WO2010105962A1 - Agent de lavage ou de nettoyage comportant éventuellement un complexe de métaux de transition généré in situ à pouvoir blanchissant renforcé - Google Patents

Agent de lavage ou de nettoyage comportant éventuellement un complexe de métaux de transition généré in situ à pouvoir blanchissant renforcé Download PDF

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WO2010105962A1
WO2010105962A1 PCT/EP2010/053084 EP2010053084W WO2010105962A1 WO 2010105962 A1 WO2010105962 A1 WO 2010105962A1 EP 2010053084 W EP2010053084 W EP 2010053084W WO 2010105962 A1 WO2010105962 A1 WO 2010105962A1
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Prior art keywords
acid
formula
cleaning
weight
compound
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PCT/EP2010/053084
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German (de)
English (en)
Inventor
Anette Nordskog
Robin Ghosh
Philipp Spuhler
Siglinde Erpenbach
Thomas Weber
Patrick Kahlke
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Henkel Ag & Co. Kgaa
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Publication of WO2010105962A1 publication Critical patent/WO2010105962A1/fr

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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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/40—Dyes ; Pigments
    • C11D3/42—Brightening agents ; Blueing agents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/168—Organometallic compounds or orgometallic complexes
    • 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
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3932—Inorganic compounds or complexes

Definitions

  • the present invention relates to the use of a particular triazine capable of complexing with transition metal ions or a suitably pre-formed transition metal complex to enhance cleaning performance of detergents against soils and to detergents and cleaners containing the triazine or complex.
  • Inorganic peroxygen compounds particularly hydrogen peroxide and solid peroxygen compounds which dissolve in water to release hydrogen peroxide, such as sodium perborate and sodium carbonate perhydrate, have long been used as oxidizing agents for disinfecting and bleaching purposes.
  • the oxidation effect of these substances in dilute solutions depends strongly on the temperature; Thus, for example, with H 2 O 2 or perborate in alkaline bleaching liquors only at temperatures above about 80 0 C, a sufficiently fast bleaching of soiled textiles.
  • the oxidation effect of the inorganic peroxygen compounds can be improved by adding so-called bleach activators which are able to provide peroxycarboxylic acids under the abovementioned perhydrolysis conditions and for the numerous proposals, especially from the classes of N- or O-acyl compounds, for example reactive esters, polyacylated alkylenediamines, in particular N, N, N ', N' -Tetraacetylethylendiamin (TAED), acylated glycolurils, especially tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, Hydrotriazine, urazoles, piperazine diketo-, sulfuryl amides and cyanurates, also Carboxylic anhydrides, in particular phthalic anhydride, carboxylic acid esters, in particular sodium nonanoyloxy-benzenesulfonate (NOBS), sodium isononan
  • transition metal compounds for increasing the oxidation power of peroxygen compounds or atmospheric oxygen in detergents and cleaners has also been proposed on various occasions.
  • the transition metal compounds proposed for this purpose include, for example, manganese, iron, cobalt, ruthenium or molybdenum-salene complexes, manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes, manganese, iron, cobalt, Ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands, and manganese complexes with polyazacycloalkane ligands, such as TACN.
  • An object of the invention is accordingly the use of a bleach catalyst in the form of a complex of Ag, Au, Co, Cu, Fe, Mo, Mn, Ni, Pt, Rh, Ru, Ti, V and / or Zn with a ligand of the formula ( I),
  • Further objects of the invention are a process for washing textiles and a process for cleaning hard surfaces, in particular for machine dishwashing, using a compound according to formula (I) or a bleach catalyst in the form of a complex of Ag, Au, Co, Cu , Fe, Mo, Mn, Ni, Pt, Rh, Ru, Ti, V and / or Zn with a ligand of formula (I).
  • the concentration of the compound of the formula (I) in the aqueous washing or cleaning liquor is 0.5 ⁇ mol / l to 1500 ⁇ mol / l, in particular 1 ⁇ mol / l to 300 ⁇ mol / l is.
  • the concentration of Ag, Au, Co, Cu, Fe, Mo, Mn, Ni, Pt, Rh, Ru, Ti, V and / or Zn in the aqueous washing or cleaning liquor in the range of 0.1 .mu.mol / l to 500 .mu.mol / l, in particular 1 .mu.mol / l to 100 .mu.mol / l.
  • Preferred peroxygen concentrations (calculated as H 2 O 2 ) in the washing or cleaning liquor are in the range from 0.001 g / l to 10 g / l, in particular 0.1 g / l to 1 g / l.
  • the inventive use and the inventive method is preferably carried out at temperatures in the range of 10 0 C to 95 0 C, in particular 20 0 C to 40 0 C.
