EP1363986B1 - Produits vaisselle "3 en 1" et procede de fabrication de ces produits - Google Patents

Produits vaisselle "3 en 1" et procede de fabrication de ces produits Download PDF

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Publication number
EP1363986B1
EP1363986B1 EP02706745A EP02706745A EP1363986B1 EP 1363986 B1 EP1363986 B1 EP 1363986B1 EP 02706745 A EP02706745 A EP 02706745A EP 02706745 A EP02706745 A EP 02706745A EP 1363986 B1 EP1363986 B1 EP 1363986B1
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Prior art keywords
weight
acid
copolymer
acid groups
sulphonic acid
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German (de)
English (en)
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EP1363986A1 (fr
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Christian Nitsch
Bernd Richter
Rolf Bayersdörfer
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0091—Dishwashing tablets
    • 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
    • C11D3/378—(Co)polymerised monomers containing sulfur, e.g. sulfonate

Definitions

  • the present invention relates to automatic dishwashing detergents, especially such cleaning agents.
  • the benefits of detergent and rinse aid in provide a product and the production process for such rinse aids and cleaning agents are other objects of the present invention.
  • German patent application DE 100 32 612.9 discloses the use of copolymers of i) unsaturated carboxylic acids, ii) monomers containing sulfonic acid groups and iii) optionally further ionic or nonionic monomers in automatic dishwashing detergents. Rinse aids and automatic dishwashing detergents containing such polymers are also described there, the agents being in solid or liquid form. eg as powders, granules, extrudates, tablets, liquids or gels.
  • the object of the present invention was to provide a solid machine dishwashing detergent, the sulfonic acid-containing copolymers may be contained in any amount, without that there are product problems such as clumping, posthardening or poor dissolving properties comes.
  • a process should be provided which facilitates the incorporation of the Sulfonic acid-containing copolymers in automatic dishwashing detergents in any quantities without compromising process safety or sustaining production equipment be contaminated.
  • ionic or nonionic monomers are in particular ethylenically unsaturated Compounds considered.
  • the content is preferably that used according to the invention Polymers of monomers of group iii) less than 20 wt .-%, based on the polymer.
  • Particularly preferred polymers to be used consist only of monomers of the groups i) and ii).
  • the copolymers used according to the invention may contain the monomers from groups i) and ii) and, where appropriate, (iii) in varying amounts, all representatives of the Group i) with all representatives from group ii) and all representatives from the group iii) can be combined.
  • Particularly preferred polymers have certain structural units on, which are described below.
  • Acrylic acid and / or methacrylic acid can also be copolymerized completely analogously with sulfonic acid-containing methacrylic acid derivatives, whereby the structural units in the molecule are changed.
  • maleic acid can also be used as a particularly preferred monomer from group i).
  • the sulfonic acid groups can be completely or partially neutralized present, i. that the acidic acid of the sulfonic acid group in some or all sulfonic acid groups against metal ions, preferably alkali metal ions and in particular against Sodium ions, can be replaced.
  • metal ions preferably alkali metal ions and in particular against Sodium ions
  • the sulfonic acid groups are partially or fully neutralized in the copolymer, are preferred according to the invention
  • compositions according to the invention which additionally contain from 0.1 to 30% by weight of homo- and / or copolymeric polycarboxylic acids or their salts and / or heteroatom-containing polymers / copolymers, especially those containing amino or phosphono groups.
  • the combination with amino- and / or phosphono phenomenon restroomn polymers / capolymers is advantageous in builder systems, which only partially. phosphate-based, e.g. Phosphate / citrate mixing systems.
  • the monomer distribution in the sulfonic acid-containing copolymers in copolymers containing only monomers from groups i) and ii), in each case 5 to 95 Wt .-% i) or ii), particularly preferably 50 to 90 wt .-% of monomer from the group i) and 10 bis 50 wt .-% monomer from group ii), each based on the polymer.
  • the terpolymers contain 20 to 85 wt .-% of monomer from the Group i), from 10 to 60% by weight of monomer from group ii) and from 5 to 30% by weight of monomer Group iii).
  • the molecular weight of the sulfonic acid group-containing copolymers can be varied to tailor the properties of the polymers to the desired end use.
  • Preferred sulfonic acid-containing copolymers are characterized in that they have molecular weights of 2000 to 200,000 gmol -1 , preferably from 4000 to 25,000 gmol -1 and in particular from 5000 to 15,000 gmol -1 .
  • the above-described sulfonic acid blowing-containing copolymers used in particulate form contain the sulfonic acid groups Contain copolymers in the form of discrete, isolable particles. These particles may consist entirely of the sulfonic acid-containing copolymers or so-called Compounds, which additionally contain other substances, such as carrier materials. Decisive for the success of the invention is the particulate form, which only by adding is achieved as a solid during the manufacturing process (see below).
  • in particulate form means that the agents according to the invention contain an (optionally Tablets or phases thereof compressed) particle mixture of a particle variety (builders, optional bleaches, etc.) in which the sulfonic acid group-containing copolymers form a part of the particle matrix.
  • the particles in the Agents containing sulfonic acid-containing copolymers certain particle size criteria. At least 50% by weight, preferably at least 60% by weight, particularly preferably at least 75 % By weight and in particular at least 90% by weight of the particles of the sulfonic acid group-containing particles present in the middle Copolymers have particle sizes above 200 microns.
  • the particle sizes or the fulfillment of the particle size criteria can be determined by sieving the Determine polymer particles in the manner known in the art. In other words, that means for the agents described above, that at least 50 wt .-%, preferably at least 60% by weight, more preferably at least 75% by weight and in particular at least 90% by weight of the particles of the sulfonic acid group-containing copolymer present in the middle remain on sieves with a mesh size of 200 microns.
  • the polymer particles are even coarser, so that, for example, at least 50% by weight, preferably at least 50% by weight, more preferably at least 60% by weight and in particular at least 80% by weight of the particles of the sulphonic acid group-containing particles present in the middle Copolymer on sieves with a mesh size of 400 microns remain.
  • the particle size range is preferably limited.
  • the polymer has a particle size distribution, at the maximum 60 wt .-%, preferably at most 50% by weight and in particular not more than 40% by weight of the average amount contained in the composition Particles of the sulfonic acid group-containing copolymer on sieves with a mesh size of 800 microns remain.
  • Coarse and fines are preferably present only to a minor extent, so that preferred automatic dishwashing detergents are characterized in that a maximum of 20 wt .-%, preferably at most 15% by weight and in particular not more than 10% by weight of the particles present in the middle of the sulfonic acid group-containing copolymer particle sizes below 200 microns or above 1200 microns have.
  • the present invention contained in the agents particles of the sulfonic acid-containing copolymer preferably have a certain water content. By providing such Controlled in their water content particles can be the successes of the invention even further increase. Too high water content of polymer particles can be, for example, by Drying be easily and in the art known manner be lowered.
  • the dishwasher according to the invention is the water content of im Contained particles of the sulfonic acid-containing copolymer 3 to 12 wt .-%, preferably 4 to 11 wt .-% and in particular 5 to 10 wt .-%, each based on the copolymer particles.
  • the water content of the polymer particles can be easily by titration determined by Karl Fischer.
  • the weight of the shaft according to the invention contained in the agents of the Sulfonsaure phenomenon-containing Copolymer is preferably within a certain range.
  • Under Bulk density is to be understood as meaning the weight of a loose bulk, that is not the ramming weight.
  • automatic dishwashing agents according to the invention are particularly preferred the bulk density of the particles of sulfonic acid groups contained in the middle Copolymer 550 to 850 g / l, preferably 570 to 800 g / l, more preferably 590 to 750 g / l and especially 600 to 720 g / l.
  • the amounts in which the / the sulfonic acid group-containing copolymer (s) used will be / are between 0.1 and 70 wt .-%. in each case based on the total mean.
  • automatic dishwashing detergents according to the invention which are characterized in that they contain the sulfonic acid group-containing copolymer (s) in amounts of 0.25 to 50% by weight. preferably from 0.5 to 35% by weight, more preferably from 0.75 to 20 Wt .-% and in particular from 1 to 15 wt .-%.
  • inventive automatic dishwashing detergents which additionally contain from 2 to 40% by weight, preferably 3 to 30 wt .-% and in particular 5 to 20 wt .-% of one or more ingredients having a melting or softening point below 60 ° C, with non-ionic (s) Surfactant (s) is / are preferred.
