EP1319059A1 - Waschmittelzusammensetzungen - Google Patents
WaschmittelzusammensetzungenInfo
- Publication number
- EP1319059A1 EP1319059A1 EP01970847A EP01970847A EP1319059A1 EP 1319059 A1 EP1319059 A1 EP 1319059A1 EP 01970847 A EP01970847 A EP 01970847A EP 01970847 A EP01970847 A EP 01970847A EP 1319059 A1 EP1319059 A1 EP 1319059A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- clay
- composition
- alkyl
- weight
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
- C11D3/3776—Heterocyclic compounds, e.g. lactam
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/001—Softening compositions
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
- C11D3/1246—Silicates, e.g. diatomaceous earth
- C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
- C11D3/126—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite in solid compositions
Definitions
- the present invention relates to solid fabric or cleaning compositions, especially laundry detergent compositions that provide fabric softening benefits during the washing process.
- the Inventors have surprisingly found that by using a combination of specific clays, these clays provide an improved fabric softening benefit over several washing cycles, compared to when the same amount of a single clay type is used.
- a combination of specific types of clay acts in such a manner as to disperse better and more readily deposit onto fabric in such a manner so that the fabric softening benefit over several washing cycles is improved, compared to when only one clay type is used.
- the Inventors have found that when the two clay types are present in a solid detergent composition in the form ofan agglomerate, then the fabric softening benefit provided by the solid detergent composition during the washing cycle is further improved.
- the Inventors have also found that when the two clay types are present in the same agglomerate, then the fabric softening benefit provided is further improved, compared to two separate clay agglomerates being used.
- the Inventors have also found that adding a hydrophobically modified cellulosic based polymer to a solid detergent composition comprising specific types of clay, further improves the fabric softening benefit provided and also provides a fabric anti- wrinkling benefit, over several washing cycles.
- a solid detergent composition which comprises hectorite clay and dioctahedral smectite clay, wherein the weight ratio of said hectorite clay to said dioctahedral smectite clay is less than 1:1.
- a solid detergent composition comprising hectorite clay and dioctahedral smectite clay, wherein the weight ratio of said hectorite clay to said dioctahedral smectite clay is less than 1:1, to provide fabric softening benefits to fabric, is provided.
- a solid detergent composition comprising hectorite clay, dioctahedral smectite clay and a hydrophobically modified cellulosic based polymer, wherein the weight ratio of said hectorite clay to said dioctahedral smectite clay is less than 1:1, to provide fabric softening benefits and fabric anti- wrinkling benefits to fabric, is provided.
- composition herein comprises hectorite clay.
- Typical hectorite clay for use herein has the general formula
- x is a number from 0.1 to 0.5, preferably from 0.2 to 0.4, more preferably from 0.25 to 0.35.
- z is a number from 0 to 2.
- the value of (x+y) is the layer charge of said first clay, preferably the value of (x+y) is in the range of from 0.1 to 0.5, preferably from 0.2 to 0.4, more preferably from 0.25 to 0.35.
- the hectorite clay for use herein preferably has a volume weight mean particle size of from 5 micrometers to 20 micrometers, preferably from 7 micrometers to 19 micrometers, more preferably from 10 micrometers to 18 micrometers, more preferably from 12 micrometers to 17 micrometers, more preferably from 14 micrometers to 16 micrometers.
- the method for determining said volume weight mean particle size of said first clay is described in more detail hereinafter
- the inventors have found that when the hectorite clay has a lath like primary platelet shape, typically defined by an aspect ratio of greater than 3:1, then the fabric softening benefit provided is further improved. Therefore the hectorite clay, especially the primary platelets of said hectorite clay, has an aspect ratio of greater than 3:1, more preferably greater than 5:1, more preferably greater then 7 : 1 , or preferably from 7 : 1 to 15 : 1.
- the aspect ratio of the primary platelets is typically defined as the ratio of the average length of the primary platelets to the average width of the primary platelets.
- hectorite clays for use herein are those having a cationic exchange capacity of at least 90meq/100g.
- the cationic exchange capacity of clays can be measured using the method described in Grimshaw, The Chemistry and Physics of Clays, Interscience Publishers, Inc., pp. 264-265 (1971).
- hectorite clay is that supplied by Rlieox under the trade name Bentone HC.
- Other preferred hectorite clays for use herein are those hectorite clays supplied by CSM Materials under the trade name Hectorite U and Hectorite R, respectively.
- composition herein comprises a dioctahedral smectite clay.
- Any dioctahedral smectite clay can be used herein, preferred dioctahedral smectite clays for use herein are montmorillonite clays .
- Dioctahedral smectite clays for use herein typically have the general formula
- x is a number from 0.1 to 0.5, preferably from 0.2 to 0.4.
- Preferred dioctahedral smectite clays are low charge montmorillonite clays (also known as a sodium montmorillonite clay or Wyoming type montmorillonite clay) which have a general formula corresponding to formula (II) above, or high charge montmorillonite clays (also known as a calcium montmorillonite clay or Cheto type montmorillonite clay) which have a general formula corresponding to formula (III).
- the Inventors have found that when the dioctahedral smectite clay has a specific volume weight mean particle size, typically of more than 20 micrometers, then the fabric softening benefit provided is further improved.
- the dioctahedral smectite clay has a volume weight mean particle size of more than 20 micrometers, preferably more than 23 micrometers, preferably more than 25 micrometers, or preferably from 21 micrometers to 60 micrometers, more preferably from 22 micrometers to 50 micrometers, more preferably from 23 micrometers to 40 micrometers, more preferably from 24 micrometers to 30 micrometers, more preferably from 25 micrometers to 28 micrometers.
- the method for determining said volume weight mean particle size of said second clay is described in more detail hereinafter.
- the volume weight mean particle size of the hectorite clay and dioctahedral smectite clay, respectively, is determined using the following method:
- 12g clay is placed in a glass beaker containing 250ml distilled water and vigorously stirred for 5 minutes to form a clay solution.
- the clay is not sonicated, or microfluidised in a high pressure microfluidizer processor, but is added to said beaker of water in an unprocessed form (i.e. it's raw form).
- 1ml clay solution is added to the reservoir volume of an Accusizer 780 single-particle optical sizer (SPOS) using a micropipette.
- SPOS single-particle optical sizer
- the clay solution that is added to the reservoir volume of said Accusizer 780 SPOS is diluted in more distilled water to form a diluted clay solution, this dilution occurs in the reservoir volume of said Accusizer 780 SPOS and is an automated process that is controlled by said Accusizer 780 SPOS which determines the optimum concentration of said diluted clay solution, for determining the volume weight mean particle size of the clay particles in the diluted clay solution.
- the diluted clay solution is left in the reservoir volume of said Accusizer 780 SPOS for 3 minutes.
- the clay solution is vigorously stirred for the whole period of time that it is in the reservoir volume of said Accusizer 780 SPOS.
- the diluted clay solution is then sucked through the sensors of said Accusizer 780 SPOS, this is an automated process that is controlled by said Accusizer 780 SPOS which determines the optimum flow rate of the diluted clay solution through the sensors, for determining the volume weight mean particle size of the clay particles in the diluted clay solution. All of the steps of this method are carried out at a temperature of 20°C. This method is carried out in triplicate and the mean of these results determined.
- the composition herein preferably comprises (by weight of said composition) from 0.01% to 50%, preferably from 0.05% to 20%, more preferably from 0.05% to 15%, more preferably from 0.05% to 10%, more preferably from 0.05% to 5%, more preferably from 0.05% to 3%, more preferably from 0.1% to 2% a hydrophobically modified cellulosic based polymer.
- the hydrophobically modified cellulosic based polymers herein include polymers, oligomers, copolymers and also cross-linked polymers, oligomers and copolymers.
- the term "hydrophobically modified cellulosic based polymer" is herein referred to as "cellulosic based polymer".
