EP2115109A2 - Détergents - Google Patents

Détergents

Info

Publication number
EP2115109A2
EP2115109A2 EP07822100A EP07822100A EP2115109A2 EP 2115109 A2 EP2115109 A2 EP 2115109A2 EP 07822100 A EP07822100 A EP 07822100A EP 07822100 A EP07822100 A EP 07822100A EP 2115109 A2 EP2115109 A2 EP 2115109A2
Authority
EP
European Patent Office
Prior art keywords
group
acid
weight
bleach
monomers
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.)
Withdrawn
Application number
EP07822100A
Other languages
German (de)
English (en)
Inventor
Nadine Warkotsch
Johannes Zipfel
Christian Nitsch
Arnd Kessler
Thomas Holderbaum
Cornelius Bessler
Susanne Tondera
Thomas Müller-Kirschbaum
Sven Müller
Arno DÜFFELS
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
Priority claimed from DE102007006629A external-priority patent/DE102007006629A1/de
Priority claimed from DE102007006630A external-priority patent/DE102007006630A1/de
Priority claimed from DE102007006627A external-priority patent/DE102007006627A1/de
Priority claimed from DE102007006628A external-priority patent/DE102007006628A1/de
Priority claimed from PCT/EP2007/059203 external-priority patent/WO2008028896A2/fr
Priority claimed from DE200710044417 external-priority patent/DE102007044417A1/de
Priority claimed from DE102007044418A external-priority patent/DE102007044418A1/de
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to EP07822100A priority Critical patent/EP2115109A2/fr
Priority claimed from PCT/EP2007/061753 external-priority patent/WO2008095554A2/fr
Publication of EP2115109A2 publication Critical patent/EP2115109A2/fr
Withdrawn legal-status Critical Current

