EP0269169B1 - Compositions détergentes contenant de la cellulose - Google Patents

Compositions détergentes contenant de la cellulose Download PDF

Info

Publication number
EP0269169B1
EP0269169B1 EP87202190A EP87202190A EP0269169B1 EP 0269169 B1 EP0269169 B1 EP 0269169B1 EP 87202190 A EP87202190 A EP 87202190A EP 87202190 A EP87202190 A EP 87202190A EP 0269169 B1 EP0269169 B1 EP 0269169B1
Authority
EP
European Patent Office
Prior art keywords
cellulase
composition
composition according
detergent
compositions
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
EP87202190A
Other languages
German (de)
English (en)
Other versions
EP0269169A2 (fr
EP0269169A3 (en
Inventor
Christian Roland Barrat
Wilfrieda Alice Ceulemans
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 European Technical Center
Procter and Gamble Co
Original Assignee
Procter and Gamble European Technical Center
Procter and Gamble Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=10607739&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0269169(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Procter and Gamble European Technical Center, Procter and Gamble Co filed Critical Procter and Gamble European Technical Center
Priority to AT87202190T priority Critical patent/ATE79398T1/de
Publication of EP0269169A2 publication Critical patent/EP0269169A2/fr
Publication of EP0269169A3 publication Critical patent/EP0269169A3/en
Application granted granted Critical
Publication of EP0269169B1 publication Critical patent/EP0269169B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/38Products with no well-defined composition, e.g. natural products
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/38Products with no well-defined composition, e.g. natural products
    • C11D3/386Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38645Preparations containing enzymes, e.g. protease or amylase containing cellulase
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3703Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3723Polyamines or polyalkyleneimines

