WO2008119830A2 - Fixation de substances odorantes d'agents de lavage et de nettoyage sur des surfaces dures et molles - Google Patents

Fixation de substances odorantes d'agents de lavage et de nettoyage sur des surfaces dures et molles Download PDF

Info

Publication number
WO2008119830A2
WO2008119830A2 PCT/EP2008/053991 EP2008053991W WO2008119830A2 WO 2008119830 A2 WO2008119830 A2 WO 2008119830A2 EP 2008053991 W EP2008053991 W EP 2008053991W WO 2008119830 A2 WO2008119830 A2 WO 2008119830A2
Authority
WO
WIPO (PCT)
Prior art keywords
alkyl
groups
formula
compound
carbon atoms
Prior art date
Application number
PCT/EP2008/053991
Other languages
German (de)
English (en)
Other versions
WO2008119830A3 (fr
Inventor
Nadine Warkotsch
Birgit Middelhauve
Marc-Steffen Schiedel
Jürgen HILSMANN
Original Assignee
Henkel Ag & Co. Kgaa
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DE102007016383A external-priority patent/DE102007016383A1/de
Priority claimed from DE200710023874 external-priority patent/DE102007023874A1/de
Priority claimed from DE200710038453 external-priority patent/DE102007038453A1/de
Application filed by Henkel Ag & Co. Kgaa filed Critical Henkel Ag & Co. Kgaa
Publication of WO2008119830A2 publication Critical patent/WO2008119830A2/fr
Publication of WO2008119830A3 publication Critical patent/WO2008119830A3/fr

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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3281—Heterocyclic compounds
    • 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
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
    • 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
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
    • C11D3/3742—Nitrogen containing silicones
    • 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
    • C11D3/50—Perfumes
    • C11D3/502—Protected perfumes
    • 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/267—Heterocyclic compounds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/005—Compositions containing perfumes; Compositions containing deodorants