  • Such ingredients with melting or softening points below 60 ° C can from a Come from a variety of substance classes. Many of these ingredients show no sharply defined Melting point, as it usually occurs with pure, crystalline substances, but one under In some circumstances several degrees Celsius melting range. This is the above described preferred means below 60 ° C, this limit is not the width of Melting area, but only his "location". Preferably, the width of the Melting range at least 1 ° C, preferably about 2 to about 3 ° C.
  • waxes are usually met by so-called waxes.
  • “Waxing” is understood to mean a number of natural or artificial substances, usually melt above 40 ° C without decomposition and relatively little above the melting point low viscosity and non-stringy. They have a strongly temperature-dependent Consistency and solubility. According to their origin, the waxes are divided into three groups, the natural waxes, chemically modified waxes and the synthetic waxes.
  • Natural waxes include, for example, vegetable waxes such as candelilla wax, Carnauba wax, japan wax, esparto wax, cork wax, guaruma wax, rice germ oil wax, Sugar cane wax, ouricury wax, or montan wax, animal waxes such as beeswax, Shellac wax, spermaceti, lanolin (woolwax), or raffia fat, mineral waxes such as ceresin or Ozokerite (ground wax), or petrochemical waxes such as petrolatum, paraffin waxes or Microcrystalline waxes.
  • vegetable waxes such as candelilla wax, Carnauba wax, japan wax, esparto wax, cork wax, guaruma wax, rice germ oil wax, Sugar cane wax, ouricury wax, or montan wax
  • animal waxes such as beeswax, Shellac wax, spermaceti, lanolin (woolwa
  • the chemically modified waxes include, for example, hard waxes such as montan ester waxes, Sassol waxes or hydrogenated jojoba waxes.
  • Synthetic waxes are generally polyalkylene waxes or polyalkylene glycol waxes Understood. Can be used as wrapping materials and compounds from other classes that the meet the requirements regarding the softening point.
  • suitable synthetic Compounds for example, have higher esters of phthalic acid, in particular Dicyclohexyl phthatate, commercially available under the name Unimoll® 66 (Bayer AG), proved.
  • synthetically produced waxes from lower carboxylic acids and Fatty alcohols for example dimyristyl tartrate, sold under the name Cosmacol® ETLP (Condea) is available.
  • synthetic or partially synthetic esters of lower alcohols can be used with fatty acids from natural sources.
  • the Tegin® 90 falls into this class of substances (Goldschmidt), a glycerol monostearate palmitate.
  • the Wax alcohols are higher molecular weight, water-insoluble Fatty alcohols with usually about 22 to 40 carbon atoms.
  • the waxy alcohols come for example in the form of wax esters of higher molecular weight fatty acids (wax acids) as the main constituent many natural waxes.
  • wax alcohols are lignoceryl alcohol (1-tetracosanol), Cetyl alcohol, myristyl alcohol or melissyl alcohol.
  • the wrapping of the Wool wax alcohols may optionally also be coated according to the invention which is understood to mean triterpenoid and steroidal alcohols, for example lanolin for example, under the trade name Argowax® (Pamentier & Co). Also can be used at least proportionally as part of the envelope in the context of the present Invention Fatty acid glycerol esters or fatty acid alkanolamides but optionally also water-insoluble or only slightly water-soluble polyalkylene glycol compounds.
  • waxes described above may be used for sustained release of ingredients be incorporated into the funds at a certain time in the cleaning cycle. Suitable for this purpose For example, so-called “fatty substances", which also melting or softening points below 60 ° C.
  • fatty substances are solid at normal temperature (20 ° C.) Substances from the group of fatty alcohols, fatty acids and fatty acid derivatives, in particular the fatty acid ester, understood.
  • Fatty substances which may be preferred according to the invention are fatty alcohols and fatty alcohol mixtures, fatty acids and fatty acid mixtures, fatty acid esters with alkanols or diols or polyols, fatty acid amides, fatty amines, etc. use.
  • Preferred detergent components contain as ingredient c) one or more substances from the groups of fatty alcohols, fatty acids and fatty acid esters.
  • fatty alcohols for example, the available from natural fats and oils alcohols 1-hexanol (caproic alcohol), 1-heptanol ( ⁇ nanthalkohol), 1-octanol (caprylic alcohol), 1-nonanol (pelargonalkohol), 1-decanol (Caprinalkohol), 1-undecanol , 10-undecene-1-ol,) 1-dodecanol (lauryl alcohol), 1-tridecanol, 1-tetradecanol (myristyl alcohol), 1-pentadecanol, 1-hexadecanol (cetyl alcohol), 1-heptadecanol, 1-octadecanol (stearyl alcohol), 9-cis-octadecen-1-ol (oleyl alcohol), 9-trans-octadecen-1-ol (erucyl alcohol), 9-cis-octadecene-1,12-diol (ric
  • Guerbet alcohols and oxo alcohols for example C 13-15 oxo alcohols or mixtures of C 12-18 alcohols with C 12-14 alcohols, can also be used without problems as fatty substances.
  • alcohol mixtures for example those such as C 16-18 -alcohols produced by ethylene polymerization according to Ziegler.
  • Specific examples of alcohols which can be used as component c) are the abovementioned alcohols as well as lauryl alcohol, palmityl and stearyl alcohol and mixtures thereof.
  • fatty acids are fatty substances. These are technically largely derived from native fats and oils by hydrolysis. While the alkaline saponification already carried out in the past century led directly to the alkali salts (soaps), today only large amounts of water are used for cleavage, which cleaves the fats into glycerol and the free fatty acids. Examples of industrially applied processes are the autoclave cleavage or continuous high pressure cleavage. For example, hexanoic acid (caproic acid), heptanoic acid (enanthic acid), octanoic acid (caprylic acid), nonanoic acid (pelargonic acid), decanoic acid (capric acid), undecanoic acid, etc.
  • Fatty acids such as dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), eicosanoic acid (arachidic acid), docosanoic acid (behenic acid), tetracosanic acid (lignoceric acid), hexacosanoic acid (cerotic acid), triacotanic acid (melissic acid) and unsaturated secies 9c-hexadecenoic acid (palmitoleic acid), 6c-octadecenoic acid (petroselinic acid), 6t-octadecenoic acid (petroselaidic acid), 9c-octadecenoic acid (oily acid), 9t-octadecenoic acid (elaidic acid), 9c, 12c-oct
  • tridecanoic acid pentadecanoic acid, margaric acid, nonadecanoic acid, erucic acid, elaeostearic acid and arachidonic acid can be used.
  • Such mixtures are for example coconut oil (about 6 wt .-% C 8 , 6 wt .-% C 10 , 48 wt .-% C 12 , 18 wt .-% C 14 , 10 wt .-% C 16 , 2 wt % C 18 , 8% by weight C 18 , 1% by weight C 18 " ), palm kernel oil fatty acid (about 4% by weight C 8 , 5% by weight C 10 , 50% by weight C 12 , 15 wt .-% C 14 , 7 wt .-% C 16 , 2 wt .-% C 18 , 15 wt .-% C 18 ' , 1 wt .-% C 18'' ), tallow fatty acid (approx 3 wt% C 14 , 26 wt% C 16 , 2 wt% C 16 ' , 2 wt% C 17 , 17 wt% C 18 , 44 wt% C
  • fatty acid esters it is possible to use the esters of fatty acids with alkanols, diols or polyols, wherein fatty acid polyol esters are preferred.
  • fatty acid polyol are mono- or Diesters of fatty acids with certain polyols into consideration.
  • the fatty acids with the polyols are esterified, are preferably saturated or unsaturated fatty acids having 12 to 18 carbon atoms, For example, lauric, myristic, palmitic or stearic, with preferred the technically occurring mixtures of the fatty acids are used, for example the acid mixtures derived from coconut, palm kernel or tallow fat.
  • acids or Mixtures of acids having 16 to 18 carbon atoms such as tallow fatty acid are for esterification suitable with the polyhydric alcohols.
  • polyols those with the above Fatty acids are esterified in the context of the present invention sorbitol, trimethylolpropane, Neopentyl glycol, ethylene glycol, polyethylene glycols, glycerol and polyglycerols in Consideration.
  • compositions according to the invention can also substances with melting or softening points which are usually included in the funds to the performance of the funds improve.
  • substances are in particular nonionic surfactants.
  • the cleaning agent according to the invention contains nonionic surfactants from the group of the alkoxylated alcohols.
  • nonionic surfactants preference is given to using alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol in which the alcohol radical is linear or preferably methyl-branched in the 2-position may contain or linear and methyl-branched radicals in the mixture, 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 EO per mole of alcohol are preferred.
