EP0797656A1 - Waschmittelzusammensetzung - Google Patents

Waschmittelzusammensetzung

Info

Publication number
EP0797656A1
EP0797656A1 EP95941064A EP95941064A EP0797656A1 EP 0797656 A1 EP0797656 A1 EP 0797656A1 EP 95941064 A EP95941064 A EP 95941064A EP 95941064 A EP95941064 A EP 95941064A EP 0797656 A1 EP0797656 A1 EP 0797656A1
Authority
EP
European Patent Office
Prior art keywords
composition
weight
hydrophillic
compositions
polymer
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
Application number
EP95941064A
Other languages
English (en)
French (fr)
Other versions
EP0797656B1 (de
EP0797656B2 (de
Inventor
Paul Johan M. W. L. Birker
Tino A. A. Fonteijn
Peter Graham Montague
Charles Cornelis Verburg
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.)
Unilever PLC
Unilever NV
Original Assignee
Unilever PLC
Unilever NV
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=8217941&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0797656(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Priority to EP95941064A priority Critical patent/EP0797656B2/de
Publication of EP0797656A1 publication Critical patent/EP0797656A1/de
Publication of EP0797656B1 publication Critical patent/EP0797656B1/de
Application granted granted Critical
Publication of EP0797656B2 publication Critical patent/EP0797656B2/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0004—Non aqueous liquid compositions comprising insoluble particles
    • 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

