EP2814930B1 - Produit de nettoyage contenant des enzymes et des alcools polyvalents - Google Patents

Produit de nettoyage contenant des enzymes et des alcools polyvalents Download PDF

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Publication number
EP2814930B1
EP2814930B1 EP13700509.6A EP13700509A EP2814930B1 EP 2814930 B1 EP2814930 B1 EP 2814930B1 EP 13700509 A EP13700509 A EP 13700509A EP 2814930 B1 EP2814930 B1 EP 2814930B1
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EP
European Patent Office
Prior art keywords
cleaning agent
acid
amount
water
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.)
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EP13700509.6A
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German (de)
English (en)
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EP2814930A1 (fr
Inventor
Konstantin Benda
Thomas Eiting
Nina Mussmann
Thorsten Bastigkeit
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority to PL13700509T priority Critical patent/PL2814930T3/pl
Publication of EP2814930A1 publication Critical patent/EP2814930A1/fr
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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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2065—Polyhydric alcohols
    • 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
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
    • C11D17/043—Liquid or thixotropic (gel) compositions
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2041—Dihydric alcohols
    • 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
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • 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
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38663—Stabilised liquid enzyme compositions

Definitions

  • the present invention relates to high-viscosity liquid enzyme-containing detergents contained in a water-soluble packaging and containing polyhydric alcohols. Consumers have become accustomed to conveniently dosing pre-portioned automatic dishwashing detergents and use these products primarily in the form of tablets. On the other hand, liquid product forms in the form of multifunctional gels are increasingly gaining acceptance in the market. Above all, the fast solubility and the associated rapid availability of the active ingredients offers advantages in particular in shorter-lasting rinsing programs. From the consumer's point of view, it is desirable to combine the advantages of both offer types and to offer a pre-portioned liquid product.
  • a first object of the present invention is therefore a liquid enzyme-containing cleaning agent as defined in claim 1.
  • the cleaning agent according to the invention is preferably a dishwasher detergent, in particular a machine dishwashing detergent.
  • Another object of the present invention is also a machine dishwashing process in which a detergent according to the invention is used.
  • the amount of polyhydric alcohol used in cleaning agents according to the invention is at least 25 wt .-%, more preferably at least 28 wt .-%, especially at least 30 wt .-%.
  • a preferred amount range is 28 to 40% by weight.
  • An inventively used polyhydric alcohol is 1,2-propylene glycol. 1,2-Propylene glycol is used in inventive compositions in an amount of 15 to 35 wt .-%, particularly preferably in an amount of 20 to 30 wt .-%.
  • Glycerol is used in inventive compositions in an amount of 1 to 10 wt .-%, preferably in an amount of 3 to 7 wt .-%. It is used a mixture of glycerol and 1,2-propylene glycol.
  • the glycerin is used here in an amount of 1 to 10 wt .-%, preferably in an amount of 3 to 7 wt .-%.
  • the 1,2-propylene glycol is used here in an amount of 15 to 35 wt .-%, preferably in an amount of 20 to 30 wt .-%, each based on the total amount of the cleaning agent, wherein the total amount of glycerol and 1 , 2-propylene glycol 25 to 45 wt .-%, in particular 28 to 40 wt .-%, especially 28.5 to 32.0 wt .-%, is.
  • the liquid cleaning agent is preferably a water-containing composition.
  • the water content of the composition according to the invention is preferably at a maximum of 25 wt .-%, preferably below 20 wt .-%.
  • Preferred quantitative ranges here are 5 to 25 wt .-%, in particular 15 to 20 wt .-%, especially 18 to 19.8 wt .-%.
  • the viscosity of inventive detergents is above 4000 mPas (Brookfield Viscometer DV-II + Pro, spindle 25, 30 rpm, 20 ° C), preferably between 4000 and 7000 mPas, in particular between 4500 and 6500 mPas, especially between 5000 and 6000 mPas.