Definitions

  • the present invention relates to the use of polycarbonate, polyurethane and / or polyurea-polyorganosiloxane compounds or of precursor compounds which can be used in their preparation with certain reactive groups for fixing fragrances to hard and soft surfaces, such as textiles, in particular at their laundry.
  • fragrances are high-quality ingredients of detergents and cleaners, one strives to use them only in small quantities. The loss of these ingredients (for example in a washing machine) is equally unsatisfactory for the manufacturers and consumers of such agents.
  • the present invention therefore provides the use of polycarbonate, polyurethane and / or polyurea-polyorganosiloxane compounds containing at least one structural element of the formula (I):
  • each A independently is selected from S, O and NR 1 ,
  • Y is selected from bivalent to polyvalent, especially tetravalent, straight-chain, cyclic or branched, saturated, unsaturated or aromatic, substituted or unsubstituted hydrocarbon radicals having up to 1000 carbon atoms (the
  • R 1 is hydrogen or a straight, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radical having up to 40 carbon atoms which is one or more
  • R 2 is a straight-chain, cyclic or branched, saturated, unsaturated or aromatic
  • Hydrocarbon radical having up to 40 carbon atoms which may contain one or more groups selected from -O-, - (CO) - and -NH-,
  • R 3 is a straight-chain, cyclic or branched, saturated, unsaturated or aromatic
  • Hydrocarbon radical having up to 100 carbon atoms, which may contain one or more groups selected from -O-, - (CO) - and -NH-, or is a bivalent radical, the cyclic
  • R 1 or R 2 or R 3 must be identical with the proviso that in the entire compound at least one of the radicals Y comprises a Polyorganosiloxanhow having 2 to 1000 silicon atoms, or their acid addition compounds and / or salts for fixing fragrances to hard and / or soft surfaces.
  • Soft surfaces should be understood in this context as meaning both human skin and hair and textiles, also of different composition, for example cotton, wool, silk, polyester, polyamide, viscose and blended fabrics of any kind.
  • Compounds of the general formula (I) can be obtained by reacting diisocyanates, bis-chloroformates or amides or phosgene with thiols, alcohols or amines containing the structural element Y.
  • these starting compounds having the structural element Y have at least 2 of the said functional groups.
  • Suitable end groups are compounds which otherwise correspond to the structural element Y but are only monofunctional.
  • polycarbonate and / or polyurethane-polyorganosiloxane compounds are those which contain at least one structural element of the formula (II) or (III):
  • Z is selected from the divalent, straight-chain, cyclic or branched, saturated or unsaturated, optionally substituted hydrocarbon radicals having 1 to 12 carbon atoms.
  • These structural elements can be obtained by ring opening of cyclic carbonates (carbonic acid esters of vicinal diols) with the thiols, alcohols or amines containing the structural element Y.
  • the polycarbonate, polyurethane and / or polyurea-polyorganosiloxane compound preferably has the structural element of the formula (I) several times in succession, the multiply occurring in each case corresponding radicals A or Y or Z or R 1 or R 2 or R 3 may be the same or different.
  • the term acid addition compound means a salt-like compound which can be obtained by protonation of basic groups in the molecule, such as in particular the optionally present amino groups, for example by reaction with inorganic or organic acids.
  • the acid addition compounds may be used as such or may optionally form under conditions of use of the compounds defined above. If the polycarbonate, polyurethane and / or polyurea-polyorganosiloxane compound contains moieties - (N + R 2 R 3 ) -, common counter anion ions, such as halide, hydroxide, sulfate, carbonate, are present in order to ensure charge neutrality.
  • the polycarbonate, polyurethane and / or polyurea-polyorganosiloxane compounds contain on average at least two, in particular at least three of said polyorganosiloxane structural elements.
  • R 4 is preferably a straight-chain or cyclic or branched, saturated or unsaturated or aromatic C 1 - to C 2 O-, in particular C 1 to C 7 hydrocarbon radical, particularly preferably methyl or phenyl, and p is in particular 1 to 199, particularly preferably 1 to 99. In a preferred embodiment, all radicals R 4 are the same.
  • Preferred polycarbonate, polyurethane and / or polyurea polyorganosiloxane compounds used according to the invention are linear, ie all Y units in the structural element of the formula (I) are in each case divalent radicals.
  • branched compounds according to the invention are also included in which at least one of the radicals Y is trivalent or polyvalent, preferably tetravalent, so that branched structures having linear repeat structures of structural elements of the formula (I) are formed.
  • At least one of the Y units according to the structural element of the formula (I) has a grouping -NR 2 - and / or at least one of the Y units according to structural element of the formula (I) a grouping - (N + R 2 R 3 ) - on.
  • R 2 and R 3 are preferably methyl groups.
  • a further embodiment relates to the multiple regular appearance of -O- groupings in at least one of the units Y, R 1 , R 2 and / or R 3 according to structural element of the formula (I), preferably in the form of oligoethoxy and / or oligopropoxy groups their degrees of oligomerization are preferably in the range of 2 to 60.
  • At least one of the units Y, R 1 , R 2 and / or R 3 according to the structural element of the formula (I) contains oligoethylenimine groups whose degrees of oligomerization are in particular in the range from 10 to 15 000.
  • Reactive cyclic carbonates and ureas, processes for their preparation and their reaction with polymeric substrates are described in international patent application WO 2005/058863.
  • Another object of the invention is therefore the use of compounds of general formulas IV or V,
  • R 2 is alkylene of Ci-Ci; k is a number greater than 0,
  • C 1 -C 30 -alkyl ammonium C 1 -C 30 -alkyl, polyoxyalkylene-C 1 -C 30 -alkyl, polysiloxanyl-C 1 -C 30 -alkyl,
  • Alkylene-O (CO) - or (CO) -OC 2 -C 6 alkylene-O (CO) groups is bound, or
  • C 1 -C 30 -alkyl groups is bonded, when k is greater than 1, and / or polymers obtainable by reacting a polymeric substrate having functional groups selected from hydroxy groups, primary and secondary amino groups, with a compound of general Formulas IV or V, for fixing fragrances on hard and / or soft surfaces.
  • polymeric substrates suitable in connection with the latter aspect of the invention include in particular polyvinyl alcohols, polyalkyleneamines such as polyethyleneimines, polyvinylamines, polyallylamines, polyethylene glycols, chitosan, polyamide-epichlorohydrin resins, polyaminostyrenes, aminoalkyl-terminated or polysiloxanes such as polydimethylsiloxanes, peptides, Polypeptides, and proteins and mixtures thereof.
  • Particularly preferred polymeric substrates are selected from polyethyleneimines having molecular weights in the range of 5,000 to 100,000, in particular 15,000 to 50,000,
  • the compound of formula IV is preferably selected from
