EP0972823B1 - Compositions détergents liquides, non aqueuses contenant un agent de blanchiment - Google Patents

Compositions détergents liquides, non aqueuses contenant un agent de blanchiment Download PDF

Info

Publication number
EP0972823B1
EP0972823B1 EP99113021A EP99113021A EP0972823B1 EP 0972823 B1 EP0972823 B1 EP 0972823B1 EP 99113021 A EP99113021 A EP 99113021A EP 99113021 A EP99113021 A EP 99113021A EP 0972823 B1 EP0972823 B1 EP 0972823B1
Authority
EP
European Patent Office
Prior art keywords
alkyl
group
nonaqueous liquid
agents
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP99113021A
Other languages
German (de)
English (en)
Other versions
EP0972823A1 (fr
Inventor
Bernd Dr. Richter
Ulrich Dr. Pegelow
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.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and 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
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0972823A1 publication Critical patent/EP0972823A1/fr
Application granted granted Critical
Publication of EP0972823B1 publication Critical patent/EP0972823B1/fr
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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary ammonium 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
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3947—Liquid compositions

Definitions

  • the present invention relates to non-aqueous, liquid detergents for washing or cleaning, which contain non-ionic surfactant (s), builders (s) and bleach and one have increased bleach stability. Another aspect of the invention relates to Use of special stabilizers to stabilize bleach in non-aqueous liquid washing and / or cleaning agents.
  • EP 340 989 proposes to use C 5-21 fatty acids, fatty acid salts or fatty acid glyceryl mono- or diesters as stabilizers in non-aqueous liquid detergents which contain bleaching agents and bleach activators.
  • the use of vicinal hydroxy compounds for this purpose is disclosed in EP 344 909 (Colgate).
  • WO93 / 06201 (Henkel) describes a non-aqueous, liquid to pasty washing or cleaning agent containing 5 to 20% by weight of hydrated zeolite A, 50 to 80% by weight of anionic and / or nonionic surfactant, 5 to 20% by weight. -% bleach, up to 6% by weight of bleach activator and up to 6% by weight of a complexing agent for heavy metals.
  • WO96 / 10072 discloses a process for producing non-aqueous bleach-containing liquid detergents which have high chemical and physical stability and outstanding washing and bleaching results by suspending fine-grain detergent components in a non-aqueous liquid matrix made from alcohol ethoxylates.
  • the present invention was based on the object of containing a stable bleach to provide liquid detergents and cleaners which are solid Contains bleach in the form of a stable dispersion.
  • the bleaches are not supposed to Loss of activity, even if the funds are stored for a longer period become.
  • non-aqueous includes means understand that only small amounts of free, so not as crystal water or in any other Way bound to contain water. Because even non-aqueous solvents and raw materials (especially such technical qualities) have certain water contents completely water-free agents on an industrial scale only with great effort and high cost to manufacture.
  • non-aqueous agents of the present invention thus small amounts of free water tolerable, preferably less than 5% by weight below 2% by weight, based in each case on the finished composition.
  • the liquid agents of the present invention can be used within a wide range of viscosities getting produced. So not only are viscous and easily movable according to the invention Medium can be produced, but also viscous to pasty medium higher viscosities. The consistency of the pasty agents can also be spreadable or be able to cut - the use of cationic stabilizers also leads to such agents to the effects of bleach stabilization according to the invention.
  • the cationic stabilizing agents can be used in varying amounts in the inventive Funds are brought in.
  • the content of the invention Agents of cationic stabilizers of the formulas mentioned 0.5 to 10 % By weight, preferably 1 to 6% by weight and in particular 2 to 4% by weight.
  • Cationic stabilizers which are to be used preferentially are caused by the esterification obtained from triethanolamine with long-chain fatty acids and subsequent quaternization. Both the esterification and the quaternization take place in a manner known per se Manner, wherein the use of dimethyl sulfate as the quaternizing reagent is preferred is.
  • Preferred agents contain one as a cationic stabilizing agent quaternized triethanolamine ester.
  • Such cationic stabilizers are commercially available, for example, under the names Stepantex® VA 90, Stepantex® VS 90 (trademark of Stepan) or Dehyquart® AU 46 or Dehyquart® AU 57 (trademark of Henkel / Pulcra).
  • the cationic stabilizers to be used according to the invention can be used alone or in combination with other stabilizing agents known from the prior art can be used together.
  • the stabilizing agents described in the prior art can be divided into three large groups: antioxidants, drying agents and complexing agents.
  • Phenols, bisphenols and thiobisphenols substituted by sterically hindered groups can be used as antioxidants.
