EP0583512B1 - Reinigungsmittelzusätze - Google Patents

Reinigungsmittelzusätze Download PDF

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Publication number
EP0583512B1
EP0583512B1 EP19920202534 EP92202534A EP0583512B1 EP 0583512 B1 EP0583512 B1 EP 0583512B1 EP 19920202534 EP19920202534 EP 19920202534 EP 92202534 A EP92202534 A EP 92202534A EP 0583512 B1 EP0583512 B1 EP 0583512B1
Authority
EP
European Patent Office
Prior art keywords
detergent
additive according
surfactant
hydrophobic
detergent additive
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.)
Expired - Lifetime
Application number
EP19920202534
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English (en)
French (fr)
Other versions
EP0583512A1 (de
Inventor
Athanasios Surutzidis
Roger J. Jones
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
Priority to EP19920202534 priority Critical patent/EP0583512B1/de
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to DE1992625968 priority patent/DE69225968T2/de
Priority to ES92202534T priority patent/ES2117030T3/es
Priority to PCT/US1993/007088 priority patent/WO1994004267A1/en
Priority to JP6506286A priority patent/JPH08500144A/ja
Priority to AU47896/93A priority patent/AU4789693A/en
Priority to US08/381,893 priority patent/US5494600A/en
Priority to TR00719/93A priority patent/TR27709A/xx
Priority to CN93117787A priority patent/CN1039430C/zh
Publication of EP0583512A1 publication Critical patent/EP0583512A1/de
Application granted granted Critical
Publication of EP0583512B1 publication Critical patent/EP0583512B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38672—Granulated or coated enzymes
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/525—Carboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain two or more hydroxy groups per alkyl group, e.g. R3 being a reducing sugar rest