- an oligomer is a molecule consisting of only a few monomer units while polymers comprise considerably more monomer units.
- oligomers are defined as molecules having a weight average molecular weight of below 1,000 and polymers are molecules having a weight average molecular weight of greater than 1,000.
- One suitable type of cellulosic based polymer herein has a weight average molecular weight of from about 5,000 to about 2,000,000, preferably from about 50,000 to about 1,000,000.
- the cellulosic based polymer for use herein is preferably of the following formula:
- each R is selected from the group consisting of R2, Re, and wherein:
- each R2 is independently selected from the group consisting of H and C1-C4 alkyl
- each R H is independently selected from the group consisting of C5 -C20 alkyl, C5-C7 cycloalkyl, C7-C20 alkylaryl, C7-C20 arylalkyl, substituted alkyl, hydroxyalkyl, 1-C20 alkoxy-2-hydroxyalkyl, C7-C20 alkylaryloxy-2-hydroxyalkyl, ( ⁇ - alkyl, (R4) 2 N-2-hydroxyalkyl, (1*4)3 -alkyl, (114)3 N-2-hydroxyalkyl, aryloxy-2-hydroxyalkyl,
- each R4 is independently selected from the group consisting of H, C1-C20 alkyl, C5- C7 cycloalkyl, C7-C20 alkylaryl, C7-C20 arylalkyl, aminoalkyl, alkylaminoalkyl, dialkylaminoalkyl, piperidinoalkyl, morpholinoalkyl, cycloalkylaminoalkyl and hydroxyalkyl;
- each R5 is independently selected from the group consisting of H, Cj -C20 alkyl, C5-
- M is a suitable cation selected from the group consisting of Na, K, l/2Ca, and l/2Mg; each x is from 0 to about 5; each y is from about 1 to about 5; and provided that:
- the Degree of Substitution for group R H is between about 0.001 and 0.1, more preferably between about 0.005 and 0.05, and most preferably between about 0.01 and 0.05;
- the Degree of Substitution for group Rc wherein Z is H or M is between about 0.2 and 2.0, more preferably between about 0.3 and 1.0, and most preferably between about 0.4 and 0.7;
- - two R4's on the same nitrogen can together form a ring structure selected from the group consisting of piperidine and morpholine.
- the "Degree of Substitution” for group R H which is sometimes abbreviated herein “DS RH “, means the number of moles of group R H components that are substituted per anhydrous glucose unit, wherein an anhydrous glucose unit is a six membered ring as shown in the repeating unit of the general structure above.
- the “Degree of Substitution” for group R c which is sometimes abbreviated herein “DS RC”, means the number of moles of group R ⁇ components, wherein Z is H or M, that are substituted per anhydrous glucose unit, wherein an anhydrous glucose unit is a six membered ring as shown in the repeating unit of the general structure above.
- the composition herein may preferably comprise a flocculation agent, preferably present at a level of from 0.005% to 10%, more preferably from 0.01% to 5%, more preferably from 0.05% or even 0.1 % to 1% by weight of said composition.
- the flocculation agent may be present in said composition as part of the detergent base granule, or if the clay system is present in said composition as a separate pre-formed particle, the flocculation agent may be present in the composition as part of said separate pre-formed particle.
- Preferred flocculation agents herein are organic polymeric materials having a weight average molecular weight of from 100000 tolOOOOOOO, preferably from 150000 to 5000000, more preferably from 200000 to 2000000.
- Suitable organic polymeric materials comprise homopolymers or copolymers containing monomeric units selected from alkylene oxide, particularly ethylene oxide, acrylamide, acrylic acid, vinyl alcohol, vinyl pyrrolidone and ethylene imine. Homopolymers of ethylene oxide, acrylamide and acrylic acid are preferred. European patents no.s EP-A-299,575 and EP-A-313146 in the name of The Procter and Gamble Company describe preferred organic polymeric flocculation agents for use herein. Highly preferred are polyethylene oxides of a weight average molecular weight of from 150000 to 3000000. Inorganic flocculation agents may also be suitable for use herein, typical examples of which include lime and alum.
- the composition herein comprises one or more cyclic amine based polymer.
- the composition herein may comprise (by weight of said composition) from 0.05% to 10%, preferably from 0.05% to 5% or even from 0.05% to 3% or even 0.1% to 2% cyclic amine based polymer.
- 'polymers' include not only polymers, but also oligomers, co-polymers, co-oligomers, present in any structural arrangement, also including cross-linked arrangements. As will be apparent to those skilled in the art, an oligomer is a molecule consisting of only a few monomer units while polymers comprise considerably more monomer units.
- oligomers are defined as molecules having an average molecular weight below 1,000 and polymers are molecules having an average molecular weight of greater than 1,000; copolymers or co-oligomers are materials wherein two or more dissimilar monomers have been simultaneously or sequentially polymerized.
- Copolymers or co-oligomers for use herein can include, for example, polymers or oligomers polymerized from a mixture of a primary cyclic amine based monomer, e.g., piperadine, and a secondary cyclic amine monomer, e.g., morpholine.
- each T is independently selected from the group consisting of H, C1-C12 alkyl, substituted alkyl, C7-C12 alkylaryl,
- W comprises at least one cyclic constituent selected from the group consisting of:
- W may also comprise an aliphatic or substituted aliphatic moiety of the general structure
- each B is independently C1-C12 alkylene, C1-C12 substituted alkylene, C3-C12 alkenylene, Cg-C ⁇ dialkylarylene, Cg-C ⁇ dialkylarylenediyl, and -(R5 ⁇ ) n R5- ;
- each D is independently C2-C6 alkylene
- each Q is independently selected from the group consisting of hydroxy, C ⁇ -C ⁇ g alkoxy, 2-C ⁇ g hydroxyalkoxy, amino, C ⁇ -C ⁇ g alkylamino, dialkylamino, trialkylamino groups, heterocyclic monoamino groups and diamino groups;
- -each Ri is independently selected from the group consisting of H, C ⁇ -Cg alkyl and C ⁇ -
- each R2 is independently selected from the group consisting of Cj-C ⁇ alkylene, C ⁇ - C12 alkenylene, -C ⁇ -CHCOR -C ⁇ , C -C ⁇ alkarylene, C4-C12 dihydroxyalkylene, poly(C2-C4 alkyleneoxy)alkylene, H2CH(OH)CH 2 OR2 ⁇ CH 2 CH(OH)CH2-, and C 3 -C ⁇ 2 hydrocarbyl moieties; provided that when R 2 is a C3-C12 hydrocarbyl moiety the hydrocarbyl moiety can comprise from about 2 to about 4 branching moieties of the general structure:
- each R3 is independently selected from the group consisting of H, O, R2, C1-C20 hydroxyalkyl, C1-C20 alkyl, substituted alkyl, Cg-Cu aryl, substituted aryl, C7-
- each R4 is independently selected from the group consisting of H, C1-C22 alkyl, C -
- the cyclic amine based polymer may comprise combinations of these cyclic amine based materials.
- a mixture of piperadine and epihalohydrin condensates can be combined with a mixture of morpholine and epihalohydrin condensates to achieve the desired fabric treatment results.
- the molecular weight of the cyclic polymers can vary as is illustrated herein.