  • the water hardness of the water used for preparing the aqueous washing or cleaning liquor is preferably in the range from 0 ° dH to 16 ° dH, in particular 0 ° dH to 3 ° dH.
  • the use according to the invention and the method according to the invention is preferably carried out at pH values in the range from pH 5 to pH 12, in particular from pH 7 to pH 11.
  • the uses according to the invention or the processes according to the invention can be realized particularly simply by the use of a washing or cleaning agent which contains a compound according to formula (I) or a bleach catalyst obtainable therefrom by complex formation with a transition metal ion mentioned.
  • a washing or cleaning agent which contains a compound according to formula (I) or a bleach catalyst obtainable therefrom by complex formation with a transition metal ion mentioned.
  • Detergents for cleaning textiles and agents for cleaning hard surfaces, in particular dishwashing detergents and among these preferably those for machine use, the surfactant and a compound of formula (I) or a bleach catalyst obtainable therefrom by complex formation with a transition metal ion mentioned in addition to customary compatible therewith Contain ingredients are therefore further objects of the invention.
  • the use of the invention or the inventive method can also be carried out in the presence of peroxygen bleach or a composition of the invention may additionally contain peroxygen bleach.
  • a bleach-catalyzing complex comprising a ligand of formula (I) may also contain other anion, neutral or cationic ligands such as H 2 O, NH 3 , organic anions such as citrate, oxalate, tartrate, formate, a C 2 _i 8 -carboxylate, a Ci_i 8 -alkyl- sulfate, in particular methosulfate, or a corresponding alkanesulfonate, inorganic anions, such as, for example, halide, in particular chloride, perchlorate, tetrafluoroborate, hexafluorophosphate, nitrate, hydrogensulfate, hydroxide or hydroperoxide. It may also have bridging ligands such as alkylenediamines so that it may optionally be biennial or polynuclear.
  • organic anions such as citrate, oxalate, tartrate, formate, a C 2 _i 8
  • the agent additionally comprises an Ag, Au, Co, Cu, Fe, Mo, Mn, Ni, Pt, Rh, Ru , Ti, V and / or Zn salt and / or an Ag, Au, Co, Cu, Fe, Mo, Mn, Ni, Pt, Rh, Ru, Ti, V and / or Zn complex without a ligand which corresponds to the compound according to formula (I) contains.
  • the molar ratio of said transition metal or the sum of said transition metals to the compound of formula (I) is preferably in the range of 0.001: 1 to 2: 1, especially 0.01: 1 to 1: 1.
  • Preferred transition metals in the context of the use according to the invention, the process according to the invention and the agent according to the invention are Fe and Mn, in particular Mn.
  • Peroxygen compounds optionally contained in the compositions are, in particular, organic peracids or persalts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid or salts of diperdodecanedioic acid, hydrogen peroxide and inorganic salts which release hydrogen peroxide under the washing conditions, such as perborate, percarbonate and / or persilicate consideration.
  • Hydrogen peroxide can also be produced by means of an enzymatic system, ie an oxidase and its substrate. If solid peroxygen compounds are to be used, they can be used in the form of powders or granules, which can also be enveloped in a manner known in principle.
  • alkali metal percarbonate alkali metal perborate monohydrate, alkali metal perborate tetrahydrate or hydrogen peroxide in the form of aqueous solutions which contain from 3% by weight to 10% by weight of hydrogen peroxide.
  • peroxygen compounds are present in amounts of up to 50% by weight, in particular from 5% by weight to 30% by weight, in detergents or cleaners according to the invention.
  • compositions according to the invention which can be in the form of homogeneous solutions or suspensions in particular as pulverulent solids, in densified particle form, may contain, in principle, all known ingredients customary in such agents apart from the ligand or bleach catalyst to be used according to the invention.
  • the agents according to the invention In particular, builder substances, surface-active surfactants, water-miscible organic solvents, enzymes, sequestering agents, electrolytes, pH regulators, polymers with special effects, such as soil release polymers, color transfer inhibitors, grayness inhibitors, wrinkle-reducing polymeric active ingredients and form-retaining polymeric active compounds, and other auxiliaries, such as optical brighteners, foam regulators, additional peroxygen activators, dyes and fragrances.
  • An agent according to the invention can contain conventional antimicrobial agents in addition to the ingredients mentioned above to enhance the disinfecting action, for example against special germs.
  • antimicrobial additives are contained in the disinfectants according to the invention preferably in amounts of up to 10 wt .-%, in particular from 0.1 wt .-% to 5 wt .-%.
  • customary bleach activators which form peroxycarboxylic acids or peroxoimidic acids under perhydrolysis conditions and / or customary bleach-activating transition metal complexes can be used.
