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WO2007073801A1 - Détergent pour lave-vaisselle - Google Patents

Détergent pour lave-vaisselle Download PDF

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Publication number
WO2007073801A1
WO2007073801A1 PCT/EP2006/010744 EP2006010744W WO2007073801A1 WO 2007073801 A1 WO2007073801 A1 WO 2007073801A1 EP 2006010744 W EP2006010744 W EP 2006010744W WO 2007073801 A1 WO2007073801 A1 WO 2007073801A1
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WO
WIPO (PCT)
Prior art keywords
weight
acid
machine dishwashing
dishwashing agent
agent according
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.)
Ceased
Application number
PCT/EP2006/010744
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German (de)
English (en)
Inventor
Johannes Zipfel
Arnd Kessler
Arno DÜFFELS
Maren Jekel
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
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Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of WO2007073801A1 publication Critical patent/WO2007073801A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C11D3/3796—Amphoteric polymers or zwitterionic polymers
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/825—Mixtures of compounds all of which are non-ionic
    • 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
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • 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
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3773—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines in liquid 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups

Definitions

  • the subject of this application are automatic dishwashing agents, in particular automatic dishwashing agents with integrated clarifying function
  • the automatic cleaning of dishes in household dishwashing machines usually includes a forward, a main and a rinse cycle, which are interrupted by intermediate circuits.
  • the booster for heavily soiled dishes is switchable, but is chosen only in exceptional cases by the consumer, so that in most Depending on the machine type and program level selection, the temperature of the main pulse varies between 40 and 65 ° C.
  • EP-B1 0 197 434 discloses liquid clear wipers which contain mixed ethers as nonionic surfactants.
  • a large number of different materials glass, metal, silver, plastic, porcelain
  • This type of material must be wetted as well as possible in the clear wash cycle
  • Klarspulerformuherungen containing as surfactant component exclusively mixed ethers do not meet these requirements or only to a small extent, so that the Klarspul- or drying effect is unsatisfactory, especially in plastic surfaces
  • the storage tank in the dishwasher must be filled at regular intervals with plain winder, with a filling for 10 to 50 Spulgange sufficient depending on the type of machine is forgotten filling the tank, so glasses in particular by limescale and flooring unsightly
  • some solution proposals exist to integrate a rinse spooler into the machine dishwashing detergent are tied to the offer form of the compact body
  • European patent application EP-AO describes 851,024 (Unilever) two-layer detergent tablets, the first layer contains peroxy bleaching agents, builders and enzyme, while the second layer acidifying agent and a continuous medium having a melting point between 55 and 70 0 C, and scale inhibitors containing By the refractory continuous medium to the acid (s) and Belags ⁇ nh ⁇ b ⁇ tor (s) (s) are released delayed and cause a Klarspul clear Powdered automatic dishwashing or surfactant Klarspulsysteme are not mentioned in this document
  • the new dishwashing agents should have their cleaning and rinsing performance independent of the preparation form, in particular without develop the addition of high-melting additives
  • detergents provide above average cleaning and rinse results which contain as constituents polymers with positively charged monomer units and special nonionic surfactants
  • a first subject of the present application is therefore a machine dishwashing agent comprising a) from 0.001 to 10% by weight of at least one polymer having a molecular weight of 2000 gmol 1 or above which has at least one positive charge, b) from 0.1 to 10 %
  • the dishwashing agents according to the invention contain from 0.001 to 10% by weight of a polymer having a molecular weight of 2000 gmol -1 or above which has at least one positive charge
  • the aforementioned polymers with cationic charge may in principle be cationic or amphoteric polymers.
  • Preferred automatic dishwashing agents according to the invention are characterized in that the polymer comprising cationic monomer units is a cationic polymer and / or an amphoteric polymer
  • “Cationic polymers” in the sense of the present invention are polymers which carry at least one positive charge but no negative charge in the polymer molecule. This can be realized, for example, by (alkyl) ammonium groups present in the polymer chain or other positively charged groups in individual or all monomer units preferred cationic polymers are from the groups of quaternized cellulose derivatives, the polysiloxanes with quaternary groups, the cationic guar derivatives, the polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid, the copolymers of vinylpyrrohydone with quaternized derivatives of dialkylaminoacrylate and methacrylates, the vinylpyrrolidone-methoimidazolinium chloride copolymers, the quaternized polyvinyl alcohols or the polymers listed under the INCI names Polyquaternium 2, Polyquaternium 17, Polyquatermum 18 and Polyquaternium 27
  • Amphorere polyesters in the sense of the present invention furthermore have negatively charged groups or monomer units in addition to a positively charged group or monomer unit in the polymer chain.
  • groups may be, for example, carboxylic acids, sulfonic acids or phosphonic acids
  • particularly preferred cationic or amphoteric polymers comprise as monomer unit a compound of the general formula (VII)
  • X represents a counterion, preferably a counterion from the group chloride, bromide, iodide, Sulfate, hydrogensulfate, methosulfate, laurylsulfate, dodecylbenzenesulfonate, p-toluenesulfonate (tosylate), cumene sulfonate, xylenesulfonate, phosphate, citrate, formate, acetate or mixtures thereof
  • Preferred radicals R 1 and R 4 in the above formula (VII) are selected from -CH 3 , -CH 2 -CH 3 , -CH 2 -CH 2 -CH 3 , -CH (CH 3 ) -CH 3 , -CH 2 -OH, -CH 2 -CH 2 -OH, -CH (OH) -CH 3 , -CH 2 -CH 2 -CH 2 -OH, -CH 2 -CH (OH) -CH 3 , -CH (OH ) -CH 2 -CH 3 , and - (CH 2 CH 2 -O) n H
  • DADMAC diallyldimethylammonium chloride
  • cationic or amphoteric polymers which are particularly preferred for the purposes of the present application comprise a monomer unit of the general formula
  • R 1 HC CR 2 C (O) NH (CH 2) ⁇ x NR 3 R 4 R 5 X (VIII)
  • R 1 , R 2 , R 3 , R 4 and R 5 independently of one another represent a linear or branched, saturated or unsaturated alkyl, or hydroxyalkyl radical having 1 to 6 carbon atoms, preferably a linear or branched alkyl radical selected from -CH 3 , -CH 2 -CH 3 , -CH 2 - CH 2 -CH 3 , -CH (CH 3 ) -CH 3 , -CH 2 -OH, -CH 2 -CH 2 -OH, -CH (OH) -CH 3 , -CH 2 -CH 2 -CH 2 -OH 1 -CH 2 - CH (OH) -CH 3 , -CH (OH) -CH 2 -CH 3 , and - (CH 2 CH 2 -O) n H and x is an integer between 1 and 6
  • H 2 C C (CH 3 ) C (O " ) NH (CH 2 ); N (CH 3 ) 3 X
  • preferred automatic dishwashing agents are characterized in that the polymer a) has diallyldimethylammonium salts and / or acrylamidopropyltimethylammonium salts as monomer units
  • amphoteric polymers have not only cationic groups but also anionic groups or monomer units.
  • anionic monomer units are derived, for example, from the group of linear or branched, saturated or unsaturated carboxylates, linear or branched, saturated or unsaturated phosphonates, linear or branched , saturated or unsaturated sulfates or the linear or branched, saturated or unsaturated sulfonates
  • Preferred monomer units are acrylic acid, (meth) acrylic acid, (dimethyl) acrylic acid, (ethyl) acrylic acid, cyanoacrylic acid, vinylessingic acid, allylacetic acid, crotonic acid .
