EP3440176A1

EP3440176A1 - Dishwashing detergent containing urea derivatives

Info

Publication number: EP3440176A1
Application number: EP17713658.7A
Authority: EP
Inventors: Inga Kerstin Vockenroth; Doris Dahlmann; Thomas Weber; Claudia Ottow
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 2016-04-04
Filing date: 2017-03-27
Publication date: 2019-02-13
Also published as: WO2017174384A1; DE102016205489A1

Abstract

The invention relates to a dishwashing detergent, in particular a dishwashing detergent for a dishwasher, having an improved rinsing power and containing, based on the total weight of the dishwashing detergent, 0.1 to 5.0 wt.% of at least one urea derivative as defined here, and to the use thereof in a dishwashing method. In formula (I), • each R₁ represents H or a linear or branched, saturated or mono- or polyunsaturated hydrocarbon group with 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms; • each alk independently of one another represents a linear or branched alkyl group with 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms; • A represents a chemical bond or a bivalent hydrocarbon group with 1 to 30 carbon atoms, preferably 4 to 22 carbon atoms; and • each ------ represents a single or double bond, wherein preferably all ------ represent a single or double bond, in particular a double bond.

Description

Dishwashing detergent containing urea derivatives

The present invention relates to dishwashing detergent with improved rinse performance, the

Use of these dishwashing detergents and a method of automatic dishwashing using these dishwashing detergents.

Machine-washed dishes are often subject to more stringent requirements today than manually-washed dishes. So even a completely cleaned of leftovers dishes is then rated as not flawless if it has after dishwasher washing whitish, based on water hardness or other mineral salts stains that come from lack of wetting agent from dried water droplets. Such staining and streaking is in principle observable on surfaces of all kinds (porcelain, glass, plastic, stainless steel), but especially on glass surfaces. This harness is the consumer - often by hand - post-treated, which is not very user-friendly. Therefore, there is a need for automatic dishwashing agents that reduce the formation of so-called spotting and filming stains and deposits.

To obtain glossy and spotless dishes are used in dishwashing formulations

Used rinse agent agents. Through a mediated by these agents film formation on the dishes, the water should run as completely as possible from the dishes, so that the surfaces are residue-free and flawless gloss at the end of the wash program. Although the use of such rinse aids is known in the art, there is still a need for

Dishwashing agents that show improved rinse performance.

The object underlying the present invention was therefore to a

To provide dishwashing detergent with improved rinse performance.

It has now surprisingly been found that the invention used

Substituted urea derivatives bring about improved film formation on Spülgutoberflächen, whereby the water can run off the dishes in a thin, coherent film, so that remain in the subsequent drying process, no water droplets, stripes or films. As a result, the formation of streaks on items to be washed, in particular glass, is suppressed and the drying and rinsing performance is significantly improved, even with low-temperature cleaning cycles (<50 ° C). A first aspect of the present invention therefore relates to a dishwashing detergent, in particular a machine dishwashing detergent, containing, based on the total weight of the

Dishwashing agent, 0, 1 to 5.0 wt .-%, preferably 1, 0 to 2.0 wt .-% of at least one compound of formula (I):

in which

each R is H or a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having from 1 to 10 carbon atoms, preferably from 1 to 6 carbon atoms, more preferably from 1 to 4 carbon atoms;

each Alk independently represents a linear or branched alkyl group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms;

A for a chemical bond or a bivalent hydrocarbon radical having 1 to 30

Carbon atoms, preferably 4 to 22 carbon atoms; and

each represents a single or double bond, wherein preferably all are a single or all a double bond, in particular all are a double bond.

Likewise provided by the present invention is the use of a dishwashing agent according to the invention in a machine dishwashing process, in particular the use for improving the rinsing performance when cleaning dishes in an automatic dishwashing machine.

Yet another object of the invention is a machine dishwashing process in which a dishwasher detergent according to the invention is used, in particular for the purpose of improving the rinse performance.

Finally, the use of the compounds used according to the invention for improving the rinsing performance of a machine dishwashing detergent is also the subject of the present invention.

These and other aspects, features, and advantages of the invention will become apparent to those skilled in the art from a study of the following detailed description and claims. Any feature of one aspect of the invention may be employed in any other aspect of the invention. Further, it is to be understood that the examples contained herein are the invention describe and illustrate, but not limit, and in particular the invention is not limited to these examples. Numeric ranges specified in the format "from x to y" include the above values.If multiple preferred numeric ranges are specified in this format, it is understood that all ranges resulting from the combination of the various endpoints, also be recorded.

"At least one" as used herein means 1 or more, ie 1, 2, 3, 4, 5, 6, 7, 8, 9 or more. With respect to an ingredient, the indication refers to the kind of the ingredient and not to the absolute number of molecules. "At least one nonionic surfactant" thus means, for example, at least one type of nonionic surfactant, ie that kind of

nonionic surfactant or a mixture of several different nonionic surfactants. The term, together with weights, refers to all compounds of the type indicated which are included in the composition / mixture, i. that the

Composition beyond the specified amount of the corresponding compounds addition no further compounds of this kind.

"Phosphate-free" as used herein means that the composition in question is substantially free of phosphates, ie, in particular, contains phosphates in amounts less than 1% by weight, preferably less than 0.1% by weight, based on the total composition. Accordingly, as used herein, "free of" means that the respective fabric is present in amounts less than 1% by weight, preferably less than 0.1% by weight, more preferably less than 0.01% by weight of the Total composition is included. In particular, this also means that the corresponding substance is not deliberately added.

All percentages given in connection with the compositions described herein, unless explicitly stated otherwise, relate to% by weight, in each case based on the composition in question.

"Approximately" or "ca." As used herein in connection with a numerical value refers to the numerical value ± 10%, preferably ± 5%.

Whenever alkaline earth metals are referred to below as counterions for monovalent anions, this means that the alkaline earth metal is present only in half - as sufficient to charge balance - amount of substance as the anion.

The dishwashing compositions of the invention contain a urea compound of the formula (I) as defined above. In various embodiments, the compound of the formula (I) comprises several, in particular 2, 3 or 4, substituents R, which are each bonded directly to the ring. In this case, each R independently for a linear or branched, saturated or on or

polyunsaturated hydrocarbon radical having 1 to 10 carbon atoms, preferably having 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms.

In various embodiments, R is an alkyl radical, alkenyl radical, alkynyl radical, aryl radical or alkylaryl radical, preferably a linear or branched C1-10 alkyl radical, in particular a methyl, ethyl, propyl or butyl radical. As used herein, "propyl radicals" include 1-propyl and 2-propyl radicals. Also, the term "butyl radical" as used herein includes n-butyl, 2-butyl and tert-butyl radicals. If only one radical R is contained, it is preferably in ortho or para position to the urea radical, preferably in the ortho position.

In the compounds of formula (I), each "alk" independently represents a linear or branched alkyl group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, but especially methyl, ethyl or propyl In preferred embodiments, the alk is methyl or ethyl. In various embodiments, the two may be attached to a common nitrogen atom

For example, both radicals Alk may be methyl radicals, both may be ethyl radicals or one may be a methyl radical and the other may be an ethyl radical or propyl radical.