  • enzymes include in particular proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably mixtures thereof. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents, which are preferably used accordingly.
  • Detergents contain enzymes preferably in total amounts of 1 ⁇ 10 -6 to 5 wt .-% based on active protein. The protein concentration can be determined by known methods, for example the BCA method or the biuret method.
  • subtilisin type those of the subtilisin type are preferable.
  • these are the subtilisins BPN 'and Carlsberg and their further developed forms, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase which can no longer be assigned to the subtilisins in the narrower sense, Proteinase K and the proteases TW3 and TW7.
  • amylases which can be used according to the invention are the ⁇ -amylases from Bacillus licheniformis, from B. amyloliquefaciens, from B. stearothermophilus, from Aspergillus niger and A. oryzae and the improved for use in detergents developments of the aforementioned amylases. Furthermore, for this purpose, the ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).
  • lipases or cutinases are also usable according to the invention, in particular because of their triglyceride-splitting activities, but also in order to generate in situ peracids from suitable precursors.
  • lipases or cutinases include, for example, the lipases originally obtainable from Humicola lanuginosa ( Thermomyces lanuginosus ) or further developed, in particular those with the amino acid exchange D96L.
  • Oxidoreductases for example oxidases, oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can be used according to the invention to increase the bleaching effect.
  • a protein and / or enzyme may be particularly protected during storage against damage such as inactivation, denaturation or degradation, such as by physical influences, oxidation or proteolytic cleavage.
  • Detergents may for this purpose contain stabilizers, such as boric acid or its derivatives.
  • the cleaning agents according to the invention are essentially free from boric acid and its derivatives, since these ingredients can lead to undesired interactions with the water-soluble film.
  • the cleaning agent is also substantially free of further enzyme stabilizers, in particular free of calcium salts, with the exception of the polyhydric alcohols to be used according to the invention.
  • “Substantially free” here means that the cleaning agent less than 0.3 wt .-%, preferably less than 0.1 wt .-%, more preferably less than 0.05 wt .-%, of the relevant component (s) contains. Most preferably, the cleaning agent is completely free from the relevant component.
  • Cleaning-active proteases and amylases are generally not provided in the form of the pure protein but rather in the form of storage and transportable preparations. Such prefabricated preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel-form detergents, solutions of the enzymes, advantageously as concentrated as possible, sparing in water and / or auxiliaries.
  • the enzymes may be encapsulated for both the solid and liquid dosage forms, for example by spray-drying or extruding the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core with a water, air and / or Chemical-impermeable protective layer is coated.
  • additional active ingredients for example emulsifiers, pigments, bleaches or dyes may additionally be applied.
  • Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes.
  • such granules for example by applying polymeric film-forming agent, low in dust and storage stable due to the coating. Furthermore, it is possible to assemble two or more enzymes together so that a single granule has several enzyme activities.
  • the enzyme protein forms only a fraction of the total weight of conventional enzyme preparations.
  • Protease and amylase preparations preferably used according to the invention contain between 0.1 and 40% by weight, preferably between 0.2 and 30% by weight, particularly preferably between 0.4 and 20% by weight and in particular between 0, 8 and 10 wt .-% of the enzyme protein.
  • detergents which, based in each case on their total weight, contain 0.1 to 12% by weight, preferably 0.2 to 10% by weight and in particular 0.5 to 8% by weight, of enzyme preparations.
  • sulfopolymers causes further stabilization of the composition so that further at least one sulfopolymer is included in the composition.