  • Other substance classes are aromatic amines, preferably secondary aromatic amines and substituted p-phenylenediamines, phosphorus compounds with trivalent phosphorus such as phosphines, phosphites and phosphonites, compounds containing endiol groups, so-called reductones, such as ascorbic acid and its derivatives, organosulfur compounds, such as the esters of 3 , 3'-thiodipropionic acid with C 1-18 alkanols, in particular C 10-18 alkanols, metal ion deactivators which are able to complex the metal ions catalyzing the autooxidation, such as copper, such as EDTA, nitrilotriacetic acid, etc and their mixtures.
  • a large number of examples of such antioxidants is summarized in DE 196 16 570 (BASF AG) - the antioxidants
  • Desiccants in the context of the present invention in combination with cationic Stabilizers can be used, for example, inorganic Salts that are capable of hydrate formation and thereby bind free water.
  • exemplary anhydrous magnesium or sodium sulfate may be mentioned here.
  • over-dried Silicates and aluminum silicates such as aerogels or over-dried zeolites belong to this connection class.
  • organic ones can also be used
  • Use desiccants examples of which are substances that absorb water swell and the absorbed water under the conditions in the non-aqueous Do not dispense liquid washing or cleaning agents. For example, fall into this class Cellulose and starch and their derivatives such as carboxymethyl cellulose and starch, hydroxypropyl cellulose and starch, etc.
  • alkali metal salts of ethylenediaminetetraacetic acid fall into the group of complexing agents (EDTA) or nitrilotriacetic acid (NTA) and alkali metal salts of anionic polyelectrolytes such as polyacrylates, polymaleates and polysulfonates.
  • EDTA complexing agents
  • NTA nitrilotriacetic acid
  • anionic polyelectrolytes such as polyacrylates, polymaleates and polysulfonates.
  • Farther are low molecular weight hydroxycarboxylic acids such as citric acid, tartaric acid, malic acid or gluconic acid and its salts.
  • Suitable complexing agents can also be selected from organophosphonates such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP), Aminotri (methylenephosphonic acid) (ATMP), Diethylenetriaminepenta (methylenephosphonic acid) and 2-phosphonobutane-1,2,4-tricarboxylic acid (PBS-AM). These complexing agents can be used, for example, in amounts between 0.1 and 5% by weight, preferably in amounts of around 1% by weight, in the agents according to the invention be introduced.
  • organophosphonates such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP), Aminotri (methylenephosphonic acid) (ATMP), Diethylenetriaminepenta (methylenephosphonic acid) and 2-phosphonobutane-1,2,4-tricarboxylic acid (PBS-AM).
  • organophosphonates such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP), Aminotri (methylenephosphonic acid) (ATMP
  • the agents according to the invention contain one or more nonionic surfactant (s) as an essential component.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or can contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • EO ethylene oxide
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
  • the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 9-11 alcohol with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12-14 alcohol with 3 EO and C 12-18 alcohol with 5 EO.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • alkyl glycosides of the general formula RO (G) x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.
  • nonionic surfactants which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, such as them are described, for example, in Japanese patent application JP 58/217598 or which are preferably produced by the process described in international patent application WO-A-90/13533 .
  • nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half of it.
  • Suitable surfactants are polyhydroxy fatty acid amides of the formula (IV), in which RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms, R 5 for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (V) in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 6 represents a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R 7 represents a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, C 1-4 -alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this remainder.
  • V formula (V) in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 6 represents a linear, branched or cyclic alkyl radical
  • [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a reduced sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can then, for example according to the teaching of international application WO-A-95/ 07331, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • non-aqueous liquid detergents are preferred the 5 to 70% by weight, preferably 15 to 65% by weight and in particular 20 to 60% by weight one or more nonionic surfactants from the group of the alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, alcohols and / or carboxylic acids with 8 to 28, preferably 10 to 20 and in particular 12 to 18 carbon atoms, contain.
  • the agents according to the invention can contain anionic surfactants.
  • Anionic surfactants used are, for example, those of the sulfonate and sulfate type.
  • the surfactants of the sulfonate type are preferably C 9-13- alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C 12-18 monoolefins with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