  • the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 9-11 alcohols with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 -alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12-14 -alconol with 3 EO and C 12-18 -alcohol with 5 EO.
  • the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • nonionic surfactants preference may be given to using propoxylated and / or butoxylated nonionic surfactants, particular importance being attached to the mixed alkoxylated, advantageously propoxylated and ethoxylated nonionic surfactants.
  • the C chain length in the alkyl radical is preferably 8 to 18 C atoms, where C 9-11- alkyl radicals, C 12-13 -alkyl radicals and C 16-18 -alkyl radicals are of particular importance.
  • nonionic surfactants are preferred which have been obtained from C 9-11 or C 12-13 oxo alcohols.
  • nonionic surfactants on average 1 to 20 moles of alkylene oxide (AO) are used per mole of alcohol, wherein AO is the sum of EO and PO.
  • Particularly preferred nonionic surfactants of this group contain 1 to 5 moles of PO and 5 to 15 moles of EO.
  • a particularly preferred member of this group is a C 12-20 oxo alcohol alkoxylated with 2 PO and 15 EO, which is available under the trade name Plurafac® LF 300 (BASF).
  • preferred nonionic surfactants may also have butylene oxide groups.
  • the abovementioned alkyl radicals, in particular the oxoalcohol radicals, are again preferred.
  • the number of BO groups in preferred nonionic surfactants is 1, 2, 3, 4 or 5, wherein the total number of alkylene oxide groups is preferably in the range of 10 to 25.
  • a particularly preferred member of this group is available under the trade name Plurafac® LF 221 (BASF) and can be described by the formula C 13-15 -O- (EO) 9-10 (BO) 1-2
  • nonionic surfactants and alkyl glycosides of the general formula RO (G) x can be used in which R is a primary straight-chain or methyl-branched, especially in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon 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 indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.
  • nonionic surfactants used either alone nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl ester.
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamide may be suitable.
  • the amount of these nonionic surfactants is preferably no longer than that of the ethoxylated fatty alcohols, especially not more than half of them.
  • polyhydroxy fatty acid amides of the formula (IX) in the RCO 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 (X) in the 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 and R 2 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, with C 1-4 alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this residue.
  • 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
  • [Z] is preferably obtained by reductive amination of a reduced sugar, for example Glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a reduced sugar for example Glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy or N-aryloxy-substituted compounds can then be converted by reaction with fatty acid methyl esters in the presence of an alkoxide as a catalyst in the desired polyhydroxy fatty acid amides be transferred.
  • nonionic surfactant having a melting point above Room temperature.
  • preferred automatic dishwashing detergents which are nonionic (s) Surfactant (s) having a melting point above 20 ° C, preferably above 25 ° C, more preferably between 25 and 60 ° C and in particular between 26.6 and 43.3 ° C, in Amounts from 5.5 to 20 wt .-%, preferably from 6.0 to 17.5 wt .-%, particularly preferably from 6.5 to 15 and in particular from 7.0 to 12.5 wt .-%, each based on the total Means, included.
  • Suitable nonionic surfactants are, for example, low-foaming nonionic surfactants which Room temperature can be solid or highly viscous. Become highly viscous at room temperature Nonionic surfactants used, it is preferred that these have a viscosity above 20 Pas, preferably above 35 Pas and in particular above 40 Pas. Also Niotenside, the have waxy consistency at room temperature are preferred.
  • Preferred nonionic surfactants to be used at room temperature are from the groups the alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures these surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants. Drawing such (PO / EO / PO) nonionic surfactants Beyond that by good foam control.
  • the nonionic surfactant having a melting point above room temperature is an ethoxylated nonionic surfactant consisting of the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 carbon atoms, preferably at least 12 mol, more preferably at least 15 mol, especially at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol emerged.
  • nonionic surfactant (s) is (are) ethoxylated nonionic surfactant (s) selected from C 6-20 monohydroxyalkanols or C 6-20 alkylphenols or C 16- 20 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 was obtained (n), are therefore preferred.
  • a particularly preferred room temperature solid nonionic surfactant is obtained 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 especially at least 20 moles of ethylene oxide , Of these, the so-called “narrow range ethoxylates" (see above) are particularly preferred
  • the nonionic surfactant solid at room temperature preferably additionally has propylene oxide units in the molecule.
  • such PO units make up to 25% by weight. particularly preferred up to 20% by weight and in particular up to 15% by weight of the total molecular weight of the nonionic Surfactants.
  • Machine dishwashing detergents, the 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 surfactant are preferred embodiments of the present invention.
  • nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally having polyoxyethylene-polyoxypropylene block copolymer units.
  • the alcohol- or alkylphenol part 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 Molar mass of such nonionic surfactants.
  • nonionic surfactants with melting points above room temperature contain 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend, the 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% by weight of a Block copolymers of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.
  • Nonionic surfactants which can be used with particular preference are, for example available under the name Poly Tergent® SLF-18 from Olin Chemicals.
  • a further preferred surfactant can be defined by 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 having 4 to 18 carbon atoms or mixtures thereof, 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.
  • Machine dishwashing detergents characterized in that they contain nonionic 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 having 4 to 18 carbon atoms or mixtures thereof, 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, are therefore preferred.
  • nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2 in which R 1 and R 2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R 3 is H or a methyl, ethyl, n-propyl, iso-propyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5.
  • each R 3 in the above formula may be different.
  • R 1 and R 2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred.
  • R 3 H, -CH 3 or -CH 2 CH 3 are particularly preferred.
  • Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.
  • each R 3 in the above formula may be different if x ⁇ 2
  • the alkylene oxide unit in the square bracket can be varied.
  • the value 3 for x has been selected here by way of example and may well be greater, with the variation width increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,
  • R 1 , R 2 and R 3 are as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18.
  • Particularly preferred are surfactants in which the radicals R 1 and R 2 has 9 to 14 C atoms, R 3 is H and x assumes values of 6 to 15.
  • the end-capped poly (oxyalkylated) nonionic surfactants of the formula R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2 in which R 1 and R 2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R 3 is H or a methyl, ethyl, n-propyl, iso-propyl, x is n-butyl, 2-butyl or 2-methyl-2-butyl, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5, surfactants of the type R 1 O [CH 2 CH (R 3 ) O] x CH 2 CH (OH) CH 2 OR 2 in which x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18, are particularly preferred.
  • nonionic surfactants from group a) have already been described in detail above, with particular preference for the automatic dishwashing compositions containing the abovementioned mixtures, C 12-14 fatty alcohols with 5EO and 4PO and C 12-18 fatty alcohols with an average of 9 EO have proven to be outstanding. With similar preference end-capped nonionic surfactants, in particular C 12-18 fatty alcohol-9 EO-butyl ether, can be used.
  • Surfactants from group b) show outstanding clear rinse effects and reduce stress corrosion cracking on plastics. Furthermore, they have the advantageous property that their network behavior is constant over the entire usual temperature range. Especially preferred are the surfactants from the group b) hydroxyl-containing alkoxylated alcohols. All there hydroxy mixed ethers disclosed are without exception preferred as surfactant from the group b) in contain the dishwashing detergents preferred according to the invention.
  • surfactant-capped surfactants and nonionic surfactants with butoxy groups are preferably also usable as nonionic surfactants.
  • the first group includes in particular representatives of the formula R 1 O [CH 2 CH (R 3 ) O] x R 2 , in the R 1 for a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical having 1 to 30 C atoms, R 2 is a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical having 1 to 30 C atoms, which is optionally substituted with 1, 2, 3, 4 or 5 hydroxy groups and optionally with further ether groups, R 3 is -H or methyl, ethyl, n- propyl, iso- propyl, n- butyl, iso- butyl or tert- butyl and x can take values between 1 and 40.
  • R 2 may optionally be alkoxylated, wherein the alkoxy group is preferably selected from
  • Particularly preferred surfactants can be defined by the formulas C 9-11 (EO) 8 -C (CH 3 ) 2 CH 2 CH 3 , C 11-15 (EO) 15 (PO) 6 -C 12-14 , C 9-11 (EO) 8 (CH 2 ) 4 CH 3 .
  • R 1 is a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical having 1 to 30, preferably 6 to 20 C atoms, a for values between 2 and 30, b for values between 0 and 30 and c is between 1 and 30, preferably between 1 and 20.
  • the EO and PO groups in the above formula may also be reversed so that surfactants of the general formula R 1 (PO) b (EO) a (BO) c , in the R 1 for a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical having 1 to 30, preferably 6 to 20 C atoms, a for values between 2 and 30, b for values between 0 and 30 and c for values between 1 and 30, preferably between 1 and 20, is also used with preference.