Links

Definitions

  • the present patent application describes detergents, in particular detergents for the machine cleaning of dishes.
  • This application relates in particular to phosphate-free automatic dishwashing detergents which contain bleach catalysts.
  • Machine-washed dishes are often subject to more stringent requirements today than manually-washed dishes.
  • a tableware that has been completely cleaned at first glance of food waste is then rated as not having any flaw if, after machine dishwashing, it still has discolorations which are based, for example, on the attachment of vegetable dyes to the dish surface.
  • bleaching agents are used in automatic dishwashing detergents.
  • this bleaching agent and to cleaning at temperatures of 60 0 C and below to achieve an improved bleaching effect containing machine dishwashing detergents usually further bleach activators or bleach catalysts, particularly the bleach catalysts have proved to be particularly effective.
  • bleach catalysts may not yet be considered satisfactory to one skilled in the art.
  • bleach catalysts especially in low-alkaline, for example, phosphate-free, automatic dishwashing detergents, unexpectedly poor bleaching effects are frequently observed.
  • the object of the present application was to provide a phosphate-free automatic dishwashing detergent, which has an improved bleaching action.
  • the bleaching action of lead catalysts from the group of bleach-enhancing transition metal salts and transition metal complexes can be increased by the addition of hydrophobically modified acid-containing copolymers.
  • a first subject of this application is therefore a phosphate-free, bleach-containing automatic dishwashing detergent containing a) citrate b) bleach catalyst selected from the group of bleach-enhancing transition metal salts and transition metal complexes c) copolymer (s) comprising i) acid group-containing (s) Monomer (s) ii) other hydrophobic monomer (s)
  • a first characteristic constituent of agents according to the invention is the citrate.
  • the term "citrate” also encompasses citric acid and its salts, in particular their alkali metal salts.
  • citrate in quantities of 5 to 60% by weight, preferably 10 to 55% by weight and in particular 15 to 50
  • Citrate or citric acid have proven to be particularly effective in bleaching performance over builders other than those used in combination with the bleach catalyst and the hydrophobically modified copolymer.
  • the automatic dishwashing compositions according to the invention may contain, in addition to the citrates, additional builders, in particular silicates, carbonates or organic cobuilders.
  • preferred machine dishwashing detergents contain as builder crystalline layered silicates of general formula NaMSi x O 2x + I ⁇ y H 2 O wherein M is sodium or hydrogen, x is a number from 1, 9 to 22, preferably from 1, 9-4 where particularly preferred values for x are 2, 3 or 4 and y is a number from 0 to 33, preferably from 0 to 20.
  • amorphous sodium silicates with a Na 2 O: SiO 2 modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which preferably delayed release and have secondary washing properties.
  • Automatic dishwashing detergents preferred in the context of the present invention comprise from 1 to 15% by weight, preferably from 2 to 12% by weight and in particular from 2 to 8% by weight, of silicate (s). Particularly preferred is the use of carbonate (s) and / or bicarbonate (s), preferably alkali metal carbonate (s), more preferably sodium carbonate, in amounts of 5 to 50 wt .-%, preferably from 10 to 40 wt .-% and in particular from 15 to 30 wt .-%, each based on the weight of the automatic dishwashing detergent.
  • organic co-builders are polycarboxylates / polycarboxylic acids, polymeric carboxylates, aspartic acid, polyacetals, dextrins and organic cobuilders, including the 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 adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and mixtures thereof.
  • NTA nitrilotriacetic acid
  • the free acids also typically have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners.
  • succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures of these may be mentioned here.
  • polymeric polycarboxylates for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular mass of 500 to 70,000 g / mol.
  • Suitable polymers are, in particular, polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may again be preferred from this group.
  • 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.
  • the content of preferred automatic dishwashing agents on (co) polymeric polycarboxylates is preferably 0.5 to 20% by weight and in particular 3 to 10% by weight, in each case based on the total weight of the automatic dishwashing detergent.
  • Preferred automatic dishwashing agents according to the invention are free from carboxymethylinulin.
  • Preferred aminoalkane phosphonates are ethylenediamine tetramethylene phosphonate (EDTMP), diethylene triamine pentamethylene phosphonate (DTPMP) and their higher homologs. They are preferably in the form of neutral sodium salts, eg. B. as the hexasodium salt of EDTMP or as hepta- and octa-sodium salt of DTPMP used.
  • the builder used here is preferably HEDP from the class of phosphonates.
  • the aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, in particular if the agents also contain bleach, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.
  • An automatic dishwashing agent preferred in the context of this application contains one or more phosphonate (s) from the group a) aminotrimethylenephosphonic acid (ATMP) and / or salts thereof; b) ethylenediaminetetra (methylenephosphonic acid) (EDTMP) and / or salts thereof; c) diethylenetriamine penta (methylenephosphonic acid) (DTPMP) and / or salts thereof; d) 1-hydroxyethane-1, 1-diphosphonic acid (HEDP) and / or salts thereof; e) 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC) and / or salts thereof; f) hexamethylenediaminetetra (methylenephosphonic acid) (HDTMP) and / or salts thereof; g) nitrilotri (methylenephosphonic acid) (NTMP) and / or salts thereof.
  • ATMP aminotrimethylenephosphonic acid
  • ETMP ethylenedi
  • automatic dishwashing detergents which contain, as phosphonates, 1-hydroxyethane-1,1-diphosphonic acid (HEDP) or diethylenetriaminepenta (methylenephosphonic acid) (DTPMP).
  • HEDP 1-hydroxyethane-1,1-diphosphonic acid
  • DTPMP diethylenetriaminepenta
  • the automatic dishwashing compositions of the invention may contain two or more different phosphonates.
  • the proportion by weight of the phosphonates is preferably 0.5 to 14 wt .-%, preferably 1 to 12 wt .-% and in particular 2 to 8 wt .-%.
  • a second essential ingredient of dishwashing compositions according to the invention is a bleaching system of bleach and bleach catalyst.
  • bleach machine dishwashing detergents contain an oxygen bleaching agent from the group sodium percarbonate, Natriumperborattetrahydrat and Natriumperboratmonohydrat.
  • Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
  • bleaching agents from the group of organic bleaching agents can also be used.
  • Typical organic bleaches are the diacyl peroxides such as dibenzoyl peroxide.
  • Other typical organic bleaching agents are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids. Because of its good bleaching performance, sodium percarbonate is particularly preferred.
  • Preferred automatic dishwashing detergents are characterized in that the dishwashing detergent 1, 0 to 20 wt .-%, preferably 4.0 to 18 wt .-% and in particular 8 to 15 wt .-% of an oxygen bleaching agent, preferably 1, 0 to 20 wt. %, preferably 4.0 to 18 wt .-% and in particular 8 to 15 wt .-% sodium percarbonate.
  • a preferred subject of this application is therefore a phosphate-free automatic dishwashing detergent containing a) citrate b) bleach catalyst selected from the group of bleach-enhancing transition metal salts and transition metal complexes c) copolymer (s) comprising i) acid group-containing monomer (s) ii) further hydrophobic monomer (s) d) 2.0 to 15% by weight of sodium percarbonate.
  • the bleach activators are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.
  • complexes of manganese in the oxidation state II, III, IV or IV are used, which preferably contain one or more macrocyclic ligand (s) with the donor functions N, NR, PR, O and / or S.
  • ligands are used which have nitrogen donor functions.
  • bleach catalyst (s) in the compositions of the invention, which as macromolecular ligands 1, 4,7-trimethyl-1, 4,7-triazacyclononan (Me-TACN), 1, 4,7-Triazacyclononan (TACN), 1, 5,9-trimethyl-1, 5,9-triazacyclododecane (Me-TACD), 2-methyl-1, 4,7-trimethyl-1, 4,7-triazacyclononane (Me / Me-TACN ) and / or 2-methyl-1, 4,7-triazacyclononane (Me / TACN).
  • macromolecular ligands 1, 4,7-trimethyl-1, 4,7-triazacyclononan (Me-TACN), 1, 4,7-Triazacyclononan (TACN), 1, 5,9-trimethyl-1, 5,9-triazacyclododecane (Me-TACD), 2-methyl-1, 4,7-trimethyl-1, 4,7-triazacyclononane (Me / Me-TACN )
  • Suitable manganese complexes are, for example, [Mn m 2 ( ⁇ -O) 1 ( ⁇ -OAc) 2 (TACN) 2 ] (CIO 4 ) 2, [Mn 1 "Mn lv ( ⁇ -O) 2 ( ⁇ -OAc) 1 ( TACN) 2 ] (BPh 4 ) 2, [Mn ' V 4 ( ⁇ -O) 6 (TACN) 4 ] (Cl ⁇ 4) 4, [Mn I " 2 ( ⁇ -O) 1 ( ⁇ -OAc) 2 (Me -TACN) 2 ] (CIO 4 ) 2, [Mn " 1 Mn lv ( ⁇ -O) 1 ( ⁇ OOAAcc)) 22 ((MMee - TTAACCNN)) 22 ]] ((CCIO 4 ) 3 , [Mn ' v 2 ( ⁇ -O) 3 (Me-TACN) 2 ] (PF 6 ) 2 and [Mn' v 2 ( ⁇ -O) 3 (Me / Me-TACN) 2
  • Automatic dishwashing detergent characterized in that it comprises a bleach catalyst selected from the group of bleach-enhancing transition metal salts and transition metal complexes, preferably from the group of complexes of manganese with 1, 4,7-trimethyl-1, 4,7-triazacyclononane (Me 3 - TACN) or 1, 2,4,7-tetramethyl-1, 4,7-triazacyclononane (Me 4 -TACN) are particularly preferred according to the invention.
  • a bleach catalyst selected from the group of bleach-enhancing transition metal salts and transition metal complexes, preferably from the group of complexes of manganese with 1, 4,7-trimethyl-1, 4,7-triazacyclononane (Me 3 - TACN) or 1, 2,4,7-tetramethyl-1, 4,7-triazacyclononane (Me 4 -TACN) are particularly preferred according to the invention.
  • the aforementioned bleach catalysts selected from the group of bleach-enhancing transition metal salts and transition metal complexes, in particular with the central atoms Mn and Co, are preferably in an amount up to 5 wt .-%, in particular from 0.01 to 3.0 wt .-%, preferably 0 , 02 to 2.0 wt .-% and in particular 0.02 to 1, 0 wt .-%, each based on the total weight of the bleach activator-containing agents used. In special cases, however, more bleach activator can also be used.
  • a further preferred subject of this application is therefore a phosphate-free automatic dishwashing detergent containing a) citrate b) from 0.01 to 3.0% by weight of bleach catalyst selected from the group of bleach-enhancing transition metal salts and transition metal complexes c) copolymer (e) comprising i) acid group-containing monomer (s) ii) further hydrophobic monomer (s) d) 2.0 to 15 wt .-% sodium percarbonate.
  • the bleaching system according to the invention comprising bleach and bleach catalyst is supplemented by a bleach activator.
  • bleach activators it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
  • Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups.
  • Preference is given to polyacylated alkylenediamines, with tetraacetylethylenediamine (TAED) having proven particularly suitable.
  • TAED tetraacetylethylenediamine
  • bleach activators in particular TAED, 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. , in each case based on the total weight of the bleach activator-containing agents used.
  • the automatic dishwashing compositions of the invention contain a hydrophobically modified copolymer comprising acid group-containing monomer and hydrophobic monomer.
  • the proportion by weight of this copolymer in the total weight of the automatic dishwashing agent is preferably 0.1 to 30 wt .-%, preferably 0.5 to 25 wt .-% and in particular 1, 0 to 20 wt .-%.
  • Machine dishwashing detergent characterized in that the dishwashing detergent contains 0.1 to 30% by weight, preferably 0.5 to 25% by weight and in particular 1 to 0% by weight of copolymer (s), comprising i) acid group Containing monomer (s) ii) contains further hydrophobic monomer (s) are preferred according to the invention.
  • Copolymer (s) comprising i) acid group-containing monomer (s) ii) other hydrophobic monomer (s)
  • copolymers c) may vary in the chemical nature of their monomers.
  • further ionic or nonionic monomers may be present in the copolymer.
  • a first group of preferred automatic dishwashing detergents is therefore characterized in that the dishwasher detergent copolymer (e) c) comprising i) monomers from the group of mono- or polyunsaturated carboxylic acids ii) monomers from the group of mono- or polyunsaturated hydrocarbon radicals with 2 contains up to 26 carbon atoms.
  • Copolymer comprising i) monomers from the group of mono- or polyunsaturated carboxylic acids ii) monomers from the group of mono- or polyunsaturated hydrocarbon radicals having 2 to 26 carbon atoms
  • a second group of preferred automatic dishwashing detergents are characterized in that the dishwashing detergent comprises copolymer (e) c) comprising i) monomers from the group of mono- or polyunsaturated sulfonic acids ii) monomers from the group of mono- or polyunsaturated hydrocarbon radicals having 2 to Contains 26 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, S-methacrylamido-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of said acids or their water-soluble
  • the sulfonic acid groups may be wholly or partially in neutralized form, i. the acidic acid of the sulfonic acid group in some or all sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions.