  • alkanesulfonates obtained from C 12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • the esters of ⁇ -sulfofatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.
  • Suitable anionic surfactants are sulfonated fatty acid glycerol esters.
  • fatty acid glycerol esters the mono-, di- and triesters and their mixtures are to be understood as they in the production by esterification of a monoglycerin with 1 to 3 moles of fatty acid or obtained in the transesterification of triglycerides with 0.3 to 2 mol of glycerol.
  • Preferred sulfonated fatty acid glycerol esters are the sulfonation products of saturated Fatty acids with 6 to 22 carbon atoms, for example caproic acid, caprylic acid, Capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
  • alk (en) yl sulfates are the alkali and especially the sodium salts of the sulfuric acid half esters of C 12 -C 18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
  • C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates as well as C 14 -C 15 alkyl sulfates are preferred from the point of view of washing technology.
  • 2,3-Alkyl sulfates which are produced, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from the Shell Oil Company under the name DAN®, are also suitable anionic surfactants.
  • the sulfuric acid monoesters of the straight-chain or branched C 7-21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide such as 2-methyl-branched C 9-11 alcohols with an average of 3.5 mol of ethylene oxide (EO) or C 12-18 - Fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.
  • Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols.
  • alcohols preferably fatty alcohols and especially ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8-18 fatty alcohol residues or mixtures thereof.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue, which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below).
  • sulfosuccinates the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • Soaps are particularly suitable as further anionic surfactants.
  • saturated fatty acid soaps such as the salts of lauric acid, myristic acid, palmitic acid, Stearic acid, hydrogenated erucic acid and behenic acid and in particular from natural Fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.
  • the anionic surfactants including the soaps can be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono- or dioder Triethanolamine.
  • the anionic surfactants are preferably in the form their sodium or potassium salts, especially in the form of the sodium salts.
  • Preferred liquid detergents additionally contain anionic surfactants, preferably from the group of alkyl sulfates, alkyl sulfonates, alkyl benzene sulfonates and fatty acid soaps.
  • non-aqueous liquid builders In addition to surfactant components and the cationic stabilizer the non-aqueous liquid builders according to the invention.
  • Builders usually used in detergents and cleaning agents in the washing and Detergent tablets are introduced, in particular thus zeolites, silicates, Carbonates, organic cobuilders and -where no ecological prejudices against theirs Use also - the phosphates.
  • Suitable crystalline, layered sodium silicates have the general formula NaMSi x O 2x + 1 .H 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4.
  • M sodium or hydrogen
  • x is a number from 1.9 to 4
  • y is a number from 0 to 20 and preferred values for x 2, 3 or 4.
  • Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514 .
  • Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicate Na 2 Si 2 O 5 .yH 2 O are preferred, wherein ⁇ -sodium disilicate can be obtained, for example, by the method described in international patent application WO-A-91/08171 .
  • the delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying.
  • the term “amorphous” is also understood to mean “X-ray amorphous”.
  • silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle.
  • it can very well lead to particularly good builder properties if the silicate particles provide washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred.
  • Such so-called X-ray amorphous silicates which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024 .
  • Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.
  • the finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P.
  • zeolite P zeolite MAP® (commercial product from Crosfield) is particularly preferred.
  • zeolite X and mixtures of A, X and / or P are also suitable.
  • zeolite X and zeolite A (about 80% by weight of zeolite X)
  • VEGOBOND AX® sold by CONDEA Augusta SpA under the brand name VEGOBOND AX® and by the formula nNa 2 O ⁇ (1-n) K 2 O ⁇ Al 2 O 3 ⁇ (2 - 2.5) SiO 2 ⁇ (3.5 - 5.5) H 2 O
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
  • the zeolites can also be used as over-dried zeolites with lower water contents and are then suitable due to their hygroscopicity for removing unwanted traces of free water.
  • the sodium salts of the orthophosphates are particularly suitable, the pyrophosphates and especially the tripolyphosphates.
  • Useful organic builders are, for example, those in the form of their sodium salts usable polycarboxylic acids, such as citric acid, adipic acid, succinic acid, Glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and Mixtures of these.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, Adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures from these, with sodium citrate being particularly preferred.