Definitions

  • the present invention relates to detergent active compounds and use thereof in detergent compositions. More particularly, it relates to detergent active compounds having improved storage stability within a full detergent composition.
  • Some of these actives include enzymes, bleaches, colourants, catalysts and other detergent active compounds.
  • enzyme deactivation occurs in aqueous detergent compositions containing proteolytic enzymes or mixtures of enzymes one of which is proteolytic.
  • JP-A-5913930 discloses solid particle coated with cellulose derivatives for controlled release of vaporisation - diffusing substance.
  • the present invention to provide a stabilization system that can be used to protect any detergent active compound in any detergent formulation.
  • a detergent additive comprising a detergent active compound characterized in that said compound is mixed with a surfactant before absorption into a porous hydrophobic material, said porous material subsequently being coated with a hydrophobic material.
  • the present invention provides detergent compositions comprising detergent active compounds which have improved stability upon storage.
  • the porous hydrophobic material comprising a detergent active compound being absorbed into said hydrophobic material can be used to store said detergent active compounds in the form of non-dusting granulates.
  • the present invention provides a detergent additive comprising a water-soluble or water-dispersible detergent active compound characterized in that a mixture of said compound with a surfactant is absorbed into a porous hydrophobic material, said porous material being coated with a hydrophobic material.
  • the present invention relates to a stabilization system for detergent active compounds having improved storage stability within a full detergent composition.
  • stabilization refers to protecting the detergent active compounds by isolating and protecting them from their hostile environment upon storage but releasing said compounds during washing conditions.
  • the detergent active compounds are isolated from their hostile environment by reversibly absorbing said compounds into a porous hydrophobic material.
  • the porous hydrophobic material serves as a "cage” wherein the detergent active compound is enclosed.
  • the pores of the detergent additive filled hydrophobic porous material are sealed by dispersing said porous material into a hydrophobic liquid.
  • the hydrophobic liquid acts as a "shell", thereby protecting the detergent additive from its environment.
  • the present invention provides a detergent additive comprising a hydrophilic detergent active compound characterized in that said compound is mixed with a surfactant before absorption into a porous hydrophobic material, said porous material subsequently being coated with a hydrophobic material.
  • the present invention also provides a process whereby a detergent active compound is reversibly absorbed into particles of a porous hydrophobic material, said particles subsequently being dispersed into a hydrophobic liquid.
  • the detergent active solution comprises a detergent active compound and a surfactant.
  • a detergent active compound can be significantly impaired in detergent compositions by interaction between the active compound and other coingredients of the detergent composition.
  • detergency enzymes can be affected by interaction with other enzymes, bleaches, acids and bases.
  • Perfumes and bleaches can be effected by bleach activators.
  • Cationic fabric conditioners can be effected by interaction with anionic surfactants ; organic bleaches can be effected by moisture, metal contamination ; brighteners/fluorescers can be affected with bleaches.
  • the detergent active compounds suitable for the present invention include enzymes, bleaches, bleach activators, bleach catalysts, perfumes, photoactivators, dyes, brighteners/fluorescers, through the wash sanitizers, fabric softening or conditioning agents, hydrolysable surfactants, and other detergent active compounds which are water-soluble or water-dispersible and mixtures thereof.
  • a preferred class of a detergent active compound is a detergency enzyme.
  • enzymes suitable for the present invention are enzymes which are active in the removal of soils or stains such as protease, lipase, amylase, carboxylase, cellulase, oxidase, peroxidase or mixtures thereof.
  • the enzyme may be present in the form of an enzyme solution, e.g. in water or a lower water miscible, mono-,di- or polyhydric alcohol such as propylene glycol and optionally containing enzyme stabilizers such as is known in the art.
  • Enzyme stabilizers which may be present include lower alcohols, e.g. glycerol, lower mono- or di- carboxylic acid and their salts, especially formates and oxidates, borates and calcium salts.
  • Suitable detergent active compounds can also be represented by bleaches, bleach activator and bleach catalysts.
  • Suitable inorganic bleaches include perborates, percarbonates.
  • Suitable organic bleaches include peroxyacids known in art.
  • Suitable bleach precursors are peracetic acid bleach precursors such as tetraacetylethylenediamine, triacetin, and acethyl trimethyl citrate.
  • detergent active compounds suitable for the present invention are fabric softening or conditioning agents, fluorescers, dyes, photoactivators through the wash sanitizers such as phenoxyethanol, and other detergent active compounds which are water-soluble or water-dispersible and which tend to be unstable upon storage, and mixtures thereof.
  • An essential feature of the present invention is that the detergent active compound is mixed with a surfactant before being absorbed into the porous material.
  • the detergent active does not spontaneously wet the surfaces of the hydrophobic material. It has been found that by adding surfactant the detergent active solution is readily absorbed into the pores of the hydrophobic material.
  • the surfactant suitable for the present invention should be compatible with the detergent active compound.
  • One class of nonionic surfactants useful in the present invention are condensates of ethylene oxide with a hydrophobic moiety to provide a surfactant having an average hydrophilic-lipophilic balance (HLB) in the range from 8 to 17, preferably from 9.5 to 13.5, more preferably from 10 to 12.5.
  • HLB hydrophilic-lipophilic balance
  • the hydrophobic (lipophilic) moiety may be aliphatic or aromatic in nature and the length of the polyoxyethylene group which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
  • Especially preferred nonionic surfactants of this type are the C 9 -C 15 primary alcohol ethoxylates containing 3-8 moles of ethylene oxide per mole of alcohol, particularly the C 14 -C 15 primary alcohols containing 6-8 moles of ethylene oxide per mole of alcohol and the C 12 -C 14 primary alcohols containing 3-5 moles of ethylene oxide per mole of alcohol.
