CN110603312B

CN110603312B - Detergent composition

Info

Publication number: CN110603312B
Application number: CN201880029113.0A
Authority: CN
Inventors: H·J·M·阿拉博斯瑟; O·C·P·比尔斯; T·A·布伊特拉尔
Original assignee: Unilever IP Holdings BV
Current assignee: Unilever IP Holdings BV
Priority date: 2017-05-04
Filing date: 2018-04-06
Publication date: 2021-10-15
Anticipated expiration: 2038-04-06
Also published as: EP3619288B1; EP3619288A1; ZA201906400B; BR112019022999A2; WO2018202383A1; CN110603312A

Abstract

A detergent composition comprising: 20-80% by weight of an alkali metal carbonate; and 1.0 to 10 weight percent of a nonionic surfactant; and 1.0 to 10 weight percent of a copolymer comprising: i. a sulfonic acid group-containing monomer; additional ionic and/or nonionic monomers; and 0.1 to 9.0% by weight of a mixture of: a) phosphonate, phosphonic acid, or combinations thereof; and b) phosphate, phosphoric acid or a combination thereof.

Description

Detergent composition

Technical Field

The present invention relates to detergent compositions and their use to reduce spotting on dishware treated in a machine dishwasher.

Background

Detergent compositions typically comprise a number of different active ingredients including builders, surfactants, enzymes and bleaching agents.

Surfactants are used to remove stains and soils and to disperse the released components into the cleaning solution. Enzymes help remove stubborn stains of protein, starch and lipids by hydrolyzing these components. Bleaching agents remove stains by oxidizing the components that make up these stains.

Calcium and magnesium ions in the wash liquor can negatively impact stain/soil removal by the detergent composition. In order to reduce the negative effects of such ions, so-called "builders" (complexing agents) are often used in detergent compositions. Phosphorus-based builders have been used in a variety of detergent compositions for many years. Some of these phosphorus-based builders, such as trisodium phosphate and Sodium Tripolyphosphate (STPP), have set benchmarks in the dishwasher detergent industry for superior performance in reducing spotting and filming of dishware (e.g., glassware). Thus, phosphorus containing builder components are generally considered to be "high performance" builders. As builders, they are generally present at relatively high levels in detergent compositions. For example, sodium tripolyphosphate levels of 20-50% are typical for phosphorus-based building detergents. High levels of phosphorus-based builders in detergent compositions are nowadays considered undesirable. The use of phosphorus-based builders in detergent compositions has led to environmental problems such as eutrophication. To reduce such problems, many jurisdictions have or are enacting laws and regulations to limit the maximum level of phosphorus in detergent compositions. Thus, there is a need for more environmentally friendly alternative builders that have equivalent efficacy and are also cost effective. Examples of alternative builders are alkali metal carbonates, glutamic-N, N-diacetic acid salt (GLDA), methylglycine diacetic acid salt (MGDA) and citrates.

In particular, alkali metal carbonates are widely used as low cost builders in detergent compositions. An additional benefit of alkali metal carbonate builders is that they provide effective buffering of the wash liquor. However, the use of alkali metal carbonates as builders generally means that they are present in relatively high levels, which poses certain problems. Carbonate builders that remove calcium and/or magnesium ions from the wash liquor tend to precipitate. This in turn can cause scale formation and spot formation, and is particularly problematic for machine dishwashing applications of detergent compositions, as soil and spots are readily visible on the dishware after the machine dishwashing process. The main reasons for the formation of spots in machine dishwashing are incomplete wetting during the main wash phase and the appearance of dirt-containing (e.g. calcium carbonate-containing) droplets at the beginning of the drying phase. Clearly, the presence of spots on the dishes after the machine dishwashing process is complete is highly undesirable because it leaves an impression that the dishes are unclean.

US2004/0058846 recognizes the problem of spotting on glassware when washed using a machine dishwasher and mentions that such spotting can be removed by further manual cleaning using a rag. This solution is clearly unsatisfactory, since it involves a further cleaning step and requires further effort by the consumer.

It is an object of the present invention to provide a detergent composition comprising alkali metal carbonate (in an amount of 20-80 wt.%), which when used as a detergent in a machine dishwasher, results in less spot formation on treated dishes. While providing good dishware cleanliness and gloss with little or no filming and corrosion of the dishware.

The formation of specks on glass and metal surfaces is particularly undesirable. These tend to be smooth surfaces (e.g., as compared to wooden articles). Moreover, glass surfaces are generally favored for their transparency, while metal surfaces are generally favored for their highly reflective, even mirror-like, nature. Thus, the formation of spots on glass and/or metal surfaces not only gives an unclean impression of the article, but can also negatively affect the particular quality to which such surfaces are generally appreciated.

It is another object of the present invention to provide a detergent composition comprising an alkali metal carbonate (in an amount of 20-80 wt.%), which when used as a detergent in a machine dishwasher, results in less spot formation on the treated metal and/or glass surface while providing good surface cleanliness and gloss, and causes little or no filming and corrosion of the surface.

Disclosure of Invention

One or more of the above objects are achieved by a detergent composition comprising:

20-80% by weight of an alkali metal carbonate; and

1.0-10% by weight of a nonionic surfactant; and

1.0 to 10% by weight of a copolymer comprising:

i. a sulfonic acid group-containing monomer;

additional ionic and/or nonionic monomers; and

0.1-9.0% by weight of a mixture of:

a) phosphonate, phosphonic acid, or combinations thereof; and

b) phosphate, phosphoric acid or a combination thereof.

It has surprisingly been found that the use of a detergent composition according to the invention in machine dishwashing provides effective cleaning of dishware (also providing good shine with little or no filming and corrosion), with little or no spotting. This is particularly effective in reducing the amount of spotting on the treated glass and metal surfaces. More surprisingly, the use of 0.1-9.0 wt.% of a mixture of a) and b) in the detergent composition according to the invention acts synergistically to reduce spot formation when compared to the use of a) or b) alone. Overall, these findings are more surprising, as the total amount of phosphonate, phosphonic acid, phosphate and phosphoric acid is much lower than typical builder levels.

Detailed Description

Definition of

Weight percent (wt%) is based on the total weight of the composition, unless otherwise specified. It will be appreciated that the total weight of the components will not exceed 100 wt% based on the total weight of the composition. Whenever an amount or concentration of a component is quantified herein, unless otherwise indicated, the quantified amount or concentration is relative to the component itself, even though such component is typically added in solution or blended form with one or more other ingredients. Furthermore, it will be understood that the verb "to comprise" and its conjugations is used in its non-limiting sense to mean that items following the word are included, but items not specifically mentioned are not excluded. Finally, the reference to an element by the indefinite article "a" does not exclude the possibility that more than one of the element is present, unless the context clearly requires that only one of the element is present. Thus, the indefinite article "a" or "an" usually means "at least one".

