EP3102657A1 - Produit de nettoyage préalablement proportionné - Google Patents

Produit de nettoyage préalablement proportionné

Info

Publication number
EP3102657A1
EP3102657A1 EP15702493.6A EP15702493A EP3102657A1 EP 3102657 A1 EP3102657 A1 EP 3102657A1 EP 15702493 A EP15702493 A EP 15702493A EP 3102657 A1 EP3102657 A1 EP 3102657A1
Authority
EP
European Patent Office
Prior art keywords
weight
liquid phase
cleaning agent
agent according
acid
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.)
Granted
Application number
EP15702493.6A
Other languages
German (de)
English (en)
Other versions
EP3102657B1 (fr
Inventor
Volker Blank
Noelle Wrubbel
Martina Hutmacher
Matthias Sunder
Ulrich Pegelow
Oliver Kurth
von den Karl-Josef DRIESCH
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to PL15702493T priority Critical patent/PL3102657T3/pl
Publication of EP3102657A1 publication Critical patent/EP3102657A1/fr
Application granted granted Critical
Publication of EP3102657B1 publication Critical patent/EP3102657B1/fr
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

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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
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3707—Polyethers, e.g. polyalkyleneoxides
    • 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
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • 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
    • 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
    • C11D17/045—Multi-compartment

