EP3440176A1 - Détergent pour vaisselle contenant des dérivés d'urée - Google Patents

Détergent pour vaisselle contenant des dérivés d'urée

Info

Publication number
EP3440176A1
EP3440176A1 EP17713658.7A EP17713658A EP3440176A1 EP 3440176 A1 EP3440176 A1 EP 3440176A1 EP 17713658 A EP17713658 A EP 17713658A EP 3440176 A1 EP3440176 A1 EP 3440176A1
Authority
EP
European Patent Office
Prior art keywords
carbon atoms
dishwashing detergent
radical
acid
dishwashing
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Withdrawn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
EP17713658.7A
Other languages
German (de)
English (en)
Inventor
Inga Kerstin Vockenroth
Doris Dahlmann
Thomas Weber
Claudia Ottow
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP3440176A1 publication Critical patent/EP3440176A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/32—Amides; Substituted amides
    • C11D3/323—Amides; Substituted amides urea or derivatives thereof

Definitions

  • the present invention relates to dishwashing detergent with improved rinse performance
  • Machine-washed dishes are often subject to more stringent requirements today than manually-washed dishes. So even a completely cleaned of leftovers dishes is then rated as not flawless if it has after dishwasher washing whitish, based on water hardness or other mineral salts stains that come from lack of wetting agent from dried water droplets. Such staining and streaking is in principle observable on surfaces of all kinds (porcelain, glass, plastic, stainless steel), but especially on glass surfaces. This harness is the consumer - often by hand - post-treated, which is not very user-friendly. Therefore, there is a need for automatic dishwashing agents that reduce the formation of so-called spotting and filming stains and deposits.
  • the object underlying the present invention was therefore to a
  • a first aspect of the present invention therefore relates to a dishwashing detergent, in particular a machine dishwashing detergent, containing, based on the total weight of the
  • Dishwashing agent 0, 1 to 5.0 wt .-%, preferably 1, 0 to 2.0 wt .-% of at least one compound of formula (I):
  • each R is H or a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having from 1 to 10 carbon atoms, preferably from 1 to 6 carbon atoms, more preferably from 1 to 4 carbon atoms;
  • each Alk independently represents a linear or branched alkyl group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms;
  • Carbon atoms preferably 4 to 22 carbon atoms.
  • each represents a single or double bond, wherein preferably all are a single or all a double bond, in particular all are a double bond.
  • a dishwashing agent according to the invention in a machine dishwashing process, in particular the use for improving the rinsing performance when cleaning dishes in an automatic dishwashing machine.
  • Yet another object of the invention is a machine dishwashing process in which a dishwasher detergent according to the invention is used, in particular for the purpose of improving the rinse performance.
  • At least one as used herein means 1 or more, ie 1, 2, 3, 4, 5, 6, 7, 8, 9 or more. With respect to an ingredient, the indication refers to the kind of the ingredient and not to the absolute number of molecules. "At least one nonionic surfactant” thus means, for example, at least one type of nonionic surfactant, ie that kind of
  • nonionic surfactant or a mixture of several different nonionic surfactants.
  • the term, together with weights, refers to all compounds of the type indicated which are included in the composition / mixture, i. that the
  • composition beyond the specified amount of the corresponding compounds addition no further compounds of this kind.
  • Phosphate-free as used herein means that the composition in question is substantially free of phosphates, ie, in particular, contains phosphates in amounts less than 1% by weight, preferably less than 0.1% by weight, based on the total composition. Accordingly, as used herein, "free of” means that the respective fabric is present in amounts less than 1% by weight, preferably less than 0.1% by weight, more preferably less than 0.01% by weight of the Total composition is included. In particular, this also means that the corresponding substance is not deliberately added.
  • alkaline earth metals are referred to below as counterions for monovalent anions, this means that the alkaline earth metal is present only in half - as sufficient to charge balance - amount of substance as the anion.
  • the dishwashing compositions of the invention contain a urea compound of the formula (I) as defined above.
  • the compound of the formula (I) comprises several, in particular 2, 3 or 4, substituents R, which are each bonded directly to the ring.
  • each R independently for a linear or branched, saturated or on or
  • polyunsaturated hydrocarbon radical having 1 to 10 carbon atoms, preferably having 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms.
  • R is an alkyl radical, alkenyl radical, alkynyl radical, aryl radical or alkylaryl radical, preferably a linear or branched C1-10 alkyl radical, in particular a methyl, ethyl, propyl or butyl radical.
  • propyl radicals include 1-propyl and 2-propyl radicals.
  • butyl radical as used herein includes n-butyl, 2-butyl and tert-butyl radicals. If only one radical R is contained, it is preferably in ortho or para position to the urea radical, preferably in the ortho position.
  • each "alk” independently represents a linear or branched alkyl group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, but especially methyl, ethyl or propyl In preferred embodiments, the alk is methyl or ethyl. In various embodiments, the two may be attached to a common nitrogen atom
  • both radicals Alk may be methyl radicals, both may be ethyl radicals or one may be a methyl radical and the other may be an ethyl radical or propyl radical.
  • A is a chemical bond or a bivalent hydrocarbon radical having 1 to 30 carbon atoms, preferably 4 to 22 carbon atoms, in particular an alkylaryl radical or an alkylcycloalk (en) yl radical.
  • A is a chemical bond such that the second urea moiety is also directly attached to the ring.
  • the two urea radicals are preferably in meta position to each other.
  • A is an alkylaryl radical, in particular a benzyl radical (phenylmethyl radical) which is substituted by the urea group of the formula -NH-C (O) -N (Alk) 2.
  • the alkylaryl group is preferably ortho or para to the urea group at the central ring of the compound of formula (I).
  • Urea group of the formula -NH-C (O) -N (Alk) 2 with which this alkylaryl radical is substituted replaces a hydrogen atom of the aryl radical and is preferably in ortho or para position to the bridging alkyl radical.
  • each represents a single or double bond. It is preferred that either all are a single or all double bond, in particular all are a double bond.
  • the urea compounds are those of the formula (II)
  • R is methyl or ethyl, in particular methyl.
  • Each alk is also preferably methyl, ethyl or propyl, more preferably all the radicals are alk methyl or all are ethyl, especially all are methyl. All are preferably double bonds, so that the ring is an aromatic ring.
