EP3080238B1 - Maschinelle geschirrspülmittel enthaltend oxazolidin-riechstoffvorläufer - Google Patents

Maschinelle geschirrspülmittel enthaltend oxazolidin-riechstoffvorläufer Download PDF

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Publication number
EP3080238B1
EP3080238B1 EP14808657.2A EP14808657A EP3080238B1 EP 3080238 B1 EP3080238 B1 EP 3080238B1 EP 14808657 A EP14808657 A EP 14808657A EP 3080238 B1 EP3080238 B1 EP 3080238B1
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Prior art keywords
unsubstituted
substituted
branched
linear
odorant
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German (de)
English (en)
French (fr)
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EP3080238A1 (de
Inventor
Marc Weyhe
Ursula Huchel
Elke Maria MÜNZEL
Lukas Baron
Isabelle LEVERT
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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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/50—Perfumes
    • C11D3/502—Protected perfumes
    • C11D3/507—Compounds releasing perfumes by thermal or chemical activation
    • 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces

Definitions

  • the present invention relates to the use of perfume precursors in the form of oxazolidines for preventing and / or controlling malodors in dishwashing machines, particularly in the form of automatic dishwashing detergents containing these oxazolidine fragrance precursors, the dishwashing compositions per se, and a machine dishwashing method using the same this dishwashing detergent.
  • dishwashing detergents usually contain fragrances, they are not suitable for satisfactorily controlling the bad odors which develop after prolonged non-use of the dishwasher in its interior.
  • the object of the present invention was to provide compounds for use in automatic dishwashing detergents which cover unpleasant odors which arise in the course of automatic dishwashing and, in particular, prolonged non-use of the dishwasher and / or storage of dirty dishes in the interior thereof reduce or even completely neutralize it.
  • perfume precursors in the form of oxazolidines are surprisingly able to cover such malodors effectively over a period of several days of non-use of the dishwasher.
  • a first aspect of the present invention therefore relates to means for use in an automatic dishwashing machine as defined in claim 1.
  • Another aspect of the invention is directed to the use of such an agent for controlling or neutralizing bad odors in a machine dishwashing machine.
  • Yet another aspect relates to automatic dishwashing processes, characterized in that an agent, in particular a machine dishwashing detergent, according to the invention is used.
  • the invention also relates to the use of an oxazolidine precursor compound of a fragrance according to claim 9 for controlling or neutralizing malodors in a machine dishwashing machine.
  • At least one refers to 1 or more, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9 or more. In the context of ingredients of the compositions described herein, this indication does not refer to the absolute amount of molecules but to the nature of the ingredient.
  • at least one nonionic surfactant means, for example, one or more different nonionic surfactants, i. one or more different types of nonionic surfactants. Together with quantities, the quantities refer to the total amount of the corresponding designated type of ingredient as defined above.
  • Substituted as used herein in connection with the definition of oxazolidine compounds means that one hydrogen atom is replaced by another group.
  • Suitable groups include, but are not limited to, linear or branched C 1-22 hydrocarbon groups including alkyl, alkenyl, alkynyl (the latter including 2-22 carbon atoms), -OH, -CN, -NO 2 -C (O). H, -C (O) OR ', -C (O) NR'R ", -NR'-C (O) -R", -NR'R ", where R' and R" are C 1-12 linear or branched alkyl.
  • Heterocyclyl refers to heteroalicyclic compounds which may contain one or more double bonds and one or more hetero ring atoms, especially O, N or S, but are not aromatic.
  • (Hetero) aryl refers to aryl and heteroaryl compounds, the latter containing one or more hetero ring atoms, especially selected from O, N and S.
  • R 1 is H and R is a group represented by the formula gives a fragrance aldehyde.
  • R 1 and R are not hydrogen, but radicals represented by the formula result in a fragrance ketone.
  • oxazolidine precursors described herein are, in particular, reaction products of a fragrance aldehyde or ketone of the formula: wherein R and R 1 are as defined above and further provided that in the fragrance aldehydes R 1 is H and in the fragrance ketones R 1 is not H, with a ⁇ -aminoalcohol of the formula: wherein R 3 -R 6 are as defined above.