Definitions

  • the present invention relates to pre-portioned detergents, in particular automatic dishwashing detergents and their use.
  • Hard surface cleaners such as dishwashing detergents
  • dishwashing detergents are available to the consumer in a variety of forms.
  • traditional solid agents are gaining increasingly increasingly flowable and especially liquid to gel detergent in importance.
  • the consumer particularly appreciates the rapid solubility and the associated rapid availability of the ingredients in the cleaning liquor, especially in short-dishwashing programs and at low temperatures.
  • compositions in which in particular the water content is reduced compared to conventional compositions, increases.
  • compositions whose water content is as low as possible are particularly desirable.
  • Multichamber shaped articles in particular those made of water-soluble material, such as e.g. Container made of PVA, produced by injection molding.
  • Disposable portions in particular water-soluble bags or multi-chamber tablets made of water-soluble material, enjoy the consumer not only because of increasing popularity, because the consumer with the chemical composition is no longer in contact, but not least because of the attractive appearance of the bag. For the consumer, it is therefore a nuisance if the bags lose their attractive appearance.
  • Multifunctional automatic dishwashing detergents save the user the separate use of rinse aid and the refilling of salt in the dishwasher.
  • certain builders are used in their formulations which achieve a good rinse aid result and counteract the formation of coatings even at higher water hardness. Modern dishwashers see one for the dosage of cleaning products
  • Dosing which automatically opens during the wash program and releases the product.
  • the size of the metering chamber is however limited in its capacity.
  • Functional blocks of the dishwashing detergent formulation such as builder, alkalinity, enzymes, surfactants, etc. are provided. This means that the available volume of the dosing chamber must be used optimally in order to produce a sufficient amount of the active substances and thus a good cleaning performance.
  • waxy and solid surfactants are used, which lead to a phase separation within the low-water means, wherein the agent separates into two liquid phases.
  • the object of the present invention was to provide a pre-portioned detergent, in particular dishwashing detergent, preferably machine dishwashing detergent, in particular multi-phase detergent, with at least one liquid and at least one solid, especially preferably pulverulent, phase which fits into the dispensing compartment of the dishwasher and still exhibits good cleaning performance ,
  • Machine dishwashing detergent in a packaging with, comprising at least one liquid phase, characterized in that the liquid phase at least one polyalkylene glycol having an average molecular weight between about 1500 and about 8000, in particular between about 2000 and about 6000, in particular between about 3000 and about 4500 contains.
  • the polyalkylene glycols are selected from
  • the liquid phase or the liquid phases of the cleaning agents according to the invention preferably contains a polyalkylene glycol which is selected from the polyalkylene glycols of the formula (I)
  • polyalkylene glycols especially those of the formula (i) with the abovementioned radicals, with an average molecular weight between about 1500 and about 8000, in particular between about 2000 and about 6000, in particular between about 3000 and about 4500, included.
  • polyethylene glycols in particular polyethylene glycols having an average molecular weight of about 4000 (INCI: PEG 4000), contained in the stated amount.
  • other polyethylene glycols having other molecular weights may be included.
  • co-builders In particular in cleaning agents, in particular in those which contain only small amounts of phosphate or which are substantially free of phosphates, co-builders must be used in addition to the phosphate-containing and / or phosphate-free builders in order to achieve sufficiently high complexation of divalent cations To ensure the rinse water used, usually local tap water, which otherwise leave on the dishes coverings.
  • Polymeric, polycarboxylate-containing cobuilders are usually marketed as aqueous preparations. In aqueous machine dishwashing detergents, they are therefore usually formulated directly into the aqueous cleaning agents. If they are to be used in solid formulations, they must first be dried time-consuming and energy-intensive and then formulated as granules. Then they are particularly suitable for solid, especially granular products.
  • substantially anhydrous or non-aqueous cleaning agents in particular in machine dishwashing detergents, the aqueous preparations of co-builders are not suitable due to the high water input.
  • a multi-phase pre-portioned detergent in particular
  • Machine dishwashing detergent containing at least one solid and one liquid phase optimized with respect to the dimensions of the metering chamber in dishwashers
  • liquid cleaning agents in particular liquid machine dishwashing detergents which are substantially free of water
  • solid components must be finely distributed (as dispersion) in an organic matrix and also remain stable in storage in the dispersion and should not sediment. It is best in such liquid formulations, which are substantially free of water, the dried (freed from water)
  • Polycarboxylatumble component and / or the sulfonic acid-containing polymers used in finely ground form Polycarboxylatumble component and / or the sulfonic acid-containing polymers used in finely ground form.
  • the cleaning agent according to the invention in particular machine dishwashing detergent, contains a total of between 0.5 wt .-% and 30 wt .-%, preferably 1 to 20 wt .-%, in particular 2 to 10 wt .-% (based on the total weight of the composition) of polymeric or co-polymers
  • Polycarboxylates or sulfonic acid-containing polymers are examples of polycarboxylates or sulfonic acid-containing polymers.
  • it contains in total between 0.5% by weight and 30% by weight, preferably 1 to 20% by weight, in particular 2 to 10% by weight (based on the total weight of the composition) of (co) polymeric polycarboxylates and sulfonic acid group-containing polymers.
  • the solid phase (or solid phases) of the cleaning agent according to the invention in particular machine dishwashing detergent, contains less than 10% by weight, preferably less than 5% by weight, in particular less than 3% by weight (based on the weight of the solid phase ), polymeric or co-polymeric polycarboxylates.
  • the solid phase (or solid phases) of the cleaning agent according to the invention in particular machine dishwashing detergent, contains less than 10% by weight, preferably less than 5% by weight, in particular less than 3% by weight (based on the weight of the solid phase )
  • the solid phase (or solid phases) of the invention is preferably, the solid phase (or solid phases) of the invention
  • Cleaning agent in particular machine dishwashing detergent, less than 10 wt .-%, preferably less than 5 wt .-%, in particular less than 3 wt .-% (based on the weight of the solid phase), polymeric or co-polymeric polycarboxylates and sulfonic acid-containing polymers ,
  • the polymeric or copolymeric polycarboxylates are suitable according to the invention as builders, these being, for example, the alkali metal salts of polyacrylic acid or of polymethacrylic acid, for example those having a relative molecular mass of 500 to 70,000 g / mol.
  • the polyacrylate or the polyacrylates are here in particular in a dried, particularly preferably in a dried and granulated (solid) mold, which may optionally be additionally ground.
  • Suitable polymers are, in particular, polyacrylates which preferably have a molecular weight of from 1,000 to 20,000, in particular from 2,000 to 10,000 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.
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Their relative molecular weight, based on free acids is generally from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.
  • polycarboxylic acids (carboxylic acids having more than one carboxylate function) in monomeric form are not to be understood as polymeric polycarboxylates.
  • polycarboxylic acids as described in detail below as organic cobuilders and which may be present in the liquid phase (s) as well as the solid phase (s) according to the invention (ie they are is not included in the amounts indicated for polymeric polycarboxylates and are thus not taken into account for the quantitative restrictions).