  • maleic acid, fumaric acid, cinnamic acid and its derivatives, allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid or allylphosphonic acids
  • Preferred usable amphoteric polymers are selected from the group of the alkylacrylamide / acrylic acid copolymers, the alkylacrylamide / methacrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid copolymers, the alkylacrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the
  • Preferred zwitterionic polymers are selected from the group of acrylamidoalkyltrialkylammonium chloride / acrylic acid copolymers and their alkali metal and ammonium salts, the acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and their alkali metal and ammonium salts and the methacroylethylbetaine / methacrylate copolymers
  • amphoteric polymers which in addition to one or more anionic monomers as cationic monomers Methacrylamidoalkyl trialkylammoniumchlo ⁇ d and D ⁇ methyl (d ⁇ allyl) ammon ⁇ umchlor ⁇ d include
  • amphoteric polymers are from the group of methacrylamidoalkyl- t ⁇ alkylammon ⁇ umchlor ⁇ d / D ⁇ methyl (d ⁇ allyl) ammon ⁇ umchlo ⁇ d / acrylic acid copolymers, the Methacryl- am ⁇ doalkyltr ⁇ alkylammon ⁇ umchlor ⁇ d / D ⁇ methyl (d ⁇ allyl) ammon ⁇ umchlor ⁇ d / methacrylic acid copolymers and the Methacrylamidoalkylt ⁇ alkylammoniumchlo ⁇ d / DimethyKdiallyOammoniumchlorid / alkyl
  • amphoteric polymers from the group of:
  • the polymers contained in the inventive compositions with a molecular weight of 2000 gmol '1 or above in prefabricated form to confection of the polymers is suitable here, inter alia, the encapsulation of the polymers by means of water-soluble or water-dispersible coating compositions, preferably by means water-soluble or water-dispersible natural or synthetic polymers, Encapsulation of the polymers medium of water-insoluble, meltable coating agents, preferably by means of water-insoluble coating agents from the group of waxes or paraffins having a melting point above 3O 0 C, the co-granulation of the polymers with inert Shinmate ⁇ alien, preferably with Tragermate ⁇ alien from the group of washing or cleaning-active substances, particularly preferably from the group of builders (scaffolds) or cobuilders
  • the proportion by weight of the polymer a) in the total weight of the automatic dishwashing agent may vary within the limits stated above.
  • the weight fraction of the polymer a) is between 0.002 and 8% by weight, preferably between 0 005 and 6% by weight, preferably between 0 , 01 and 4% by weight, particularly preferably between 0.01 and 2% by weight and in particular between 0.01 and 1% by weight, in each case based on the total weight of the automatic dishwashing agent
  • the machine dishwashing agents according to the invention contain from 0.1 to 10% by weight of a nonionic surfactant of the general formula R 1 O [CH 2 CH (R 3 ) O] X H in which R 1 is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 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 and x stands for values between 40 and 200
  • Machine dishwashing agent according to one of claims 1 to 6, characterized in that it contains n ⁇ cht ⁇ on ⁇ sche (s) Tens ⁇ d (e) of the general formula R 1 O [CH 2 CH 2 O] x H, in the R 1 for linear or branched, saturated or is unsaturated, aliphatic hydrocarbon radicals having 6 to 30 carbon atoms and x stands for values between 40 and 120, preferably for values between 42 and 120, particularly preferably for values between 45 and 120
  • the proportion by weight of the surfactant b) in the total weight of the automatic dishwashing agent is preferably between 0.2 and 8% by weight, preferably between 0.5 and 7% by weight and in particular between 1, 0 and 5% by weight.
  • the machine dishwashing agents according to the invention may of course also contain further washing or cleaning-active ingredients, particular preference being given to substances from the group of surfactants, surfactants, polymers, bleaches, bleach activators, enzymes, glass corrosion inhibitors, corrosion inhibitors, disintegration aids, fragrances and perfume carriers
  • surfactants surfactants
  • polymers polymers
  • bleaches bleach activators
  • enzymes glass corrosion inhibitors
  • corrosion inhibitors corrosion inhibitors
  • disintegration aids fragrances and perfume carriers
  • crystalline layered silicates of the general formula NaMSi x O 2x + IyH 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 x is 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20
  • the crystalline layer-form silicates of the formula NaMSi x O 2x + Iy H 2 O are described, for example, by Cla ⁇ ant GmbH (Germany Examples of these silicates are Na-SKS-1 (Na 2 Si 22 O 45 ⁇ H 2 O, Kenyaite), Na-SKS-2 (Na 2 Si 14 O 29 ⁇ H 2 O), Magadnt), Na-SKS-3 (Na 2 Si 8 O 17 ⁇ H 2 O) or Na-SKS-4 (Na 2 Si 4 O 9 ⁇ H 2 O, makatite)
  • crystalline phyllosilicates of the formula NaMSi x O 2x + 1yH 2 O, in which x is 2
  • both ⁇ - and ⁇ -sodium disilicates are Na 2 Si 2 O 5 y H 2 O.
  • Na-SKS-5 ⁇ -Na 2 S ⁇ 2 0 5
  • Na-SKS-7 ⁇ -Na 2 S ⁇ 2 0 5 , Natrosiht
  • Na-SKS-9 NaHSi 2 O 5 H 2 O
  • Na-SKS-10 NaHSi 2 O 5 3 H 2 O kanemite
  • Na-SKS-11 t-Na 2 S ⁇ 2 0 5
  • Na-SKS-13 NaHSi 2 O 5
  • Na-SKS-6 5-Na 2 Si 2 O 5
  • Detergents or cleaning agents preferably contain a proportion by weight of the crystalline layered silicate of the formula NaMSi x O 2 ⁇ + 1 y H 2 O from 0.1 to 20% by weight, preferably from 0.2 to 15% by weight and in particular from 0.4 to 10% by weight, in each case based on the total weight of these agents
  • 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, which are preferably loosely delayed and have secondary wash properties Loseverzog für compared to conventional amorphous Nat ⁇ umsilikaten can thereby be caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying
  • the term "amorphous" understood that the silicates in X-ray extenuations do not provide sharp X-rays, such as they are typical of crystalline substances, but at most one or more maxima of the scattered X-radiation, which have a width of several degrees of the diffraction angle, cause
  • X-ray silicates are used whose silicon particles exhibit blurred or even sharp diffraction maxima in electron diffraction phenomena. This is to be interpreted as meaning that the products have microcrystalline regions of the order of ten to a few hundred nm Up to 50 nm and in particular up to 20 nm are preferred.
  • Rontgenamorphe silicates also have a Loseverzog für compared to conventional waterglass
  • Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and dried X-ray silicates
  • the alkali metal phosphates have, with particular preference, pentasodium or pentapotassium phosphate (sodium or potassium polyphosphate) in the Detergents and cleaners industry the greatest importance
  • Alkalimetallphosphate is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric (HPO 3 ) n and orthophosphoric H 3 PO 4 in addition to high molecular weight representatives
  • the phosphates combine several advantages in They act as alkali storage, prevent limescale on machine parts or Kalkinkrustationen in tissues and also contribute to the cleaning performance
  • Pentanat ⁇ umtriphosphat Na 5 P 3 O 10 (Natriumt ⁇ polyphosphat) and the corresponding potassium salt Pentakaliumt ⁇ phosphat, K 5 P 3 Oi 0 (Kaliumt ⁇ polyphosphat) According to the invention preferably continue to be used Nat ⁇ umkaliumtripolyphosphate
  • phosphates are used as detergents or cleaning agents in the context of the present application, preferred agents include phosphate (s) phosphate (s), preferably alkali metal metal phosphate (s), particularly preferably pentasodium or pentapotassium phosphate (sodium or potassium polyphosphate) ), in amounts of from 5 to 80% by weight, preferably from 15 to 75% by weight and in particular from 20 to 70% by weight, based in each case on the weight of the washing or cleaning agent
  • alkali metal stabilizers are alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogencarbonates, alkali metal sesquicarbonates, the alkali metal silicates mentioned, alkali metal catechols, and mixtures of Particular preference is given to a builder system comprising a mixture of Tnpolyphosphat and Nat ⁇ umcarbonat Also particularly preferred is a builder system comprising a mixture of Tnpolyphosphat and Nat ⁇ umcarbonat Nat ⁇ umdisilikat and Natmumdisilikat Due to their in the Compared with other builder substances of low chemical compatibility with the other ingredients of detergents or cleaners, the alkali metal hydroxides are preferably only in small amounts, preferably in amounts below 10% by weight, preferably below 6% by weight, more preferably below 4% by weight and in particular below 2% by weight, in each case based on the total weight of the washing or cleaning agent used. Particularly preferred are agents which, based on their
  • compositions which, based on the weight of the washing or cleaning agent, are less than 20% by weight, preferably less than 17% by weight, preferably less as 13% by weight and in particular less than 9% by weight of carbonate (s) and / or bicarbonate (s), preferably alkali metal carbonate (s), particularly preferably sodium carbonate
  • organic cobuilders include polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders and phosphonates. These classes of substances are described below
  • Useful organic framework substances are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or their sodium salts, polycarboxylic acids being understood to mean those carboxylic acids which carry more than one acid function.