  • Preferred compounds of formula (II) include, but are not limited to, 3,3 '- (4-methyl-1, 3-phenylene) bis (1, 1-dimethylurea), 3,3' - (4-methyl -1, 3-phenylene) bis (1,1-diethylurea), 3,3 '- (4-methyl-1, 3-phenylene) bis (1,1-dipropylurea) and 3,3' - (4-methyl -1, 3-phenylene) bis (1-ethyl-1-methylurea).
  • Such compounds are known as curing accelerators for epoxy resins and are commercially available, for example under the trade name Dyhard® UR500 (3,3 '- (4-methyl-1, 3-phenylene) bis (1, 1-dimethylurea), AlzChem AG, DE). ,
  • the urea compounds used according to the invention are those of the formula (III)
  • R 2 is defined as R, ie each R 2 is H or a linear or branched, saturated or mono- or polysubstituted
  • unsaturated hydrocarbon radical having 1 to 10 carbon atoms, preferably having 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms.
  • the compound of formula (III) comprises several, i. 2, 3 or 4,
  • each R 2 can independently be a linear or branched, saturated or mono- or polyunsaturated Hydrocarbon radical having 1 to 10 carbon atoms, preferably 1 to 6
  • Carbon atoms more preferably 1 to 4 carbon atoms.
  • R 2 is an alkyl radical, alkenyl radical or alkynyl radical, preferably a linear or branched C 1-10 alkyl radical, in particular a methyl, ethyl, propyl or butyl radical. If only one radical R 2 is included, it is preferably in the ortho or para position to the methylene group connecting the rings, preferably in the ortho position.
  • R and / or R 2 are hydrogen, in particular both are hydrogen.
  • each alk is preferably methyl, ethyl or propyl, more preferably all alk are methyl or all are ethyl, especially all are methyl. All ⁇ zzz, ie in both rings are preferred
  • Compounds are also known as curing accelerators for epoxy resins.
  • the urea derivatives described above are present in the dishwashing detergents preferably in amounts of from 0.1 to 5% by weight, based on the total weight of the dishwashing detergent, in particular from 1.0 to 2.0% by weight.
  • the dishwashing compositions of the invention may also contain combinations of several of the urea compounds described above.
  • the dishwashing detergent preferably contains at least one surfactant, in particular a rinse aid surfactant.
  • Low-foaming nonionic surfactants are preferably used, in particular alkoxylated, especially ethoxylated, low-foaming nonionic surfactants.
  • the automatic dishwashing detergents contain nonionic surfactants from the group of the alkoxylated alcohols. Particular preference is given to nonionic surfactants which have a melting point above room temperature.
  • surfactants come from the groups of alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures of these surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants).
  • Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.
  • Particularly preferred nonionic surfactants are those of the formula
  • R 3 0 [CH 2 CH 2 0] x CH 2 CH (OH) R 4 in addition to a radical R 3 , which is linear or branched, saturated or mono- or polyunsaturated, hydrocarbon radicals having 2 to 30 carbon atoms, preferably with 4 to 22 carbon atoms, more preferably 8 to 10 carbon atoms, furthermore have a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical R 4 having 1 to 30 carbon atoms, where x is from 1 to 90, preferably from 10 to 60 and especially for values of 15 to 40 stands.
  • hydrocarbon radicals R 3 and / or R 4 are preferably aliphatic
  • alkyl radical having 2 to 30 carbon atoms, preferably 4 to 22
  • R 4 is preferably an alkyl radical of 1 to 30 carbon atoms, preferably 2 to 20 carbon atoms, more preferably 6 to 12 carbon atoms.
  • R 4 is an alkyl group having 8 carbon atoms and thus forms an etherified with the ethylene oxide 2-hydroxydecyl.
  • nonionic surfactants include, for example, the C4-22 fatty alcohol (EO) io-so-2-hydroxyalkyl ethers, in particular also the C8-12 fatty alcohol (EO) 22-2-hydroxydecyl ethers and the C4-22 fatty alcohol (EO) 4o 8o-2-hydroxyalkyl ethers.
  • this nonionic surfactant (i) is a C8-12 fatty alcohol (EO) 22-2-hydroxydecyl ether.
  • "EO” in this context means "ethylene oxide", ie a group of formula (CH2CH2O).
  • Such surfactants are preferably used in amounts of 1 to 10 wt .-%, preferably 2 to 5 wt .-% based on the total weight of the dishwashing detergent.
  • the amount of urea derivatives used is about 0.8 to 1.5% by weight and the amount of rinse aid surfactants used as defined above is 2.4 to 4.5% by weight, based in each case on the total weight of the dishwashing detergent.
  • the amounts of surfactant and urea derivative used per application can be, for example, in the range of 1 to 2-10 g / job, preferably in the range of 2 to 5 g / job.
  • the dishwashing detergent may contain other nonionic surfactants.
  • Suitable surfactants include, for example, (end-capped) hydroxy mixed ethers. It refers to
  • Nonionic surfactants having 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 5 O [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 O] yCH 2 CH (OH) R 6 , in which R 5 is a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R 6 is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x is between 0.5 and 1, 5 and y is a value of at least 15.
  • the group of these nonionic surfactants include, for example, the C2-26 fatty alcohol (PO) i- (EO) i5-4o-2-hydroxyalkyl ethers, in particular also the coco-fatty alcohol (PO) i (EO) 22-2-hydroxydecyl ethers ,
  • the compositions according to the invention may contain surfactants in the surfactant mixture, in particular further nonionic or else anionic surfactants, but also cationic or amphoteric surfactants.
  • Suitable further nonionic surfactants are, for example, alkyl glycosides of the general formula RO (G) x in which R corresponds to 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 Is a 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.
  • Another class of useful nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain.
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-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.
  • surfactants are the polyhydroxy fatty acid amides known as PHFA.
  • the total amount of nonionic surfactants in the dishwashing agents according to the invention is preferably 1 to 10 wt .-%, more preferably 2 to 5 wt .-%.
  • Suitable anionic surfactants are all anionic surfactants. These are characterized by a water-solubilizing, anionic group such as. Legs
  • glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups may be present in the molecule.
  • Suitable anionic surfactants are preferably in the form of the sodium, potassium and ammonium as well as the mono-, di- and
  • Preferred anionic surfactants are fatty alcohol sulfates, fatty alcohol ether sulfates, dialkyl ether sulfates, monoglyceride sulfates, alkylbenzenesulfonates, olefinsulfonates, alkanesulfonates, ether sulfonates, n-alkyl ether sulfonates, ester sulfonates and lignosulfonates.
  • fatty acid cyanamides sulfosuccinates (sulfosuccinic acid esters), in particular Sulfosuccinic acid mono- and di-alkyl esters of 8 to 18 carbon atoms, sulfosuccinamates,
  • Fatty acid sarcosinates Fatty acid sarcosinates, ether carboxylic acids and alkyl (ether) phosphates and ⁇ -sulfofatty acid salts, acylglutamates, monoglyceride disulfates and alkyl ethers of glycerol disulfate.