  • Anionic or cationic surfactants are less likely to be used. However, if the absorbed detergent active is unaffected by these surfactants they can alternatively be used.
  • the level of surfactant used in the present invention should be such to ensure sufficient wetting of the hydrophobic material. At high levels of surfactant, agglomerates can be formed. Therefore, the level of surfactant that can be used should be such to maintain a free flowing hydrophobic powder.
  • the active-filled porous hydrophobic material may contain additional ingredients, which can be premixed with the surfactant before they are absorbed into the porous hydrophobic material.
  • additional ingredients include other active compounds such as perfumes, brighteners, bleaches, softeners and other conventional optional ingredients such as buffers, electrolytes, etc. as far as they are chemically compatible with the surfactant active solution.
  • the surfactant containing detergent active solution is absorbed into the pores of the hydrophobic material.
  • the porous hydrophobic material suitable for the present invention can be any hydrophobic porous material having an average pore diameter larger than the size of the molecules that are to be absorbed in the porous material. Pore volumes and pore size distributions may be measured by the recognized technique of mercury intrusion porosimetry.
  • the detergent active compound is an enzyme
  • an average pore diameter of the hydrophobic material of 500 angstroms or higher is preferred.
  • the preferred hydrophobic material that then can be used is silica.
  • the average pore diameter of the currently used silica is 1000 ⁇ while the absorbed enzyme molecules have diameters in the range of 50 to 150 ⁇ .
  • the silica particles can be rendered hyrophobic by treating them with dialkylsilane groups and/or trialkylsilane groups either bonded directly onto the silica or by means of silicone resin.
  • the silica is further characterized by a high absorption value. The absorption can be expressed as Dibutylphthalate (DBP) number.
  • DBP Dibutylphthalate
  • Porous silica suitable for the present invention is available under the trade name Sipernat (R) from Degussa.
  • the hydrophobic coating material provides a protective coating for the active-filled porous hydrophobic materials herein.
  • Coating the pores of the hydrophobic material isolates the detergent active compound from environments which causes the degradation of the active compounds.
  • the active compounds remain in their stabilized material environment without interacting with other potentially harmful detergent ingredients or the environment is protected from the detergent active compound itself.
  • the level of hydrophobic coating material should be such that appropriate coverage of all additive-filled porous hydrophobic material is secured.
  • the hydrophobic coating material herein is preferably a hydrophobic liquid polymer.
  • Such a polymer may be an organo polysiloxane oil, e.g. a polydi(alkyl) siloxane, especially a polydi(methyl) siloxane.
  • organo polysiloxane oil e.g. a polydi(alkyl) siloxane, especially a polydi(methyl) siloxane.
  • hydrophobic silicone oils which have been proposed for use as antifoam in liquid detergents.
  • the silicone oil to enzyme-filled silica ratio should be at least 1.5:1.
  • the hydrophobic coating material may be a high molecular weight hydrocarbon like petroleum jelly, wax, or water insoluble but water permeable polymeric material such as carboxymethylcellulose, polyvinyl alcohol, polyvinyl pyrrolidone or caprolactone.
  • detergent compositions comprising the detergent active composition of the present invention, and further comprising detergent ingredients.
  • Detergent compositions within the meaning herein, include laundry detergent compositions, dishwashing compositions or hard surface cleaning compositions.
  • Detergent ingredients include surfactants, builders and optional detergent additives. A wide range of anionic, nonionic, cationic, zwitterionic and/or ampholytic surfactants can be used in the detergent composition of the present invention.
  • anionic surfactants are particularly suitable herein, especially mixtures of sulphonate and sulphate surfactants in a weight ratio of from 5:1 to 1:2, preferably from 3:1 to 2:3, more preferably from 3:1 to 1:1.
  • Preferred sulphonates include alkyl benzene sulphonates having from 9 to 15, especially 11 to 13 carbon atoms in the alkyl radical, and alpha-sulphonated methyl fatty acid esters in which the fatty acid is derived from a C 12 -C 18 fatty source preferably from a C 16 -C 18 fatty source.
  • the cation is an alkali metal, preferably sodium.
  • Preferred sulphate surfactants are alkyl sulphates having from 12 to 18 carbon atoms in the alkyl radical, optionally in admixture with ethoxy sulphates having from 10 to 20, preferably 10 to 16 carbon atoms in the alkyl radical and an average degree of ethoxylation of 1 to 6.
  • alkyl sulphates herein are tallow alkyl sulphate, coconut alkyl sulphate, and C 14-15 alkyl sulphates.
  • the cation in each instance is again an alkali metal cation, preferably sodium.
  • One class of nonionic surfactants useful in the present invention are condensates of ethylene oxide with a hydrophobic moiety to provide a surfactant having an average hydrophilic-lipophilic balance (HLB) in the range from 8 to 17, preferably from 9.5 to 13.5, more preferably from 10 to 12.5.
  • HLB hydrophilic-lipophilic balance
  • the hydrophobic (lipophilic) moiety may be aliphatic or aromatic in nature and the length of the polyoxyethylene group which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
  • Especially preferred nonionic surfactants of this type are the C 9 -C 15 primary alcohol ethoxylates containing 3-8 moles of ethylene oxide per mole of alcohol, particularly the C 14 -C 15 primary alcohols containing 6-8 moles of ethylene oxide per mole of alcohol and the C 12 -C 14 primary alcohols containing 3-5 moles of ethylene oxide per mole of alcohol.
  • Nonionic surfactants comprises alkyl polyglucoside compounds of general formula RO (C n H 2n O) t Z x wherein Z is a moiety derived from glucose; R is a saturated hydrophobic alkyl group that contains from 12 to 18 carbon atoms; t is from 0 to 10 and n is 2 or 3; x is from 1.3 to 4, the compounds including less than 10% unreacted fatty alcohol and less than 50% short chain alkyl polyglucosides.
  • Compounds of this type and their use in detergent are disclosed in EP-B 0 070 077, 0 075 996 and 0 094 118.
  • nonionic surfactants are poly hydroxy fatty acid amide surfactants of the formula wherein R 1 is H, or R 1 is C 1-4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof, R 2 is C 5-31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof.