In the compounds of the formula (I), A is a chemical bond or a bivalent hydrocarbon radical having 1 to 30 carbon atoms, preferably 4 to 22 carbon atoms, in particular an alkylaryl radical or an alkylcycloalk (en) yl radical. In various preferred embodiments, A is a chemical bond such that the second urea moiety is also directly attached to the ring. In such cases, the two urea radicals are preferably in meta position to each other. In other embodiments, A is an alkylaryl radical, in particular a benzyl radical (phenylmethyl radical) which is substituted by the urea group of the formula -NH-C (O) -N (Alk) 2. In such cases, the alkylaryl group is preferably ortho or para to the urea group at the central ring of the compound of formula (I). The

Urea group of the formula -NH-C (O) -N (Alk) 2 with which this alkylaryl radical is substituted replaces a hydrogen atom of the aryl radical and is preferably in ortho or para position to the bridging alkyl radical. In various embodiments, each represents a single or double bond. It is preferred that either all are a single or all double bond, in particular all are a double bond.

In various embodiments of the invention, the urea compounds are those of the formula (II)

(Alk) ₂ N ^ ON (Alk) ₂ (ii)

Here, R, Alk and are as defined above. In particular, R is methyl or ethyl, in particular methyl. Each alk is also preferably methyl, ethyl or propyl, more preferably all the radicals are alk methyl or all are ethyl, especially all are methyl. All are preferably double bonds, so that the ring is an aromatic ring. Preferred compounds of formula (II) include, but are not limited to, 3,3 '- (4-methyl-1, 3-phenylene) bis (1, 1-dimethylurea), 3,3' - (4-methyl -1, 3-phenylene) bis (1,1-diethylurea), 3,3 '- (4-methyl-1, 3-phenylene) bis (1,1-dipropylurea) and 3,3' - (4-methyl -1, 3-phenylene) bis (1-ethyl-1-methylurea). Such compounds are known as curing accelerators for epoxy resins and are commercially available, for example under the trade name Dyhard® UR500 (3,3 '- (4-methyl-1, 3-phenylene) bis (1, 1-dimethylurea), AlzChem AG, DE). ,

In other embodiments, the urea compounds used according to the invention are those of the formula (III)

Here, R, Alk and are as defined above. R ² is defined as R, ie each R ² is H or a linear or branched, saturated or mono- or polysubstituted

unsaturated hydrocarbon radical having 1 to 10 carbon atoms, preferably having 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms. In different

In embodiments, the compound of formula (III) comprises several, i. 2, 3 or 4,

Substituents R ² , which are each bonded directly to the ring. In this case, each R ^{2 can} independently be a linear or branched, saturated or mono- or polyunsaturated Hydrocarbon radical having 1 to 10 carbon atoms, preferably 1 to 6

Carbon atoms, more preferably 1 to 4 carbon atoms.

In various embodiments, R ^{2 is} an alkyl radical, alkenyl radical or alkynyl radical, preferably a linear or branched C 1-10 alkyl radical, in particular a methyl, ethyl, propyl or butyl radical. If only one radical R ^{2 is} included, it is preferably in the ortho or para position to the methylene group connecting the rings, preferably in the ortho position.

In preferred embodiments of the compounds of the formula (III), however, R and / or R ^{2 are} hydrogen, in particular both are hydrogen. In such compounds, each alk is preferably methyl, ethyl or propyl, more preferably all alk are methyl or all are ethyl, especially all are methyl. All ^ zzz, ie in both rings are preferred

Double bonds, so that both rings are aromatic rings, or all are

Single bonds, so that both rings are cyclohexyl rings.

Preferred compounds of formula (III) include, but are not limited to, urons derived from the methylene di (phenyl isocyanate) s, such as (1, 1 '-methylenediphenylene) bis (3,3-dimethylurea) (= 4 , 4'-diphenylmethane-bis (3,3-dimethylurea)), 2,2'-diphenylmethane-bis (3,3-dimethylurea), 2,4'-diphenylmethane-bis (3,3-dimethylurea), 4, 4'-diphenylmethane-bis (3,3-diethylurea)), 2,2'-diphenylmethane-bis (3,3-diethylurea) and 2,4'-diphenylmethane-bis (3,3-diethylurea), as well as derivatives thereof where the urea groups are substituted with other combinations of methyl, ethyl or propyl groups. Such

Compounds are also known as curing accelerators for epoxy resins.

The urea derivatives described above are present in the dishwashing detergents preferably in amounts of from 0.1 to 5% by weight, based on the total weight of the dishwashing detergent, in particular from 1.0 to 2.0% by weight. The dishwashing compositions of the invention may also contain combinations of several of the urea compounds described above.

In addition to the urea derivatives, the dishwashing detergent preferably contains at least one surfactant, in particular a rinse aid surfactant.

Low-foaming nonionic surfactants are preferably used, in particular alkoxylated, especially ethoxylated, low-foaming nonionic surfactants. With particular preference, the automatic dishwashing detergents contain nonionic surfactants from the group of the alkoxylated alcohols. Particular preference is given to nonionic surfactants which have a melting point above room temperature. Nonionic (s) surfactants having a melting point above 20 ° C, preferably above 25 ° C, more preferably between 25 and 60 ° C and especially between 26.6 and 43.3 ° C, is / are particularly preferred.

Preferably used surfactants come from the groups of alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures of these surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants). Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.

Particularly preferred nonionic surfactants are those of the formula

R ³ 0 [CH ₂ CH ₂ 0] x CH ₂ CH (OH) R ⁴ , in addition to a radical R ³ , which is linear or branched, saturated or mono- or polyunsaturated, hydrocarbon radicals having 2 to 30 carbon atoms, preferably with 4 to 22 carbon atoms, more preferably 8 to 10 carbon atoms, furthermore have a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical R ⁴ having 1 to 30 carbon atoms, where x is from 1 to 90, preferably from 10 to 60 and especially for values of 15 to 40 stands.

The hydrocarbon radicals R ³ and / or R ⁴ are preferably aliphatic

Hydrocarbon radicals, in particular linear or branched alkyl radicals. R ³ is thus

preferably an alkyl radical having 2 to 30 carbon atoms, preferably 4 to 22

Carbon atoms, more preferably 8 to 10 carbon atoms, or a mixture of such radicals, and R ⁴ is preferably an alkyl radical of 1 to 30 carbon atoms, preferably 2 to 20 carbon atoms, more preferably 6 to 12 carbon atoms. In particularly preferred embodiments, R ^{4 is} an alkyl group having 8 carbon atoms and thus forms an etherified with the ethylene oxide 2-hydroxydecyl.

The group of these nonionic surfactants include, for example, the C4-22 fatty alcohol (EO) io-so-2-hydroxyalkyl ethers, in particular also the C8-12 fatty alcohol (EO) 22-2-hydroxydecyl ethers and the C4-22 fatty alcohol (EO) 4o 8o-2-hydroxyalkyl ethers. Most preferably, this nonionic surfactant (i) is a C8-12 fatty alcohol (EO) 22-2-hydroxydecyl ether. "EO" in this context means "ethylene oxide", ie a group of formula (CH2CH2O). Such surfactants are preferably used in amounts of 1 to 10 wt .-%, preferably 2 to 5 wt .-% based on the total weight of the dishwashing detergent.