  • the optional, especially in amounts of 0.5 wt .-% to 6 wt .-%, present component of the bleach activators includes the commonly used N- or O-acyl compounds, for example, polyacylated alkylenediamines, especially tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, urazoles, diketopiperazines, sulphurylamides and cyanurates, furthermore carboxylic acid anhydrides, in particular phthalic acid anhydride, carboxylic acid esters, in particular sodium isononanoylphenolsulphonate, and acyl
  • Diace- tyl-2,4-dioxohexahydro-1, 3,5-triazine, and / or formulated in particulate Trialkylammoniu- macetonitrile is particularly preferred.
  • Such bleach activators are preferably contained in detergents or cleaners in amounts of up to 8% by weight, in particular from 2% by weight to 6% by weight, based in each case on the total agent.
  • compositions according to the invention may comprise one or more additional surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof, but it is also possible for cationic and / or amphoteric surfactants to be present.
  • additional surfactants in particular anionic surfactants, nonionic surfactants and mixtures thereof, but it is also possible for cationic and / or amphoteric surfactants to be present.
  • Suitable nonionic surfactants are, in particular, alkyl glycosides and ethoxylation and / or propoxylation products of alkyl glycosides or linear or branched alcohols having in each case 12 to 18 C atoms in the alkyl moiety and 3 to 20, preferably 4 to 10, alkyl ether groups.
  • Suitable anionic surfactants are in particular soaps and those which contain sulfate or sulfonate groups with preferably alkali ions as cations.
  • Usable soaps are preferably the alkali salts of the saturated or unsaturated fatty acids having 12 to 18 carbon atoms. Such fatty acids can also be used in incompletely neutralized form.
  • Useful surfactants of the sulfate type include the salts of the sulfuric acid half-esters of fatty alcohols having 12 to 18 carbon atoms and the sulfation products of said nonionic surfactants having a low degree of ethoxylation.
  • Suitable surfactants of the sulfonate type include linear alkylbenzenesulfonates having 9 to 14 carbon atoms in the alkyl moiety, alkane sulfonates having 12 to 18 carbon atoms, and olefin sulfonates having 12 to 18 carbon atoms, which are formed in the reaction of corresponding monoolefins with sulfur trioxide, and alpha-sulfofatty acid esters resulting from the sulfonation of fatty acid methyl or ethyl esters.
  • Such surfactants are present in the cleaning or washing agents according to the invention in proportions of preferably 5 wt .-% to 50 wt .-%, in particular from 8 wt .-% to 30 wt .-%, while the disinfectant according to the invention as well as inventive cleaning agent preferably 0.1 wt .-% to 20 wt .-%, in particular 0.2 wt .-% to 5 wt .-% surfactants.
  • compositions according to the invention may in particular comprise one or more of the cationic, textile-softening substances of the general formulas X, XI or II as cationic active substances having a textile-softening action XII contain:
  • the cationic surfactants have customary anions in the charge balance necessary type and number, which can be selected in addition to, for example halides also from the anionic surfactants.
  • quaternary ammonium compounds in particular C 12 alkyl -is- (hydroxyethyl) dimethylammonium, and preferably their halides, in particular chlorides, are used.
  • An agent according to the invention preferably contains 0.5% by weight to 25% by weight, in particular 1% by weight to 15% by weight, of cationic surfactant.
  • An agent according to the invention preferably contains at least one water-soluble and / or water-insoluble, organic and / or inorganic builder.
  • the water-soluble organic builder substances include polycarboxylic acids, in particular citric acid and sugar acids, monomeric and polymeric aminopolycarboxylic acids, in particular methylglycinediacetic acid, nitrilotriacetic acid and ethylenediaminetetraacetic acid and polyaspartic acid, polyphosphonic acids, in particular aminotris (methylenephosphonic acid), ethylenediaminetetrakis (methylenephosphonic acid) and 1-hydroxyethane-1, 1-diphosphonic acid, polymeric hydroxy compounds such as dextrin and polymeric (poly) carboxylic acids, in particular by oxidation of polysaccharides or dextrins accessible polycarboxylates, and / or polymeric acrylic acids, methacrylic acids, maleic acids and copolymers of these, which also small amounts of polymerizable siers
  • the molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 5,000 and 200,000, that of the copolymers between 2,000 and 200,000, preferably 50,000 to 120,000, in each case based on the free acid.
  • a particularly preferred acrylic acid-maleic acid copolymer has a molecular weight of 50,000 to 100,000.
  • Suitable, though Less preferred compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of the acid is at least 50% by weight.
