EP3080238A1 - Produit de lavage pour lave-vaisselle contenant des précurseurs de substances odorantes à base d'oxazolidine - Google Patents

Produit de lavage pour lave-vaisselle contenant des précurseurs de substances odorantes à base d'oxazolidine

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Publication number
EP3080238A1
EP3080238A1 EP14808657.2A EP14808657A EP3080238A1 EP 3080238 A1 EP3080238 A1 EP 3080238A1 EP 14808657 A EP14808657 A EP 14808657A EP 3080238 A1 EP3080238 A1 EP 3080238A1
Authority
EP
European Patent Office
Prior art keywords
unsubstituted
substituted
methyl
branched
linear
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.)
Granted
Application number
EP14808657.2A
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German (de)
English (en)
Other versions
EP3080238B1 (fr
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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Priority to PL14808657T priority Critical patent/PL3080238T3/pl
Publication of EP3080238A1 publication Critical patent/EP3080238A1/fr
Application granted granted Critical
Publication of EP3080238B1 publication Critical patent/EP3080238B1/fr
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Anticipated expiration legal-status Critical

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/50—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 fragrance precursors in the form of
  • Dishwashing machines in particular being dishwashing detergents containing these oxazolidine fragrance precursors, the dishwashing detergents themselves, and a machine dishwashing process using these dishwashing detergents.
  • 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 provide unpleasant odors in the course of automatic dishwashing and, in particular, during prolonged non-use of the dishwasher
  • Dishwasher and / or storage of dirty dishes in their interior arise, cover and thereby reduce or even neutralize completely.
  • 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 compositions for use in an automatic dishwashing machine characterized in that they contain at least one oxazolidine precursor compound of a fragrance, in particular a fragrance aldehyde or ketone.
  • Another aspect of the invention is directed to the use of such an agent for controlling or neutralizing bad odors in a machine
  • Dishwasher 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, in particular a fragrance aldehyde or ketone, for controlling or
  • nonionic surfactant ", based on the total amount of nonionic surfactants contained in the middle.
  • 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 components of those described herein
  • At least one nonionic surfactant means one or more different nonionic surfactants, ie, one or more different types of nonionic surfactants the quantities given to the total amount of the corresponding designated type of ingredient, as already defined above.
  • Preferred oxazolidine precursors capable of liberating a fragrance aldehyde or fragrance ketone by hydrolysis include compounds of the formula
  • R is selected from substituted or unsubstituted, branched or linear Ce-24 alk (en) yl, substituted or unsubstituted Ce-24 cycloalk (en) yl, substituted or unsubstituted Ce-24 (hetero) aryl and substituted or unsubstituted Ce-24 heterocyclyl;
  • R is selected from H, substituted or unsubstituted, branched or linear C 1-10 alkyl, substituted or unsubstituted, branched or linear C 2-10 alkenyl, substituted or unsubstituted C 3-15 cycloalk (en) yl, substituted or unsubstituted Ce-is (hetero) aryl and substituted or unsubstituted Ce-24 heterocyclyl, or
  • R and R together with the carbon atom to which they are attached form a 3- to 10-membered substituted or unsubstituted cycloalk (en) yl or heterocyclyl ring or a 5-10 membered (hetero) aryl ring;
  • R 2 , R 3 , R 4 , R 5 and R 6 are independently selected from H, substituted or unsubstituted, branched or linear C 1-10 alkyl, substituted or unsubstituted, branched or linear C 2-10 alkenyl, substituted or unsubstituted C 3-6 alkyl, 15 Cycloalk (en) yl, substituted or unsubstituted Ce-is (hetero) aryl, substituted or unsubstituted Ce-24 heterocyclyl, -OH, - (CH 2 ) x COR 7 , and - (CR 0 R) y (CHR 2 CHR 3 O) z R 14 , or
  • R 2 , R 3 , R 4 , R 5 and R 6 together with the carbon atom (s) to which they are attached are a 3- to 10-membered substituted or unsubstituted cycloalk (en) yl or heterocyclyl ring or a 5-10 membered (hetero) aryl ring, or R 2 and R 3 or R 4 and R 5 together form a carbonyl group;
  • R 7 is selected from -OH, -OR 8 , -N (R 9 ) 2, substituted or unsubstituted, branched or linear C 1-22 alkyl, substituted or unsubstituted, branched or linear C 2-22 alkenyl, substituted or unsubstituted C 3-22 Cycloalk (en) yl, substituted or
  • R 8 is selected from H, substituted or unsubstituted, branched or linear C 1-15 alkyl, substituted or unsubstituted, branched or linear C 2-22 alkenyl, and M, wherein M is a water-soluble cation;
  • R is selected from H and substituted or unsubstituted, branched or linear C1 is selected 9 6 alkyl;
  • R 0 , R and R 2 are independently selected from H, -OH and C 1-4 alkyl; or R 0 and R together with the carbon atom to which they are attached form a 3- to 10-membered substituted or unsubstituted cycloalk (en) yl or heterocyclyl ring, a 5-10 membered one
  • R 3 and R 4 are independently selected from H and C 1-4 alkyl
  • x is an integer from 0 to 22;
  • y is an integer from 1 to 10;
  • z is an integer from 1 to 50.
  • R is selected from substituted or unsubstituted, branched or linear Ce-24 alk (en) yl, substituted or unsubstituted Ce-24 cycloalk (en) yl, substituted or unsubstituted Ce-24 (hetero) aryl and substituted or unsubstituted Ce-24 heterocyclyl;