  • the detergents according to the invention may further comprise a sulfonic acid group-containing polymer (hereinafter also referred to as sulfopolymer).
  • a sulfonic acid group-containing polymer hereinafter also referred to as sulfopolymer.
  • the proportion by weight of the sulfopolymer in the total weight of the inventive cleaning agent is preferably from 0.1 to 20% by weight, in particular from 0.5 to 18% by weight .-%, preferably 1, 0 to 15 wt .-%, very particularly preferably 2.0 to 14 wt .-%, in particular from 4 to 14 wt .-%, especially from 4.5 to 12% by weight
  • the sulfopolymer is used here in particular in a dried, particularly preferably in a dried and granulated (solid) form, wherein this may optionally additionally be ground.
  • the sulfopolymer used is preferably a copolymeric polysulfonate, for example a hydrophobically modified copolymeric polysulfonate.
  • the copolymers may have two, three, four or more different monomer units.
  • Preferred copolymeric polysulfonates contain sulfonic acid group-containing (s)
  • Monomer (s) at least one monomer from the group of unsaturated carboxylic acids.
  • unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, alpha-chloroacrylic acid, alpha-cyanoacrylic acid, crotonic acid, alpha-phenyl-acrylic acid,
  • 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-sulfo - Propylmethacrylat, sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of said acids or their water-
  • 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.
  • Sulfonic acid-containing copolymers is inventively preferred.
  • 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 share of
  • 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 ⁇ preferably of 4000 to 25,000 gmol " and in particular of 5000 to 15,000 gmol -1 .
  • the copolymers include besides
  • Carboxyl-containing monomer and sulfonic acid-containing monomer further 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.
  • Anionic copolymers comprising monomers containing carboxylic acid groups, monomers containing sulfonic acid groups and nonionic monomers, in particular hydrophobic monomers, are therefore preferred according to the invention.
  • nonionic monomers are preferably monomers of the general formula
  • 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, ethylcyclohexyne, 1-octene, alpha-olefins having 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and
  • 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.
  • polymeric or co-polymeric polycarboxylates and / or sulfonic acid group-containing polymers in particular acrylic acid and sulfopolymers.
  • organic co-builders are polycarboxylates / polycarboxylic acids, aspartic acid, polyacetals, dextrins, other organic cobuilders and phosphonates. 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 citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid,
  • NTA nitrilotriacetic acid
  • Acidification and thus also serve to set a lower and milder pH of the automatic dishwashing detergent.
  • citric acid here are citric acid,
  • Succinic acid glutaric acid, adipic acid, gluconic acid and any mixtures thereof.
  • aminocarboxylic acids and / or their salts.
  • Particularly preferred members of this class are methylglycinediacetic acid (MGDA) or its salts and glutamic diacetic acid (GLDA) or its salts or ethylenediamine diacetic acid or its salts (EDDS).
  • MGDA methylglycinediacetic acid
  • GLDA glutamic diacetic acid
  • EDDS ethylenediamine diacetic acid or its salts
  • IDS iminodisuccinic acid
  • Iminodiacetic acid IDA
  • Aminocarboxylic acids and their salts can be used together with the abovementioned builders, in particular also with the phosphate-free builders.
  • MGDA MGDA
  • GLDA GLDA
  • salts thereof MGDA
  • MGDA MGDA
  • MGDA can be used preferably as granules, and particularly preferably in the solid phase. Particular preference is given to those MGDA granules which contain as little water as possible and / or have low hygroscopicity.
  • MGDA or salts thereof in a total amount of 3 to 50 wt .-% based on the total weight of the cleaning agent.
  • the detergents may contain, in particular, phosphonates as builder.
  • the phosphonate compound used is preferably a hydroxyalkane and / or aminoalkane phosphonate.
  • hydroxyalkane phosphonates is 1-hydroxyethane-1,1-diphosphonate (HEDP) of particular importance.
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • Aminoalkanphosphonate are preferably
  • ETMP Ethylenediaminetetramethylenephosphonate
  • DTPMP Diethylentriaminpentamethylenphosphonat
  • Phosphonate-containing components are contained in the compositions 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.
  • Aminoalkan portion contain the agents of the invention from 0.01 to 25 wt .-%, preferably 5 to 20 wt .-%, 8 to 15 wt .-% phosphonate (in each case based on the total weight of the composition).
  • the phosphonates are preferably contained in the solid phase (s).
  • substantially free of water means that a composition contains less than 7% by weight, in particular less than 5% by weight, preferably less than 3% by weight, more preferably less than 1% by weight.
  • the water content as defined herein refers to the water content determined by Karl Fischer titration.
  • the liquid phase is according to "substantially free of water", this means that the liquid phase less than 7 wt .-%, in particular less than 5 wt .-%, preferably less than 3 wt .-%, more preferably less than
  • the water content as defined herein refers to the water content determined by Karl Fischer titration.
  • each of the individual phases contains less than 7 wt .-%, in particular less than 5 wt .-%, preferably less than 3 wt%, more preferably less than 1 wt .-% Water (in each case based on the total weight of the respective phase).
  • Liquid as used herein in reference to the cleaning agent of the present invention includes all flowable compositions and more particularly includes gels and pastes
  • compositions which also includes non-Newtonian fluids having a yield point.
  • At least one means 1 or more, for example, 1, 2, 3, 4, 5, or more.
  • Solid as used herein in reference to the cleaning composition of the invention includes all solid compositions, and includes in particular powdered, granulated, amorphous, compressed, in particular pressed, tabletted compositions In addition to powdery constituents, in some cases compositions may also contain granules.
  • the detergent is in a water-soluble packaging.
  • the water-soluble packaging allows a portioning of the detergent.
  • 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 detergent is preferably in an amount sufficient to carry out the cleaning, in machine dishwashing detergents in particular a cycle or a complete program run one
  • the cleaning agent according to the invention preferably comprises at least one solid, preferably pulverulent phase and at least one liquid phase.
  • the water-soluble packaging at least two or more spatially separate compartments (chambers), in which spatially separated at least one solid, preferably powdery, and at least one liquid phase are filled.
  • two-chamber bags or two-chamber tablets which contain a solid and a liquid phase in separate compartments.
  • multi-chamber packaging multi-chamber bag or
  • a phase is here understood to mean a detergent (partial) composition which, in combination with the other phase (s), results in a cleaning agent, in particular a machine dishwashing detergent.
  • the cleaning agent according to the invention in particular machine dishwashing detergent, can also be present in a water-soluble packaging, which in particular contains more than two, so for example, three, four, five or six compartments.
  • the package contains two, three or more chambers (compartments), wherein one, two or more of these chambers are filled with liquid phases, which are preferably different from each other, and in particular one or more mutually different ingredients.
  • liquid phases which are preferably different from each other, and in particular one or more mutually different ingredients.
  • pre-portioned detergents in which the water-soluble package has one, two or more chambers in addition to one, two or more liquid phases
  • Solid phases containing solid phases.
  • two or more solid phases it is preferred that they be of different composition and / or have a different solid form.
  • pre-portioned cleaning compositions which have at least one solid, preferably at least one pulverulent phase and at least one liquid phase in separate compartments.
  • pre-portioned detergents containing at least one solid, preferably at least one compressed phase and one liquid phase in separate