  • the first acidic monomer or its salt is derived from a monoethylenically unsaturated C 3 -C 8 -carboxylic acid and preferably from a C 3 -C 4 -monocarboxylic acid, in particular from (meth) -acrylic acid.
  • the second acidic monomer or its salt may be a derivative of a C 4 -C 8 -dicarboxylic acid, with maleic acid being particularly preferred, and / or a derivative of an allylsulfonic acid which is substituted in the 2-position by an alkyl or aryl radical.
  • Such polymers generally have a molecular weight between 1,000 and 200,000.
  • Further preferred copolymers are those which have as monomers acrolein and acrylic acid / acrylic acid salts or vinyl acetate.
  • the organic builder substances can be used, in particular for the preparation of liquid agents, in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions. All of the acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.
  • organic builder substances may be present in amounts of up to 40% by weight, in particular up to 25% by weight and preferably from 1% by weight to 8% by weight. Quantities close to the stated upper limit are preferably used in paste-form or liquid, in particular water-containing, agents according to the invention.
  • Suitable water-soluble inorganic builder materials are, in particular, polymeric alkali metal phosphates, which may be in the form of their alkaline neutral or acidic sodium or potassium salts. Examples of these are tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate and the corresponding potassium salts or mixtures of sodium and potassium salts. Crystalline or amorphous alkali metal aluminosilicates, in amounts of up to 50% by weight, preferably not more than 40% by weight, and in liquid agents, in particular from 1% by weight to 5% by weight, are particularly suitable as water-insoluble, water-dispersible inorganic builder materials. used.
  • detergent grade crystalline sodium aluminosilicates especially zeolite A, P and optionally X.
  • Quantities near the upper limit mentioned are preferably used in solid, particulate agents.
  • suitable aluminosilicates have no particles with a particle size greater than 30 .mu.m and preferably consist of at least 80% by weight of particles having a size of less than 10 .mu.m.
  • Their calcium binding capacity which can be determined according to the specifications of the German patent DE 24 12 837, is generally in the range of 100 to 200 mg CaO per gram.
  • Suitable substitutes or partial substitutes for the said aluminosilicate are crystalline alkali silicates which may be present alone or in a mixture with amorphous silicates.
  • the alkali metal silicates useful as builders in the compositions according to the invention preferably have a molar ratio of alkali metal oxide to SiO 2 of less than 0.95, in particular of 1: 1, 1 to 1: 12, and may be amorphous or crystalline.
  • Preferred alkali metal silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio of Na 2 O: SiO 2 of 1: 2 to 1: 2.8.
  • the crystalline silicates which may be present alone or in admixture with amorphous silicates, are crystalline layer silicates with the general formula Na 2 Si x O 2x + I y H 2 O are used in which x, known as the modulus, an integer of 1, 9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4.
  • Preferred crystalline phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3. In particular, both ⁇ - and ⁇ -sodium disilicates (Na 2 Si 2 O 5 y H 2 O) are preferred.
  • compositions according to the invention can be prepared from amorphous alkali silicates, practically anhydrous crystalline alkali silicates of the abovementioned general formula in which x is a number from 1, 9 to 2.1, can be used in inventive compositions.
  • a crystalline sodium layer silicate with a modulus of 2 to 3 is used, as can be prepared from sand and soda. Crystalline sodium silicates with a modulus in the range of 1.9 to 3.5 are used in a further preferred embodiment of compositions according to the invention.
  • a granular compound of alkali silicate and alkali carbonate is used, as is commercially available, for example, under the name Nabion® 15.
  • the weight ratio of aluminosilicate to silicate is preferably 1:10 to 10: 1.
  • the weight ratio of amorphous alkali metal silicate to crystalline alkali metal silicate is preferably 1: 2 to 2: 1 and especially 1: 1 to 2: 1.
  • Builder substances are preferably present in the detergents or cleaners according to the invention in amounts of up to 60% by weight, in particular from 5% by weight to 40% by weight.
  • an agent according to the invention has a water-soluble builder block.
  • builder block is intended to express that the agents do not contain any further builder substances than those which are water-soluble, ie all builder substances contained in the agent are combined in the "block” characterized in this way, at most the amounts of Substances are excluded, which may be present as impurities or stabilizing additives in small amounts in the other ingredients of the products commercially.
  • water-soluble is to be understood as meaning that the builder block is formed at the concentration which results from the use of the agent containing it under the usual conditions, Residues without residue.