  • metal ions preferably alkali metal ions and in particular for sodium ions.
  • partially or fully neutralized sulfonic acid-containing copolymers is preferred according to the invention.
  • the monomer distribution of the copolymers preferably used according to the invention in the case of copolymers which contain only monomers from groups i) and ii) is preferably in each case from 5 to 95% by weight i) or ii), particularly preferably from 50 to 90% by weight monomer from group i) and from 10 to 50% by weight of monomer from group ii), in each case based on the polymer.
  • 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 automatic dishwashing detergents are characterized in that the copolymers have molar masses of from 2000 to 200,000 gmol -1 , preferably from 4000 to 25,000 gmol -1, and in particular from 5000 to 15,000 gmol -1 .
  • Particularly preferred unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, chloroacrylic acid, cyanoacrylic acid, crotonic acid, phenyl-acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid, sorbic acid, cinnamic acid or mixtures thereof.
  • the copolymers further comprise at least one additional ionic monomer in addition to at least one carboxylic acid group-containing monomer.
  • Copoylmer '0.1 to 30 0.5 to 25 1, 0 to 20 1, 0 to 20
  • Copolymer comprising i) monomers from the group of mono- or polyunsaturated sulfonic acids ii) monomers from the group of mono- or polyunsaturated
  • Unsaturated hydrocarbon radicals ii) in the copolymers c), ie, for example, in the preferred copolymers c) described above, which contain a carboxylic acid or sulfonic acid group-containing monomer i), preferably monomers of the general formula R 1 (R 2 ) C C (R 3 ) -XR 4 used, in which R 1 to R 3 are independently -H, -CH 3 or -C 2 H 5 , X is an optional spacer group which is selected from -CH 2 -, -C (O) O- and -C (O) -NH-, and R 4 represents a straight-chain or branched saturated alkyl radical having 2 to 22 carbon atoms or an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms.
  • Particularly preferred unsaturated hydrocarbon radicals 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-Dimehtylhexan-1, ethylcyclohexyn, 1-octene, -Olefone having 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecen
  • hydrophobically modified machine dishwashing detergents may contain further copolymers, wherein according to the invention copolymer (s) comprising i) carboxylic acid group-containing monomer (s) ii) sulfonic acid group-containing monomer (s) are preferred become.
  • copolymers are preferably used in amounts of 0.1 to 30 wt .-%, preferably 0.5 to 25 wt .-% and in particular 1, 0 to 20 wt .-%, each based on the total weight of the automatic dishwashing detergent.
  • compositions according to the invention may furthermore contain surfactants.
  • the group of surfactants includes nonionic, anionic, cationic and amphoteric surfactants.
  • the automatic dishwashing detergents contain nonionic surfactant (s), the weight fraction of the nonionic surfactant (s) in the total weight of the automatic dishwashing agent preferably being from 1 to 10% by weight, preferably from 2 to 8% by weight. and in particular 3 to 6 wt .-% is.
  • nonionic surfactants it is possible to use 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, in particular 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol is that for a glycose unit having 5 or 6 C atoms, preferably for Glucose, stands.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is an arbitrary number between 1 and 10; preferably x is 1, 2 to 1, 4.
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the 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 thereof.
  • washing or cleaning agents in particular automatic dishwashing detergents, contain nonionic surfactants from the group of the alkoxylated alcohols.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol residue can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten.
  • EO ethylene oxide
  • alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 moles of EO per mole of alcohol are preferred.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow rank ethoxylates, NRE).
  • NRE narrow rank ethoxylates
  • fatty alcohols with more than 12 EO can also be used. Examples of these are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • ethoxylated nonionic surfactant selected from C 6 - alkanols 2 o-monohydroxy or C 6 - 2 o-alkyl phenols or C 6 - 2 o-fatty alcohols and more than 12 mol, preferably more than 15 mol and in particular more than 20 moles of ethylene oxide per mole of alcohol were used.
  • a particularly preferred nonionic surfactant is selected from a straight chain fatty alcohol having 16 to 20 carbon atoms (C- ⁇ 6 - 2 o-alcohol), preferably a min- d 8 alcohol and at least 12 mol, preferably at least 15 mol and in particular at least 20 mol of ethylene oxide obtained.
  • the so-called “narrow ranks ethoxylates" are particularly preferred.
  • Nonionic surfactants which have a melting point above room temperature.
  • 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 Pas, preferably above 35 Pas and in particular above 40 Pas. Also, nonionic surfactants having waxy consistency at room temperature are preferred depending on their purpose.
  • 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 units make up to 25 wt .-%, more preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic surfactant from.
  • Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units.
  • the alcohol or alkylphenol content of such nonionic surfactant molecules preferably makes up more than 30% by weight, more preferably more than 50% by weight and in particular more than 70% by weight, of the total molecular weight of such nonionic surfactants.
  • Preferred agents are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule up to 25 wt .-%, preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic Make up surfactants.
  • 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).
  • structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants).
  • Such (PO / EO / PO) nonionic surfactants are also distinguished by good visual control.
  • nonionic surfactants having melting points above room temperature contain from 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend containing 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25 Wt .-% of a block copolymer of polyoxyethylene and polyoxypropylene, initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane contains.
  • 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, 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 1 is a straight-chain or branched, saturated or mono- or polyunsaturated C 6 - 24 represents alkyl or alkenyl; 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 ) 2 and the indices w, x, y, z independently stand for 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 or alkylene oxide.