  • the pre-portioned cleaning agent may also be preferable for the pre-portioned cleaning agent to have two or more solid phases, of which at least one powdery and at least one compressed and at least one, also two, three or more liquid phases are in each case separate compartments.
  • the pre-portioned cleaning agent in particular in a multi-chamber bag, contains a solid, one of which is different powdery and two liquid phases in each case separate compartments.
  • the at least one liquid phase in the cleaning agent according to the invention is substantially free of organic components which have an average molecular weight of less than 175 g / mol, preferably less than 150 g / mol;
  • Molecular weight of less than 175 g / mol, preferably less than 150 g / mol means that in the liquid phase (in the case of several liquid phases in each individual liquid phase) less than 5 wt .-%, preferably less than 3 wt .-% of such organic compounds are included, which have an average molecular weight of less than 175 g / mol, preferably of less than 150 g / mol.
  • the presence of usually short-chain organic solvents which a
  • Dipropylene glycol dimethyl ether preferably of less than 150 g / mol, such as decane, octane, dipropylene glycols, glycerol, propanediols, monoethanolamine, diethanolamine are avoided, which are particularly prone to migration between the compartments.
  • said organic components preferably organic solvents, which have an average molecular weight of less than 175 g / mol, preferably less than 150 g / mol, in each case only to a proportion of less be contained as 5 wt .-%, preferably of less than 3 wt .-% (each based on the composition of the individual liquid phase).
  • the pre-portioned cleaning agent in particular machine dishwashing detergent, comprises a plurality of liquid phases in separate compartments
  • each of the liquid phases is essentially free of organic components having an average molecular weight of less than 175 g / mol, preferably less than 150 g / mol (except those mentioned under a)) components, since otherwise a migration of the components between the individual liquid phases in the separated
  • the liquid phase (are the liquid phases) of the cleaning agent according to the invention in particular machine dishwashing, in
  • Substantially free of organic components which have an average molecular weight of less than 175 g / mol, preferably less than 150 g / mol and liquid at 20 ° C and 1 bar.
  • At least one is in the liquid phase
  • nonionic surfactant which is liquid at 20 ° C and 1 bar, preferably in amounts between 5 and 60 wt .-%, in particular between 8 and 40 wt .-%, preferably between 10 and 30% by weight (based on the weight the liquid phase).
  • At least one is in the liquid phase
  • nonionic surfactant which is waxy or solid at 20 ° C and 1 bar, preferably in amounts between 5 and 60 wt .-%, in particular between 10 and 50 wt .-%, preferably between 15 and 30 wt .-% (based on the weight of the liquid phase).
  • at least one nonionic surfactant which is liquid at 20 ° C. and 1 bar and at least one nonionic surfactant which is waxy or solid at 20 ° C. and 1 bar are used together in the abovementioned amounts.
  • the pre-portioned detergents according to the invention in particular machine dishwashing detergents, preferably additionally contain in the liquid phase, in one of the liquid phases, in particular in all liquid phases
  • R is selected from -H, -CH 3 , straight-chain or branched, saturated or mono- or polyunsaturated, C2-24-alkyl or alkenyl radical;
  • R 2 , R 3 , R 4 , R 5 are each independently selected from -H, -CH 3 , -
  • R 6 is selected from -H, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -CH 2 -CH 2 -
  • R 7 represents a straight-chain or branched, saturated or mono- or polyunsaturated C 6-26-alkyl or alkenyl radical
  • the liquid phase or the liquid phases of the cleaning agents according to the invention contain at least one component according to a).
  • polyalkylene glycol preferably polyethylene glycols or polypropylene glycols, in particular
  • Polyethylene glycols having an average molecular weight between 150 and 1000, preferably 200 to 800, in particular between 300 and 600, for example 400.
  • the additional polyalkylene glycol in an amount of 10 to 40 wt .-%, preferably from 15 to 35 wt .-%, in particular (based on the weight of the liquid n phase) is included.
  • the liquid phase (s) is at least one polyalkylene glycol, preferably at least one polyethylene glycol (PEG), which has an average molecular weight between 2000 and 6000 g / mol, in particular a PEG having an average molecular weight of approx. PEG 4000 (INCI: PEG 4000).
  • the liquid phase is a PEG having an average molecular weight of about 400, in particular in amounts of 15 to 35 wt.%, And a PEG having an average molecular weight of about 4000, in particular in amounts from 4 to 10 wt .-% (each based on the amount in the liquid phase).
  • Formula (I) are also a large part of the nonionic surfactants to grasp. Preference is given to weakly foaming alkoxylated nonionic surfactants, in particular ethoxylated,
  • the automatic dishwashing agents contain nonionic surfactants from the group of alkoxylated alcohols.
  • Cleaning agent in the liquid phase at least one nonionic surfactant, in particular selected from surfactants according to formula (I).
  • surfactants come from the groups of alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures of these surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants).
  • Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.
  • nonionic surfactants used are low-foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units.
  • surfactants with EO-AO-EO-AO blocks are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows.
  • R-O- (CH 2 -CH (R 2 ) -O) w- (CH 2 -CH (R 3 ) -O) x- (CH 2 -CH (R 4 ) -O) y - (CH 2 -CH (R 5 ) -0) zR 6 in which R is a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24-alkyl or alkenyl radical; R 2 , R 4 , R 6 each -H; each group R 3 or R 5 is independently selected from -Chta, -CH 2 CH 3, -CH 2 CH 2 -CH 3, CH (CH 3) 2 and the indices w, x, y, z independently represent integers from 1 to 6.
  • nonionic surfactants having a C9-alkyl group with 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units, followed by 1 to 4
  • nonionic surfactants are those of the general formula
  • R is H or a linear or branched hydrocarbon radical having 2 to 26 carbon atoms
  • R 2 , R 3 , R 4 , R 5 are each independently selected from -H, -Chta, -CH 2 CH 3 , -CH 2 CH 2 CH 3 , CH (CH 3 ) 2, preferably -H or -CH 3 ;
  • R 6 is selected from -CH 2 CH (OH) R 7
  • R 7 for a straight-chain or branched, saturated or on or
  • w, x, y and z are values between 1 and 120, where x, y and / or z can also be 0.
  • nonionic surfactants of the general formula (I) have proven to be particularly effective.
  • R is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms
  • R 6 is selected from -CH 2 CH (OH) R 7
  • R 7 for a straight-chain or branched, saturated or on or
  • the group of these nonionic surfactants includes, for example, the C4-22 fatty alcohol (EO) io-8o-2-hydroxyalkyl ethers, in particular also the C8-12 fatty alcohol (EO) 22-2-hydroxydecyl ethers and the C4-22 fatty alcohol (EO) 4o 8o-2-hydroxyalkyl ethers.
  • nonionic surfactants include, for example, the C2-26 fatty alcohol (PO) i- (EO) is-4o-2-hydroxyalkyl ethers, in particular the coco fatty alcohol (PO) i (EO) 22-2-hydroxydecyl ethers ,
  • R 7 represents a straight-chain or branched, saturated or mono- or polyunsaturated C 6-26-alkyl or alkenyl radical
  • the cleaning agent in particular machine dishwashing detergent
  • in the liquid phase at least one, preferably at least two, in particular at least three of the components according to a) have a melting point (at 1 bar) of ⁇ 30 ° C., preferably ⁇ 25 ° C. in particular ⁇ 20 ° C.
  • the liquid phase or the liquid phases of the cleaning agent according to the invention preferably additionally comprise at least one nonionic surfactant, preferably one which likewise represents a component according to a) according to formula I.
  • R is selected from straight-chain or branched, saturated Ce-alkyl radicals
  • R 2 and R 4 are -H
  • R 3 and R 5 are -CH 3
  • R 6 is selected from -H, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -CH 2 -CH 2 -
  • w 1 to 6, preferably 1, 5 to 4.5, in particular 2 to 3;
  • x 1 to 6, preferably 1, 5 to 4.5, in particular 2 to 3;
  • y 0 to 6, preferably 1, 5 to 4.5, 2 to 3;
  • z 0 to 6, preferably 1, 5 to 4.5, 2 to 3, is contained.
  • At least one nonionic surfactant is selected from those nonionic surfactants which are liquid at 20 ° C and 1 bar.