  • Preferred anionic surfactants include those of the formula
  • R 0 is -O- (AO) n -SO 3 - X + .
  • R 0 is a linear or branched, substituted or unsubstituted alkyl, aryl or alkylaryl radical, preferably a linear, unsubstituted alkyl radical, more preferably a fatty alcohol radical.
  • Preferred radicals R 0 are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and mixtures thereof, where the representatives with even number of carbon atoms Atoms are preferred.
  • radicals R 0 are derived from C 12 -C 18 -fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or from C 10 -C 20 oxo alcohols.
  • AO represents an ethylene oxide (EO) or propylene oxide (PO) moiety, preferably an ethylene oxide moiety.
  • the index n stands for an integer from 1 to 50, preferably from 1 to 20 and especially from 2 to 10. Most preferably, n stands for the numbers 2, 3, 4, 5, 6, 7 or 8.
  • X stands for a monovalent cation or the nth part of an n-valent cation, the alkali metal ions are preferred, and Na + or K + including Na, with Na + being extremely preferred.
  • Other cations X + can be selected from NhV, V Mn 2+ , and mixtures thereof.
  • an anionic surfactant of the formula R-A-S0 3 " Y + may be present in the dishwashing detergent
  • R is a linear or branched, substituted or unsubstituted alkyl, aryl or alkylaryl radical and the
  • certain radicals R are preferred.
  • R preferably represents a linear, unsubstituted alkyl radical, particularly preferably a fatty alcohol radical.
  • Preferred radicals R are selected from decyl, Undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl and mixtures thereof, with the even number of C atoms being preferred.
  • Particularly preferred radicals R are derived from C 12 -C 18 -fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or from C 10 -C 20 oxo alcohols.
  • Y stands for a monovalent cation or the n-th part of an n-valent cation, the alkali metal ions being preferred, and Na + or K + being preferred, Na + being extremely preferred. More cations Y + may be selected from NHV, Zn 2+ / 2 Mg 2+ / 2 Ca 2+ / 2 Mn 2+, and mixtures thereof.
  • dishwashing agents according to the invention contain anionic surfactants in amounts of up to 5% by weight.
  • the content of anionic surfactants is preferably less than 4 wt .-%, more preferably less than 2 wt .-% and in particular less than 1 wt .-%, based on the total weight of the dishwashing detergent.
  • Suitable amphoteric surfactants are, for example, betaines of the formula (R iii ) (R iv ) (R v ) N + CH 2 COO _ in which R i is an alkyl radical optionally interrupted by hetero atoms or heteroatom groups having 8 to 25, preferably 10 to 21 carbon atoms and R iv and R v are identical or different alkyl radicals having 1 to 3 carbon atoms, in particular Cio-Cis-alkyl dimethylcarboxymethylbetain and Cn-Ci7-alkylamidopropyl-dimethylcarboxymethylbetain.
  • Suitable cationic surfactants are i.a. the quaternary ammonium compounds of the formula
  • R VI (R VI ) (R vii ) (R viii ) (R ix ) N + X "
  • R vi to R ix for four identical or different, in particular two long and two short-chain, alkyl radicals and X " for an anion , in particular a halide ion, for example, didecyl-dimethyl-ammonium chloride, alkyl-benzyl-didecyl-ammonium chloride and mixtures thereof.
  • Suitable cationic surfactants are the quaternary
  • surface-active compounds in particular with a sulfonium, phosphonium, iodonium or arsonium group, which are also known as antimicrobial agents.
  • the agent can be designed with an antimicrobial effect or its possibly existing antimicrobial effect due to other ingredients can be improved.
  • the content of cationic and / or amphoteric surfactants is preferably less than 4 wt .-%, more preferably less than 2 wt .-% and
  • Dishwashing detergents containing no cationic or amphoteric surfactants are particularly preferred.
  • the total surfactant content of the dishwashing agent is preferably 1 to 15% by weight, preferably 2 to 10% by weight.
  • the agents according to the invention may comprise at least one, preferably two or more further constituents, preferably selected from the group consisting of builders, enzymes, thickeners, sequestering agents, electrolytes, corrosion inhibitors, in particular silver protectants, glass corrosion inhibitors, polymers, bleaches, bleach activators, foam inhibitors, dyes, fragrances , Bitter substances and antimicrobial agents.
  • the dishwashing compositions of the invention are preferably phosphate-free.
  • Builders which may be present in the dishwashing detergent are, in particular, silicates, aluminum silicates (in particular zeolites), carbonates, organic (co) builders, such as, for example, salts of organic di- and polycarboxylic acids, and mixtures of these substances.
  • NaMSix02x + i ⁇ y H2O are used, wherein M is sodium or hydrogen, x is a number from 1, 9 to 22, preferably from 1: 9 to 4, wherein particularly preferred values for x being 2, 3 or 4, and y a number from 0 to 33, preferably from 0 to 20 stands.
  • silicates Na-SKS-1 (Na 2 Si 2 2045 ⁇ x H 2 O, kenyaite), Na-SKS-2 (Na 2 Si 4 O 29 ⁇ x H 2 O, magadiite), Na-SKS-3 (Na 2 Si 8 0i7 ⁇ x H2O) or Na-SKS-4 (Na 2 Si 4 09 ⁇ x H2O, makatite).
  • Particularly suitable for the purposes of the present invention are crystalline phyllosilicates of the formula
  • Na-SKS-5 a-Na2Si20s
  • Na-SKS-7 .beta.-Na2 Si2 05, natrosilite
  • Na-SKS-9 NaHSi 2 0 5 ⁇ H2O
  • Na-SKS-10 NaHSi 2 0 5 ⁇ 3 H2O, kanemite
  • Na-SKS-1 1 t-Na 2 Si 2 05
  • Na-SKS-13 Na-SKS-13
  • the dishwashing detergents contain in various embodiments, a weight ratio of the crystalline layered silicate of the formula NaMSi x 02x + y i ⁇ H2O of 0.1 to 20 wt .-%, preferably from 0.2 to 15 wt .-% and in particular 0.4 to 10 wt .-%, each based on the total weight of these agents.
  • the agents are free of such silicates.
  • amorphous sodium silicates with a modulus Na 2 O: SiO 2 of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which are preferably Delayed and have secondary washing properties.
  • the dissolution delay compared to conventional amorphous sodium silicates can in various ways, for example by surface treatment, compounding, compaction / compaction or by
  • amorphous is understood to mean that 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 , cause.
  • the agents are free of these silicates.
  • alkali carriers are examples of alkali carriers.
  • alkali metal carbonates in particular sodium carbonate, sodium bicarbonate or sodium sesquicarbonate
  • a builder system comprising a mixture of sodium carbonate and sodium disilicate. Because of their low chemical compatibility with the other ingredients of mechanical compared to other builders
  • the optional alkali metal hydroxides are preferably only in small amounts, preferably in amounts below 10 wt .-%, preferably below 6 wt .-%, more preferably below 4 wt .-% and in particular below 2 wt .-%, each based on the total weight of the dishwashing detergent used.
  • Particularly preferred are agents which, based on their total weight less than 0.5 wt .-% and in particular no
  • the dishwashing detergents can contain as further builders in particular also phosphonates, which according to the invention are not subsumed under the phosphates.
  • the phosphonate compound used is preferably a hydroxyalkane and / or aminoalkane phosphonate.