  • the active ingredient described herein (the polycarbonate, polyurethane and / or polyurea-polyorganosiloxane compound, the reactive Cylische carbonate or the reactive Cylische urea or the latter from the latter by reaction with a polymeric substrate polymer) in amounts by weight, based on the Perfume, in the range of 5: 1 to 0.5: 1, in particular from 2: 1 to 0.5: 1, particularly preferably from 1: 1 to 0.5: 1 used.
  • perfumes e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used. Fragrance compounds of the ester type are known e.g. Benzylacetate, phenoxyethylisobutyrate, p-tert-butylcyclohexylacetate, linalylacetate, dimethylbenzylcarbinylacetate, phenylethylacetate, linalylbenzoate, benzylformate, ethylmethylphenylglycinate, allylcyclohexylpropionate, styrallylpropionate and benzylsalicylate.
  • Fragrance compounds of the ester type are known e.g. Benzylacetate, phenoxyethylisobutyrate, p-tert-butylcyclohexylacetate, linalylacetate, dimethylbenzylcarbinylacetate, phenylethyla
  • the ethers include, for example, benzyl ethyl ether, to the aldehydes e.g. the linear alkanals having 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones e.g. the alcohols include anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol; the hydrocarbons mainly include the terpenes and balsams.
  • mixtures of different fragrances are used, which together produce an attractive fragrance.
  • Such mixtures of individual substances are considered as perfumes in the context of the present application.
  • fragrances may also include natural fragrance mixtures, such as are available from plant or animal sources, e.g. Pine, citrus, jasmine, lily, rose or ylang-ylang oil.
  • lower volatility volatile oils which are most commonly used as aroma components, are useful as perfume oils, e.g. Sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, lime blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil, labdanum oil and lavandin oil.
  • bergamot oil dihydromyrcenol, lilial, lyral, citronellol, phenylethyl alcohol, ⁇ -hexylcinnamaldehyde, geraniol, benzylacetone, cyclamen aldehyde, linalool, Boisambrene Forte, Ambroxan, indole, hedione, Sandelice, citron oil, tangerine oil, orange oil, Allylamylglycolat, Cyclovertal, Lavandinöl, Muskateller Sage oil, ⁇ -damascone, geranium oil Bourbon, cyclohexyl salicylate, Vertofix Coeur, Iso-E-Super, fixolide NP, evernyl, iraldeine gamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide, romilate, iroty
  • Another object of the invention is a method for fixing fragrances on hard and / or soft surfaces, in particular on textiles, which is characterized that the surface with the fragrance and an active ingredient described above, in particular under the action of mechanical forces such as occur in household washing machines, in the presence of water over a period of 2 minutes to 90 minutes at a temperature below 95 0 C, especially in the range from 20 0 C to 60 0 C, treated. Treatment times in the range of 5 minutes to 60 minutes are preferred.
  • the temperature is preferably in the range of 20 0 C to 60 0 C, preferably from 20 0 C to 40 0 C, and particularly preferably during the entire time of treatment of the surface with the inventive combination used, the temperature in the range of 20 0 C to 40 0 C is.
  • the concentration of said active ingredient in the process according to the invention is preferably in the range from 0.05 g / l to 5 g / l, in particular from 0.1 g / l to 3 g / l, while the concentration of perfume in the aqueous treatment liquor preferably in Range from 0.01 g / l to 0.25 g / l, in particular from 0.05 g / l to 0.15 g / l.
  • the process according to the invention can be carried out particularly advantageously with the aid of a washing or cleaning agent which contains a fragrance and the active substance defined above.
  • Another object of the invention is therefore a detergent or cleaning agent containing a perfume, in particular selected from fragrance compounds of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons and mixtures thereof, and an active ingredient described above.
  • the agent may also contain several different of the named active ingredients.
  • agents according to the invention preferably 1 wt .-% to 50 wt .-%, in particular 1 wt .-% to 10 wt .-%, more preferably 0.2 wt .-% to 1 wt .-% of perfumes present.
  • An agent according to the invention can be used as such or after mixing or dilution with water in the process according to the invention or within the context of the use according to the invention.
  • Such a composition may in particular be a textile detergent or textile care agent, which may be in particulate or liquid form, a present in a corresponding form cleaning agent for hard surfaces, such as a tile, a bath or sanitary cleaner, or a cleaning agent for the human body, for example a hair shampoo, a cleansing lotion, a shower gel or a bar soap, act.
  • a cleaning agent for the human body for example a hair shampoo, a cleansing lotion, a shower gel or a bar soap, act.
  • the teaching according to the invention can also be used in the personal care sector in conditioners, for hair dyeing, colorant or perming preparations and depilatories, as well as for agents which, for example. to adjust the pH, lower amines included.
  • agents used according to the invention or used in the process according to the invention which may be in the form of homogeneous solutions or suspensions, in particular in powdered solids, have all conventional ingredients, as long as they do not interact with the described active ingredient or, in particular, with the perfume the desired effect of enhancing scent fixation on the Surface is missing.
  • Detergents or cleaning agents according to the invention may in particular be builders, surface-active surfactants, enzymes, organic and / or inorganic peroxygen compounds, peroxygen activators, water-miscible organic solvents, sequestering agents, electrolyte, pH regulators, thickeners and other auxiliaries, such as soil release agents Brightener, grayness inhibitors, color transfer inhibitors, foam regulators and dyes included.
  • compositions of the invention may contain surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof, as well as cationic surfactants in question.
  • Suitable nonionic surfactants are, in particular, ethoxylation and / or propoxylation products of alkyl glycosides and / or linear or branched alcohols having in each case 12 to 18 C atoms in the alkyl moiety and 3 to 20, preferably 4 to 10, alkyl ether groups.
  • ethoxylation and / or propoxylation products of N-alkylamines, vicinal diols, fatty acid esters and fatty acid amides which correspond to said long-chain alcohol derivatives with respect to the alkyl moiety and of alkylphenols having 5 to 12 carbon atoms in the alkyl radical are useful.
  • Suitable anionic surfactants are in particular soaps and those which contain sulfate or sulfonate groups with preferably alkali ions as cations.
  • Usable soaps are preferably the alkali salts of the saturated or unsaturated fatty acids having 12 to 18 carbon atoms. Such fatty acids can also be used in incompletely neutralized form.
  • Useful surfactants of the sulfate type include the salts of the sulfuric acid half-esters of fatty alcohols having 12 to 18 carbon atoms and the sulfation products of said nonionic surfactants having a low degree of ethoxylation.