- Preferred cyclic amine based polymers that fall within this general structure include compounds: - wherein each R is H; and
- -at least one W is selected from the group consisting of:
- -at least one W is selected from the group consisting of:
- -at least one W is selected from the group consisting of:
- Preferred compounds to be used as the linking group R2 include, but are not limited to: polyepoxides, ethylenecarbonate, propylenecarbonate, urea, ⁇ , ⁇ -unsaturated carboxylic acids, esters of , ⁇ -unsaturated carboxylic acids, amides of ⁇ , ⁇ -unsaturated carboxylic acids, anhydrides of , ⁇ -unsaturated carboxylic acids, di- or polycarboxylic acids, esters of di- or polycarboxylic acids, amides of di- or polycarboxylic acids, anhydrides of di- or polycarboxylic acids, glycidylhalogens, chloroformic esters, chloroacetic esters, derivatives of chloroformic esters, derivatives of chloroacetic esters, epihalohydrins, glycerol dichlorohydrins, bis-(halohydrins), polyetherdihalo-compounds, phosgene, polyhalogen
- R2 can also comprise a reaction product formed by reacting one or more of polyetherdiamines, alkylenediamines, polyalkylenepolyamines, alcohols, alkyleneglycols and polyalkyleneglycols with ⁇ , ⁇ -unsaturated carboxylic acids, esters of ⁇ , ⁇ -unsaturated carboxylic acids, amides of ⁇ , ⁇ -unsaturated carboxylic acids and anhydrides of , ⁇ - unsaturated carboxylic acids provided that the reaction products contain at least two double bonds, two carboxylic groups, two amide groups or two ester groups.
- cyclic amine based polymers for use herein include adducts of two or more compounds selected from the group consisting of piperazine, piperadine, epichlorohydrin, epichlorohydrin benzyl quat, epichlorohydrin methyl quat, morpholine and mixtures thereof.
- Imidazole-epi chlorohydrin copolymers Highly preferred cyclic amine based polymers herein are referred to as Imidazole-epi chlorohydrin copolymers.
- cyclic amine based polymers can be linear or branched.
- One specific type of branching can be introduced using a polyfunctional crosslinking agent.
- An example of such a polymer is exemplified below.
- composition herein may comprise the following detergent ingredients:
- composition herein preferably contains one or more surfactants selected from anionic, nonionic, cationic, ampholytic, amphoteric and zwitterionic surfactants and mixtures thereof.
- ampholytic, amphoteric and zwitteronic surfactants are generally used in combination with one or more anionic and/or nonionic surfactants.
- composition herein preferably comprise an additional anionic surfactant.
- anionic surfactants useful for detersive purposes can be comprised in the composition herein. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of the anionic sulfate, sulfonate, carboxylate and sarcosinate surfactants. Anionic sulfate and sulfonate surfactants are preferred.
- surfactants systems comprising a sulfonate and a sulfate surfactant, preferably a linear or branched alkyl benzene sulfonate and alkyl ethoxylsulfates, as described herein, preferably combined with a cationic surfactants as described herein.
- anionic surfactants include the isethionates such as the acyl isethionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated C, -,-C ⁇ o monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C ⁇ -C, . diesters), N-acyl sarcosinates.
- Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tallow oil.
- Anionic sulfate surfactants suitable for use herein include the linear and branched primary and secondary alkyl sulfates, alkyl ethoxysulfates, fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, the C5-C1 acyl-N-(C ⁇ -C4 alkyl) and -N-(C ⁇ - C2 hydroxyalkyl) glucamine sulfates, and sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds described herein).
- Alkyl sulfate surfactants are preferably selected from the linear and branched primary ClO"Cl8 lkyl sulfates, more preferably the C 1-C15 branched chain alkyl sulfates and the Ci2"Cl4 linear chain alkyl sulfates.
- Alkyl ethoxysulfate surfactants are preferably selected from the group consisting of the l0"Cl8 alkyl sulfates which have been ethoxylated with from 0.5 to 20 moles of ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate surfactant is a C ⁇ - Cig, most preferably C ⁇ ⁇ -C ⁇ alkyl sulfate which has been ethoxylated with from 0.5 to 7, preferably from 1 to 5, moles of ethylene oxide per molecule.
- Anionic sulfonate surfactants suitable for use herein include the salts of C5-C20 linear alkylbenzene sulfonates, alkyl ester sulfonates, Cg-C22 primary or secondary alkane sulfonates, C5-C24 olefin sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates, and any mixtures thereof.
- Suitable anionic carboxylate surfactants include the alkyl ethoxy carboxylates, the alkyl polyethoxy poly carboxylate surfactants and the soaps ('alkyl carboxyls'), especially certain secondary soaps as described herein.
- Suitable alkyl ethoxy carboxylates include those with the formula RO(CH2CH2 ⁇ ) x
- R is a C ⁇ to C g alkyl group
- x ranges from O to 10
- the ethoxylate distribution is such that, on a weight basis, the amount of material where x is 0 is less than 20 % and M is a cation.
- Suitable alkyl polyethoxy polycarboxylate surfactants include those having the formula RO-(CHR ⁇ -CHR2-O)-R3 wherein R is a Cfr to Cjg alkyl group, x is from 1 to 25, R and R2 are selected from the group consisting of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid radical, and mixtures thereof, and R3 is selected from the group consisting of hydrogen, substituted or uhsubstituted hydrocarbon having between 1 and 8 carbon atoms, and mixtures thereof.
- Suitable soap surfactants include the secondary soap surfactants which contain a carboxyl unit connected to a secondary carbon.
- Preferred secondary soap surfactants for use herein are water-soluble members selected from the group consisting of the water-soluble salts of 2-methyl-l-undecanoic acid, 2-ethyl-l-decanoic acid, 2-propyl-l-nonanoic acid, 2- butyl- 1-octanoic acid and 2-pentyl-l-heptanoic acid. Certain soaps may also be included as suds suppressers.
- alkali Metal Sarcosinate Surfactant Other suitable anionic surfactants are the alkali metal sarcosinates of formula R-CON
- R 1 (R 1 ) CH2 COOM, wherein R is a C5-C1 linear or branched alkyl or alkenyl group, R 1 is a C1-C4 alkyl group and M is an alkali metal ion.
- R is a C5-C1 linear or branched alkyl or alkenyl group
- R 1 is a C1-C4 alkyl group
- M is an alkali metal ion.
- Preferred examples are the myristyl and oleoyl methyl sarcosinates in the form of their sodium salts.
- any alkoxylated nonionic surfactants are suitable herein.
- the ethoxylated and propoxylated nonionic surfactants are preferred.
- Preferred alkoxylated surfactants can be selected from the classes of the nonionic condensates of alkyl phenols, nonionic ethoxylated alcohols, nonionic ethoxylated/propoxylated fatty alcohols, nonionic ethoxylate/propoxylate condensates with propylene glycol, and the nonionic ethoxylate condensation products with propylene oxide/ethylene diamine adducts.
- the condensation products of aliphatic alcohols with from 1 to 25 moles of alkylene oxide, particularly ethylene oxide and/or propylene oxide, are suitable for use herein.
- the alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from 6 to 22 carbon atoms.
- Particularly preferred are the condensation products of alcohols having an alkyl group containing from 8 to 20 carbon atoms with from 2 to 10 moles of ethylene oxide per mole of alcohol.
- Polyhydroxy fatty acid amides suitable for use herein are those having the structural formula R 2 CONR 1 Z wherein : Rl is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, ethoxy, propoxy, or a mixture thereof, preferable C1-C4 alkyl, more preferably C ⁇ or C2 alkyl, most preferably C alkyl (i.e., methyl); and R2 is a C5-C31 hydrocarbyl, preferably straight-chain C5-C19 alkyl or alkenyl, more preferably straight-chain C9-C17 alkyl or alkenyl, most preferably straight-chain C ⁇ -C ⁇ j alkyl or alkenyl, or mixture thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof.
- Z
- Nonionic Fatty Acid Amide Surfactant Suitable fatty acid amide surfactants include those having the formula: R"CON(R ⁇ )2 wherein R ⁇ is an alkyl group containing from 7 to 21, preferably from 9 to 17 carbon atoms and each R? is selected from the group consisting of hydrogen, C1-C4 alkyl, C ⁇ - C4 hydroxyalkyl, and -(C2H4 ⁇ ) x H, where x is in the range of from 1 to 3.