  • the fragrance can be released again by hydrolysis.
  • the conditions for the release are the typical environmental conditions encountered in a machine dishwasher.
  • the release is preferably delayed such that the fragrances are released over a period of several days, in particular of up to 10 days, preferably over a period of 1-5 days.
  • the aldehyde or ketone component is the actual fragrance
  • the beta-aminoalcohol may be a fragrance.
  • both the aldehyde / ketone and the aminoalcohol may be a fragrance.
  • the fragrance aldehyde may be selected from adoxal (2,6,10-trimethyl-9-undecenal), anisaldehyde (4-methoxybenzaldehyde), cymal (3- (4-isopropylphenyl) -2-methylpropanal), Ethyl vanillin, florhydral (3- (3-isopropylphenyl) butanal]), helional (3- (3,4-methylenedioxyphenyl) -2-methylpropanal), heliotropin, hydroxycitronellal, lauraldehyde, lyral (3- and 4- (4-hydroxy) 4-methylpentyl) -3-cyclohexene-1-carboxaldehyde), methylnonylacetaldehyde, Lilial (3- (4-tert-butylphenyl) -2-methylpropanal), phenylacetaldehyde, undecylenealdehyde, vanillin,
  • Preferred aldehydes include, without limitation, lilial, helional, anisaldehyde, cyclamen aldehyde, triplal, melonal, methyl undecanal, undecanal, nonanal and octanal.
  • Suitable ketones include, but are not limited to, methyl-beta-naphthyl ketone, muskedanone-1-one (1,2,3,5,6,7-hexahydro-1,1,2,3,3-pentamethyl-4H-indene-4 on), tartalide (6-acetyl-1,1,2,4,4,7-hexamethyltetralin), alpha-damascone, beta-damascone, delta-damascone, iso-damascone, damascenone, methyldihydrojasmonate, menthone, carvone, camphor, Koavon (3,4,5,6,6-pentamethylhept-3-en-2-one), fenchone, alpha-ionone, beta-ionone, gamma-methyl-ionone, fleuramon (2-heptylcyclopentanone), dihydrojasmon, cis- Jasmon, 1 - (1,2,3,4,5,6,7
  • fragrance aldehydes and / or fragrance ketones basically all the usual fragrance aldehydes and / or fragrance ketones can be used, which are used in particular to bring about a pleasant smell sensation in humans.
  • perfume aldehydes and / or perfume ketones are known in the art and also in the patent literature, for example in US 2003/0158079 A1 , Paragraphs [0154] and [0155].
  • suitable fragrances be on Steffen Arctander, Aroma Chemicals Volume 1 and Volume 2 (published 1960 and 1969, reissue 2000; ISBN: 0-931710-37-5 and 0-931710-38-3 ).
  • a compound of the general formula of the formula: wherein R 3 -R 6 are as defined above be reacted with aldehydes, ketones or mixtures of ketones and aldehydes with ring closure.
  • the reaction is preferably carried out in a suitable solvent or in situ. Suitable solvents are, for example, aromatic hydrocarbons such as toluene.
  • the reaction is preferably carried out at a temperature in the range of 80 to 150 ° C, more preferably 100 to 140 ° C.
  • the aminoalcohol having the general formula shown above under a nitrogen atmosphere together with the desired ketone and / or aldehyde in the solvent is heated. Often, it is then heated under reflux at the water separator.
  • the resulting reaction product is isolated by conventional methods and optionally purified.
  • the oxazolidine compounds used have the property of at least partially masking malodors that develop in the interior of automatic dishwashers during prolonged non-use or the storage of soiled dishes and to mitigate or even neutralize the perceived by people as unpleasant odors.
  • the oxazolidine precursors described above are used in the compositions according to the invention as mixtures with at least one further perfume.
  • the other fragrances which may optionally be included in the compositions are not particularly limited.
  • individual fragrance compounds of natural or synthetic origin for example of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons can be used.
  • Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate (DMBCA), phenylethylacetate, benzylacetate, ethylmethylphenylglycinate, allylcyclohexylpropionate, styrallylpropionate, benzylsalicylate, cyclohexylsalicylate, floramate, melusate and jasmacyclate.