  • surfactants of the general formula R 1 (PO) b (EO) a (BO) c in the R 1 for a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical having 1 to 30, preferably 6 to 20 C atoms, a for values between 2 and 30, b for values between 0 and 30 and c for values between 1 and 30, preferably between 1 and 20, is also used with preference.
  • Particularly preferred representatives of this group of surfactants can be distinguished by the formulas C 9-11 (PO) 3 (EO) 13 (BO) 15 , C 9-11 (PO) 3 (EO) 13 (BO) 6 , C 9- 11 (PO) 3 (EO) 13 (BO) 3 , C 9-11 (EO) 13 (BO) 6 , C 9-11 (EO) 13 (BO) 3 , C 9-11 (PO) (EO) 13 (BO) 3 , C 9-11 (EO) 8 (BO) 3 , C 9-11 (EO) 8 (BO) 2 , C 12-15 (EO) 7 (BO) 2 , C 9-11 ( EO) 8 (BO) 2 , C 9-11 (EO) 8 (BO).
  • a particularly preferred surfactant of the formulas C 13-15 (EO) 9-10 (BO) 1-2 is commercially available under the name Plurafac® LF 221.
  • Another particularly preferred 10 EO and 2 BO surfactant is available under the trade name Genapol® 25 EB 102. It is also possible to use a surfactant of the formula C 12-13 (EO) 10 (BO) 2 .
  • nonionic surfactant s / e
  • the introduction of the nonionic surfactant (s / e) in the compositions of the invention can done different way.
  • the surfactants may, for example, in a slick condition on the otherwise ready-made agent is sprayed on or the agent in the form of compounds or surfactant formulations.
  • Suitable crystalline layered sodium silicates have the general formula NaMSi x O 2x + 1 H 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2 , 3 or 4 are.
  • Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3. In particular, both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 .yH 2 O are preferred.
  • 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 Delayed and have secondary washing properties.
  • the dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying.
  • the term "amorphous” is also understood to mean "X-ray amorphous”.
  • the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle. However, it may very well lead to particularly good builder properties if the silicate particles give washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, values of up to max. 50 nm and in particular up to max. 20 nm are preferred. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.
  • the finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P.
  • zeolite P zeolite MAP® (commercial product from Crosfield) is particularly preferred.
  • zeolite X and mixtures of A, X and / or P are particularly preferred.
  • Commercially available and preferably usable in the context of the present invention is, for example, a cocrystal of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by the company CONDEA Augusta SpA under the brand name VEGOBOND AX® and by the formula n Na 2 O. (1-n) K 2 O. Al 2 O 3 .
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
  • the alkali metal phosphates have particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate) in the washing and cleaning industry the greatest importance.
  • Alkali metal phosphates is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric acids (HPO 3 ) n and orthophosphoric H 3 PO 4 in addition to higher molecular weight representatives.
  • the phosphates combine several advantages: they act as alkali carriers, prevent lime deposits on machine parts or lime incrustations in fabrics and also contribute to the cleaning performance.
  • Sodium dihydrogen phosphate, NaH 2 PO 4 exists as a dihydrate (density 1.91 gcm -3 , melting point 60 °) and as a monohydrate (density 2.04 gcm -3 ). Both salts are white powders which are very soluble in water and which lose their water of crystallization when heated and at 200 ° C into the weak acid diphosphate (disodium hydrogen diphosphate, Na 2 H 2 P 2 O 7 ), at higher temperature in sodium trimetaphosphate (Na 3 P 3 O 9 ) and Maddrell's salt (see below).
  • NaH 2 PO 4 is acidic; It arises when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed.
  • Potassium dihydrogen phosphate potassium phosphate primary or monobasic potassium phosphate, KDP
  • KH 2 PO 4 is a white salt of 2.33 gcm -3 density, has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO 3 ) x ] and is light soluble in water.
  • Disodium hydrogen phosphate (secondary sodium phosphate), Na 2 HPO 4 , is a colorless, very slightly water-soluble crystalline salt. It exists anhydrous and with 2 moles (density 2.066 gcm -3 , loss of water at 95 °), 7 moles (density 1.68 gcm -3 , melting point 48 ° with loss of 5 H 2 O) and 12 moles water ( Density 1.52 gcm -3 , melting point 35 ° with loss of 5 H 2 O) becomes anhydrous at 100 ° C and, upon increased heating, passes into the diphosphate Na 4 P 2 O 7 .
  • Disodium hydrogen phosphate is prepared by neutralization of phosphoric acid with soda solution using phenolphthalein as an indicator.
  • Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K 2 HPO 4 , is an amorphous, white salt that is readily soluble in water
  • Trisodium phosphate, tertiary sodium phosphate, Na 3 PO 4 are colorless crystals which have a density of 1.62 gcm -3 as dodecahydrate and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P 2 O 5 ) have a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P 2 O 5 ) have a density of 2.536 gcm -3 .
  • Trisodium phosphate is readily soluble in water under alkaline reaction and is prepared by evaporation of a solution of exactly 1 mole of disodium phosphate and 1 mole of NaOH.
  • Tripotassium phosphate (tertiary or tribasic potassium phosphate), K 3 PO 4 , is a white, deliquescent, granular, density 2 powder. 56 gcm -3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction. It arises, for example, when heating Thomasschlacke with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over the corresponding sodium compounds in the detergent industry.
  • Tetrasodium diphosphate (sodium pyrophosphate), Na 4 P 2 O 7 , exists in anhydrous form (density 2.534 gcm -3 , melting point 988 °, also indicated 880 °) and as decahydrate (density 1.815-1.836 gcm -3 , melting point 94 ° with loss of water) , For substances are colorless, in water with alkaline reaction soluble crystals.
  • Na 4 P 2 O 7 is formed on heating of disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying.
  • the decahydrate complexes heavy metal salts and hardness agents and therefore reduces the hardness of the water.
  • Potassium diphosphate (potassium pyrophosphate), K 4 P 2 O 7 , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm -3 , which is soluble in water, the pH being 1% Solution at 25 ° 10.4.
  • Sodium and potassium phosphates in which one can distinguish cyclic representatives, the sodium or Kaliummetaphosphate and chain types, the sodium or potassium polyphosphates. In particular, for the latter are a variety of names in use: hot or cold phosphates, Graham's salt, Kurrolsches and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates
  • pentasodium triphosphate Na 5 P 3 O 10 (sodium tripolyphosphate)
  • sodium tripolyphosphate sodium tripolyphosphate
  • n 3
  • pentanate triphosphate In the preparation of pentanate triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dehydrated by spraying. Similar to Graham's theorem and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentakaliumtriphosphat, K 5 P 3 O 10 (potassium tripolyphosphate), for example, in the form of a 50 wt .-% solution (> 23% P 2 O 5 , 25% K 2 O) in the trade. The potassium polyphosphates are widely used in the washing and cleaning industry.
  • sodium potassium tripolyphosphates which can also be used in the context of the present invention. These arise, for example, when hydrolyzed sodium trimetaphosphate with KOH: (NaPO 3 ) 3 + 2 KOH ⁇ Na 3 K 2 P 3 O 10 + H 2 O
  • sodium tripolyphosphate potassium tripolyphosphate or mixtures can be used from these two; also mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate are used according to the invention.
  • organic cobuilders can be used in the machine dishwashing detergents according to the invention in particular polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, Polyacetals, dextrins, other organic cobuilders (see below) and phosphonates used become. These classes of substances are described below.
  • Useful organic builders are, for example, those in the form of their sodium salts usable polycarboxylic acids, understood by polycarboxylic acids such carboxylic acids which carry more than one acidity function.
  • these are citric acid, adipic acid, Succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, Aminocarboxylic acids, nitrilotriacetic acid (NTA), provided such use of ecological Reasons are not objectionable, as well as mixtures of these.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, Tartaric acid, sugar acids and mixtures of these.
  • the acids themselves can also be used.
  • the acids have besides their builder effect typically also the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners.
  • here are citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and to name any mixtures of these.
  • Suitable builders are polymeric polycarboxylates, for example the alkali metal salts the polyacrylic acid or the polymethacrylic acid, for example those with a relative Molecular weight of 500 to 70000 g / mol.
  • the molecular weights stated for polymeric polycarboxylates are weight-average molar masses M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this document.