In various embodiments, the mass ratio of the used

Urea derivatives of the formulas (I), (II) or (III) to the nonionic surfactants described above 1: 4 to 4: 1, in particular 1: 1 to 1: 4. In preferred embodiments, the amount of urea derivatives used is about 0.8 to 1.5% by weight and the amount of rinse aid surfactants used as defined above is 2.4 to 4.5% by weight, based in each case on the total weight of the dishwashing detergent. The amounts of surfactant and urea derivative used per application can be, for example, in the range of 1 to 2-10 g / job, preferably in the range of 2 to 5 g / job.

As an alternative to the above, although not preferred, or in addition, the dishwashing detergent may contain other nonionic surfactants. Suitable surfactants include, for example, (end-capped) hydroxy mixed ethers. It refers to

Nonionic surfactants having alternating ethylene oxide and alkylene oxide units. Among these, in turn, surfactants with EO-AO-EO-AO blocks are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows.

Particularly preferred are surfactants of the formula

R ⁵ O [CH ₂ CH (CH ₃ ) O] x [CH ₂ CH ₂ O] yCH ₂ CH (OH) R ⁶ , in which R ^{5 is} a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R ^{6 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x is between 0.5 and 1, 5 and y is a value of at least 15. The group of these nonionic surfactants include, for example, the C2-26 fatty alcohol (PO) i- (EO) i5-4o-2-hydroxyalkyl ethers, in particular also the coco-fatty alcohol (PO) i (EO) 22-2-hydroxydecyl ethers ,

Particular preference is furthermore given to those end-capped poly (oxyalkylated) nonionic surfactants of the formula R ⁷ O [CH ₂ CH ₂ O] x [CH ₂ CH (R ⁹ ) O] _y CH ₂ CH (OH) R ⁸ in which R ⁷ and R ⁸ independently of one another are linear or branched, saturated or single or multiple

unsaturated hydrocarbon radical having 2 to 26 carbon atoms, R ^{9 is} independently selected from -CH 3, -CH 2 CH 3, -CH 2 CH 2 -CH 3, -CH (CH 3) 2, but preferably is -CH 3, and x and y independently of each other for between values 1 and 32, with nonionic surfactants with R ³ = -CH ³ and values for x of 15 to 32 and y of 0.5 and 1.5 being very particularly preferred. In addition to the abovementioned nonionic surfactants, the compositions according to the invention may contain surfactants in the surfactant mixture, in particular further nonionic or else anionic surfactants, but also cationic or amphoteric surfactants.

Suitable further nonionic surfactants are, for example, alkyl glycosides of the general formula RO (G) x in which R corresponds to a primary straight-chain or methyl-branched, in particular 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the Is a symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1, 2 to 1, 4.

Another class of useful nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain.

Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.

Further suitable surfactants are the polyhydroxy fatty acid amides known as PHFA.

The total amount of nonionic surfactants in the dishwashing agents according to the invention is preferably 1 to 10 wt .-%, more preferably 2 to 5 wt .-%.

Suitable anionic surfactants are all anionic surfactants. These are characterized by a water-solubilizing, anionic group such as. Legs

Carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group having about 8 to 30 carbon atoms. In addition, glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups may be present in the molecule. Suitable anionic surfactants are preferably in the form of the sodium, potassium and ammonium as well as the mono-, di- and

Trialkanolammoniumsalze with 2 to 4 carbon atoms in the alkanol group. Preferred anionic surfactants are fatty alcohol sulfates, fatty alcohol ether sulfates, dialkyl ether sulfates, monoglyceride sulfates, alkylbenzenesulfonates, olefinsulfonates, alkanesulfonates, ether sulfonates, n-alkyl ether sulfonates, ester sulfonates and lignosulfonates. Also usable in the context of the present invention are fatty acid cyanamides, sulfosuccinates (sulfosuccinic acid esters), in particular Sulfosuccinic acid mono- and di-alkyl esters of 8 to 18 carbon atoms, sulfosuccinamates,

Sulfosuccinamides, fatty acid isethionates, acylaminoalkanesulfonates (fatty acid taurides),

Fatty acid sarcosinates, ether carboxylic acids and alkyl (ether) phosphates and α-sulfofatty acid salts, acylglutamates, monoglyceride disulfates and alkyl ethers of glycerol disulfate.

Preferred anionic surfactants include those of the formula

R ^{0 is} -O- (AO) _n -SO ₃ - X ⁺ .

In this formula, R ^{0 is} a linear or branched, substituted or unsubstituted alkyl, aryl or alkylaryl radical, preferably a linear, unsubstituted alkyl radical, more preferably a fatty alcohol radical. Preferred radicals R ⁰ are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and mixtures thereof, where the representatives with even number of carbon atoms Atoms are preferred. Particularly preferred radicals R ⁰ are derived from C 12 -C 18 -fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or from C 10 -C 20 oxo alcohols.

AO represents an ethylene oxide (EO) or propylene oxide (PO) moiety, preferably an ethylene oxide moiety. The index n stands for an integer from 1 to 50, preferably from 1 to 20 and especially from 2 to 10. Most preferably, n stands for the numbers 2, 3, 4, 5, 6, 7 or 8. X stands for a monovalent cation or the nth part of an n-valent cation, the alkali metal ions are preferred, and Na ⁺ or K ⁺ including Na, with Na ^{+ being} extremely preferred. Other cations X ⁺ can be selected from NhV, V Mn ²⁺ , and mixtures thereof.

Additionally or alternatively, an anionic surfactant of the formula R-A-S0 ₃ ^" Y ^{+ may be present} in the dishwashing detergent In this formula, R is a linear or branched, substituted or unsubstituted alkyl, aryl or alkylaryl radical and the

Grouping -A- for -O- or a chemical bond. In other words, sulfate (A = O) or sulfonate (A = chemical bond) surfactants can be described by the above formula. Depending on the choice of the group A, certain radicals R are preferred. In the case of the sulfate surfactants (A = O), R preferably represents a linear, unsubstituted alkyl radical, particularly preferably a fatty alcohol radical. Preferred radicals R are selected from decyl, Undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl and mixtures thereof, with the even number of C atoms being preferred. Particularly preferred radicals R are derived from C 12 -C 18 -fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or from C 10 -C 20 oxo alcohols. Y stands for a monovalent cation or the n-th part of an n-valent cation, the alkali metal ions being preferred, and Na ⁺ or K ⁺ being preferred, Na ^{+ being} extremely preferred. More cations Y + may be selected from NHV, Zn ²⁺ / ₂ Mg ²⁺ / ₂ Ca ²⁺ / ₂ Mn ^2+, and mixtures thereof.

In various embodiments, dishwashing agents according to the invention contain anionic surfactants in amounts of up to 5% by weight. In preferred embodiments, the content of anionic surfactants is preferably less than 4 wt .-%, more preferably less than 2 wt .-% and in particular less than 1 wt .-%, based on the total weight of the dishwashing detergent.

Suitable amphoteric surfactants are, for example, betaines of the formula (R ⁱⁱⁱ ) (R ^iv ) (R ^v ) N ⁺ CH 2 COO ^_ in which R ^{i is} an alkyl radical optionally interrupted by hetero atoms or heteroatom groups having 8 to 25, preferably 10 to 21 carbon atoms and R ^iv and R ^{v are} identical or different alkyl radicals having 1 to 3 carbon atoms, in particular Cio-Cis-alkyl dimethylcarboxymethylbetain and Cn-Ci7-alkylamidopropyl-dimethylcarboxymethylbetain.