  • R 1 is methyl
  • R 2 is a straight C 11-15 alkyl or alkenyl chain such as coconut alkyl or mixtures thereof
  • Z is derived from a reducing sugar such as glucose, fructose, maltose, lactose, in a reductive amination reaction.
  • compositions according to the present invention may further comprise a builder system.
  • a builder system Any conventional builder system is suitable for use herein including aluminosilicate materials, silicates, polycarboxylates and fatty acids, materials such as ethylenediamine tetraacetate, metal ion sequestrants such as aminopolyphosphonates, particularly ethylenediamine tetramethylene phosphonic acid and diethylene triamine pentamethylenephosphonic acid.
  • phosphate builders can also be used herein.
  • Suitable builders can be an inorganic ion exchange material, commonly an inorganic hydrated aluminosilicate material, more particularly a hydrated synthetic zeolite such as hydrated zeolite A, X, B or HS.
  • Another suitable inorganic builder material is layered silicate, e.g. SKS-6 (Hoechst).
  • SKS-6 is a crystalline layered silicate consisting of sodium silicate (Na 2 Si 2 O 5 ).
  • Suitable polycarboxylates builders for use herein include citric acid, preferably in the form of a water-soluble salt, derivatives of succinic acid of the formula R-CH(COOH)CH2(COOH) wherein R is C10-20 alkyl or alkenyl, preferably C12-16, or wherein R can be substituted with hydroxyl, sulfo sulfoxyl or sulfone substituents.
  • Specific examples include lauryl succinate , myristyl succinate, palmityl succinate2-dodecenylsuccinate, 2-tetradecenyl succinate.
  • Succinate builders are preferably used in the form of their water-soluble salts, including sodium, potassium, ammonium and alkanolammonium salts.
  • Other suitable polycarboxylates are oxodisuccinates and mixtures of tartrate monosuccinic and tartrate disuccinic acid such as described in US 4,663,071.
  • Especially suitable fatty acid builders for use herein are saturated or unsaturated C10-18 fatty acids, as well as the corresponding soaps.
  • Preferred saturated species have from 12 to 16 carbon atoms in the alkyl chain.
  • the preferred unsaturated fatty acid is oleic acid.
  • Another preferred builder system for liquid compositions is based on dodecenyl succinic acid.
  • Suitable water-soluble organic salts are the homo- or copolymeric acids or their salts, in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms.
  • Polymers of this type are disclosed in GB-A-1,596,756.
  • Examples of such salts are polyacrylates of MW 2000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 20,000 to 70,000, especially about 40,000.
  • detergency builder salts are normally included in amounts of from 10% to 80% by weight of the composition preferably from 20% to 70% and most usually from 30% to 60% by weight.
  • detergent compositions may be employed, such enzymes and stabilizers or activators therefore, soil-suspending agents, soil-release agents, optical brighteners, abrasives, bactericides, tarnish inhibitors, coloring agents, and perfumes.
  • the laundry detergent compositions according to the present invention can be in the liquid form and in particular in "compact form"; in such case, the liquid detergent compositions according to the present invention will contain a lower amount of water, compared to conventional liquid detergents.
  • the detergent additive in liquid form according to the present invention will typically be emulsified in said liquid detergent composition.
  • the laundry detergent compositions according to the present invention can be in granular form and incorporate a builder salt.
  • Granular compositions according to the present invention can also be in in "compact form”; i.e. they may have a relatively higher density than conventional granular detergent compositions according to the present invention will contain a lower amount of "inorganic filler salt", compared to conventional granular detergents; typical filler salts are alkaline earth metal salts of sulphates and chlorides, typically sodium sulphate; "compact" detergents typically comprise not more than 10% filler salt.
  • the detergent additives herein in liquid form will typically be sprayed onto the granules of said detergent compositions.
  • Liquid dishwashing compositions according to the present invention typically contains an enzyme or a mixture of enzymes as the protected detergent active.
  • Liquid dishwashing compositions and hard surface cleaning compositions are described in, resp., International Applications WO 92/06171 and EP-A- 428 816.
  • a detergent additive according to the present invention is processed by adsorbing the enzyme solution into the pores of hydrophobic silica which is then dispersed in silicone oil.
  • the silicone oil dispersion is finally dispersed in the liquid detergent matrix.
  • the process encompasses the following steps and is exemplified with silica as a porous hydrophobic material and silica oil as a hydrophobic protective coating layer :
  • the porous hydrophobic material suitable for the present invention has a high absorption value and an average pore diameter larger than the average enzyme molecular size.
  • DBP Dibutyl Phthalate
  • Pore Volume (PV) 2.289 cm 3 /g of silica
  • the following detergent compositions are prepared, all based on a liquid detergent composition.
  • a liquid detergent composition typically contains the following ingredients : % by weight of the total detergent composition I II Linear alkylbenzene sulfonate 10 15 Alkyl sulphate 4 Fatty alcohol (C 12 -C 15 ) ethoxylate 9 14 Fatty acid 5 10 Oleic acid 4 Citric acid 5 9 KOH 3 NaOH 5.4 Monoethanolamine 9 Propanediol 1.5 9 Ethanol 5 1 Minors up to 100
  • the stability of protected enzymes according to the present invention is demonstrated by storage tests.
  • the storage stability of the "caged" enzyme formulated in a detergent compositions is compared versus the stability of a "free” (not encaged) enzyme.
  • the extent of the enzyme release and the activity of the released enzyme was measured in the presence of other enzymes, More in particular, the stability of caged and free cellulase was determined in the presence of Savinase.
  • the liquid detergent composition of Table I was supplemented as indicated below :
  • the samples containing caged cellulase-solution were processed according to Example I.
  • the samples were stored at 35°C and analyzed for residual cellulase activity at the end of 1 week of storage.
  • the cellulase activity was determined indirectly by Launderometer tests. The degree of depilling of the fabrics was visually observed.
  • the samples containing caged cellulase according to the present invention are found to exhibit substantially improved retention of enzyme activity compared with samples containing free enzyme in the presence of Savinase.