  • the radical R 1 in the above formula may 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 being selected from alcohols of natural origin having 12 to 18 C atoms, for example from coconut, palm, tallow or Oleyl alcohol, are preferred.
  • Alcohols which are accessible from synthetic sources are, for example, the Guerbet alcohols or methyl-branched or linear and methyl-branched radicals in the 2-position, as usually present in oxo alcohol 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.
  • 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.
  • alkylene oxide unit which is contained in the preferred nonionic surfactants in alternation with the ethylene oxide unit, in particular butylene oxide is considered in addition to propylene oxide.
  • R 2 or R 3 are independently selected from -CH 2 CH 2 -CH 3 or -CH (CH 3 ) 2 are suitable.
  • R 2 or R 3 is a radical -CH 3 , w and x independently of one another for values of 3 or 4 and y and z independently of one another are values of 1 or 2.
  • Nonionic surfactants are particularly preferred
  • the 9 have a C .i 5 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 the required low viscosity in aqueous solution and can be used according to the invention 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 of one another represent a straight-chain or branched, saturated or mono- or polyunsaturated C 2 .
  • A, A ', A "and A'” independently represent a radical from the group -CH 2 CH 2 , -CH 2 CH 2 -CH 2 , -CH 2 -CH (CH 3 ), -CH 2 -CH 2 -CH 2 - CH 2 , -CH 2 -CH (CHs) -CH 2 -, -CH 2 -CH (CH 2 -CH 3 ); and w, x, y and z are values between 0.5 and 90, where x, y and / or z can also be 0 are preferred according to the invention.
  • end-capped poly (oxyalkylated) nonionic surfactants which, in accordance with the formula R 1 O [CH 2 CH 2 O] x CH 2 CH (OH) R 2 , in addition to a radical R 1 , which is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having from 2 to 30 carbon atoms, preferably having from 4 to 22 carbon atoms, furthermore having a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R 2 having from 1 to 30 carbon atoms, where x is from 1 to 30 carbon atoms 90, preferably for values between 30 and 80 and in particular for values between 30 and 60.
  • surfactants of the formula R 1 O [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 O] y CH 2 CH (OH) R 2 , in which R 1 is a linear or branched aliphatic hydrocarbon radical with 4 R 2 is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x is values between 0.5 and 1, 5 and y is a value of at least 15.
  • nonionic surfactants having a free hydroxyl group on one of the two terminal alkyl radicals can, in comparison to conventional polyfunctional alkoxylated fatty alcohols without free hydroxyl group, the formation of coatings in the machine dishwashing are significantly improved.
  • nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R 1 O [CH 2 CH (R 3 P] x [CH 2 J k CH (OH) [CH 2 ] J OR 2 in which R 1 and R 2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R 3 is H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl - or 2-methyl-2-butyl radical, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5.
  • each R 3 in the R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] J OR 2 may be different R 1 and R 2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having from 6 to 22 carbon atoms, radicals having from 8 to 18 carbon atoms being particularly preferred, and the radical R 3 being H, -CH 3 or -CH 2 CH 3 nder preferred. Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.
  • each R 3 in the above formula may be different if x> 2.
  • the alkylene oxide unit in the square bracket can be varied.
  • the value 3 for x has been selected here by way of example and may well be greater, with the variation width increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,
  • R 1 , R 2 and R 3 are as defined above and x is from 1 to 30, preferably from 1 to 20, and in particular especially from 6 to 18.
  • the stated C chain lengths and degrees of ethoxylation or degrees of alkoxylation of the abovementioned nonionic surfactants represent statistical mean values which, for a specific product, may be an integer or a fractional number. Due to the manufacturing process, commercial products of the formulas mentioned are usually not made of an individual representative, but of mixtures, which may result in mean values for the C chain lengths as well as for the degrees of ethoxylation or degrees of alkoxylation and subsequently broken numbers.
  • nonionic surfactants can be used not only as individual substances, but also as surfactant mixtures of two, three, four or more surfactants.
  • Mixtures of surfactants are not mixtures of nonionic surfactants which fall in their entirety under one of the abovementioned general formulas, but rather mixtures which contain two, three, four or more nonionic surfactants which can be described by different general formulas ,
  • Copolymer comprising i) monomers from the group of mono- or polyunsaturated sulfonic acids ii) monomers from the group of mono- or polyunsaturated hydrocarbon radicals having 2 to 26 carbon atoms
  • preferred automatic dishwashing contain other ingredients, preferably active ingredients from the group of washing and cleaning active polymers, enzymes, corrosion inhibitors, fragrances or dyes.
  • the group of washing- or cleaning-active polymers includes, for example, the rinse aid polymers and / or polymers which act as softeners, in particular the cationic or amphoteric polymers.
  • amphoteric polymers further comprise, in addition to a positively charged group in the polymer chain, also negatively charged groups or monomer units on. These groups may be, for example, carboxylic acids, sulfonic acids or phosphoric acids.
  • X represents a counterion, preferably a counterion selected from the group consisting of chloride, bromide, iodide, sulfate, hydrogensulfate, methosulfate, laurylsulfate, dodecylbenzenesulfonate, p-toluenesulfonate (tosylate), cumene sulfonate, xylenesulfonate, phosphate, citrate, formate, acetate or mixtures thereof.
  • a counterion selected from the group consisting of chloride, bromide, iodide, sulfate, hydrogensulfate, methosulfate, laurylsulfate, dodecylbenzenesulfonate, p-toluenesulfonate (tosylate), cumene sulfonate, xylenesulfonate, phosphate, citrate, formate, acetate
  • 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) -CH 3, -CH 2 -OH , -CH 2 -CH 2 -OH, -CH (OH) -CH 3 , -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
  • R1 HC CR2-C (O) -NH- (CH 2) -N + R3R4R5
  • MAPTAC Metalacrylamidopropyl trimethylammonium chloride
  • amphoteric polymers have not only cationic groups but also anionic groups or monomer units.
  • anionic monomer units are 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 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 their derivatives, the allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid or the allylphosphonic acids.