- Suitable alkylpolysaccharides for use herein are disclosed in U.S. Patent 4,565,647, Llenado, issued January 21, 1986, having a hydrophobic group containing from 6 to 30 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group containing from 1.3 to 10 saccharide units.
- Preferred alkylpolyglycosides have the formula:
- R 2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from 10 to 18 carbon atoms; n is 2 or 3; t is from 0 to 10, and x is from 1.3 to 8.
- the glycosyl is preferably derived from glucose.
- amphoteric Surfactant Suitable amphoteric surfactants for use herein include the amine oxide surfactants and the alkyl amphocarboxylic acids.
- Suitable amine oxides include those compounds having the formula R3(OR4) X NO(R5)2 wherein R ⁇ is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containing from 8 to 26 carbon atoms; R ⁇ is an alkylene or ydroxyalkylene group containing from 2 to 3 carbon atoms, or mixtures thereof; x is from 0 to 5, preferably from 0 to 3; and each R-> is an alkyl or hydroxyalkyl group containing from 1 to 3, or a polyethylene oxide group containing from 1 to 3 ethylene oxide groups.
- Preferred are CiQ-Cig alkyl dimethylamine oxide, and C ⁇ -18 acylamido alkyl dimethylamine oxide.
- a suitable example of an alkyl aphodicarboxylic acid is Miranol(TM) C2M Cone, manufactured by Miranol, Inc., Dayton, NJ.
- Zwitterionic surfactants can also be incorporated into the composition herein. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Betaine and sultaine surfactants are exemplary zwitterionic surfactants for use herein.
- Suitable betaines are those compounds having the formula RCR' ⁇ N+R ⁇ COO- wherein R is a Cg-C ⁇ hydrocarbyl group, each Rl is typically C1-C3 alkyl, and R 2 is a C1-C5 hydrocarbyl group.
- Preferred betaines are C ⁇ . ⁇ dimethyl-ammonio hexanoate and the ClO-18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines.
- Complex betaine surfactants are also suitable for use herein.
- Suitable cationic surfactants to be used in the composition herein include the quaternary ammonium surfactants.
- the quaternary ammonium surfactant is a mono Cg-
- N positions are substituted by methyl, hydroxy ethyl or hydroxypropyl groups.
- Preferred are also the mono-alkoxylated and bis-alkoxylated amine surfactants.
- cationic surfactants which can be used in the composition herein are cationic ester surfactants.
- the cationic ester surfactant is a, preferably water dispersible, compound having surfactant properties comprising at least one ester (i.e. -COO-) linkage and at least one cationically charged group.
- Suitable cationic ester surfactants including choline ester surfactants, have for example been disclosed in US Patents No.s 4228042, 4239660 and 4260529.
- ester linkage and cationically charged group are separated from each other in the surfactant molecule by a spacer group consisting of a chain comprising at least three atoms (i.e. of three atoms chain length), preferably from three to eight atoms, more preferably from three to five atoms, most preferably three atoms.
- the atoms forming the spacer group chain are selected from the group consisting of carbon, nitrogen and oxygen atoms and any mixtures thereof, with the proviso that any nitrogen or oxygen atom in said chain connects only with carbon atoms in the chain.
- spacer groups having, for example, -O-O- (i.e.
- the spacer group chain comprises only carbon atoms, most preferably the chain is a hydrocarbyl chain.
- cationic mono-alkoxylated amine surfactant preferably of the general formula I:
- R is an alkyl or alkenyl moiety containing from about 6 to about 18 carbon atoms, preferably 6 to about 16 carbon atoms, most preferably from about 6 to about 14 carbon atoms;
- R 2 and R ⁇ are each independently alkyl groups containing from one to about three carbon atoms, preferably methyl, most preferably both R 2 and R ⁇ are methyl groups;
- R ⁇ is selected from hydrogen (preferred), methyl and ethyl;
- X- is an anion such as chloride, bromide, methylsulfate, sulfate, or the like, to provide electrical neutrality;
- A is a alkoxy group, especially a ethoxy, propoxy or butoxy group; and
- p is from 0 to about 30, preferably 2 to about 15, most preferably 2 to about 8.
- Particularly preferred ApR ⁇ groups are — CH 2 CH OH, — CH2CH 2 CH 2 OH, — CH 2 CH(CH 3 )OH and —
- R groups are linear alkyl groups. Linear R groups having from 8 to 14 carbon atoms are preferred.
- Another highly preferred cationic mono-alkoxylated amine surfactants for use herein are of the formula
- R is Ci ⁇ -Cig hydrocarbyl and mixtures thereof, especially C10-C1 alkyl, preferably CJQ an ⁇ ⁇ Cj2 alkyl, and X is any convenient anion to provide charge balance, preferably chloride or bromide.
- the levels of the cationic mono-alkoxylated amine surfactants used in the composition herein is preferably from 0.1% to 20%, more preferably from 0.2% to 7%, most preferably from 0.3% to 3.0% by weight of said composition.
- Cationic bis-alkoxylated amine surfactant preferably has the general formula II:
- Rl is an alkyl or alkenyl moiety containing from about 8 to about 18 carbon atoms, preferably 10 to about 16 carbon atoms, most preferably from about 10 to about 14 carbon atoms;
- R 2 is an alkyl group containing from one to three carbon atoms, preferably methyl;
- R ⁇ and R4 can vary independently and are selected from hydrogen
- methyl and ethyl, X- is an anion such as chloride, bromide, methylsulfate, sulfate, or the like, sufficient to provide electrical neutrality.
- a and A' can vary independently and are each selected from C1-C4 alkoxy, especially ethoxy, (i.e., - CH2CH2O-), propoxy, butoxy and mixtures thereof; p is from 1 to about 30, preferably 1 to about 4 and q is from 1 to about 30, preferably 1 to about 4, and most preferably both p and q are 1.
- Highly preferred cationic bis-alkoxylated amine surfactants for use herein are of the formula
- Rl is CiQ-Cig hydrocarbyl and mixtures thereof, preferably CIQ, C ⁇ 2, 4 alkyl and mixtures thereof.
- X is any convenient anion to provide charge balance, preferably chloride.
- cationic bis-alkoxylated amine surfactants useful herein include compounds of the formula:
- Rl is C10-C18 hydrocarbyl, preferably C10-C1 alkyl, independently p is 1 to about 3 and q is 1 to about 3, R 2 is C1-C3 alkyl, preferably methyl, and X is an anion, especially chloride or bromide.
- composition herein may comprise one or more building agents.
- building agents are described in more detail hereinafter. These building agents may be water- soluble building compounds, also herein referred to as water-soluble builder compounds, or water-insoluble or partially water-insoluble building agents, also herein referred to as insoluble builder compounds or partially soluble builder compounds.
- composition herein may preferably contain a water-soluble builder compound, typically present in said compositions at a level of from 1% to 80% by weight, preferably from 10%) to 60% by weight, most preferably from 15% to 40% by weight of the composition.
- composition herein may preferably comprise phosphate-containing builder material. Preferably present at a level of from 0.5% to 60%, more preferably from 5% to 50%, more preferably from 8% to 40% by weight of the composition.
- the phosphate-containing builder material preferably comprises tetrasodium pyrophosphate or even more preferably anhydrous sodium tripolyphosphate.
- Suitable water-soluble builder compounds include the water soluble monomeric polycarboxylates, or their acid forms, homo or copolymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxylic radicals separated from each other by not more that two carbon atoms, borates, and mixtures of any of the foregoing.
- the carboxylate or polycarboxylate builder can be monomeric or oligomeric in type although monomeric polycarboxylates are generally preferred for reasons of cost and performance.
- Suitable carboxylates containing one carboxy group include the water soluble salts of lactic acid, glycolic acid and ether derivatives thereof.
- Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid,
- polycarboxylates or their acids containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No. 1,379,241, lactoxysuccinates described in British Patent No.