  • At least 15 wt .-% and up to 55 wt .-%, in particular 25 wt .-% to 50 wt .-% of water-soluble builder block in the inventive compositions is preferably composed of the components a) 5 wt .-% to 35 wt .-% citric acid, alkali citrate and / or alkali metal carbonate, which may be at least partially replaced by alkali metal bicarbonate, b) up to 10 wt .-% alkali metal silicate with a modulus in the range of 1.8 to 2.5, c) up to 2% by weight of phosphonic acid and / or alkali phosphonate, d) up to 50% by weight of alkali phosphate, and e) up to 10% by weight of polymeric Polycarboxylate, wherein the amounts are based on the entire detergent or cleaning agent. This also applies to all following quantities, unless expressly stated otherwise.
  • the water-soluble builder block contains at least 2 of components b), c), d) and e) in amounts greater than 0% by weight.
  • component a in a preferred embodiment of the composition according to the invention, 15% by weight to 25% by weight of alkali carbonate, which may at least partly be replaced by alkali metal hydrogencarbonate, and up to 5% by weight, in particular 0.5% by weight. % to 2.5% by weight of citric acid and / or alkali citrate.
  • inventive compositions are as component a) 5 wt .-% to 25 wt .-%, in particular 5 wt .-% to 15 wt .-% citric acid and / or alkali citrate and up to 5 wt .-%, in particular 1 wt .-% to 5 wt .-% alkali carbonate, which may be at least partially replaced by alkali metal bicarbonate included. If both alkali metal carbonate and alkali metal bicarbonate are present, the component comprises a) alkali carbonate and alkali metal bicarbonate, preferably in a weight ratio of 10: 1 to 1: 1.
  • component b) in a preferred embodiment of the composition according to the invention 1 wt .-% to 5 wt .-% alkali metal silicate with a modulus in the range of 1, 8 to 2.5 included.
  • agents according to the invention contain from 0.05% by weight to 1% by weight of phosphonic acid and / or alkali metal phosphonate.
  • Phosphonic acids are also understood as meaning optionally substituted alkylphosphonic acids, which may also have a plurality of phosphonic acid groups (so-called polyphosphonic acids).
  • They are preferably selected from the hydroxy and / or aminoalkylphosphonic acids and / or their alkali salts, for example dimethylaminomethane diphosphonic acid, 3-aminopropane-1-hydroxy-1,1-diphosphonic acid, 1-amino-1-phenylmethane diphosphonic acid, 1 Hydroxyethane-1, 1-diphosphonic acid, amino-tris (methylenephosphonic acid), N, N, N ', N'-ethylene di- amine tetrakis (methylenephosphonic acid) and acylated derivatives of phosphorous acid, which can also be used in any mixtures.
  • dimethylaminomethane diphosphonic acid 3-aminopropane-1-hydroxy-1,1-diphosphonic acid
  • 1-amino-1-phenylmethane diphosphonic acid 1 Hydroxyethane-1, 1-diphosphonic acid
  • amino-tris methylenephosphonic acid
  • alkali metal phosphate in particular trisodium polyphosphate, are contained.
  • Alkali phosphate is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric acids (HPO 3 ) n and orthophosphoric H 3 PO 4 in addition to high molecular weight representatives.
  • the phosphates combine several advantages: they act as alkali carriers, prevent lime deposits on machine parts or lime incrustations in fabrics and also contribute to the cleaning performance.
  • Sodium dihydrogen phosphate, NaH 2 PO 4 exists as dihydrate (density 1, 91 like “3 , melting point 60 °) and as monohydrate (density 2.04 like “ 3 ). Both salts are white powders which are very slightly soluble in water and which lose the water of crystallization when heated and at 200 ° C. into the weak acid diphosphate (disodium hydrogen diphosphate, Na 2 H 2 P 2 O 7 ), at higher temperature in sodium trimetaphosphate (Na 3 P 3 O 9 ) and pass on Madrell's salt.
  • NaH 2 PO 4 is acidic; It arises when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed.
  • Potassium dihydrogen phosphate (potassium primary or monobasic potassium phosphate, potassium biphosphate, KDP), KH 2 PO 4 , is a white salt of density 2.33 '' 3 , has a melting point of 253 ° (decomposition to form (KPO 3 ) X , potassium polyphosphate) and is slightly soluble in water.
  • Disodium hydrogen phosphate (secondary sodium phosphate), Na 2 HPO 4 , is a colorless, very slightly water-soluble crystalline salt.
  • Disodium hydrogen phosphate is by neutralization of phosphoric acid with sodium carbonate solution under Use of phenolphthalein as an indicator
  • Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K 2 HPO 4
  • K 2 HPO 4 is an amorphous, white salt which is readily soluble in water
  • Trisodium phosphate, sodium tertiary phosphate, Na 3 PO 4 are colorless crystals as Dode- cahydrat a density of 1, 62 like 3 and a melting point of 73-76 0 C (decomposition), as decahydrate (corresponding to 19-20% P 2 O 5 ) has a melting point of 100 0 C and in anhydrous form (corresponding to 39-40% P 2 O 5 ) a density of 2.536 "3 .