  • the proportion by weight of the sulfopolymer in the total weight of the cleaning agent according to the invention is preferably from 0.1 to 20 wt .-%, in particular from 0.5 to 18 wt .-%, particularly preferably 1.0 to 15 wt .-%, in particular from 4 to 14 wt .-%, especially from 6 to 12 wt .-%.
  • the sulfopolymer used is preferably a copolymeric polysulfonate, preferably a hydrophobically modified copolymeric polysulfonate.
  • the copolymers may have two, three, four or more different monomer units.
  • Preferred copolymeric polysulfonates contain not only sulfonic acid group-containing monomer (s) but also at least one monomer selected from the group consisting of unsaturated carboxylic acids.
  • unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, ⁇ -chloroacrylic acid, ⁇ -cyanoacrylic acid, crotonic acid, ⁇ -phenyl-acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid, sorbic acid, cinnamic acid or mixtures thereof. It goes without saying that it is also possible to use the unsaturated dicarboxylic acids.
  • Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3 Methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propenylsulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate , Sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of said acids or their water-soluble salt
  • the sulfonic acid groups may be wholly or partially in neutralized form, i. the acidic acid of the sulfonic acid group in some or all sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions.
  • metal ions preferably alkali metal ions and in particular for sodium ions.
  • partially or fully neutralized sulfonic acid-containing copolymers is preferred according to the invention.
  • the monomer distribution of the copolymers preferably used according to the invention in the case of copolymers containing only monomers containing carboxylic acid groups and monomers containing sulfonic acid groups is preferably from 5 to 95% by weight, more preferably from 50 to 90% by weight of the sulfonic acid group-containing monomer. % and the proportion of the carboxylic acid group-containing monomer 10 to 50 wt .-%, the monomers are hereby preferably selected from the aforementioned.
  • the molar mass of the sulfo copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired end use.
  • Preferred cleaning agents are characterized in that the copolymers have molar masses of 2000 to 200,000 gmol -1 , preferably from 4000 to 25,000 gmol -1 and in particular from 5000 to 15,000 gmol -1 .
  • the copolymers in addition to the carboxyl group-containing monomer and the monomer containing the sulfonic acid group, the copolymers further comprise at least one nonionic, preferably hydrophobic monomer.
  • the use of these hydrophobically modified polymers has made it possible in particular to improve the rinse aid performance of automatic dishwashing detergents according to the invention.
  • nonionic monomers are butene, isobutene, pentene, 3-methylbutene, 2-methylbutene, cyclopentene, hexene, hexene-1, 2-methylpentene-1, 3-methylpentene-1, cyclohexene, methylcyclopentene, cycloheptene, methylcyclohexene, 2,4 , 4-trimethylpentene-1, 2,4,4-trimethylpentene-2,3,3-dimethylhexene-1, 2,4-dimethylhexene-1, 2,5-dimethlyhexene-1,3,5-dimethylhexene-1,4 , 4-dimethylhexane-1, ethylcyclohexyn, 1-octene, ⁇ -olefins having 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and C
  • the monomer distribution of the hydrophobically modified copolymers preferably used according to the invention is preferably in each case from 5 to 80% by weight, with respect to the sulfonic acid group-containing monomer, the hydrophobic monomer and the carboxylic acid group-containing monomer, the proportion of the sulfonic acid group-containing monomer and of the each hydrophobic monomer 5 to 30 wt .-% and the proportion of the carboxylic acid group-containing monomer 60 to 80 wt .-%, the monomers are in this case preferably selected from the aforementioned.
  • the cleaning agent according to the invention is contained in a water-soluble packaging.
  • the water-soluble packaging allows a portioning of the cleaning agent.
  • the amount of Detergent in the sachet is preferably 5 to 50 g, more preferably 10 to 30 g, especially 15 to 25 g.
  • the water-soluble packaging preferably comprises a water-soluble polymer.
  • Some preferred water-soluble polymers which are preferably used as water-soluble packaging are polyvinyl alcohols, acetalated polyvinyl alcohols, polyvinylpyrrolidones, polyethylene oxides, celluloses and gelatin, polyvinyl alcohols and acetalated polyvinyl alcohols being particularly preferably used.