  • these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, Fumaric acid, sugar acids, aminocarboxylic acids, Nit ⁇ lotnessigsaure (NTA), if such use is not objectionable for environmental reasons, and mixtures of these
  • the free acids have in addition to their builder effect typically also the property of an acid component and thus serve to set a lower and milder pH value of detergents or cleaning agents
  • citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures thereof may be mentioned here
  • the use of citric acid and / or citrates in these compositions has proven to be particularly advantageous for the cleaning and rinsing performance
  • Automatic dishwashing agents are therefore preferred according to the invention in that the automatic dishwashing agent contains citric acid or a salt of citric acid and the proportion by weight the citric acid or the salt of citric acid is preferably more than 10% by weight, preferably more than 15% by weight and in particular between 20 and 40% by weight
  • polymeric polycarboxylates are suitable, these are for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular mass of 500 to 70000 g / mol
  • the molecular weights given for polymeric polycarboxylates are weight-average molar masses M w of the particular acid form, which were determined in principle by gel permeation chromatography (GPC) using a UV detector. The measurement was carried out against an external polyacrylic acid standard which gives realistic molecular weight values owing to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data in which polystyrenesulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this specification
  • 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, this group can in turn comprise the short-chain polyacrylates, the molar masses of 2,000 to 10,000 g / mol, and particularly preferably 3,000 to 5,000 g / mol, have, be preferred
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and 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 are particularly suitable 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
  • the (co) polymeric polycarboxylates can be used either as a powder or as a wet solution.
  • the content of detergents or cleaning agents in (co) polymeric polycarboxylates is preferably from 0.5 to 20% by weight and in particular from 3 to 10% by weight.
  • the polymers may also contain allylsulfonic acids, such as allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer
  • allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid
  • biodegradable polymers of more than two different monomer units for example those which contain as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or the salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives as monomers
  • copolymers are those which have as their monomers acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate
  • softening effective polymers are, for example, the sulfonic acid-containing polymers, which are used with particular preference
  • Copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally further ionogenic or nonionogenic monomers are particularly preferably usable as sulfonic acid group-containing polymers
  • R 1 to R 3 independently of one another are -H, -CH 3 , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, NH 2 , -OH or -COOH substituted alkyl or alkenyl radicals or -COOH or -COOR 4 , wherein R 4 is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms
  • 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, Methacrylam ⁇ do-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 water-soluble salts of said acids
  • ethylenically unsaturated compounds are suitable as further ionic or nonionogenic monomers.
  • the content of the polymers used in these other ionic or nonionogenic monomers is less than 20% by weight, based on the polymer.
  • copolymers consist of (i) one or more unsaturated carboxylic acids from the group of acrylic acid,
  • the copolymers may contain the monomers from groups (I) and (I) as well as, if appropriate, in varying amounts, it being possible to combine all representatives from group (I) with all representatives from group (I) and all representatives from group (III) Preferred polymers have certain structural units which are described below
  • copolymers which are structural units of the formula are preferred.
  • Acrylic acid and / or methacrylic acid can also be copolymerized completely analogously with methacrylic acid derivatives containing sulfonic acid groups, as a result of which the structural units in the molecule are changed.
  • maleic acid can also be used as a particularly preferred monomer from the group ⁇ .
  • the sulfonic acid groups may be wholly or partially in neutralized form, ie that the acidic acid of the Sulfonsaureoli in some or all sulfonic acid groups may be exchanged for metal ions, preferably alkali metal and in particular against sodium ions.
  • the use of partially or fully neutralized sulfonic acid group-containing copolymers according to the invention prefers
  • the monomer distribution of the copolymers preferably used according to the invention is in the case of copolymers which contain only monomers from groups (I) and (II), preferably in each case from 5 to 95% by weight or preferably from 50 to 90% by weight of monomer from the group ⁇ ) and 10 to 50% by weight of monomer from the group ⁇ ), each based on the polymer
  • terpolymers particular preference is given to those containing from 20 to 85% by weight of monomer from the group I), from 10 to 60% by weight of monomer from the group I) and from 5 to 30% by weight of monomer from the group III)
  • the molecular weight 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 purpose.
  • Preferred detergents or cleaners are characterized in that the copolymers have molar masses of 2000 to 200,000 gmol 1 , preferably 4000 to 25,000 gmol 1 and in particular from 5000 to 15,000 gmol 1 have
  • polymeric aminodicarboxylic acids their salts or their precursors
  • Substances are particularly preferred polyaspartic acids or their salts
  • polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups.
  • Preferred polyacetals are prepared from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyolcarboxylic acids such as gluconic acid and / or glucoheptonic acid
  • organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
  • the hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes.
  • the hydrolysis products have average molecular weights in the region of 400 up to 500000 g / mol.
  • a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 is preferred, DE being a useful measure of the reducing action of a polysaccharide in comparison to dextrose, Usable are both Maltodext ⁇ ne with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 and so-called yellow dextrins and white dextrins with higher molecular weights in the range of 2000 to 30,000 g / mol
  • oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide to the carboxylic acid function
  • Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine are further suitable cobuilders It is Ethylend ⁇ am ⁇ n-N, N '- disuccinate (EDDS) is preferably in the form of its sodium or magnesium salts thereof Furthermore, Glyce ⁇ ndisuccinate and Glyce ⁇ ntrisuccinate are preferred in this context are quantities used at 3 to 15% by weight
  • the automatic dishwashing agents according to the invention particularly preferably contain methylglycinediacetic acid or a salt of methylglycinediacetic acid, where the proportion by weight of methylglycinediacetic acid or of the salt of methylglycinediacetic acid is preferably between 0 5 and 15% by weight, preferably between 0.5 and 10% by weight and in particular between 0, 5 and 6% by weight
  • organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups
  • compositions according to the invention may contain further surfactants, the nonionic, the anionic, the cationic and the amphoteric surfactants being paid to the group of surfactants
  • Suitable nonionic surfactants are all nonionic surfactants known to the person skilled in the art Suitable nonionic surfactants are, for example, alkyl glycosides of the general formula RO (G) x in which R is a primary straight-chain or methyl-branched, especially methyl-branched, aliphatic radical of 8 to 22, preferably corresponds to 12 to 18 C atoms and G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose, the degree of oligomerization x, which determines the distribution of mono- glycosides and oligoglycosides is any number between 1 and 10, preferably x is 1, 2 to 1, 4
  • nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dimethylhydroxylamine, and fatty acid alkanolamides may also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols. especially not more than half of them
  • surfactants are polyhydroxy fatty acid amides of the formula
  • R is an aliphatic acyl group having 6 to 22 carbon atoms
  • R 1 is hydrogen, an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms
  • [Z] is a linear or branched polyhydroxyalkyl group having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula
  • R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 1 is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms
  • R 2 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, wherein C 1-4 -AtKyI- or phenyl radicals are preferred and
  • [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this residue [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • Nonionic surfactants are used as preferred surfactants. Particular preference is given to detergents or cleaners, in particular automatic dishwashing detergents, nonionic surfactants from the group of alkoxylated alcohols.
  • Nonionic surfactants are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 C atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol used in which the alcohol radical may be linear or methyl-branched preferably in the 2-position or contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten particular
  • alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms z B of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 moles of EO per mole of alcohol are preferably the preferred ethoxylated alcohols go ören for example, C 2 -
  • ethoxylated nonionic surfactants which are from C 6 . 20 - monohydroxyalkanols or C 6 . 2 o-alkylphenols or C 16 . 2 o-fatty alcohols and more than 12 moles, preferably more than 15 moles and in particular more than 20 moles of ethylene oxide per mole of alcohol
  • a particularly preferred nonionic surfactant is selected from a straight-chain fatty alcohol having 16 to 20 carbon atoms (C 16 20 -alcohol) , preferably a C 18 -alcohol and at least 12 moles, preferably at least 15 moles and in particular at least 20 moles of ethylene oxide recovered.