  • Hydroxyalkane phosphonates is the 1-hydroxyethane-1,1-diphosphonate (HEDP) of particular importance.
  • Preferred aminoalkanephosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs.
  • Phosphonates are contained in the compositions preferably in amounts of 0.1 to 10 wt .-%, in particular in amounts of 0.3 to 8 wt .-%, each based on the total weight of the dishwashing detergent.
  • organic (co) builders are polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders and the phosphonates already mentioned above as builders. These classes of substances are described below.
  • Useful organic builders are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function.
  • these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid,
  • NTA nitrilotriacetic acid
  • Acidification and thus also serve to set a lower and milder pH of the dishwashing detergent.
  • citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.
  • machine dishwashing detergents are preferred according to the invention in that the dishwasher detergent contains citric acid or a salt of citric acid and the weight proportion of citric acid or citric acid salt is preferably from 1 to 40% by weight, preferably from 2 to 30, particularly preferably from 2 to 15 Wt .-% and in particular between 3 and 10 wt .-% is.
  • phosphate-free builders are aminocarboxylic acids and / or their salts. Particularly preferred members of this class are
  • Methylglycinediacetic acid (MGDA) or its salts and glutamic diacetic acid (GLDA) or its salts or ethylenediaminediacetic acid (EDDS) or its salts.
  • MGDA Methylglycinediacetic acid
  • GLDA glutamic diacetic acid
  • EDDS ethylenediaminediacetic acid
  • Particularly suitable are methylglycinediacetic acid (MGDA) or its salts, and glutamic diacetic acid (GLDA) or its salts.
  • GLDA glutamic diacetic acid
  • Very particular preference is GLDA or its salts. The content of these
  • Amino carboxylic acids or their salts may for example be between 0.1 and 25 wt .-%, preferably between 5 and 25 wt .-% and in particular between 15 and 25 wt .-% amount.
  • Aminocarboxylic acids and their salts can be used, for example, together with the abovementioned builders, in particular together with citrate and the abovementioned phosphonates.
  • compositions of the invention may further contain a sulfopolymer.
  • the proportion by weight of the sulfopolymer in the total weight of the composition according to the invention is preferably from 0.1 to 20% by weight, in particular from 0.5 to 18% by weight, particularly preferably from 0.1 to 15% by weight, in particular from 4 to 14 wt .-%, especially from 6 to 12 wt .-%.
  • the sulfopolymer is usually used in the form of an aqueous solution, the aqueous solutions typically containing 20 to 70 wt .-%, in particular 30 to 50 wt .-%, preferably about 35 to 40 wt .-% sulfopolymers.
  • the sulfopolymer used is preferably a copolymeric polysulfonate, preferably a hydrophobically modified copolymeric polysulfonate.
  • the copolymers may have two, three, four or more different monomer units.
  • Preferred copolymeric polysulfonates contain not only sulfonic acid group-containing monomer (s) but also at least one monomer selected from the group consisting of unsaturated carboxylic acids.
  • unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, ⁇ -chloroacrylic acid, ⁇ -cyanoacrylic acid, crotonic acid, ⁇ -phenyl-acrylic acid, maleic acid,
  • Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3 Methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propenylsulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfo - Propylmethacrylat, sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of said acids or their water-
  • the sulfonic acid groups may be wholly or partially in neutralized form, i. the acidic acid of the sulfonic acid group in some or all sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions.
  • metal ions preferably alkali metal ions and in particular for sodium ions.
  • the monomer distribution of the copolymers preferably used in accordance with the invention is in the case of copolymers which contain only monomers containing carboxylic acid groups and sulfonic acid group-containing monomers
  • Monomers contain, preferably in each case 5 to 95 wt .-%, particularly preferably the proportion of the sulfonic acid-containing monomer is 50 to 90 wt .-% and the proportion of
  • the molar mass of the sulfo copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired end use.
  • Preferred cleaning agents are characterized in that the copolymers have molecular weights of 2000 to 200,000 gmol -1 , preferably from 4000 to 25,000 gmol and in particular from 5000 to 15,000 gmol -1 .
  • other polymers can be used in the compositions of the invention.
  • the group of polymers includes, in particular, the washing or cleaning-active polymers, for example the rinse aid polymers and / or polymers which act as softeners.
  • cationic, anionic and amphoteric polymers can be used in automatic dishwashing detergents in addition to nonionic polymers.
  • the sulfo (co) polymers described above are, for example, anionic polymers.
  • amphoteric polymers furthermore have, in addition to a positively charged group in the polymer chain, negatively charged groups or monomer units, for example, these may be carboxylic acids, sulfonic acids or phosphonic acids.
  • Preferred usable amphoteric polymers are from the group of
  • 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 , the alkylacrylamide / methylmethacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / alkymethacrylate / alkylaminoethylmethacrylate / alkylmethacrylate copolymers and the copolymers of unsaturated carboxylic acids, cationically derivatized unsaturated carboxylic acids and optionally further ionic or nonionic monomers.
  • Preferred zwitterionic polymers are from the group of acrylamidoalkyl trialkyl ammonium 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 Methacroylethylbetain / methacrylate copolymers.
  • “Cationic polymers” are polymers which carry a positive charge in the polymer molecule, which can be realized, for example, by (alkyl) ammonium groups or other positively charged groups present in the polymer chain.
  • Particularly preferred cationic polymers originate from the groups of the quaternized cellulose derivatives, the polysiloxanes with quaternary groups, the cationic guar derivatives, the polymeric
  • the aforementioned amphoteric, zwitterionic or cationic polymers are in prefabricated form. To prepare the polymers u.a.
  • Coating compositions preferably by means of water-insoluble coating agents from the group of waxes or paraffins having a melting point above 30 ° C;
  • Support materials from the group of washing or cleaning-active substances particularly preferably from the group of builders (builders) or cobuilders.
  • enzymes As enzymes, various enzyme preparations or enzyme compositions known in the art can be used. These enzyme preparations or
  • Enzyme compositions usually contain at least one protease and one or more additional enzymes.
  • suitable enzymes include, but are not limited to, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably mixtures thereof. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents, which are preferably used accordingly.