Alkali metal carbonate

The use of alkali metal carbonates is known in the field of detergent manufacture. In particular, alkali metal carbonates are appreciated for their dual function as builders and buffers. The detergent composition according to the invention comprises 20-80 wt% of alkali metal carbonate. The preferred amount of alkali metal carbonate is 30-75 wt.%, more preferably 35-70 wt.%, even more preferably 40-65 wt.%. Such levels of alkali metal carbonate provide good Ca for most types of water hardness levels²⁺And Mg²⁺Ion scavenging, and other builder effects, for example, providing good buffering capacity. Preferred alkali metal carbonates are sodium carbonate and/or potassium, with sodium carbonate being particularly preferred. It is further preferred that the sodium carbonate constitutes at least 75 wt.%, more preferably at least 85 wt.%, even more preferably at least 90 wt.% of the total weight of the alkali metal carbonates.

The alkali metal carbonate present in the composition according to the invention may be present as such or as part of a more complex ingredient (for example sodium carbonate in sodium percarbonate). The determination of the total amount of alkali metal carbonate takes into account the amount of alkali metal carbonate added as such as well as the amount of alkali metal carbonate added as part of the more complex component.

Additional builders

In addition to the alkali metal carbonate, the compositions of the present invention may also comprise additional builders.

Additional builders useful in detergent compositions according to the invention may be non-aminocarboxylate polycarboxylic acid builders and/or salts thereof. Examples of preferred non-aminocarboxylic acid builders are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, salts thereof, or mixtures thereof. Among them, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid, salts thereof, or mixtures thereof are particularly preferable. Citric acid and/or citrate are particularly beneficial because, in addition to functioning as a builder, they are highly biodegradable and have been found to further reduce spot formation on dishware washed with a dishwasher. Therefore, more preferably, the detergent composition according to the present invention comprises citric acid, a citrate salt or a mixture thereof. In general, salts are preferred over the acid forms of these non-aminocarboxylate builders, with sodium and/or potassium salts being particularly preferred. If present, the total amount of citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids and salts thereof is preferably from 3 to 35% by weight, more preferably from 7 to 30% by weight, even more preferably from 10 to 25% by weight, wherein the weight of the salts is based on acid equivalents.

Other examples of preferred additional builders also include aminocarboxylates. These are well known in the detergent industry and are sometimes referred to as aminocarboxylate chelants. Aminocarboxylates are beneficial because they are generally strong builders. Examples of preferred aminocarboxylates are glutamic acid N, N-diacetic acid (GLDA), methylglycine diacetic acid (MGDA), iminodisuccinic acid (IDS), ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), hydroxyethyliminodiacetic acid (HEIDA), nitrilotriacetic acid (NTA), aspartic acid diethoxysiluccinic Acid (AES), aspartic acid-N, N-diacetic acid (ASDA), hydroxyethylethylenediaminetetraacetic acid (HEDTA), hydroxyethylethylenediaminetriacetic acid (HEEDTA), iminodifumaric acid (IDF), iminoditartaric acid (IDT), iminodimaleic acid (IDMAL), iminodicarboxylic acid (IDM), ethylenediamine difumaric acid (EDDF), ethylenediamine dimalic acid (EDDM), ethylenediamine ditartaric acid (EDDT), ethylenediamine disuccinic acid (EDDS), ethylenediamine dimaleic acid (EDDMAL), dipyridformic acid, salts thereof, and combinations thereof. Generally, aminocarboxylates are more preferred than acid forms, with sodium and/or potassium salts being particularly preferred. More preferably GLDA, MGDA, IDS, HEIDA, EDDS, NTA or mixtures thereof. Even more preferably GLDA, MGDA, IDS or mixtures thereof. MGDA is particularly preferred. If present, the amount of aminocarboxylate is preferably 5 to 60 wt.%, more preferably 10 to 40 wt.%.

Preferably, the detergent composition according to the present invention comprises the following builder combination:

20-80% by weight of an alkali metal carbonate; and

3 to 35% by weight in total of citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid, salts thereof, or mixtures thereof, wherein the weight of the salts is based on acid equivalents; and/or

Aminocarboxylates in a total amount of 5 to 60% by weight.

As mentioned above, aminocarboxylates are strong builders. Preferably, if the total amount of GLDA and MGDA is 10 to 40 wt%, the preferred amount of alkali metal carbonate is 30 to 50 wt%.

Especially preferred are detergent compositions according to the invention comprising the following builder combination:

20-75% by weight of an alkali metal carbonate; and

7-30% by weight of citric acid, a salt of citric acid or a mixture thereof, wherein the weight of said salt of citric acid is based on acid equivalents.

a) Mixtures of b) and

the composition according to the invention comprises 0.1-9.0 wt.% of a mixture of a) phosphonates, phosphonic acids or combinations thereof and b) phosphates, phosphoric acids or combinations thereof. This means that the composition according to the invention will comprise one or more of the following combinations: phosphonate + phosphate; phosphonate + phosphoric acid; phosphonic acid + phosphate; or phosphonic acid + phosphoric acid. "comprising 0.1 to 9.0% by weight of the mixture of a) and b)" means that the total amount of a) + b) is 0.1 to 9.0% by weight. The compositions according to the invention preferably comprise from 0.2 to 9.0% by weight, from 0.3 to 9.0% by weight, from 0.4 to 9.0% by weight or from 0.5 to 9.0% by weight of a mixture of a) and b). Further preferred amounts are from 0.6 to 8.0% by weight, more preferably from 1.0 to 7.0% by weight, even more preferably from 2.0 to 6.0% by weight, of the mixture of a) and b). a) These preferred amounts of the mixture of b) provide excellent results on the one hand while keeping the total phosphorus load low. The terms phosphonic acid and phosphoric acid both include partially neutralized acids thereof.