Definitions

  • the present invention relates to detergent compostions which comprise a detergent cellulase and a low level of a narrowly defined polymer.
  • Preferred compositions further contain a fabric-softening clay.
  • the present invention relates to detergent compositions comprising a detergent cellulase.
  • the compositions are formulated to provide a near-neutral or mildly alkaline wash liquor pH. They contain a low level of a narrowly defined soil release polymer.
  • cellulolytic enzymes i.e. cellulase
  • a harshness reducing agent in fabric softening compositions is taught in British Patent 1.368.599.
  • EP-A 0 120 528 teaches alkaline softening detergent compositions comprising a synergistic mixture of a water-insoluble C10-C26 tertiary amine and cellulase.
  • EP-A 0 177 165 discloses alkaline softening detergent compositions containing a mixture of smectite clay and cellulase.
  • the present invention answers the abvove need, and provides efficient near neutral or mildly alkaline detergent compositions, which exhibit good cleaning properties, especially on cotton fabrics.
  • EP-A 0 112 593 describes alkoxylated amines having clay-soil removal/anti-redeposition properties when used in detergent compositions.
  • EP-A 0 137 615 describes solvent-based liquid detergent compositions containing alkoxylated polyamines.
  • the present invention relates to detergent compositions comprising a surface-active agent and a detergent cellulase.
  • the detergent compositions of this invention are characterized in that they contain from 0.1% to 1% of an alkoxylated polyamine as defined herein below, and in that the pH of a 1% solution of the detergent compositions in distilled water is from 6.5 to 9.5.
  • Preferred are detergent compositions which further comprise from 1% to 20% of a fabric softening clay material, preferably a bentonite clay.
  • Preferred are also compositions that are essentially free of water-insoluble, long-chain alkyl amines, or derivatives thereof.
  • the detergent cellulase is preferably a bacterial or fungal cellulase having an optimum pH in the range of from 5 to 11.5, more preferably from 6.5 to 9.5.
  • the amount of cellulase in the composition is preferably such that the cellulase activity of the composition ranges from 5 to 100 CMCase units per gram.
  • compositions that comprise from 0.5% to 5% of a water-soluble quaternary ammonium compound.
  • detergent compositions having a pH in 1% aqueous solution in the range of from 6.5 to 9.5.
  • the clay soil removal performance of such compositions is relatively poor as compared to compositions formulated to provide a wash liquor pH of 10 or above.
  • Certain water-soluble quaternary ammonium compounds are highly desirable as cationic co-surfactants in detergent compositions, as these compounds provide important greasy soil removal benefits. Due to their positive charge, however, these cationics tend to negatively interact with the clay soil removal performance of a detergent composition. This effect is more pronounced at relatively low pH, at which clay particles are less able to peptize viz negative charge repulsion effects than at pH>10.
  • the surface-active agent is the surface-active agent
  • the surface-active agent useful herein preferably contains at least 50% by weight, more preferably from 60% to 100% by weight of the surface active agent of a non-soap anionic surface-active agent (salt form).
  • anionic surfactants can be used in the compositions of the present invention.
  • Suitable anionic surfactants are water-soluble salts of alkyl benzene sulphonates, alkyl sulphates, alkyl polyethoxy ether sulphates, paraffin sulphonates, alpha-olefin sulphonates, alpha-sulphocarboxylates and their esters, alkyl glyceryl ether sulphonates, fatty acid monoglyceride sulphates and sulphonates, alkyl phenol polyethoxy ether sulphates, 2-acyloxy-alkane-1-sulphonates, and beta-alkyloxy alkane sulphonates.
  • alkyl benzene sulphonates have from 9 to 15 carbon atoms in a linear or branched alkyl chain, especially from 11 to 13 carbon atoms.
  • Suitable alkyl sulphates have from 10 to 22 carbon atoms in the alkyl chain, more especially from 12 to 18 carbon atoms.
  • Suitable alkyl polyethoxy ether sulphates have from 10 to 18 carbon atoms in the alkyl chain and have an average of from 1 to 12 - CH2CH2O- groups per molecule, especially from 10 to 16 carbon atoms in the alkyl chain and an average of from 1 to 6 -CH2CH2O-groups per molecule.
  • Suitable paraffin sulphonates are essentially linear and contain from 8 to 24 carbon atoms, more particularly rom 14 to 18 carbon atoms.
  • Suitable alpha-olefin sulphonates have from 10 to 24 carbon atoms, more particularly from 14 to 16 carbon atoms; alpha-olefin sulphonates can be made by reaction with sulphur trioxide, followed by neutralization under conditions such that any sultones present are hydrolyzed to the corresponding hydroxy alkane sulphonates.
  • Suitable alpha-sulphocarboxylates contain from 6 to 20 carbon atoms; included herein are not only the salts of alpha-sulphonated fatty acids but also their esters made from alcohols containing 1 to 14 carbon atoms.
  • Suitable alkyl glyceryl ether sulphates are ethers of alcohols having from 10 to 18 carbon atoms, more particularly those derived from coconut oil and tallow.
  • Suitable alkyl phenol polyethoxy ether sulphates have from 8 to 12 carbon atoms in the alkyl chain and an average of from 1 to 6 - CH2CH2O-groups per molecule.
  • Suitable 2-acyloxyalkane-1-sulphonates contain from 2 to 9 carbon atoms in the acyl group and from 9 to 23 carbon atoms in the alkane moiety.
  • Suitable beta-alkyloxy alkane sulphonates contain from 1 to 3 carbon atoms in the alkyl group and from 8 to 20 carbon atoms in the alkane moiety.