Definitions

  • the present invention relates to compositions which comprise polymer material and to a method of preparing such compositions.
  • Detergent compositions may be aqueous or non-aqueous, both either in solid or in liquid form.
  • Non-aqueous liquid detergent compositions are known in the art and have been described in quite a number of patent publications, e.g. in US-A-4,316,812, US-A-4 ,874 , 537 and EP-A-0,484 , 095.
  • the free water content of non-aqueous liquid detergent compositions is less than 5% by weight, preferably less than 3% by weight, more preferably less than 2% by weight, most preferably substantially nil.
  • Non- aqueous liquid detergent compositions provide a way of concentrating liquid detergents without giving in on washing performance.
  • Non-aqueous liquid detergent compositions normally comprise a non-aqueous liquid phase having incorporated therein as dispersion, solution or combination thereof, the usual detergent components and adjuncts depending on the purpose of use, primarily surfactants and builders.
  • the non-aqueous liquid phase often comprises a nonionic surfactant as major component, which apart from acting as carrier liquid for the other detergent components, usually and preferably also has detergent-active properties, thereby acting wholly or in part as the surfactant ingredient.
  • non-aqueous liquid detergent compositions are characterized by the following weakness: they may tend to suffer from gelling and the ingredients tend to stick together. As a consequence thereof, the product may disperse only slowly in water and this may have a negative influence on the cleaning performance of the product, e.g. the product will not uniformly and timely dissolve in the washing liquor.
  • liquid phases comprising a nonionic surfactant, such as mixtures of C13-C15 alcohols with an average of 3 ethoxy groups and C13-C15 alcohols with an average of 7 ethoxy groups and liquid phases as described in GB-A-1 , 462 , 134 , WO-A-91/12313 , WO-A-91/14765 and EP-A-0 , 510 , 762 and more in particular for liquids comprising a dispersed solid particulate phase.
  • a nonionic surfactant such as mixtures of C13-C15 alcohols with an average of 3 ethoxy groups and C13-C15 alcohols with an average of 7 ethoxy groups and liquid phases as described in GB-A-1 , 462 , 134 , WO-A-91/12313 , WO-A-91/14765 and EP-A-0 , 510 , 762 and more in particular for liquids comprising a dispersed solid particulate phase.
  • these solvent materials may be beneficial in at least partially overcoming the gelling problem of non-aqueous liquid detergent compositions.
  • these materials are only effective to overcome gelling caused at relatively high water levels, whereas they are less effective or even ineffective in overcoming relatively low water level gelling problems, e.g. at water levels in which 5 to 50% by weight of water is added to the product.
  • Gelling problem of non-aqueous liquids are not only noticeable for non-aqueous liquid containing a non-aqueous phase, but also, and in particular, when solid dispersed particles are present.
  • dispersion problems of non-aqueous liquid detergent compositions may occur upon dilution with water.
  • Low dispersion may for example lead to high concentrations of product on the cloth that may have negative effects on the cloth's quality.
  • a further problem related to the use of non-aqueous liquid compositions is dissolution. Slow dissolution of the concentrated composition may result in liberation of the components to the wash liquor only at a late stage during the washing process, at which point they may be less effective.
  • Another problem that is in particular important in the industrial area is the dispensing problem of non-aqueous liquids, i.e. the blocking of pipes and valves of the dosing system for non-aqueous liquid detergent compositions.
  • This problem has e.g. been described in EP-A- 480,490 (Unilever) .
  • compositions comprising from 10 to 90% by weight of surfactant material.
  • the compositions are preferably non-aqueous (either solid or preferably liquid) ,
  • compositions are preferably non-aqueous (either solid or preferably liquid) .
  • compositions are preferably non-aqueous (either solid or preferably liquid) .
  • Non-aqueous liquids comprising polymeric material have for example been described in EP-A-510,762 (Unilever) that discloses non-aqueous liquids comprising a polymer material comprising at least one group capable of association with the solid phase and at least one group capable of extending from the solid phase.
  • the polymer is amongst other incorporated to lower the viscosity and the clear layer separation.
  • WO 94/01524 discloses non-aqueous liquids comprising a polymeric material with a group that exhibits self association to reduce viscosity and the clear layer formation of the liquids.
  • WO 94/12611 discloses non-aqueous liquids comprising dry particulate solubilised biopoly er material to improve the dispersion of the liquid.
  • Preferred biopoly ers are polysaccharides and polypeptides.
  • EP-A-413,616 discloses non-aqueous liquid detergent compositions comprising nonionic surfactants, solid particles and a polymer derived from ⁇ ,j3-mono- ethylenically unsaturated carboxy-containing monomers.
  • EP-A-359,491 (Unilever) and EP-A-359,492 (Unilever) disclose non-aqueous liquids comprising respectively low and high molecular weight vinyl pyrrolidone polymers.
  • EP-A-28,849 discloses non-aqueous liquids comprising a stabilising polymer that is an at least partially hydrolysed copolymer of maleic anhydride with ethylene or vinylmethylether.
  • GB-A-2 , 228, 944 discloses non-aqueous liquids comprising polymeric materials that may comprise acryl amide monomers.
  • the present invention provides a non-aqueous liquid detergent composition comprising a non-aqueous liquid phase, wherein the composition comprises a polymeric hydrotrope comprising hydrophillic and hydrophobic monomers.
  • the non-aqueous liquids according to the invention comprise an electrolyte material.
  • liquid composition of the present invention further comprise at least one ingredient selected from abrasives, bleaches, bleach catalysts, bleach precursors, corrosion inhibitors, dispersants, enzymes, fabric softening agents, icrobiocides and mixtures thereof.
  • these ingredients are included at levels of from 0.01 to 90% by weight of the composition.
  • the non-aqueous liquids according to the invention comprise solid dispersed particles which are more preferably selected from bleaches, builders, abrasives, dispersants, enzymes, solid surfactants, fluorescers, enzymes, bleach precursors, bleach catalysts, colorants, pigments, opacifying agents and mixtures thereof.
  • the present invention further provides a composition comprising from 10 to 90% by weight of surfactant material and further comprising a polymeric hydrotrope.
  • the invention further provides a method of preparing a non- aqueous liquid detergent composition comprising a non- aqueous phase and a polymeric hydrotrope, wherein the polymeric hydrotrope is added to the non-aqueous phase in a form comprising 25% or less by weight of water.
  • the invention further provides a method of applying a composition by mixing the composition with a polymeric hydrotrope, whereafter the composition with the polymer is applied to a washing machine.
  • the composition comprises surfactant material and more preferably nonionic surfactant material.
  • the composition is non- aqueous (either solid or preferably liquid) .
  • the invention further provides a method of mixing a composition with water, wherein the composition is prepared by mixing a surfactant with a polymeric hydrotrope, whereafter the composition is mixed with water.
  • the composition comprises surfactant material and more preferably nonionic surfactant material.
  • the composition is non-aqueous (either solid or preferably liquid) .
  • the composition is mixed with water in a washing machine. Description of the Invention
  • non-aqueous liquids comprising the polymeric hydrotrope show reduced gelling characteristics upon dilution, improved dispersion, dissolution and/or dispensing.