a) The preferred total weight of phosphonate and phosphonic acid is 0.5 to 6.0 wt.%, more preferably 0.75 to 4.0 wt.%, even more preferably 1.0 to 3.0 wt.%. Preferred phosphonates and phosphonic acids are complex-forming phosphonates/phosphonic acids, of which 1-hydroxyethane-1, 1-diphosphonic acid (HEDP), diethylenetriamine-penta (methylenephosphonic acid) (DTPMP), Ethylenediaminetetramethylenephosphonate (EDTMP), or mixtures thereof are particularly preferred. These may include higher homologues thereof. They are preferably used in the form of the sodium salts which exhibit a neutral reaction, for example as the hexasodium salt of EDTMP or as the heptasodium and octasodium salts of DTPMP. Further preferred are DTPMP and/or HEDP, with HEDP even more preferred. It is particularly preferred that at least 50 wt.%, more preferably at least 75 wt.%, even more preferably at least 90 wt.% of the total weight of a) is HEDP, DTPMP, EDTMP or a mixture thereof.

b) The preferred total weight of phosphate and phosphoric acid is 0.05 to 5.0 wt.%, more preferably 0.2 to 3.0 wt.%, even more preferably 0.5 to 2.0 wt.%. Alkali metal salts of tripolyphosphate, pyrophosphate or mixtures thereof are particularly preferred, with Sodium Tripolyphosphate (STPP) being even more preferred. Preferably at least 50 wt.%, more preferably at least 75 wt.%, even more preferably at least 90 wt.% of the total weight of b) is an alkali metal tripolyphosphate, pyrophosphate or a mixture thereof.

Particularly good results are obtained with a certain weight ratio of a) to b) in the composition according to the invention. Therefore preferred are detergent compositions according to the present invention wherein the ratio of the total weight of a) phosphonate and phosphonic acid to the total weight of b) phosphate and phosphoric acid is from 0.2:1 to 10:1, more preferably from 0.5:1 to 8:1, even more preferably from 1:1 to 5:1, still even more preferably from 1.5:1 to 4:1, still even more preferably from 1.6:1 to 3: 1.

Even better results were obtained with certain specific combinations of a) and b). The composition according to the invention therefore preferably comprises from 0.6 to 8.0% by weight of a mixture of:

a) HEDP in an amount of 0.5-6.0 wt%; and

b) an alkali metal salt of tripolyphosphate in an amount of 0.05-5.0 wt%,

wherein the weight ratio between a) and b) is preferably from 0.5:1 to 8: 1.

Copolymer

The composition according to the invention comprises 1.0 to 10 wt% of a copolymer comprising i) a sulfonic acid group containing monomer and ii) further ionic and/or non-ionic monomers. It was found that the use of such copolymers in detergent compositions according to the invention further reduces the spotting of the dishware after treatment in a dishwasher. The amount of copolymer used in the composition according to the invention is preferably from 1.5 to 8.0% by weight, more preferably from 2.0 to 5.0% by weight, even more preferably from 2.5 to 4.0% by weight.

The copolymer may comprise two, three, four or more different monomer units. Preferred sulfonic acid group-containing monomers are those having the formula:

R⁵(R⁶)C＝C(R⁷)-X-SO₃H

wherein R is⁵-R⁷Independently of one another represents-H, -CH₃A linear or branched, saturated alkyl residue having 2 to 12 carbon atoms, a linear or branched, mono-or polyunsaturated alkenyl residue having 2 to 12 carbon atoms, or a substituted or unsubstituted alkyl residue, with-NH₂-OH or-COOH substituted alkyl or alkenyl residue, or-COOH or-COOR⁴，R⁴Is a saturated or unsaturated, linear or branched hydrocarbon residue having from 1 to 12 carbon atoms, and X represents an optionally present spacer selected from the group consisting of- (CH)₂)_n-, where n is 0 to 4; -COO- (CH)₂)_k-, where k is 1-6; -C (O) -NH-C (CH)₃)₂-; and-C (O) -NH-CH (CH)₂CH₃)-。

Preferred among these monomers are those having the formula:

H₂C＝CH-X-SO₃H

H₂C＝C(CH₃)-X-SO₃H

HO₃S-X-(R⁶)C＝C(R⁷)-X-SO₃H，

wherein R is⁶And R⁷Independently of one another, from-H, -CH₃，-CH₂CH₃，-CH₂CH₂CH₃，-CH(CH₃)₂And X represents an optionally present spacer selected from- (CH)₂)_n-, where n is 0 to 4; -COO- (CH)₂)_k-, where k is 1-6; -C (O) -NH-C (CH)₃)₂-; and-C (O) -NH-CH (CH)₂CH₃)-。

Particularly preferred monomers containing at least one sulfonic acid group are 1-acrylamido-1-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-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, sulfomethacrylamide, sulfomethylmethacrylamide, or a mixture thereof. Water soluble salts of these acids and mixtures of salts and acids are equally preferred.

The sulphonic acid groups may be present in the polymer in fully or partially neutralised form, i.e. the acidic hydrogen atoms of the sulphonic acid groups may be replaced in some or all of the sulphonic acid groups by metal ions, preferably alkali metal ions, and especially sodium ions. According to the invention, preference is given to using copolymers which contain partially or completely neutralized sulfonic acid groups.

In those copolymers which contain only monomers from groups i and ii, the monomer distribution is preferably in each case in an amount of from 5 to 95% by weight of i or ii, particularly preferably in each case from 50 to 90% by weight of monomers of group i and from 10 to 50% by weight of monomers of group ii, relative to the copolymer.

The molar mass of the sulfocopolymers preferably used according to the invention can be varied to adapt the properties of the polymers to the desired intended application. Preferred automatic dishwashing agents are characterized in that the molar mass of the copolymer is 2000-200,000gmol^-1Preferably 4000-25,000gmol^-1Particularly 5000-^-1。

The copolymers according to the invention also comprise ionic and/or nonionic monomers. Preferred ionic monomers are unsaturated carboxylic acids. Preferred unsaturated carboxylic acids are those having the formula R¹(R²)C＝C(R³) Those of COOH, wherein R¹-R³Independently of one another, represents-H, -CH as defined above₃Straight-chain or branched saturated alkyl residues having 2 to 12 carbon atoms, having 2 to 12 carbon atomsStraight-chain or branched mono-or polyunsaturated alkenyl residues, substituted by-NH₂-OH or-COOH substituted alkyl or alkenyl residue, or-COOH or-COOR⁴，R⁴Is a saturated or unsaturated, straight-chain or branched hydrocarbon residue having 1 to 12 carbon atoms.

Preferred carboxyl group-containing monomers are acrylic acid, methacrylic acid, ethacrylic acid, chloroacrylic acid, cyanoacrylic acid, crotonic acid, phenylacrylic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid, sorbic acid, cinnamic acid or mixtures thereof.