  • Trisodium phosphate is readily soluble in water under alkaline reaction and is prepared by evaporating a solution of exactly 1 mole of disodium phosphate and 1 mole of NaOH.
  • Tripotassium phosphate (tertiary or tri-basic potassium phosphate), K 3 PO 4 , is a white, deliquescent, granular powder with a density of 2.56 '3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction. It arises, for example, when heating Thomasschlacke with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over the corresponding sodium compounds in the detergent industry.
  • Tetranatri- umdiphosphat (sodium pyrophosphate), Na 4 P 2 O 7 , exists in anhydrous form (density 2.534 like "3 , melting point 988 °, also indicated 880 °) and as decahydrate (density 1, 815-1, 836 like '3 , melting point 94 Substances are colorless crystals which are soluble in water with an alkaline reaction Na 4 P 2 O 7 is formed by heating disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dehydrating the solution by spraying. the decahydrate complexes heavy metal salts and hardness salts and, therefore, reduces the hardness of the water.
  • potassium diphosphate (potassium pyrophosphate), K 4 P 2 O 7, exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 represents gcm -3 , which is soluble in water, wherein the pH of the 1% solution at 25 ° is 10.4
  • condensation of NaH 2 PO 4 and KH 2 PO 4 arise higher molar sodium and potassium phosphates, in the One cyclic representatives, the sodium or Kaliummetaphosphate and chain types, the sodium or Kaliumpolyphosphate distinguish.
  • a variety of names are in use: hot or cold phosphates, Graham's salt, Kurrolsches and Madrell's salt.
  • All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.
  • n 3.
  • 100 g of water dissolve at room temperature about 17 g, at 60 ° about 20 g, at 100 ° around 32 g of the salt water-free salt; after two hours of heating the solution to 100 ° caused by hydrolysis about 8% orthophosphate and 15% diphosphate.
  • pentasodium triphosphate In the preparation of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dehydrated by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentakaliumtriphosphat, K 5 P 3 Oi 0 (potassium tripolyphosphate), for example, in the form of a 50 wt .-% solution (> 23% P 2 O 5 , 25% K 2 O) in the trade. The potassium polyphosphates are widely used in the washing and cleaning industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These arise, for example, when hydrolyzed sodium trimetaphosphate with KOH:
  • component e in a preferred embodiment of the composition according to the invention 1.5 to 5 wt .-% polymeric polycarboxylate, in particular selected from the polymerization or copolymerization of acrylic acid, methacrylic acid and / or maleic acid. Among these, particularly preferred are the homopolymers of acrylic acid and, among these, those having an average molecular weight in the range from 5,000 D to 15,000 D (PA standard).
  • enzymes which can be used in the compositions apart from the abovementioned oxidase, those from the class of the proteases, lipases, cutinases, amylases, pullulanases, mannanases, cellulases, hemicellulases, xylanases and peroxidases and mixtures thereof are suitable, for example proteases such as BLAP®, Optimase®, Opticlean®, Maxacal®, Maxapem®, Alcalase®, Esperase®, Savinase®, Durazym® and / or Purafect® OxP, amylases such as Termamyl®, Amylase-LT®, Maxamyl®, Duramyl® and / or Purafect® OxAm Lipases such as Lipolase®, Lipomax®, Lumafast® and / or Lipozym®, cellulases such as Celluzyme® and / or Carezyme®.
  • proteases such as
  • enzymatic active ingredients obtained from fungi or bacteria, such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes or Pseudomonas cepacia.
  • the optionally used enzymes may be adsorbed to carriers and / or embedded in encapsulants to protect against premature inactivation. They are preferably present in the detergents, cleaners and disinfectants according to the invention in amounts of up to 10% by weight, in particular from 0.2% by weight to 2% by weight, particular preference being given to stabilizing enzymes which are stabilized against oxidative degradation become.
  • the agent contains 5% by weight to 50% by weight, in particular 8-30% by weight of anionic and / or nonionic surfactant, up to 60% by weight, in particular 5-40% by weight.
  • organic solvents which can be used in the compositions according to the invention, especially if they are in liquid or pasty form, are alcohols having 1 to 4 C atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols having 2 to 4 C atoms , in particular ethylene glycol and propylene glycol, and mixtures thereof and the derivable from said classes of compound ethers.
  • Such water-miscible solvents are preferably present in the detergents according to the invention not more than 30% by weight, in particular from 6% by weight to 20% by weight.
  • the compositions according to the invention can be system and environmentally compatible.