  • Fatty alcohol alkoxylates these are preferably in amounts between 5 and 60 wt .-%, in particular between 8 and 40 wt .-%, preferably between 10 and 30 wt .-% (based on the weight of the liquid phase).
  • components according to a) are particularly advantageous, since they (possibly in addition to liquid polyalkylene glycols) can provide a basis for the liquid phase, without thereby organic components, in particular organic solvents which have an average molecular weight of less than 175 g / mol, preferably less than 150 g / mol, must be used.
  • a polyalkylene glycol preferably at least one polyethylene glycol, which has an average molecular weight between 300 and 4000 g / mol, is used.
  • the liquid phase (s) comprises a PEG having an average molecular weight of about 400 (INCI: PEG 400) and a PEG having a middle molecular weight
  • Components used as further component according to a) is at least one ethoxylated hydroxy mixed ether of the formula (I)
  • R is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms
  • R 6 is selected from -CH 2 CH (OH) R 7
  • R 7 for a straight-chain or branched, saturated or on or
  • C 4-22 fatty alcohol (EO) io-8o-2-hydroxyalkyl ethers particularly preferred are in particular also the C 8-12 fatty alcohol (EO) 22-2-hydroxydecyl ethers and the C 4-22 fatty alcohol (EO) 4-alcohols. 8o-2-hydroxyalkyl ethers.
  • At least one nonionic surfactant which is waxy or solid at 20 ° C. and 1 bar is present in the liquid phase.
  • fatty alcohol hydroxy mixed ethers specified hereinbefore. These are preferably used in amounts of between 5 and 60% by weight, in particular between 10 and 50% by weight, preferably between 15 and 30% by weight (based on the weight of the liquid phase). In this case, it is preferred that the amount of all components mentioned as being preferred according to a) in the liquid phase is between 10 to 80% by weight, preferably between 20 and 70% by weight (in each case based on the total weight of the liquid phase) ,
  • the amount of all the components mentioned in accordance with a) in the liquid phase is between 10 to 80 wt .-%, preferably between 20 to 70 wt .-% (each based on the total weight of the liquid phase) ,
  • the liquid phase (at least one of the liquid phase, if appropriate all liquid phases) in each case based on the respective
  • R is selected from straight-chain or branched, saturated Ce-alkyl radicals
  • R 2 and R 4 are -H
  • R 3 and R 5 are -CH 3
  • R 6 is selected from -H, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -CH 2 -CH 2 -
  • w 1 to 6, preferably 1, 5 to 4.5, in particular 2 to 3;
  • x 1 to 6, preferably 1, 5 to 4.5, in particular 2 to 3;
  • y 0 to 6, preferably 1, 5 to 4.5, 2 to 3;
  • z 0 to 6, preferably 1, 5 to 4.5, 2 to 3, is contained,
  • R is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms
  • R 6 is selected from -CH 2 CH (OH) R 7
  • R 7 for a straight-chain or branched, saturated or on or
  • polyalkylene glycols preferably polyethylene glycol, having an average molecular weight between 1500 and 8000, in particular between 2000 and 6000, in particular between 3000 and 4500, is contained.
  • Components in the liquid phase between 15 to 80 wt .-%, preferably between 20 to 70 wt .-% (in each case based on the total weight of the liquid phase).
  • the liquid phase (at least one of the liquid phase, if appropriate all liquid phases) in each case based on the respective
  • R is selected from straight-chain or branched, saturated Ce-alkyl radicals
  • R 2 and R 4 are -H
  • R 3 and R 5 are -CH 3
  • R 6 is selected from -H, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -CH 2 -CH 2 -CH 2 CH 3 , -CH 2 CH (CH 3 ) 2, -C (CH 3 ) 3, Cs -20-alkyl (linear or branched), and are independently selected
  • w 1 to 6, preferably 1, 5 to 4.5, in particular 2 to 3;
  • x 1 to 6, preferably 1, 5 to 4.5, in particular 2 to 3;
  • y 0 to 6, preferably 1, 5 to 4.5, 2 to 3;
  • z 0 to 6, preferably 1, 5 to 4.5, 2 to 3, is contained,
  • R is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms
  • R 6 is selected from -CH 2 CH (OH) R 7
  • R 7 for a straight-chain or branched, saturated or on or
  • Components in the liquid phase between 15 to 80 wt .-%, preferably between 20 to 70 wt .-% (in each case based on the total weight of the liquid phase).
  • the liquid phase (at least one of the liquid phase, if appropriate all liquid phases) in each case based on the respective
  • R is selected from straight-chain or branched, saturated Ce-alkyl radicals
  • R 2 and R 4 are -H
  • R 3 and R 5 are -CH 3
  • R 6 is selected from -H, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -CH 2 -CH 2 -CH 2 CH 3 , -CH 2 CH (CH 3 ) 2, -C (CH 3 ) 3, Cs -20-alkyl (linear or branched), and are independently selected
  • w 1 to 6, preferably 1, 5 to 4.5, in particular 2 to 3;
  • x 1 to 6, preferably 1, 5 to 4.5, in particular 2 to 3;
  • y 0 to 6, preferably 1, 5 to 4.5, 2 to 3;
  • z 0 to 6, preferably 1, 5 to 4.5, 2 to 3, is contained,
  • R is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms
  • R 6 is selected from -CH 2 CH (OH) R 7
  • R 7 for a straight-chain or branched, saturated or on or
  • Components in the liquid phase between 15 to 80 wt .-%, preferably between 20 to 70 wt .-% (in each case based on the total weight of the liquid phase).
  • the liquid phase (at least one of the liquid phase, if appropriate all liquid phases) in each case based on the respective
  • R is selected from straight-chain or branched, saturated Ce-alkyl radicals
  • R 2 and R 4 are -H
  • R 3 and R 5 are -CH 3
  • R 6 is selected from -H, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -CH 2 -CH 2 -CH 2 CH 3 , -CH 2 CH (CH 3 ) 2, -C (CH 3 ) 3, Cs -20-alkyl (linear or branched), and are independently selected
  • w 1 to 6, preferably 1, 5 to 4.5, in particular 2 to 3;
  • x 1 to 6, preferably 1, 5 to 4.5, in particular 2 to 3;
  • y 0 to 6, preferably 1, 5 to 4.5, 2 to 3;
  • z 0 to 6, preferably 1, 5 to 4.5, 2 to 3, is contained,
  • R is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms
  • R 6 is selected from -CH 2 CH (OH) R 7
  • R 7 for a straight-chain or branched, saturated or on or
  • polyethylene glycols preferably polyethylene glycol
  • polyalkylene glycols preferably polyethylene glycol, having an average molecular weight between 1500 and 8000, in particular between 2000 and 6000, in particular between 3000 and 4500, having.
  • Components in the liquid phase between 15 to 80 wt .-%, preferably between 20 to 70 wt .-% (in each case based on the total weight of the liquid phase).
  • the liquid phase (at least one of the liquid phase, if appropriate all liquid phases) in each case based on the respective
  • R is selected from straight-chain or branched, saturated Ce-alkyl radicals
  • R 2 and R 4 are -H
  • R 3 and R 5 are -CH 3
  • R 6 is selected from -H, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -CH 2 -CH 2 -CH 2 CH 3 , -CH 2 CH (CH 3 ) 2, -C (CH 3 ) 3, Cs -20-alkyl (linear or branched), and are independently selected
  • w 1 to 6, preferably 1, 5 to 4.5, in particular 2 to 3;
  • x 1 to 6, preferably 1, 5 to 4.5, in particular 2 to 3;
  • y 0 to 6, preferably 1, 5 to 4.5, 2 to 3;
  • z 0 to 6, preferably 1, 5 to 4.5, 2 to 3, is contained,
  • R is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms
  • R 6 is selected from -CH 2 CH (OH) R 7
  • R 7 for a straight-chain or branched, saturated or on or
  • Polyalkylenglycole preferably polyethylene glycol, having an average molecular weight between 300 and 600 g / mol and
  • polyalkylene glycols preferably polyethylene glycol, with a middle
  • the amount of all of the components referred to as preferred according to a) in the liquid phase is between 10 to 80 wt .-%, preferably between 20 to 70 wt .-% (each based on the total weight of the liquid phase) ,
  • liquid phase in the liquid phase (the liquid phases) additionally a end-capped nonionic surfactant according to formula II
  • R 8 and R 0 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms
  • R 9 is H or a methyl, ethyl, n-propyl, iso-propyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical
  • h are values between 1 and 30
  • k and j are values between 1 and 12, preferably between 1 and 5. If the value h> 2, then any R 9 in the formula above can
  • R 8 0 [CH 2 CH (R 9 ) 0] h [CH 2 ] kCH (OH) [CH 2] jOR ° be different.
  • R 8 and R 0 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 9 H, -Chta or -CH 2 CH 3 are particularly preferred.
  • Particularly preferred values for h are in the range from 1 to 20, in particular from 6 to 15.
  • each R 9 in the above formula may be different if h> 2.
  • the alkylene oxide unit in the square bracket can be varied.