Preferred nonionic monomers are those having the formula R¹(R²)C＝C(R³)-X-R⁴Wherein R is¹-R⁴Independently of one another represents-H, -CH₃or-C₂H₅And X represents an optionally present spacer selected from the group consisting of-CH₂-, - (O) O-and-C (O) -NH-, and R⁴Denotes a straight-chain or branched, saturated alkyl residue having from 2 to 22 carbon atoms or an unsaturated, preferably aromatic residue having from 6 to 22 carbon atoms.

More preferred nonionic monomers are butene, isobutene, pentene, 3-methylbutene, 2-methylbutene, cyclopentene, hexene, 1-hexene, 2-methyl-1-pentene, 3-methyl-1-pentene, cyclohexene, methylcyclopentene, cycloheptene, methylcyclohexene, 2,4, 4-trimethyl-1-pentene, 2,4, 4-trimethyl-2-pentene, 2, 3-dimethyl-1-hexene, 2, 4-dimethyl-1-hexene, 2, 5-dimethyl-1-hexene, 3, 5-dimethyl-1-hexene, 4, 4-dimethyl-1-hexane, ethylcyclohexyne, 1-octene, alkenes having 10 or more carbon atoms, for example 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and C₂₂-1-olefin, 2-styrene, -methylstyrene, 3-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, methyl methacrylate, N- (meth) acrylamide, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylateEsters, N- (2-ethylhexyl) acrylamide, octyl acrylate, octyl methacrylate, N- (octyl) acrylamide, lauryl acrylate, lauryl methacrylate, N- (lauryl) acrylamide, stearyl acrylate, stearyl methacrylate, N- (stearyl) acrylamide, behenyl acrylate, behenyl methacrylate and N- (behenyl) acrylamide or mixtures thereof.

Nonionic surfactant

The compositions according to the invention comprise from 1.0 to 10% by weight of nonionic surfactant. The preferred total amount of nonionic surfactant is from 2.0 to 8% by weight, more preferably from 2.5 to 5.0% by weight. The nonionic surfactant used in the composition according to the invention may be a single nonionic surfactant or a mixture of two or more nonionic surfactants.

Nonionic surfactants of the amine oxide type, such as N-cocoalkyl-N, N-dimethyl amine oxide and N-tallow-N, N-dihydroxymethyl amine oxide, and also of the fatty acid alkanolamide type, are also suitable. The amount of these nonionic surfactants preferably does not exceed the amount of ethoxylated fatty alcohols, in particular does not exceed half the amount thereof.

Another preferred class of nonionic surfactants that can be used as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain.

Low foaming nonionic surfactants are used as preferred surfactants. Detergent compositions, especially for machine dishwashing, particularly preferably comprise nonionic surfactants from alkoxylated alcohols. Alkoxylated, advantageously ethoxylated, in particular primary alcohols, preferably having 8 to 18C atoms and an average of 1 to 12 moles of Ethylene Oxide (EO) per mole of alcohol, where the alcohol residue may be linear or, preferably, methyl-branched in the 2-position, or may contain linear and methyl-branched residues in the mixture, as is usually present in oxo alcohol residues, are preferably usedA nonionic surfactant. In particular, however, preference is given to alcohol ethoxylates having a linear residue, which are prepared from alcohols of natural origin having 12 to 18C atoms, for example from coconut oil alcohol, palm oil alcohol, tallow oil alcohol or oleyl alcohol, and have an average of from 2 to 8 mol EO per mol of alcohol. Preferred ethoxylated alcohols include, for example, C with 3EO-4EO_12-14Alcohols, C with 7EO_9-12Alcohols, C with 3EO, 5EO, 7EO or 8EO_13-15Alcohols, C with 3EO, 5EO or 7EO_12-18Alcohols, and mixtures of these, e.g. C with 3EO_12-14Alcohols with C having 5EO_12-19A mixture of alcohols. The degree of ethoxylation is a statistical average, which may be an integer or a fraction for a particular product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols having more than 12EO (ethylene oxide groups) may also be used. Examples of these are tallow fatty alcohols with 14EO, 25EO, 30EO, 40EO or 80 EO. Preferred tallow fatty alcohols having more than 12EO have 60-100EO, more preferably 70-90 EO. Particularly preferred tallow fatty alcohols having more than 12EO are tallow fatty alcohols having 80 EO.

Likewise particular preference is given to using nonionic surfactants from alkoxylated alcohols, particularly preferably from mixed alkoxylated alcohols, in particular from EO-AO-EO nonionic surfactants.

The nonionic surfactant preferably contains a propylene oxide unit in its molecule. Such PO units preferably constitute at most 25 wt%, more preferably at most 20 wt%, even more preferably at most 15 wt% of the total molar mass of the nonionic surfactant. Particularly preferred nonionic surfactants are ethoxylated monohydric alkanols or alkylphenols which additionally comprise polyoxyethylene/polyoxypropylene block copolymer units. The alcohol or alkylphenol portion of such nonionic surfactant molecules here preferably constitutes more than 30 wt.%, more preferably more than 50 wt.%, even more preferably more than 70 wt.% of the total molar mass of such nonionic surfactants. Preferred detergent compositions are characterised in that they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units constitute at most 25 wt%, more preferably at most 20 wt%, even more preferably at most 15 wt% of the total molar mass of the nonionic surfactant per molecule.

The surfactants preferably used originate from the group comprising alkoxylated nonionic surfactants, in particular ethoxylated primary alcohols, and mixtures of these surfactants with surfactants of complex structure, such as polyoxypropylene/polyoxyethylene/polyoxypropylene ((PO/EO/PO) surfactants). Such (PO/EO/PO) nonionic surfactants are also distinguished by good foam control. Particularly preferred additional nonionic surfactants used which have a melting point above room temperature contain from 40 to 70% of a polyoxypropylene/polyoxyethylene/polyoxypropylene block polymer blend which contains 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene having 17mol of ethylene oxide and 44mol of propylene oxide and 25% by weight of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.

Nonionic surfactants which have proven particularly preferred for the purposes of the present invention are low-foaming nonionic surfactants comprising alternating ethylene oxide and alkylene oxide units. Of these, surfactants having EO-AO-EO-AO blocks are again preferred, in each case from one to ten EO or AO groups being linked to one another, followed by a block of the respective other group. Preferred nonionic surfactants are those having the general formula:

wherein R is¹Represents a linear or branched saturated or mono-or polyunsaturated C_6-24An alkyl or alkenyl residue; each radical R²Or R³Independently of one another from-CH₃，-CH₂CH₃，-CH₂CH₂-CH₃，-CH(CH₃)₂And the subscripts w, x,y, z independently of one another denote an integer from 1 to 6.