  • the alkyl chains of the foregoing anionic surfactants can be derived from natural sources such as coconut oil or tallow, or can be made synthetically as for example by using the Ziegler or Oxo processes. Water-solubility can be achieved by using alkali metal, ammonium, or alkanol-ammonium cations; sodium is preferred. Mixtures of anionic surfactants are contemplated by this invention; a satisfactory mixture contains alkyl benzene sulphonate having 11-13 carbon atoms in the alkyl group and alkyl sulphate having 12 to 18 carbon atoms in the alkyl group.
  • Nonionic surfactants may be incorporated in the compositions herein, in limited amounts (less than 50%).
  • Suitable nonionics are water-soluble ethoxylated materials of HLB 11.5-17.0 and include (but are not limited to) C10-C20 primary and secondary alcohol ethoxylates and C5-C10 alkylphenol ethoxylates.
  • C14-C18 linear primary alcohols condensed with from seven to thirty moles of ethylene oxide per mole of alcohol are preferred, examples being C14-C15 (EO)7, C16-C18 (EO)25 and especially C16-C18 (EO)11.
  • surfactants can be used in limited amounts, in combination with the anionic surface-active agent. They include zwitterionic amphoteric, as well as cationic surfactants.
  • Cationic co-surfactants which can be used herein, include water-soluble quaternary ammonium compounds of the form R4R5R6R7N+X ⁇ , wherein R4 is alkyl having from 10 to 20, preferably from 12-18 carbon atoms, R5, R6 and R7 are independently, C1-C4 alkyl, and X ⁇ is an anion, e.g. chloride.
  • R4 is alkyl having from 10 to 20, preferably from 12-18 carbon atoms
  • R5, R6 and R7 are independently, C1-C4 alkyl
  • X ⁇ is an anion, e.g. chloride.
  • Examples are the trimethyl ammonium compounds, including c12-c14 alkyl trimethyl ammonium chloride and cocoalkyl trimethyl ammonium methosulfate.
  • Alkoxylated polyamines suitable as clay-soil removal/anti-redeposition agents, as well as their preparation, are disclosed in EP-PA 0 112 593, the disclosures of which are incorporated herein by reference.
  • polyamines as used herein represents generically the alkoxylated polyamines, both in their amine form and in their quaternarized form.
  • Such materials can conventiently be represented as molecules of the empirical structures with repeating units : and Wherein R is a hydrocarbyl group, usually of 2-6 carbon atoms; R1 may be a C1-C20 hydrocarbon; the alkoxy groups are ethoxy, propoxy, butoxy and the like, and y is 2-30, most preferably 10-20; n is an integer of at least 2, preferably from 2-20, most preferably 3-5; and X ⁇ is an anion such as halide or methylsulfate, resulting from the quaternization reaction.
  • polyamines for use herein are the so-called ethoxylated polyethylene imines, i.e., the polymerized reaction product of ethylene oxide with ethylene-imine, having the general formula : wherein n is an integer of 3 to 5 and y is an integer of 10 to 20.
  • the cellulase usable in the present invention may be any bacterial or fungal cellulase having a pH optimum of between 5 and 9.5.
  • Suitable cellulases are disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832.
  • cellulases examples include cellulases produced by a strain of Humicola insolens (Humicola grisea var. thermoidea), particularly the Humicola strain DSM 1800, and cellulases produced by a fungus of Bacillus N or a cellulase 212-producing fungus belonging to the genus Aeromonas, and cellulase extracted from the hepatopancreas of a marine mullosc (Dolabella Auricula Solander).
  • the cellulase added to the composition of the invention may be in the form of a non-dusting granulate, e.g. "marumes” or “prills”, or in the form of a liquid in which the cellulase is provided as a cellulase concentrate suspended in e.g. a nonionic surfactant or dissolved in an aqueous medium.
  • a non-dusting granulate e.g. "marumes” or "prills”
  • a liquid in which the cellulase is provided as a cellulase concentrate suspended in e.g. a nonionic surfactant or dissolved in an aqueous medium.
  • Activity determination for the cellulase herein is based on the hydrolysis of carboxymethyl cellulose. Generated low molecular reducing carbohydrates are colorimetrically determined by the ferrocyanide reaction as descirbed by W.S. Hoffman "J. Biol. Chem.” 120,51 (1973). Key conditions of incubation are pH-7.0, temperature of 40°C and incubation time of 20 minutes.
  • One CMCase unit is defined as the amount of enzyme which forms per minute an amount of reducing carbohydrate equivalent to 10 ⁇ 6 mole of glucose, in the above-described conditions.
  • a highly preferred range of cellulase activity in the present context is from 5 to 100 CMCase activity units/gram of composition.
  • compositions herein are essentially free of water-insoluble long-chain alkyl amine softening agents, and derivatives thereof, since it has surprisingly been discovered that such compounds negatively interact with cellulase under the pH conditions as used herein.
  • the cellulase-incompatible amines generally have the formula R8R9R10N, wherein R8 and R9 are, independently, C10-C22 alkyl, and R10 is hydrogen or C1-C3 alkyl. Derivatives of these amines like, e.g., the corresponding amides, also negatively interact with cellulase.
  • compositions herein are formulated at a pH in the range of from 6.5 to 9.5, measured as a 1% solution of the composition in distilled water. At this pH-range, the cellulase for use herein have their optimum performance.
  • compositions herein may contain, in addition to the essential ingredients, optional ingredients, which can be highly desirable.
  • the compositions herein contain a clay softening agent, in combination with the cellulase.
  • clay softening agents are well-known in the detergency patent literature and are in broad commercial use, both in Europe and in the United States. Included among such clay softeners are various heat-treated kaolins and various multi-layer smectites.