  • the use of the polymeric hydrotrope in non-aqueous liquids according to the invention may have certain advantages compared with use of conventional hydrotropes, including low foaming properties, good surfactant solubilising characteristics, chemical stability, ease of handling, cost effective, substantially free of nitrosamines commonly associated with compositions using nitrogen-based hydrotropes or solubilisers, such as amine oxides.
  • polymer hydrotrope has been found to lead to reduced gelling, improved dispersion, dissolution and/or dispensing of compositions comprising high surfactant levels.
  • a surfactant-composition with a polymeric hydrotrope leads to reduced gelling characteristics upon dilution, improved dispersion, dissolution and/or dispensing when mixing the composition with water.
  • the polymeric hydrotrope may be a homopolymer or a copolymer, in block and/or random form.
  • the polymer comprises hydrophillic and hydrophobic monomers.
  • the hydrophillic ronomers are sufficiently water soluble. They preferably have a water solubility at ambient temperature and at a pH of 3.0 to 12.5 (preferably 7.0) of more than 1 g/1, r.ore preferably more than 5g/l, most preferred more than lOg/l.
  • the hydrophobic monomers have a low water solubility. Preferably less than 1 g/1, more preferred less than 0.5 g/1, most preferred less than 0.1 g/1 of the hydrophobic monomer will dissolve in water at ambient temperature and a pH of 3.0 to 12.5, preferably 7.0.
  • Hydrophillic monomers are preferably selected from monomers of formula I :
  • E is a hydrophillic functional groups, preferably selected from (Cl-8 alk(en) yl/aryl) carboxylate, (Cl-8 alk (en) yl/aryl) sulphonate, sulphate, amide and pyrolidon;
  • R is independently selected from H, a lower (C,-C 8 ) alk(en)yl group and a hydrophillic functional group.
  • E is carboxylic and R is H, (Cl-8) lower alkyl or carboxylic.
  • Hydrophobic monomers are preferably selected from monomers of formula II:
  • R... are independently selected from H, C3-C20 alk(en)yl, 0-C Mll alkyl, (substituted) aryl, carboxylate or sulphonate esterified with C1-C10 alk(en)yl, C1-C10 alk(en)yl esters of sulphate and two R groups forming a ring structure (e.g. cyclohexene) .
  • At least 1 R is not H and, more preferably, R, is styrene and R,_, represent an H.
  • the molar ratio between the hydrophillic and the hydrophobic monomers in the polymer is from 5:1 to 1:5, preferably 3:1 to 1:3, more preferably 2:1 to 1:2.
  • the hydrophillic monomer is preferably selected from acrylic acid and substituted acrylic acids (eg. methacrylic acid, maleic acid and half-ester thereof) crotonic and itaconic acids and other alkene carboxylic acids and their derivatives, carboxylated styrene, sulphonated styrene, ethylene sulphonic acid, and certain nitrogen-based monomers (eg. acryla ide, vinyl pyrollidone) and mixtures of such hydrophillic monomers.
  • acrylic acid and substituted acrylic acids eg. methacrylic acid, maleic acid and half-ester thereof
  • crotonic and itaconic acids and other alkene carboxylic acids and their derivatives carboxylated styrene, sulphonated styrene, ethylene sulphonic acid
  • nitrogen-based monomers eg. acryla ide, vinyl pyrollidone
  • the hydrophobic monomer is preferably selected from the group: styrene and substituted styrenes (eg. alpha-methyl styrene) , alpha-olefins (eg. C ⁇ -alpha-olefin) , vinyl ethers (eg. butyl vinyl ether), allyl ethers (eg. butyl allyl ether) , unsaturated hydrocarbons (eg. ethylene, propylene, cyclohexene) and dienes (eg. 1,6 hexadiene) , divinyl benzene, cyclohexadiene, esters of acrylic and substituted acrylic acids (eg.
  • styrene and substituted styrenes eg. alpha-methyl styrene
  • alpha-olefins eg. C ⁇ -alpha-olefin
  • vinyl ethers eg. butyl vinyl
  • esters of other ethylenically unsaturated carboxylic acids eg. of itaconic acid, crotonic acid
  • esters of ethylenically unsaturated sulphonic acids eg. alkyl styrene sulphonates
  • alkyl and aryl vinyl sulphonates and sulphates alkyl and aryl allyl sulphonates and sulphates.
  • hydrophobic moieties may also be introduced into the polymer by chain transfer agents and initiators (eg. mercaptans such as dodecyl mercaptans) and peroxides and azo initiators, eg. dilauryl peroxide, AIBN (azo-iso- butyro-nitrile) .
  • chain transfer agents and initiators eg. mercaptans such as dodecyl mercaptans
  • peroxides and azo initiators eg. dilauryl peroxide, AIBN (azo-iso- butyro-nitrile)
  • AIBN azo-iso- butyro-nitrile
  • One preferred polymer comprises acrylic acid and styrene, possibly with minor amounts of dodecylmercaptan (DDM) .
  • Acrylic acid is preferably present in an amount in the range 50-80% by wt
  • the styrene is preferably present in an amount in the range 20-50 % by weight
  • DDM is preferably present in an amount up to about 1% by weight, eg. 0.1-1% by weight.
  • a particularly preferred polymer comprises 50.81 wt% acrylic acid, 48.93 wt% styrene, 0.26 wt% DDM, with a molecular weight of about 1,000 and substantially no cross- linking. This polymer is found to be very versatile and to have a wide range of uses and applications.
  • Another preferred polymer comprises 54 wt% methacrylic acid and 46% styrene, with a molecular weight of about 100,000 and substantially no cross-linking.
  • Such a polymer is found to be hypochlorite-stable and to be an effective thickener in hypochlorite bleach.
  • the polymer is preferably substantially non cross-linked, although a degree of cross- linking can be tolerated.
  • the polymer typically has a molecular weight of between about 1,000 and 1,000,000.
  • polymers with molecular weights at the bottom end of the range are preferred, as these generally make better hydrotropes.
  • a polymer with a molecular weight of about 1000 is found to be very versatile and useful in a wide range of applications.
  • Polymers with higher molecular weights, eg. about 100,000, also function well as hydrotropes and may additionally perform a thickening function which may be desirable in certain applications, eg. production of thickened compositions.
  • the molecular weight of polymers according to the invention is at least 500, more preferably at least 750 and preferably at most 10,000, more preferably at most 5,000, most preferably at most 3,000, e.g. 1,000.
  • Suitable polymers can be readily made in conventional manner, eg. by emulsion or solution polymerisation, and are preferably in the form of low viscosity non-aqueous solutions or powders.
  • the polymer is present in an appropriate amount to achieve desired results, such as particular desired composition properties, and suitable amounts can be readily determined by experiment. Typically amounts in the range 0.1 to 15% by wt as active material are suitable, preferably 0.5 to 10% by wt. Electrolyte material
  • electrolyte material is incorporated in compositions according to the invention.
  • electrolyte material is defined as material that dissociates at least for 10% by weight of the total amount of electrolyte upon dilution of lg in 100ml of water at 25°C.
  • the electrolyte material may include builder, bleach or other materials.
  • the electrolyte material according to the invention is ionisable and water soluble. More preferably, the electrolyte material is an alkaline material, i.e. the salt form of the electrolyte has a 1% pH in water at 25°C and 1 atm of higher than 7, preferably 7.5 or higher, more preferably 8.0 or higher.
  • the electrolyte material is selected from salts (e.g. alkali metal) organic and mineral acids.
  • salts e.g. alkali metal
  • examples of such electrolyte material are phosphates (e.g. STP) , silicates (eg. metasilicates, disilicates) , hypochlorites, carbonates (e.g. bicarbonates and percarbonates) , hydroxides, halides (e.g. chloride) , sulphates (e.g. sulphate) , sequestrants (e.g. ethylene- diamine-tetracetic acid and sodium nitrilotriacetate) , citrates and borates (e.g. perborates) .
  • the corresponding acids can be used, as these generally turn into the effective salt form in the non-aqueous liquid product itself or immediately upon dilution in the wash solution.
  • Electrolyte is typically present in an amount of at least 0.5%, preferably 1.0%, more preferably 2% and preferably at most 60%, more preferably at most 50% by weight of the composition.