  • DMBCA dimethylbenzylcarbinylacetate
  • benzylacetate ethylmethylphenylglycinate
  • allylcyclohexylpropionate styrallylpropionate
  • benzylsalicylate cyclohexylsalicylate
  • floramate melusate
  • the ethers include, for example, benzyl ethyl ether and ambroxane, to the aldehydes the above-mentioned, for example, the linear alkanals having 8 - 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde (3- (4-propan-2-ylphenyl) butanal), Lilial and bourgeonal, among the ketones, for example, the ionones, [alpha] -Isomethylionon and methylcedryl ketone to the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons include mainly terpenes such as limonene and pinene.
  • compositions according to the invention may also contain natural fragrance mixtures, such as those obtainable from plant sources, for example pine, citrus, jasmine, patchouly, rose or ylang-ylang oil.
  • natural fragrance mixtures such as those obtainable from plant sources, for example pine, citrus, jasmine, patchouly, rose or ylang-ylang oil.
  • suitable fragrance mixtures such as those obtainable from plant sources, for example pine, citrus, jasmine, patchouly, rose or ylang-ylang oil.
  • Natural fragrance mixtures such as those obtainable from plant sources, for example pine, citrus, jasmine, patchouly, rose or ylang-ylang oil.
  • suitable are Muskateller sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, lime blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil and orange blossom oil, neroli oil, orange peel oil and sandalwood oil.
  • fragrances which may be present in the compositions according to the invention in the context of the present invention are, for example, the essential oils such as angelica root oil, aniseed oil, arnica blossom oil, basil oil, Bay oil, Champacablütenöl, Edeltannöl, Edeltannenzapfen oil, Elemiöl, Eucalyptusöl, Fennelöl, Fichtennadelöl, Galbanumöl, Geranium oil, ginger grass oil, guaiac wood oil, gurdy balm oil, helichrysum oil, ho oil, ginger oil, iris oil, cajeput oil, calamus oil, chamomile oil, camphor oil, kanga oil, cardamom oil, cassia oil, pine oil, kopaivabalam oil, coriander oil, spearmint oil, caraway oil, cumin oil, lavender oil, lemongrass oil, Lime oil, Tangerine oil, Melissa oil, Musk grain oil, Myrrh oil, Clove oil, Neroli oil, Ni
  • the claimed agents use the oxazolidine fragrance precursors with the corresponding aldehydes and / or ketones.
  • such compositions are characterized in that the molar ratio of fragrance aldehyde and / or fragrance ketone to the corresponding oxazolidine fragrance precursor 20: 1 to 1:20 preferably 10: 1 to 1:10, advantageously 5 : 1 to 1: 5, more preferably 3: 1 to 1: 3, more preferably 2: 1 to 1: 2 and especially 1.2: 1 to 1: 1.2.
  • perfume aldehyde and / or perfume ketone and corresponding oxazolidine perfume precursors produce particularly good results in the sense of this invention, especially with regard to stability and fragrance of the agents, as well as with regard to the fragrance of it treated dishwashers.
  • the agent may in principle comprise further constituents, in particular further fragrances, as defined above, and / or solvents.
  • typical perfume compositions may include adjuvants such as antioxidants (generic term for compounds of various chemical structure which inhibit or prevent undesirable changes due to oxygenation and other oxidative processes in the compositions to be protected), preservatives (collective term for compounds of various chemical types) Structure that inhibit or prevent undesirable changes in the compositions to be protected due to the action of microorganisms or microorganisms) or eg fixatives.
  • adjuvants such as antioxidants (generic term for compounds of various chemical structure which inhibit or prevent undesirable changes due to oxygenation and other oxidative processes in the compositions to be protected), preservatives (collective term for compounds of various chemical types) Structure that inhibit or prevent undesirable changes in the compositions to be protected due to the action of microorganisms or microorganisms) or eg fixatives.
  • Fixatives which are optionally used as auxiliaries, are substances that can give fragrances increased resistance.
  • fixers are particularly suitable are the so-called self-fixatives which retain their odor for a long time without hindering other, more volatile components in their odor development, in particular the synthetic musk body, furthermore the so-called pseudofixates as low-odor substances, such as diethylene glycol methyl ether, and further by Adsorber fixing fixatives, such as in particular extracts of Labdanum, Styrax, Tolubalsam, Benzoin, Iris, Oakmoss or Opopanax etc ..