  • Suitable surfactants of the sulfonate type include linear alkylbenzenesulfonates having 9 to 14 carbon atoms in the alkyl moiety, alkane sulfonates having 12 to 18 carbon atoms, and olefin sulfonates having 12 to 18 carbon atoms, which are formed in the reaction of corresponding monoolefins with sulfur trioxide, and alpha-sulfofatty acid esters resulting from the sulfonation of fatty acid methyl or ethyl esters.
  • Cationic surfactants are preferably selected from esterquats and / or quaternary ammonium compounds (QAV) according to the general formula (R ') (R ") (R"') (R IV ) N + X " , in which R 1 to R iv are 22 alkyl, C 7 28 arylalkyl radicals, or heterocyclic radicals, or in the case of an aromatic compound such as pyridine-even three groups together with the nitrogen atom forming the heterocycle, for example a pyridinium or imidazolinium
  • QAV quaternary ammonium compounds
  • QACs are formed by reaction of tertiary amines with Alkylating agents such as methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide produced.
  • Alkylating agents such as methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide produced.
  • Amines which have three long alkyl radicals or hydroxy-substituted alkyl radicals are less reactive and are quaternized, for example, with dimethyl sulfate.
  • suitable QACs are benzalkonium chloride (N alkyl-N, N dimethyl-benzylammonium chloride), benzalkone B (m, p-dichlorobenzyl-dimethyl-C 12 -alkylammonium chloride, benzoxonium chloride (benzyl-dodecyl-bis (2-hydroxyethyl) -ammonium chloride ), Cetrimonium bromide (N-hexadecyl-N, N-trimethyl-ammonium bromide), benzetonium chloride (N, N-dimethyl-N [2- [2- [2- [p- (1,1,3,3-tetramethylbutyl) -phenoxy] -ethoxy] ethylbenzylammonium chloride),
  • Esterquats are here compounds of the general formula VI,
  • R 5 is an alkyl or alkenyl radical having 12 to 22 carbon atoms and 0, 1, 2 or 3 double bonds
  • R 6 and R 7 are independently H, OH or O (CO)
  • R 5 , s, t and u are each independently of the other the value 1, 2 or 3
  • X is an anion, in particular halide, methosulphate, methophosphate or phosphate and mixtures thereof
  • R 6 are the group O (CO) R 5 and for R 5 contain an alkyl radical having 16 to 18 carbon atoms.
  • Particularly preferred are compounds in which R 7 additionally represents OH.
  • Examples of compounds of the formula (VI) are methyl N- (2-hydroxyethyl) -N, N di (tallowacyl oxyethyl) ammonium methosulfate, bis (palmitoyl) ethyl hydroxyethyl methyl ammonium methosulfate or methyl N, N-bis (acyloxyethyl) -N- (2-hydroxyethyl) ammonium methosulfate quaternized compounds of the formula (VI) which have unsaturated groups are preferred, the acyl groups whose k corresponding fatty acids have an iodine value between 5 and 80, preferably between 10 and 60 and in particular between 15 and 45 and / or which has a cis / trans isomer ratio (in mol%) of greater than 30:70, preferably greater than 50:50 and in particular greater than 70:30.
  • Surfactants are present in the detergents according to the invention in proportions of preferably from 5% by weight to 50% by weight, in particular from 8% by weight to 30% by weight. Particularly in laundering agents, preferably up to 30% by weight, in particular from 5% by weight to 15% by weight, of surfactants, among these preferably at least partially cationic surfactants, are used.
  • An agent according to the invention preferably contains at least one water-soluble and / or water-insoluble, organic and / or inorganic builder.
  • the water-soluble organic builder substances include polycarboxylic acids, in particular citric acid and sugar acids, monomeric and polymeric aminopolycarboxylic acids, in particular methylglycine diacetic acid, nitrilotriacetic acid and ethylenediaminetetraacetic acid and polyaspartic acid, polyphosphonic acids, in particular aminotris (methylenephosphonic acid), ethylenediaminetetrakis (methylenephosphonic acid) and 1-hydroxyethane-1, 1-diphosphonic acid, polymeric hydroxy compounds such as dextrin and polymeric (poly) carboxylic acids, in particular the accessible by oxidation of polysaccharides polycarboxylates of European Patent EP 0 609 273, polymeric acrylic acids, methacrylic acids, maleic acids and copolymers thereof, which also small amounts of polymerizable May contain copo
  • the molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 5,000 and 200,000, that of the copolymers between 2,000 and 200,000, preferably 50,000 to 120,000, in each case based on the free acid.
  • a particularly preferred acrylic acid-maleic acid copolymer has a molecular weight of 50,000 to 100,000.
  • Suitable, although less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of the acid is at least 50% by weight.
  • the first acidic monomer or its salt is derived from a monoethylenically unsaturated C 3 -C 8 bonklare -carbonyl and preferably from a C 3 -C 4 monocarboxylic acid, in particular (meth) -acryl- acid from.
  • the second acidic monomer or its salt may be a derivative of a C 4 -C 8 dicarboxylic acid, with maleic acid being particularly preferred.
  • the third monomeric unit is formed in this case of vinyl alcohol and / or preferably an esterified vinyl alcohol.
  • vinyl alcohol derivatives which are an ester of short chain carboxylic acids, for example of C 1 -C 4 carboxylic acids, with vinyl alcohol.
  • Preferred polymers contain 60 wt .-% to 95 wt .-%, in particular 70 wt .-% to 90 wt .-% of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, and maleic acid or Maleinate and 5 wt .-% to 40 wt .-%, preferably 10 wt .-% to 30 wt .-% of vinyl alcohol and / or vinyl acetate.
  • the second acidic monomer or its salt may also be a derivative of an allylsulfonic acid which is in the 2-position with an alkyl radical, preferably with a C 1 -C 4 -alkyl radical, or an aromatic radical which is preferably derived from benzene or benzene derivatives derives, is substituted.
  • Preferred terpolymers contain from 40% by weight to 60% by weight, in particular from 45 to 55% by weight, of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, from 10% by weight to 30% by weight. %, preferably 15 wt .-% to 25 wt .-% methallylsulfonic acid or Methallylsulfonat and as the third monomer 15 wt .-% to 40 wt .-%, preferably 20 wt .-% to 40 wt .-% of a carbohydrate.
  • This carbohydrate may be, for example, a mono-, di-, oligo- or polysaccharide, mono-, di- or oligosaccharides being preferred. Particularly preferred is sucrose.
  • the use of the third monomer presumably incorporates predetermined breaking points into the polymer which are responsible for the good biodegradability of the polymer.
  • These terpolymers generally have a molecular weight between 1,000 and 200,000, preferably between 200 and 50,000 and in particular between 3,000 and 10,000.
  • Further preferred copolymers are those which have as monomers acrolein and acrylic acid / acrylic acid salts or vinyl acetate.
  • the organic builder substances can be used, in particular for the preparation of liquid agents, in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions. All of the acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.
  • organic builder substances may be present in amounts of up to 40% by weight, in particular up to 25% by weight and preferably from 1% by weight to 8% by weight. Quantities close to the stated upper limit are preferably used in paste-form or liquid, in particular water-containing, agents according to the invention.
  • laundry after-care compositions according to the invention may also be free of organic builder.