  • the value 3 for h has been selected here by way of example and may well be greater, with the range of variation increasing with increasing h values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,
  • R 8 0 [CH 2 CH (R 9 ) 0] hCH 2 CH (OH) CH 2 OR ° simplified.
  • R 8 , R 0 and R 9 is 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 8 and R 0 have 9 to 14 carbon atoms, R 9 stands for H and h assumes values of 6 to 15.
  • the amount of all components according to a) in the liquid phase is between 10 and 80% by weight, preferably between 20 and 70% by weight (in each case based on the total weight of the liquid phase).
  • the ratio of the weight of one or more solid phases (of which preferably at least one solid phase is powdery, (in the case of several solid / powder phases the total weight of all solid and powder phases) to the weight of one or more liquid phases (in the case of several liquid phases preferably 1:10 to 10: 1, particularly preferably 1: 5 to 5: 1, very particularly preferably 4: 1 to 1: 2.
  • the cleaning agent in particular
  • Machine dishwashing detergents essentially free of anionic surfactants
  • Substantially free of anionic surfactants as used herein means that a composition is less than 7% by weight, preferably less than 5% by weight, more preferably less than 3% by weight, most preferably less than 1% by weight. -%, particularly preferably less than 0.1 wt .-% anionic surfactant (based on the total weight of the composition).
  • the water-soluble coating of the detergent, the package is preferably formed from a water-soluble film material selected from the group consisting of polymers or polymer blends.
  • the wrapper may be formed of one or two or more layers of the water-soluble film material.
  • the water-soluble film material of the first layer and the further layers, if present, may be the same or different. Particularly preferred are films which, for example, can be glued and / or sealed to packages such as hoses or cushions after being filled with an agent.
  • the water-soluble coating be polyvinyl alcohol or a
  • Water-soluble coatings containing polyvinyl alcohol or a polyvinyl alcohol copolymer have a good stability with a sufficiently high water solubility, in particular cold water solubility on.
  • Suitable water-soluble films for producing the water-soluble coating are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer whose
  • Molecular weight in the range of 10,000 to 1,000,000 gmor, preferably from 20,000 to 500,000 gmol "1 , more preferably from 30,000 to 100,000 gmol " 1 and in particular from 40,000 to 80,000 gmol 1 .
  • polyvinyl alcohol is usually carried out by hydrolysis of polyvinyl acetate, since the direct synthesis route is not possible.
  • polyvinyl alcohol copolymers which are prepared from correspondingly polyvinyl acetate copolymers. It is preferred if at least one layer of the water-soluble coating comprises a polyvinyl alcohol whose degree of hydrolysis makes up 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.
  • a polymer selected from the group comprising a polyvinyl alcohol-containing sheet material suitable for producing the water-soluble sheath is selected from the group comprising a polyvinyl alcohol-containing sheet material suitable for producing the water-soluble sheath
  • (Meth) acrylic acid-containing (co) polymers polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers, polylactic acid or mixtures of the above polymers may be added.
  • a preferred additional polymer is polylactic acids.
  • Preferred polyvinyl alcohol copolymers include, in addition to vinyl alcohol, dicarboxylic acids as further monomers.
  • Suitable dicarboxylic acids are itaconic acid, malonic acid, succinic acid and
  • polyvinyl alcohol copolymers include, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt or its esters.
  • Such polyvinyl alcohol copolymers particularly preferably contain, in addition to vinyl alcohol, acrylic acid, methacrylic acid, acrylates, methacrylates or mixtures thereof.
  • the film material contains further additives.
  • the film material may include, for example, plasticizers such as dipropylene glycol, ethylene glycol, diethylene glycol,
  • Additives include, for example, release aids, fillers, crosslinking agents, surfactants, antioxidants, UV absorbers, antiblocking agents, detackifiers, or mixtures thereof.
  • Suitable water-soluble films for use in the water-soluble casings of the water-soluble packaging according to the invention are films sold by the company MonoSol LLC, for example under the designation M8630, C8400 or M8900.
  • Other suitable films include films named Solublon® PT, Solublon® GA, Solublon® KC or Solublon® KL from Aicello Chemical Europe GmbH or the films VF-HP from Kuraray.
  • the cleaning agents according to the invention can be used as dishwashing agents, in particular automatic dishwasher detergents. The corresponding use is also the subject of the invention.
  • the invention likewise relates to a dishwashing process, in particular a machine dishwashing process, in which a cleaning agent according to the invention is used.
  • the cleaning agents according to the invention are preferably a
  • Dishwashing agent in particular a machine dishwashing detergent.
  • the invention is pre-portioned
  • Cleaning agent in particular machine dishwashing detergent, is substantially free of phosphates.
  • Substantially free of phosphates means that the total cleaning agent resulting from the addition of all phases (or all ingredients of all compartments) is preferably substantially free of phosphate-containing components. As phosphates or too
  • Phosphate-containing components in the context of the present invention are, in particular, phosphates, polyphosphates and pyrophosphates. However, phosphonates or hexafluorophosphate are not covered by this term.
  • the total detergent thus contains less than 1% by weight, preferably 0.5% by weight, of phosphate based on the total weight of the detergent (i.e., the total weight of all phases (i.e., all liquid and solid phases).
  • the detergents according to the invention in particular machine dishwashing detergents, comprise builders, such as, for example, zeolites, silicates, carbonates, in particular the alkali metal carbonates, for example sodium carbonate, sodium bicarbonate or sodium sesquicarbonate, and organic cobuilders.
  • builders such as, for example, zeolites, silicates, carbonates, in particular the alkali metal carbonates, for example sodium carbonate, sodium bicarbonate or sodium sesquicarbonate, and organic cobuilders.
  • silicates are, in particular crystalline layered silicates of general formula NaMSix02x + i ⁇ y H2O wherein 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 being 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20, into consideration. It is also possible to use amorphous sodium silicates having a modulus Na 2 O: SiO 2 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 are preferably delayed in dissolution and secondary wash properties.
  • the content of silicates based on the total weight of the cleaning agent, to amounts below 10 wt .-%, preferably below 5 wt .-%.
  • the agents according to the invention preferably comprise at least one further constituent, preferably selected from the group consisting of cationic and amphoteric surfactants, bleaching agents, bleach activators, bleach catalysts, enzymes, thickeners,
  • Sequestering agents electrolytes, corrosion inhibitors, in particular silver protectants, glass corrosion inhibitors, foam inhibitors, dyes, perfumes, bitter substances, and antimicrobial agents.
  • detergents preferably dishwashing detergents, in particular machine
  • Dishwashing agents can also be used bleaching agents.
  • bleaching agents include sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Further useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and peroxygenic salts or peracids which yield H2O2, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. It is also possible to use all other inorganic or organic agents known to the person skilled in the art
  • bleaching agent As a bleaching agent and chlorine or bromine releasing substances can be used. Examples of suitable chlorine or bromine releasing materials
  • heterocyclic N-bromo- and N-chloroamides for example trichloroisocyanuric acid
  • Tribromoisocyanuric acid Tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium into consideration.
  • DICA dichloroisocyanuric acid
  • Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.
  • cleaning agents preferably dishwashing detergents, in particular machine