Suitable cationic surfactants are i.a. the quaternary ammonium compounds of the formula

(R ^VI ) (R ^vii ) (R ^viii ) (R ^ix ) N ⁺ X ^" , in which R ^vi to R ^ix for four identical or different, in particular two long and two short-chain, alkyl radicals and X ^" for an anion , in particular a halide ion, for example, didecyl-dimethyl-ammonium chloride, alkyl-benzyl-didecyl-ammonium chloride and mixtures thereof. Other suitable cationic surfactants are the quaternary

surface-active compounds, in particular with a sulfonium, phosphonium, iodonium or arsonium group, which are also known as antimicrobial agents. Through the use of quaternary surface-active compounds with antimicrobial action, the agent can be designed with an antimicrobial effect or its possibly existing antimicrobial effect due to other ingredients can be improved.

In dishwashing detergents, the content of cationic and / or amphoteric surfactants is preferably less than 4 wt .-%, more preferably less than 2 wt .-% and

in particular less than 1 wt .-%. Dishwashing detergents containing no cationic or amphoteric surfactants are particularly preferred. The total surfactant content of the dishwashing agent is preferably 1 to 15% by weight, preferably 2 to 10% by weight.

The agents according to the invention may comprise at least one, preferably two or more further constituents, preferably selected from the group consisting of builders, enzymes, thickeners, sequestering agents, electrolytes, corrosion inhibitors, in particular silver protectants, glass corrosion inhibitors, polymers, bleaches, bleach activators, foam inhibitors, dyes, fragrances , Bitter substances and antimicrobial agents.

The dishwashing compositions of the invention are preferably phosphate-free.

Builders which may be present in the dishwashing detergent are, in particular, silicates, aluminum silicates (in particular zeolites), carbonates, organic (co) builders, such as, for example, salts of organic di- and polycarboxylic acids, and mixtures of these substances.

For example, crystalline layered silicates of the general formula

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. The crystalline layered silicates of the formula NaMSix02x + i ^■ y H2O, for example, by Clariant GmbH (Germany) under the trade name Na-SKS. Examples of these silicates are Na-SKS-1 (Na ₂ Si ₂ 2045 ^· x H ₂ O, kenyaite), Na-SKS-2 (Na ₂ Si ₄ O ^{29 ·} x H ₂ O, magadiite), Na-SKS-3 (Na ₂ Si ₈ 0i7 ^■ x H2O) or Na-SKS-4 (Na ₂ Si ₄ 09 ^■ x H2O, makatite). Particularly suitable for the purposes of the present invention are crystalline phyllosilicates of the formula

NaMSix02x + i ^■ y H2O, where x is 2. In particular, both ß- and

δ-sodium Na2Si20s ^■ y H2O and further especially 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) and Na-SKS-13 (NaHSi ₂ 0 _5), but especially Na-SKS-6 (5-Na ₂ Si ₂ 05) is preferred.

The dishwashing detergents contain in various embodiments, a weight ratio of the crystalline layered silicate of the formula NaMSi _x 02x + y i ^■ H2O of 0.1 to 20 wt .-%, preferably from 0.2 to 15 wt .-% and in particular 0.4 to 10 wt .-%, each based on the total weight of these agents. In various embodiments, the agents are free of such silicates.

It is also possible to use amorphous sodium silicates with a modulus Na 2 O: SiO 2 of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which are preferably Delayed and have secondary washing properties. The dissolution delay compared to conventional amorphous sodium silicates can in various ways, for example by surface treatment, compounding, compaction / compaction or by

Overdrying caused. In the context of this invention, the term "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.

In various embodiments, these silicate (s), preferably alkali metal silicates, more preferably crystalline or amorphous Alkalidisilikate, in the compositions in amounts of from 3 to 60 wt .-%, preferably from 8 to 50 wt .-% and in particular from 20 to 40 wt .-%, each based on the weight of the dishwashing detergent to be included. In other embodiments, the agents are free of these silicates.

Further builders are the alkali carriers. Examples of alkali carriers are

Alkali metal hydroxides, alkali metal carbonates, alkali metal bicarbonates, alkali metal sesquicarbonates, the said alkali metal silicates, alkali metal silicates, and mixtures of

aforementioned substances, wherein for the purposes of this invention preferably the alkali metal carbonates, in particular sodium carbonate, sodium bicarbonate or sodium sesquicarbonate can be used. Also particularly preferred is a builder system comprising a mixture of sodium carbonate and sodium disilicate. Because of their low chemical compatibility with the other ingredients of mechanical compared to other builders

Dishwashing agents, the optional alkali metal hydroxides are preferably only in small amounts, preferably in amounts below 10 wt .-%, preferably below 6 wt .-%, more preferably below 4 wt .-% and in particular below 2 wt .-%, each based on the total weight of the dishwashing detergent used. Particularly preferred are agents which, based on their total weight less than 0.5 wt .-% and in particular no

Contain alkali metal hydroxides.

In various embodiments, carbonate (s) and / or bicarbonate (s), preferably alkali metal carbonate (s), more preferably sodium carbonate, in amounts of 2 to 50 wt .-%, preferably from 5 to 40 wt .-% and in particular from 7 , 5 to 30 wt .-%, each based on the weight of the dishwashing detergent are used.

The dishwashing detergents can contain as further builders in particular also phosphonates, which according to the invention are not subsumed under the phosphates. The phosphonate compound used is preferably a hydroxyalkane and / or aminoalkane phosphonate. Among the Hydroxyalkane phosphonates is the 1-hydroxyethane-1,1-diphosphonate (HEDP) of particular importance. Preferred aminoalkanephosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. Phosphonates are contained in the compositions preferably in amounts of 0.1 to 10 wt .-%, in particular in amounts of 0.3 to 8 wt .-%, each based on the total weight of the dishwashing detergent.

Particularly suitable organic (co) builders are polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders and the phosphonates already mentioned above as builders. These classes of substances are described below.

Useful organic builders are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. For example, these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid,

Maleic acid, fumaric acid, sugar acids, nitrilotriacetic acid (NTA), provided such use is not objectionable for environmental reasons, and mixtures thereof. In addition to their builder effect, the free acids typically also have the property of a

Acidification and thus also serve to set a lower and milder pH of the dishwashing detergent. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.

The use of citric acid and / or citrates has proved to be particularly advantageous for the cleaning and rinsing performance. Therefore, machine dishwashing detergents are preferred according to the invention in that the dishwasher detergent contains citric acid or a salt of citric acid and the weight proportion of citric acid or citric acid salt is preferably from 1 to 40% by weight, preferably from 2 to 30, particularly preferably from 2 to 15 Wt .-% and in particular between 3 and 10 wt .-% is.

Another important class of phosphate-free builders are aminocarboxylic acids and / or their salts. Particularly preferred members of this class are

Methylglycinediacetic acid (MGDA) or its salts, and glutamic diacetic acid (GLDA) or its salts or ethylenediaminediacetic acid (EDDS) or its salts. Particularly suitable are methylglycinediacetic acid (MGDA) or its salts, and glutamic diacetic acid (GLDA) or its salts. Very particular preference is GLDA or its salts. The content of these

Amino carboxylic acids or their salts, preferably MGDA sodium salt or GLDA sodium salt, in particular GLDA sodium salt, may for example be between 0.1 and 25 wt .-%, preferably between 5 and 25 wt .-% and in particular between 15 and 25 wt .-% amount. Aminocarboxylic acids and their salts can be used, for example, together with the abovementioned builders, in particular together with citrate and the abovementioned phosphonates.