  • Suitable water-soluble inorganic builder materials are, in particular, alkali metal silicates and polyphosphates, preferably sodium triphosphate.
  • water-insoluble, water-dispersible inorganic builder materials in particular crystalline or amorphous alkali metal nanosilicates, in amounts of up to 50% by weight, preferably not more than 40% by weight, and in liquid gen agents in particular from 1 wt .-% to 5 wt .-%, used.
  • preferred are the detergent grade crystalline sodium aluminosilicates, especially zeolite A, P and optionally X. Amounts near the above upper limit are preferably used in solid, particulate agents.
  • suitable aluminosilicates have no particles with a particle size greater than 30 .mu.m and preferably consist of at least 80% by weight of particles having a size of less than 10 .mu.m.
  • Their calcium binding capacity which can be determined according to the specifications of the German patent DE 24 12 837, is generally in the range of 100 to 200 mg CaO per gram.
  • Suitable substitutes or partial substitutes for the said aluminosilicate are crystalline alkali silicates which may be present alone or in a mixture with amorphous silicates.
  • the alkali metal silicates useful as builders in the compositions according to the invention preferably have a molar ratio of alkali metal oxide to SiO 2 of less than 0.95, in particular of 1: 1, 1 to 1: 12, and may be amorphous or crystalline.
  • Preferred alkali metal silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio of Na 2 O: SiO 2 of 1: 2 to 1: 2.8.
  • crystalline silicates which may be present alone or in admixture with amorphous silicates, are crystalline layer silicates with the general formula Na 2 Si x O 2x + I y H 2 O are used in which x, known as the modulus, an integer of 1, 9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4.
  • Preferred crystalline phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicates are preferred.
  • amorphous alkali silicates practically anhydrous crystalline alkali silicates of the abovementioned general formula in which x is a number from 1, 9 to 2.1, can be used in inventive compositions.
  • a crystalline sodium layer silicate with a modulus of 2 to 3 is used, as can be prepared from sand and soda. Crystalline sodium silicates with a modulus in the range of 1.9 to 3.5 are used in a further preferred embodiment of compositions according to the invention.
  • the weight ratio of aluminosilicate to silicate is preferably 1:10 to 10: 1.
  • the weight ratio of amorphous alkali metal silicate to crystalline alkali metal silicate is preferably 1: 2 to 2: 1 and especially 1: 1 to 2: 1.
  • Builder substances are preferably present in the detergents according to the invention in amounts of up to 60% by weight, in particular from 5% by weight to 40% by weight.
  • Laundry aftertreatment agents according to the invention are preferably free of inorganic builder.
  • Suitable peroxygen compounds are, in particular, organic peracids or pers acid salts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid or salts of diperdodecanedioic acid, hydrogen peroxide and inorganic salts which release hydrogen peroxide under the conditions of use, such as perborate, percarbonate and / or persilicate.
  • solid peroxygen compounds are to be used, they can be used in the form of powders or granules, which can also be enveloped in a manner known in principle. Particular preference is given to using alkali metal percarbonate, alkali metal percarbonate monohydrate or, in particular, in liquid media, hydrogen peroxide in the form of aqueous solutions which contain from 3% by weight to 10% by weight of hydrogen peroxide. If a detergent according to the invention contains peroxygen compounds, these are present in amounts of preferably up to 50% by weight, in particular from 5% by weight to 30% by weight. The addition of small amounts of known bleach stabilizers such as phosphonates, borates or metaborates and metasilicates and magnesium salts such as magnesium sulfate may be useful.
  • bleach stabilizers such as phosphonates, borates or metaborates and metasilicates and magnesium salts such as magnesium sulfate may be useful.
  • bleach activators it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
  • Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups.
  • polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5-diacetoxy- 2,5-dihydrofuran and enol esters
  • TAED
  • Hydrophilic substituted acyl acetals and acyl lactams are also preferably used.
  • Combinations of conventional bleach activators can also be used.
  • Such bleach activators are contained in the customary amount range, preferably in amounts of from 1% by weight to 10% by weight, in particular from 2% by weight to 8% by weight, based on the total agent.
  • Transition metal complexes may be included as so-called bleach catalysts.
  • Suitable transition metal compounds include, in particular, manganese, iron, cobalt, ruthenium or molybdenum-salene complexes and their N-analogues, manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes, manganese, iron, , Cobalt, ruthenium, molybdenum, titanium, vanadium, and copper complexes with nitrogen-containing tripod ligands, cobalt, iron, copper, and ruthenium-ammine complexes.
  • Bleach-enhancing transition metal complexes in particular having the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, are used in customary amounts, preferably in an amount of up to 1% by weight, in particular 0.0025% by weight. % to 0.25 wt .-% and particularly preferably from 0.01 wt .-% to 0.1 wt .-%, each based on the total agent used.
  • Suitable enzymes which can be used in the compositions are those from the class of proteases, cutinases, amylases, pullulanases, hemicellulases, cellulases, lipases, oxidases and peroxidases and mixtures thereof. Particularly suitable are from fungi or bacteria, such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes or Pseudomonas cepacia derived enzymatic agents.
  • the optionally used enzymes may be adsorbed to carriers and / or embedded in encapsulants to protect against premature inactivation. They are preferably not more than 5% by weight, in particular from 0.2% by weight to 2% by weight, in the detergents according to the invention.
  • the agents may contain, for example, derivatives of diaminostilbenedisulfonic acid or their alkali metal salts as optical brighteners.
  • salts of 4,4'-bis (2-anilino-4-morpholino-1, 3,5-triazinyl-6-amino) stilbene-2,2'-disulphonic acid or compounds of similar construction which are used instead of the morpholino Group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group.
  • brighteners of the substituted diphenylstyrene type may be present, for example the alkali metal salts of 4,4'-bis (2-sulfostyryl) -diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) -diphenyls. Mixtures of the aforementioned brightener can be used.
  • Suitable foam inhibitors include, for example, organopolysiloxanes and mixtures thereof with microfine, optionally silanized silica and also Pa raffinwachse and mixtures thereof with silanated silica or bis-fatty acid alkylenediamides. It is also advantageous to use mixtures of various foam inhibitors, for example those of silicones, paraffins or waxes.
  • the foam inhibitors, especially silicone and / or paraffin-containing foam inhibitors are a granular, water-soluble or dispersible carrier substance bound. In particular, mixtures of paraffin waxes and bistearylethylenediamides are preferred.