  • Dishwashing agents which contain 1 to 35% by weight, preferably 2.5 to 30% by weight, particularly preferably 3.5 to 25% by weight, very particularly preferably 4.0 to 20% by weight and in particular 5 up to 18% by weight (based on the total weight of the cleaning agent) of bleaching agent,
  • the cleaning agents preferably dishwashing detergents, in particular automatic dishwashing detergents, may contain bleach catalysts.
  • Useful bleach catalysts include, but are not limited to, the group of bleach-enhancing transition metal salts and transition metal complexes, preferably Mn, Fe, Co, Ru or Mo complexes, more preferably from the group of manganese and / or cobalt salts and / or or complexes, in particular the cobalt (ammin) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, the manganese sulfate and the complexes of manganese with 1, 4,7- trimethyl-1, 4,7-triazacyclononane (Mm-TACN) or 1, 2,4,7-tetramethyl-1, 4,7-triazacyclononane (Mm-TACN).
  • the group of bleach-enhancing transition metal salts and transition metal complexes preferably Mn, Fe, Co, Ru or Mo complexes, more preferably from the group of manganese and / or cobalt salts and /
  • cleaning agents preferably dishwashing detergents, in particular machine
  • Dishwashing agent preferably, the 0.001 to 1 wt .-%, preferably 0.01 to 0, 1 wt .-% (each based on the total weight of the cleaning agent) bleach catalyst, preferably a Mn complex, in particular a complex of manganese with 1, 4 , 7-trimethyl-1, 4,7-triazacyclononane (Mm-TACN) or 1, 2,4,7-tetramethyl-1, 4,7-tri-azacyclononane (Mm-TACN).
  • Mm-TACN 1, 4,7-trimethyl-1, 4,7-triazacyclononane
  • Mm-TACN 2,4,7-tetramethyl-1, 4,7-tri-azacyclononane
  • the cleaning agents preferably dishwashing agents, in particular automatic dishwasher detergents, additionally comprise at least one bleach activator.
  • bleach activators it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
  • acylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT) Glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS) are particularly preferably used.
  • TAED tetraacetylethylenediamine
  • DADHT 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine
  • Glycolurils in particular tetraacety
  • Combinations of conventional bleach activators can also be used. These bleach activators are preferably used in amounts of up to 10% by weight, in particular 0.1% to 8% by weight, especially 2 to 8% by weight and more preferably 2 to 6% by weight, based in each case on the total weight of the detergents used.
  • the bleaching agent and also bleach catalysts and / or bleach activators are preferably contained in the solid phase (s).
  • Suitable amphoteric surfactants are, for example, betaines of the formula (R iii ) (R iv ) (R v ) N + CH 2 COO " , in which R i is an alkyl radical optionally interrupted by hetero atoms or heteroatom groups having 8 to 25, preferably 10 to 21 carbon atoms and R iv as well R v like or various alkyl radicals having 1 to 3 carbon atoms, in particular Cio-Cis-alkyl dimethylcarboxymethylbetain and Cn-Ci7-alkylamidopropyl-dimethylcarboxymethylbetain.
  • Suitable cationic surfactants are i.a. the quaternary ammonium compounds of the formula
  • R VI (R VI ) (R vii ) (R viii ) (R ix ) N + X "
  • R vi to R ix for four identical or different, in particular two long and two short-chain, alkyl radicals and X " for an anion , in particular a halide ion, for example, didecyl-dimethyl-ammonium chloride, alkyl-benzyl-didecyl-ammonium chloride and mixtures thereof.
  • Suitable cationic surfactants are the quaternary
  • surface-active compounds in particular with a sulfonium, phosphonium, iodonium or arsonium group, which are also known as antimicrobial agents.
  • the agent can be designed with an antimicrobial effect or its possibly existing antimicrobial effect due to other ingredients can be improved.
  • the 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 according to the invention contain enzymes
  • 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 as well as the further developments of the aforementioned amylases which are improved for use in cleaning agents. Furthermore, for this purpose, the ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and cyclodextrin glucanotransferase (CGTase) from B. agaradherens
  • lipases or cutinases are also usable according to the invention.
  • these include, for example, the lipases originally obtainable from, or further developed, Humicola lanuginosa (Thermomyces lanuginosus), in particular those having one or more of the following amino acid exchanges starting from said lipase in positions D96L, T213R and / or N233R, most preferably all of the exchanges D96L, T213R and N233R.
  • enzymes can be used which are termed hemicellulases
  • mannanases xanthan lyases
  • pectin lyases pectinases
  • pectin esterases pectin esterases
  • xyloglucanases xylanases
  • pullulanases and ⁇ -glucanases.
  • 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.
  • oxidases oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases
  • organic, more preferably aromatic, enzyme-interacting compounds to enhance the activity of the respective oxidoreductases (enhancers) or to react at greatly varying redox potentials between the oxidizing enzymes and the
  • 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.
  • damage such as inactivation, denaturation or degradation, such as by physical influences, oxidation or proteolytic cleavage.
  • inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases.
  • Detergents may contain stabilizers for this purpose; the provision of such means constitutes a preferred embodiment of the present invention.
  • Cleaning-active proteases and amylases are generally not provided in the form of the pure protein but rather in the form of stabilized, 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, low in water and / or added with stabilizers or further auxiliaries.
  • the enzymes can be encapsulated for both the solid and liquid dosage forms, for example by spray drying or extrusion of 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.
  • further active ingredients for example stabilizers, 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
  • 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, more preferably between 0.4 and 20% by weight and
  • Total weight 0, 1 to 12 wt .-%, preferably 0.2 to 10 wt .-% and in particular 0.5 to 8 wt .-% enzyme preparations.
  • the enzymes in particular the amylase (s) and / or protease (s), are preferably present in (one) of the solid phase (s), preferably as granules or granules.
  • Glass corrosion inhibitors used are metal salts, in particular zinc salts or bismuth salts, preferably zinc salts, in particular zinc acetate. Also preferred as glass corrosion inhibitors are polyethyleneimines and polyvinylamines, for example those obtainable under the name Lupasol® or Lupamin® from BASF, in particular nonalkoxylated
  • 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.
  • the detergent immediately after production has a viscosity above 4000 mPas (Brookfield Viscometer DV-II + Pro, spindle 25, 30 rpm, 20 ° C), in particular between 5000 and 20,000 mPas.
  • the viscosity may be higher, for example greater than 20,000 mPas, for example in the range 10000-50000 mPas, (Brookfield Viscometer DV-II + Pro, spindle 25, 5 rpm, 20 ° C). It is preferred that the agent is at least substantially fluid at room temperature.
  • the cleaning agents according to the invention are characterized in that they are stable in storage and even after a prolonged period, no phase separation occurs.
  • a further subject of the present invention is also a machine dishwashing process in which a cleaning agent according to the invention is used.
  • the invention also relates to the use of the cleaning agent according to the invention as a dishwashing detergent, in particular automatic dishwashing detergent.
  • Another object is the use of polyalkylene glycols (in particular as described above) having an average molecular weight between 1500 and 8000, in particular between 2000 and 6000, in particular between 3000 and 4500 to improve the storage stability of liquid low-water detergents or cleaners, preferably machine dishwashing detergents.
  • inventive detergent component E1 (E1 according to Table 1) and a corresponding comparative formulation V1 (V1 according to Table 1) were prepared.
  • the amounts indicated in the tables are in% by weight of active substance.
  • 5 g of the liquid phase (E1 or V1) were sealed in a bag of polyvinyl alcohol.
  • the comparative formulation shows a visible phase separation within 4 weeks when stored at 40 ° C, the inventive examples E1 and E2 are stable under these conditions and have a higher color brilliance and viscosity.