  • acids in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid, but also mineral acids, in particular sulfuric acid, or bases, in particular ammonium or alkali metal hydroxides.
  • pH regulators are preferably not more than 20 wt .-%, in particular from 1, 2 wt .-% to 17 wt .-%, contained in the inventive compositions.
  • Soil release polymers often referred to as "soil release” agents or because of their ability to soil-repel the treated surface, e.g., fiber, for example, are called nonionic or cationic cellulose derivatives.
  • the particularly polyester-active soil release polymers include copolyesters of dicarboxylic acids, for example adipic acid, phthalic acid or terephthalic acid, diols, for example ethylene glycol or propylene glycol, and polydiols, for example polyethylene glycol or polypropylene glycol.
  • Preferred soil release polymers include those compounds which are formally accessible by esterification of two monomeric moieties, wherein the first monomer is a dicarboxylic acid HOOC-Ph-COOH and the second monomer is a diol HO- (CHR 11 -) a OH, also known as polymeric Diol H- (O- (CHRi i-) a ) b OH may be present.
  • Ph is an o-, m- or p-phenylene radical which can carry 1 to 4 substituents selected from alkyl radicals having 1 to 22 C atoms, sulfonic acid groups, carboxyl groups and mixtures thereof
  • R 11 denotes hydrogen
  • a is a number from 2 to 6
  • b is a number from 1 to 300.
  • the polyesters obtainable from these monomers both Mondiol- O- (CHR- ⁇ -
  • the molar ratio of monomer diol units to polymer diol units is preferably 100: 1 to 1: 100, in particular 10: 1 to 1:10.
  • the degree of polymerization b is preferably in the range from 4 to 200, in particular from 12 to 140.
  • the molecular weight or the average molecular weight or the maximum of the molecular weight distribution of preferred soil release polyesters is in the range from 250 to 100,000, in particular from 500 to 50 000.
  • the acid underlying the remainder Ph is preferably selected from terephthalic acid, isophthalic acid, phthalic acid, trimellitic acid, mellitic acid, the isomers of sulfophthalic acid, sulfoisophthalic acid and sulfoterephthalic acid and mixtures thereof. If their acid groups are not part of the ester bonds in the polymer, they are preferably in salt form, in particular as alkali or ammonium salt. Among these, the sodium and potassium salts are particularly preferable.
  • acids having at least two carboxyl groups may be included in the soil release-capable polyester.
  • these include, for example, alkylene and alkenylene dicarboxylic acids such as malonic acid, succinic acid, fumaric acid, maleic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid.
  • HO- (CHR 11 -) a OH include those in which R 11 is hydrogen and a is a number from 2 to 6, and those in which a has the value 2 and R 11 is selected from hydrogen and the alkyl radicals having 1 to 10, in particular 1 to 3, carbon atoms.
  • R 11 is hydrogen and a is a number from 2 to 6
  • R 11 is selected from hydrogen and the alkyl radicals having 1 to 10, in particular 1 to 3, carbon atoms.
  • those of the formula HO-CH 2 -CHR 11 -OH in which R 11 has the abovementioned meaning are particularly preferred.
  • diol components are ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 8-octanediol, 1, 2-decanediol, 1, 2-dodecanediol and neopentyl glycol.
  • Particularly preferred among the polymeric diols is polyethylene glycol having an average molecular weight in the range of 1000 to 6000. If desired, these polyesters may also be end developmentver consideration, with alkyl groups having 1 to 22 carbon atoms and esters of monocarboxylic acids in question as end groups.
  • the end groups may also be based on hydroxymonocarboxylic acids having 5 to 22 carbon atoms, which include, for example, hydroxyvaleric acid, hydroxycaproic acid, ricinoleic acid, their hydrogenation product hydroxystearic acid, and o-, m- and p-hydroxybenzoic acid.
  • the hydroxymonocarboxylic acids may in turn be linked to one another via their hydroxyl group and their carboxyl group and thus be present several times in an end group.
  • the number of hydroxymonocarboxylic acid units per end group is in the range from 1 to 50, in particular from 1 to 10.
  • the color transfer inhibitors which are suitable for use in laundry detergents according to the invention include in particular polyvinylpyrrolidones, polyvinylimidazoles, polymeric N-oxides such as poly (vinylpyridine-N-oxide) and copolymers of vinylpyrrolidone with vinylimidazole and optionally other monomers.
  • the inventive compositions for use in the textile laundry may contain anti-crease agents, since textile fabrics, in particular of rayon, wool, cotton and mixtures thereof, may tend to wrinkle because the individual fibers against bending, buckling, pressing and Squeezing transverse to the fiber direction are sensitive.