  • Composition of the present invention may comprise surfactant material, non-surfactant material, solvent material and other liquid material such as deflocculant material.
  • compositions of the invention may comprise from 10 to 90% by weight of a non-aqueous liquid phase.
  • the level of the liquid phase is at most 75%, or at most 70% and preferably, at least 20%, more preferably at least 30%.
  • Non-aqueous liquids to which the hydrotrope may be added contain a non-aqueous phase comprising a single surfactant or a mixture of surfactants selected from a wide range, including the following.
  • Detergent compositions according to the invention may comprise anionic, nonionic, cationic, amphoteric and/or zwitterionic surfactant material, preferably in levels of from 10 to 90% by weight of the composition.
  • Typical blends of surfactants include a nonionic and/or non-alkoxylated anionic and/or alkoxylated anionic surfactant. Cationic, zwitterionic and amphoteric surfactants may also be present in minor amounts as desired. These and other surfactants are described in "Surface Active Agents” Vol I, by Schwartz & Perry, Interscience 1949 and "Surface Active Agents” Vol II by
  • compositions often and preferably comprise a liquid nonionic surfactant as major component.
  • Nonionic detergent surfactants are well-known in the art.
  • They normally consist of a water-solubilising polyalkoxylene (preferably from 3-10 ethoxy and/or propoxy groups) or a mono- or di-alkanolamide group in chemical combination with an organic hydrophobic group derived from, for example, fatty alcohols with from 9 to 15 carbon atoms (optionally branched, e.g.
  • alkylphenol ⁇ (preferably from 12 to 20 carbon atoms) in which the alkyl group contains from about 6 to about 12 carbon atoms, dialkylphenols in which each alkyl group contains from 6 to 2 carbon atoms, primary, secondary or tertiary aliphatic alcohols (or alkyl-capped derivatives thereof) , monocarboxylic acids having from 10 to about 24 carbon atoms in the alkyl group and polyoxypropylenes.
  • Fatty acid mono- and dialkanolamides in which the alkyl group of the fatty acid radical contains from 10 to about 20 carbon atoms and the alkyloyl group having from 1 to 3 carbon atoms are also common.
  • the polyalkoxylene moiety usually consists of an average of from 2 to 20 groups of ethylene oxide, propylene oxide groups or mixtures thereof.
  • the latter class includes those described in European Patent Specification EP-A-0, 225, 654 , especially for use as all or part of the liquid phase.
  • ethoxylated nonionics which are condensation products of fatty alcohols with from 9 to 15 carbon atoms condensed with 3 to 7 moles of ethylene oxide.
  • condensation products of Cll-13 alcohols with 3 or 7 moles of ethylene oxide may be used as the sole nonionic surfactant or in combination with those described in EP-A-O,225, 654.
  • Suitable examples of such nonionics are Vista 1012-6.2, which is a C I(M , alcohol ethoxylated with on average 6.2 ethoxy groups, and Dobanol 25-3, which is a C 10 . 15 alcohol ethoxylated with on average 3 ethoxy groups.
  • alkyl saccharides polyglycosides/oligosaccharides
  • suitable nonionics include the alkyl saccharides (polyglycosides/oligosaccharides) and, in particular those described in the following patent specifications, US-A-3 , 6 0, 998 ; US-A-3 , 346, 558 ; US-A- 4,223,129; EP-A-0, 092 , 355; EP-A-0, 099, 183 ; EP-A-0,070, 074 ,* EP-A-0, 070, 075; EP-A-0, 070, 075; EP-A-0, 070, 076; EP-A-0, 070,077; EP-A-0, 075, 994 ; EP-A-0, 075,995 and EP-A-0, 075,996.
  • nonionic detergent surfactants may also be used.
  • Mixtures of nonionic detergent surfactants with other detergent surfactants such as anionic, cationic or ampholytic surfactants and soaps may also be used.
  • the level of nonionic surfactant is from 10 to 90% by weight of the composition, more preferably from 20 to 70% by weight of the composition and, most preferably, from 35 to 50% by weight of the composition.
  • Solvent material may be included in compositions according to the present invention and in particular materials as disclosed in our co-pending PCT application EP/94/01289, i.e. an ester of a C,_ 6 carboxylic acid and/or poly- carboxylic acid and an alcohol selected from dihydric alcohols, ether alcohols and sterically hindered alcohols.
  • the ester is present in amounts of from 0.01 to 50% by weight of the composition.
  • a suitable ester material is propyleneglycoldiacetate.
  • Other examples are disclosed in GB-A-2, 169, 613, GB-A-2 , 177 , 716 and EP-A-413,616 (Colgate) .
  • liquid bleach precursors such as for example glyceroltriacetate
  • solvent material for example ethanol and dodecanol
  • deflocculant material such as described in EP-A-0, 266, 199.
  • the level of liquid precursors is preferably 0 to 20% by weight, more preferably 0 to 10% by weight.
  • the level of solvents, other than nonionic surfactants is preferably from 0 to 20% by weight, more preferably 0 to 10%.
  • any material may be used as a deflocculant provided it fulfils the deflocculation test described in European Patent Specification EP-A-0, 266, 199 (Unilever).
  • EP-A-0, 266, 199 Unilever
  • the capability of a substance to act as a deflocculant will partly depend on the solids/liquid phase combination. However, especially preferred are acids.
  • Deflocculants are preferably selected from Bronsted acids and Lewis acids. Examples thereof are transition metals, anhydrides, organic acids, inorganic mineral acids and salts, C x -C 61 , fatty acids and salts, C,-C ⁇ alkanoic acids, substituted anhydrous alkali-metal aluminosilicate, alkyl, alkenyl aryl, aralkyl and aralkenyl sulphonic or carboxylic acids and salts and halogenated derivatives thereof, zwitterionic surfactants, anionic surfactants of the formula R-L-A-Y, as defined in EP-A-0, 266, 199 , and compounds having an acidic -P-OH group.
  • deflocculants in the acid form are used.
  • Deflocculant material if included, may be present at levels of from 0 to 15%, preferably at least 0.01 and most preferably at least 1% by weight.
  • the amount of deflocculant material will be from 2 to 12 % by weight, preferably 4 to 10% by weight based on the final composition.
  • Composition according to the invention may be isotropic (i.e. may not contain solid particles) or they may comprise solid (dispersed) particles in which case the solid phases may include one or more components selected from abrasives, bleaches, bleach catalysts, colorants, bleach precursors, builders, dispersants, enzymes, fluorescers, opacifying agents, pigments, solid surfactants and mixtures thereof.
  • compositions according to the invention contain from 0 to 90% (or even up to 95 or up to 100% in case of a solid composition) by weight of a solid phase.
  • the level of the solid phase is at least 10%, more preferably at least 20%.
  • the particle size of the solid phase in terms of D(3,2) will be less than 500, preferably not more than 250 ⁇ m, more preferably not more than lOO ⁇ m.
  • the particle size is at least O.l ⁇ .
  • D(3,2) refers to average particle diameter, which is an average surface weighted, volume/weight mean diameter.
  • compositions of the present invention may comprise a bleach system.
  • Suitable bleaches for inclusion in the detergent compositions of the invention include halogen, particularly chlorine bleaches, such as are provided in the form of alkali-metal hypohalites (e.g. hypochlorites) , as well as peroxygen bleach.
  • peroxygen bleaches are preferred, for example, in the form of an inorganic peroxybleach, optionally in combination with one or more bleach activators.
  • Typical examples of suitable peroxy bleach are alkali-metal perborates, both tetrahydrates and monohydrates, alkali metal percarbonates, persulphates, persilicates, perphosphates and peracids.
  • Perborate and percarbonate are preferred, in particular in the sodium form.
  • Compositions according to the invention comprise preferably additionally to the peroxygen bleach, a bleach activator, which makes the bleach more effective at lower temperatures, i.e. in the range from ambient temperature to about 60°C.
  • Bleach activators may be selected from bleach precursors, bleach catalysts and mixtures thereof.