  • Polyvinyl alcohols (abbreviated PVAL, occasionally PVOH) is the name for polymers of the general structure in small proportions (about 2%) also structural units of the type contain.
  • polyvinyl alcohols which are offered as white-yellowish powders or granules with degrees of polymerization in the range of about 100 to 2500 (molar masses of about 4000 to 100,000 g / mol), have degrees of hydrolysis of 87-99 mol%, that is to say contain one more Residual content of acetyl groups.
  • the water-soluble packaging at least partly comprises a polyvinyl alcohol whose degree of hydrolysis is preferably 70 to 100 mol%, in particular 80 to 90 mol%, particularly preferably 81 to 89 mol% and especially 82 to 88 mole%.
  • the water-soluble packaging consists of at least 20 wt .-%, more preferably at least 40 wt .-%, most preferably at least 60 wt .-% and in particular at least 80 wt .-% of a polyvinyl alcohol, the Hydrolysis degree 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%, is.
  • Polyvinyl alcohols of a certain molecular weight range are preferably used as materials for the packaging, it being preferred according to the invention for the packaging material to comprise a polyvinyl alcohol whose molecular weight is in the region of 5,000 to 100,000 gmol-1, preferably from 10,000 to 90,000 gmol-1, particularly preferably from 12,000 to 80,000 gmol-1 and in particular from 15,000 to 70,000 gmol-1.
  • the degree of polymerization of such preferred polyvinyl alcohols is between about 200 to about 2100, preferably between about 220 to about 1890, more preferably between about 240 to about 1680, and most preferably between about 260 to about 1500.
  • the water solubility of polyvinyl alcohol can be altered by post-treatment with aldehydes (acetalization) or ketones (ketalization).
  • aldehydes acetalization
  • ketones ketalization
  • polyvinyl alcohols have been found to be acetalated or ketalized with the aldehyde or keto groups of saccharides or polysaccharides or mixtures thereof.
  • reaction products of polyvinyl alcohol and starch are also be changed by complexing with Ni or Cu salts or by treatment with dichromates, boric acid, borax and thus set specifically to desired values.
  • the water-soluble packaging preferably has a thickness of 10 .mu.m to 500 .mu.m, in particular from 20 .mu.m to 400 .mu.m, more preferably from 30 .mu.m to 300 .mu.m, especially from 40 .mu.m to 200 .mu.m, in particular from 50 .mu.m to 150 .mu.m.
  • a particularly preferred polyvinyl alcohol is available, for example, under the trade name M8630 (Monosol).
  • the pH of cleaning agents according to the invention is preferably between 6 and 10, more preferably between 7 and 9, especially between 7 and 8.
  • Detergents according to the invention preferably also contain at least one nonionic surfactant.
  • nonionic surfactants it is possible to use all nonionic surfactants known to the person skilled in the art. Low-foaming nonionic surfactants are preferably used.
  • the cleaning performance of inventive compositions can be significantly improved both in comparison to surfactant-free system as well as in comparison to systems containing alternative nonionic surfactants, for example from the group of polyalkoxylated fatty alcohols.
  • nonionic surfactants having one or more free hydroxyl groups on one or both terminal alkyl radicals, the stability of the enzymes contained in the detergent formulations according to the invention can be markedly improved.
  • end-capped poly (oxyalkylated) nonionic surfactants which, in accordance with the formula R 1 O [CH 2 CH 2 O] x CH 2 CH (OH) R 2 , in addition to a radical R 1 , which is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having from 2 to 30 carbon atoms, preferably having from 4 to 22 carbon atoms, furthermore having a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R 2 having from 1 to 30 carbon atoms, where x is from 1 to 30 carbon atoms 90, preferably for values between 30 and 80 and in particular for values between 30 and 60.
  • surfactants of the formula R 1 O [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 O] y CH 2 CH (OH) R 2 , in which R 1 is a linear or branched aliphatic hydrocarbon radical with 4 R 2 is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x is values between 0.5 and 1.5 and y is a value of at least 15.