  • anti-crease agents include, for example, synthetic products based on fatty acids, fatty acid esters, fatty acid amides, alkylol esters, alkylol amides or fatty alcohols, which are usually reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid ester.
  • Graying inhibitors have the task of keeping suspended from the hard surface and in particular from the textile fiber suspended dirt in the fleet.
  • Water-soluble colloids of mostly organic nature are suitable for this purpose, for example starch, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or of cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • water-soluble polyamides containing acidic groups are suitable for this purpose.
  • starch derivatives can be used, for example aldehyde starches.
  • cellulose ethers such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof, for example in amounts of from 0.1 to 5% by weight, based on the means used.
  • the agents may contain optical brighteners, among these in particular derivatives of diaminostilbenedisulfonic acid or its alkali metal salts.
  • optical brighteners among these in particular derivatives of diaminostilbenedisulfonic acid or its alkali metal salts.
  • salts of 4,4'-bis (2-anilino-4-morpholino-1, 3,5-triazinyl-6-amino) stilbene-2,2'-disulphonic acid or similarly constructed compounds which are substituted for the morpholino Group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group.
  • brighteners of the substituted diphenylstyrene type may be present, for example, the alkali salts of 4,4'-bis (2-sulfostyryl) -diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl, or A - (4-chlorostyryl) -4 '- (2-sulfostyryl) -diphenyls. Mixtures of the aforementioned optical brightener can be used.
  • foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C 18 -C 24 fatty acids.
  • Suitable non-surfactant foam inhibitors are, for example, organopolysiloxanes and mixtures thereof with microfine, optionally signed silica and paraffins, waxes, microcrystalline waxes and mixtures thereof with silanated silicic acid or bis-fatty acid alkylenediamides.
  • mixtures of various foam inhibitors for example those of silicones, paraffins or waxes.
  • the foam inhibitors in particular silicone and / or paraffin-containing foam inhibitors, to a granular, water-soluble or dispersible carrier substance bound.
  • mixtures of paraffins and bistearylethylenediamide are preferred.
  • silver corrosion inhibitors are organic disulfides, dihydric phenols, trihydric phenols, optionally alkyl- or aminoalkyl-substituted triazoles such as benzotriazole and cobalt, manganese, titanium, zirconium, hafnium, vanadium or cerium salts and / or complexes in which the Metals in one of the oxidation states II, IM, IV, V or VI are present.
  • the compound according to formula (I) or the correspondingly preformed complex may be present in the form of powders or as granules, which may optionally also be coated and / or colored and may contain conventional carrier materials and / or granulation aids. In the case of their use as granules, if desired, these may also contain further active substances, in particular bleach activator.
  • compositions according to the invention presents no difficulties and can be carried out in a manner known in principle, for example by spray-drying or granulation, with peroxygen compound and bleach activator combination optionally being added later.
  • a process comprising an extrusion step is preferred.
  • Detergents, cleaners or disinfectants according to the invention in the form of aqueous or other conventional solvent-containing solutions are particularly advantageously prepared by simply mixing the ingredients, which can be added in bulk or as a solution in an automatic mixer. In a preferred embodiment of means for the particular machine cleaning of dishes, these are tablet-shaped.
  • the primary washing power was determined in a miniaturized washing test. It was worked with a simplified wash liquor consisting of H 2 O 2 and catalyst.
  • Aqueous solutions (M1) of 0.35 g / l H 2 O 2 and 50 ⁇ mol / l of Mn-2,4,6-tripyridin-2-yl-1,3,5-triazine complex prepared by Heating a mixture of 2,4,6-tripyridin-2-yl-1, 3,5-triazine and Mn (III) acetate in a molar ratio of 3: 1 in ethanol for 2 hours to 8O 0 C, was used the entire ethanolic solution) or (V1) of 0.35 g / l H 2 O 2 and 50 ⁇ mol / l Mn (III) acetate, whose pH values had been adjusted to pH 10.5 by means of NaOH.

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Abstract

L'objectif de cette invention est de renforcer le pouvoir nettoyant d'agents de lavage et de nettoyage. A cet effet, on utilise une triazine pouvant former des complexes avec des ions de métaux de transition, ou un complexe de métaux de transition formé préalablement de manière adéquate.
PCT/EP2010/053084 2009-03-20 2010-03-11 Agent de lavage ou de nettoyage comportant éventuellement un complexe de métaux de transition généré in situ à pouvoir blanchissant renforcé WO2010105962A1 (fr)

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DE102009001692.9 2009-03-20
DE200910001692 DE102009001692A1 (de) 2009-03-20 2009-03-20 Wasch- oder Reinigungsmittel mit gegebenenfalls in situ erzeugtem bleichverstärkendem Übergangsmetallkomplex

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