- the most preferred polycarboxylic acid containing three carboxy groups is citric acid, preferably present at a level of from 0.1% to 15%, more preferably from 0.5% to 8% by weight of the composition.
- Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed in British Patent No. 1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1, 3, 3 -propane tetracarboxylates and 1,1, 2, 3 -propane tetracarboxylates.
- Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448, and the sulfonated pyrolysed citrates described in British Patent No. 1,439,000.
- Preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.
- the parent acids of the monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts e.g. citric acid or citrate/citric acid mixtures are also contemplated as useful builder components.
- water-soluble phosphate builders are the alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymeta/phosphate in which the degree of polymerization ranges from about 6 to 21, and salts of phytic acid.
- Partially Soluble or Insoluble Builder Compound is the alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymeta/phosphate in which the degree of polymerization ranges from about 6 to 21, and salts of phytic acid.
- compositions herein may contain a partially soluble or insoluble builder compound, typically present at a level of from 0.5% to 60% by weight, preferably from 5% to 50% by weight, most preferably from 8% to 40% by weight of the composition.
- Examples of largely water insoluble builders include the sodium aluminosilicates.
- Suitable aluminosilicate zeolites have the unit cell formula Na z [(Al ⁇ 2) z (Si ⁇ 2)y]- XH2O wherein z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276, more preferably from 10 to 264.
- the aluminosilicate material are in hydrated form and are preferably crystalline, containing from 10% to 28%, more preferably from 18% to 22% water in bound form.
- the aluminosilicate zeolites can be naturally occurring materials, but are preferably synthetically derived. Synthetic crystalline aluminosilicate ion exchange materials are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS and mixtures thereof. Zeolite A has the formula:
- Zeolite X has the formula Nag6 [(Al ⁇ 2)g6(Si ⁇ 2)l06]- 276 H 2 O.
- zeolite MAP builder Another preferred aluminosilicate zeolite is zeolite MAP builder.
- the zeolite MAP can be present at a level of from 1% to 80%, more preferably from 15% to 40% by weight of the composition.
- Zeolite MAP is described in EP 384070A (Unilever). It is defined as an alkali metal alumino-silicate of the zeolite P type having a silicon to aluminium ratio not greater than 1.33, preferably within the range from 0.9 to 1.33 and more preferably within the range of from 0.9 to 1.2.
- zeolite MAP having a silicon to aluminium ratio not greater than 1.15 and, more particularly, not greater than 1.07.
- the zeolite MAP detergent builder has a particle size, expressed as a d5Q value of from 1.0 to 10.0 micrometres, more preferably from 2.0 to 7.0 micrometres, most preferably from 2.5 to 5.0 micrometres.
- the d5Q value indicates that 50% by weight of the particles have a diameter smaller than that figure.
- the particle size may, in particular be determined by conventional analytical techniques such as microscopic determination using a scanning electron microscope or by means of a laser granulometer. Other methods of establishing d5Q values are disclosed in EP 384070 A.
- composition herein may comprise one or more chelating agents, also herein referred to as heavy metal ion sequestrant.
- Preferred chelating agents are described in more detail hereinafter.
- compositions herein preferably contain as an optional component a heavy metal ion sequestrant.
- heavy metal ion sequestrant it is meant herein components which act to sequester (chelate) heavy metal ions. These components may also have calcium and magnesium chelation capacity, but preferentially they show selectivity to binding heavy metal ions such as iron, manganese and copper.
- Heavy metal ion sequestrants are generally present at a level of from 0.005% to 10%, preferably from 0.1% to 5%, more preferably from 0.25% to 7.5% and most preferably from 0.3%) to 2% by weight of the composition.
- Suitable heavy metal ion sequestrants for use herein include organic phosphonates, such as the amino alkylene poly (alkylene phosphonates), alkali metal ethane 1 -hydroxy disphosphonates and nitrilo trimethylene phosphonates.
- Preferred among the above species are diethylene triamine penta (methylene phosphonate), ethylene diamine tri (methylene phosphonate) hexamethylene diamine tetra (methylene phosphonate) and hydroxy-ethylene 1,1 diphosphonate, 1,1 hydroxyethane diphosphonic acid and 1,1 hydroxyethane dimethylene phosphonic acid.
- Suitable heavy metal ion sequestrant for use herein include nifrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminotetracetic acid, ethylenediamine disuccinic acid, ethylenediamine diglutaric acid, 2-hydroxypropylenediamine disuccinic acid or any salts thereof.
- Suitable heavy metal ion sequestrants for use herein are iminodiacetic acid derivatives such as 2-hydroxyethyl diacetic acid or glyceryl imino diacetic acid, described in EP-A-317,542 and EP-A-399,133.
- iminodiacetic acid-N-2- hydroxypropyl sulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl-3- sulfonic acid sequestrants described in EP-A-516,102 are also suitable herein.
- EP-A-476,257 describes suitable amino based sequestrants.
- EP-A-510,331 describes suitable sequestrants derived from collagen, keratin or casein.
- 528,859 describes a suitable alkyl iminodiacetic acid sequestrant. Dipicolinic acid and 2-phosphonobutane-l,2,4-tricarboxylic acid are also suitable. Glycinamide- N,N'-disuccinic acid (GADS), ethylenediamine-N-N'-diglutaric acid (EDDG) and 2-hydroxypropylenediamine-N-N'-disuccinic acid (HPDDS) are also suitable.
- Glycinamide- N,N'-disuccinic acid Glycinamide- N,N'-disuccinic acid (GADS)
- EDDG ethylenediamine-N-N'-diglutaric acid
- HPDDS 2-hydroxypropylenediamine-N-N'-disuccinic acid
- diethylenetriamine pentacetic acid ethylenediamine-N,N'- disuccinic acid (EDDS) and 1,1 hydroxyethane diphosphonic acid or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof.
- EDDS ethylenediamine-N,N'- disuccinic acid
- 1,1 hydroxyethane diphosphonic acid or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof.
- composition herein may comprise one or bleaching agents. Preferred bleaching agents for use herein are described in more detail hereinafter.
- a preferred additional bleaching agent is a perhydrate bleach, such as metal perborates, metal percarbonates, particularly the sodium salts.
- Perborate can be mono or tetra hydrated.
- Sodium percarbonate has the formula corresponding to 2Na2CO3.3H2O2, and is available commercially as a crystalline solid.
- Potassium peroxymonopersulfate, sodium per is another optional inorganic perhydrate salt of use in the composition herein.
- composition herein is an organic peroxyacid bleaching system.
- the bleaching system contains a hydrogen peroxide source and an organic peroxyacid bleach precursor compound.
- the production of the organic peroxyacid occurs by an in situ reaction of the precursor with a source of hydrogen peroxide.
- Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches, such as the perborate bleach.
- a preformed organic peroxyacid is incorporated directly into the composition herein.
- the composition herein may contain mixtures of a hydrogen peroxide source and organic peroxyacid precursor in combination with a preformed organic peroxyacid.
- Peroxyacid bleach precursors are compounds which react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid.
- peroxyacid bleach precursors may be represented as O X-C-L
- L is a leaving group and X is essentially any functionality, such that on perhydroloysis the structure of the peroxyacid produced is
- Peroxyacid bleach precursor compounds are preferably incorporated at a level of from 0.5% to 20%) by weight, more preferably from 1%> to 15% by weight, most preferably from 1.5% to 10% by weight of the composition herein.
- Suitable peroxyacid bleach precursor compounds typically contain one or more N- or O- acyl groups, which precursors can be selected from a wide range of classes.
- Suitable classes include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. Examples of useful materials within these classes are disclosed in GB-A- 1586789. Suitable esters are disclosed in GB-A-836988, 864798, 1147871, 2143231 and EP-A-0170386.