Preferred nonionic surfactants of the above formula can be prepared by known methods from the corresponding alcohols R¹-OH and ethylene oxide or alkylene oxide. Residue R in the above formula¹And may vary depending on the source of the alcohol. If natural sources are used, the residue R¹Contain an even number of carbon atoms and are generally unbranched, preferably straight-chain residues from alcohols of natural origin having 12 to 18C atoms, for example from coconut, palm, tallow or oleyl alcohol. Alcohols obtainable from synthetic sources are, for example, Guerbet alcohols or straight-chain and methyl-branched residues in methyl-branched residues or mixtures in the 2-position, as are usually present in oxygen-containing alcohol residues. Regardless of the nature of the alcohol used to produce the nonionic surfactant in the preparation, preferred nonionic surfactants are those in which R is in the above formula¹Denotes those having allyl residues with 6 to 24, more preferably with 8 to 20, even more preferably with 9 to 15, still even more preferably with 9 to 11 carbon atoms.

In addition to propylene oxide, butylene oxide may be particularly considered as alkylene oxide units alternating with ethylene oxide units in the preferred nonionic surfactants. However, wherein R²Or R³Independently of one another from-CH₂CH₂-CH₃or-CH (CH)₃)₂Also suitable are the additional alkylene oxides of (a). The nonionic surfactants of the above formula which are preferably used are those wherein R is²Or R³Represents a residue-CH₃W and x represent, independently of one another, values of 3 or 4, and y and z represent, independently of one another, values of 1 or 2.

In summary, preferred nonionic surfactants comprise in particular a C having 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units, followed by 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units_9-15Those of alkyl residues. In aqueous solutions, these surfactants exhibit the necessary low viscosity and can be used particularly preferably according to the invention.

Having the formula R¹-CH(OH)CH₂O-(AO)_w-(A'O)_x-(A”O)_y-(A”'O)_z-R²The surfactant of (1), wherein R¹And R²Independently of one another, represents a linear or branched, saturated or mono-or polyunsaturated C_2-40An alkyl or alkenyl residue; a, A 'and A' ″ independently of one another denote a residue from-CH₂CH₂，-CH₂CH₂-CH₂，-CH₂-H(CH₃)，-CH₂-CH₂-CH₂-CH₂，-CH₂-CH(CH₃)-CH₂-，-CH₂-CH(CH₂-CH₃) A residue of (a); and w, x, y and z represent values between 0.5 and 90, wherein x, y and/or z may also be 0, are preferred according to the invention.

In particular, preferred end-group-capped poly (oxyalkylated) nonionic surfactants are according to formula R¹O[CH₂CH₂O]_xCH₂CH(OH)R²Of which the residue R is removed¹Besides, it means a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon residue having 2 to 30 carbon atoms, preferably having 4 to 22 carbon atoms, and further comprising a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon residue R having 1 to 30 carbon atoms²X represents a value between 1 and 90, preferably between 30 and 80, in particular between 30 and 60.

Particularly preferred surfactants are those having the formula R¹O[CH₂CH(CH₃)]O]_x[CH₂CH₂O]_yCH₂CH(OH)R²Wherein R is¹Denotes straight-chain or branched aliphatic hydrocarbon residues having 4 to 18 carbon atoms or mixtures thereof. R²Denotes a straight-chain or branched hydrocarbon residue having from 2 to 26 carbon atoms or a mixture thereof, x denotes a value between 0.5 and 1.5 and y denotes a value of at least 15.

The use of the above-described nonionic surfactants having a free hydroxyl group on one of the two terminal alkyl residues can help to form film deposits in machine dishwashing.

Particularly preferred end-group-capped poly (oxyalkylated) nonionic surfactantsThe surfactant is also of the formula R¹O[CH₂CH₂O]_x[CH₂CH(R³)O]_yCH₂CH(OH)R²Wherein R is¹And R²Independently of one another, represents a linear or branched, saturated or mono-or polyunsaturated hydrocarbon residue having from 2 to 26 carbon atoms, R³Independently of one another from-CH₃，-CH₂CH₃，-CH₂CH₂-CH₃，-CH(CH₃)₂But preferably represents-CH₃And x and y independently of one another represent a value between 1 and 32, where R³＝-CH₃And nonionic surfactants in which x has a value of from 15 to 32 and y has a value of from 0.5 to 1.5 are very particularly preferred.

Another useful nonionic surfactant is one having the formula R¹O[CH₂CH(R³)O]_x[CH₂]_kCH(OH)[CH₂]_jOR²The terminal-terminated poly (oxyalkylated) nonionic surfactant of (1), wherein R¹And R²Denotes a straight-chain or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon residue having from 1 to 30 carbon atoms, R³Represents H or a methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl or 2-methyl-2-butyl residue, x represents a value between 1 and 30, k and j represent values between 1 and 12, preferably between 1 and 5. If x is greater than or equal to 2, then R is represented by the formula¹O[CH₂CH(R³)O]_x[CH₂]_kCH(OH)[CH₂]_jOR²Each R in (1)³May be different. R¹And R²Preference is given to straight-chain or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon residues having from 6 to 22 carbon atoms, particularly preferably residues having from 8 to 18 carbon atoms. H, -CH₃or-CH₂CH₃For the residue R³Is particularly preferred. Particularly preferred values of x are in the range from 1 to 20, in particular from 6 to 15.

As described above, if x ≧ 2, each R in the above formula³May be different. In this way, the alkylene oxide units in brackets can be changed. For example, if x represents 3, the residue may be selectedRadical R³To form ethylene oxide (R)³H) or propylene oxide (R)³＝CH₃) Units, which may be linked to each other in any order, such as (EO) (PO) (EO), (EO) (EO) (PO), (EO) (EO) (EO) (PO), (PO) (PO) (PO) (EO) and (PO) (PO) (PO). The value 3 of x has been chosen here as an example and may well be increased, with the range of variation increasing with increasing value of x, for example comprising a large number of (EO) groups combined with a small number of (PO) groups, and vice versa.

Particularly preferred end-capped poly (oxyalkylated) alcohols having the above formula have values of k ═ 1 and j ═ 1, such that the above formula is simplified to R¹O[CH₂CH(R³)O]_xCH₂CH(OH)CH₂OR². In the formula, R¹，R²And R³As defined above, x represents a number from 1 to 30, preferably from 1 to 20, in particular from 6 to 18. Particularly preferred surfactants are those in which the residue R¹And R²Containing 9 to 14 carbon atoms, R³Those which represent H and x takes a value of 6-15.