  • Suitable optional solvents are, in particular, those customary in perfumery, such as preferably dipropylene glycol, diethylene glycol, isopropyl myristate, ethanol, propylene glycol and / or castor oil.
  • Other suitable optional auxiliaries are, for example, complexing agents.
  • the agents of the invention may be, for example, automatic dishwashing detergents, automatic dishwashing detergents, rinse aids or automatic dishwashing perfume compositions.
  • the agents of the invention in particular the dishwashing perfume compositions (“dishwashing deodorant”) may, in certain embodiments, consist essentially only of perfume aldehyde and / or perfume ketone and an oxazolidine corresponding to exactly this perfume aldehyde and / or perfume ketone -Riechstoffvorierr, which can release the same fragrance aldehyde or the same fragrance ketone and which satisfies the above formula exist. "Substantially” here means that these agents to> 90 wt .-%, preferably> 95 wt .-% and in particular to> 99 wt .-% or even to 100 wt .-% consists of said components.
  • Such agents may contain the at least one oxazolidine precursor compound of a fragrance based on the total weight of the agent in amounts up to 30% by weight, especially up to 25% by weight.
  • the agents described herein may contain the at least one oxazolidine precursor compound of a fragrance based on the total weight of the agent in amounts of from 0.01 to 30% by weight, more preferably from 0.01 to 25% by weight, more preferably from 0.01 to 10 wt .-% included.
  • Some agents for example dishwashing detergents, dishwashing detergents or rinse aids, contain the at least one oxazolidine precursor compound of a perfume, based on the total weight of the agent, usually in amounts of from 0.01 to 2% by weight, in particular from 0.05 to 1% by weight. more preferably from 0.1 to 0.5% by weight.
  • compositions according to the invention in particular automatic dishwasher detergents, can be solid or liquid in nature and can be present in particular as pulverulent solids, in densified particle form, as homogeneous solutions or suspensions.
  • the means, in particular the automatic dishwashing detergent in a pre-portioned form.
  • such a composition has a plurality of spatially separate compositions, whereby it is possible to separate incompatible ingredients from one another, or to offer compositions in combination, which are used at different times in the dishwasher. This is particularly advantageous when the agents are in pre-portioned form.
  • At least one of the compositions is solid and / or at least one of the compositions is liquid, and the oxazolidine fragrance precursors are present in at least one of the compositions, but may also be present in several compositions.
  • the agents according to the invention preferably comprise at least one further constituent, in particular at least two further constituents selected from the group consisting of builders, surfactants, polymers, bleaches, bleach activators, bleach catalysts, in particular catalysts based on manganese or cobalt, enzymes, corrosion inhibitors and glass corrosion inhibitors, Disintegration aids and perfume carriers.
  • compositions according to the invention in particular the automatic dishwasher detergents.
  • dishwashing detergent in particular, it is clear to the person skilled in the art that similar ingredients can also be used in other of the abovementioned agents.
  • rinse aids typically typically contain surfactants, for example, those described below.
  • surfactants for example, those described below.
  • builders can be used.
  • the builders include, in particular, the zeolites, silicates, carbonates, organic cobuilders and, where there are no ecological prejudices against their use, also the phosphates.
  • the crystalline layer-form silicates of the formula NaMSi x O 2x + 1 .yH 2 O are sold, for example, by the company Clariant GmbH (Germany) under the trade name Na-SKS.
  • silicates Na-SKS-1 (Na 2 Si 22 O 45 .xH 2 O, Kenyaite), Na-SKS-2 (Na 2 Si 14 O 29 .xH 2 O, magadiite), Na-SKS -3 (Na 2 Si 8 O 17 .xH 2 O) or Na-SKS-4 (Na 2 Si 4 O 9 .xH 2 O, Makatite).
  • NaMSi x O 2x + 1 .yH 2 O, in which x is 2 are particularly suitable.