  • R is selected from H, substituted or unsubstituted, branched or linear C3-10 alkyl, substituted or unsubstituted, branched or linear C4-10 alkenyl, substituted or unsubstituted C3-15 cycloalk (en) yl, substituted or unsubstituted Ce-is (hetero -) aryl and substituted or unsubstituted Ce-24 heterocyclyl, or
  • R and R together with the carbon atom to which they are attached form a 3- to 10-membered substituted or unsubstituted cycloalk (en) yl or heterocyclyl ring or a 5-10 membered (hetero) aryl ring;
  • R 2 , R 3 , R 4 , R 5 and R 6 are independently selected from H, substituted or unsubstituted, branched or linear C 3-10 alkyl, substituted or unsubstituted, branched or linear C 4-10 alkenyl, substituted or unsubstituted C 3-10 alkyl, 15 Cycloalk (en) yl, substituted or unsubstituted Ce-is (hetero) aryl, substituted or unsubstituted Ce-24 heterocyclyl, -OH, - (CH 2 ) x COR 7 , and - (CR 0 R) y (CHR 2 CHR 3 O) z R 14 , or
  • R 2 , R 3 , R 4 , R 5 and R 6 together with the carbon atom (s) to which they are attached are a 3- to 10-membered substituted or unsubstituted cycloalk (en) yl or heterocyclyl ring or a 5-10 membered (hetero) aryl ring, or R 2 and R 3 or R 4 and R 5 together form a carbonyl group;
  • R 7 is selected from -OH, -OR 8 , -N (R 9 ) 2, substituted or unsubstituted, branched or linear C 3-22 alkyl, substituted or unsubstituted, branched or linear C 4-22 alkenyl, substituted or unsubstituted C 3-22 Cycloalk (en) yl, substituted or
  • R 8 is selected from H, substituted or unsubstituted, branched or linear C 3-15 alkyl, substituted or unsubstituted, branched or linear C 4-22 alkenyl, and M, wherein M is a water-soluble cation;
  • R is selected from H and substituted or unsubstituted, branched or linear C3 is selected 9 6 alkyl;
  • R 0 , R and R 2 are independently selected from H, -OH and C 1-4 alkyl; or R 0 and R together with the carbon atom to which they are attached form a 3- to 10-membered substituted or unsubstituted cycloalk (en) yl or heterocyclyl ring, a 5-10 membered one
  • R 3 and R 4 are independently selected from H and C 1-4 alkyl
  • x is an integer from 0 to 22;
  • y is an integer from 1 to 10;
  • z is an integer from 1 to 50.
  • substituted as used herein in connection with the definition of the oxazolidine compounds means that one hydrogen atom is replaced by another group Suitable groups include, but are not limited to, linear or branched C1-22
  • Hydrocarbon groups including alkyl, alkenyl, alkynyl (the latter 2-22
  • Heterocyclyl refers to heteroalicyclic compounds containing one or more
  • Double bonds and one or more hetero ring atoms, in particular O, N or S, may contain, but are not aromatic compounds.
  • (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 2 and / or R 3 and / or R 4 are hydrogen or C 1-6 alkyl, preferably hydrogen; and or
  • R 5 is an alkyl radical, in particular methyl, ethyl or hydroxymethyl
  • R 6 is hydrogen or together with R 5 forms a ring, in particular one
  • R is H and R is a group represented by the formula
  • R and R are not hydrogen, but radicals represented by the formula
  • oxazolidine precursors described herein are, in particular, reaction products of a fragrance aldehyde or ketone of the formula: wherein R and R are as defined above and further provided that in the fragrance aldehydes is RH and in the fragrance ketones R is not H, with a ⁇ -aminoalcohol of the formula:
  • R 3 -R 6 are as defined above.
  • the fragrance can be released again by hydrolysis.
  • the conditions for the release are the typical ones
  • 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, 2,
  • Preferred aldehydes include, without limitation, lilial, helional, anisaldehyde,
  • Cyclamenaldehyde Triplal, Melonal, Methylundecanal, Undecanal, Nonanal and Octanal.
  • Suitable ketones include, but are not limited to, methyl-beta-naphthyl ketone, muskedanone-1-one (2,3,3,6,6-hexahydro-1,1,3,3,3-pentamethyl-4H-inden-4-one). , Tartalide (6-acetyl-1,1,1,4,4,7-hexamethyltetralin), alpha-damascone, beta-damascone, delta-damascone, iso-damascone, damascenone, methyldihydrojasmonate, menthone, carvone, camphor, koavon
  • fragrance aldehydes and / or fragrance ketones basically all the usual fragrance aldehydes and / or fragrance ketones can be used, which are used in particular for bringing about a pleasant sense of smell in humans.
  • perfume aldehydes and / or perfume ketones are known to the person skilled in the art and are also described in the patent literature, for example in US 2003/0158079 A1, paragraphs [0154] and [0155].
  • suitable fragrances see 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.
  • oxazolidine precursors described above are preferably used in the compositions according to the invention as mixtures with at least one further perfume.
  • fragrances which may optionally be included in the compositions are not particularly limited.
  • individual fragrance compounds of natural or synthetic origin e.g. of the type of esters, ethers, aldehydes, ketones, alcohols and hydrocarbons. Fragrance compounds of the ester type are known e.g.
  • DMBCA Dimethylbenzylcarbinylacetate
  • phenylethylacetate benzylacetate
  • the ethers include, for example, benzyl ethyl ether and ambroxane, to the aldehydes the above-mentioned e.g. the linear alkanals having 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde (3- (4-propan-2-ylphenyl) butanal), lilial and bourgeonal, to the ketones e.g.
  • the hydrocarbons mainly include terpenes such as limonene and pinene.
  • terpenes such as limonene and pinene.
  • mixtures of different fragrances are used, which together produce an attractive fragrance.
  • compositions of this invention may also contain natural fragrance mixtures such as are available from vegetable sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are Muskateller sage oil, camomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, lime blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and
  • 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,