The C chain length and the degree of ethoxylation or alkoxylation of the above nonionic surfactants are statistical averages which may be whole or fractional for a particular product. Due to the production method, the commercial products of the above formulae do not consist essentially of individual representatives, but of mixtures, so that not only the carbon chain length but also the degree of ethoxylation or alkoxylation can be average values and thus fractional values.

The most preferred nonionic surfactants are according to the formula:

wherein n is 0 to 5 and m is 10 to 50, more preferably wherein n is 0 to 3 and m is 15 to 40, even more preferably wherein n is 0 and m is 18 to 25. It was found that the surfactants according to this formula further reduce the spotting of the dishes treated in the machine dishwasher. Preferably at least 50 wt% of the nonionic surfactant comprised in the composition according to the invention is a nonionic surfactant according to this formula. Such nonionic surfactants are commercially available, for example under the trade names Dehypon WET (supplier: BASF) and Genapol EC50 (supplier: Clariant).

Of course, the above nonionic surfactants can be used not only as a single substance but also as a surfactant mixture of two, three, four or more surfactants.

Preferred are detergent compositions according to the present invention wherein the nonionic surfactant comprises a nonionic surfactant according to the formula:

wherein n is 0 to 5 and m is 10 to 50, more preferably wherein n is 0 to 3 and m is 15 to 40, even more preferably wherein n is 0 and m is 18 to 25;

and wherein the composition further comprises 3-35% by weight of citric acid, a salt of citric acid, or a mixture thereof, wherein the weight of said salt of citric acid is based on acid equivalents.

Particularly good results are obtained with further preferred detergent compositions according to the invention wherein the nonionic surfactant comprises one or more nonionic surfactants according to the formula:

wherein n is 0 to 5 and m is 10 to 50, more preferably wherein n is 0 to 3 and m is 15 to 40, even more preferably wherein n is 0 and m is 18 to 25; and

wherein the amount of the mixture of a) and b) is from 0.6 to 8.0% by weight, and wherein

a) HEDP in an amount comprising 0.5 to 6.0 wt%; and wherein

b) Comprising an alkali metal salt of tripolyphosphate in an amount of 0.05-5.0% by weight,

and wherein the weight ratio between a) and b) is from 0.5:1 to 8:1

And wherein the composition further comprises 3-35 wt% citric acid, a citrate salt, or a mixture thereof, wherein the weight of the citrate salt is based on acid equivalents.

Composition comprising a metal oxide and a metal oxide

Preferably, the machine dishwashing composition according to the present invention comprises an additional detergent active, more preferably a detergent active selected from the group consisting of enzymes, enzyme stabilizers, bleaches, bleach activators, bleach catalysts, bleach scavengers, drying aids, silicates, metal conditioners, colorants, odorants/perfumes, lime soap dispersants, antifoams, rust inhibitors and preservatives.

It is preferred that the detergent composition according to the invention comprises at least 5 wt%, more preferably at least 8 wt%, even more preferably at least 10 wt% of bleach based on the total weight of the composition. The bleaching agent of the composition of the present invention preferably comprises a chlorine or bromine releasing agent or a peroxy compound. Preferably, the bleaching agent is selected from the group consisting of peroxides (including peroxide salts, such as sodium percarbonate), organic peracids, salts of organic peracids and combinations thereof. More preferably, the bleaching agent is a peroxide. Most preferably, the bleaching agent is percarbonate. Examples of peroxides are monopersulfates, perborate monohydrate, perborate tetrahydrate and the acids and corresponding salts of percarbonates. Organic peracids useful herein include alkyl and aryl peroxyacids, such as peroxybenzoic acid and cyclo-substituted peroxybenzoic acids (e.g., peroxy-alpha-naphthoic acid), aliphatic and substituted aliphatic monoperoxy acids (e.g., peroxylauric acid and peroxystearic acid), and phthaloyl amidoperoxycaproic acid (PAP). Typical diperoxy acids useful in the present invention include alkyl diperoxy acids and aryl diperoxy acids such as 1, 12-diperoxydodecanedioic acid (DPDA), 1, 9-diperoxyazelaic acid, diperoxycarbazelaic acid, diperoxydecanedioic acid and diperoxyiisophthalic acid, and 2-decyldiperoxybutane-1, 4-diacid. Preferably, the bleaching agent is present as dispersed particles. Particularly preferably, the composition of the present invention comprises a coated bleach particle, and further preferably, the coated bleach particle comprises a water-soluble coating. The water-soluble coating layer advantageously comprises a coating agent selected from alkali metal sulfates, alkali metal carbonates or alkali metal chlorides and combinations thereof. Preferably, the coating comprises a sulfate. The application of the bleaching agent can be accomplished, for example, by crystallization or by spray granulation. Suitable coated bleaching agents are described, for example, in EP-A0136580 and EP-A0863842. Most preferably, spray granulated coated percarbonate is used.

The detergent composition may comprise one or more bleach activators, for example peroxyacid bleach precursors. Peroxyacid bleach precursors are well known in the art. As non-limiting examples, mention may be made of N, N, N ', N' -Tetraacetylethylenediamine (TAED), Sodium Nonanoyloxybenzenesulfonate (SNOBS), sodium benzoyloxybenzenesulfonate (SBOBS) and cationic peroxyacid precursors (SPCC) as described in U.S. Pat. No. 4, 4751015.

Preferably, the composition according to the invention comprises a bleach catalyst. It is particularly preferred that the composition comprises ｃA bleach catalyst which is ｃA manganese complex, for example Mn-Me TACN as described in EP- ｃA-0458397, and/or sulphenamide as described in US- ｃA-5,041,232 and US- ｃA-5,047,163. Advantageously, the bleach catalyst is present in the composition in the form of an encapsulate, particularly an encapsulate separate from the bleach particle (to avoid premature bleach activation). Cobalt or iron catalysts may also be used.

Preferably, the composition according to the invention further comprises a protease, an amylase or a combination thereof, and more preferably a combination of a protease and an amylase.

Silicates are known ingredients in the field of machine dishwashing detergent compositions. Silicates are included to provide dishwashing care benefits and to reduce corrosion of dishware, especially glass and aluminum surfaces. Silicates may also have some builder activity, but silicates are not considered builders in this specification. Silicates are preferably used in the detergent compositions according to the invention. Particularly preferred silicates are sodium disilicate, sodium metasilicate and crystalline phyllosilicates or mixtures thereof. If present, the total amount of silicate is preferably from 1 to 15 wt%, more preferably from 2 to 10 wt%, even more preferably from 2.5 to 5.0 wt% of the composition.