  • Peroxygen bleach such as sodium perborate, both the monohydrate and the tetrahydrate, acts to release active oxygen in solution, and the precursor which is usually an organic compound having one or more reactive acyl residues which causes the formation of peroxy acids; the latter providing for more effective bleaching action at lower temperatures than the peroxybleach compound alone.
  • Precursors according to the invention include compounds with N- and O-acyl groups.
  • Suitable classes include anhydrides, esters, imides and acylated derivatives of imidazoles and oxi es, and examples of useful materials within these classes are disclosed in GB-A-1, 586, 789, GB-A- 0,836,988, GB-A-0,864 ,798, GB-A-1, 147 , 871, GB-A-2 , 143, 231 and GB-A-0, 855, 735 and GB-A-1, 246, 338.
  • O- acetylated precursor compounds include 2 , 3 , 3-tri-methyl hexanoyl oxybenzene sulfonates, benzyl oxybenzene sulfonates and penta acetyl glucose.
  • Particularly preferred precursor compounds are the N-,N,N1N1 tetra acetylated compounds of which tetra acetyl methylene diamine (TAMD) , tetraacetyl ethylene diamine (TAED) and tetraacetyul hexylene diamine (TAHD) are preferred examples.
  • the ratio of the peroxybleach to the precursor is from 20:1 to about 1:1.
  • the preferred level of the peroxybleach compound in the composition is from 0 to 30% by weight.
  • the preferred level of precursor is from 0 to 20% by weight of the composition.
  • bleach catalysts and, in particular, transition metal catalysts may also be advantageous.
  • Such catalysts optionally together with stabilisers, as hereinafter defined, can be used to activate peroxide compounds to make them more suitable for use for bleaching at lower temperatures, e.g. from 20 to 60°C.
  • Such catalysts may be incorporated in the form of a particulate product according to the invention.
  • Such catalysts which only need be present in such detergent composition in small amounts such as from 0.005 to 5% by weight of the composition.
  • Bleach catalysts may include those based on metal ion delivered by simple salts such as Cu(II) sulphate.
  • Preferred bleach catalysts are based on transition metal coordination complexes as has been described and defined in EP-A-0, 458, 397, EP-A-0, 458, 398, EP-A-0, 522 ,817, EP-A- 0,544,440, EP-A-0, 544 , 490, EP-A-0, 549, 272 , EP-A-0,549,271, EP-A-0, 544 , 91, US-A-5, 194 , 1 , WO 93/25562, WO 94/00439, and WO 94/05422. These references are incorporated in the present application by reference.
  • compositions according to the present invention are oxygen transfer agents as described and defined in EP-A-446, 981, EP-A-453,003 and EP- A-446,982. These references are incorporated in the present application by reference.
  • compositions may also be desirable to include in the compositions a stabiliser for the bleach or bleach system, for example hydroxyethylidene-l , 1-diphosphonic acid, ethylene diamine tetramethylene phosphonate and diethylene triamine pentamethylene phosphonate or other appropriate organic phosphonates or salts thereof, such as the Dequest" range of materials.
  • a stabiliser for the bleach or bleach system for example hydroxyethylidene-l , 1-diphosphonic acid, ethylene diamine tetramethylene phosphonate and diethylene triamine pentamethylene phosphonate or other appropriate organic phosphonates or salts thereof, such as the Dequest" range of materials.
  • the detergency builders are those materials which counteract the effects of calcium, or other ion, water hardness, either by precipitation or by an ion sequestering effect. They comprise both inorganic and organic builders. They may also be sub-divided into the phosphorus-containing and non-phosphorus types, the latter being preferred when environmental considerations are important.
  • the inorganic builders comprise the various phosphate-, carbonate-, silicate-, borate- and alu ino- silicates-type materials, particularly the alkali-metal salt forms. Mixtures of these may also be used.
  • Examples of phosphorus-containing builders are the water-soluble salts, especially alkali metal pyrophosphates, orthophosphates, polyphosphates and phosphonates.
  • Examples of non-phosphorus-containing inorganic builders are water-soluble alkali metal carbonates, bicarbonate ⁇ , borates, silicates, metasilicates, and crystalline and amorphous aluminosilicates.
  • organic builders include the alkali metal, ammonium and substituted ammonium, citrates, succinates, malonates, fatty acid sulphonates, carboxymethoxy succinates, ammonium polyacetates, carboxylates, polycarboxylates, aminopolycarboxylates, polyacetyl carboxylates and polyhydroxysulphonates.
  • specific examples include salts of ethylenediaminetetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, melitic acid, benzene polycarboxylic acids and citric acid.
  • suitable organic builders include the higher molecular weight polymers and co-polymers known to have builder properties, for example appropriate polyacrylic acid, polymaleic acid and polyacrylic/poly aleic acid co-polymers and their salts, such as those sold by BASF under the Sokalan " Trade Mark. Polyacrylates or their derivatives may also be useful for their anti-ashing properties.
  • the level of builder materials is from 5 to 50% by weight of the composition, more preferably 10 to 40%, most preferably 15 to 35%.
  • Dispersants The physical stability of non-aqueous liquid detergent compositions can be improved and/or setting problems can be minimised, if dispersants are used.
  • a dispersant material is a material, of which the main purpose is to stabilise the composition.
  • the dispersant is selected from hydrophobically modified dispersant materials, metal oxides as defined in EP-A-515,435 incorporated herein by reference (preferably having a bulk density of 200 to 1000 g/1) , finely divided clay material, aluminium tri-stearate and mixtures thereof.
  • a preferred material is hydrophobically modified (HM) silica containing dispersants are used as described and defined in EP-A-515,418 incorporated herein by reference.
  • ingredients comprise those remaining ingredients which may be used in detergent compositions, such as fabric conditioning agents, abrasive material, enzymes, enzyme stabilising agents (if necessary) , fluorescers, perfumes (including deoperfu e ⁇ ) , micro-biocides, soil-suspending agents (anti-redeposition agent) , corrosion inhibitors, and lather depressants.
  • fabric conditioning agents which may be used, either in fabric washing liquids or in rinse conditioners, are fabric softening materials such as fabric softening clays, quaternary ammonium salts, imidazolinium salts, fatty amines and cellulase ⁇ .
  • Abrasive are particularly preferred for incorporation in hard surface cleaners (liquid abrasive cleaners) .
  • Enzymes which can be used in compositions according to the present invention include proteolytic enzymes (protease) , amylolytic enzymes (a ylase) , lipolytic enzymes (lipases) and cellulolytic enzymes (cellulase) .
  • the preferred level of enzyme materials is from 0.01 to 5% by weight of the composition.
  • the total amount of the fluorescent agent or agents used in a composition is generally from 0.02 to 2% by weight.
  • the amount thereof is normally from about 0.1% to about 5% by weight, preferably from about 0.2% to about 2.5% by weight of the total composition.
  • compositions according to the present invention may be formulated in a very wide range of specific forms, according to the intended use. They may be formulated as cleaners for hard surfaces (with or without abrasive) or as agents for warewashing (cleaning of dishes, cutlery etc) either by hand or mechanical means, as well as in the form of specialised cleaning products, such as for surgical apparatus or artificial dentures.
  • compositions of the invention are formulated as agents for washing and/or conditioning of fabrics and then the compositions contain at least one agent which promotes the cleaning and/or conditioning of the article(s) in question, selected according to the intended application.
  • this agent will be selected from surfactants, enzymes, bleaches, builders, buffers, microbiocides, (for fabrics) fabric softening agents and (in the case