  • Agents according to the invention preferably contain enzymes in total amounts of from 1 ⁇ 10 -6 to 5% by weight, based on active protein. The active protein concentration can be determined by known methods, for example the BCA method or the biuret method.
  • An enzyme may be particularly resistant to damage such as inactivation, denaturation or degradation during storage, such as by physical influences, oxidation or degradation protected proteolytic cleavage.
  • inhibition of the proteolysis is particularly preferred, especially if the agents also contain proteases.
  • the agents may contain stabilizers for this purpose; the provision of such means constitutes a preferred embodiment of the present invention.
  • Cleaning-active enzymes are generally not provided in the form of the pure protein but rather in the form of stabilized, storable and transportable preparations.
  • Such prefabricated preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel-form detergents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or added with stabilizers or further auxiliaries.
  • the enzymes may be encapsulated for both the solid and liquid dosage forms, for example by spray-drying or extruding the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core with a water, air and / or
  • Chemical-impermeable protective layer is coated.
  • further active ingredients for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied.
  • Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes.
  • such granules for example by applying polymeric
  • enzyme protein forms only a fraction of the total weight of conventional enzyme preparations.
  • Enzyme preparations preferably used according to the invention contain between 0.1 and 40% by weight, preferably between 0.2 and 30% by weight, more preferably between 0.4 and 20% by weight and in particular between 0.8 and 10 % By weight of the enzyme protein.
  • compositions described herein may also include enzyme stabilizers.
  • enzyme stabilizers are reversible protease inhibitors. Benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters are frequently used for this purpose, including, in particular, derivatives with aromatic groups, for example ortho, meta or para-substituted
  • Phenylboronic in particular 4-formylphenyl-boronic acid, or the salts or esters of said compounds.
  • peptide aldehydes that is oligopeptides with a reduced C-terminus, especially those of 2 to 50 monomers are used for this purpose.
  • peptidic reversible protease inhibitors include ovomucoid and leupeptin.
  • specific, reversible peptide inhibitors for the protease subtilisin and fusion proteins from proteases and specific peptide inhibitors are suitable.
  • enzyme stabilizers are amino alcohols such as mono-, di-, triethanol- and -propanolamine and mixtures thereof, aliphatic carboxylic acids up to C12, such as succinic acid, other dicarboxylic acids or salts of said acids. End-capped fatty acid amide alkoxylates are also suitable for this purpose. Certain organic acids used as builders are capable, as disclosed in WO 97/18287, of additionally stabilizing a contained enzyme.
  • Bleaching agents are washing or cleaning substances.
  • the compounds serving as bleaches in water H2O2 are sodium percarbonate,
  • Sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Further useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and peroxygenic salts or peracids which yield H2O2, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. It is also possible to use all other inorganic or organic agents known to the person skilled in the art
  • the dishwashing agents may contain 1 to 35% by weight,
  • bleaching agent preferably sodium percarbonate.
  • the dishwashing agents additionally contain at least one bleach activator.
  • bleach activators compounds mentioned in U.S. Pat
  • Perhydrolysis aliphatic peroxycarboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid, are used.
  • Bleach activators are 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) are particularly
  • bleach activators are preferably used in amounts of up to 10% by weight, in particular 0.1% by weight to 8% by weight, especially 2 to 8% by weight and more preferably 2 to 6% by weight, based in each case on the total weight of bleach activator-containing agents.
  • the pH of the agent can be adjusted by means of customary pH regulators, the pH value being selected depending on the desired application.
  • the pH is in a range of 5.5 to 12, preferably 6 to 1 1, more preferably 7 to 10, especially greater than 7, especially in the range 7.5 to 9.5.
  • the pH adjusting agents are acids and / or alkalis, preferably alkalis. Suitable acids are in particular organic acids such as acetic acid, citric acid, glycolic acid, lactic acid, succinic acid, adipic acid, malic acid, tartaric acid and gluconic acid or amidosulfonic acid. In addition, however, it is also possible to use the mineral acids hydrochloric acid, sulfuric acid and nitric acid or mixtures thereof.
  • Suitable bases are selected from the group of alkali and alkaline earth metal hydroxides and carbonates, in particular the alkali metal hydroxides, of which potassium hydroxide and especially sodium hydroxide is preferred.
  • volatile alkali for example in the form of ammonia and / or alkanolamines, which may contain up to 9 carbon atoms in the molecule.
  • the alkanolamine here is preferably selected from the group consisting of mono-, di-, triethanol- and -propanolamine and mixtures thereof.
  • the alkanolamine is preferably contained in agents according to the invention in an amount of from 0.5 to 10% by weight, in particular in an amount of from 1 to 6% by weight.
  • the composition according to the invention may also contain one or more buffer substances (INCI Buffering Agents), usually in amounts of 0.001 to 5 wt .-%. Preference is given to buffer substances which are at the same time complexing agents or even chelating agents (chelating agents, INCI chelating agents). Particularly preferred buffer substances are citric acid or citrates, in particular the sodium and potassium lead,
  • 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 originate from the group of bismuth, magnesium and zinc salts as well as bismuth, magnesium and zinc complexes, in particular zinc acetate.
  • alkoxylated or non-alkoxylated, in particular not alkoxylated, singly or in combination with the abovementioned salts or complexes are also preferably used
  • the content of zinc salt in dishwashing agents is preferably between 0.1 and 5 wt.%, Preferably between 0.1 and 4 wt.% And in particular between 0.2 and 3 wt.
  • the content of zinc in oxidized form (calculated as Zn 2+ ) is between 0.01 and 1% by weight, preferably between 0.02 and 0.5% by weight and in particular between 0.04 and 0.2% by weight. %, in each case based on the total weight of the
  • 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, patchouli, rose or ylang-ylang oil.
  • preservatives may be included in the compositions. Suitable examples are preservatives from the groups of alcohols, aldehydes, antimicrobial acids and / or their salts, carboxylic acid esters, acid amides, phenols, phenol derivatives, diphenyls,