  • C 16 20 -alcohol straight-chain fatty alcohol having 16 to 20 carbon atoms
  • C 18 -alcohol preferably a C 18 -alcohol and at least 12 moles, preferably at least 15 moles and in particular at least 20 moles of ethylene oxide recovered.
  • Machine dishwashing agent which comprises n ⁇ cht ⁇ on ⁇ sche (s) Tens ⁇ d (e) of the general formula R 1 O [CH 2 CH 2 O] x [CH 2 CH 2 CH 2 OI y H in which R 1 represents linear or branched, saturated or unsaturated, aliphatic hydrocarbon radicals having 6 to 30 carbon atoms, x for values between 15 and 120, preferably for values between 40 and 120, particularly preferably for values between 45 and 120 and y stands for values between 2 and 80, are used with particular preference, since the addition of these surfactants to the compositions according to the invention a further unexpected increase in the cleaning and Klarspul antique could be achieved
  • nonionic surfactants which have a melting point above room temperature N ⁇ cht ⁇ on ⁇ sche (s)
  • nonionic surfactants which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which may be solid or highly viscous at room temperature. If nonionic surfactants are used which are highly viscous at room temperature, it is preferred that they have a viscosity above 20 Pa Also, nonionic surfactants having waxy consistency at room temperature are preferred depending on their application
  • Nonionic surfactants from the group of alkoxylated alcohols are also used with particular preference
  • the nonionic surfactant solid at room temperature preferably has propylene oxide units in the molecule.
  • such PO monomers make up to 25% by weight, more preferably up to 20% by weight and in particular up to 15% by weight of the total molecular weight of the nonionic surfactant
  • particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units
  • More particularly preferred nonionic surfactants having melting points above room temperature contain from 40 to 70% of a polyoxyethylene / polyoxypropylene polyoxypropylene / polyoxyethylene / polyoxypropylene block copolymer blended of 75% by weight with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight of one Block copolymers of polyoxyethylene and polyoxypropylene, initiated with T ⁇ methylolpropan and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole T ⁇ methylolpropan containing
  • nonionic surfactants have been low foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units.
  • surfactants with EO-AO-EO-AO blocks are preferred, where in each case one to ten EO or AO groups are bonded together before one block follows from the other groups.
  • R 1 is a straight-chain or branched, saturated or mono- or polyunsaturated C 6 24 alkyl or alkenyl radical
  • each group R 2 or R 3 is independently selected from -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 -CH 3 , CH (CH 3 J 2 and the indices w, x, y, z independently of one another are integers from 1 to 6
  • the preferred nonionic surfactants of the above formula can be prepared by known methods from the corresponding alcohols R 1 -OH and ethylene oxide or alkylene oxide.
  • the radical R 1 in the above formula can vary depending on the origin of the alcohol. If native sources are used, the radical R 1 has an even number of carbon atoms and is usually unbranched, the linear radicals are selected from alcohols of natural origin having 12 to 18 carbon atoms, such as coconut, palm, Taigfett- or oleyl alcohol, are preferably accessible from synthetic sources alcohols For example, the Guerbet alcohols or methyl-branched or linear and methyl-branched radicals in the 2-position are present in oxoalcohol radicals.
  • nonionic surfactants in which R 1 in the above Formula is an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 1 1 carbon atoms
  • butylene oxide is also suitable as the alkylene oxide unit which is present in the preferred nonionic surfactants in alternation with the ethylene oxide unit.
  • R 2 or R 3 are selected independently of one another from -CH 2 CH 2 -CH 3 or -CH ( CH 3 ) 2 are suitable
  • nonionic surfactants preferred are a C 9 15 alkyl radical having 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units, followed by 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units, these surfactants have in wass ⁇ ger solution the required low Viscosity and are inventively used with particular preference
  • R 1 -CH (OH) CH 2 O- (AO) w - (A'O) x - (A "O) y - (A" O) z -R 2 Surfactants of the general formula R 1 -CH (OH) CH 2 O- (AO) w - (A'O) x - (A "O) y - (A" O) z -R 2 , in which R 1 and R 2 independently represent a straight-chain or branched, saturated or mono- or polyunsaturated C 2 .
  • end-capped poly (oxyalkyl ⁇ erten) 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 between 1 and 30 carbon atoms 90, preferably for values between 30 and 80 and in particular for values between 30 and 60
  • 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
  • R 1 and R 2 independently of one another is a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms
  • R 3 is independently selected from -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 -CH 3 , -CH (CH)
  • nonionic surfactants are the end-capped poly (oxyalkyl ⁇ erten) 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 is a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical 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, x for values between 1 and 30, k and j for values between 1 and 12, preferably between 1 and 5 If the value x> 2, 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 be different R 1 and R 2 are preferably linear or branched, saturated or unsaturated,
  • each R 3 in the above formula may be different if x> 2.
  • the alkylene oxide unit in the square bracket may be varied.
  • the value 3 for x has been chosen as an example and can be quite large where the range of variation increases with increasing x values and includes, for example, a large number of (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 represents numbers from 1 to 30, preferably from 1 to 20 and in particular 6 to 18 particularly preferred surfactants in which the radicals R 1 and R 2 have 9 to 14 C atoms, R 3 is H and x assumes values of 6 to 15
  • the stated C chain lengths and degrees of ethoxylation or degrees of alkoxylation of the aforementioned nonionic surfactants represent statistical averages which may be an integer or a fractional number for a particular product. Because of the production processes, commercial products of the formulas mentioned are usually not made of an individual but of mixtures Both for the C chain lengths and for the degrees of ethoxylation or degrees of alkoxylation, mean values and, consequently, fractional numbers
  • nonionic surfactants can be used not only as individual substances but also as surfactant mixtures of two, three, four or more surfactants.
  • Surfactant mixtures are not mixtures of nonionic surfactants which in their entirety fall under one of the abovementioned general formulas rather, such mixtures containing two, three, four or more nonionic surfactants which can be described by different of the aforementioned general formulas
  • anionic surfactants are used as constituents of automatic dishwashing agents, their content, based on the total weight of the compositions, is preferably less than 4% by weight, preferably less than 2% by weight and very particularly preferably less than 1% by weight of automatic dishwashing agents which do not contain anionic surfactants are particularly preferred
  • cationic active substances for example, cationic compounds of the following formulas can be used
  • each R 1 group is independently selected from CI_ 6 alkyl, alkenyl or hydroxyalkyl groups
  • each group R 2 is independently selected from C 8-28 alkyl or alkenyl
  • R 3 R 1 or ( CH 2 ) n -TR 2
  • R 4 R 1 or R 2 or (CH 2 ) n -TR 2
  • T -CH 2 -, -O-CO- or -CO-O- and
  • n is an integer from O to 5 is
  • the content of cationic and / or amphoteric surfactants is preferably less than 6% by weight, preferably less than 4% by weight, very preferably less than 2% by weight and in particular less than 1% by weight automatic dishwashing agents, which do not contain cationic or amphoteric surfactants are particularly preferred
  • the group of polymers in particular pay the detergents or cleaning-active polymers, for example the clear-spooled polymers and / or polymers which are effective as softeners.
  • the detergents or cleaning-active polymers for example the clear-spooled polymers and / or polymers which are effective as softeners.
  • cationic, anionic and amphoteric polymers can be used in detergents or cleaners in addition to nonionic polymers
  • “Cationic polymers” in the context of the present invention are polymers which carry a positive charge in the polymer molecule. This can be realized, for example, by (alkyl) ammonium groups or other positively charged groups present in the polymer chain.
  • Particularly preferred cationic polymers are derived from the groups of the quaternized cellulose Derivatives of quaternary group polysiloxanes, cationic guar derivatives, polymeric dimethyldiallylammomium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid, copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylate and methacrylate, vinylpyrrolidone-methoimidazolinium chloride copolymers, the quaternized polyvinyl alcohols or the polymers indicated under the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27
  • amphoteric polymers furthermore have, in addition to a positively charged group in the polymer chain, also negatively charged groups or monomer units. These groups may, for example, be carboxylic acids, sulfonic acids or phosphonic acids
  • particularly preferred cationic or amphoteric polymers contain as monomer unit a compound of the general formula
  • R 1 and R 4 independently of one another are H or a linear or branched hydrocarbon radical having 1 to 6 carbon atoms
  • R 2 and R 3 independently of one another are an alkyl, hydroxyalkyl, or aminoalkyl group in which the alkyl radical is linear or branched is and has between 1 and 6 carbon atoms, which is preferably a methyl group
  • x and y independently of one another are integers between 1 and 3.