  • Salicylic acid isoamyl ester, salicylic acid methyl ester, salicylic acid hexyl ester,
  • Salicylic acid cyclohexyl esters, santalol, sandelice, skatole, terpineol, thymes, thymol, troenan, ⁇ -undelactone, vanillin, veratrumaldehyde, cinnamaldehyde, cinnamyl alcohol, cinnamic acid, cinnamic acid ethyl ester, cinnamic acid benzyl ester, diphenyloxide, limonene, linalool, linalyl acetate and propionate, melusate, menthol, menthone , Methyl-n-heptenone, pinene, phenylacetaldehyde, terpinyl acetate, citral, citronellal and mixtures thereof.
  • the oxazolidine fragrance precursors be used with the corresponding aldehydes and / or ketones.
  • such compositions are characterized in that the molar ratio of perfume aldehyde and / or perfume 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, even more advantageously 2: 1 to 1: 2 and in particular 1, 2: 1 to 1: 1, 2.
  • 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.
  • 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 musks, 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 adjuvants are e.g. Complexing agent.
  • the agents of the invention may be, for example, automatic dishwashing detergents, automatic dishwashing detergents, rinse aids or
  • Perfume compositions for automatic dishwashers act.
  • 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 Perfume precursor which is capable of releasing the same perfume aldehyde or fragrance ketone and which satisfies the above formula. "Substantially” means that these agents are>
  • 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.
  • agents described herein may include 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, especially from 0.01 to 25% by weight, more preferably from 0.01 to 10% by weight.
  • 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 dishwashing agents, can be solid or liquid in nature and, in particular, as powdered solids, in a recompressed state
  • the means in particular the automatic dishwashing detergent, in a pre-portioned form.
  • such a composition has several spatially separate compositions, whereby it is possible to separate incompatible ingredients, or
  • At least one of the compositions is solid and / or at least one of the compositions is liquid, wherein 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.
  • 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).
  • crystalline layer silicates with the formula NaMSix02x + i ⁇ H2O y, in which x stands for 2 h.
  • 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
  • Machine dishwashing detergents preferably contain a weight proportion of crystalline layered silicate of formula NaMSix02x + i y ⁇ H2O of 0.1 to 20 wt .-%, preferably from 0.2 to 15 wt .-% and in particular from 0.4 to 10 wt. -%, in each case based on the total weight of these funds.
  • amorphous sodium silicates having a modulus Na 2 O: SiO 2 of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which are preferably delayed in dissolution and secondary wash 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.
  • Alkalimetallphosphate is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids in which one
  • Metaphosphoric acids (HP03) n and orthophosphoric acid H3PO4 can distinguish 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 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 examples of alkali carriers.
  • alkali metal carbonates in particular sodium carbonate, sodium bicarbonate or sodium sesquicarbonate
  • 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 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 automatic dishwashing detergent.
  • citric acid here are citric acid,
  • Succinic acid glutaric acid, adipic acid, gluconic acid and any mixtures thereof.
  • citric acid and / or citrates in these compositions has proved to be particularly advantageous for the cleaning and rinsing performance of agents according to the invention. Therefore, according to the invention, preference is given to automatic dishwasher detergents, characterized in that the automatic dishwashing agent contains citric acid or a salt of citric acid and the weight proportion of citric acid or of the salt of citric acid is preferably more than 10% by weight, preferably more than 15% by weight and in particular between 20 and 40 wt .-% is.
  • phosphate-free builders are aminocarboxylic acid and / or its salts. Particularly preferred members of this class are
  • Methylglycinediacetic acid or its salts and glutamic diacetic acid (GLDA) or its salts or ethylenediaminediacetic acid or its salts (EDDS). The content of these
  • Aminocarboxylic acids or their salts may, for example, between 0, 1 and 15 wt .-%, preferably between 0.5 and 10 wt .-% and in particular between 0.5 and 6 wt .-% make up.
  • Aminocarboxylic acids and their salts can be used together with the abovementioned builders, in particular also with the phosphate-free builders.
  • Other suitable builders are polymeric polycarboxylates, for example the Alka II metal salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular mass of 500 to 70,000 g / mol.
  • Suitable polymers are, in particular, polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may again be preferred from this group.
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Their relative molecular weight, based on free acids is generally from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.
  • the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution.
  • the content of automatic dishwashing detergents on (co) polymers can be used either as a powder or as an aqueous solution.
  • Polycarboxylates is preferably 0.5 to 20 wt .-% and in particular 3 to 10 wt .-%.
  • the polymers may also contain allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid as a monomer.
  • copolymers are those which are used as monomers acrolein and