  • Preferred clay softeners are smectite softener clays that are described in German patent document 23 34 899 and in U.K. patent 1,400,898, which can be referred to for details.
  • the most preferred clay fabric softening materials include those materials of bentonitic origin, bentonites being primarily montmorillonite type clays together with various impurities, the level and nature of which depends on the source of the clay material.
  • Softener clays are used in the preferred compositions at levels of at least 1%, generally 1-20°, preferably 2-10%.
  • the alkoxy polyamine does not negatively interact with the deposition of softener clays.
  • the detergent compositions contain a detergent builder and/or metal ion sequestrant.
  • detergent builders include the nitrilotriacetates, polycarboxylates, citrates, water-soluble phosphates such as tri-polyphosphate and sodium ortho- and pyro-phosphates, and mixtures thereof.
  • Metal ion sequestrants include all of the above, plus materials like ethylenediaminetetraacetate, the amino-polyphosphonates and a wide variety of other poly-functional organic acids and salts too numerous to mention in detail here. See U.S. Patent 3.579.454 for typical examples of the use of such materials in various cleaning compositions.
  • Preferred polyfunctional organic acids species for use herein are citric acid, ethylene diamine tetramethylenephosphonic acid, and diethylene triaminepentamethylenephosphonic acid.
  • a further class of detergency builder materials useful in the present invention are insoluble sodium aluminosilicates.
  • the 1-10 ⁇ m size zeolite (e.g., zeolite A) builders disclosed in German Parent 24.22.655 are especially preferred for use in low-phsophate or non-phosphate compositions.
  • the builder/sequestrant will comprise from 0.5% to 45% of the composition.
  • compositions herein can also contain fatty acids, saturated or unsaturated, and the corresponding soaps.
  • Suitable fatty acids, saturated or unsaturated have from 10 to 18 carbon atoms in the alkyl chain.
  • Preferred are unsaturated species having from 14 to 18 carbon atoms in the alkyl chain, most preferably oleic acid.
  • the corresponding soaps can also be used.
  • the optional fatty acid/soaps are used in levels up to 20%.
  • compositions herein can also contain compounds of the general formula R-CH(COOH)CH2(COOH) i.e. derivatives of succinic acid, wherein R is C10-C20 alkyl or alkenyl, preferably C12-C16, wherein R may be substituted with hydroxyl, sulfo, sulfoxy or sulfone substituents.
  • the succinate builders are preferably used in the form of their water-soluble salts, including the sodium, potassium, ammonium and alkanoammonium salts.
  • succinate builders include : lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinate (preferred), 2-pentadecenyl succinate, and the like.
  • Also useful as builders in the present context are the compounds described in US patent 4.663.071, i.e. mixtures of tartrate monosuccinic acid and tartrate disuccinic acid in a weight ratio of monosuccinic to disuccinic of from 97:3 to 20:80, preferably 95:5 to 40:60.
  • bleaching agent Another optional ingredient is a bleaching agent.
  • peroxygen bleaching agents such as sodium perborate, commercially available in the form of mono- and tetra-hydrates, sodium carbonate peroxyhydrate, sodium pyrophosphate peroxyhydrate and urea peroxyhydrate.
  • Bleach activators may be used in combination with the above peroxygen bleaching agents.
  • Classes of bleach activators include esters, imides, imidazoles, oximes, and carbonates.
  • preferred materials include methyl o-acetoxy benzoates; sodium-p-acetoxy benzene sulfonates such as sodium 4-octanoyloxybenzene sulfonate; sodium-4-octanoyloxybenzene sulfonate, and sodium-4-decanoyloxybenzenesulfonate : biophenol diacetate; tetra acetyl ethylene diamine; tetra acetyl hexamethylene diamine; tetra acetyl methylene diamine.
  • alpho-substituted alkyl or alkenyl esters such as sodium-4(2-chlorooctanoyloxy) benzene sulfonate, sodium 4-(3,5,5-trimethyl hexanoyloxy)benzene sulfonate.
  • Suitable peroxyacids are also peroxygen bleach activators such as described in published European Patent Application 0 166 571, i.e., compounds of the general type RXAOOH and RXAL, wherein R is a hydroxcarbyl group, X is a hetero-atom, A is a carbonyl bridging group and L is a leaving group, especially oxybenzenesulfonate.
  • Enzymes other than cellulases can be used in combination with the cellulase herein.
  • All generally known enzyme stabilizing systems can be used in the liquid executions of the compositions herein at the art established levels. Examples of suitable stabilizing systems include short C 1-4 chain carboxylic acid, particularly formic acid in combination with a low level of calcium, boric acid and the water-soluble salts thereof possibly in combination with polyols.
  • compositions herein can contain, in addtion to ingredients already mentioned, various other optioal ingredients typically used in commercial products to provide aesthetic or additional product performance benefits.
  • Typical ingredients include pH regulants, perfumes, dyes, optical brighteners, soil suspending agents, hydrotropes and gel-control agents, freeze-thaw stabilizers, bactericides, preservatives, suds control agents, bleach stabilizing agents.
  • the detergent compositions of this invention can be present in any suitable physical state inclusive of granular, liquid, pasty, or sheet-like form. They may be prepared in any way, as appropriate to their physical form, by mixing the components, co-agglomerating them, micro-encapsulating them, dispersing them in a liquid carrier, and releasably adsorbing or coating them onto a non-particulate substrate, such as a non-woven or paper sheet.
  • Granular detergents were prepared, having the following compositions :
  • liquid detergent composition was also prepared :