  • the group of these nonionic surfactants includes, for example, the C 2-26 fatty alcohol (PO) 1 - (EO) 15-40 -2-hydroxyalkyl ethers, in particular also the C 8-10 fatty alcohol (PO) 1 - (EO) 22 -2 -hydroxydecylether.
  • nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2 in which R 1 and R 2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R 3 is H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2 Butyl or 2-methyl-2-butyl radical, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5.
  • each R 3 in the above formula R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2 may be different.
  • R 1 and R 2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred.
  • R 3 H, -CH 3 or -CH 2 CH 3 are particularly preferred.
  • Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.
  • each R 3 in the above formula may be different if x ⁇ 2.
  • the alkylene oxide unit in the square bracket can be varied.
  • the value 3 for x has been selected here by way of example and may well be greater, with the variation width increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,
  • R 1 , R 2 and R 3 are as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18.
  • Particularly preferred are surfactants in which the radicals R 1 and R 2 has 9 to 14 C atoms, R 3 is H and x assumes values of 6 to 15.
  • Preferred liquid cleaning agents are characterized in that the cleaning agent contains at least one nonionic surfactant, preferably a nonionic surfactant from the group of hydroxy mixed ethers, wherein the weight fraction of the nonionic surfactant in the total weight of the cleaning agent preferably 0.5 to 10 wt .-%, preferably 1 , 0 to 8.0 wt .-% and in particular 2.0 to 6.0 wt .-% is.
  • cleaning agents according to the invention preferably contain one or more builder (s).
  • the proportion by weight of these builders in the total weight of cleaning agents according to the invention is preferably from 15 to 80% by weight and in particular from 20 to 70% by weight.
  • These builders include in particular carbonates, phosphates, citrates, phosphonates, MGDA, GLDA, EDDS, organic cobuilders and silicates.
  • phosphate Preference is also the use of phosphate.
  • alkali metal phosphates with a particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), have the greatest importance in the washing and cleaning agent industry.
  • Alkalimetallphosphate is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids in which metaphosphoric acids (HPO 3 ) n and orthophosphoric H 3 PO 4 in addition to high molecular weight representatives can differentiate.
  • 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.
  • Particularly preferred phosphates according to the invention are the pentasodium triphosphate, Na 5 P 3 O 10 (sodium tripolyphosphate) and the corresponding potassium salt pentapotassium triphosphate, K 5 P 3 O 10 (potassium tripolyphosphate).
  • the sodium potassium tripolyphosphates are also preferably used according to the invention.
  • phosphates are used as cleaning-active substances in the cleaning agents in the context of the present application, these contain phosphate (s), preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), in amounts of from 5 to 60 Wt .-%, preferably from 15 to 45 wt .-% and in particular from 20 to 40 wt .-%, each based on the weight of the cleaning agent.
  • phosphate preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate)
  • the use of phosphates is largely or completely omitted.
  • the agent in this embodiment preferably contains less than 5% by weight, more preferably less than 3% by weight, in particular less than 1% by weight of phosphate (s).
  • the agent is completely phosphate-free in this embodiment.
  • organic co-builders are polycarboxylates / polycarboxylic acids, polymeric carboxylates, aspartic acid, polyacetals, dextrins and organic cobuilders. These classes of substances are described below.
  • Useful organic builders are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and mixtures of these.
  • the free acids typically also have the property of an acidifying component and thus also serve for setting a lower and milder pH of cleaning agents.
  • citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.
  • Particularly preferred cleaning agents according to the invention contain citrate as one of their essential builders.
  • Detergents characterized in that they contain 2 to 40 wt .-%, preferably 5 to 30 wt .-% and in particular 5 to 20 wt .-% citrate, are inventively preferred.