The compositions of the invention may further contain a sulfopolymer. The proportion by weight of the sulfopolymer in the total weight of the composition according to the invention is preferably from 0.1 to 20% by weight, in particular from 0.5 to 18% by weight, particularly preferably from 0.1 to 15% by weight, in particular from 4 to 14 wt .-%, especially from 6 to 12 wt .-%. The sulfopolymer is usually used in the form of an aqueous solution, the aqueous solutions typically containing 20 to 70 wt .-%, in particular 30 to 50 wt .-%, preferably about 35 to 40 wt .-% sulfopolymers.

The sulfopolymer used is preferably a copolymeric polysulfonate, preferably a hydrophobically modified copolymeric polysulfonate. The copolymers may have two, three, four or more different monomer units. Preferred copolymeric polysulfonates contain not only sulfonic acid group-containing monomer (s) but also at least one monomer selected from the group consisting of unsaturated carboxylic acids.

Unsaturated carboxylic acid (s) used are, with particular preference, unsaturated carboxylic acids of the formula R (R ² ) C =C (R ³ ) COOH, in which R ¹ to R ³ independently of one another represent -H, -CH 3, a straight-chain or branched one saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH 2, -OH or -COOH substituted alkyl or alkenyl radicals as defined above or for -COOH or -COOR ⁴ wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

Particularly preferred unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, α-chloroacrylic acid, α-cyanoacrylic acid, crotonic acid, α-phenyl-acrylic acid, maleic acid,

Maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid, sorbic acid, cinnamic acid or mixtures thereof. It goes without saying that it is also possible to use the unsaturated dicarboxylic acids.

In the sulfonic acid-containing monomers are those of the formula

R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-S0 ₃ H in which R ⁵ to R ⁷ independently of one another are -H, -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals or -COOH or -COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X is an optional spacer group which is selected from - (CH ₂ ) n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - , -C (O) -NH-C (CH ₃ ) ₂ -CH ₂ - and -C (O) -NH-CH (CH ₃ ) -CH ₂ -.

Preferred among these monomers are those of the formulas

H ₂ C = CH-X-SO ₃ H

H ₂ C = C (CH ₃ ) -X-SO ₃ H

H0 ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-S0 ₃ H,

in which R ⁶ and R ^{7 are} independently selected from -H, -CH ₃ , -CH ₂ CH ₃ , - CH ₂ CH ₂ CH ₃ and -CH (CH ₃ ) ₂ and X is an optional spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ -, - C (O) -NH-C (CH ₃ ) ₂ -CH ₂ - and -C (O) -NH-CH (CH ₃ ) -CH ₂ -.

Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3 Methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propenylsulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfo - Propylmethacrylat, sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of said acids or their water-soluble salts.

In the polymers, the sulfonic acid groups may be wholly or partially in neutralized form, i. the acidic acid of the sulfonic acid group in some or all sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions. The use of partially or fully neutralized

Sulfonsäuregruppenhaltigen copolymers is inventively preferred.

The monomer distribution of the copolymers preferably used in accordance with the invention is in the case of copolymers which contain only monomers containing carboxylic acid groups and sulfonic acid group-containing monomers Monomers contain, preferably in each case 5 to 95 wt .-%, particularly preferably the proportion of the sulfonic acid-containing monomer is 50 to 90 wt .-% and the proportion of

Carboxylic acid-containing monomers 10 to 50 wt .-%, the monomers are hereby preferably selected from the aforementioned.

The molar mass of the sulfo copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired end use. Preferred cleaning agents are characterized in that the copolymers have molecular weights of 2000 to 200,000 gmol ^-1 , preferably from 4000 to 25,000 gmol and in particular from 5000 to 15,000 gmol ^-1 .

In various embodiments, other polymers can be used in the compositions of the invention. The group of polymers includes, in particular, the washing or cleaning-active polymers, for example the rinse aid polymers and / or polymers which act as softeners. In general, cationic, anionic and amphoteric polymers can be used in automatic dishwashing detergents in addition to nonionic polymers. The sulfo (co) polymers described above are, for example, anionic polymers.

For the purposes of the present invention, "amphoteric polymers" furthermore have, in addition to a positively charged group in the polymer chain, negatively charged groups or monomer units, for example, these may be carboxylic acids, sulfonic acids or phosphonic acids.

Preferred usable amphoteric polymers are from the group of

Alkylacrylamide / acrylic acid copolymers, the alkylacrylamide / methacrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid copolymers, the alkylacrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers , the alkylacrylamide / methylmethacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / alkymethacrylate / alkylaminoethylmethacrylate / alkylmethacrylate copolymers and the copolymers of unsaturated carboxylic acids, cationically derivatized unsaturated carboxylic acids and optionally further ionic or nonionic monomers.

Preferred zwitterionic polymers are from the group of acrylamidoalkyl trialkyl ammonium chloride / acrylic acid copolymers and their alkali metal and ammonium salts, the acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and their alkali metal and ammonium salts and the Methacroylethylbetain / methacrylate copolymers. "Cationic polymers" are polymers which carry a positive charge in the polymer molecule, which can be realized, for example, by (alkyl) ammonium groups or other positively charged groups present in the polymer chain.Particularly preferred cationic polymers originate from the groups of the quaternized cellulose derivatives, the polysiloxanes with quaternary groups, the cationic guar derivatives, the polymeric

Dimethyldiallylammoniumsalze and their copolymers with esters and amides of acrylic acid and methacrylic acid, the copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylats and methacrylate, the vinylpyrrolidone-Methoimidazoliniumchlorid copolymers, the quaternized polyvinyl alcohols or under the INCI names Polyquaternium 2, Polyquaternium 17 , Polyquaternium 18 and Polyquaternium 27 indicated polymers.

In various embodiments of the present invention, the aforementioned amphoteric, zwitterionic or cationic polymers are in prefabricated form. To prepare the polymers u.a.

the encapsulation of the polymers by means of water-soluble or water-dispersible coating compositions, preferably by means of water-soluble or water-dispersible natural or synthetic polymers;

the encapsulation of the polymers by means of water-insoluble, fusible

Coating compositions, preferably by means of water-insoluble coating agents from the group of waxes or paraffins having a melting point above 30 ° C;

the co-granulation of the polymers with inert support materials, preferably with

Support materials from the group of washing or cleaning-active substances, particularly preferably from the group of builders (builders) or cobuilders.

As enzymes, various enzyme preparations or enzyme compositions known in the art can be used. These enzyme preparations or

Enzyme compositions usually contain at least one protease and one or more additional enzymes. Other suitable enzymes include, but are not limited to, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably mixtures thereof. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents, which are preferably used accordingly. Agents according to the invention preferably contain enzymes in total amounts of from 1 × 10 ^-6 to 5% by weight, based on active protein. The active protein concentration can be determined by known methods, for example the BCA method or the biuret method.

An enzyme may be particularly resistant to damage such as inactivation, denaturation or degradation during storage, such as by physical influences, oxidation or degradation protected proteolytic cleavage. In the case of microbial recovery of the enzymes, inhibition of the proteolysis is particularly preferred, especially if the agents also contain proteases. The agents may contain stabilizers for this purpose; the provision of such means constitutes a preferred embodiment of the present invention.