  • Diphenylalkanes urea derivatives, oxygen, nitrogen acetals and formals, benzamidines, isothiazoles and their derivatives, such as isothiazolines and isothiazolinones, phthalimide derivatives,
  • the dishwashing detergent may be a low-water, liquid dishwashing detergent containing water in amounts up to a maximum of 25% by weight, preferably up to 20% by weight, based on the total weight of the composition.
  • low in water means that the composition thus characterized contains less than 25% by weight of water, preferably less than 20% by weight of water.
  • the water content as defined herein refers to the water content determined by Karl Fischer titration.
  • dishwashing agents described herein can be carried out in different ways.
  • the agents may be in solid or liquid form as well as in a combination of solid and liquid forms. Powder, granules, extrudates, compacts, 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.
  • the agents can be formulated in the form of single-phase or multi-phase products. The individual phases of multiphase agents may be the same or different
  • Liquid as used herein with respect to the agent of the invention therefore includes all flowable compositions and, in particular, also encompasses gels and pastes
  • the dishwashing agents described herein are preferably automatic dishwashing agents, which may be in solid or liquid form.
  • the solid moldings described below are particularly preferably also liquid agents, in particular in the form of gels.
  • the dishwashing detergents can be present as shaped bodies. In order to facilitate the disintegration of such prefabricated moldings, it is possible Disintegrationstosmittel, so-called
  • Tablet disintegrants to incorporate into these agents to shorten the disintegration times.
  • tablet disintegrants or disintegrants are meant excipients which are responsible for the rapid disintegration of tablets in water or other media and for the rapid release of the Active ingredients provide.
  • Desintegrationstosmittel in amounts of 0.5 to 10 wt .-%, preferably 3 to 7 wt .-% and in particular 4 to 6 wt .-%, each based on the
  • the dishwashing agents described herein are preferably prefabricated into dosage 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 16 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.
  • the dishwashing agents in particular the prefabricated metering units, with particular preference have a water-soluble coating.
  • the water-soluble coating is preferably formed from a water-soluble film material selected from the group consisting of polymers or polymer blends.
  • the wrapper may be formed of one or two or more layers of the water-soluble film material.
  • the water-soluble film material of the first layer and the further layers, if present, may be the same or different. Particularly preferred are films which, for example, can be glued and / or sealed to packages such as hoses or cushions after being filled with an agent.
  • the water soluble package may have one or more chambers.
  • the agent may be contained in one or more chambers, if any, of the water soluble envelope.
  • the amount of agent preferably corresponds to the full or half dose needed for a rinse.
  • the water-soluble coating be polyvinyl alcohol or a
  • Water-soluble coatings containing polyvinyl alcohol or a polyvinyl alcohol copolymer have a good stability with a sufficiently high water solubility, in particular cold water solubility on.
  • Suitable water-soluble films for producing the water-soluble coating are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer whose
  • Molecular weight in the range of 10,000 to 1,000,000 gmor, preferably from 20,000 to 500,000 gmol "1 , more preferably from 30,000 to 100,000 gmol " 1 and in particular from 40,000 to 80,000 gmol 1 .
  • polyvinyl alcohol is usually carried out by hydrolysis of polyvinyl acetate, since the direct synthesis route is not possible.
  • polyvinyl alcohol copolymers which are prepared from correspondingly polyvinyl acetate copolymers. It is preferred if at least one layer of the water-soluble coating comprises a polyvinyl alcohol whose degree of hydrolysis makes up 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.
  • a polymer selected from the group comprising a polyvinyl alcohol-containing sheet material suitable for producing the water-soluble sheath is selected from the group comprising a polyvinyl alcohol-containing sheet material suitable for producing the water-soluble sheath
  • (Meth) acrylic acid-containing (co) polymers polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers, polylactic acid or mixtures of the above polymers may be added.
  • a preferred additional polymer is polylactic acids.
  • Preferred polyvinyl alcohol copolymers include, in addition to vinyl alcohol, dicarboxylic acids as further monomers.
  • Suitable dicarboxylic acids are itaconic acid, malonic acid, succinic acid and mixtures thereof, with itaconic acid being preferred.
  • polyvinyl alcohol copolymers include, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt or its esters.
  • Such polyvinyl alcohol copolymers particularly preferably contain, in addition to vinyl alcohol, acrylic acid, methacrylic acid, acrylates, methacrylates or mixtures thereof.
  • the film material contains further additives.
  • the film material may include, for example, plasticizers such as dipropylene glycol, ethylene glycol, diethylene glycol,
  • Additives include, for example, release aids, fillers, crosslinking agents, surfactants, antioxidants, UV absorbers, antiblocking agents, detackifiers, or mixtures thereof.
  • Suitable water-soluble films for use in the water-soluble casings of the water-soluble packaging according to the invention are films sold by the company MonoSol LLC, for example under the designation M8630, C8400 or M8900.
  • Other suitable films include films named Solublon® PT, Solublon® GA, Solublon® KC or Solublon® KL from Aicello Chemical Europe GmbH or the films VF-HP from Kuraray.
  • the corresponding use of the dishwasher detergent according to the invention is likewise
  • the invention likewise relates to a dishwashing process, in particular a machine dishwashing process, in which a dishwashing detergent according to the invention is used.
  • the subject matter of the present application is therefore furthermore a process for the cleaning of dishes in a dishwashing machine, in which the agent according to the invention is metered into the interior of a dishwasher during the passage of a dishwashing program before the main wash cycle or during the main wash cycle.
  • Dishwasher can be done manually, but preferably the agent is metered by means of the metering chamber in the interior of the dishwasher.
  • the invention also relates to the use of the compounds described herein for improving the rinsing performance of a dishwashing detergent, in particular machine
  • Nonionic surfactant 4 50 3,50
  • Filming is determined in the Miele G698 at 50 ° C. Water hardness 21 ° dH. After completion of the rinse cycle, the machine is fully opened for 30 minutes and then the clear rinse effect is visually determined in the black box (black-painted room, D6500 daylight lamp). On the crockery and cutlery remaining dried water drops, streaks, coverings and films are scored on a scale of 1 - 10. 10 means no drops / films, 1 means heavy drops / filming.