  • 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 may again, the short-chain polyacrylates, the molecular weights of 2000 to 10,000 g / mol, and especially preferably from 3000 to 5000 g / mol, have to be preferred.
  • 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 (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution.
  • the content of (co) polymeric polycarboxylates in the compositions is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.
  • biodegradable polymers of more than two different Monomer units for example those containing as monomers salts of acrylic acid and the Maleic acid and vinyl alcohol or vinyl alcohol derivatives or the salts of acrylic acid as monomers and the 2-alkylallylsulfonic acid and sugar derivatives.
  • copolymers are those containing as monomers preferably acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
  • builder substances are polymeric aminodicarboxylic acids, their To name salts or their precursors.
  • Particularly preferred are polyaspartic acids or their salts and derivatives, which in addition to cobuilder properties also a bleach-stabilizing Have effect.
  • polyacetals which are prepared by reaction of dialdehydes with polyol carboxylic acids having 5 to 7 C atoms and at least 3 hydroxyl groups, can be obtained.
  • Preferred polyacetals are selected from dialdehydes such as glyoxal, Glutaraldehyde, terephthalaldehyde and mixtures thereof and from Polyolcarbon Textren such as gluconic acid and / or glucoheptonic acid.
  • dextrins for example oligomers or Polymers of carbohydrates that can be obtained by partial hydrolysis of starches.
  • the hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes be performed.
  • they are hydrolysis products having average molecular weights in the range of 400 to 500,000 g / mol.
  • This is a polysaccharide with a dextrose equivalent (DE) in the range of 0.5 to 40, especially from 2 to 30 preferred, wherein DE a common measure of the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100 is.
  • DE dextrose equivalent
  • maltodextrins 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 30000 g / mol.
  • the 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 ring to the carboxylic acid function.
  • a product oxidized to C 6 of the saccharide ring may be particularly advantageous.
  • oxydisuccinates and other derivatives of disuccinates are other suitable cobuilders.
  • ethylenediamine-N, N'-disuccinate (EDDS) is preferred used in the form of its sodium or magnesium salts.
  • EDDS ethylenediamine-N, N'-disuccinate
  • glycerol disuccinates and glycerol trisuccinates are also related. Suitable quantities are in zeolithissen and / or silicate-containing formulations at 3 to 15 wt .-%.
  • organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts. which may optionally also be present in lactone form and which at least 4 carbon atoms and at least one hydroxy group and a maximum of two acid groups contain.
  • phosphonates these are in particular hydroxyalkane or aminoalkanephosphonates.
  • hydroxyalkane phosphonates For example, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder. It is preferably used as the sodium salt, wherein the disodium salt neutral and the tetrasodium salt alkaline (pH 9) reacts as Aminoalkanphosphonate come preferably ethylenediamine tetramethylene phosphonate (EDTMP), diethylene triamine pentamethylene phosphonate (DTPMP) and their higher homologues in question.
  • ETMP ethylenediamine tetramethylene phosphonate
  • DTPMP diethylene triamine pentamethylene phosphonate
  • the neutral reacting sodium salts eg. B. as hexasodium salt of EDTMP or hepta- and octa-sodium salt of DTPMP.
  • EDTMP hexasodium salt of EDTMP
  • hepta- and octa-sodium salt of DTPMP e.g. EDTMP
  • DTPMP hepta- and octa-sodium salt of DTPMP.
  • the aminoalkane phosphonates also have a pronounced Heavy metal binding capacity. Accordingly, it may, especially if the Agents also contain bleach, preferably, aminoalkanephosphonates, in particular DTPMP, to use or mixtures of the phosphonates mentioned.
  • sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Other useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
  • Cleaning agents according to the invention may also contain bleaching agents from the group of organic bleaching agents. Typical organic bleaches are the diacyl peroxides such as dibenzoyl peroxide.
  • peroxyacids examples of which include the alkyl peroxyacids and the aryl peroxyacids.
  • Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy- ⁇ -naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, e-phthalimidoperoxycaproic acid [Phthaloiminoperoxyhexanoic acid (PAP)] , o-carboxybenzamidoperoxycaproic acid, N-nonenyl-amidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,
  • Chloro or bromine-releasing materials include, for example, heterocyclic N-bromo and N-chloroamides, for example, trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or salts thereof with cations such as potassium and sodium hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable
  • the bleaching agents mentioned can also be used to achieve a "after-bleaching" in the final rinse cycle or partially via the rinse aid particles according to the invention in the machine according to the invention Dishwashing agents are introduced.
  • bleach activators that aid in the action of the bleaching agents have been described above possible ingredient of the rinse aid particles mentioned.
  • Known bleach activators are compounds, which contain one or more N- or O-acyl groups, such as substances from the class of Anhydrides, esters, imides and acylated imidazoles or oximes.
  • Examples are tetraacetylethylenediamine TAED, tetraacetylmethylenediamine TAMD and tetraacetylhexylenediamine TAHD, but also pentaacetylglucose PAG, 1,5-diacetyl-2,2-dioxo-hexahydro-1,3,5-triazine DADHT and isatoic anhydride ISA.
  • bleach activators it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
  • Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups.
  • polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5-diacetoxy- 2,5-dihydrofuran, n-methyl-morph
  • Hydrophilic substituted acyl acetals and acyl lactams are also preferably used.
  • Combinations of conventional bleach activators can also be used.
  • so-called bleach catalysts can also be incorporated into the rinse aid particles.
  • These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo saline 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.
  • Bleach activators from the group of the multiply acylated alkylenediamines in particular Tetraacetylethylenediamine (TAED), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA), preferably in Amounts up to 10 wt .-%, in particular 0.1 wt .-% to 8 wt .-%. especially 2 to 8 wt .-% and particularly preferably 2 to 6 wt .-% based on the total agent used
  • TAED Tetraacetylethylenediamine
  • N-acylimides especially N-nonanoylsuccinimide (NOSI)
  • NOSI N-n
  • Bleach-enhancing transition metal complexes in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, preferably selected from the group of manganese and / or cobalt salts and / or complexes, more preferably the cobalt (ammin) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, manganese sulfate are used in conventional amounts, preferably in an amount of up to 5% by weight, in particular from 0.0025% by weight to 1% by weight and more preferably from 0.01% by weight to 0.25% by weight. each based on the total agent used. But in special cases can also more bleach activator can be used.
  • enzymes in the detergents according to the invention in particular those from the Classes of hydrolases such as proteases, esterases, lipases or lipolytic enzymes, Amylases, glycosyl hydrolases and mixtures of said enzymes in question. All these Hydrolases contribute to the removal of stains such as protein, fat or starchy Stains in. For bleaching and oxidoreductases can be used. Especially good are suitable from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus cinereus and Humicola insolens and from their genetically engineered modified variants obtained enzymatic agents.
  • proteases of the subtilisin type and in particular proteases derived from Bacillus lentus.
  • proteases are enzyme mixtures, for example from protease and amylase or protease and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes, in particular However, protease and / or lipase-containing mixtures or mixtures with lipolytic acting enzymes of particular interest. Examples of such lipolytic enzymes are the known cutinases. Peroxidases or oxidases have also been found in some Cases proved to be suitable.
  • Suitable amylases include, in particular, alpha-amylases, Iso-amylases, pullulanases and pectinases.
  • the enzymes may be adsorbed to carriers or embedded in encapsulating substances to them to protect against premature decomposition.
  • the proportion of enzymes, enzyme mixtures or enzyme granules may, for example, about 0.1 to 5 wt .-%. preferably from 0.5 to about 4.5% by weight be.
  • Dyes and fragrances can be added to the automatic dishwasher detergents according to the invention to improve the aesthetic impression of the resulting products and the Consumers in addition to performance a visually and sensory "typical and unmistakable" To provide product.
  • perfume oils or perfumes individual fragrance compounds, e.g. the synthetic products of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons are used. Fragrance compounds of the ester type are e.g.
  • the ethers include, for example Benzyl ethyl ether, to the aldehydes e.g.
  • the linear alkanals with 8-18 C atoms Citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and Bourgeonal, to the ketones e.g. the ionone, ⁇ -isomethylionone and methyl cedryl ketone, to the Alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, too
  • the hydrocarbons mainly include the terpenes such as limonene and pinene.
  • fragrance oils may also contain natural fragrance mixtures, as available from plant sources, e.g. Pine, Citrus, Jasmine, Patchouly, Rose or Ylang-Ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, Melissa oil, mint oil, cinnamon leaf oil, lime blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil, as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.