  • X represents a counterion, preferably a counterion from the group consisting of chloride, bromide, iodide, sulfate, Hydrogen sulfate, methosulfate, lauryl sulfate, dodecylbenzenesulfonate, p-toluenesulfonate (tosylate), cumene sulfonate, xylene sulfonate, phosphate, citrate, formate, acetate or mixtures thereof
  • Preferred radicals R 1 and R 4 in the above formula are selected from -CH 3, -CH 2 -CH 3, - CH 2 -CH 2 -CH 3, -CH (CH 3 J-CH 3, -CH 2 -OH , -CH 2 -CH 2 -OH, -CH (OH) -CH 3 , -CH 2 -CH 2 -CH 2 -OH, -CH 2 -CH (OH) -CH 3 , -CH (OH) -CH 2 -CH 3 , and - (CH 2 CH 2 -O) n H
  • cationic or amphoteric polymers contain a monomer unit of the general formula
  • R i HC C-R2 C (O) -NH- (CH 2) -N + R 3 R 4 R 5
  • X " in the R 1 , R 2 , R 3 , R 4 and R 5 are independently of one another a linear or branched, saturated or unsaturated alkyl or hydroxyalkyl radical having 1 to 6 carbon atoms, preferably a linear or branched alkyl radical selected from CH 3 , -CH 2 -CH 3 , -CH 2 - CH 2 -CH 3 , -CH (CH 3 ) -CH 3 , -CH 2 -OH, -CH 2 -CH 2 -OH, -CH (OH) -CH 3 , -CH 2 -CH 2 -CH 2 -OH, -CH 2 - CH (OH) -CH 3 , -CH (OH) -CH 2 -CH 3 , and - (CH 2 CH 2 -O) n is H and x is an integer between 1 and 6
  • H 2 C C (CH 3 ) -C (O) -NH- (CH 2 ) X -N (CH 3 ) 3
  • amphoteric polymers have not only cationic groups but also anionic groups or monomer units.
  • anionic monomer units are derived, for example, from the group of linear or branched, saturated or unsaturated carboxylates, of the linear or branched, saturated or unsaturated phosphonates, of the linear or branched, saturated or unsaturated sulfates or of the linear or branched, saturated or unsaturated sulfonates
  • Preferred monomer units are acrylic acid, (meth) acrylic acid, (dimethyl) acrylic acid, the (ethyl) acrylic acid, the cyanoacrylic acid, the vinylessingic acid, the allylacetic acid, the crotonic acid, the maleic acid, the fumaric acid, the cinnamic acid and its derivatives, the allylsulfonic acids, such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid or the allylphosphonic acids
  • Preferred usable amphoteric polymers come from the group of the alkylacrylamide / acrylic acid copolymers, the alkylacrylamide / methacrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid copolymers, the alkylacrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the
  • Preferably usable zwitterionic polymers are selected from the group of acrylamidoalkyltnalkylammonium chloride / acrylic acid copolymers and their alkali metal and Ammomumsalze, the Acrylamidoalkylt ⁇ alkylammoniumchlo ⁇ d / methacrylic acid copolymers and their alkali metal and Ammomumsalze and Methacroylethylbetain / methacrylate copolymers
  • amphoteric polymers which in addition to one or more anionic monomers as cationic monomers Methacrylamidoalkyl-t ⁇ alkylammoniumchlo ⁇ d and D ⁇ methyl (d ⁇ allyl) ammon ⁇ umchlo ⁇ d include
  • amphoteric polymers are from the group of methacrylamidoalkyl trialkylammon ⁇ umchlo ⁇ d / D ⁇ methyl (d ⁇ allyl) ammon ⁇ umchlor ⁇ d / acrylic acid copolymers, the Methacryl- am ⁇ doalkyltr ⁇ alkylammon ⁇ umchlo ⁇ d / D ⁇ methyl (d ⁇ allyl) ammon ⁇ umchlor ⁇ d / methacrylic acid copolymers and the Methacrylamidoalkyltrialkylammoniumchlo ⁇ d / DimethyKdiallylJammoniumchlo ⁇ d / alkyl
  • amphoteric polymers from the group of:
  • the polymers are present in prefabricated form.
  • the polymers inter alia encapsulation of the polymers by means of water-soluble or water-dispersible substances is suitable
  • Coating compositions preferably by means of water-soluble or water-dispersible natural or synthetic polymers, the encapsulation of the polymers by means of water-insoluble, fusible
  • Coating composition preferably by means of water-insoluble coating agent from the
  • Tragermate ⁇ ahen from the group of washing or cleaning-active substances, particularly preferably from the group of builders (scaffolds) or cobuilders
  • Washing or cleaning agents preferably contain the abovementioned cationic and / or amphoteric polymers in amounts of between 0.01 and 10% by weight, based in each case on the total weight of the washing or cleaning agent.
  • the bleaching agents are a washing or cleaning substance which is used with particular preference.
  • the compounds which serve as bleaching agents in water H 2 O 2 sodium percarbonate, sodium borate tetrahydrate and natnuterate borate monohydrate are of particular importance.
  • Further useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H 2 O.
  • peracid salts or peracids such as perbenzoates, peroxophthalates, diperazelic acid, Phthaloiminopersaure or Diperdodecandisaure also bleaches from the group of organic bleaches can be used
  • Typical organic bleaches are the diacyl peroxides, such as dibenzoyl peroxide
  • Further typical organic bleaching agents are the peroxyacids, wherein Examples especially mentioning the alkyl peroxyacids and the aryl peroxyacids Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkyl peroxybenzoic acids, but au peroxy- ⁇ -naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylic acid, peroxystearic acid, ⁇ -phthalimidoperoxycaproic acid [phthaliminoperoxyhexanoic
  • Nonenylamidopersuccmate and (c) aliphatic and araliphatic Peroxydicarbonsauren, such as 1, 12-D ⁇ peroxycarbonsaure, 1, 9-D ⁇ peroxyazela ⁇ nsaure, Diperocysebacinsaure, Diperoxybrassylic acid, the diperoxyphthalic acids, 2-Decyld ⁇ peroxybutan-1, 4-diacid, N 1 N-terephthaloyl-d ⁇ (6-am ⁇ nopercapronsaue)
  • Chlorine or bromine-releasing substances can also be used as the bleaching agent.
  • suitable chlorine or bromine-releasing materials are heterocyclic N-bromo- and N-chloramides, for example trichloroisocyanuric acid, tribromoisuricacid, dibromoisocyanuric acid and / or dicholicuric acid (DICA) and / or salts thereof Cations such as potassium and sodium into consideration HydantoinENSen, such as 1, 3-D ⁇ chlor-5,5-d ⁇ methylhydantho ⁇ n are also suitable
  • washing or cleaning agents in particular automatic dishwashing agents, are preferred which contain 1 to 35% by weight, preferably 2.5 to 30% by weight, particularly preferably 3.5 to 20% by weight and in particular 5 to 15% by weight of bleaching agent , preferably Nat ⁇ umpercarbonat included
  • the active oxygen content of the washing or cleaning agents, in particular the automatic dishwashing agents is in each case based on the total weight of the composition, preferably between 0.4 and 10% by weight, particularly preferably between 0.5 and 8% by weight and in particular between 0, 6 and 5% by weight of particularly preferred compositions have an active oxygen content above 0.3% by weight, preferably above 0.7% by weight, more preferably above 0.8% by weight and in particular above 1.0% by weight
  • Bleach activators are used in detergents or cleaners, for example, to achieve an improved bleaching effect when cleaning at temperatures of 60 ° C and below.
  • bleach activators compounds which under perhydrolysis conditions aliphatic peroxocarboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to 4 C Suitable are substances which carry O- and / or N-acyl groups of said carbon atom number and / or optionally substituted benzoyl groups.
  • polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated T ⁇ azinderivate, in particular 1,5-D ⁇ acetyl-2,4-d ⁇ oxohexahydro-1, 3,5-tr ⁇ az ⁇ n (DADHT), acylated Glykolu ⁇ le, especially Tetraacetylglykolunl (TAGU), N-Acyl ⁇ m ⁇ de, in particular N-Nonanoylsucc ⁇ n ⁇ m ⁇ d (NOSI), acylated phenolsulfonates , in particular n-nonanoyl or Isononanoyloxybenzolsulfonat (n- or iso-NOBS), Carbonsaureanhyd ⁇ de, in particular Phthalsaureanhyd ⁇ d, acylated polyhydric alcohols, in particular Tnacetin, ethylene glycol diacetate and 2,5-D ⁇ acet
  • bleach activators are preferably used in amounts of up to 10% by weight, in particular 0.1% by weight 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 bleach activator-containing agents used
  • bleach activators which are preferably used in the context of the present application are compounds from the group of cationic nitrenes, in particular cationic nitlels of the formula
  • R 1 is -H, -CH 3, a C 2 - 24 alkyl or alkenyl group, a substituted C 2-24 -alkyl or -alkenyl radical having at least one substituent from the group -Cl, -Br, 1, - OH, -NH 2 , -CN, an alkyl or Alkenylarylrest with a C ⁇ alkyl group, or for a substituted alkyl or Alkenylarylrest with a C 1 .
  • bleach catalysts can also be used. These substances are bleaching-intensifying transition metal salts or transition metal complexes, such as Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes. Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing T ⁇ pod ligands and Co, Fe, Cu and Ru ammine complexes can be used as bleach catalysts
  • Bleach-enhancing transition metal complexes in particular with the central atoms Mn, Fe, Co, Cu 1 Mo, V, Ti and / or Ru, preferably selected from the group of manganese and / or cobalt salts and / or complexes, particularly preferably cobalt (ammine) Complexes of the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, of the manganese sulfate are used in customary amounts, preferably in an amount of up to 5% by weight, in particular of 0.0025% by weight. % to 1% by weight and more preferably from 0.01% by weight to 0.25% by weight, based in each case on the total weight of the bleach activator-containing agents. In special cases, however, it is also possible to use more bleach activator
  • complexes of manganese in the oxidation state II, III, IV or IV which preferably contain one or more makrocycl ⁇ sche (s) L ⁇ gand (s) with the donor functions N, NR, PR, O and / or S.
  • ligands It is particularly preferred to use lead compound (s) in the agents according to the invention, which are macromolecular ligands 1, 4,7-trimethyl-1, 4,7-t-azacyclononane (Me-TACN), 1, 4,7-triazacyclononane (TACN), 1, 5,9-tri methyl-1,5,9-triazacyclododecane (Me-TACD), 2-methyl-1, 4,7-tri-methyl-1, 4,7-triazacyclononane ( MeMe-TACN) and / or 2-methyl-1,4,7-t-azacyclononane (Me / TACN).
  • Me-TACN macromolecular ligands 1 4,7-trimethyl-1, 4,7-t-azacyclononane
  • TACN 1, 4,7-triazacyclononane
  • MeMe-TACN MeMe-TACN
  • 2-methyl-1,4,7-t-azacyclononane MeMe-TACN
  • Suitable manganese complexes are, for example, [Mn I " 2 ( ⁇ -O) 1 ( ⁇ -OAc) 2 (TACN) 2 ] (CIO 4 ) 2 , [Mn '"Mn lv ( ⁇ -O) 2 ( ⁇ -OAc) 1 (TACN) 2 ] (BPh 4 ) 2 , [Mn' V 4 ( ⁇ -O) 6 (TACN) 4 ] (CIO 4 ) 4l [Mn III 2 ( ⁇ -O) 1 ( ⁇ -OAc) 2 (Me-TACN) 2 ] (CIO 4 ) 2 , [[MMnn "" II MMnn llvv (( ⁇ - OO)) 11 (( ⁇ - OOAAcc)) 22 ((MMee - TTAACCNN)) 22]] ((CCIIOO 44)) 33 ,, [Mn 'v 2 ( ⁇ -O) 3 (Me-TACN) 2 ] (PF 6 ) 2 and [Mn ⁇ v 2
  • proteases amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, as well as their mixtures, are preferred.
  • These enzymes are in principle of natural origin, starting from the natural molecules are available for use in detergents or cleaning agents improved variants available, which are preferably used accordingly detergents or cleaning agents contain enzymes preferably in total amounts of 1 x 10 "6 b ⁇ s 5 wt -% based on active protein
  • the protein concentration can be determined by known methods, for example the BCA method or the Biuret method
  • amylases which can be used according to the invention are the ⁇ -amylases from Bacillus licheniformis, B amyloliquefaciens, S stearothermophilus, Aspergillus niger and A oryzae and the further developments of the abovementioned amylases which are improved for use in detergents and cleaners - Amylase from Bacillus sp A 7-7 (DSM 12368) and the cyclodextnn glucanotransferase (CGTase) from ß agaradherens (DSM 9948)
  • lipases or cutinases in particular because of their T ⁇ glyce ⁇ d-cleaving activities, but also to generate from suitable precursors in situ Persauren
  • lipases or cutinases include, for example, originally from Humicola lanugmosa (Th ⁇ rmomyces lanuginosus) obtainable, or further developed lipases, especially those with the Furthermore, for example, the cutinases which were originally isolated from Fusanum solam pisi and Humicola insolens can be used.
  • Lipases, or cutinases, whose initial enzymes were originally isolated from Pseudomonas mendocma and Fusanum solanu can also be used
  • Oxidoreductases for example oxidases, oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignamic, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can advantageously be used according to the invention to increase the bleaching effect additionally preferably organic, particularly preferably aromatic, interacting with the enzymes compounds added to enhance the activity of the respective oxidoreductases (enhancer) or to ensure at very different redox potentials between the oxidizing enzymes and the Anschmutzunge ⁇ the electron flow (mediators)
  • the enzymes can be used in any form established according to the prior art.
  • the enzymes can 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 is coated with a water, air and / or chemical impermeable protective layer in superposed layers may additionally contain other active ingredients, such as stabilizers, emulsifiers, pigments, bleaches or dyes Capsules of this kind are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes.
  • granules of this type for example by application of polymeric film formers, are low in dust and storage-stable due to the coating
  • a protein and / or enzyme can be protected against damage, for example inactivation, denaturation or decomposition, for example by physical influences, oxidation or proteolytic cleavage, especially during storage.
  • damage for example inactivation, denaturation or decomposition, for example by physical influences, oxidation or proteolytic cleavage, especially during storage.
  • inhibition of proteolysis is particularly preferred
  • Detergents or cleaning agents which contain agents for this purpose may also contain stabilizers. The provision of such agents constitutes a preferred embodiment of the present invention
  • enzymes and / or enzyme preparations preferably solid protease preparations and / or amylase preparations, in amounts of from 0.1 to 5% by weight, preferably from 0.2 to 4.5% by weight and in particular of 0.4 to 4% by weight, based in each case on the total enzyme-containing agent used
  • Preferred glass corrosion inhibitors come from the group of magnesium and zinc salts and the magnesium and zinc complexes
  • the spectrum of the preferred zinc salts according to the invention preferably organic acids, more preferably organic carboxylic acids, ranges from salts which are difficult or insoluble in water, ie a solubility below 100 mg / l, preferably below 10 mg / l, in particular below 0.01 mg / l, to those salts which have a solubility in water above 100 mg / l, preferably above 500 mg / l, more preferably above 1 g / l and especially above 5 g / l (all Loshchkeiten at 20 ° C.
  • the first group of zinc salts includes, for example, cadmium nitrate, zinc oleate and zinc stearate, and the group of soluble zinc salts includes, for example, zinc formate, zinc acetate, zinc lactate and zinc gluconate
  • the glass corrosion inhibitor used is at least one zinc salt of an organic carboxylic acid, particularly preferably a zinc salt from the group consisting of zinc stearate, zinc oleate, zinc gluconate, zinc acetate, zinc lactate and zinc citrate.