  • Preferred amphoteric polymers which can be used are 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 alkylacrylamide / methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers which cationically derivatized alkylacrylamide / methylmethacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / alkymethacrylate / alkylaminoethyl methacrylate / alkyl methacrylate copolymers and the copolymers of unsaturated carboxylic acids unsaturated carboxylic acids and optionally further ionic or nonionic monomers
  • Preferred zwitterionic polymers are from the group of acrylamidoalkyltri alkylammonium 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 comprise, in addition to one or more anionic monomers as cationic monomers, methacrylamidoalkyltrialkylammonium chloride and dimethyl (diallyl) ammonium chloride.
  • amphoteric polymers are selected from the group consisting of the methacrylamidoalkyltri-alkylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, the methacrylamidoalkyltrialkylammonium chloride / dimethyl (diallyl) ammonium chloride / methacrylic acid copolymers and the methacrylamidoalkyltrialkylammonium chloride / dimethy1-diallyl ammonium chloride / alkyl -
  • the polymers are present in prefabricated form.
  • encapsulation of the polymers by means of water-soluble or water-dispersible coating compositions is suitable, 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 agents, preferably by means of water-insoluble coating agents from the group of waxes or paraffins having a melting point above 30 0 C; the co-granulation of the polymers with inert carrier materials, preferably with carrier materials from the group of washing- or cleaning-active substances, more preferably from the group of builders or cobuilders.
  • Detergents or cleaning agents contain the aforementioned cationic and / or amphoteric polymers preferably in amounts of between 0.01 and 10 wt .-%, each based on the total weight of the detergent or cleaning agent.
  • detergents or cleaners enzymes can be used. These 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 or cleaning agents, which are preferably used accordingly.
  • Detergents or cleaning agents contain enzymes preferably in total amounts of 1 ⁇ 10 -6 to 5 wt .-% based on active protein. The protein concentration can be determined by known methods, for example the BCA method or the biuret method.
  • subtilisin type those of the subtilisin type are preferable.
  • these are the subtilisins BPN 'and Carlsberg and their further developed forms, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase which can no longer be assigned to the subtilisins in the narrower sense, Proteinase K and the proteases TW3 and TW7.
  • amylases which can be used according to the invention are the ⁇ -amylases from Bacillus licheniformis, from ⁇ . amyloliquefaciens, from ⁇ .
  • ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and cyclodextrin glucanotransferase (CGTase) from ⁇ . agaradherens (DSM 9948).
  • lipases or cutinases are also usable according to the invention.
  • these include, for example, the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the amino acid exchange D96L.
  • the cutinases can be used, which were originally isolated from Fusarium solani pisi and Humicola insolens. It is also possible to use lipases, or cutinases, whose initial enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii.
  • Dishwashing detergents which are preferred according to the invention are characterized in that they contain enzyme granules having an enzyme content of less than 5% by weight, preferably less than 4% by weight, of the active substance of the enzyme.
  • 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.
  • the enzymes can be used in any form known in the art. These include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel-form detergents, solutions of the enzymes, advantageously as concentrated as possible, sparing in water and / or added with stabilizers.
  • the enzymes may be encapsulated for both the solid and liquid dosage forms, for example by spray-drying or extruding the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type in which an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer.
  • capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes.
  • granules for example by applying polymeric film-forming agent, low in dust and storage stable due to the coating.
  • 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.
  • Copolymer comprising i) monomers from the group of mono- or polyunsaturated carboxylic acids ii) monomers from the group of mono- or polyunsaturated hydrocarbon radicals having 2 to 26 carbon atoms
  • a particularly preferred subject of this application is a machine dishwashing detergent containing a) 10 to 55 wt .-% citrate b) 0.01 to 2 wt .-% bleach catalyst selected from the group of bleach-enhancing transition metal salts and transition metal complexes c) 0.5 to 25 % By weight of copolymer (s) comprising i) acid group-containing monomer (s) ii) further hydrophobic monomer (s) d) 2 to 15% by weight sodium percarbonate e) 2 to 8% by weight nonionic surfactant (s) f) 1, 0 to 6 wt .-% enzyme.
  • Glass corrosion inhibitors prevent the occurrence of haze, streaks and scratches, but also iridescence of the glass surface of machine-cleaned glasses.
  • Preferred glass corrosion inhibitors come from the group of magnesium and zinc salts and magnesium and zinc complexes.
  • preferred zinc salts preferably organic acids, particularly preferably organic carboxylic acids, ranging 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 have 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 in particular above 5 g / l (all solubilities at 2O 0 C. water temperature).
  • the first group of zinc salts includes, for example, the zinc nitrate, the zinc oleate and the 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 at least one zinc salt of an organic carboxylic acid, more preferably a zinc salt from the group zinc stearate, zinc oleate, zinc gluconate, zinc acetate, zinc lactate and Zinkeitrat used.
  • Zinc ricinoleate, 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.
  • the content of zinc in oxidized form (calculated as Zn 2+ ) between 0.01 to 1 wt .-%, preferably between 0.02 to 0.5 wt .-% and in particular between 0.04 to 0, 5 wt .-%, each based on the total weight of the glass corrosion inhibitor-containing agent.
  • Corrosion inhibitors serve to protect the items to be washed or the machine, with particular silver protectants being of particular importance in the field of automatic dishwashing. It is possible to use the known substances of the prior art. In general, silver protectants selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes may be used be used. Benzotriazole and / or alkylaminotriazole are particularly preferred.