  • the amount of builders in the agents according to the invention is usually 1 to 30 % By weight, preferably 10 to 25% by weight.
  • Preferred non-aqueous liquid detergents contain as builders water-soluble builders, preferably from the group of Oligo- and polycarboxylates, the carbonates and the crystalline and / or amorphous silicates.
  • the salts of citric acid have been found to be special proven suitable, the alkali and, in particular, the sodium salts preferred are.
  • the non-aqueous liquid detergents for washing or cleaning contain one or more bleaching agents.
  • bleaching agents include sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Further bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid.
  • the amount of bleaching agent in the agents according to the invention is usually above 10% by weight, preferably between 15 and 35% by weight and in particular between 20 and 30% by weight, in each case based on the total agent.
  • the agents according to the invention can contain further ingredients of detergents and cleaning agents, for example from the group bleach activators, enzymes, pH regulators, fragrances, perfume carriers, fluorescent agents, Dyes, foam inhibitors, silicone oils, anti-redeposition agents, optical Brighteners, graying inhibitors, color transfer inhibitors and corrosion inhibitors.
  • group bleach activators enzymes, pH regulators, fragrances, perfume carriers, fluorescent agents, Dyes, foam inhibitors, silicone oils, anti-redeposition agents, optical Brighteners, graying inhibitors, color transfer inhibitors and corrosion inhibitors.
  • bleach activators can be incorporated into the agents according to the invention become.
  • bleach activators can be compounds that are under perhydrolysis conditions aliphatic peroxocarboxylic acids with preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid, be used.
  • Suitable substances are the O- and / or N-acyl groups of the above C number of carbon atoms and / or optionally substituted benzoyl groups.
  • TAED tetraacety
  • bleaching catalysts can be incorporated into the agents according to the invention.
  • These substances are bleach-enhancing transition metal salts or Transition metal complexes such as Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru amine complexes can be used as bleaching catalysts.
  • the content of bleach activators or bleach catalysts in the agents according to the invention can be between 1 and 15% by weight, preferably between 2 and 12% by weight and in particular between 5 and 10% by weight.
  • Enzymes come from the class of proteases, lipases, amylases, cellulases or their mixtures in question.
  • Bacterial strains or are particularly well suited Mushrooms such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus enzymatic agents.
  • Proteases of the subtilisin type and in particular are preferred Proteases obtained from Bacillus lentus are used.
  • enzyme mixtures for example from protease and amylase or protease and lipase or Protease and cellulase or from cellulase and lipase or from protease, amylase and Lipase or protease, lipase and cellulase, but in particular mixtures containing cellulase of special interest.
  • Peroxidases or oxidases have also been found in some Cases proved to be suitable.
  • the enzymes can be adsorbed on carriers and / or embedded in coating substances in order to prevent them from premature decomposition protect.
  • the proportion of the enzymes, enzyme mixtures or enzyme granules in the inventive For example, about 0.1 to 10 wt .-%, preferably 0.5 to be about 5% by weight.
  • the agents according to the invention can also contain components which positively affect the oil and fat washability from textiles (so-called soil repellents). This effect becomes particularly clear when a textile is soiled previously several times with a detergent according to the invention, the oil and contains fat-dissolving component, was washed.
  • nonionic cellulose ethers such as methyl cellulose and methylhydroxy-propyl cellulose with a proportion of methoxyl groups of 15 to 30 wt .-% and of hydroxypropoxyl groups of 1 to 15 wt .-%, each based on the non-ionic cellulose ether, as well as those known from the prior art
  • Polymers of phthalic acid and / or terephthalic acid or of their derivatives in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives of these.
  • the sulfonated derivatives of phthalic and are particularly preferred Terephthalic acid polymers.
  • the non-aqueous agents for washing or cleaning can be used as optical brighteners contain the diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'disulfonic acid or similarly structured compounds that replace the morpholino group a diethanolamino group, a methylamino group, an anilino group or carry a 2-methoxyethylamino group. Brighteners of the substituted type can also be used Diphenyl styrenes are present, e.g.
  • Dyes and fragrances are added to the agents according to the invention in order to improve the aesthetics Improve impression of the products and the consumer in addition to the washing or Cleaning performance a visually and sensory "typical and distinctive" product to provide.
  • perfume oils or fragrances individual fragrance compounds, e.g. synthetic products of the ester, ether, aldehyde, ketone type, Alcohols and hydrocarbons can be used. Fragrance compounds of the type the esters are e.g.