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Medicines Containing Material From Animals Or Micro-Organisms (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Claims (9)

  1. Une composition détergente (pour le nettoyage et l'assouplissement des tissus) comprenant un agent de surface et une cellulase détergente, caractérisée en ce que
    - la composition contient 0,1% à 1% d'un polymère qui détache les salissures argileuses comportant les motifs
    Figure imgb0010
    dans lesquels R est un hydrocarbyle possédant 2 à 6 atomes de carbone, R¹ est un groupe hydrocarboné en C₁ à C₂₀, l'alcoxy est choisi parmi les éthoxy, propoxy, butoxy ou leurs mélanges, y est 2-30, n est un nombre entier d'au moins 2 et X⁻ est un anion, et
    - le pH d'une solution à 1% de la composition détergente dans de l'eau distillée s'étend de 6,5 à 9,5.
  2. Une composition selon la revendication 1, dans laquelle la polyamine alcoxylée est le produit de réaction polymérisé de l'oxyde d'éthylène avec de l'éthylène-imine, répondant à la formule générale :
    Figure imgb0011
    dans laquelle n est un nombre entier de 3 à 5 et y est un nombre entier de 10 à 20.
  3. Une composition selon la revendication 2, dans laquelle la cellulase possède un pH optimal dans la gamme de 6,5 à 9,5.
  4. Une composition selon l'une quelconque des revendications précédentes possédant une activité cellulase de 5 à 100 unités CMCase par gramme de composition.
  5. Une composition selon l'une quelconque des revendications précédentes, dans laquelle l'agent de surface contient 60% à 100% en poids d'un agent de surface anionique.
  6. Une composition selon l'une quelconque des revendications précédentes qui contient en outre 1% à 20% d'une matière argileuse pour l'assouplissement des tissus.
  7. Une composition selon l'une quelconque des revendications précédentes qui contient en outre 0,5% à 5% d'un composé d'ammonium quaternaire soluble dans l'eau de formule R₄R₅R₆R₇N⁺X⁻ où R4 est un alkyle comportant 10 à 20 atomes de carbone, R₅, R₆ et R₇ sont, indépendamment, un alkyle en C₁-C₄ et X⁻ est un anion.
  8. Une composition selon l'une quelconque des revendications précédentes, caractérisée en outre en ce qu'elle est essentiellement exempte d'alkylamines à longue chaîne insolubles dans l'eau ou de leurs dérivés.
  9. Une composition selon l'une quelconque des revendications précédentes, caractérisée en ce que le pH d'une solution à 1% de la composition dans de l'eau distillée s'étend de 8,5 à 9,5.
EP87202190A 1986-11-21 1987-11-11 Compositions détergentes contenant de la cellulose Expired - Lifetime EP0269169B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT87202190T ATE79398T1 (de) 1986-11-21 1987-11-11 Reinigungsmittel, die cellulase enthalten.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB868627915A GB8627915D0 (en) 1986-11-21 1986-11-21 Detergent compositions
GB8627915 1986-11-21