  • Particularly preferred cleaning agents according to the invention are characterized in that the cleaning agent contains at least two builders from the group of phosphates, carbonates and citrates, wherein the proportion by weight of these builders, based on the total weight of the cleaning agent according to the invention, preferably 5 to 60 wt .-%, preferably 15 to 50 wt .-% and in particular 25 to 40 wt .-% is.
  • the combination of two or more builders from the above-mentioned group has proved to be advantageous for the cleaning and rinsing performance of automatic dishwashing agents according to the invention.
  • a mixture of phosphate and citrate or a mixture of GLDA and citrate is used, the amount of phosphate or GLDA preferably being from 10 to 35% by weight and the amount of citrate preferably from 2 to 10% by weight .-%, in each case based on the total amount of the cleaning agent, is, wherein the total amount of these builders is preferably 20 to 35 wt .-%, in particular 25 to 35 wt .-%, is.
  • polymeric polycarboxylates for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular mass of 500 to 70,000 g / mol.
  • Suitable polymers are, in particular, polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may again be preferred from this group.
  • the content of (homo) polymeric polycarboxylates according to the invention is preferably from 0.5 to 20% by weight and in particular from 3 to 10% by weight.
  • the cleaning agents according to the invention may contain in particular phosphonates as further builder.
  • the phosphonate compound used is preferably a hydroxyalkane and / or aminoalkane phosphonate.
  • hydroxyalkane phosphonates 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance.
  • Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs.
  • Phosphonates are in agents according to the invention preferably in amounts of 0.1 to 10 wt .-%, in particular in amounts of 0.5 to 8 wt .-%, each based on the total weight of the cleaning agent.
  • At least one compound selected from MGDA, GLDA and EDDS is preferably used, in particular in phosphate-reduced and phosphate-free compositions.
  • MGDA methylglycinediacetic acid
  • GLDA glutamic acid-N, N-diacetic acid
  • EDDS ethylenediamine-N, N'-disuccinic acid
  • Detergents according to the invention can furthermore comprise, as builder, crystalline layered silicates of the general formula NaMSi x O 2x + 1 .yH 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, Particularly preferred values for x are 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20. It is also possible to use amorphous sodium silicates with a Na 2 O: SiO 2 modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which preferably delayed release and have secondary washing properties.
  • the content of silicates is limited to amounts below 10% by weight, preferably below 5% by weight and in particular below 2% by weight.
  • Particularly preferred cleaning agents according to the invention are silicate-free.
  • the agents according to the invention may contain alkali metal hydroxides.
  • These alkali carriers are preferred in the cleaning agents only in small amounts, preferably in amounts below 10 wt .-%, preferably below 6 wt .-%, preferably below 5 wt .-%, particularly preferably between 0.1 and 5 wt .-% and in particular between 0.5 and 5 wt .-%, each based on the total weight of the cleaning agent used.
  • Alternative cleaning agents according to the invention are free of alkali metal hydroxides.
  • Agents according to the invention preferably comprise at least one further constituent, preferably selected from the group consisting of anionic, cationic and amphoteric surfactants, bleaching agents, bleach activators, bleach catalysts, further solvents, thickeners, sequestering agents, electrolytes, corrosion inhibitors, in particular Silver protectants, glass corrosion inhibitors, foam inhibitors, dyes, fragrances and antimicrobial agents.
  • solvent agents according to the invention preferably contain at least one alkanolamine.
  • the alkanolamine here is preferably selected from the group consisting of mono-, di-, triethanol- and -propanolamine and mixtures thereof.
  • the alkanolamine is preferably contained in agents according to the invention in an amount of from 0.5 to 10% by weight, in particular in an amount of from 1 to 6% by weight.
  • Zinc salts are preferably used as glass corrosion inhibitors.
  • Glass corrosion inhibitors are preferably present in compositions according to the invention in an amount of from 0.05 to 5% by weight, in particular in an amount of from 0.1 to 2% by weight.

