EP0972823A1 - Compositions détergents liquides, non aqueuses contenant un agent de blanchiment - Google Patents

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

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Publication number
EP0972823A1
EP0972823A1 EP99113021A EP99113021A EP0972823A1 EP 0972823 A1 EP0972823 A1 EP 0972823A1 EP 99113021 A EP99113021 A EP 99113021A EP 99113021 A EP99113021 A EP 99113021A EP 0972823 A1 EP0972823 A1 EP 0972823A1
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EP
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Prior art keywords
alkyl
group
aqueous liquid
agents
liquid detergent
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German (de)
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EP0972823B1 (fr
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Bernd Dr. Richter
Ulrich Dr. Pegelow
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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    • 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

  • 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% by weight hydrated zeolite A, 50 to 80% by weight 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 the production of non-aqueous bleach-containing liquid detergents which have high chemical and physical stability as well as outstanding washing and bleaching results by suspending detergent components of fine grain size 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 means in the context of the present invention understand that only small amounts of free, so not as crystal water or in any other Way bound to contain water. Since even non-aqueous solvents and Raw materials (especially those of technical quality) have certain water contents, are completely water-free agents on an industrial scale only with great effort and high costs.
  • non-aqueous compositions of the present invention So small amounts of free water are tolerable, preferably less than 5% by weight below 2% by weight, based in each case on the finished agent.
  • the liquid agents of the present invention can be used within a wide range of viscosities getting produced. So not only are fluid and easy to move Agents according to the invention can be produced, but also viscous to pasty agents higher viscosities. The consistency of the pasty agents can also be spreadable or be able to cut - the use of cationic stabilizers also results in such agents on the effects of bleach stabilization according to the invention.
  • the cationic stabilizers can be used in varying amounts in the inventive Funds are brought in.
  • Cationic stabilizers to be used with preference are the result of 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 Way, the use of dimethyl sulfate as a quaternizing reagent is preferred.
  • 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.
  • 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).
  • HEDP 1-hydroxyethane-1,1-diphosphonic acid
  • ATMP aminotri (methylenephosphonic acid)
  • DBS-AM 2-phosphonobutane
  • 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 linearly or preferably 2-branched methyl or may 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 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 rest.
  • 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.
  • Preferred surfactants of the sulfonate type are 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 sulfonating with gaseous sulfur trioxide and then undergoes 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 sulfated 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 in particular the sodium salts of the sulfuric acid half esters of C 12 -C 18 fatty alcohols, for example from coconut oil 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, straight-chain alkyl radical prepared on a petrochemical basis and 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-, di- or 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 are.
  • 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.
  • 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 n Na 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 overdried 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 peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid 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 named C number of carbon atoms and / or optionally substituted benzoyl groups.
  • TAED te
  • 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 tripod ligands containing N 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 lie between 5 and 10% by weight.
  • Enzymes come from the mass 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 especially 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 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 already 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.
  • sulfonated derivatives of phthalic acid and Terephthalic acid polymers are particularly preference is given to the sulfonated derivatives of phthalic acid and 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 compounds of the same structure, instead of 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 may be 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, 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 are available from plant sources, e.g. Pine, Citrus, Jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, 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.
  • natural fragrance mixtures included as are available from plant sources, e.g. Pine, Citrus, Jasmine, patchouly, rose or ylang-ylang oil.
  • muscatel 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
  • the fragrances can be incorporated directly into the agents according to the invention but can also be advantageous to apply the fragrances to the carrier, which increase 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 colored 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 prepared in a manner known per se Mix 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 further increase.
  • 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 decomposition process 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 retain this property even 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 one in a system amount of heat produced in joules over 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 recipes 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 acid 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

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
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 true EP0972823A1 (fr) 2000-01-19
EP0972823B1 EP0972823B1 (fr) 2004-09-22

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

Cited By (1)

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EP3130656A1 (fr) * 2015-08-06 2017-02-15 Henkel AG & Co. KGaA Fluides pauvres en eau pour le traitement de textiles, contenant au moins un composé cationique spécial et au moins un tensio-actif supplémentaire

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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
WO2006044875A1 (fr) * 2004-10-18 2006-04-27 The Procter & Gamble Company Compositions actives d'adoucissant pour toile concentrees
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
US10633614B2 (en) * 2015-11-02 2020-04-28 Vanguard Soap LLC Natural laundry soaps
CA3185070A1 (fr) 2020-07-09 2022-01-13 Edward Asirvatham Tensioactifs acides amines ramifies
KR20230051181A (ko) 2020-07-13 2023-04-17 어드밴식스 레진즈 앤드 케미컬즈 엘엘씨 건강관리 제품에 사용하기 위한 분지형 아미노산 계면활성제
KR20230049631A (ko) 2020-07-13 2023-04-13 어드밴식스 레진즈 앤드 케미컬즈 엘엘씨 오일 및 가스 생산을 위한 분지형 아미노산 계면활성제
AU2021307398B2 (en) 2020-07-13 2024-06-27 Advansix Resins & Chemicals Llc Branched amino acid surfactants for electronics products
AU2021309628B2 (en) 2020-07-13 2024-05-30 Advansix Resins & Chemicals Llc Branched amino acid surfactants for inks, paints, and adhesives

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WO1993006201A1 (fr) * 1991-09-25 1993-04-01 Henkel Kommanditgesellschaft Auf Aktien Agent de lavage ou de nettoyage liquide ou pateux
EP0688859A1 (fr) * 1994-06-22 1995-12-27 The Procter & Gamble Company Procédé de traitement de textiles et compositions utilisées à cet effet

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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
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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
CA2199816A1 (fr) 1994-09-26 1996-04-04 The Procter & Gamble Company Procede de preparation de compositions detergentes liquides, non aqueuses et contenant un agent de blanchiment
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US4789496A (en) * 1985-08-20 1988-12-06 Colgate-Palmolive Company Built nonaqueous liquid nonionic laundry detergent composition containing
WO1993006201A1 (fr) * 1991-09-25 1993-04-01 Henkel Kommanditgesellschaft Auf Aktien Agent de lavage ou de nettoyage liquide ou pateux
EP0688859A1 (fr) * 1994-06-22 1995-12-27 The Procter & Gamble Company Procédé de traitement de textiles et compositions utilisées à cet effet

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3130656A1 (fr) * 2015-08-06 2017-02-15 Henkel AG & Co. KGaA Fluides pauvres en eau pour le traitement de textiles, contenant au moins un composé cationique spécial et au moins un tensio-actif supplémentaire

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US6372703B1 (en) 2002-04-16
EP0972823B1 (fr) 2004-09-22
DE19831702A1 (de) 2000-01-20
ATE277164T1 (de) 2004-10-15
DE59910563D1 (de) 2004-10-28

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