- L group The leaving group, hereinafter L group, must be sufficiently reactive for the perhydrolysis reaction to occur within the optimum time frame (e.g., a wash cycle). However, if L is too reactive, this activator will be difficult to stabilize for use herein.
- Preferred L groups are selected from the group consisting of:
- R is an alkyl, aryl, or alkaryl group containing from 1 to
- R 3 is an alkyl chain containing from 1 to 8 carbon atoms
- R 4 is H or R
- Y is H or a solubilizing group. Any ofR , R and R may be substituted by essentially any functional group including, for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl ammonium groups.
- the preferred solubilizing groups are -SO 3 " M + , -CO 2 " M + , -SO 4 " M + , -N + (R 3 ) 4 X " and
- M is an alkyl chain containing from 1 to 4 carbon atoms
- M is a cation which provides solubility to the bleach activator
- X is an anion which provides solubility to the bleach activator.
- M is an alkali metal, ammonium or substituted ammonium cation, with sodium and potassium being most preferred
- X is a halide, hydroxide, methylsulfate or acetate anion.
- Alkyl percarboxylic acid bleach precursors form percarboxylic acids on perhydrolysis.
- Preferred precursors of this type provide peracetic acid on perhydrolysis.
- Preferred alkyl percarboxylic precursor compounds of the imide type include the N-
- TAED Tetraacetyl ethylene diamine
- alkyl percarboxylic acid precursors include sodium 3,5,5-tri-methyl hexanoyloxybenzene sulfonate (iso-NOBS), sodium nonanoyloxybenzene sulfonate (NOBS), sodium acetoxybenzene sulfonate (ABS) and pentaacetyl glucose.
- Amide substituted alkyl peroxyacid precursor compounds are suitable for use herein, including those of the following general formulae:
- Rl is an alkyl group with from 1 to 14 carbon atoms
- R 2 is an alkylene group containing from 1 to 14 carbon atoms
- R ⁇ is H or an alkyl group containing 1 to 10 carbon atoms and L can be essentially any leaving group.
- Amide substituted bleach activator compounds of this type are described in EP-A-0170386. Preformed Organic Peroxyacid
- composition herein may contain, in addition to, or as an alternative to, an organic peroxyacid bleach precursor compound, a preformed organic peroxyacid , typically at a level of from 1%> to 15% by weight, more preferably from 1% to 10% by weight of the composition.
- a preferred class of organic peroxyacid compounds are the amide substituted compounds of the following general formulae:
- Rl is an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms
- R 2 is an alkylene, arylene, and alkarylene group containing from 1 to 14 carbon atoms
- R ⁇ is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms.
- Amide substituted organic peroxyacid compounds of this type are described in EP-A-0170386.
- organic peroxyacids include diacyl and tetraacylperoxides, especially diperoxydodecanedioc acid, diperoxytetradecanedioc acid and diperoxyhexadecanedioc acid.
- diacyl and tetraacylperoxides especially diperoxydodecanedioc acid, diperoxytetradecanedioc acid and diperoxyhexadecanedioc acid.
- Mono- and diperazelaic acid, mono- and diperbrassylic acid and N- phthaloylaminoperoxicaproic acid are also suitable herein.
- Another preferred ingredient useful in the composition herein is one or more additional enzymes.
- Preferred additional enzymatic materials include the commercially available lipases, cutinases, amylases, neutral and alkaline proteases, celmlases, endolases, esterases, pectinases, lactases and peroxidases conventionally incorporated into the composition herein. Suitable enzymes are discussed in US Patents 3,519,570 and 3,533,139.
- protease enzymes include those sold under the tradenames Alcalase, Savinase, Primase, Durazym, and Esperase by Novo Industries A S (Denmark), those sold under the tradename Maxatase, Maxacal and Maxapem by Gist- Brocades, those sold by Genencor International, and those sold under the tradename Opticlean and Optimase by Solvay Enzymes.
- Protease enzyme may be incorporated into the composition herein at a level of from 0.0001% to 4% active enzyme by weight of the composition.
- Preferred amylases include, for example, ⁇ -amylases obtained from a special strain of B licheniformis, described in more detail in GB- 1,269,839 (Novo).
- Preferred commercially available amylases include for example, those sold under the tradename Rapidase by
- Amylase enzyme may be incorporated into the composition herein at a level of from
- Lipolytic enzyme may be present at levels of active lipolytic enzyme of from 0.0001% to 2% by weight, preferably 0.001 % to 1 % by weight, most preferably from 0.001 % to 0.5% by weight of the composition.
- the lipase may be fungal or bacterial in origin being obtained, for example, from a lipase producing strain of Humicola sp., Thermomyces sp. or Pseudomonas sp. including Pseudomonas pseudoalcaligenes or Pseudomas fluorescens. Lipase from chemically or genetically modified mutants of these strains are also useful herein.
- a preferred lipase is derived from Pseudomonas pseudoalcaligenes, which is described in Granted European Patent, EP-B-0218272.
- Another preferred lipase herein is obtained by cloning the gene from Humicola lanuginosa and expressing the gene in Aspergillus oryza, as host, as described in European Patent Application, EP-A-0258 068, which is commercially available from Novo Industri A/S, Bagsvaerd, Denmark, under the trade name Lipolase. This lipase is also described in U.S. Patent 4,810,414, Huge- Jensen et al, issued March 7, 1989.
- composition herein when formulated for use in machine washing compositions, may comprise a suds suppressing system present at a level of from 0.01% to 15%, preferably from 0.02% to 10%, most preferably from 0.05% to 3% by weight of the composition.
- Suitable suds suppressing systems for use herein may comprise essentially any known antifoam compound, including, for example silicone antifoam compounds and 2-alkyl alcanol antifoam compounds.
- antifoam compound any compound or mixtures of compounds which act such as to depress the foaming or sudsing produced by a solution of a detergent composition, particularly in the presence of agitation of that solution.
- Particularly preferred antifoam compounds for use herein are silicone antifoam compounds defined herein as any antifoam compound including a silicone component. Such silicone antifoam compounds also typically contain a silica component.
- silicone antifoam compounds as used herein, and in general throughout the industry, encompasses a variety of relatively high molecular weight polymers containing siloxane units and hydrocarbyl group of various types.
- Preferred silicone antifoam compounds are the siloxanes, particularly the polydimethylsiloxanes having trimethylsilyl end blocking units.
- Suitable antifoam compounds include the monocarboxylic fatty acids and soluble salts thereof. These materials are described in US Patent 2,954,347, issued September 27, 1960 to Wayne St. John.
- the monocarboxylic fatty acids, and salts thereof, for use as suds suppressor typically have hydrocarbyl chains of 10 to 24 carbon atoms, preferably 12 to 18 carbon atoms.
- Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts.
- Other suitable antifoam compounds include, for example, high molecular weight fatty esters (e.g.
- fatty acid triglycerides fatty acid esters of monovalent alcohols
- aliphatic 18- 40 ketones e.g. stearone
- N-alkylated amino triazines such as tri- to hexa- alkylmelamines or di- to terra alkyldiamine chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, bis stearic acid amide and monostearyl di-alkali metal (e.g. sodium, potassium, lithium) phosphates and phosphate esters.