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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)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Dispersion Chemistry (AREA)
  • Detergent Compositions (AREA)

Claims (7)

  1. Agent de nettoyage liquide contenant des enzymes placé dans un emballage soluble dans l'eau, l'agent de nettoyage contenant de 25 à 45% en poids d'alcools polyvalents, caractérisé en ce que
    a) il a une viscosité d'au moins 4000 mPas (viscosimètre Brookfield DV-II + Pro, broche 25, 30 tours par minute, 20 °C) ;
    b) il ne contient pas d'acide borique ou de dérivés d'acide borique ;
    c) il contient un mélange de glycérol et de 1,2-propylène-glycol, le glycérol étant utilisé dans une quantité de 1 à 10% en poids, de préférence de 3 à 7% en poids, et le 1,2-propylène-glycol étant utilisé dans une quantité de 15 à 35% en poids, de préférence de 20 à 30% en poids, à chaque fois sur la base de la quantité totale de l'agent de nettoyage, et la quantité totale de glycérol et le 1,2-propylène-glycol étant de 25 à 45% en poids, en particulier de 28 à 40% en poids, surtout de 28,5 à 32,0% en poids ;
    d) il contient au moins un polymère sulfoné.
  2. Agent de nettoyage selon la revendication 1, caractérisé en ce qu'il ne contient pas d'autres stabilisants enzymatiques.
  3. Agent de nettoyage selon l'une des revendications précédentes, caractérisé en ce que le polymère sulfoné est un polymère comprenant
    i) des monomères contenant un groupe acide carboxylique,
    ii) des monomères contenant un groupe acide sulfonique,
    iii) des monomères éventuellement non-ioniques, notamment hydrophobes,
    la quantité totale de polymère sulfoné étant de préférence de 1 à 15% en poids, en particulier de 4 à 14% en poids, surtout de 6 à 12% en poids.
  4. Agent de nettoyage selon l'une des revendications précédentes, caractérisé en ce que la composition contient au maximum 25% en poids d'eau, de préférence de 15 à 20% en poids, de façon particulièrement préférée de 18 à 19,8% en poids d'eau.
  5. Agent de nettoyage selon l'une des revendications précédentes, caractérisé en ce qu'il contient un mélange de phosphate et de citrate ou un mélange d'acide glutamique-N,N-acide diacétique (GLDA) et de citrate,
    la quantité de phosphate ou GLDA allant de préférence de 10 à 35% en poids et la quantité de citrate allant de préférence de 2 à 10% en poids, à chaque fois sur la base de la quantité totale d'agent de nettoyage, la quantité totale de ces adjuvants de lavage allant de préférence de 20 à 35% en poids, en particulier de 25 à 35% en poids.
  6. Agent de nettoyage selon l'une des revendications précédentes, caractérisé en ce que l'emballage soluble dans l'eau est un film contenant de l'alcool polyvinylique.
  7. Procédé de lavage de la vaisselle en machine, caractérisé en ce que l'on utilise un agent de nettoyage selon l'une des revendications précédentes.
EP13700509.6A 2012-02-14 2013-01-08 Produit de nettoyage contenant des enzymes et des alcools polyvalents Not-in-force EP2814930B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL13700509T PL2814930T3 (pl) 2012-02-14 2013-01-08 Zawierający enzym środek do czyszczenia z alkoholami wielowodorotlenowymi

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102012202178A DE102012202178A1 (de) 2012-02-14 2012-02-14 Enzymhaltiges Reinigungsmittel mit mehrwertigen Alkoholen
PCT/EP2013/050207 WO2013120635A1 (fr) 2012-02-14 2013-01-08 Produit de nettoyage contenant des enzymes et des alcools polyvalents

Publications (2)

Publication Number Publication Date
EP2814930A1 EP2814930A1 (fr) 2014-12-24
EP2814930B1 true EP2814930B1 (fr) 2017-12-20

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US (1) US20140349912A1 (fr)
EP (1) EP2814930B1 (fr)
DE (1) DE102012202178A1 (fr)
ES (1) ES2658212T3 (fr)
HU (1) HUE036647T2 (fr)
PL (1) PL2814930T3 (fr)
WO (1) WO2013120635A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102012107728A1 (de) * 2012-08-22 2014-02-27 Witty-Chemie Gmbh & Co. Kg Phosphorfreies Reinigungsmittel für Geschirrspülanlagen und Verfahren dafür
CA3149849A1 (fr) * 2019-09-30 2021-04-08 Ecolab Usa Inc. Compositions detergentes enzymatiques stabilisees

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1298196A1 (fr) * 2001-09-28 2003-04-02 Unilever N.V. Emballage hydrosoluble et contenu liquide de celui-ci
WO2013104607A1 (fr) * 2012-01-11 2013-07-18 Henkel Ag & Co. Kgaa Emballage parfumé soluble dans l'eau