Cleaning-active enzymes are generally not provided in the form of the pure protein but rather in the form of stabilized, storable and transportable preparations. Such prefabricated preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel-form detergents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or added with stabilizers or further auxiliaries.

Alternatively, 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. In deposited layers, further active ingredients, for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied. Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes. Advantageously, such granules, for example by applying polymeric

Film former, low-dust and storage-stable due to the coating.

Furthermore, it is possible to assemble two or more enzymes together so that a single granule has several enzyme activities.

As can be seen from the previous comments, the enzyme protein forms only a fraction of the total weight of conventional enzyme preparations. Enzyme preparations preferably used according to the invention contain between 0.1 and 40% by weight, preferably between 0.2 and 30% by weight, more preferably between 0.4 and 20% by weight and in particular between 0.8 and 10 % By weight of the enzyme protein.

Particular preference is given to those agents which, based in each case on their total weight, contain 0.1 to 12% by weight, preferably 0.1 to 10% by weight and in particular 0.2 to 5% by weight, of enzyme preparations. The compositions described herein may also include enzyme stabilizers. One group of stabilizers are reversible protease inhibitors. Benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters are frequently used for this purpose, including, in particular, derivatives with aromatic groups, for example ortho, meta or para-substituted

Phenylboronic, in particular 4-formylphenyl-boronic acid, or the salts or esters of said compounds. Also, peptide aldehydes, that is oligopeptides with a reduced C-terminus, especially those of 2 to 50 monomers are used for this purpose. Among the peptidic reversible protease inhibitors include ovomucoid and leupeptin. Also, specific, reversible peptide inhibitors for the protease subtilisin and fusion proteins from proteases and specific peptide inhibitors are suitable.

Other enzyme stabilizers are amino alcohols such as mono-, di-, triethanol- and -propanolamine and mixtures thereof, aliphatic carboxylic acids up to C12, such as succinic acid, other dicarboxylic acids or salts of said acids. End-capped fatty acid amide alkoxylates are also suitable for this purpose. Certain organic acids used as builders are capable, as disclosed in WO 97/18287, of additionally stabilizing a contained enzyme.

Other enzyme stabilizers are known to those skilled in the art.

Bleaching agents are washing or cleaning substances. Among the compounds serving as bleaches in water H2O2 are sodium percarbonate,

Sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and peroxygenic salts or peracids which yield H2O2, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. It is also possible to use all other inorganic or organic agents known to the person skilled in the art

Peroxy.

In various embodiments, the dishwashing agents may contain 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.

In various embodiments of the invention, the dishwashing agents additionally contain at least one bleach activator. As bleach activators, compounds mentioned in U.S. Pat

Perhydrolysis aliphatic peroxycarboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid, are used. Of all those skilled in the art known from the prior art Bleach activators are polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS) are particularly preferably used. Combinations of conventional bleach activators can also be used. As bleach activator according to the invention TAED, especially in combination with a percarbonate bleach, preferably sodium percarbonate, is very particularly preferred.

These bleach activators are preferably used in amounts of up to 10% by weight, in particular 0.1% by weight to 8% by weight, especially 2 to 8% by weight and more preferably 2 to 6% by weight, based in each case on the total weight of bleach activator-containing agents.

In general, the pH of the agent can be adjusted by means of customary pH regulators, the pH value being selected depending on the desired application. In various embodiments, the pH is in a range of 5.5 to 12, preferably 6 to 1 1, more preferably 7 to 10, especially greater than 7, especially in the range 7.5 to 9.5. The pH adjusting agents are acids and / or alkalis, preferably alkalis. Suitable acids are in particular organic acids such as acetic acid, citric acid, glycolic acid, lactic acid, succinic acid, adipic acid, malic acid, tartaric acid and gluconic acid or amidosulfonic acid. In addition, however, it is also possible to use the mineral acids hydrochloric acid, sulfuric acid and nitric acid or mixtures thereof. Suitable bases are selected from the group of alkali and alkaline earth metal hydroxides and carbonates, in particular the alkali metal hydroxides, of which potassium hydroxide and especially sodium hydroxide is preferred. However, particularly preferred is volatile alkali, for example in the form of ammonia and / or alkanolamines, which may contain up to 9 carbon atoms in the molecule. The alkanolamine here is preferably selected from the group consisting of mono-, di-, triethanol- and -propanolamine and mixtures thereof. The alkanolamine is preferably contained in agents according to the invention in an amount of from 0.5 to 10% by weight, in particular in an amount of from 1 to 6% by weight.

To adjust and / or stabilize the pH, the composition according to the invention may also contain one or more buffer substances (INCI Buffering Agents), usually in amounts of 0.001 to 5 wt .-%. Preference is given to buffer substances which are at the same time complexing agents or even chelating agents (chelating agents, INCI chelating agents). Particularly preferred buffer substances are citric acid or citrates, in particular the sodium and potassium lead,

for example, trisodium citrate 2H20 and tripotassium citrate Ή2Ο. Glass corrosion inhibitors prevent the occurrence of haze, streaks and scratches, but also iridescence of the glass surface of machine-cleaned glasses. Preferred glass corrosion inhibitors originate from the group of bismuth, magnesium and zinc salts as well as bismuth, magnesium and zinc complexes, in particular zinc acetate. As glass corrosion inhibitors, alkoxylated or non-alkoxylated, in particular not alkoxylated, singly or in combination with the abovementioned salts or complexes are also preferably used

Polyethyleneimines, such as those available under the name Lupasol® BASF available. In the context of the present invention, the content of zinc salt in dishwashing agents is preferably between 0.1 and 5 wt.%, Preferably between 0.1 and 4 wt.% And in particular between 0.2 and 3 wt. the content of zinc in oxidized form (calculated as Zn ²⁺ ) is between 0.01 and 1% by weight, preferably between 0.02 and 0.5% by weight and in particular between 0.04 and 0.2% by weight. %, in each case based on the total weight of the

Glaskorrosioninhibitor-containing agent.

As perfume oils or perfumes, within the scope of the present invention, individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance. Such perfume oils may also contain natural fragrance mixtures such as are available from vegetable sources, e.g. Pine, citrus, jasmine, patchouli, rose or ylang-ylang oil.

Furthermore, preservatives may be included in the compositions. Suitable examples are preservatives from the groups of alcohols, aldehydes, antimicrobial acids and / or their salts, carboxylic acid esters, acid amides, phenols, phenol derivatives, diphenyls,

Diphenylalkanes, urea derivatives, oxygen, nitrogen acetals and formals, benzamidines, isothiazoles and their derivatives, such as isothiazolines and isothiazolinones, phthalimide derivatives,

Pyridine derivatives, antimicrobial surface-active compounds, guanidines, antimicrobial amphoteric compounds, quinolines, 1, 2-dibromo-2,4-dicyanobutane, iodo-2-propynyl-butyl-carbamate, iodine, iodophores and peroxides. Preferred antimicrobial agents are

preferably selected from the group comprising ethanol, n-propanol, i-propanol, 1, 3-butanediol, phenoxyethanol, 1, 2-propylene glycol, glycerol, undecylenic acid, citric acid, lactic acid, benzoic acid, salicylic acid, thymol, 2-benzyl-4 chlorophenol, 2,2'-methylenebis (6-bromo-4-chlorophenol), 2,4,4'-trichloro-2'-hydroxydiphenyl ether, N- (4-chlorophenyl) -N- (3,4- dichlorophenyl) urea, N, N '- (1, 10-decanediyldi-1 -pyridinyl-4-ylidene) bis (1-octanamine) dihydrochloride, N, N'-bis (4-chlorophenyl) -3 , 12-diimino-2,4,1,1,1,3-tetraazatetradecandiimidamide, antimicrobial quaternary surface active compounds, guanidines. However, particularly preferred preservatives are selected from the group comprising salicylic acid, quaternary Surfactants, especially benzalkonium chloride and isothiazoles and their derivatives such as isothiazolines and isothiazolinones.