- aliphatic 18- 40 ketones e.g. stearone
- N-alkylated amino triazines such as tri- to hexa- alkylmelamines or di- to terra alkyldiamine chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary
- a preferred suds suppressing system comprises:
- antifoam compound preferably silicone antifoam compound, most preferably a silicone antifoam compound comprising in combination
- silica at a level of from 1%> to 50%>, preferably 5% to 25% by weight of the silicone/silica antifoam compound;
- silica/silicone antifoam compound is incorporated at a level of from 5% to 50%, preferably 10% to 40% by weight;
- a dispersant compound most preferably comprising a silicone glycol rake copolymer with a polyoxyalkylene content of 72-78% and an ethylene oxide to propylene oxide ratio of from 1:0.9 to 1:1.1, at a level of from 0.5% to 10%, preferably 1% to 10% by weight;
- a particularly preferred silicone glycol rake copolymer of this type is DCO544, commercially available from DOW Corning under the tradename DCO544;
- an inert carrier fluid compound most preferably comprising a C g-C 1 g ethoxylated alcohol with a degree of ethoxylation of from 5 to 50, preferably 8 to 15, at a level of from 5% to 80%, preferably 10% to 70%, by weight;
- a highly preferred particulate suds suppressing system is described in EP-A-0210731 and comprises a silicone antifoam compound and an organic carrier material having a melting point in the range 50°C to 85°C, wherein the organic carrier material comprises a monoester of glycerol and a fatty acid having a carbon chain containing from 12 to 20 carbon atoms.
- EP-A-0210721 discloses other preferred particulate suds suppressing systems wherein the organic carrier material is a fatty acid or alcohol having a carbon chain containing from 12 to 20 carbon atoms, or a mixture thereof, with a melting point offrom 45°C to 80°C.
- suds suppressing systems comprise polydimethylsiloxane or mixtures of silicone, such as polydimethylsiloxane, aluminosilicate and polycarboxylic polymers, such as copolymers of laic and acrylic acid.
- composition herein may also comprise from 0.01% to 10 %, preferably from 0.05%> to 0.5% by weight of polymeric dye transfer inhibiting agents.
- the polymeric dye transfer inhibiting agents are preferably selected from polyamine N- oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidonepolymers or combinations thereof, whereby these polymers can be cross-linked polymers.
- composition herein also optionally contain from about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners.
- Hydrophilic optical brighteners useful herein include those having the structural formula:
- R ⁇ is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl
- R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, mo ⁇ hilino, chloro and amino
- M is a salt-forming cation such as sodium or potassium.
- R ⁇ is anilino
- R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium
- the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine- 2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt.
- This particular brightener species is commercially marketed under the tradename Tinopal-UNPA-GX by Ciba- Geigy Co ⁇ oration.
- Tinopal-CBS-X and Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the composition herein.
- Rj is anilino
- R2 is N-2-hydroxyethyl-N-2-methylamino
- M is a cation such as sodium
- the brightener is 4,4'-bis[(4-anilino-6-(N-2-hydroxyethyl- N-methylamino)-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid disodium salt.
- This particular brightener species is commercially marketed under the tradename Tinopal 5BM-GX by Ciba-Geigy Co ⁇ oration.
- R ⁇ is anilino
- R2 is mo ⁇ hilino
- M is a cation such as sodium
- the brightener is 4,4'-bis[(4-anilino-6-mo ⁇ hilino-s-triazine-2-yl)amino]2,2'- stilbenedisulfonic acid, sodium salt.
- This particular brightener species are commercially marketed under the tradename Tinopal-DMS-X and Tinopal AMS-GX by Ciba Geigy Co ⁇ oration.
- Optional Ingredients include perfumes, colours and filler salts, with sodium sulfate being a preferred filler salt.
- the composition herein may contain from about 2% to about 10% by weight of an organic acid, preferably citric acid.
- an organic acid preferably citric acid.
- minor amounts e.g., less than about 20% by weight
- neutralizing agents e.g., buffering agents, phase regulants, hydrotropes, enzyme stabilizing agents, polyacids, suds regulants, opacifiers, anti-oxidants, bactericides and dyes, such as those described in US Patent 4,285,841 to Barrat et al., issued August 25, 1981, can be present.
- the composition herein is a solid detergent composition.
- the composition herein can be in any solid form, such as a granular composition or for example a tablet, flake, extradate, agglomerate or granule containing composition.
- the composition herein can be made by methods such as dry-mixing, agglomerating, compaction, spray drying of various ingredients comprised in the composition herein, or a combination thereof.
- the composition herein preferably has a bulk density of from 300g/litre or even 350g/litre or 450g/litre to preferably 1500g/litre or lOOOg/litre or even to 850g/litre.
- the composition herein comprises a hectorite clay and a dioctrahedral smectite clay.
- the ratio of said hectorite clay to said dioctrahedral smectite clay is less than 1:1, preferably less than 0.8:1, more preferably less than 0.6:1, or preferably from 0.1:1 to 0.9:1, more preferably from 0.2:1 to 0.7:1, more preferably from 0.2:1 to 0.5:1.
- said composition comprises (by weight of said composition) an amount of clay of no more than 10%, or preferably from 1%> to 10%), preferably from 5% to 15%>, more preferably from 7% to 10%>.
- said clay comprises (by weight of said clay) no more than 35%), preferably less than 35% impurities such as mineral impurities, typical mineral impurities include calcite.
- the clay is present in said composition as a separate preformed particle or as a coating for a detergent ingredient particle, preferably as a separate preformed particle.
- said preformed particle has a weight average particle size of from 250 micrometers to 1500 micrometers, more preferably from 500 micrometers to 1350 micrometers, more preferably from 600 micrometers to 1200 micrometers, more preferably from 800 micrometers to 1000 micrometers.
- Said hectorite clay and said dioctrahedral smectite clay may be present in the same separate preformed particle or may be present in different preformed particles.
- Said preformed particle may comprise additional detergent ingredients such as surfactant, building agent, chelating agent, bleaching agent, filler agent or combination thereof.
- said preformed particle comprises one or more binding agents.
- Typical binding agents for use herein include humectant and/or hydrophobic compounds, preferably a wax or oil such as paraffin oil.
- Preferred binding agents are organic compounds, including propylene glycol, ethylene glycol, dimers or trimers of glycol, most preferably glycerol. Another preferred binding agent is water. It may also be preferred that the preformed particle comprises a flocculation agent, said flocculation agent is described in more detail herein.
- said preformed particle is in the form of an agglomerate, extrudate, spray dried granule or combination thereof, preferably an agglomerate.
- said preformed particle is in the form of an agglomerate and comprises a binding agent.
- Laundry washing methods herein typically comprise treating soiled laundry with an aqueous wash solution for washing by machine or for washing by hand, having dissolved or dispensed therein an effective amount of the composition herein.
- an effective amount of the composition it is meant from 40g to 300g of said composition dissolved or dispersed in a wash solution of volume from 1 to 65 litres, as are typical product dosages and wash solution volumes commonly employed in conventional laundry methods.
- Other laundry washing processes known in the art can also be used.
- 150g hectorite clay powder supplied by Rheox under the trade name Bentone HC and 300g montmorillonite clay powder supplied by CSM under the trade name "AP base" is added to a food mixer and mixed at half speed for 10 seconds to form a clay mixture.
- 22.5g glyerol is slowly added to the clay mixture which is being constantly mixed at half speed during the period of glycerol addition to form a glycerol-clay mixture.
- 90g distilled water is slowly added to the glycerol-clay mixture which is being constantly mixed at full speed during the period of water addition to form moist clay agglomerates.
- 15g molten paraffin wax at a temperature of 70°C is added to the moist clay agglomerates and the agglomerates are mixed at full speed in the food mixer for 5 seconds.
- the moist clay agglomerates are then transferred to a Sherwood fluidised bed dryer and dried for 5 minutes to form clay agglomerates.
- the air temperature in the drier is 60°C and the air flow rate in the drier is 1.2meter/second during the drying period.
- the moisture content of the clay agglomerates after the drying step is 5% by weight of the agglomerates.
- the clay agglomerates are then sieved using a ROTAP sieve with mesh sizes of 250 micrometers and 1180 micrometers, and the clay agglomerates having a particle size of from 250 micrometers to 1180 micrometers are collected.
- 15g clay agglomerates are added to 120g base detergent powder comprising ester carboxymethyl cellulose, polyethylene oxide, surfactant, sodium carbonate, sodium sulphate, zeolite, enzymes and suds suppressor, to form a solid detergent composition in accord with the present invention.