  • 3-amino-5-alkyl-1,2,4-triazoles or their physiologically tolerated salts preference is given to using 3-amino-5-alkyl-1,2,4-triazoles or their physiologically tolerated salts, these substances being particularly preferably present in a concentration of 0.001 to 10% by weight, preferably 0.0025 to 2 Wt .-%, particularly preferably 0.01 to 0.04 wt .-% are used.
  • perfume oils or perfumes within the scope of the present invention, individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance.
  • perfume oils may also contain natural fragrance mixtures such as are available from vegetable sources, e.g. Pine, Citrus, Jasmine, Patchouly, Rose or Ylang-Ylang oil.
  • the fragrances can be processed directly, but it can also be advantageous to apply the fragrances on carriers that provide a slower fragrance release for long-lasting fragrance.
  • carrier materials for example, cyclodextrins have been proven, the cyclodextrin-perfume complexes can be additionally coated with other excipients.
  • Preferred dyes the selection of which presents no difficulty for 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 crockery do not stain them.
  • Copolymer comprising i) monomers from the group of mono- or polyunsaturated carboxylic acids ii) monomers from the group of mono- or polyunsaturated hydrocarbon radicals having 2 to 26 carbon atoms
  • the automatic dishwashing compositions according to the invention can be formulated in solid or liquid form but can also be present, for example, as a combination of solid and liquid forms.
  • Powder, granules, extrudates or compactates, in particular tablets, are particularly suitable as firm supply forms.
  • the liquid supply forms based on water and / or organic solvents may be thickened, in the form of gels.
  • Inventive agents can be formulated as single-phase or multi-phase products.
  • automatic dishwashing detergents with one, two, three or four phases are preferred.
  • Machine dishwashing detergents characterized in that they are in the form of a prefabricated dosing unit with two or more phases, are particularly preferred.
  • the individual phases of multiphase agents may have the same or different states of matter.
  • Machine dishwashing detergents which have at least two different solid phases and / or at least two liquid phases and / or at least one solid and at least one liquid phase are preferred.
  • Automatic dishwasher detergents according to the invention are preferably prefabricated to form metering units. These metering units preferably comprise the necessary for a cleaning cycle amount of washing or cleaning-active substances. Preferred metering units have a weight between 12 and 30 g, preferably between 14 and 26 g and in particular between 15 and 22 g.
  • the volume of the aforementioned metering units and their spatial form are selected with particular preference so that a metering of the prefabricated units is ensured via the metering chamber of a dishwasher.
  • the volume of the dosing 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 dishwasher detergents according to the invention in particular the prefabricated metering units, have a water-soluble coating, with particular preference.
  • disintegration aids so-called tablet disintegrants
  • these substances which are also referred to as “explosives” due to their effect, increase their volume upon ingress of water, on the one hand increasing the intrinsic volume (swelling), and on the other hand creating a pressure via the release of gases which can break the tablet into smaller particles disintegrates.
  • disintegration aids are, for example, carbonate / citric acid systems, although other organic acids can also 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, alginates or casein derivatives.
  • PVP polyvinylpyrrolidone
  • disintegration aids 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 aid-containing agent.
  • Preferred disintegrating agents are cellulosic disintegrating agents, so that preferred washing or cleaning agents comprise such cellulose-based disintegrants 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. % contain.
  • 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 it is added to the premixes to be tabletted.
  • the particle sizes of such disintegrating agents are usually above 200 .mu.m, preferably at least 90 wt .-% between 300 and 1600 .mu.m and in particular at least 90 wt .-% between 400 and 1200 microns.
  • Preferred disintegration aids preferably a cellulose-based disintegration assistant, preferably in granular, cogranulated or compacted form, are present in the desintegration 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 wt .-%, each based on the total weight of the desintegration agent-containing agent.
  • gas-evolving effervescent systems can furthermore be used as tablet disintegration auxiliaries.
  • the gas-evolving effervescent system may consist of a single substance that releases a gas upon contact with water.
  • these compounds mention should be made in particular of magnesium peroxide, which liberates oxygen on contact with water.
  • preferred effervescent systems consist of at least two components which react with one another to form gas, for example from alkali metal carbonate and / or bicarbonate and an acidifying agent which is suitable for liberating carbon dioxide from the alkali metal salts in aqueous solution.
  • Acidifying agents which release carbon dioxide from the alkali metal salts in aqueous solution include, for example, boric acid and alkali metal hydrogen sulfates, alkali metal dihydrogen phosphates and other inorganic salts.
  • organic acidifying agents preference is given to using organic acidifying agents, the citric acid being a particularly preferred acidifying agent.
  • Acidifying agents in the effervescent system from the group of organic di-, tri- and oligocarboxylic acids or mixtures are preferred.
  • the present application further relates to a method for cleaning dishes in a dishwasher using automatic dishwashing agents according to the invention, wherein the automatic dishwashing agents are preferably metered into the interior of a dishwasher during the passage of a dishwashing program, before the main wash cycle or during the main wash cycle.
  • the metering or the entry of the agent according to the invention into the interior of the dishwasher can be done manually, but preferably the agent is metered into the interior of the dishwasher by means of the metering chamber of the dishwasher.
  • no additional water softener and no additional rinse aid is dosed into the interior of the dishwasher.
  • a kit for a dishwasher comprising a) a machine dishwashing detergent according to the invention; (b) instructions instructing the consumer to use the automatic dishwashing detergent without the addition of a rinse aid and / or a softening salt are another subject of this application.
  • composition of the dishwashing agents used can be found in the following table:

