

Payment date: 20220118

Year of fee payment: 17

Ref country code: BE

Payment date: 20220118

Year of fee payment: 17

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: FI

Ref legal event code: MGE

27W Patent revoked

Effective date: 20211008

GBPR Gb: patent revoked under art. 102 of the ep convention designating the uk as contracting state

Effective date: 20211008

REG Reference to a national code

Ref country code: AT

Ref legal event code: MA03

Ref document number: 692672

Country of ref document: AT

Kind code of ref document: T

Effective date: 20211008

REG Reference to a national code

Ref country code: GR

Ref legal event code: NF

Ref document number: 20150400052

Country of ref document: GR

Effective date: 20220707