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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)
  • Detergent Compositions (AREA)

Abstract

L'invention concerne un produit de nettoyage préalablement proportionné, en particulier un agent détergent pour lave-vaisselle, et son utilisation, qui contient au moins un polyalkylèneglycol ayant un poids moléculaire moyen compris entre 150 et 8000. L'invention a également pour objet l'utilisation du polyalkylèneglycol, pour l'amélioration de la stabilité au stockage de produits de nettoyage liquides faiblement aqueux.
EP15702493.6A 2014-02-06 2015-02-04 Produit de nettoyage préalablement proportionné Not-in-force EP3102657B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL15702493T PL3102657T3 (pl) 2014-02-06 2015-02-04 Wstępnie porcjowany środek czyszczący

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102014202225.8A DE102014202225A1 (de) 2014-02-06 2014-02-06 Vorportioniertes Reinigungsmittel
PCT/EP2015/052296 WO2015118009A1 (fr) 2014-02-06 2015-02-04 Produit de nettoyage préalablement proportionné

Publications (2)

Publication Number Publication Date
EP3102657A1 true EP3102657A1 (fr) 2016-12-14
EP3102657B1 EP3102657B1 (fr) 2018-04-25

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EP15702493.6A Not-in-force EP3102657B1 (fr) 2014-02-06 2015-02-04 Produit de nettoyage préalablement proportionné

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EP (1) EP3102657B1 (fr)
DE (1) DE102014202225A1 (fr)
ES (1) ES2675196T3 (fr)
PL (1) PL3102657T3 (fr)
WO (1) WO2015118009A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6982626B2 (ja) * 2017-03-30 2021-12-17 ダウ グローバル テクノロジーズ エルエルシー 分散剤混合物を含む自動食器洗浄用組成物
US10717953B2 (en) 2018-03-01 2020-07-21 Henkel IP & Holding GmbH Detergent single dose packs and methods of producing the same
USD1088343S1 (en) 2022-05-11 2025-08-12 People Against Dirty Holdings Limited Packet

Family Cites Families (6)

* 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
US5498295A (en) * 1993-11-01 1996-03-12 The Procter & Gamble Company Cleaning methods and compositions for produce
US6228825B1 (en) * 2000-10-13 2001-05-08 Colgate Palmolive Company Automatic dishwashing cleaning system
GB2376238A (en) * 2001-06-07 2002-12-11 Reckitt Benckiser Inc Hard surface cleaner in a container
GB0917740D0 (en) * 2009-10-09 2009-11-25 Reckitt Benckiser Nv Detergent composition
WO2011100411A1 (fr) * 2010-02-12 2011-08-18 The Procter & Gamble Company Compositions avantageuses comprenant des esters de polyglycérol

Also Published As

Publication number Publication date
DE102014202225A1 (de) 2015-08-06
WO2015118009A1 (fr) 2015-08-13
ES2675196T3 (es) 2018-07-09
EP3102657B1 (fr) 2018-04-25
PL3102657T3 (pl) 2018-09-28

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