- 450g hectorite clay powder supplied by Rheox under the trade name Bentone is added to a food mixer.
- 22.5g glyerol is slowly added to the clay mixture which is being constantly mixed at half speed during the period of glycerol addition to form a glycerol-clay mixture.
- 120g distilled water is slowly added to the glycerol-clay mixture which is being constantly mixed at full speed during the period of water addition to form moist hectorite clay agglomerates.
- 15g molten paraffin wax at a temperature of 70°C is added to the moist hectorite clay agglomerates and the agglomerates are mixed at full speed in the food mixer for 5 seconds.
- the moist hectorite clay agglomerates are then transferred to a Sherwood fluidised bed dryer and dried for 6 minutes to form hectorite clay agglomerates.
- the air temperature in the drier is 60°C and the air flow rate in the drier is 1.2meter/second during the drying period.
- the moisture content of the hectorite clay agglomerates after the drying step is 5% by weight of the agglomerates.
- the hectorite clay agglomerates are then sieved using a ROTAP sieve with mesh sizes of 250 micrometers and 1180 micrometers, and the hectorite clay agglomerates having a particle size of from 250 micrometers to 1180 micrometers are collected.
- 450g montmorillonite clay powder supplied by CSM under the trade name "AP base" is added to a food mixer.
- 22.5g glyerol is slowly added to the clay mixture which is being constantly mixed at half speed during the period of glycerol addition to form a glycerol-clay mixture.
- 70g distilled water is slowly added to the glycerol-clay mixture which is being constantly mixed at full speed during the period of water addition to form moist montmorillonite clay agglomerates.
- 15g molten paraffin wax at a temperature of 70°C is added to the moist montmorillonite clay agglomerates and the agglomerates are mixed at full speed in the food mixer for 5 seconds.
- the moist montmorillonite clay agglomerates are then transferred to a Sherwood fluidised bed dryer and dried for 4 minutes to form montmorillonite clay agglomerates.
- the air temperature in the drier is 60°C and the air flow rate in the drier is 1.2meter/second during the drying period.
- the moisture content of the montmorillonite clay agglomerates after the drying step is 5% by weight of the agglomerates.
- the montmorillonite clay agglomerates are then sieved using a ROTAP sieve with mesh sizes of 250 micrometers and 1180 micrometers, and the montmorillonite clay agglomerates having a particle size of from 250 micrometers to 1180 micrometers are collected.
- 5g hectorite clay agglomerates and lOg montmorillonite clay agglomerates are added to 120g base detergent powder comprising, ester carboxymethyl cellulose, polyethylene oxide, surfactant, sodium carbonate, sodium sulphate, zeolite, enzymes and suds suppressor, to form a solid detergent composition in accord with the present invention.
- base detergent powder comprising, ester carboxymethyl cellulose, polyethylene oxide, surfactant, sodium carbonate, sodium sulphate, zeolite, enzymes and suds suppressor
- 3g hectorite clay powder supplied by Rheox under the trade name Bentone HC and 7g montmorillonite clay powder supplied by CSM under the trade name "AP base” are added to and dry mixed with 125g base detergent powder comprising ester carboxymethyl cellulose, polyethylene oxide, surfactant, sodium carbonate, sodium sulphate, zeolite, enzymes and suds suppressor, to form a solid detergent composition in accord with the present invention.
- compositions are solid detergent compositions in accord with the present invention.
- the amounts of the detergent ingredients are shown as % by weight of said composition.
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0022906A GB2366801A (en) | 2000-09-19 | 2000-09-19 | Detergent compositions with clay fabric softeners |
| GB0022906 | 2000-09-19 | ||
| PCT/US2001/028476 WO2002024850A1 (en) | 2000-09-19 | 2001-09-13 | Detergent compositions |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP1319059A1 true EP1319059A1 (de) | 2003-06-18 |
| EP1319059B1 EP1319059B1 (de) | 2004-11-10 |
Family
ID=9899690
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP01970847A Expired - Lifetime EP1319059B1 (de) | 2000-09-19 | 2001-09-13 | Waschmittelzusammensetzungen |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP1319059B1 (de) |
| JP (1) | JP2004515573A (de) |
| AT (1) | ATE282079T1 (de) |
| AU (1) | AU2001290804A1 (de) |
| DE (1) | DE60107102T2 (de) |
| ES (1) | ES2231548T3 (de) |
| GB (1) | GB2366801A (de) |
| WO (1) | WO2002024850A1 (de) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB0207481D0 (en) | 2002-03-28 | 2002-05-08 | Unilever Plc | Solid fabric conditioning compositions |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ZA734721B (en) * | 1972-07-14 | 1974-03-27 | Procter & Gamble | Detergent compositions |
| US3862058A (en) * | 1972-11-10 | 1975-01-21 | Procter & Gamble | Detergent compositions containing a smectite-type clay softening agent |
| US3993573A (en) * | 1973-02-16 | 1976-11-23 | The Procter & Gamble Company | Softening additive and detergent composition |
| US4196104A (en) * | 1977-09-26 | 1980-04-01 | The Procter & Gamble Company | Process for producing antistatic, fabric-softening detergent composition |
| DE3069768D1 (en) * | 1979-09-29 | 1985-01-17 | Procter & Gamble Ltd | Detergent compositions |
| ES8400768A1 (es) * | 1980-11-06 | 1983-11-01 | Procter & Gamble | Un procedimiento para preparar una composicion granular ac- tivadora del blanqueo. |
| GB8310698D0 (en) * | 1983-04-20 | 1983-05-25 | Procter & Gamble | Detergent compositions |
| DE3437721A1 (de) * | 1984-10-15 | 1986-04-17 | Süd-Chemie AG, 8000 München | Waschmittelzusatz |
| SE8603087L (sv) * | 1985-07-25 | 1987-01-26 | Colgate Palmolive Co | Textilmjukgorande och antistatisk detergentkomposition |
| MY103738A (en) * | 1987-06-30 | 1993-09-30 | Procter & Gamble | Detergent/softening compositions containing hectorite clays |
| US5234620A (en) * | 1989-06-02 | 1993-08-10 | Lever Brothers Company, Division Of Conopco, Inc. | Detergent composition containing modified dioctanedral fabric softening clay having from 100-10,000 micrograms of non-exchangeable lithium per gram of clay |
-
2000
- 2000-09-19 GB GB0022906A patent/GB2366801A/en not_active Withdrawn
-
2001
- 2001-09-13 JP JP2002529248A patent/JP2004515573A/ja not_active Withdrawn
- 2001-09-13 EP EP01970847A patent/EP1319059B1/de not_active Expired - Lifetime
- 2001-09-13 AU AU2001290804A patent/AU2001290804A1/en not_active Abandoned
- 2001-09-13 ES ES01970847T patent/ES2231548T3/es not_active Expired - Lifetime
- 2001-09-13 AT AT01970847T patent/ATE282079T1/de not_active IP Right Cessation
- 2001-09-13 DE DE60107102T patent/DE60107102T2/de not_active Expired - Fee Related
- 2001-09-13 WO PCT/US2001/028476 patent/WO2002024850A1/en not_active Ceased
Non-Patent Citations (1)
| Title |
|---|
| See references of WO0224850A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1319059B1 (de) | 2004-11-10 |
| JP2004515573A (ja) | 2004-05-27 |
| GB0022906D0 (en) | 2000-11-01 |
| AU2001290804A1 (en) | 2002-04-02 |
| ES2231548T3 (es) | 2005-05-16 |
| DE60107102T2 (de) | 2005-11-10 |
| ATE282079T1 (de) | 2004-11-15 |
| WO2002024850A8 (en) | 2003-06-19 |
| DE60107102D1 (de) | 2004-12-16 |
| GB2366801A (en) | 2002-03-20 |
| WO2002024850A1 (en) | 2002-03-28 |
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