  • the ethers include, for example, benzyl ethyl ether and the aldehydes e.g.
  • the linear alkanals with 8-18 C atoms citral, citronellal, citronellyloxyacetaldehyde, Cyclamenaldehyde, Hydroxycitronellal, Lilial and Bourgeonal
  • ketones e.g. the Jonone, ⁇ -isomethyl ionone and methyl cedryl ketone
  • Citronellol Citronellol
  • eugenol geraniol
  • linalool phenylethyl alcohol and terpineol
  • perfume oils can also contain natural fragrance mixtures included as they are available from plant sources, e.g. Pine, Citrus, Jasmine, patchouly, rose or ylang-ylang oil. Muscatels are also suitable, Sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, Vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, Neroliol, orange peel oil and sandalwood oil.
  • the fragrances can be incorporated directly into the agents according to the invention but it can also be advantageous to apply the fragrances to the carrier, which have the liability of the perfume on the laundry and by a slower fragrance release for long-lasting fragrance of the textiles.
  • Such carrier materials have, for example Cyclodextrins have proven themselves, with the cyclodextrin-perfume complexes additionally can be coated with other auxiliaries.
  • the agents according to the invention can be dyed with suitable dyes.
  • Preferred dyes their selection the expert has no difficulty, have a high storage stability and Insensitivity to the other ingredients of the agent and to light as well no pronounced substantivity towards textile fibers in order not to dye them.
  • the viscosity of the non-aqueous liquid compositions according to the invention can be adapted to the special requirements of different fields of application. In this way it is possible to formulate viscous and easily movable agents, but also viscous to pasty agents for washing or cleaning, which are known in the market as gels, can be produced. Agents which do not flow under the influence of gravity, that is to say are no longer pourable and have a consistency which can be spread or cut, can also be produced without problems in the context of the present invention.
  • T 70 ° C., shear rate: 100 s -1
  • a significantly higher viscosity may be indicated - this can lead to dimensionally stable masses in which a viscosity in the above sense can no longer be meaningfully stated .
  • the agents according to the invention are produced in a manner known per se Mixing the ingredients in stirred tanks. Unless it's for a specific end product is desired, the solids contained in the agents according to the invention can by be further crushed a wet grinding step to ensure the separation stability of the agents to increase further.
  • Such operations familiar to the person skilled in the art are suitable, for example Colloid mills, roller mills or annular gap or agitator ball mills.
  • the cationic stabilizing agents to be used according to the invention can be added take place at any point in such a conventional manufacturing process. For example it is possible to coat the bleach with the cationic stabilizers and these coat bleach particles in a stirred tank to the other ingredients to give, whereby here, of course, a grinding step can follow. Also one Add the cationic stabilizing agent as a solid or pasty pure substance or as Solution is easily possible both before and after a grinding step. Usually bleach and bleach activators are not used together before Grinding incorporated into the media because the intimate contact of the substances during the grinding process decomposes them can promote. If the bleach activators are added after a grinding step, the cationic stabilizers can be added in this stirring and homogenization step be, it is of course also possible to use the bleach activators to coat the cationic stabilizers.
  • the use of the compounds mentioned leads to liquid agents which have increased bleach stability and which also maintain this property over long storage intervals.
  • the isothermal microcalometry has proven to be particularly suitable.
  • the heat of the usually exothermic decomposition reaction is also detected very sensitively in small sample quantities.
  • the stability compared to the decomposition of a given system the smaller the smaller in one amount of heat produced is in joules for a certain period of time.
  • TAM 2277 microcalorimeter was used for the present investigations (Thermometric AB, Sweden). This continuously records the pro Unit of heat generated in a sample in watts.
  • the investigated liquid detergent E according to the invention contained a cationic stabilizing agent, while the comparative example V was free of the stabilizing agents used according to the invention. Small amounts of water and Fe (III) ions were added to both formulations in order to simulate realistic conditions (contamination from production plants, etc.).
  • the composition of the liquid detergents is shown in Table 1.
  • composition of liquid detergents (parts by weight) e V C 12-18 fatty alcohol with 7 EO 50.0 50.0 Sodium perborate monohydrate 20.0 20.0 3,5-di-tert-butyl-4-hydroxytoluene 0.1 0.1 Hydroxyethane-1,1-diphosphonic 0.6 0.6 trisodium citrate 10.0 10.0 C 12-18 fatty acid, Na salt 0.2 0.2 tetraacetylethylenediamine 6.0 6.0 Stepantex® VA 90 2.0 - water 1.0 1.0 Fe 3+ 10 ppm 10 ppm