Solvents that are suitable for the compositions used according to the invention, in addition to water as the preferred solvent generally water-miscible organic solvents, such as, without limitation, ethanol, propanol, 1, 2-propanediol and glycerol. In various embodiments, the dishwashing detergent may be a low-water, liquid dishwashing detergent containing water in amounts up to a maximum of 25% by weight, preferably up to 20% by weight, based on the total weight of the composition.

The term "low in water" as used herein means that the composition thus characterized contains less than 25% by weight of water, preferably less than 20% by weight of water. The water content as defined herein refers to the water content determined by Karl Fischer titration.

In general, the formulation of dishwashing agents described herein can be carried out in different ways. The agents may be in solid or liquid form as well as in a combination of solid and liquid forms. Powder, granules, extrudates, compacts, in particular tablets, are particularly suitable as firm supply forms. The liquid supply forms based on water and / or organic solvents may be thickened, in the form of gels. The agents can be formulated in the form of single-phase or multi-phase products. The individual phases of multiphase agents may be the same or different

Have aggregate states.

"Liquid" as used herein with respect to the agent of the invention therefore includes all flowable compositions and, in particular, also encompasses gels and pastes

Compositions.

The dishwashing agents described herein are preferably automatic dishwashing agents, which may be in solid or liquid form. However, the solid moldings described below are particularly preferably also liquid agents, in particular in the form of gels.

The dishwashing detergents can be present as shaped bodies. In order to facilitate the disintegration of such prefabricated moldings, it is possible Disintegrationshilfsmittel, so-called

Tablet disintegrants to incorporate into these agents to shorten the disintegration times. By tablet disintegrants or disintegrants are meant excipients which are responsible for the rapid disintegration of tablets in water or other media and for the rapid release of the Active ingredients provide. Desintegrationshilfsmittel in amounts of 0.5 to 10 wt .-%, preferably 3 to 7 wt .-% and in particular 4 to 6 wt .-%, each based on the

Total weight of the disintegration aid-containing agent used.

The dishwashing agents described herein are preferably prefabricated into dosage units. These metering units preferably comprise the necessary for a cleaning cycle amount of washing or cleaning-active substances. Preferred metering units have a weight between 12 and 30 g, preferably between 14 and 26 g and in particular between 16 and 22 g. The volume of the aforementioned metering units and their spatial form are selected with particular preference so that a metering of the prefabricated units is ensured via the metering chamber of a dishwasher. The volume of the dosing unit is therefore preferably between 10 and 35 ml, preferably between 12 and 30 ml.

The dishwashing agents, in particular the prefabricated metering units, with particular preference have a water-soluble coating.

The water-soluble coating is preferably formed from a water-soluble film material selected from the group consisting of polymers or polymer blends. The wrapper may be formed of one or two or more layers of the water-soluble film material. The water-soluble film material of the first layer and the further layers, if present, may be the same or different. Particularly preferred are films which, for example, can be glued and / or sealed to packages such as hoses or cushions after being filled with an agent.

The water soluble package may have one or more chambers. The agent may be contained in one or more chambers, if any, of the water soluble envelope. The amount of agent preferably corresponds to the full or half dose needed for a rinse.

It is preferred that the water-soluble coating be polyvinyl alcohol or a

Contains polyvinyl alcohol copolymer. Water-soluble coatings containing polyvinyl alcohol or a polyvinyl alcohol copolymer have a good stability with a sufficiently high water solubility, in particular cold water solubility on.

Suitable water-soluble films for producing the water-soluble coating are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer whose

Molecular weight in the range of 10,000 to 1,000,000 gmor, preferably from 20,000 to 500,000 gmol ^"1 , more preferably from 30,000 to 100,000 gmol ^{" 1} and in particular from 40,000 to 80,000 gmol ¹ .

The production of polyvinyl alcohol is usually carried out by hydrolysis of polyvinyl acetate, since the direct synthesis route is not possible. The same applies to polyvinyl alcohol copolymers which are prepared from correspondingly polyvinyl acetate copolymers. It is preferred if at least one layer of the water-soluble coating comprises a polyvinyl alcohol whose degree of hydrolysis makes up 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.

In addition, a polymer selected from the group comprising a polyvinyl alcohol-containing sheet material suitable for producing the water-soluble sheath

(Meth) acrylic acid-containing (co) polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers, polylactic acid or mixtures of the above polymers may be added. A preferred additional polymer is polylactic acids.

Preferred polyvinyl alcohol copolymers include, in addition to vinyl alcohol, dicarboxylic acids as further monomers. Suitable dicarboxylic acids are itaconic acid, malonic acid, succinic acid and mixtures thereof, with itaconic acid being preferred.

Likewise preferred polyvinyl alcohol copolymers include, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt or its esters. Such polyvinyl alcohol copolymers particularly preferably contain, in addition to vinyl alcohol, acrylic acid, methacrylic acid, acrylates, methacrylates or mixtures thereof.

It may be preferred that the film material contains further additives. The film material may include, for example, plasticizers such as dipropylene glycol, ethylene glycol, diethylene glycol,

Propylene glycol, glycerol, sorbitol, mannitol or mixtures thereof. Further

Additives include, for example, release aids, fillers, crosslinking agents, surfactants, antioxidants, UV absorbers, antiblocking agents, detackifiers, or mixtures thereof.

Suitable water-soluble films for use in the water-soluble casings of the water-soluble packaging according to the invention are films sold by the company MonoSol LLC, for example under the designation M8630, C8400 or M8900. Other suitable films include films named Solublon® PT, Solublon® GA, Solublon® KC or Solublon® KL from Aicello Chemical Europe GmbH or the films VF-HP from Kuraray. The corresponding use of the dishwasher detergent according to the invention is likewise

Subject of the invention. The invention likewise relates to a dishwashing process, in particular a machine dishwashing process, in which a dishwashing detergent according to the invention is used. The subject matter of the present application is therefore furthermore a process for the cleaning of dishes in a dishwashing machine, in which the agent according to the invention is metered into the interior of a dishwasher during the passage of a dishwashing program before the main wash cycle or during the main wash cycle. The dosing or the entry of the agent according to the invention in the interior of the

Dishwasher can be done manually, but preferably the agent is metered by means of the metering chamber in the interior of the dishwasher.

Finally, the invention also relates to the use of the compounds described herein for improving the rinsing performance of a dishwashing detergent, in particular machine

Dishwashing detergent.

The embodiments described in context with the agents according to the invention are readily transferable to the methods and uses of the invention and vice versa.