The detergent composition according to the invention may be in any suitable form, such as a liquid, (encapsulated) powder, granule, lozenge, paste, slurry or tablet.

The compositions are preferably provided as water-soluble or water-dispersible unit doses, particularly in the form of sachets (i.e. containing non-shape-stable ingredients, such as liquids and/or powders) or tablets. Preferably, the unit dose is sized and shaped to fit into a detergent cup of a conventional household machine dishwasher, as is known in the art.

If the composition is in the form of a tablet, it is highly preferred to wrap the tablet for the purpose of improving hygiene and consumer safety. The packaging material may be water soluble or water insoluble. Water-soluble packaging materials, for example based on polyvinyl alcohol (PVA), are preferred. This prevents the detergent composition from coming into direct contact with the skin of the consumer when a unit dose is placed into the detergent cup of a machine dishwasher. Of course, another benefit is that the consumer does not need to remove the water-soluble wrapper before placing it in the detergent cup.

The unit dose pouch may have one or more compartments. In the case of a multi-compartment unit dose pouch, preferably at least one compartment contains a powder or a liquid, such as a liquid surfactant.

Preferred unit dose tablets are those having more than one visually distinct tablet region. Such areas may be formed, for example, by two different (colored) layers or tablets having a body and different inserts, for example, forming nested eggs. Regardless of orientation, one benefit of such a multi-compartment pouch/multi-region tablet is that it can be used to reduce/prevent unwanted chemical reactions between two or more ingredients during storage by (partial) physical isolation.

More preferably, the detergent composition according to the invention is in the form of a tablet, particularly preferably a multi-layer tablet. As a multilayer tablet, at least part of the bleach catalyst is advantageously in a separate layer from any oxidizing agent, such as percarbonate.

The detergent composition according to the present invention preferably comprises 2.0-16 wt% of a binder, wherein preferably the binder comprises at least 50 wt% of polyethylene glycol (PEG), based on the total amount of binder. Preferred PEGs have an average molecular weight of 2000-8000g/mol, such as PEG 4000. The addition of the binder enhances the structural integrity of the tablet, which can be observed by less broken tablets and/or less powder residue when the tablet is exposed to mechanical stress (such as experienced during transport).

Detergent compositions according to the present invention may be prepared using methods and apparatus known in the art of machine dishwashing detergent composition manufacture. The detergent compositions of the present invention may be prepared by combining all the ingredients in the amounts specified in the compositions according to the present invention and then mixing.

The invention further relates to the use of a mixture of a) a phosphonate, phosphonic acid or a combination thereof and b) a phosphate, phosphoric acid or a combination thereof in a detergent composition to reduce the formation of spots on dishware, preferably glass and/or metal surfaces treated in a machine dishwasher. Preferred aspects in the context of the detergent composition according to the invention also apply mutatis mutandis in the context of the use according to the invention.

The invention will now be illustrated by the following non-limiting examples.

Examples

Spot formation evaluation

Spot formation was evaluated in a watch box, the interior of which was painted black. To assess spot formation, the articles were placed in a cabinet and illuminated from below (in the case of glass articles) or from above (in the case of non-glass articles) with a certain light source (Philips master TL-D36W/8652M, 120cm long). The spot formation score of the article is based on a count of the number of spots. A spot formation score of 9 indicates no spots, and a spot formation score of 1 indicates that the product is full of spots.

Spot formation value	Description of blob formation values
		9	Is not provided with
8	1-3 spots
		7	4-10 spots
6	11-25 spots
		5	26-35 spots
4	36-50 spots
		3	More than 50 spots, 60% of the surface was covered with spots
2	75% of the surface is covered with spots
		1	The whole surface is covered with spots

Formulations according to example 1 and comparative examples A-C

Detergent compositions were prepared with the formulations listed in table 1. In each case, the respective ingredients are incorporated in powder or granular form and dry-blended, and then compressed into tablets.

TABLE 1 formulations according to example 1 and comparative examples A, B and C. The amounts represent the weight% of the ingredients.

	Comparative example A	Comparative example B	Comparative example C	Example 1
					Citric acid sodium salt	25.0	25.0	25.0	25.0
Sodium carbonate	34.2	34.2	34.2	34.2
					Sodium disilicate	3.0	3.0	3.0	3.0
Sodium percarbonate	13.0	13.0	13.0	13.0
					Bleach catalyst particles	1.5	1.5	1.5	1.5
Protease enzyme	0.9	0.9	0.9	0.9
					Amylase	0.6	0.6	0.6	0.6
Acrylic acid/sulfonic acid copolymer	4.2	4.2	4.2	4.2
					Acrylic acid homopolymer	1.3	1.3	1.3	1.3
Nonionic surfactant	3.3	3.3	3.3	3.3
					PEG4000	7.5	7.5	7.5	7.5
STPP	-	-	3.0	3.0
					Na-HEDP	-	2.0	-	2.0
Other minor ingredients	To 100 percent	To 100 percent	To 100 percent	To 100 percent

Machine dishwashing test

20 grams of the detergent composition according to example 1 or comparative examples a, B or C were applied as detergent in a Miele GSL dishwasher. The following machine dishwashing conditions were used:

program: 50 deg.C

Method of dosing detergent composition: by distributor (detergent cup)

Water supply: the water temperature of the water tank is 15 DEG C

Ballast soil: 1 cup thawed Tensio soil

Program repetition: 1

Washing 6 times

A variety of cutlery items were placed in the machine dishwasher and the cleaning procedure was carried out using the above conditions. The tableware articles were then evaluated for spot formation, the results of which are given in table 2.

Table 2 spot formation results (larger numbers indicate less spot formation).

The result of comparative example a represents the case where HEDP or STTP was not added to the detergent composition. From the results, it can be seen that the presence of HEDP (comparative example B) or STTP (comparative example C) in the detergent composition improved the spot formation on the ceramic articles, but actually worsened the spot formation on glass and plastic articles. Thus, it was completely unexpected that by incorporating both HEDP and STTP (example 1) in a detergent composition, it improved spot formation on glass and metal articles. Indeed, the improved spot formation of example 1 indicates that the combination of HEDP and STTP acts synergistically to improve spot formation: in view of comparative example a (no HEDP, no STTP), this is more than would be expected from the sum of the effects observed for comparative examples b (HEDP) and C.