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)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)

Claims (9)

  1. Agent liquide non aqueux pour le lavage ou le nettoyage, contenant un ou des tensioactifs non ioniques, un ou des builders et un agent de blanchiment, caractérisé en ce qu'il contient, en tant que stabilisant, un ou plusieurs composés cationiques de formule I, II ou III :
    Figure 00320001
    Figure 00320002
    Figure 00320003
    où chaque groupe R1 est choisi indépendamment parmi les groupes alkyle en C1-6, alcényle en C1-6 ou hydroxyalkyle en C1-6 ; chaque groupe R2 est choisi indépendamment parmi les groupes alkyle en C8-28 ou alcényle en C8-28 ; R3 = R1 ou (CH2)n-T- R2; R4 = R1 ou R2 ou (CH2)n-T- R2 ; T = -O-CO- ou -CO-O- et n est un nombre entier de 0 à 5.
  2. Agent de lavage liquide non aqueux selon la revendication 1, caractérisé en ce qu'il contient de 0,5 à 10 % en poids, de préférence de 1 à 6 % en poids et en particulier, de 2 à 4 % en poids du stabilisant cationique.
  3. Agent de lavage liquide non aqueux selon l'une quelconque des revendications 1 ou 2, caractérisé en ce que, comme agent stabilisant cationique, on met en oeuvre un ester de triéthanolamine quaternaire.
  4. Agent de lavage liquide non aqueux selon l'une quelconque des revendications 1 à 3, caractérisé en ce que, comme stabilisant cationique, on met en oeuvre un composé de formule I dans laquelle chaque groupe R1 est choisi indépendamment parmi les groupes méthyle, éthyle et 2-hydroxyéthyle ; chaque groupe R2 est choisi indépendamment parmi les groupes alkyle en C8-28 ou alcényle en C8-28, de préférence alkyle en C10-20 ou alcényle en C10-20, et en particulier, alkyle en C12-18 ou alcényle en C12-18, T = -O-CO- et n = 1, 2 ou 3.
  5. Agent de lavage liquide non aqueux selon l'une quelconque des revendications 1 à 4, caractérisé en ce qu'il contient de 5 à 70 % en poids, de préférence de 15 à 65 % en poids et en particulier, de 20 à 60 % en poids d'un ou plusieurs tensioactifs non ioniques, appartenant au groupe constitué par des alcools et/ou acides carboxyliques alcoxylés, de préférence éthoxylés, ou éthoxylés et propoxylés, comprenant de 8 à 28, de préférence de 10 à 20 et en particulier, de 12 à 18 atomes de carbone.
  6. Agent de lavage liquide non aqueux selon l'une quelconque des revendications 1 à 5, caractérisé en ce qu'il contient en outre des tensioactifs anioniques, choisis de préférence dans le groupe constitué par les sulfates d'alkyle, des sulfonates d'alkyle, des benzènesulfonates d'alkyle et des savons d'acides gras.
  7. Agent de lavage liquide non aqueux selon l'une quelconque des revendications 1 à 6, caractérisé en ce que, comme adjuvant, on met en oeuvre des agents de structure hydrosolubles, appartenant de préférence au groupe constitué par des oligo- et polycarboxylates, des carbonates et des silicates cristallins et/ou amorphes.
  8. Agent de lavage liquide non aqueux selon l'une quelconque des revendications 1 à 7, contenant en outre une ou plusieurs substances appartenant au groupe constitué par des activateurs de blanchiment, des enzymes, des agents d'ajustement du pH, des parfums, des supports de parfum, des agents fluorescents, des colorants, des inhibiteurs de moussage, des huiles de silicone, des agents anti-redéposition, des azurants optiques, des inhibiteurs de grisaille, des inhibiteurs de transfert de coloration et des inhibiteurs de corrosion.
  9. Utilisation de stabilisants cationiques de formule I, II ou III :
    Figure 00340001
    Figure 00350001
    où chaque groupe R1 est choisi indépendamment parmi les groupes alkyle en C1-6, alcényle en C1-6 ou hydroxyalkyle en C1-6 ; chaque groupe R2 est choisi indépendamment parmi les groupes alkyle en C8-28 ou alcényle en C8-28 ; R3 = R1 ou (CH2)n-T- R2 ; R4 = R1 ou R2 ou (CH2)n-T- R2 ; T = -O-CO- ou -CO-O- et n est un nombre entier de 0 à 5, pour la stabilisation d'agents de blanchiment dans des agents de lavage liquides non aqueux.
EP99113021A 1998-07-15 1999-07-06 Compositions détergents liquides, non aqueuses contenant un agent de blanchiment Expired - Lifetime EP0972823B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19831702A DE19831702A1 (de) 1998-07-15 1998-07-15 Nichtwäßrige Flüssigwaschmittel mit Bleiche
DE19831702 1998-07-15

Publications (2)

Publication Number Publication Date
EP0972823A1 EP0972823A1 (fr) 2000-01-19
EP0972823B1 true EP0972823B1 (fr) 2004-09-22

Family

ID=7874101

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99113021A Expired - Lifetime EP0972823B1 (fr) 1998-07-15 1999-07-06 Compositions détergents liquides, non aqueuses contenant un agent de blanchiment

Country Status (4)