  • Zinccinoleate, zinc abietate and zinc oxalate are also preferred
  • the content of zinc salt in detergents or cleaners is preferably between 0.1 and 5% by weight, preferably between 0.2 and 4% by weight and in particular between 0.4 and 3% by weight
  • Content of zinc in oxidized form (calculated as Zn 2+ ) between 0.01 to 1% by weight, preferably between 0.02 to 0.5% by weight and in particular between 0.04 to 0.2% by weight, in each case based on the total weight of the glass corrosion inhibitor-containing agent
  • Corrosion inhibitors are used to protect the Spulgutes or the machine, wherein in the field of automatic dishwashing, especially silver protectants are of particular importance can be used, the known substances of the prior art Generally, especially silver protectants selected from the group of T ⁇ azole, the Benzotnazole, Bisbenzot ⁇ azole, the Particularly preferred to use Benzot ⁇ azol and / or Alkylaminot ⁇ azol According to the invention preferably 3-Am ⁇ no-5-alkyl-1, 2,4-tr ⁇ azole or their physiologically acceptable salts are used, these substances with particular preference in a concentration of 0.001 to 10% by weight, preferably 0.0025 to 2% by weight, particularly preferably 0.01 to 0.04% by weight are used Preferred acids for salt formation are hydrochloric acid, sulfuric acid, phosphoric acid, Carbonic acid, sulphurous acid, organic Ca Acids such as acetic, glycolic, citric and succinic acids Very particularly effective are 5-pentyl, 5-heptyl
  • cleaner formulations often contain active chlorine-containing agents which can markedly reduce the corrosion of the silver surface.
  • active chlorine-containing agents such as di- and trihydric phenols, for example hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid phloroglucinol, pyrogallol or derivatives of these classes of compounds also used salt- and complex-like inorganic compounds, such as salts of the metals Mn, Ti , Zr, Hf, V, Co and Ce are frequently used.
  • transition metal salts which are selected from the group of the manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammine) complexes, the cobalt (Acetate) complexes, the cobalt (carbonyl) complexes of the chlorides of cobalt or manganese and of manganese sulfate.
  • Zinc compounds can also be used to prevent corrosion on the product being wadded
  • redox-active substances can be used. These substances are preferably inorganic redox-active substances from the group of manganese, titanium, zirconium, hafnium, vanadium, cobalt and cerium oxides. Salts and / or complexes, wherein the metals are preferably present in one of the oxidation states II, III, IV, V or VI
  • the metal salts or metal complexes used should be at least partially soluble in water.
  • the counterions suitable for salt formation comprise all conventional mono-, di-, or tri-negatively charged inorganic anions, for example oxide, sulfate, nitrate, fluoride, but also organic anions such as stearate
  • metal salts and / or metal complexes are selected from the group MnSO 4 , Mn (II) -citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (II) - [1-hydroxyethane-1, 1- diphosphonate], V 2 O 5 , V 2 O 4 , VO 2 , TiOSO 4 , K 2 TiF 6 , K 2 ZrF 6 , CoSO 4 , Co (NO 3 ) 2 , Ce (NO 3 ) 3 , and mixtures thereof, such that the metal salts and / or metal complexes are selected from the group MnSO 4 , Mn (II) -citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (II) - [1-hydroxyethane-1, 1- diphosphonate], V 2 O 5 , V 2 O 4 , VO 2 ,
  • the inorganic redox-active substances are preferably coated, ie completely coated with a water-tight material which is readily soluble in the cleaning temperatures in order to prevent their premature decomposition or oxidation during storage.
  • Preferred coating materials which are prepared by known processes, for example melt-coating processes according to Sandwik from the food industry, are paraffins, microwaxes, waxes of natural origin such as carnauba wax candellila wax, beeswax, high-melting alcohols such as hexadecanol, soaps or fatty acids
  • the metal salts and / or metal complexes mentioned are contained in cleaning agents, preferably in an amount of 0.05 to 6% by weight, preferably 0.2 to 2.5% by weight, in each case based on the total agent
  • disintegration aids so-called tablet disintegrants
  • Disintegrators for tablets or disintegrators are understood to be excipients which are used for rapid disintegration of tablets in water or other media and for the drained release of the active ingredients
  • disintegration aids are, for example, carbonate / citric acid systems, although other organic acids can be used.
  • Swelling disintegration aids are, for example, synthetic polymers such as polyvinylpyrrolidone (PVP) or natural polymers or modified natural substances such as cellulose and starch and their derivatives, algmates or casein denvates
  • Disintegration aids are preferably used in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, based in each case on the total weight of the disintegration-containing agent
  • Preferred disintegrating agents are cellulosic disintegrating agents, so that preferred detergents or cleaners contain such disintegrants based on cellulose in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight cellulose has the formal empirical composition (C 6 H 10 O) n and, formally, is a beta-1, 4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose Suitable celluloses consist of about 500 to 5000 glucose units and consequently have average molar masses of 50,000 to 500,000.
  • Cellulosic disintegrating agents which can be used in the context of the present invention are cellulose derivatives obtainable by polymer-analogous reactions of cellulose.
  • Such chemically modified celluloses include, for example, products of esterifications or etherifications in which Hydroxy-hydrogen atoms substit Celluloses in which the hydroxy groups have been replaced by functional groups which are not bonded via an oxygen atom can also be used as cellulose derivatives.
  • the group of cellulose derivatives includes, for example, alkali metal celluloses, carboxymethyl cellulose (CMC) cellulose esters and ethers and aminocelluloses
  • CMC carboxymethyl cellulose
  • the cellulose derivatives mentioned are preferably not used alone as disintegrating agents based on cellulose, but instead in cellulose
  • the content of these mixtures of cellulose derivatives is preferably below 50% by weight, more preferably below 20% by weight, based on the cellulose-based disintegrating agent. It is particularly preferred to use pure cellulose-based disintegrating agent which is free of cellulose derivatives
  • the cellulose used as a disintegration aid is preferably not used in finely divided form, but converted into a coarser form, for example granulated or compacted before mixing into the premixes to be compressed.
  • the particle sizes of such disintegrating agents are generally above 200 .mu.m, preferably at least 90% by weight 300 and 1600 ⁇ m and in particular at least 90% by weight between 400 and 1200 ⁇ m
  • Microcrystalline cellulose may be used as a further cellulose-based disintegrant or as a component of this component.
  • This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which attack and completely dissolve only the amorphous regions (about 30% of the total cellulose mass) of the celluloses
  • subsequent disaggregation of the microfine celluloses produced by the hydrolysis yields the microcrystalline celluloses which have particle sizes of about 5 ⁇ m and can be compacted, for example, into granules with an average particle size of 200 ⁇ m
  • Preferred disintegration auxiliaries preferably a cellulose-based disintegration assistant, preferably in granular, co-annealed or compacted form, are present in the disintegrating agent-containing agents in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight -%, in each case based on the total weight of the disintegrating agent-containing agent
  • the gas-evolving effervescent system may consist of a single substance which releases a gas on contact with water.
  • these compounds is in particular the magnesium peroxide, which releases oxygen upon contact with water
  • gas-releasing effervescent system in turn of at least two components that react with each other to form gas
  • Preferred effervescent systems consist of alkali metal carbonate and / or bicarbonate and an acidifying agent which is suitable from the Al kalimetallsalzen in wass ⁇ ger solution to release carbon dioxide
  • boric acid and alkali metal hydrogen sulfates, alkali metal dihydrogen phosphates and other inorganic salts can be used.
  • organic acidifiers preference is given to using organic acidifiers, with citric acid being a particularly preferred acidifying agent.
  • acidifying agents in the effervescent system selected from the group consisting of organic acids Di-, tri- and oligocarboxylic acids or mixtures
  • perfume oils or perfumes may be selected from the group consisting of synthetic esters, ethers, aldehydes, ketones, alcohols and hydrocarbons. Preferably, however, mixtures of different fragrances are used which together produce an attractive fragrance.