Landscapes

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

Abstract

L'invention concerne un détergent pour vaisselle, en particulier un détergent pour lave-vaisselle, présentant un pouvoir de rinçage à l'eau claire amélioré, contenant, par rapport au poids total du détergent pour la vaisselle, 0,1 à 5,0 % en poids d'au moins un dérivé d'urée tel que défini dans la description, et son utilisation dans un procédé de lavage de vaisselle. Dans la formule (I) • chaque R1 représente H ou un radical hydrocarboné linéaire ou ramifié, saturé ou mono-insaturé ou polyinsaturé, comprenant 1 à 10 atomes de carbone, de préférence 1 à 6 atomes de carbone, encore plus préférablement 1 à 4 atomes de carbone; • chaque Alk représente, indépendamment, un radical alkyle linéaire ou ramifié comprenant 1 à 10 atomes de carbone, de préférence 1 à 6 atomes de carbone, encore plus préférablement 1 à 4 atomes de carbone; • A représente une liaison chimique ou un radical hydrocarboné bivalent comprenant 1 à 30 atomes de carbone, de préférence 4 à 22 atomes de carbone; et • chaque ------ représente une simple ou une double liaison, les liaisons étant de préférence toutes une simple liaison ou toutes une double liaison, en particulier toutes une double liaison.
EP17713658.7A 2016-04-04 2017-03-27 Détergent pour vaisselle contenant des dérivés d'urée Withdrawn EP3440176A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102016205489.9A DE102016205489A1 (de) 2016-04-04 2016-04-04 Geschirrspülmittel enthaltend Harnstoffderivate
PCT/EP2017/057177 WO2017174384A1 (fr) 2016-04-04 2017-03-27 Détergent pour vaisselle contenant des dérivés d'urée