Publications (3)

Publication Number Publication Date
EP0269169A2 EP0269169A2 (fr) 1988-06-01
EP0269169A3 EP0269169A3 (en) 1989-06-07
EP0269169B1 true EP0269169B1 (fr) 1992-08-12

Family

ID=10607739

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87202190A Expired - Lifetime EP0269169B1 (fr) 1986-11-21 1987-11-11 Compositions détergentes contenant de la cellulose

Country Status (14)

Country Link
EP (1) EP0269169B1 (fr)
JP (1) JPS63213598A (fr)
KR (1) KR880006355A (fr)
CN (1) CN87107307A (fr)
AT (1) ATE79398T1 (fr)
AU (1) AU8143287A (fr)
DE (1) DE3781101T2 (fr)
DK (1) DK611587A (fr)
EG (1) EG18326A (fr)
FI (1) FI86884C (fr)
GB (1) GB8627915D0 (fr)
GR (1) GR3006203T3 (fr)
IE (1) IE60696B1 (fr)
TR (1) TR23328A (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6660711B1 (en) 1999-07-16 2003-12-09 The Procter & Gamble Company Laundry detergent compositions comprising zwitterionic polyamines and mid-chain branched surfactants
US6696402B2 (en) 1999-11-09 2004-02-24 The Procter & Gamble Company Laundry detergent compositions comprising zwitterionic polyamines
US6903059B2 (en) 1999-07-16 2005-06-07 The Procter & Gamble Company Laundry detergent compositions comprising polyamines and mid-chain branched surfactants
US7163985B2 (en) 2002-09-12 2007-01-16 The Procter & Gamble Co. Polymer systems and cleaning compositions comprising the same
US9540595B2 (en) 2013-08-26 2017-01-10 The Procter & Gamble Company Compositions comprising alkoxylated polyalkyleneimines having low melting points

Families Citing this family (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8627914D0 (en) * 1986-11-21 1986-12-31 Procter & Gamble Softening detergent compositions
NZ230842A (en) * 1988-10-21 1992-05-26 Colgate Palmolive Co Nonionic heavy duty particulate detergent containing protease, amylase and cellulase
US5120463A (en) * 1989-10-19 1992-06-09 Genencor International, Inc. Degradation resistant detergent compositions based on cellulase enzymes
EP0495258A1 (fr) * 1991-01-16 1992-07-22 The Procter & Gamble Company Compositions de détergent contenant de la cellulase de haute activité et de l'argile adoucissant
US5443750A (en) * 1991-01-16 1995-08-22 The Procter & Gamble Company Detergent compositions with high activity cellulase and softening clays
US5520838A (en) * 1991-01-16 1996-05-28 The Procter & Gamble Company Compact detergent compositions with high activity cellulase
WO1994003577A1 (fr) * 1992-07-29 1994-02-17 Henkel Kommanditgesellschaft Auf Aktien Detergent aux enzymes
WO1997000936A1 (fr) * 1995-06-20 1997-01-09 The Procter & Gamble Company Compositions detergentes non aqueuses comprenant des polymeres capables d'enlever les salissures argileuses
US5747440A (en) * 1996-01-30 1998-05-05 Procter & Gamble Company Laundry detergents comprising heavy metal ion chelants
EP0794245B1 (fr) * 1996-03-04 2003-07-09 The Procter & Gamble Company Procédé de prétraitement pour le lavage du ligne et compositions de blanchiment
WO1997042283A1 (fr) * 1996-05-03 1997-11-13 The Procter & Gamble Company Compositions pour detergents en barres
KR100329879B1 (ko) * 1996-05-03 2002-08-27 더 프록터 앤드 갬블 캄파니 양이온성계면활성제와개질된폴리아민오물분산제를포함하는세탁용세제조성물
BR9710664A (pt) * 1996-05-03 1999-08-17 Procter & Gamble Composi-Æo de detergente compreendendo pol¡meros de poliamina modificada e enzimas de celulase
CN1224446A (zh) * 1996-05-03 1999-07-28 普罗格特-甘布尔公司 含聚胺清除剂和酶的洗涤剂组合物
DE69714736T2 (de) * 1996-05-03 2003-04-24 Procter & Gamble Polyaminen mit erhöhten nutzen für das aussehen von gewebe
US5858948A (en) * 1996-05-03 1999-01-12 Procter & Gamble Company Liquid laundry detergent compositions comprising cotton soil release polymers and protease enzymes
WO1998004233A1 (fr) * 1996-07-31 1998-02-05 The Procter & Gamble Company Compositions de shampooing traitant avec polyalkylene amine polyalkoxylee
WO1998012295A1 (fr) * 1996-09-19 1998-03-26 The Procter & Gamble Company Compositions respectant les couleurs
ZA978601B (en) * 1996-10-07 1998-03-26 Procter & Gamble Alkoxylated, quaternized polyamine detergent ingredients.
CA2242651A1 (fr) * 1997-07-22 1999-01-22 Calgon Corporation Composition et methode pour nettoyer des surfaces
US6020302A (en) * 1997-09-18 2000-02-01 The Procter & Gamble Company Color care compositions
US6565613B1 (en) 1999-04-29 2003-05-20 Genencor International, Inc. Cellulase detergent matrix