  • perfume oils may also contain natural fragrance mixtures such as those available from vegetable sources, such as pine, citrus, jasmine, patchouly, rose or ylang-ylang oil
  • a perfume In order to be perceptible, a perfume must be volatile, in addition to the nature of the functional groups and the structure of the chemical compound and the molecular weight plays an important role So most perfumes have molecular weights up to about 200 daltons, while molecular weights of 300 daltons and more represent an exception Due to the different odor of odoriferous substances, the smell of a perfume or fragrance composed of several fragrances changes during evaporation, whereby the odor impressions in "top note”, “middle note” or “middle note” Since the perception of smell is based to a large extent on the odor intensity, the top note of a perfume or fragrance is not only from volatile compounds, while the base note for the most part from less volatile, ie Adherent fragrances persists in the composition of perfumes For example, it is easier for volatile fragrances to be bound to specific fixatives, which prevents them from evaporating too quickly. The subsequent classification of the fragrances into "light volatile” or "firmly adhering” fragrances therefore depends
  • the fragrances can be processed directly, but it can also be advantageous to apply the fragrances to wearers, which provide a slower release of fragrance for long-lasting fragrance
  • the Cyclodext ⁇ n-perfume complexes additionally with other excipients can be coated Preferred dyes, the selection of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of the agents and to light and no pronounced substantivity to the substrates to be treated with the dye-containing agents such as textiles, glass, ceramics or plastic tableware do not stain them
  • Colorants which can be oxidatively destroyed in the washing process and mixtures thereof with suitable blue dyes, so-called blue toners, are preferred. It has proven advantageous to use colorants which are soluble in water or at room temperature in liquid organic substances. Suitable examples are anionic colorants. for example, anionic nitrosoréses
  • compositions according to the invention can be present in solid or liquid form or as a combination of solid and liquid forms
  • Powder, granules, extrudates or compactates, in particular tablets, are suitable as solid supply forms.
  • the liquid supply forms based on water and / or organic solvents may be thickened, in the form of gels
  • Means according to the invention can be formulated in the form of single-phase or multiphase products.
  • Machine dishwashing detergents having one, two, three or four phases are particularly preferred.
  • Automatic dishwashing detergents, which are in the form of a prefabricated dosing unit with two or more phases, are particularly preferred.
  • Machine dishwashing agents in particular, are preferred have at least two different solid phases and / or at least two liquid phases and / or at least one solid and at least one solid phase
  • Machine dishwashing agents according to the invention are preferably prefabricated into dosage units. These dosage units preferably comprise the amount of washing or cleaning substances required for a cleaning operation. Preferred metering units have a weight of between 12 and 30 g, preferably between 14 and 26 g and in particular between 16 and 22 g
  • those automatic dishwashing agents are preferred which are in the form of a prefabricated dosing unit and between 0.001 and 1 g, preferably between 0.01 and 0.1 g, particularly preferably between 0.01 and 0.07 g and in particular between 0.01 and 0.05 g of the polymer a) or between 0.1 and 2.5 g, preferably between 0.2 and 2.2 g, particularly preferably between 0.3 and 19 g and in particular between 0.4 and 1, 5 g n ⁇ cht ⁇ on ⁇ sche (s) Tens ⁇ d (e) b) included
  • the volume of the aforementioned metering units and their spatial form are particularly preferably chosen so that a metering of the prefabricated units on the dosing of a dishwasher is ensured
  • the volume of the metering unit is therefore preferably between 10 and 35 ml, preferably between 12 and 30 ml and in particular between 15 and 25 ml
  • the automatic dishwashing agents according to the invention in particular the prefabricated metering units, have a water-soluble coating, with particular preference
  • the present application further relates to a method for cleaning dishes in a dishwasher, in which the agent according to the invention is metered into the interior of a dishwasher during the passage of a dishwashing program before the start of the main course or in the course of the main course.
  • the metering or entry of the agent according to the invention into the interior of the dishwasher can be done manually, but preferably the agent is metered by means of the metering chamber into the interior of the dishwasher
  • inventive compositions are distinguished from conventional automatic dishwashing agents by an improved clear wiping effect.
  • a machine dishwashing agent according to the invention as a clear rinsing agent in automatic dishwashing is therefore a further subject matter of the present application

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention concerne des détergents pour lave-vaisselle contenant a) 0,001 à 10 % en poids d'au moins un polymère possédant une masse molaire supérieure ou égale à 2000 gmol<SUP>-1</SUP> et présentant au moins une charge positive et b) 0,1 à 10 % en poids d'un tensioactif non ionique de formule générale R<SUP>1</SUP>O[CH<SUB>2</SUB>CH(R<SUP>3</SUP>)O]<SUB>x</SUB>H, dans laquelle R<SUP>1</SUP> représente des groupes hydrocarbonés linéaires ou ramifiés, saturés ou insaturés, aliphatiques ou aromatiques comportant 6 à 30 atomes de carbone, R<SUP>3</SUP> représente un atome d'hydrogène ou un groupe méthyle, éthyle, n-propyle, iso-propyle, n-butyle, 2-butyle ou 2-méthyl-2-butyle et x présente une valeur comprise entre 40 et 200. Ces détergents se distinguent des détergents pour lave-vaisselle classiques par un pouvoir de lavage amélioré, en particulier un pouvoir de rinçage amélioré.
PCT/EP2006/010744 2005-12-15 2006-11-09 Détergent pour lave-vaisselle Ceased WO2007073801A1 (fr)

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WO2015034895A1 (fr) * 2013-09-05 2015-03-12 Rohm And Haas Company Détergent pour lavage de vaisselle automatique
US9447367B2 (en) 2014-01-10 2016-09-20 Budich International Gmbh Alkaline cleaner comprising a ternary combination of complexing agents
DE102016223589A1 (de) 2016-11-28 2018-05-30 Clariant International Ltd Copolymer enthaltendes maschinelles geschirrspülmittel
WO2020239760A1 (fr) 2019-05-28 2020-12-03 Clariant International Ltd Détergent contenant un ester de glycérol éthoxylé pour laver la vaisselle en machine
EP3839024A1 (fr) * 2019-12-17 2021-06-23 Henkel AG & Co. KGaA Système de principe actif contre la formation de taches de calcaire
WO2023057335A1 (fr) 2021-10-07 2023-04-13 Clariant International Ltd Compositions détergentes pour lave-vaisselle comprenant des esters de glycérol éthoxylés et des alcoxylates d'alcools gras modifiés
US12157868B2 (en) 2019-06-21 2024-12-03 Ecolab Usa Inc. Solidified nonionic surfactant composition comprising a solid urea binder
US12479957B2 (en) 2019-05-28 2025-11-25 Clariant International Ltd Ethoxylated glycerol esters and method for the production thereof

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EP2997121B1 (fr) * 2013-05-17 2018-12-05 Unilever N.V. Composition détergente pour lave-vaisselle
DE102016223588A1 (de) 2016-11-28 2018-05-30 Clariant International Ltd Copolymere und deren verwendung in reinigungsmittel-zusammensetzungen
DE102016223586A1 (de) 2016-11-28 2018-05-30 Clariant International Ltd Copolymere und deren verwendung in reinigungsmittel-zusammensetzungen
DE102016223590A1 (de) 2016-11-28 2018-05-30 Clariant International Ltd Copolymer enthaltende reinigungsmittelzusammensetzungen

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WO2015034895A1 (fr) * 2013-09-05 2015-03-12 Rohm And Haas Company Détergent pour lavage de vaisselle automatique
US9447367B2 (en) 2014-01-10 2016-09-20 Budich International Gmbh Alkaline cleaner comprising a ternary combination of complexing agents
DE102016223589A1 (de) 2016-11-28 2018-05-30 Clariant International Ltd Copolymer enthaltendes maschinelles geschirrspülmittel
WO2018095913A1 (fr) 2016-11-28 2018-05-31 Clariant International Ltd Détergent pour lave-vaisselle contenant un copolymère
WO2020239760A1 (fr) 2019-05-28 2020-12-03 Clariant International Ltd Détergent contenant un ester de glycérol éthoxylé pour laver la vaisselle en machine
US12480073B2 (en) 2019-05-28 2025-11-25 Clariant International Ltd Ethoxylated glycerol ester-containing detergent for machine dishwashing
US12479957B2 (en) 2019-05-28 2025-11-25 Clariant International Ltd Ethoxylated glycerol esters and method for the production thereof
US12157868B2 (en) 2019-06-21 2024-12-03 Ecolab Usa Inc. Solidified nonionic surfactant composition comprising a solid urea binder
EP3839024A1 (fr) * 2019-12-17 2021-06-23 Henkel AG & Co. KGaA Système de principe actif contre la formation de taches de calcaire
WO2023057335A1 (fr) 2021-10-07 2023-04-13 Clariant International Ltd Compositions détergentes pour lave-vaisselle comprenant des esters de glycérol éthoxylés et des alcoxylates d'alcools gras modifiés

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