  • both .beta.- and ⁇ -sodium Na 2 Si 2 O 5 ⁇ y H 2 O and further in particular Na-SKS-5 ( ⁇ -Na 2 Si 2 O 5), Na-SKS-7 (.beta.-Na 2 Si 2 O 5, natrosilite), Na-SKS-9 (NaHSi 2 O 5 ⁇ H 2 O), Na-SKS-10 (NaHSi 2 O 5 ⁇ 3 H 2 O, kanemite), Na-SKS-11 ( t-Na 2 Si 2 O 5 ) and Na-SKS-13 (NaHSi 2 O 5 ), but especially Na-SKS-6 ( ⁇ -Na 2 Si 2 O 5 ).
  • Machine dishwashing detergents preferably contain a weight fraction of the crystalline layered silicate of the formula NaMSi x O 2x + 1 .yH 2 O of from 0.1 to 20% by weight, preferably from 0.2 to 15% by weight and in particular of 0, 4 to 10 wt .-%, each based on the total weight of these agents.
  • amorphous sodium silicates with a Na 2 O: SiO 2 modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which preferably delayed release and have secondary washing properties.
  • 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.
  • 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.
  • 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 Alkaline carriers, prevent limescale deposits on machine parts or Kalkinkrustationen in tissues and also contribute to the cleaning performance.
  • phosphates are the pentasodium triphosphate, Na 5 P 3 O 10 (sodium tripolyphosphate) and the corresponding potassium salt pentapotassium triphosphate, K 5 P 3 O 10 (potassium tripolyphosphate).
  • sodium potassium tripolyphosphates Preferably usable according to the invention are the sodium potassium tripolyphosphates.
  • phosphates are used as washing or cleaning substances in machine dishwashing detergent in the present application
  • preferred agents comprise this phosphate (s), preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate ), in amounts of 5 to 80 wt .-%, preferably from 15 to 75 wt .-% and in particular from 20 to 70 wt .-%, each based on the weight of the automatic dishwashing detergent.
  • alkali carriers are, for example, alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogencarbonates, alkali metal sesquicarbonates, the cited alkali metal silicates, alkali metal silicates, and mixtures of the abovementioned substances, it being possible to use the alkali metal carbonates, in particular sodium carbonate, sodium bicarbonate or sodium sesquicarbonate, for the purposes of this invention.
  • a builder system comprising a mixture of tripolyphosphate and sodium carbonate.
  • a builder system comprising a mixture of tripolyphosphate and sodium carbonate and sodium disilicate.
  • 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 % By weight and in particular below 2% by weight, in each case based on the total weight of the automatic dishwashing detergent.
  • Particularly preferred are agents which, based on their total weight, contain less than 0.5% by weight and in particular no alkali metal hydroxides.
  • compositions which, based on the weight of the automatic dishwashing agent, are less than 20% by weight, preferably less than 17% by weight, preferably less than 13% by weight and in particular less than 9% by weight of carbonate (s) and / or hydrogencarbonate (s), preferably alkali metal carbonate (s), particularly preferably sodium carbonate.
  • organic co-builders are polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, further organic cobuilders and phosphonates. These classes of substances are described below.
  • Useful organic builders are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and mixtures of these.
  • the free acids also typically have the property of an acidifying component and thus also serve to set a lower and milder pH of the automatic dishwashing detergents.
  • citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.
  • automatic dishwashing detergents are preferred according to the invention in that the automatic dishwashing agent contains citric acid or a salt of citric acid and the weight fraction of citric acid or of the salt of citric acid is preferably more than 10% by weight, preferably more than 15% by weight in particular between 20 and 40 wt .-% is.
  • phosphate-free builders are aminocarboxylic acid and / or its 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 or its salts (EDDS).
  • MGDA methylglycinediacetic acid
  • GLDA glutamic diacetic acid
  • EDDS ethylenediaminediacetic acid or its salts
  • the content of these aminocarboxylic acids or their salts may for example be between 0.1 and 15% by weight, preferably between 0.5 and 10% by weight and in particular between 0.5 and 6% by weight.
  • Aminocarboxylic acids and their salts can be used together with the abovementioned builders, in particular also with the phosphate-free builders.
  • polymeric polycarboxylates for example the alkali metal salts of polyacrylic acid or of polymethacrylic acid, for example those having a relative molecular mass of from 500 to 70,000 g / mol.