Claims

1. A detergent composition comprising:

20-80% by weight of an alkali metal carbonate; and

1.0-10% by weight of a nonionic surfactant; and

1.0 to 10% by weight of a copolymer comprising:

i. a sulfonic acid group-containing monomer;

additional ionic and/or nonionic monomers; and

0.1-9.0% by weight of a mixture of:

a) phosphonate, phosphonic acid, or combinations thereof; and

b) phosphate, phosphoric acid or combinations thereof;

wherein the phosphonate, phosphonic acid, or combination thereof comprises HEDP, DTPMP, EDTMP, or a mixture thereof;

and wherein the phosphate, phosphoric acid, or combination thereof comprises an alkali metal salt of tripolyphosphate, pyrophosphate, or a mixture thereof;

wherein the total weight of phosphonate and phosphonic acid is 0.5 to 6.0 weight percent;

wherein the total weight of the phosphate and phosphoric acid is 0.05-5.0 wt%; and

wherein the ratio of a) the total weight of the phosphonate and phosphonic acid to b) the total weight of the phosphate and phosphoric acid is from 0.5:1 to 5: 1.

2. The composition of claim 1, wherein the amount of the copolymer is 1.5-8.0 wt%.

3. The composition of claim 1, wherein the amount of the copolymer is 2.0-5.0 wt%.

4. The composition of claim 1, wherein the amount of the copolymer is 2.5-4.0 wt%.

5. The composition of any one of claims 1-4, wherein the sulfonic acid group is of the formula R⁵(R⁶)C＝C(R⁷)-X-SO₃H, wherein R⁵-R⁷Independently of one another represents-H, -CH₃A linear or branched, saturated alkyl residue having 2 to 12 carbon atoms, a linear or branched, mono-or polyunsaturated alkenyl residue having 2 to 12 carbon atoms, or a substituted or unsubstituted alkyl residue, with-NH₂An alkyl or alkenyl residue substituted by-OH or-COOH, or represents-COOH or-COOR⁴，R⁴Is a saturated or unsaturated, linear or branched hydrocarbon residue having from 1 to 12 carbon atoms; and X represents an optional groupA spacer group present selected from- (CH)₂)_n-, where n is 0 to 4; -COO- (CH)₂)_k-, where k is 1-6; -C (O) -NH-C (CH)₃)₂-; and-C (O) -NH-CH (CH)₂CH₃)-。

6. The composition of any one of claims 1-4, wherein the ionic monomer is of formula R¹(R²)C＝C(R³) Unsaturated carboxylic acid of COOH, wherein R¹-R³Independently of one another represents-H, -CH as defined above₃A linear or branched, saturated alkyl residue having 2 to 12 carbon atoms, a linear or branched, mono-or polyunsaturated alkenyl residue having 2 to 12 carbon atoms, or a substituted or unsubstituted alkyl residue, with-NH₂An alkyl or alkenyl residue substituted by-OH or-COOH, or represents-COOH or-COOR⁴，R⁴Is a saturated or unsaturated, straight-chain or branched hydrocarbon residue having 1 to 12 carbon atoms.

7. The composition of any one of claims 1-4, wherein the nonionic monomer has the general formula R¹(R²)C＝C(R³)-X-R⁴Wherein R is¹-R⁴Independently of one another represents-H, -CH₃Or C₂H₅X represents an optional spacer selected from-CH₂-, - (O) O-and-C (O) -NH-, and R⁴Represents a straight-chain or branched saturated alkyl residue having 2 to 22 carbon atoms, or represents an unsaturated residue having 6 to 22 carbon atoms.

8. The composition of claim 7, wherein R⁴Represents an aromatic residue having 6 to 22 carbon atoms.

9. The composition of any of claims 1-4, wherein the total weight of the phosphonate and phosphonic acid is 0.75-4.0 wt%.

10. The composition of any of claims 1-4, wherein the total weight of the phosphonate and phosphonic acid is 1.0-3.0 wt%.

11. The composition of any one of claims 1-4, wherein the phosphonate, phosphonic acid, or combination thereof comprises HEDP.

12. The composition of any one of claims 1-4, wherein the total weight of the phosphate salt and phosphoric acid is 0.2-3.0 wt%.

13. The composition of any one of claims 1-4, wherein the total weight of the phosphate salt and phosphoric acid is 0.5-2.0 wt%.

14. The composition of any one of claims 1-4, wherein the phosphate, phosphoric acid, or combination thereof comprises an alkali metal salt of tripolyphosphate.

15. The composition of any one of claims 1-4, wherein the ratio of a) the total weight of phosphonate and phosphonic acid to b) the total weight of phosphate and phosphoric acid is 1:1 to 5: 1.

16. The composition of any one of claims 1-4, wherein the ratio of a) the total weight of phosphonate and phosphonic acid to b) the total weight of phosphate and phosphoric acid is 1.5:1 to 4: 1.

17. The composition of any one of claims 1-4, wherein the ratio of a) the total weight of phosphonate and phosphonic acid to b) the total weight of phosphate and phosphoric acid is 1.6:1 to 3: 1.

18. The composition according to any one of claims 1-4, wherein the total amount of alkali metal carbonate is 30-75% by weight.

19. The composition according to any one of claims 1-4, wherein the total amount of alkali metal carbonate is 35-70 wt%.

20. The composition according to any one of claims 1-4, wherein the total amount of alkali metal carbonate is 40-65% by weight.

21. The composition of any one of claims 1-4, wherein the composition comprises 20-75% by weight alkali metal carbonate, and further comprises 7-30% by weight citric acid, citrate, or a mixture thereof, wherein the weight of citrate is based on acid equivalents.

22. The composition according to any one of claims 1-4, wherein the composition comprises 10-40 wt.% total of GLDA and MGDA and 30-50 wt.% of alkali metal carbonate.

23. The composition of any one of claims 1-4, wherein the composition comprises 2.0-8 wt.% total nonionic surfactant.

24. The composition of any one of claims 1-4, wherein the composition comprises 2.5-5.0 wt.% total nonionic surfactant.

25. The composition of any one of claims 1-4, wherein the nonionic surfactant comprises a nonionic surfactant according to the formula:

wherein n is 0-5 and m is 10-50; and further comprising 3-35% by weight of citric acid, a salt of citric acid, or a mixture thereof, wherein the weight of said salt of citric acid is based on acid equivalents.

26. The composition of claim 25, wherein n is 0-3 and m is 15-40.

27. The composition of claim 25, wherein n is 0 and m is 18-25.