  • compositions may also contain components which positively influence the oil and Fettauswaschles from textiles, so-called soil release agents. This effect is particularly evident when a textile is dirty, which has been previously washed several times with a detergent according to the invention, which contains this oil and fat dissolving component.
  • nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose with a proportion of methoxyl groups of 15 to 30% by weight and of hydroxypropoxyl groups of 1 to 15% by weight, based in each case on the nonionic cellulose ethers, as well as the known from the prior art polymers of phthalic acid and / or terephthalic acid or derivatives thereof with monomeric and / or polymeric diols, especially polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionic modified Derivatives of these.
  • compositions may also color transfer inhibitors, preferably in amounts of from 0.1 wt .-% to 2 wt .-%, in particular 0.1 wt .-% to 1 wt .-%, containing in a preferred embodiment of the invention polymers Vinylpyrrolidone, vinylimidazole, vinylpyridine N-oxide or copolymers of these are.
  • enzymatic systems comprising a peroxidase and hydrogen peroxide or a substance which gives off hydrogen peroxide in water.
  • a mediator compound for the peroxidase for example an acetosyringone, a phenol derivative or a phenotiazine or phenoxazine, is preferred in this case, whereby also above-mentioned polymeric Farbübertragungsinhibitorwirkstoffe can be used.
  • Polyvinylpyrrolidone preferably has an average molecular weight in the range from 10 000 to 60 000, in particular in the range from 25 000 to 50 000, for use in compositions according to the invention.
  • those of vinylpyrrolidone and vinylimidazole in a molar ratio of 5: 1 to 1: 1 having an average molecular weight in the range of 5,000 to 50,000, especially 10,000 to 20,000 are preferred.
  • Graying inhibitors have the task of keeping suspended from the textile fiber dirt suspended in the fleet.
  • Water-soluble colloids of mostly organic nature are suitable for this purpose, for example starch, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or of cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • water-soluble polyamides containing acidic groups are suitable for this purpose.
  • starch derivatives can be used, for example aldehyde starches.
  • cellulose ethers such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof, for example in amounts of from 0.1 to 5% by weight, based on the compositions ,
  • organic solvents which can be used in the compositions according to the invention, especially if they are in liquid or pasty form, are alcohols having 1 to 4 C atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols having 2 to 4 C atoms , in particular ethylene glycol and propylene glycol, and mixtures thereof and the derivable from said classes of compound ethers.
  • Such water-miscible solvents are preferably present in the detergents according to the invention in amounts of not more than 30% by weight, in particular from 6% by weight to 20% by weight.
  • the compositions according to the invention may contain system and environmentally acceptable acids, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid, but also mineral acids, in particular sulfuric acid, or bases, in particular ammonium or alkali metal hydroxides.
  • Such pH regulators are preferably not more than 20 wt .-%, in particular from 1, 2 wt .-% to 17 wt .-%, contained in the inventive compositions.
  • compositions according to the invention presents no difficulties and can be carried out in a manner known in the art, for example by spray-drying or granulation, with peroxygen compound and bleach catalyst optionally being added later.
  • peroxygen compound and bleach catalyst optionally being added later.
  • a process comprising an extrusion step is preferred.
  • body care compositions according to the invention are a permanent wave agent, in particular a wave lotion.
  • a wave lotion Under a Wellotion is understood to mean the preparation containing the reducing agent.
  • the reducing agents used are usually mercapto compounds and / or salts of sulfurous acid.
  • Preferred mercapto compounds are thioglycolic acid, their physiologically acceptable salts and their esters. It is further preferred, although to a lesser extent, to use cysteamine, cysteine, thiolactic acid, thiomalic acid, Bunte salts and ⁇ -mercaptoethanesulfonic acid.
  • the well lotions usually contain perfume oils.
  • perfume oils there is the problem that residues of the mercapto compounds remain on the hair even after fixing the perm, in many cases even significantly longer than the perfume oils used. If these hairs are later treated with a slightly perfumed agent, for example a shampoo as part of the customary cleaning, these residues of the mercapto compound successively dissolve from the hair, with appropriate perfume development. This problem can be prevented in an outstanding manner by using the above-defined active ingredients in the well lotions according to the invention.
  • the well lotions may further all known in the art ingredients such as anionic surfactants, zwitterionic surfactants, ampholytic surfactants, nonionic surfactants, cationic surfactants, protein hydrolysates, thickeners, structural, cationic, anionic, zwitterionic, amphoteric and nonionic polymers, solubilizers, substances for adjustment pH, active ingredients such as allantoin, pyrrolidonecarboxylic acids and plant extracts, light stabilizers, chelating agents, swelling and penetrating agents, opacifiers, dyes, perfume oils, pearlescing agents and propellants.
  • active ingredients such as allantoin, pyrrolidonecarboxylic acids and plant extracts, light stabilizers, chelating agents, swelling and penetrating agents, opacifiers, dyes, perfume oils, pearlescing agents and propellants.
  • the active ingredients defined above are used according to the invention in those agents which contain volatile amines. Again, they facilitate the coverage of unwanted scents that go back to these amines.
  • agents are, in addition to the permanent wave agents already mentioned above, for example, hair dyes.
  • the teaching according to the invention can be used to significantly reduce the perfume fraction in detergents, cleaners and personal care products. This makes it possible to offer perfumed products even for those particularly sensitive consumers who can not use normally perfumed products due to specific intolerances and irritations, or only to a limited extent. Skin care products and deodorants as well as hand washing agents should be mentioned in this context. Examples
  • Washing device Miele® Novotronic® W 308
  • Table 1 Detergent compositions used (contents by weight in% by weight)
  • the fabrics were washed 3 times with a detergent W1 of the above composition containing 1% by weight of the active ingredient under the conditions indicated above and dried after the last wash.
  • textiles were treated with the detergent V1, that is, in the absence of the active substance.
  • the textiles were presented to a panel of experts from 30 people and assessed by them odor comparatively.
  • the fragrance impression when using the composition according to the invention was more intense both on wet laundry and on dry laundry than when using W1.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Detergent Compositions (AREA)