  • Suitable polymers are, in particular, polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may again be preferred from this group.
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Their relative molecular weight, based on free acids is generally from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.
  • the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution.
  • the content of the automatic dishwashing agents in (co) polymeric polycarboxylates is preferably from 0.5 to 20% by weight and in particular from 3 to 10% by weight.
  • the polymers may also contain allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid as a monomer.
  • copolymers are those which have as their monomers acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
  • compositions of the invention may contain surfactants, wherein the nonionic, the anionic, the cationic and the amphoteric surfactants are counted among the group of surfactants.
  • nonionic surfactants it is possible to use all nonionic surfactants known to the person skilled in the art.
  • Suitable nonionic surfactants are, for example, alkyl glycosides of the general formula RO (G) x in which R is a primary straight-chain or methyl-branched, in particular 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol that is for a glycose unit with 5 or 6 C atoms, preferably for 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 which can be used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain.
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-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.
  • Low-foaming nonionic surfactants can be used as preferred surfactants.
  • the automatic dishwashing detergents contain nonionic surfactants from the group of the alkoxylated alcohols.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten.
  • EO ethylene oxide
  • alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 moles of EO per mole of alcohol are preferred.
  • 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 -alcohol with 3 EO and C 12-18 -alcohol with 5 EO.
  • the stated degrees of ethoxylation represent statistical averages, which may correspond to a particular product of 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 which have a melting point above room temperature.
  • surfactants come from the groups of alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols.
  • Anionic surfactants can also be used as a component of automatic dishwashing detergents. These include in particular alkylbenzenesulfonates, (fatty) alkyl sulfates, (fatty) alkyl ether sulfates and alkanesulfonates.
  • the content of the anionic surfactant is usually 0 to 10% by weight.
  • the content of cationic and / or amphoteric surfactants is preferably less than 6% by weight, preferably less than 4% by weight, very particularly preferably less than 2% by weight and in particular less than 1% by weight. %. Automatic dishwashing detergents containing no cationic or amphoteric surfactants are particularly preferred.
  • 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.
  • 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 machine dishwashing detergents in addition to nonionic polymers.
  • “Cationic polymers” in the context of the present invention are polymers which carry a positive charge in the polymer molecule. This can be realized, for example, by (alkyl) ammonium groups or other positively charged groups present in the polymer chain.
  • Particularly preferred cationic polymers come from the groups of quaternized cellulose derivatives, the polysiloxanes with quaternary groups, the cationic guar derivatives, the polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid, the copolymers of vinylpyrrolidone with quaternized derivatives of dialkylamino and methacrylates, the vinylpyrrolidone-methoimidazolinium chloride copolymers, the quaternized polyvinyl alcohols or the polymers specified under the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27.
  • amphoteric polymers furthermore have, in addition to a positively charged group in the polymer chain, also negatively charged groups or monomer units. These groups may be e.g. to act carboxylic acids, sulfonic acids or phosphonic acids.
  • Preferred employable amphoteric polymers are from the group of the alkylacrylamide / acrylic acid copolymers, the alkylacrylamide / methacrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid copolymers, the alkylacrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / methacrylic acid / alkylaminoalkyl (meth ) -acrylic acid copolymers, 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 non
  • Preferably usable zwitterionic polymers are selected from the group of acrylamidoalkyltrialkylammonium chloride / acrylic acid copolymers and their alkali metal and ammonium salts, the acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and their alkali metal and ammonium salts and the methacroylethylbetaine / methacrylate copolymers.
  • Machine dishwashing detergents preferably contain the abovementioned cationic and / or amphoteric polymers in amounts of from 0.01 to 10% by weight, based in each case on the total weight of the automatic dishwashing detergent.
  • the bleaching agents are a substance which can be used with particular preference for washing or cleaning.
  • sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -forming peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. It is also possible to use all other inorganic or organic peroxy bleaches known to the person skilled in the art.
  • chlorine or bromine releasing substances can be used.
  • suitable chlorine or bromine releasing materials are, 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.
  • DICA dichloroisocyanuric acid
  • Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.