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2075028A (en) * 1980-04-30 1981-11-11 Novo Industri As Enzymatic additive

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0112593B1 (fr) * 1982-12-23 1989-07-19 THE PROCTER & GAMBLE COMPANY Compositions détergentes contenant des amines éthoxylées ayant des propriétés pour enlever des taches et la contre-redéposition
GB8306645D0 (en) * 1983-03-10 1983-04-13 Unilever Plc Detergent compositions
GB8512638D0 (en) * 1985-05-18 1985-06-19 Procter & Gamble Laundry detergent compositions

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2075028A (en) * 1980-04-30 1981-11-11 Novo Industri As Enzymatic additive

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6660711B1 (en) 1999-07-16 2003-12-09 The Procter & Gamble Company Laundry detergent compositions comprising zwitterionic polyamines and mid-chain branched surfactants
US6903059B2 (en) 1999-07-16 2005-06-07 The Procter & Gamble Company Laundry detergent compositions comprising polyamines and mid-chain branched surfactants
US6696402B2 (en) 1999-11-09 2004-02-24 The Procter & Gamble Company Laundry detergent compositions comprising zwitterionic polyamines
US7163985B2 (en) 2002-09-12 2007-01-16 The Procter & Gamble Co. Polymer systems and cleaning compositions comprising the same
US7442213B2 (en) 2002-09-12 2008-10-28 The Procter & Gamble Company Methods of cleaning a situs with a cleaning composition comprising a polymer system
US9540595B2 (en) 2013-08-26 2017-01-10 The Procter & Gamble Company Compositions comprising alkoxylated polyalkyleneimines having low melting points
US9540596B2 (en) 2013-08-26 2017-01-10 The Procter & Gamble Company Compositions comprising alkoxylated polyamines having low melting points

Also Published As

Publication number Publication date
EP0269169A2 (fr) 1988-06-01
DK611587D0 (da) 1987-11-20
ATE79398T1 (de) 1992-08-15
FI875138A (fi) 1988-05-22
AU8143287A (en) 1988-05-26
IE60696B1 (en) 1994-08-10
GR3006203T3 (fr) 1993-06-21
FI86884C (fi) 1992-10-26
DK611587A (da) 1988-05-22
DE3781101D1 (de) 1992-09-17
FI875138A0 (fi) 1987-11-20
FI86884B (fi) 1992-07-15
KR880006355A (ko) 1988-07-22
EP0269169A3 (en) 1989-06-07
TR23328A (tr) 1989-11-08
CN87107307A (zh) 1988-06-01
IE873151L (en) 1988-05-21
EG18326A (en) 1992-09-30
JPS63213598A (ja) 1988-09-06
DE3781101T2 (de) 1992-12-17
GB8627915D0 (en) 1986-12-31