Examples

Example 1: Formulations used

Table 1: Composition of the automatic dishwashing detergent

(Details active substance content in% by weight)

Raw materials V1 E1

Wt% wt%

Sodium citrate 28.00 28.00

HEDP 8.50 8.50

Sodium disilicate 4.50 4.50

Soda 19,50 19,50

Sodium percarbonate 15,50 15,50

Bleach catalyst 0.03 0.03

TAED 2, 10 2,10

Urea derivative ^* - 1, 00

Nonionic surfactant 4,50 3,50

Benzotriazole 0.30 0.30

Polycarboxylate 6.50 6.50

PEG4000 2.00 2.00

Protease 2.5 2.5

Amylase 0.5 0.5

Perfume 0, 10 0, 10

Dye 1, 00 1, 00

Zn salt 0.20 0.20

Sodium sulfate 1, 50 1, 50

Water, pH rest rest

Regulators,

processing aids

100 100

Urea derivative ^* = 3,3 '- (4-methyl-1,3-phenylene) bis (1,1-dimethylurea) Example 2: rinse test

To determine the rinse effect, selected and defined dishes are rinsed 4 times and visually scrapped after the 2nd, 3rd and 4th rinse cycles. The first rinse is used to condition the dishes. The parameters used are rinse notes on the basis of the optical Appearance of dry items (porcelain, glasses, plastic parts and stainless steel) awarded. The formulations mentioned above in Table 1 are metered in each case with 18.5 g. Per rinse 100 g of dirt are dosed to simulate a normally dirty load.

Filming is determined in the Miele G698 at 50 ° C. Water hardness 21 ° dH. After completion of the rinse cycle, the machine is fully opened for 30 minutes and then the clear rinse effect is visually determined in the black box (black-painted room, D6500 daylight lamp). On the crockery and cutlery remaining dried water drops, streaks, coverings and films are scored on a scale of 1 - 10. 10 means no drops / films, 1 means heavy drops / filming.

The following result was achieved:

Table 2: Rinse aid result

Glass of stainless steel

spotting

V1 2.2 3.6

E1 4,7 3,5

Filming

V1 3.4 4.0

E1 3.4 4.6

It can be clearly seen that the combination of the invention compared to the reference leads to improvement in spotting (dropping) on glass and filming (striae) on stainless steel.

Claims

claims

1. dishwashing detergent, in particular automatic dishwashing detergent, containing, based on the total weight of the dishwashing detergent, 0.1 to 5.0 wt .-%, preferably 1, 0 to 2.0 wt .-% of at least one compound of formula (I):

in which

each alk independently represents a linear or branched alkyl radical of 1 to 10

Carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms;

A is a chemical bond or a bivalent hydrocarbon radical having 1 to 30 carbon atoms, preferably 4 to 22 carbon atoms; and

each represents a single or double bond, preferably all one

Single or all are a double bond, in particular all are a double bond.

2. Dishwashing detergent according to claim 1, characterized in that

(i) R is an alkyl radical, alkenyl radical, alkynyl radical, aryl radical or alkylaryl radical, preferably a linear or branched C 1-10 alkyl radical, in particular a methyl, ethyl, propyl or butyl radical; and or

(ii) each alk is methyl, ethyl or propyl; and or

(iii) A is a chemical bond, an alkylaryl radical or a

Alkylcycloalk (en) ylrest stands.

Dishwashing detergent according to claim 1 or 2, characterized in that the at least one compound of formula (I) is a compound of formula (II)

wherein R, Alk and are as defined above.

Dishwashing detergent according to claim 1 or 2, characterized in that the at least one compound of the form (III) is

wherein R, Alk and are as defined above and each R ^{2 is} H or a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 1 to 10 carbon atoms, preferably having 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms ,

Dishwashing detergent according to one of claims 1 to 3, characterized in that the at least one compound of formula (I) is selected from 3,3 '- (4-methyl-1, 3-phenylene) bis (1, 1-dimethylurea), 3,3 '- (4-methyl-1,3-phenylene) bis (1,1-diethylurea), 3,3' - (4-methyl-1,3-phenylene) bis (1,1-dipropylurea), 3,3 '- (4-Methyl-1,3-phenylene) bis (1-ethyl-1-methylurea), (1,1' -methylenedi-p-phenylene) bis (3,3-dimethylurea) (= 4 , 4-diphenylmethane-bis (3,3-dimethylurea), 2,2'-diphenylmethane-bis (3,3-dimethylurea), 2,4'-diphenylmethane-bis (3,3-dimethylurea), 4,4 'Diphenylmethane bis (3,3-diethylurea)), 2,2'-diphenylmethane bis (3,3-diethylurea) and 2,4'-diphenylmethane bis (3,3-diethylurea).

Dishwashing detergent according to one of claims 1 to 5, characterized in that the dishwashing detergent at least one nonionic surfactant of the formula

R ³ 0 [CH ₂ CH ₂ O] x CH ₂ CH (OH) R ⁴ , where R ^{3 is} linear or branched, saturated or mono- or polyunsaturated, hydrocarbon radicals having 2 to 30 carbon atoms, preferably 4 to 22 Carbon atoms, more preferably 8 to 10 carbon atoms, R ^{4 is} a linear or branched, saturated or mono- or polyunsaturated

Hydrocarbon radical R ⁴ having 1 to 30 carbon atoms, and x is from 1 to 90, preferably from 10 to 60 and especially from 15 to 40, preferably a nonionic surfactant selected from the group of C4-22 Fatty alcohol (EO) io-8o-2-hydroxyalkyl ethers, in particular a C8-12 fatty alcohol (EO) 22-2 hydroxydecyhehe r.

7. Dishwashing detergent according to claim 6, characterized in that

(I) the urea derivatives of the formulas (I), (II) or (III) and the nonionic surfactants in one

Mass ratio of 1: 4 to 4: 1, in particular 1: 1 to 1: 4 are used; and or

(ii) the amount of the urea derivatives of the formulas (I), (II) or (III) used about 0.8 to 1, 5 wt .-% and the amount of nonionic surfactants used 2.4 to 4.5 wt .-% , in each case based on the total weight of the dishwashing detergent.

8. Dishwashing detergent according to one of claims 1 to 7, characterized in that the dishwashing detergent further surfactants, in particular further nonionic, anionic, cationic and / or amphoteric surfactants, and / or at least one further constituent, preferably at least two further constituents selected from Group consisting of builders, enzymes, thickeners, sequestering agents, electrolytes, corrosion inhibitors, in particular silver protectants, glass corrosion inhibitors, polymers, bleaching agents, bleach activators, foam inhibitors, dyes, fragrances, bittering agents and antimicrobial agents.

9. Use of a dishwashing detergent according to one of claims 1 to 8 in one

Dishwashing process, in particular a machine dishwashing process.

10. dishwashing process, in particular automatic dishwashing, thereby

in that a dishwasher detergent according to one of claims 1 to 8 is used.

1 1. Use of a compound of the formula (I):

in which

each R is H or a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having from 1 to 10 carbon atoms, preferably from 1 to 6 carbon atoms, more preferably from 1 to 4 carbon atoms; each Alk independently represents a linear or branched alkyl group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms;

each represents a single or double bond, preferably all one

Single or all are a double bond, in particular all are a double bond, to improve the final rinse performance of a dishwashing detergent, preferably a machine dishwashing detergent.