  • automatic dishwashing agents which contain from 1 to 35% by weight, preferably from 2.5 to 30% by weight, particularly preferably from 3.5 to 20% by weight and in particular from 5 to 15% by weight of bleaching agent, preferably sodium percarbonate , contain.
  • 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.
  • polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), are 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 preferably used.
  • TAED tetraacetylethylenediamine
  • DADHT 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine
  • TAGU tetraacet
  • bleach activators can also be used. These bleach activators are preferably used in amounts of up to 10% by weight, in particular from 0.1% by weight to 8% by weight, especially from 2 to 8% by weight and more preferably from 2 to 6% by weight, based in each case on the total weight of bleach activator-containing agents.
  • Enzymes can also be used to increase the washing or cleaning performance of automatic dishwasher detergents. These include in particular proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably mixtures thereof. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in automatic dishwasher detergents, which can be used correspondingly preferred.
  • Machine dishwashing detergents preferably contain enzymes in total amounts of from 1 ⁇ 10 -6 to 5% by weight, based on active protein. The protein concentration can be determined by known methods, for example the BCA method or the biuret method.
  • enzymatic systems comprising a peroxidase and hydrogen peroxide or a substance which produces hydrogen peroxide in water.
  • a mediator compound for the peroxidase for example an acetosyringone, a phenol derivative or a phenotiazine or phenoxazine, is preferred in this case, with the above-mentioned conventional polymeric color transfer inhibiting agents can additionally be used.
  • the enzymes can be used in any form known in the art. These include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel-form detergents, solutions of the enzymes, advantageously as concentrated as possible, sparing in water and / or added with stabilizers.
  • the enzymes may be encapsulated for both the solid and liquid dosage forms, for example by spray-drying or extruding the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer.
  • a plurality of enzymes and / or enzyme preparations preferably protease preparations and amylase preparations, in amounts of 0.1 to 5 wt .-%, preferably from 0.2 to 4.5 wt .-% and in particular from 0.4 to 4 wt .-%, each based on the total enzyme-containing agent used.
  • Glass corrosion inhibitors prevent the occurrence of haze, streaks and scratches, but also iridescence of the glass surface of machine-cleaned glasses.
  • Preferred glass corrosion inhibitors come from the group of magnesium and zinc salts and magnesium and zinc complexes.
  • the content of zinc salt in dishwasher detergents is preferably between 0.1 and 5 wt.%, Preferably between 0.2 and 4 wt.% And in particular between 0.4 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 .-%, each based on the total weight of the glass corrosion inhibitor-containing agent.
  • disintegration aids so-called tablet disintegrants
  • tablet disintegrants or disintegrants excipients which ensure the rapid disintegration of tablets in water or other media and for the rapid release of the active ingredients.
  • Desintegration aids may preferably be used in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, based in each case on the total weight of the disintegration assistant-containing agent.
  • the detergents are, for example, sodium carbonate as builder and / or the washing or cleaning-active polymers described above, preferably acrylate (co) polymers, which are commercially available, for example, under the trade name Acusol TM included.
  • the preparation of automatic dishwashing agents according to the invention can take place in different ways.
  • the agents may be in solid or liquid form as well as in a combination of solid and liquid forms. In particular, powder, Granules, extrudates, compacts, in particular tablets.
  • the liquid supply forms based on water and / or organic solvents may be thickened, in the form of gels.
  • Inventive agents can be formulated in the form of single-phase or multi-phase products.
  • automatic dishwashing detergents with one, two, three or four phases are preferred.
  • Machine dishwashing detergent characterized in that it is in the form of a prefabricated dosing unit with two or more phases, are particularly preferred.
  • the individual phases of multiphase agents may have the same or different states of matter.
  • Machine dishwashing detergents which have at least two different solid phases and / or at least two liquid phases and / or at least one solid and at least one solid phase are preferred.
  • Automatic dishwasher detergents according to the invention are preferably prefabricated to form metering units. These metering units preferably comprise the necessary for a cleaning cycle amount of washing or cleaning-active substances. Preferred metering units have a weight between 12 and 30 g, preferably between 14 and 26 g and in particular between 16 and 22 g.