Abstract

L'objectif de la présente invention est d'améliorer l'adhérence de substances odorantes sur des surfaces, par exemple sur des surfaces de textiles, d'objets durs ou du corps humain. Cet objectif est essentiellement atteint grâce à l'utilisation de composés de polycarbonate, de polyuréthane et/ou de polyurée-polyorganosiloxane, ou d'un composé précurseur pouvant être utilisé lors de la production de ceux-ci, lequel composé comporte des groupes réactifs définis, pour fixer des substances odorantes sur des surfaces dures et/ou molles.
PCT/EP2008/053991 2007-04-03 2008-04-03 Fixation de substances odorantes d'agents de lavage et de nettoyage sur des surfaces dures et molles WO2008119830A2 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
DE102007016383A DE102007016383A1 (de) 2007-04-03 2007-04-03 Fixierung von Duftstoffen aus Wasch- und Reinigungsmitteln an harten und weichen Oberflächen
DE102007016383.7 2007-04-03
DE102007023874.8 2007-05-21
DE200710023874 DE102007023874A1 (de) 2007-05-21 2007-05-21 Fixierung von Duftstoffen aus Wasch- und Reinigungsmitteln an harten und weichen Oberflächen
DE102007038453.1 2007-08-14
DE200710038453 DE102007038453A1 (de) 2007-08-14 2007-08-14 Fixierung von Duftstoffen aus Wasch- und Reinigungsmitteln an harten und weichen Oberflächen