  • Acrylic acid / acrylic acid salts or acrolein and vinyl acetate 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 an arbitrary 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 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.
  • Preferred ethoxylated alcohols include, for example Ci2-i4-alcohols with 3 EO or 4 EO, C9-n-alcohol with 7 EO, Ci3-is alcohols containing 3 EO, 5 EO, 7 EO or 8 EO, C 2 -i8 Alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of Ci2-i4-alcohol with 3 EO and Ci2-is-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 rank ethoxylates, NRE).
  • NRE narrow rank ethoxylates
  • 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
  • Nonionic surfactant (s) having a melting point above 20 ° C, preferably above 25 ° C, more preferably between 25 and 60 ° C and in particular between 26.6 and 43.3 ° C, is / are particularly preferred.
  • 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.
  • cationic active substances for example, cationic compounds of the following formulas can be used:
  • 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. %. Machinery
  • 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.
  • cationic, anionic and amphoteric polymers can be used in machine dishwashing detergents in addition to nonionic polymers.
  • “Cationic polymers” for the purposes of the present invention 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 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 dialkylaminoacrylate and methacrylate, the vinylpyrrolidone-methoimidazolinium chloride Copolymers, the quaternized polyvinyl alcohols or the INCI names
  • Polyquaternium 2 Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27 indicated 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.
  • the polymers are in prefabricated form.
  • For the preparation of the polymers is suitable inter alia
  • 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.
  • 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. In the context of the present application, however, preference is given to those automatic dishwashing detergents in which the
  • Weight fraction of the cationic and / or amphoteric polymers between 0.01 and 8 wt .-%, preferably between 0.01 and 6 wt .-%, preferably between 0.01 and 4 wt .-%, particularly preferably between 0.01 and 2 wt .-% and in particular between 0.01 and 1 wt .-%, each based on the total weight of the automatic dishwashing detergent, is.
  • 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.
  • Further bleaches which can be used are, for example, peroxypyrophosphates, citrate perhydrates and peroxygenic salts or peracids yielding H2O2, such as perbenzoates.
  • bleaching agent As a bleaching agent and chlorine or bromine releasing substances can be used. Examples of suitable chlorine or bromine releasing materials
  • heterocyclic N-bromo- and N-chloroamides for example trichloroisocyanuric acid
  • Hydantoin compounds, such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.
  • automatic dishwashing agents are preferred 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.
  • acylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT) 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
  • Glycolurils in particular tetraacety
  • bleach activators can also be used. These bleach activators are preferably used in amounts of up to 10% by weight, in particular 0.1% 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.
  • Dishwashing agents are also enzymes used. These include in particular proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably mixtures thereof. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in automatic dishwasher detergents, which can be used correspondingly preferred. Automatic dishwashing agents preferably contain enzymes in total amounts of 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 gives off 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 with a water, air and / or
  • Chemical-impermeable protective layer is coated.
  • a plurality of enzymes and / or enzyme preparations preferably protease preparations and amylase preparations, in amounts of from 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 to 5% by weight, preferably between 0.2 to 4% by weight and in particular between 0.4 and 3% by weight
  • 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
  • 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 of cleaning dishes in one
  • Dishwasher act in which the inventive agent during the
  • a typical framework formulation for a machine dishwashing detergent preferably used, for example in tablet form, comprises the following substances:
  • Polycarboxylate 0, 1-10% by weight
  • Nonionic surfactant 0.5-10% by weight
  • the data in% by weight are based on the total agent.
  • the or a part of 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. So are automatic dishwashing detergents and
  • Rinse aid used in normal rinsing operation. Care products are also in normal
  • 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 one described herein
  • An oxazolidine precursor compound of a fragrance in particular a fragrance aldehyde or ketone, for controlling or neutralizing malodors in a machine dishwashing machine.
  • a fragrance in particular a fragrance aldehyde or ketone
  • all embodiments disclosed in connection with the means of the invention are also applicable to the described methods and uses and vice versa.
  • all of the specific oxazolidine fragrance precursors described herein in connection with the agents of the present invention are useful in the foregoing processes and are useful in the control of
  • Detergent mixture for the bad odor test contained:
  • Harzer cheese (Loose).
  • 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)
  • 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)
  • 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)