  • the automatic dishwasher detergents according to the invention in particular the prefabricated metering units, have a water-soluble coating, with particular preference.
  • the present application furthermore relates to a process in which an agent of the invention, in particular a machine dishwashing detergent of the invention, is used.
  • the method may be a method for cleaning 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 start of the main wash cycle or during the main wash cycle.
  • the metering or the entry of the agent according to the invention into the interior of the dishwasher can be done manually, but preferably the agent is metered by means of the metering chamber into the interior of the dishwasher.
  • a typical framework formulation for a machine dishwashing detergent preferably used, for example in tablet form comprises the following substances: Na tripolyphosphate 20-50% by weight sodium 10-30% by weight sodium 5-18% by weight bleach 0.5-5% by weight bleach catalyst 0.01-1% by weight sulfopolymer 2.5-15% by weight polycarboxylate 0.1-10% by weight nonionic surfactant 0.5-10% by weight phosphonate 0.5-5% by weight protease 0.1-5% by weight amylase 0.1-5% by weight, the data in% by weight are based on the total agent.
  • the tripolyphosphate it is also possible in particular to use 10-50% by weight of citrate or MGDA or GLDA or EDDS or mixtures of two or three of these substances in the formulation.
  • the invention also relates to the use of the agents described herein for controlling or neutralizing bad odors in a machine dishwashing machine. These bad odors can be caused for example by non-use or storage of dirty dishes in the dishwasher.
  • the agents may be used in the context of such use according to their nature. For example, automatic dishwashing detergents and rinse aids are used in normal rinsing operation. Conditioners are also used in normal spills or idle, i. Spü conceptionn used without (dirty) dishes. Dishwasher perfume compositions may also be used with the means mentioned in the normal rinse cycles.
  • the compounds described herein are preferably characterized by the fact that over a relatively long period of time, usually over a period of days or weeks, the fragrances are released and, as a result, the malodor is / are continuously counteracted / neutralized.
  • the invention also relates to the use of an oxazolidine precursor compound of a fragrance, in particular a fragrance aldehyde or ketone, described herein for controlling or neutralizing malodors in a machine dishwashing machine.
  • test compositions according to the invention mediated a longer-lasting fragrance and reduced the bad odors more than the compositions without the invention

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  • Chemical & Material Sciences (AREA)
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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Fats And Perfumes (AREA)
  • Detergent Compositions (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
EP14808657.2A 2013-12-13 2014-12-08 Maschinelle geschirrspülmittel enthaltend oxazolidin-riechstoffvorläufer Active EP3080238B1 (de)

Priority Applications (1)

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PL14808657T PL3080238T3 (pl) 2013-12-13 2014-12-08 Środki do maszynowego mycia naczyń zawierające oksazolidynowe prekursory substancji pachnących

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DE102013225941.7A DE102013225941A1 (de) 2013-12-13 2013-12-13 Maschinelle Geschirrspülmittel enthaltend Oxazolidin-Riechstoffvorläufer
PCT/EP2014/076876 WO2015086522A1 (de) 2013-12-13 2014-12-08 Maschinelle geschirrspülmittel enthaltend oxazolidin-riechstoffvorläufer

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EP1123282A2 (en) * 1998-10-23 2001-08-16 The Procter & Gamble Company Fragrance pro-accords and aldehyde and ketone fragrance libraries
US6861402B1 (en) * 1999-06-01 2005-03-01 The Procter & Gamble Company Pro-fragrances
US20030158079A1 (en) 2001-10-19 2003-08-21 The Procter & Gamble Company Controlled benefit agent delivery system
DE102006060943A1 (de) * 2006-12-20 2008-06-26 Henkel Kgaa 1-Aza-3,7-dioxabicyclo[3.3.0]octan-Verbindungen und monocyclische Oxazolidine als Pro-Fragrances
DE102009026856A1 (de) * 2009-06-09 2010-12-16 Henkel Ag & Co. Kgaa Verfahren zur Verminderung von Schlechtgerüchen
DE102011081871A1 (de) * 2011-08-31 2013-02-28 Henkel Ag & Co. Kgaa Oxazolidine zur Fehlgeruchsbekämpfung

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DE102013225941A1 (de) 2015-06-18

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