Family Cites Families (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1112534A (fr) * 1976-11-03 1981-11-17 John Pardo Detergent pour lave-vaisselle automatique
US6680289B1 (en) * 1999-09-02 2004-01-20 The Proctor & Gamble Company Methods, compositions, and articles for odor control
US6995125B2 (en) * 2000-02-17 2006-02-07 The Procter & Gamble Company Detergent product
US6812199B2 (en) * 2000-04-28 2004-11-02 The Procter & Gamble Company Method for treating stained materials
US7125828B2 (en) * 2000-11-27 2006-10-24 The Procter & Gamble Company Detergent products, methods and manufacture
US6492312B1 (en) * 2001-03-16 2002-12-10 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Water soluble sachet with a dishwashing enhancing particle
EP1434715B1 (fr) * 2001-10-08 2006-06-07 The Procter & Gamble Company Procede permettant la production de sachets solubles dans l'eau et sachets ainsi obtenus
EP1314652B1 (fr) * 2001-11-23 2006-03-08 The Procter & Gamble Company Sachet soluble dans l'eau
GB0131055D0 (en) * 2001-12-28 2002-02-13 Unilever Plc Detergent compositions
EP1354939A1 (fr) * 2002-04-19 2003-10-22 The Procter & Gamble Company Compositions detergentes en sachet
WO2004018611A1 (fr) * 2002-08-20 2004-03-04 The Procter & Gamble Company Composition de detergent en gel liquide pour machine a laver la vaisselle automatique comprenant un solvant anhydre
DE10313453A1 (de) * 2003-03-25 2004-10-14 Henkel Kgaa Portionierte Wasch- oder Reinigungsmittelzusammensetzung
DE602004000316T2 (de) * 2003-03-25 2006-07-27 Unilever N.V. Wassserlösliche Verpackung mit flüssigem Inhalt
CA2527316C (fr) * 2003-06-03 2011-08-16 The Procter & Gamble Company Poche de detergent
ES2287831T3 (es) * 2004-05-11 2007-12-16 THE PROCTER & GAMBLE COMPANY Producto detergente de dosis unitaria que comprende aceite de silicona.
DE602005015532D1 (de) * 2004-11-22 2009-09-03 Procter & Gamble Wasserlöslicher Beutel gefüllt mit einer Flüssigkeit
US20060275566A1 (en) * 2005-06-01 2006-12-07 De Buzzaccarini Francesco Water-soluble, liquid-containing pouch
DE102009027812A1 (de) * 2009-07-17 2011-01-20 Henkel Ag & Co. Kgaa Flüssiges Wasch- oder Reinigungsmittel mit vergrauungsinhibierendem Polymer
US8905236B2 (en) * 2010-01-29 2014-12-09 Monosol, Llc Water-soluble film having improved dissolution and stress properties, and packets made therefrom
PL2609183T3 (pl) * 2010-08-23 2019-05-31 Henkel IP & Holding GmbH Kompozycje detergentowe w dawkach jednostkowych i sposoby ich wytwarzania i zastosowania
EP2441824A1 (fr) * 2010-10-15 2012-04-18 Cognis IP Management GmbH Liquide pour le lavage du linge adapté pour un conditionnement dans des sachets à l'alcool polyvinylique

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1298196A1 (fr) * 2001-09-28 2003-04-02 Unilever N.V. Emballage hydrosoluble et contenu liquide de celui-ci
WO2013104607A1 (fr) * 2012-01-11 2013-07-18 Henkel Ag & Co. Kgaa Emballage parfumé soluble dans l'eau

Also Published As

Publication number Publication date
WO2013120635A1 (fr) 2013-08-22
HUE036647T2 (hu) 2018-07-30
US20140349912A1 (en) 2014-11-27
PL2814930T3 (pl) 2018-05-30
EP2814930A1 (fr) 2014-12-24
DE102012202178A1 (de) 2013-08-14
ES2658212T3 (es) 2018-03-08

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