Publications (2)

Publication Number Publication Date
WO2008119830A2 true WO2008119830A2 (fr) 2008-10-09
WO2008119830A3 WO2008119830A3 (fr) 2009-04-09

Family

ID=39647070

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2008/053991 WO2008119830A2 (fr) 2007-04-03 2008-04-03 Fixation de substances odorantes d'agents de lavage et de nettoyage sur des surfaces dures et molles

Country Status (1)

Country Link
WO (1) WO2008119830A2 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0397245A2 (fr) * 1989-05-11 1990-11-14 The Procter & Gamble Company Particules de parfum destinées aux compositions de nettoyage et de conditionnement
WO2005041918A1 (fr) * 2003-10-31 2005-05-12 Firmenich Sa Systeme de liberation de parfums pour produits de nettoyage et d'entretien de surfaces
EP1541568A1 (fr) * 2003-12-09 2005-06-15 Deutsches Wollforschungsinstitut an der Rheinisch-Westfälischen Technischen Hochschule Aachen e.V. Carbonates et urées cycliques et réactifs pour la modification de biomolecules, polymères et surfaces
WO2006069742A1 (fr) * 2004-12-23 2006-07-06 Basf Aktiengesellschaft Compose urethanne contenant de maniere incorporee un derive de silicone renfermant des groupes polyether, et un heterocycle d'azote

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0397245A2 (fr) * 1989-05-11 1990-11-14 The Procter & Gamble Company Particules de parfum destinées aux compositions de nettoyage et de conditionnement
WO2005041918A1 (fr) * 2003-10-31 2005-05-12 Firmenich Sa Systeme de liberation de parfums pour produits de nettoyage et d'entretien de surfaces
EP1541568A1 (fr) * 2003-12-09 2005-06-15 Deutsches Wollforschungsinstitut an der Rheinisch-Westfälischen Technischen Hochschule Aachen e.V. Carbonates et urées cycliques et réactifs pour la modification de biomolecules, polymères et surfaces
WO2006069742A1 (fr) * 2004-12-23 2006-07-06 Basf Aktiengesellschaft Compose urethanne contenant de maniere incorporee un derive de silicone renfermant des groupes polyether, et un heterocycle d'azote

Also Published As

Publication number Publication date
WO2008119830A3 (fr) 2009-04-09

Similar Documents

Publication Publication Date Title
WO2010105873A2 (fr) Substitut de lilial
WO2010105874A1 (fr) Succédané de lilial
WO2006053615A1 (fr) Combinaison de parfum contenant du 3,7-dimethyloct-6-ene nitrile (citronellyle nitrile) comme substitut de geranonitrile
EP1660621B1 (fr) Agents prise sur la surface de substrats
WO2009124908A1 (fr) Agent de lavage ou de nettoyage protégeant les couleurs
EP2487230B1 (fr) Moyen de lavage et de nettoyage protégeant les couleurs
JP2018505944A (ja) 洗浄組成物及び／又は処理組成物
EP2440642B1 (fr) Procédé de réduction de mauvaises odeurs
WO2007079857A1 (fr) Fixation de parfums a partir d'agents de lavage et de nettoyage sur des surfaces dures ou souples
WO2013113444A1 (fr) Procédé d'atténuation de mauvaises odeurs
WO2008119830A2 (fr) Fixation de substances odorantes d'agents de lavage et de nettoyage sur des surfaces dures et molles
EP0989183B1 (fr) Fixage de parfums aux surfaces dures et douces
DE60312372T2 (de) Behandlungszusammensetzungen für wäsche und komponenten dafür
DE102007023874A1 (de) Fixierung von Duftstoffen aus Wasch- und Reinigungsmitteln an harten und weichen Oberflächen
DE102007016383A1 (de) Fixierung von Duftstoffen aus Wasch- und Reinigungsmitteln an harten und weichen Oberflächen
DE102007038453A1 (de) Fixierung von Duftstoffen aus Wasch- und Reinigungsmitteln an harten und weichen Oberflächen
WO2007079860A1 (fr) Fixation de substances odorantes à partir d'agents de lavage et de détergents
EP2211829B1 (fr) Amélioration de l'effet parfumant d'esters de substances odorantes
EP0834551A2 (fr) Fixation des parfums de détergents sur les surfaces
WO2010142480A1 (fr) Produit de lavage, de nettoyage ou d'entretien parfumé
DE102009026858A1 (de) Wasch-, Reinigungs- oder Pflegemittel zur Verminderung von Schlechtgerüchen
DE102007023828A1 (de) Farbschützendes Wasch- oder Reinigungsmittel
DE102007038450A1 (de) Farbschützendes Wasch- oder Reinigungsmittel
DE102007016391A1 (de) Farbschützendes Wasch- oder Reinigungsmittel

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 08735740

Country of ref document: EP

Kind code of ref document: A2

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 08735740

Country of ref document: EP

Kind code of ref document: A2