  • an aqueous liquor containing 0.1 to 10 %, more preferably 0.2 to 2%, of the non-aqueous detergent composition of the invention is used.
  • all equipment and raw materials should be dry and (in the case of hydratable salts) in a low hydration state, e.g. anhydrous phosphate builder, sodium perborate monohydrate and dry calcite abrasive, where these are employed in the composition.
  • a low hydration state e.g. anhydrous phosphate builder, sodium perborate monohydrate and dry calcite abrasive, where these are employed in the composition.
  • the dry, substantially anhydrous solids are blended with the liquid phase in a dry vessel. If deflocculant materials are used, the ⁇ e should preferably -at lea ⁇ t partly- be mixed with the liquid phase, prior to the addition of the solids.
  • This blend is pas ⁇ ed through a grinding mill or a combination of mill ⁇ to achieve a D(3,2) particle size of between 0.1 to 100 icron ⁇ .
  • a preferred combination of such mills is a colloid mill followed by a horizontal ball mill.
  • particulate material already having the desired particle size need not be subjected to thi ⁇ procedure.
  • the present invention further relates to a method of preparing a non-aqueous detergent composition comprising a polymeric hydrotrope, wherein the polymeric hydrotrope is added to the composition in a form comprising 25% or less by weight of water, preferably less 20% or less, more preferably 15% or less, most preferably 10% or less, in particular substantially non-aqueous.
  • the non- aqueous phase further comprises ingredients selected from abrasives , bleaches , bleach catalysts , bleach precursors , corrosion inh ibitors , dispersants , enzymes , fabric sof tening agents , microbiocides , soi l-suspending agents , solid surfactants and mixtures thereof and preferably at a level of from 0.01 to 90% by weight of the composition.
  • the polymeric hydrotrope can either be added as solid particles that are freeze-dried (less than 5% by weight of water) , or spray-dried (5-15% water) or, preferably, in the form of a non-aqueous solution or dispersion, e.g. in non ⁇ ionic surfactant material or in a solvent material.
  • compositions (A and 1) were prepared with lOg Vista
  • composition 4 additionally contained 2% of Narlex H100 polymer (PPE 1269, a Acrylic Acid/Styrene/DDM polymer, ex National Starch Chemical Company) , hereafter the Narlex polymer.
  • Composition 1 showed less gelling in the gelling test than composition A.
  • compositions (B and 2) were prepared with lOg Vista 1012-62 and Dobanol 25-3 (weight ratio 55/45) mixed with 2g STP.
  • the nonionic of composition 2 additionally contained 2% of the Narlex polymer.
  • Composition 2 showed less gelling in the gelling test than composition B.
  • compositions were prepared with lOg Vista 1012-62 and Dobanol 25-3 (weight ratio 55/45) mixed with 2g SMS.
  • the nonionic of composition 3 additionally contained 2% of the Narlex polymer.
  • Composition 3 showed less gelling in the gelling test than composition C.
  • compositions (D and 4) were prepared with lOg Vista 1012-62 and Dobanol 25-3 (weight ratio 55/45) mixed with 2g percarbonate.
  • the nonionic in composition 4 additionally contained 2% of the Narlex polymer.
  • Composition 4 showed less gelling in the gelling test than composition D.
  • Example 1.5 Soda/Percarbonate
  • compositions (E and 5-7) were prepared with lOg Vista 1012-62 and Dobanol 25-3 (weight ratio 55/45) mixed with 2g soda (compositions E and 5) or 2g percarbonate (composition 6 and 7) .
  • Composition 7 additionally contained lg soda.
  • Compositions 5-7 all contained 2% of the Narlex polymer of Example 1.1. Composition 7 showed the lowest gelling, followed by composition 5, followed by composition 6 and composition E showed the worst gelling behaviour.
  • compositions 8-11 were prepared with lOg Vista 1012- 62 and Dobanol 25-3 (weight ratio 55/45) mixed with 2g soda and 2% of the Narlex polymer.
  • Compositions 8-10 all contained lg soda.
  • Composition 9 further contained 2g STP.
  • Composition 10 further contained 0.5g Sodium citrate.
  • Composition 11 contained 2g STP. All compositions showed low gelling behaviour.
  • compositions were prepared containing lOg Vista 1012-5.5 and 2g soda.
  • Composition 12 additionally contained 2% of the Narlex polymer of Example 1.1 and had far lower gelling behaviour than composition F.
  • compositions were prepared containing lOg Dobanol 25-3 and 2g soda.
  • Composition 13 additionally contained 4% of the Narlex polymer and had far lower gelling behaviour than composition F (that showed lump formation) .
  • Example 1.9 Polymeric hydrotrope without salts
  • Four composition ⁇ were prepared (H and 14-16) were prepared with Vi ⁇ ta 1012-62 with 0, 1, 2 and 4% of the Narlex polymer, respectively.
  • Composition 16 ⁇ howed the lowest viscosity, followed by composition 15, followed by composition 14.
  • Composition H had the highest viscosity in the gelling test.
  • compositions (I and J) were prepared with Vista 1012-62 and Dobanol 25-3 (40/60 weight ratio) and 2g soda.
  • Composition J additionally contained 6% Eltesel SXS 40. Both compositions showed the same high gelling behaviour.
  • Composition 2 was prepared without polymer (K) and with 1% of the Narlex polymer of Example 1.1 (17) .
  • Composition 17 showed very low gelling compared with composition K.
  • Example 1.12 - Sodium citrate & Dobanol 25-3 Two compositions (L and 18) were prepared with lOg Dobanol 25-3 mixed with 2g Sodium citrate. The nonionic of composition 18 additionally contained 2% of the Narlex polymer. Composition 18 showed less gelling in the gelling te ⁇ t than compo ⁇ ition L.
  • compositions (M and 19) were prepared with lOg Dobanol 25-3 mixed with 2g Magnesium Sulphate.
  • the nonionic of composition 19 additionally contained 2% of the Narlex polymer.
  • Composition 19 showed less gelling in the gelling test than composition M.
  • compositions (N and 20) were prepared with lOg Dobanol 25-3 mixed with 2g Sodium EDTA.
  • the nonionic of composition 20 additionally contained 2% of the Narlex polymer.
  • Composition 20 showed less gelling in the gelling test than composition N.
  • compositions were made by adding the ingredients in the order listed. After colloid milling, the compositions were ball-milled after addition of perborate/metasilicate. The resulting compositions have a D(3,2) particle size of from l-15 ⁇ m.
  • Composition 21 (in % by weight)
  • Nonionic mix 1 46.4 LAS acid 7.0
  • composition 22 (in % by weight) Nonionic mix 1) 40.0
  • Composition 23 (in % by weight)
  • compositions were prepared according to composition 21 with respectively 0, 1 and 2% of the Narlex polymer.
  • Composition 25 showed the best dissolution followed by composition 24.
  • compositions were prepared according to composition 22 with respectively 0, 1 and 2% of the
  • Example 2.3 Composition 23 was prepared and 25% by weight of water was added, whereafter the composition wa ⁇ ⁇ tirred homogeneou ⁇ ly.
  • the composition was prepared without polymer (Q) and with 1% of the Narlex polymer of Example 1.1 (Composition 28) . Both compositions were tested in the above dis ⁇ olution test. After 4 minutes, 83% of Composition 28 was di ⁇ olved, whereas only 47% of composition Q was dissolved.
  • Example 3.1 Composition 21 was prepared without polymer (R) , with 1% Narlex polymer (29) and with 2% of the Narlex polymer (30) . Composition R was dispersed after 37 minutes, whereas composition 29 was dispersed after 23 minutes and composition 30 after 13 minutes.
  • composition 21 with 10% additional nonionic mix was prepared without polymer (S) and with 1% of Narlex polymer (31) .
  • Composition S was dispersed after 35 minutes, whereas composition 31 was dispersed after 16 minutes.
  • composition 23 was prepared without polymer (T) and with 1% Narlex polymer (32). Composition T was dispersed after 29 minutes, whereas composition 32 was dispersed after 22 minutes.
  • Example 4 Dispensing test Composition 22 was prepared without polymer (U) and with 1% additional Narlex polymer (33) . Composition 33 dispenses better in a system involving three-way valve as disclosed in the figure of EP-A-480,490 than composition U.