Abstract

La présente invention concerne l'utilisation de précurseurs de substances odorantes à base d'oxazolidine pour éviter et/ou combattre les mauvaises odeurs dans les lave-vaisselle, en particulier sous forme de produits de lavage de vaisselle contenant ces précurseurs de substances odorantes à base d'oxazolidine. L'invention concerne en outre des produits, destinés à être utilisés dans des lave-vaisselle, qui contiennent ces composés d'oxazolidone, ainsi que des procédés de lavage de vaisselle en machine utilisant ces produits.
EP14808657.2A 2013-12-13 2014-12-08 Produit de lavage pour lave-vaisselle contenant des précurseurs de substances odorantes à base d'oxazolidine Active EP3080238B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL14808657T PL3080238T3 (pl) 2013-12-13 2014-12-08 Środki do maszynowego mycia naczyń zawierające oksazolidynowe prekursory substancji pachnących

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102013225941.7A DE102013225941A1 (de) 2013-12-13 2013-12-13 Maschinelle Geschirrspülmittel enthaltend Oxazolidin-Riechstoffvorläufer
PCT/EP2014/076876 WO2015086522A1 (fr) 2013-12-13 2014-12-08 Produit de lavage pour lave-vaisselle contenant des précurseurs de substances odorantes à base d'oxazolidine

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EP3080238A1 true EP3080238A1 (fr) 2016-10-19
EP3080238B1 EP3080238B1 (fr) 2018-02-28

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EP (1) EP3080238B1 (fr)
DE (1) DE102013225941A1 (fr)
ES (1) ES2668370T3 (fr)
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WO (1) WO2015086522A1 (fr)

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US20220002637A1 (en) * 2018-12-17 2022-01-06 Givaudan Sa A method of countering malodour in a washing machine comprising the addition of a fragrance precursor

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EP1123282A2 (fr) * 1998-10-23 2001-08-16 The Procter & Gamble Company Precurseurs d'accords de parfum et bibliotheques de parfums a base d'aldehyde et de cetone
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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PL3080238T3 (pl) 2018-08-31
DE102013225941A1 (de) 2015-06-18
WO2015086522A1 (fr) 2015-06-18
EP3080238B1 (fr) 2018-02-28

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