  • the fragrances can be incorporated directly into the detergents according to the invention, it However, it may also be advantageous to apply the fragrances to carriers that the adhesion of the perfume intensify on the laundry and through a slower release of fragrance for long-lasting Fragrance of the textiles provide.
  • carrier materials are cyclodextrins proven, wherein the cyclodextrin-perfume complexes additionally coated with other excipients can be.
  • an incorporation of the perfumes in the rinse aid particles according to the invention is possible and leads to a fragrance impression when opening the machine (see above).
  • compositions produced according to the invention can (or parts thereof) are colored with suitable dyes.
  • Preferred dyes whose Selection the expert prepares no difficulty, have a high storage stability and Insensitivity to the other ingredients of the agent and against light and none pronounced substantivity to the substrates to be treated with the agents, such as glass, Ceramic or plastic utensils, so as not to stain them.
  • the cleaning agents according to the invention can be used to protect the items to be washed or the machine Corrosion inhibitors included, with particular silver protectants in the range of machine Dishwashing have a special meaning. It is possible to use the known substances of the prior art. In general, especially silver protectants can be selected from the Group of triazots, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and the transition metal salts or complexes. Especially preferred benzotriazole and / or alkylaminotriazole are to be used. One finds in cleaner formulations In addition, frequently active chlorine-containing agents that corrode the silver surface can significantly reduce.
  • chlorine-free cleaners are particularly oxygen and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, eg. Hydroquinone, Pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucin, pyrogallol or derivatives of these connection classes.
  • organic redox-active compounds such as di- and trihydric phenols, eg. Hydroquinone, Pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucin, pyrogallol or derivatives of these connection classes.
  • salt and complex inorganic compounds such as salts
  • the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used.
  • Transition metal salts selected from the group of manganese and / or cobalt salts and / or complexes, more preferably the cobalt (ammin) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese and the Manganese sulfate.
  • zinc compounds can be used to prevent corrosion on the dishes be used.
  • compositions according to the invention can be packed directly after their preparation and as particulate Cleaners are sold. But it is also possible, the funds for detergent tablets or to compress individual phases thereof in order to give the consumer the compact form of supply to make available.
  • Machine dishwashing detergent characterized in that they are in the form of a tablet, preferably in the form of a multiphase tablet, in which Content of the individual phases is different on sulfonic acid group-containing copolymer, are present, further preferred embodiments of the present invention.
  • multi-phase tablets are preferred, wherein the multi-layer tablets due their relatively simple producibility plays a special role.
  • the individual phases Such a shaped body can vary within the scope of the present invention Have spatial forms. The simplest possible realization is in two or more layers Tablets, wherein each layer of the shaped body represents a phase. It is but according to the invention also possible to produce multi-phase moldings in which individual phases the Form of incorporation into (another) phase (s).
  • ring-Kem-tablets are, for example, coated tablets or combinations of the aforementioned embodiments possible.
  • the shaped bodies according to the invention can assume any geometric shape, wherein in particular concave, convex, biconcave, biconvex, cubic, tetragonal, orthorhombic, cylindrical, spherical, segmented, disk-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoidal, pentagonal, octagonal and octagonal prismatic as well rhombohedral forms are preferred. Also completely irregular bases like arrow or Animal forms, trees, clouds etc. can be realized. Assign the invention Shaped corners and edges, so these are preferably rounded. As an additional optical Differentiation is an embodiment with rounded corners and beveled ("chamfered") Edges preferred.
  • the cavity in the compressed part of such shaped bodies according to the invention can be of any shape exhibit. It can divide the shaped body, i. an opening on different sides, For example, at the top and bottom of the molding, but it can also be a not be through the entire molding body going cavity whose opening only on a molded body side is visible.
  • the shape of the cavity can be freely selected within wide limits. For reasons of process economy, through holes have their openings Opposing surfaces of the moldings lie, and troughs with an opening a molded body side proven. In preferred washing and cleaning agent moldings has the cavity is in the form of a through hole, the openings of which are at two opposite ends Form body surfaces are located.
  • the shape of such a through hole can are freely selected, wherein moldings are preferred in which the through hole is circular, elliptical, triangular, rectangular, square, pentagonal, hexagonal, heptagonal or octagonal horizontal sections also has completely irregular hole shapes such as arrow or animal forms, trees, clouds, etc. can be realized.
  • the moldings in the case of square holes those with rounded corners and edges or with rounded ones Corners and chamfered edges preferred.
  • shaped bodies with rectangular or square base and circular Holes are made as well as round shaped bodies with octagonal holes, where There are no limits to the variety of possible combinations.
  • shaped bodies with square base and the hole cross section of the same geometric Have shape for example, shaped body with square base and zentrat integrated square hole.
  • ring shaped bodies i. circular shaped bodies with a circular hole.
  • the tablets according to the invention can also be used in the case of assume any geometric shape of this embodiment, in particular concave, convex, biconcave, biconvex, cubic, tetragonal, orthorhombic, cylindrical, spherical, cylindrical, disc-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoidal, pentagonal, pentagonal, octagonal, prismatic and rhombohedral shapes are preferred. Also completely irregular base areas such as arrow or animal forms, trees, clouds etc. can be realized. If the shaped body has corners and edges, these are preferably rounded. As additional optical differentiation is an embodiment with
  • the shape of the trough can be chosen freely, wherein moldings are preferred in which at least one trough is a concave, convex, cubic, tetragonal, orthorhombic, cylindrical, spherical, cylinder segment, disc-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoidal , five-, seven- and octagonal-prismatic as well as rhombohedral form. Completely irregular shapes such as arrow or animal shapes, trees, clouds etc. can also be realized. As with the moldings, wells with rounded corners and edges or with rounded corners and chamfered edges are preferred.
  • the size of the trough or the through hole compared to the entire shaped body depends on the desired use of the shaped body. Depending on how much additional active substance the remaining hollow volume is to be filled, the size of the cavity can vary.
  • the basic shaped body in preferred embodiments of the present invention has a high specific gravity, for example above 1000 kgdm -3 , preferably above 1025 kgdm -3 , more preferably above 1050 kgdm -3 and in particular above 1100 kgdm -3 .
  • disintegration aids so-called tablet disintegrating agents
  • tablet disintegrating agents in order to shorten the disintegration times.
  • taboo disintegrating agents or “disintegrating accelerators” is understood as meaning excipients which are suitable for rapid disintegration of tablets in water or gastric juice and for the release of the drugs in resorbable form.
  • Swelling 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, alginates or casein derivatives.
  • Preferred disintegrating agents in the context of the present invention are disintegrating agents used on cellulose basis, so that preferred detergent tablets such Cellulosic disintegrating agents in amounts of from 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6% by weight.
  • compositions according to the invention may additionally comprise a gas-developing effervescent system.
  • the gas-evolving effervescent system can consist of a single substance that is at Contact with water releases a gas.
  • these compounds is in particular the magnesium peroxide to call, which releases oxygen on contact with water.
  • Preferred effervescent systems consist of alkali metal carbonate and / or bicarbonate as well an acidifying agent which is suitable from the alkali metal salts in aqueous solution Release carbon dioxide.
  • the sodium and potassium salts are made Cost reasons over the other salts clearly preferred. Of course you have to not the respective pure alkali metal carbonates or bicarbonates are used; Rather, mixtures of different carbonates and bicarbonates from washing technical Interest be preferred.
  • detergent tablets are used as effervescent 2 to 20 wt .-%, preferably 3 to 15 wt.% And in particular 5 to 10 wt.% Of an alkali metal carbonate or hydrogen carbonate and 1 to 15, preferably 2 to 12 and in particular 3 to 10 wt .-% an Acidisersstoffs, in each case based on the entire molded body used.
  • Acidsstoffsmittel that release carbon dioxide from the alkali salts in aqueous solution, are, for example, boric acid and alkali metal hydrogen sulfates, alkali metal dihydrogen phosphates and other inorganic salts.
  • organic Acidifier used, wherein the citric acid is a particularly preferred Acidiser is.
  • the other solid mono-, oligo- and Polycarboxylic acids are tartaric acid, succinic acid, Malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid.
  • organic Sulfonic acids such as amidosulfonic acid are also usable.
  • Sokalan® DCS commercially available and as Acidaimssmittel in the context of the present invention is also preferably used Sokalan® DCS (trademark of BASF), a mixture of succinic acid (up to 31% by weight), Glutaric acid (max 50 wt%) and adipic acid (max 33 wt%).
  • Another preferred embodiment of the present invention relates to a method for Manufacture of automatic dishwasher detergents, as defined in the claims.