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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)
  • Detergent Compositions (AREA)

Claims (12)

  1. Reinigungsmitteladditiv, umfassend eine wasserlösliche oder wasserdispergierbare Reinigungsmittel-Wirkstoffverbindung, dadurch gekennzeichnet, daß eine Mischung aus der Verbindung mit einem Tensid in einem porösen, hydrophoben Material absorbiert ist, wobei das poröse Material mit einem hydrophoben Beschichtungsmaterial überzogen ist.
  2. Reinigungsmitteladditiv nach Anspruch 1, wobei die Reinigungsmittel-Wirkstoffverbindung aus Enzymen, Bleichmitteln, Bleichaktivatoren, Bleichkatalysatoren. Fotoaktivatoren, Farbstoffen. Fluoreszenzstoffen, Textil-Konditioniermitteln und hydrolysierbaren Tensiden gewählt ist.
  3. Reinigungsmitteladditiv nach den Ansprüchen 1-2, wobei das poröse hydrophobe Material Silica ist.
  4. Reinigungsmitteladditiv nach den Ansprüchen 1-3, wobei das hydrophobe Beschichtungsmaterial Siliconöl ist.
  5. Reinigungsmitteladditiv nach den Ansprüchen 1-3, wobei das hydrophobe Beschichtungsmaterial Petrolatum bzw. Rohvaseline ist.
  6. Reinigungsmitteladditiv nach den Ansprüchen 1-3, wobei das hydrophobe Beschichtungsmaterial Wachs ist.
  7. Reinigungsmitteladditiv nach den Ansprüchen 1-3, wobei das hydrophobe Beschichtungsmaterial ein wasserunlösliches, wasserpermeables, polymeres Material ist, gewählt aus Carboxymethylcellulose. Polyvinylalkohol, Polyvinylpyrrolidon und Caprolacton.
  8. Reinigungsmitteladditiv nach den Ansprüchen 1-7, wobei das Tensid mit der Reinigungsmittel-Wirkstoffverbindung verträglich ist, gewählt aus einem anionischen, nichtionischen, kationischen oder einem zwitterionischen Tensid oder Mischungen hiervon.
  9. Reinigungsmitteladditiv nach den Ansprüchen 1-8, wobei die Reinigungsmittel-Wirkstoffverbindung aus einem oder mehreren aus Protease, Lipase, Amylase, Cellulase, Oxidase und Peroxidase oder Mischungen hiervon gewählt ist.
  10. Reinigungsmitteladditiv nach Anspruch 9, wobei das Tensid ein nichtionisches Tensid oder ein anionisches Tensid oder eine Mischung hiervon ist.
  11. Reinigungsmittelzusammensetzung, umfassend das Reinigungsmitteladditiv nach den Ansprüchen 1-10 und Reinigungsmittelbestandteile.
  12. Reinigungsmittelzusammensetzung nach Anspruch 11, bei der es sich um eine Wäschewaschmittelzusammensetzung in granulärer Form, kompakter granulärer Form, flüssiger Form oder kompakter flüssiger Form handelt.
EP19920202534 1992-08-18 1992-08-18 Reinigungsmittelzusätze Expired - Lifetime EP0583512B1 (de)