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)
EP95941064A 1994-12-13 1995-11-28 Waschmittelzusammensetzung Expired - Lifetime EP0797656B2 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP95941064A EP0797656B2 (de) 1994-12-13 1995-11-28 Waschmittelzusammensetzung

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP94309299 1994-12-13
EP94309299 1994-12-13
EP95941064A EP0797656B2 (de) 1994-12-13 1995-11-28 Waschmittelzusammensetzung
PCT/EP1995/004723 WO1996018716A1 (en) 1994-12-13 1995-11-28 Detergent composition

Publications (3)

Publication Number Publication Date
EP0797656A1 true EP0797656A1 (de) 1997-10-01
EP0797656B1 EP0797656B1 (de) 2000-05-24
EP0797656B2 EP0797656B2 (de) 2004-03-17

Family

ID=8217941

Family Applications (1)

Application Number Title Priority Date Filing Date
EP95941064A Expired - Lifetime EP0797656B2 (de) 1994-12-13 1995-11-28 Waschmittelzusammensetzung

Country Status (7)

Country Link
EP (1) EP0797656B2 (de)
AU (1) AU4259696A (de)
BR (1) BR9509990A (de)
DE (1) DE69517197T3 (de)
ES (1) ES2147620T5 (de)
WO (1) WO1996018716A1 (de)
ZA (1) ZA9510369B (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3137107A1 (fr) 2022-06-28 2023-12-29 Capsum Composition de nettoyage solide comprenant au moins une cavité

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030162679A1 (en) * 2002-01-15 2003-08-28 Rodrigues Klein A. Hydrophobically modified polymer formulations
WO2008032012A1 (en) * 2006-09-15 2008-03-20 Reckitt Benckiser Inc. Cleaning article comprising melamine foam sponge
US8841246B2 (en) 2011-08-05 2014-09-23 Ecolab Usa Inc. Cleaning composition containing a polysaccharide hybrid polymer composition and methods of improving drainage
US8853144B2 (en) 2011-08-05 2014-10-07 Ecolab Usa Inc. Cleaning composition containing a polysaccharide graft polymer composition and methods of improving drainage
US8636918B2 (en) 2011-08-05 2014-01-28 Ecolab Usa Inc. Cleaning composition containing a polysaccharide hybrid polymer composition and methods of controlling hard water scale
US8679366B2 (en) 2011-08-05 2014-03-25 Ecolab Usa Inc. Cleaning composition containing a polysaccharide graft polymer composition and methods of controlling hard water scale
US8945314B2 (en) 2012-07-30 2015-02-03 Ecolab Usa Inc. Biodegradable stability binding agent for a solid detergent
BR112015002416B1 (pt) * 2012-08-03 2021-09-21 Ecolab Usa Inc Composição detergente sólida
US9365805B2 (en) 2014-05-15 2016-06-14 Ecolab Usa Inc. Bio-based pot and pan pre-soak
DE102015201698A1 (de) 2015-01-30 2016-08-04 Henkel Ag & Co. Kgaa Saures Flüssigkompaktwaschmittel enthaltend Hydroxycarbonsäure, Niotensid und a-Amylase