Country Link
US (1) US6372703B1 (fr)
EP (1) EP0972823B1 (fr)
AT (1) ATE277164T1 (fr)
DE (2) DE19831702A1 (fr)

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6683036B2 (en) * 2000-07-19 2004-01-27 The Procter & Gamble Company Cleaning composition
GB0021182D0 (en) * 2000-08-29 2000-10-18 Unilever Plc Cleaning aid
DE10257389A1 (de) 2002-12-06 2004-06-24 Henkel Kgaa Flüssiges saures Waschmittel
DE10313458A1 (de) * 2003-03-25 2004-11-18 Henkel Kgaa Wasch- oder Reinigungsmittel
DE10313455A1 (de) * 2003-03-25 2004-10-14 Henkel Kgaa Wasch- und Reinigungsmittel
DE10313457A1 (de) * 2003-03-25 2004-10-14 Henkel Kgaa Wasch- oder Reinigungsmittel
US20060089293A1 (en) * 2004-10-18 2006-04-27 Frankenbach Gayle M Concentrated fabric softener active compositions
US20100179368A1 (en) * 2008-11-07 2010-07-15 Aries Associates, Inc. Novel Chemistries, Solutions, and Dispersal Systems for Decontamination of Chemical and Biological Systems
US9273270B2 (en) 2014-02-20 2016-03-01 Church & Dwight Co., Inc. Unit dose cleaning products for delivering a peroxide-containing bleaching agent
DE102015215039A1 (de) * 2015-08-06 2017-02-09 Henkel Ag & Co. Kgaa Wasserarme Mittel für die Textilbehandlung, enthaltend mindestens eine spezielle kationische Verbindung und mindestens ein zusätzliches Tensid
US10633614B2 (en) * 2015-11-02 2020-04-28 Vanguard Soap LLC Natural laundry soaps
KR20230035612A (ko) 2020-07-09 2023-03-14 어드밴식스 레진즈 앤드 케미컬즈 엘엘씨 분지형 아미노산 계면활성제
KR20230048327A (ko) 2020-07-13 2023-04-11 어드밴식스 레진즈 앤드 케미컬즈 엘엘씨 잉크, 페인트, 및 접착제를 위한 분지형 아미노산 계면활성제
US11857515B2 (en) 2020-07-13 2024-01-02 Advansix Resins & Chemicals Llc Branched amino acid surfactants for use in healthcare products

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58217598A (ja) 1982-06-10 1983-12-17 日本油脂株式会社 洗剤組成物
DE3413571A1 (de) 1984-04-11 1985-10-24 Hoechst Ag, 6230 Frankfurt Verwendung von kristallinen schichtfoermigen natriumsilikaten zur wasserenthaertung und verfahren zur wasserenthaertung
US4789496A (en) * 1985-08-20 1988-12-06 Colgate-Palmolive Company Built nonaqueous liquid nonionic laundry detergent composition containing
US4892673A (en) 1988-05-02 1990-01-09 Colgate-Palmolive Company Non-aqueous, nonionic heavy duty laundry detergent with improved stability
US4889652A (en) 1988-05-02 1989-12-26 Colgate-Palmolive Company Non-aqueous, nonionic heavy duty laundry detergent with improved stability using microsperes and/or vicinal-hydroxy compounds
DE3914131A1 (de) 1989-04-28 1990-10-31 Henkel Kgaa Verwendung von calcinierten hydrotalciten als katalysatoren fuer die ethoxylierung bzw. propoxylierung von fettsaeureestern
YU221490A (sh) 1989-12-02 1993-10-20 Henkel Kg. Postupak za hidrotermalnu izradu kristalnog natrijum disilikata
DE4131906A1 (de) * 1991-09-25 1993-04-01 Henkel Kgaa Fluessiges oder pastenfoermiges wasch- oder reinigungsmittel
AU7716094A (en) 1993-09-09 1995-03-27 Procter & Gamble Company, The Liquid detergents with n-alkoxy or n-aryloxy polyhydroxy fatty acid amide surfactants
DE4400024A1 (de) 1994-01-03 1995-07-06 Henkel Kgaa Silikatische Builder und ihre Verwendung in Wasch- und Reinigungsmitteln sowie Mehrstoffgemische für den Einsatz auf diesem Sachgebiet
EP0688859A1 (fr) * 1994-06-22 1995-12-27 The Procter & Gamble Company Procédé de traitement de textiles et compositions utilisées à cet effet
JPH10506930A (ja) 1994-09-26 1998-07-07 ザ、プロクター、エンド、ギャンブル、カンパニー 非水性漂白剤含有液体洗剤組成物の製法
DE19616570A1 (de) 1996-04-25 1997-10-30 Basf Ag Vor exothermer Zersetzung durch Oxidation geschützte Waschmittelbestandteile
US5853430A (en) * 1997-09-03 1998-12-29 The Procter & Gamble Company Method for predissolving detergent compositions