Priority Applications (9)

Application Number Priority Date Filing Date Title
DE1992625968 DE69225968T2 (de) 1992-08-18 1992-08-18 Reinigungsmittelzusätze
ES92202534T ES2117030T3 (es) 1992-08-18 1992-08-18 Aditivos detergentes.
EP19920202534 EP0583512B1 (de) 1992-08-18 1992-08-18 Reinigungsmittelzusätze
JP6506286A JPH08500144A (ja) 1992-08-18 1993-07-28 疎水性コーティングを有する多孔質物質上に吸収された洗剤添加物
PCT/US1993/007088 WO1994004267A1 (en) 1992-08-18 1993-07-28 Detergent additive absorbed on a porous material having a hydrophobic coating
AU47896/93A AU4789693A (en) 1992-08-18 1993-07-28 Detergent additive absorbed on a porous material having a hydrophobic coating
US08/381,893 US5494600A (en) 1992-08-18 1993-07-28 Detergent additive absorbed into a porous hydrophobic material having a hydrophobic coating
TR00719/93A TR27709A (tr) 1992-08-18 1993-08-12 Hidrofil deterjan aktif bilesiklerini iceren deterjan ilave maddeleri.
CN93117787A CN1039430C (zh) 1992-08-18 1993-08-13 洗涤剂添加剂及含该洗涤剂添加剂的洗涤组合物

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP19920202534 EP0583512B1 (de) 1992-08-18 1992-08-18 Reinigungsmittelzusätze

Publications (2)

Publication Number Publication Date
EP0583512A1 EP0583512A1 (de) 1994-02-23
EP0583512B1 true EP0583512B1 (de) 1998-06-17

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP19920202534 Expired - Lifetime EP0583512B1 (de) 1992-08-18 1992-08-18 Reinigungsmittelzusätze

Country Status (8)

Country Link
EP (1) EP0583512B1 (de)
JP (1) JPH08500144A (de)
CN (1) CN1039430C (de)
AU (1) AU4789693A (de)
DE (1) DE69225968T2 (de)
ES (1) ES2117030T3 (de)
TR (1) TR27709A (de)
WO (1) WO1994004267A1 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102021114332A1 (de) 2021-06-02 2022-12-08 Henkel Ag & Co. Kgaa Stabilisierung von enzymen durch phenoxyethanol

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EP0675194A1 (de) * 1994-03-28 1995-10-04 The Procter & Gamble Company Reinigungszusätze in strukturierten Flüssigkeiten
US5543439A (en) * 1994-06-02 1996-08-06 International Flavors & Fragrances Inc. Extruded fragrance-containing polyvinyl alcohol and use thereof
EP0753569A1 (de) 1995-07-14 1997-01-15 The Procter & Gamble Company Stabile flüssige, beim Waschen weichmachende Zusammensetzungen
EP1021517A1 (de) * 1995-12-20 2000-07-26 The Procter & Gamble Company Bleichmittelkatalysator und enzymteilchen
EP0831146B1 (de) * 1996-07-23 2003-03-05 The Procter & Gamble Company Waschmittelkomponenten oder Waschmittelzusammensetzungen mit einem Schutzüberzug
CA2348896A1 (en) * 1998-11-13 2000-05-25 Douglas A. Dale Fluidized bed low density granule
KR100828022B1 (ko) * 2002-04-23 2008-05-08 주식회사 엘지생활건강 정제형 세제 조성물
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CN1085942A (zh) 1994-04-27
JPH08500144A (ja) 1996-01-09
DE69225968T2 (de) 1999-02-18
TR27709A (tr) 1995-06-22
CN1039430C (zh) 1998-08-05
WO1994004267A1 (en) 1994-03-03
EP0583512A1 (de) 1994-02-23
DE69225968D1 (de) 1998-07-23
ES2117030T3 (es) 1998-08-01
AU4789693A (en) 1994-03-15

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