Landscapes

  • Detergent Compositions (AREA)

Abstract

La présente invention concerne des détergents pour lave-vaisselle sans phosphate intégrant un agent de blanchiment. Ces détergents comprennent a) du citrate, b) un catalyseur de blanchiment choisi dans le groupe formé par les sels de métaux de transition et les complexes de métaux de transition qui renforcent le blanchiment, c) un ou plusieurs copolymères comprenant i) un ou plusieurs monomères comportant des groupes acide, et ii) un ou plusieurs autres monomères hydrophobes. Les détergents selon cette invention sont caractérisés par une meilleure puissance de blanchiment.
EP07822100A 2007-02-06 2007-10-31 Détergents Withdrawn EP2115109A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP07822100A EP2115109A2 (fr) 2007-02-06 2007-10-31 Détergents

Applications Claiming Priority (9)

Application Number Priority Date Filing Date Title
DE102007006629A DE102007006629A1 (de) 2007-02-06 2007-02-06 Reinigungsmittel
DE102007006630A DE102007006630A1 (de) 2007-02-06 2007-02-06 Reinigungsmittel
DE102007006627A DE102007006627A1 (de) 2007-02-06 2007-02-06 Reinigungsmittel
DE102007006628A DE102007006628A1 (de) 2007-02-06 2007-02-06 Reinigungsmittel
PCT/EP2007/059203 WO2008028896A2 (fr) 2006-09-08 2007-09-04 Granulé d'enzyme de concentration élevée et agent de lavage ou de nettoyage contenant un tel granulé d'enzyme de concentration élevée
DE200710044417 DE102007044417A1 (de) 2007-09-17 2007-09-17 Reinigungsmittel
DE102007044418A DE102007044418A1 (de) 2007-09-17 2007-09-17 Reinigungsmittel
EP07822100A EP2115109A2 (fr) 2007-02-06 2007-10-31 Détergents
PCT/EP2007/061753 WO2008095554A2 (fr) 2007-02-06 2007-10-31 Détergents

Publications (1)

Publication Number Publication Date
EP2115109A2 true EP2115109A2 (fr) 2009-11-11

Family

ID=41153251

Family Applications (1)

Application Number Title Priority Date Filing Date
EP07822100A Withdrawn EP2115109A2 (fr) 2007-02-06 2007-10-31 Détergents

Country Status (1)

Country Link
EP (1) EP2115109A2 (fr)

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2008095554A3 *

Similar Documents

Publication Publication Date Title
EP2115112B1 (fr) Détergents
EP2118254B1 (fr) Détergents
EP2118255B1 (fr) Composition detergente
EP2115113B1 (fr) Détergents
EP2487232B1 (fr) Produit de nettoyage
EP2364351B1 (fr) Détergents
EP2358853B1 (fr) Détergents pour lave-vaisselle
WO2009074398A1 (fr) Détergents
EP2185674A1 (fr) Détergents
WO2010076165A1 (fr) Produit de lavage pour lave-vaisselle
EP2220205A1 (fr) Produit de nettoyage
WO2009024364A1 (fr) Agents nettoyants
EP2188361B1 (fr) Nettoyants
WO2008095554A2 (fr) Détergents
WO2009037012A2 (fr) Nettoyants
EP2718414A1 (fr) Détergent vaisselle protégeant l'argenterie
WO2011032870A1 (fr) Détergent pour lave-vaisselle
EP2115109A2 (fr) Détergents
DE102014212728A1 (de) Geschirrspülmittel

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20090529

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC MT NL PL PT RO SE SI SK TR

RIN1 Information on inventor provided before grant (corrected)

Inventor name: NITSCH, CHRISTIAN

Inventor name: WARKOTSCH, NADINE

Inventor name: MUELLER, SVEN

Inventor name: TONDERA, SUSANNE

Inventor name: MUELLER-KIRSCHBAUM, THOMAS

Inventor name: ZIPFEL, JOHANNES

Inventor name: BESSLER, CORNELIUS

Inventor name: HOLDERBAUM, THOMAS

Inventor name: KESSLER, ARND

Inventor name: DUEFFELS, ARNO

DAX Request for extension of the european patent (deleted)
17Q First examination report despatched

Effective date: 20100805

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20110216