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ATE4818T1 (de) * 1979-11-09 1983-10-15 Unilever Nv Nicht-waessrige, einen komplexbildner enthaltende fluessige reinigungsmittelzusammensetzung und verfahren zu deren herstellung.
US5141664A (en) † 1987-12-30 1992-08-25 Lever Brothers Company, A Division Of Conopco, Inc. Clear detergent gel compositions having opaque particles dispersed therein
EP0381261A3 (de) * 1989-01-30 1991-03-06 Unilever N.V. Flüssiges Waschmittelerzeugnis
GB2228944A (en) * 1989-03-08 1990-09-12 Unilever Plc Non-aqueous liquid cleaning composition
CA2015832C (en) † 1989-05-15 2002-05-28 Eric K. Eisenhart Multi-stage polymer particles having a hydrophobically-modified, ionically-soluble stage
AU624634B2 (en) * 1989-08-18 1992-06-18 Colgate-Palmolive Company, The Non-aqueous, nonionic heavy duty laundry detergent
GB9108665D0 (en) * 1991-04-23 1991-06-12 Unilever Plc Liquid cleaning products
GB9108660D0 (en) * 1991-04-23 1991-06-12 Unilever Plc Polymers & their preparation
DE4131906A1 (de) * 1991-09-25 1993-04-01 Henkel Kgaa Fluessiges oder pastenfoermiges wasch- oder reinigungsmittel
EP0649462A1 (de) * 1992-07-08 1995-04-26 Unilever Plc Flüssige reinigungsprodukte
GB9315854D0 (en) † 1993-07-30 1993-09-15 Nat Starch Chem Corp Improvements in or relating to hydrotropes

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9618716A1 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3137107A1 (fr) 2022-06-28 2023-12-29 Capsum Composition de nettoyage solide comprenant au moins une cavité
WO2024003065A1 (fr) 2022-06-28 2024-01-04 Capsum Composition de nettoyage solide comprenant au moins une cavité

Also Published As

Publication number Publication date
DE69517197D1 (de) 2000-06-29
ZA9510369B (en) 1997-06-06
AU4259696A (en) 1996-07-03
BR9509990A (pt) 1997-12-30
DE69517197T2 (de) 2000-09-21
EP0797656B1 (de) 2000-05-24
EP0797656B2 (de) 2004-03-17
DE69517197T3 (de) 2004-08-12
ES2147620T3 (es) 2000-09-16
WO1996018716A1 (en) 1996-06-20
ES2147620T5 (es) 2004-11-01

Similar Documents

Publication Publication Date Title
EP0510762B1 (de) Flüssige Reinigungsmittel
CA2010444C (en) Liquid detergent products
AU633849B2 (en) Liquid cleaning products and method for their preparation
JP2000505132A (ja) 特定のアルキルベンゼンスルホネート界面活性剤を含有する非水性洗剤組成物
EP0797656B2 (de) Waschmittelzusammensetzung
AU618344B2 (en) Liquid cleaning products
NZ238047A (en) Nonaqueous liquid automatic dihwashing detergent comprising silica,
US5368767A (en) Stable nonaqueous liquid detergents containing a metal oxide of bulk density of 200-1,000 g/l
AU694421B2 (en) Non-aqueuos liquid cleaing comosition containing modified silica
EP0515418A1 (de) Flüssige reinigungsprodukte.
AU610720B2 (en) Liquid cleaning products
CA1314186C (en) Liquid cleaning products
GB2228944A (en) Non-aqueous liquid cleaning composition
AU682044B2 (en) Detergent composition
EP0649462A1 (de) Flüssige reinigungsprodukte
AU651961B2 (en) Non-aqueous liquid detergent composition containing a mixtureof nonionic compounds
GB2217727A (en) Liquid cleaning products
AU625804B2 (en) Thickened non-aqueous-liquid composition comprising polyalkoxylated material
JPH11513071A (ja) 漂白剤前駆物質を含有する非水性洗剤組成物

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

17P Request for examination filed

Effective date: 19970527

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): DE ES FR GB IT

17Q First examination report despatched

Effective date: 19971104

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE ES FR GB IT

REF Corresponds to:

Ref document number: 69517197

Country of ref document: DE

Date of ref document: 20000629

ITF It: translation for a ep patent filed
ET Fr: translation filed
REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2147620

Country of ref document: ES

Kind code of ref document: T3

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

26 Opposition filed

Opponent name: HENKEL KGAA

Effective date: 20010207

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PUAH Patent maintained in amended form

Free format text: ORIGINAL CODE: 0009272

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

Free format text: STATUS: PATENT MAINTAINED AS AMENDED

27A Patent maintained in amended form

Effective date: 20040317

AK Designated contracting states

Kind code of ref document: B2

Designated state(s): DE ES FR GB IT

REG Reference to a national code

Ref country code: ES

Ref legal event code: DC2A

Date of ref document: 20040607

Kind code of ref document: T5

ET3 Fr: translation filed ** decision concerning opposition
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20051117

Year of fee payment: 11

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

Ref country code: GB

Payment date: 20051123

Year of fee payment: 11

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

Ref country code: ES

Payment date: 20051124

Year of fee payment: 11

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

Ref country code: DE

Payment date: 20060102

Year of fee payment: 11

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

Ref country code: IT

Payment date: 20061130

Year of fee payment: 12

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

Ref country code: DE

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

Effective date: 20070601

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20061128

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20070731

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

Ref country code: GB

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

Effective date: 20061128

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20061129

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

Ref country code: FR

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

Effective date: 20061130

Ref country code: ES

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

Effective date: 20061129

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

Ref country code: IT

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

Effective date: 20071128