Publications (1)

Publication Number Publication Date
EP3440176A1 true EP3440176A1 (fr) 2019-02-13

Family

ID=58413112

Family Applications (1)

Application Number Title Priority Date Filing Date
EP17713658.7A Withdrawn EP3440176A1 (fr) 2016-04-04 2017-03-27 Détergent pour vaisselle contenant des dérivés d'urée

Country Status (3)

Country Link
EP (1) EP3440176A1 (fr)
DE (1) DE102016205489A1 (fr)
WO (1) WO2017174384A1 (fr)

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DK132665A (fr) * 1969-12-31
US4624713A (en) * 1984-11-15 1986-11-25 Economics Laboratory, Inc. Solid rinse aids and methods of warewashing utilizing solid rinse aids
US4996359A (en) * 1988-03-14 1991-02-26 Arco Chemical Technology, Inc. Process for the preparation of aromatic bis dialkyl ureas
US5064881A (en) * 1989-01-18 1991-11-12 Mitsui Petrochemical Industries, Ltd. Epoxy resin composition and semiconductor sealing material comprising same based on spherical silica
US5741767A (en) 1995-11-16 1998-04-21 Lever Brothers Company, Division Of Conopco, Inc. Peracid based dishwashing detergent composition
CN107263940A (zh) * 2011-12-22 2017-10-20 赫克赛尔控股有限责任公司 纤维增强复合材料的改进或与纤维增强复合材料有关的改进

Also Published As

Publication number Publication date
DE102016205489A1 (de) 2017-10-05
WO2017174384A1 (fr) 2017-10-12

Similar Documents

Publication Publication Date Title
EP3209762B1 (fr) Détergent pour lave-vaisselle contenant des complexes métalliques
EP3872157B1 (fr) Produit de lavage pour vaisselle les contenant des complexes métalliques
EP3436559A1 (fr) Détergents vaisselle à efficacité de rinçage améliorée
EP3431575B1 (fr) Détergent pour lave-vaisselle comportant un citrate dihydraté et anhydre
EP3481936B1 (fr) Produit vaisselle contenant de l'ose acide et de l'acide aminocarboxylique
EP3502224A1 (fr) Détergent pour lave-vaisselle à performance de nettoyage améliorée, procédé reposant sur l'utilisation dudit détergent ainsi que l'utilisation dudit détergeant
DE102018212086A1 (de) Geschirrspülmittel mit Ceteareth-9
EP3440176A1 (fr) Détergent pour vaisselle contenant des dérivés d'urée
DE102017223117A1 (de) Maschinelles Geschirrspülmittel mit verbesserter Klarspül- und Reinigungsleistung, Verfahren unter Einsatz dieses Mittels sowie Verwendung des Mittels
DE102012214027A1 (de) Verwendung von anionischen Tensiden
WO2018002178A1 (fr) Détergent permettant de réduire la corrosion du verre
WO2022100995A1 (fr) Détergents pour lave-vaisselle contenant des complexes métalliques
WO2023117380A1 (fr) Complexes métalliques et produits de lave vaisselle les contenant
DE102021214708A1 (de) Metallkomplexe und Geschirrspülmittel, die sie enthalten
DE102017223121A1 (de) Maschinelles Geschirrspülmittel mit verbesserter Klarspül- und Reinigungsleistung, Verfahren unter Einsatz dieses Mittels sowie Verwendung des Mittels
EP3502220A1 (fr) Détergent pour lave-vaisselle à performance de rinçage et de nettoyage améliorée, procédé reposant sur l'utilisation dudit détergent ainsi que l'utilisation dudit détergent
WO2017186263A1 (fr) Copolymères pour améliorer les performances de rinçage
WO2022100949A1 (fr) Détergents pour laver la vaisselle contenant des complexes métalliques
DE102020214069A1 (de) Metallkomplexe und Geschirrspülmittel, die sie enthalten
DE102021214688A1 (de) Metallkomplexe und Geschirrspülmittel, die sie enthalten
DE102014226904A1 (de) Copolymere zur Verbesserung der Klarspülleistung
DE102017223120A1 (de) Maschinelles Geschirrspülmittel mit verbesserter Reinigungsleistung, Verfahren unter Einsatz dieses Mittels sowie Verwendung des Mittels
DE102020207791A1 (de) Metallkomplexe und Geschirrspülmittel, die sie enthalten
EP2882836B1 (fr) Agent de lavage au lave-vaisselle contenant des polysaccharides à modification hydrophobe
DE102013226440A1 (de) Maschinelles Geschirrspülmittel enthaltend Emulgatoren

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

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

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

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

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

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20180911

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

RIN1 Information on inventor provided before grant (corrected)

Inventor name: WEBER, THOMAS

Inventor name: DAHLMANN, DORIS

Inventor name: OTTOW, CLAUDIA

Inventor name: VOCKENROTH, INGA KERSTIN

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
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: 20190525