  • inventive Preferred method in which the mixture of raw materials and / or compounds and solid copolymer preparation form, based on the mixture, 0.1 to 70 wt .-%, preferably 0.25 to 50 wt .-%, particularly preferably 0.5 to 35 wt .-%. very particularly preferred 0.75 to 20 wt .-% and in particular 1 to 15 wt .-% of sulfonic acid-containing Contains copolymers.
  • the solid copolymer preparation form may be pure sulfonic acid group-containing copolymer consist. However, it is also possible, according to the invention, a solid copolymer preparation form which, in addition to the sulfonic acid-containing copolymer, contains other ingredients, For example, carriers.
  • a solid copolymer preparation form which, in addition to the sulfonic acid-containing copolymer, contains other ingredients, For example, carriers.
  • methods according to the invention are preferred in which the solid copolymer preparation form the sulfonic acid group-containing copolymer (s) in Amounts of more than 50 wt .-%, preferably of more than 60 wt .-%, more preferably of more than 75 wt .-% and in particular of more than 80 wt .-%, each based on the solid copolymer preparation
  • methods according to the invention are also preferred in which at least 50 Wt.%, Preferably at least 60 wt.%, Particularly preferably at least 75 wt .-% and in particular at least 90% by weight of the particles of the solid copolymer preparation particle sizes above 200 microns, with particularly preferred method characterized are that a maximum of 20 wt.%, Preferably at most 15 wt.% And in particular at most 10% by weight of the particles of the solid copolymer preparation contained in the middle Particle sizes below 200 microns or above 1200 microns have.
  • the water content of the particles the solid copolymer preparation 3 to 12 wt.%, Preferably 4 to 11 wt.% And in particular 5 to 10 wt.%, in each case based on the copolymer particles.

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Claims (18)

  1. Produit solide de lavage de la vaisselle à la machine, contenant
    a) de 1 à 99,9 % en poids de builder(s)
    b) de 0,1 à 70 % en poids de copolymères comprenant
    i) 5 à 95 % en poids d'acides carboxyliques insaturés
    ii) 5 à 95 % en poids de monomères contenant des groupes acide sulfonique,
    caractérisé en ce qu'il contient le copolymère contenant des groupes acide sulfonique sous une forme particulaire, et en ce qu'au moins 50 % en poids des particules du copolymère contenant des groupes acide sulfonique contenues dans le produit présentent une taille particulaire supérieure à 200 µm.
  2. Produit solide de lavage de la vaisselle à la machine, contenant
    c) de 1 à 99,9 % en poids de builder(s)
    d) de 0,1 à 70 % en poids de copolymères comprenant
    i) 20 à 85 % en poids d'acides carboxyliques insaturés
    ii) 10 à 60 % en poids de monomères contenant des groupes acide sulfonique
    iii) 5 à 30 % en poids d'autres monomères ioniques ou non ionogènes,
    caractérisé en ce qu'il contient le copolymère contenant des groupes acide sulfonique sous une forme particulaire, et en ce qu'au moins 50 % en poids des particules du copolymère contenant des groupes acide sulfonique contenues dans le produit présentent une taille particulaire supérieure à 200 µm.
  3. Produit de lavage de la vaisselle à la machine selon l'une des revendications 1 ou 2, caractérisé en ce qu'au moins 60 % en poids, de façon particulièrement préférée au moins 75 % en poids et en particulier au moins 90 % en poids des particules du copolymère contenant des groupes acide sulfonique contenues dans le produit présentent une taille particulaire supérieure à 200 µm.
  4. Produit de lavage de la vaisselle à la machine selon l'une des revendications 1 à 3, caractérisé en ce qu'au maximum 20 % en poids, de préférence au maximum 15 % en poids et en particulier au maximum 10 % en poids des particules du copolymère contenant des groupes acide sulfonique contenues dans le produit présentent une taille particulaire inférieure à 200 µm ou supérieure à 1200 µm.
  5. Produit de lavage de la vaisselle à la machine selon l'une des revendications 1 à 4, caractérisé en ce que la teneur en eau des particules du copolymère contenant des groupes acide sulfonique contenues dans le produit est de 3 à 12 % en poids, de préférence de 4 à 11 % en poids et en particulier de 5 à 10 % en poids, toujours par rapport aux particules de copolymère.
  6. Produit de lavage de la vaisselle à la machine selon l'une des revendications 1 à 5, caractérisé en ce que la densité apparente des particules du copolymère contenant des groupes acide sulfonique contenues dans le produit est de 550 à 850 g/l, de préférence de 570 à 800 g/l, de façon particulièrement préférée de 590 à 750 g/l et en particulier de 600 à 720 g/l.
  7. Produit de lavage de la vaisselle à la machine selon l'une des revendications 1 à 6, caractérisé en ce qu'il contient le ou les copolymère(s) contenant des groupes acide sulfonique en des quantités de 0,25 à 50 % en poids, de préférence de 0,5 à 35 % en poids, de façon particulièrement préférée de 0,75 à 20 % en poids et en particulier de 1 à 15 % en poids.
  8. Produit de lavage de la vaisselle à la machine selon l'une des revendications 1 à 7, caractérisé en ce qu'il contient en outre de 2 à 40 % en poids, de préférence de 3 à 30 % en poids et en particulier de 5 à 20 % en poids d'un ou de plusieurs constituants ayant un point de fusion, respectivement de ramollissement inférieur à 60 °C, où l'on trouve de préférence le ou les agent(s) tensioactif(s) non-ionique(s) étant préférés.
  9. Produit de lavage de la vaisselle à la machine selon l'une des revendications 1 à 8, caractérisé en ce qu'il se présente sous la forme d'un comprimé, de préférence sous la forme d'un comprimé à plusieurs phases, dans lequel la teneur des diverses phases en copolymère contenant des groupes acide sulfonique est différente.
  10. Procédé de fabrication de produits solides de lavage de la vaisselle à la machine, caractérisé en ce qu'on mélange une forme de préparation polymère solide d'un copolymère comprenant
    i) 5 à 95 % en poids d'acides carboxyliques insaturés,
    ii) 5 à 95 % en poids de monomères contenant des groupes acide sulfonique,
    avec d'autres matières premières et/ou compounds pour obtenir un produit de lavage de la vaisselle à la machine, caractérisé en ce qu'au moins 50 % en poids des particules du copolymère contenant des groupes acide sulfonique contenues dans le produit présentent des tailles particulaires supérieures à 200 µm.
  11. Procédé de fabrication de produits solides de lavage de la vaisselle à la machine, caractérisé en ce qu'on mélange une forme de préparation polymère solide d'un copolymère comprenant
    i) 20 à 85 % en poids d'acides carboxyliques insaturés,
    ii) 10 à 60 % en poids de monomères contenant des groupes acides sulfonique,
    iii) 5 à 30 % en poids d'autres monomères ioniques ou non ionogènes,
    avec d'autres matières premières et/ou compounds pour obtenir un produit de lavage de la vaisselle à la machine, caractérisé en ce qu'au moins 50 % en poids des particules du copolymère contenant des groupes acide sulfonique contenues dans le produit présentent des tailles particulaires supérieures à 200 µm.
  12. Procédé de fabrication de comprimés de produit de nettoyage pour le lavage de la vaisselle à la machine, caractérisé en ce qu'on mélange une forme de préparation polymère solide d'un copolymère comprenant
    i) 5 à 95 % en poids d'acides carboxyliques insaturés,
    ii) 5 à 95 % en poids de monomères contenant des groupes acide sulfonique,
    avec d'autres matières premières et/ou compounds, puis en ce qu'on comprime le mélange pour obtenir des comprimés ou des phases de ces comprimés, caractérisé en ce qu'au moins 50 % en poids des particules du copolymère contenant des groupes acide sulfonique contenues dans le produit présentent des tailles particulaires supérieures à 200 µm.
  13. Procédé de fabrication de comprimés de produit de nettoyage pour le lavage de la vaisselle à la machine, caractérisé en ce qu'on mélange une forme de préparation polymère solide d'un copolymère comprenant
    i) 20 à 85 % en poids d'acides carboxyliques insaturés,
    ii) 10 à 60 % en poids de monomères contenant des groupes acide sulfonique,
    iii) 5 à 30 % en poids d'autres monomères ioniques ou non ionogènes,
    avec d'autres matières premières et/ou compounds, puis en ce qu'on comprime le mélange pour obtenir des comprimés ou des phases de ces comprimés, caractérisé en ce qu'au moins 50 % en poids des particules du copolymère contenant des groupes acide sulfonique contenues dans le produit présentent des tailles particulaires supérieures à 200 µm.