Also Published As

Publication number Publication date
DE59910563D1 (de) 2004-10-28
DE19831702A1 (de) 2000-01-20
US6372703B1 (en) 2002-04-16
ATE277164T1 (de) 2004-10-15
EP0972823A1 (fr) 2000-01-19

Similar Documents

Publication Publication Date Title
EP2001986B1 (fr) Composition solide de soin des textiles comprenant un polymere hydrosoluble
EP0972823B1 (fr) Compositions détergents liquides, non aqueuses contenant un agent de blanchiment
CH678191A5 (fr)
DE10153551A1 (de) Im wesentlichen sedimentfrei dispergierbares Wasch- oder Reinigungsmittel
EP1979451A1 (fr) Agent de nettoyage ou de lavage comportant un inhibiteur de transfert de colorant
EP1117759B1 (fr) Procede de granulation
DE10011273A1 (de) Flüssigwaschmittel mit flüssigen Bleichaktivatoren
EP2113025B1 (fr) Procédé de préparation de compositions particulaires d'agent de blanchiment
EP1106678B1 (fr) Granules de surfactant nonionique et procédé d'obtention
DE19961333B4 (de) Verfahren zur Herstellung von Zuckertensidgranulaten
DE10062585A1 (de) Teilchenförmiges Additiv für Wasch- und Reinigungsmittel
WO2003031045A1 (fr) Additifs pulverulents et colorants
EP0853117B1 (fr) Détergent granulaire pour une meilleure élimination des salissures grasses
EP1086202B1 (fr) Fabrication de granules contenant de l'alkylpolyglycoside
DE19936614B4 (de) Verfahren zur Herstellung eines Waschmittels
DE19855677A1 (de) Herstellung Aufheller-haltiger Waschmittel-Granulate
DE10016423A1 (de) Flüssigwaschmittel mit Alkylenglycolcarbonsäureester
DE102006052661A1 (de) Wasch- oder Reinigungsmittel mit verbesserten Eigenschaften
DE19920119A1 (de) Waschverfahren mit Waschmitteltabletten
DE19846439A1 (de) Waschmittel mit kationischen Alkyl- und/oder Alkenylpolyglykosiden
DE19946342A1 (de) Formkörper mit verbesserter Wasserlöslichkeit
DE10027674A1 (de) Tensidsysteme für Flüssigwaschmittel
DE102007036910A1 (de) Verdicktes, flüssiges Wasch- oder Reinigungsmittel
DE19728588A1 (de) Schweres Waschmittelgranulat mit hoher Löslichkeit und verbessertem Fettauswaschvermögen
EP1170256A2 (fr) Particules de soude stables mécaniquement

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: 19990706

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

AX Request for extension of the european patent

Free format text: AL;LT;LV;MK;RO;SI

AKX Designation fees paid

Free format text: AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

17Q First examination report despatched

Effective date: 20030124

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

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

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040922

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRE;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.SCRIBED TIME-LIMIT

Effective date: 20040922

Ref country code: IE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040922

Ref country code: GB

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040922

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040922

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: GERMAN

REF Corresponds to:

Ref document number: 59910563

Country of ref document: DE

Date of ref document: 20041028

Kind code of ref document: P

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

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20041222

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20041222

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20041222

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

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20050102

NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
GBV Gb: ep patent (uk) treated as always having been void in accordance with gb section 77(7)/1977 [no translation filed]

Effective date: 20040922

REG Reference to a national code

Ref country code: IE

Ref legal event code: FD4D

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

Ref country code: LU

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

Effective date: 20050706

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20050706

Ref country code: AT

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

Effective date: 20050706

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

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

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

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

Ref country code: MC

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

Effective date: 20050731

Ref country code: LI

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

Effective date: 20050731

Ref country code: CH

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

Effective date: 20050731

Ref country code: BE

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

Effective date: 20050731

26N No opposition filed

Effective date: 20050623

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

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

Ref country code: DE

Payment date: 20060629

Year of fee payment: 8

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

Ref country code: FR

Payment date: 20060719

Year of fee payment: 8

BERE Be: lapsed

Owner name: *HENKEL K.G.A.A.

Effective date: 20050731

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

Ref country code: PT

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

Effective date: 20050222

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: 20080201

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20080331

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: 20070731