Similar Documents

Publication Publication Date Title
EP0269169B1 (fr) Compositions détergentes contenant de la cellulose
US4479881A (en) Detergent compositions
EP0173398B1 (fr) Composition détergente
US5445755A (en) Detergent compositions containing a peroxidase/accelerator system without linear alkylbenzenesulfonate
EP0269168B1 (fr) Compositions détergentes adoucissantes contenant de la cellulase
IE61938B1 (en) Detergent compositions
EP0242919B1 (fr) Compositions détergentes d'assouplissement contenant un amide comme agent d'assouplissement
IE883161L (en) Detergent composition
WO1992013054A1 (fr) Compositions detersives contenant une lipase et des composes d'ammonium quaternaire solubles dans l'eau
EP0177165B1 (fr) Composition détergente
US4842769A (en) Stabilized fabric softening built detergent composition containing enzymes
CA1297440C (fr) Detergent liquide assouplisseur de tissu
EP0383828B1 (fr) Compositions detergentes contenant de la cellulase sous forme granulee
PH26642A (en) Granular detergent composition containing cellulase

Legal Events

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

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE CH DE FR GB GR IT LI LU NL SE

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): AT BE CH DE FR GB GR IT LI LU NL SE

17P Request for examination filed

Effective date: 19891127

17Q First examination report despatched

Effective date: 19910430

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE FR GB GR IT LI LU NL SE

REF Corresponds to:

Ref document number: 79398

Country of ref document: AT

Date of ref document: 19920815

Kind code of ref document: T

ITF It: translation for a ep patent filed

Owner name: ING. C. GREGORJ S.P.A.

REF Corresponds to:

Ref document number: 3781101

Country of ref document: DE

Date of ref document: 19920917

ET Fr: translation filed
REG Reference to a national code

Ref country code: GR

Ref legal event code: FG4A

Free format text: 3006203

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

26 Opposition filed

Opponent name: UNILEVER N.V.

Effective date: 19930511

NLR1 Nl: opposition has been filed with the epo

Opponent name: UNILEVER N.V.

EPTA Lu: last paid annual fee
EAL Se: european patent in force in sweden

Ref document number: 87202190.2

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

Ref country code: AT

Payment date: 19951113

Year of fee payment: 9

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

Ref country code: GR

Payment date: 19951128

Year of fee payment: 9

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

Ref country code: LU

Payment date: 19960101

Year of fee payment: 9

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

Ref country code: AT

Effective date: 19961111

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

Ref country code: LU

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

Effective date: 19961130

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

Ref country code: GR

Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY

Effective date: 19970531

REG Reference to a national code

Ref country code: GR

Ref legal event code: MM2A

Free format text: 3006203

APAC Appeal dossier modified

Free format text: ORIGINAL CODE: EPIDOS NOAPO

PLAW Interlocutory decision in opposition

Free format text: ORIGINAL CODE: EPIDOS IDOP

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

Ref country code: NL

Payment date: 20000929

Year of fee payment: 14

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

Ref country code: GB

Payment date: 20001004

Year of fee payment: 14

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

Ref country code: SE

Payment date: 20001103

Year of fee payment: 14

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

Ref country code: FR

Payment date: 20001107

Year of fee payment: 14

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

Ref country code: DE

Payment date: 20001124

Year of fee payment: 14

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

Ref country code: BE

Payment date: 20001214

Year of fee payment: 14

PLAW Interlocutory decision in opposition

Free format text: ORIGINAL CODE: EPIDOS IDOP

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

Ref country code: CH

Payment date: 20010103

Year of fee payment: 14

PLAW Interlocutory decision in opposition

Free format text: ORIGINAL CODE: EPIDOS IDOP

RDAH Patent revoked

Free format text: ORIGINAL CODE: EPIDOS REVO

RDAG Patent revoked

Free format text: ORIGINAL CODE: 0009271

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

Free format text: STATUS: PATENT REVOKED

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

27W Patent revoked

Effective date: 20010906

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

Free format text: 20010906

NLR2 Nl: decision of opposition
APAH Appeal reference modified

Free format text: ORIGINAL CODE: EPIDOSCREFNO