  14. Procédé selon l'une des revendications 10 à 13, caractérisé en ce que le mélange de matières premières et/ou de compounds ainsi que la forme de préparation copolymère solide contient, par rapport au mélange, de 0,1 à 70 % en poids, de préférence de 0,25 à 50 % en poids, de façon particulièrement préférée de 0,5 à 35 % en poids, de façon tout particulièrement préférée de 0,75 à 20 % en poids et en particulier de 1 à 15 % en poids de copolymères contenant des groupes acide sulfonique.
  15. Procédé selon l'une des revendications 10 à 14, caractérisé en ce que la forme de préparation copolymère solide contient le ou les copolymère(s) contenant des groupes acide sulfonique à des quantités supérieures à 50 % en poids, de préférence supérieures à 60 % en poids, de façon particulièrement préférée supérieures à 75 % en poids et en particulier supérieures à 80 % en poids, toujours par rapport à la forme de préparation copolymère solide.
  16. Procédé selon l'une des revendications 10 à 15, caractérisé en ce qu'au moins 50 % en poids, de préférence au moins 60 % en poids, de façon particulièrement préférée au moins 75 % en poids et en particulier au moins 90 % en poids des particules de la forme de préparation copolymère solide présentent des tailles particulaires supérieures à 200 µm.
  17. Procédé selon l'une des revendications 10 à 16, caractérisé en ce qu'au maximum 20 % en poids, de préférence au maximum 15 % en poids et en particulier au maximum 10 % en poids des particules de la forme de préparation copolymère solide contenues dans le produit présentent des tailles particulaires inférieures à 200 µm ou supérieures à 1200 µm.
  18. Procédé selon l'une des revendications 10 à 17, caractérisé en ce que la teneur en eau des particules de la forme de préparation copolymère solide s'élève à 3 à 12 % en poids, de préférence à 4 à 11 % en poids et en particulier à 5 à 10 % en poids, toujours par rapport aux particules de copolymère.
EP02706745A 2001-03-01 2002-02-20 Produits vaisselle "3 en 1" et procede de fabrication de ces produits Revoked EP1363986B1 (fr)

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DE10109799A DE10109799A1 (de) 2001-03-01 2001-03-01 3in1-Geschirrspülmittel und Verfahren zur Herstellung derselben
DE10109799 2001-03-01
PCT/EP2002/001757 WO2002070640A1 (fr) 2001-03-01 2002-02-20 Produits vaisselle '3 en 1' et procede de fabrication de ces produits

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EP (1) EP1363986B1 (fr)
AT (1) ATE312900T1 (fr)
DE (2) DE10109799A1 (fr)
ES (1) ES2254651T3 (fr)
WO (1) WO2002070640A1 (fr)

Families Citing this family (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7034402B1 (en) * 2000-06-28 2006-04-25 Intel Corporation Device with segmented ball limiting metallurgy
DE10258870B4 (de) * 2002-12-17 2005-04-07 Henkel Kgaa Grossvolumige Reinigungsmittelformkörper
US20050202995A1 (en) * 2004-03-15 2005-09-15 The Procter & Gamble Company Methods of treating surfaces using surface-treating compositions containing sulfonated/carboxylated polymers
US20050202996A1 (en) * 2004-03-15 2005-09-15 The Procter & Gamble Company Surface-treating compositions containing sulfonated/carboxylated polymers
DE102004048590A1 (de) * 2004-04-27 2005-11-24 Henkel Kgaa Reinigungsmittel mit Klarspül-Sulfopolymer und einer speziellen α-Amylase
DE102004048591A1 (de) * 2004-04-27 2005-11-24 Henkel Kgaa Reinigungsmittel mit Klarspültensid und einer speziellen α-Amylase
DE102004025816A1 (de) * 2004-05-24 2005-12-22 Budich International Gmbh Maschinenreiniger, insbesondere für 3in1-Geschirrspülmaschinen
US20070015674A1 (en) 2005-06-30 2007-01-18 Xinbei Song Low phosphate automatic dishwashing detergent composition
DE102005041349A1 (de) * 2005-08-31 2007-03-01 Basf Ag Reinigungsformulierungen für die maschinelle Geschirrreinigung enthaltend hydrophil modifizierte Polycarboxylate
DE102005041347A1 (de) * 2005-08-31 2007-03-01 Basf Ag Reinigungsformulierungen für die maschinelle Geschirrreinigung enthaltend hydrophil modifizierte Polycarboxylate
US20070059402A1 (en) * 2005-09-13 2007-03-15 Cryovac, Inc. Carbon monoxide modified atmosphere packaging having a time temperature indicator
GB0522658D0 (en) * 2005-11-07 2005-12-14 Reckitt Benckiser Nv Composition
GB0625586D0 (en) * 2006-12-21 2007-01-31 Reckitt Benckiser Nv Composition
DE102007006628A1 (de) * 2007-02-06 2008-08-07 Henkel Ag & Co. Kgaa Reinigungsmittel
DE102007006629A1 (de) * 2007-02-06 2008-08-07 Henkel Ag & Co. Kgaa Reinigungsmittel
ES2402940T3 (es) * 2007-08-16 2013-05-10 The Procter & Gamble Company Proceso para fabricar una composición detergente
ATE554157T1 (de) * 2007-08-16 2012-05-15 Procter & Gamble Herstellungsverfahren für eine reinigungszusammensetzung
CA2704568C (fr) * 2007-11-09 2016-01-26 The Procter & Gamble Company Compositions de nettoyage contenant des monomeres acides monocarboxyliques, monomeres dicarboxyliques et monomeres comprenant des groupes acides sulfoniques
US8389458B2 (en) * 2008-03-31 2013-03-05 The Procter & Gamble Company Automatic dishwashing composition containing a sulfonated copolymer
EP2196531B1 (fr) 2008-12-05 2014-09-03 Dalli-Werke GmbH & Co. KG Pastille de détergent revêtue d'un polymère
PL2392638T3 (pl) 2010-06-04 2018-03-30 Dalli-Werke Gmbh & Co. Kg Kompozycja w postaci cząstek o niskiej higroskopijności zawierająca jeden lub większą liczbę aminopolikarboksylanowych związków chelatujących
EP2392639B1 (fr) 2010-06-04 2018-01-24 Dalli-Werke GmbH & Co. KG Mélange d'un agent tensioactif avec un composé solide pour améliorer la performance de rinçage de détergents pour le lavage automatique de la vaisselle
GB201019988D0 (en) * 2010-11-25 2011-01-05 Reckitt Benckiser Nv Composition
EP3075832B1 (fr) 2015-03-30 2021-04-14 Dalli-Werke GmbH & Co. KG Composés d'acide aminé de manganèse dans des compositions de nettoyage

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3711296A1 (de) * 1987-04-03 1988-10-13 Basf Ag Verwendung von alkoxylierten, carboxylgruppen enthaltenden polymerisaten in waschmitteln
DE3743739A1 (de) * 1987-12-23 1989-07-06 Basf Ag Wasserloesliche polymerisate enthaltende geschirrspuelmittel
DE4008696A1 (de) 1990-03-17 1991-09-19 Basf Ag Verfahren zur herstellung von homo- und copolymerisaten monoethylenisch ungesaettigter dicarbonsaeuren und ihre verwendung
DE19516957C2 (de) 1995-05-12 2000-07-13 Stockhausen Chem Fab Gmbh Wasserlösliche Copolymere und Verfahren zu ihrer Herstellung und ihre Verwendung
US6210600B1 (en) * 1996-12-23 2001-04-03 Lever Brothers Company, Division Of Conopco, Inc. Rinse aid compositions containing scale inhibiting polymers
US5958855A (en) * 1998-03-20 1999-09-28 Colgate Palmolive Company Powdered automatic dishwashing tablets
DE19934704A1 (de) * 1999-07-23 2001-01-25 Henkel Kgaa Wasch- und Reinigungsmittelformkörper mit Dispersionsmitteln
DE10032612A1 (de) 2000-07-07 2002-02-14 Henkel Kgaa Klarspülmittel II

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ATE312900T1 (de) 2005-12-15
US6903058B2 (en) 2005-06-07
DE10109799A1 (de) 2002-09-05
US20040116319A1 (en) 2004-06-17
WO2002070640A1 (fr) 2002-09-12
EP1363986A1 (fr) 2003-11-26
ES2254651T3 (es) 2006-06-16

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