ES2962909T3 - Detergent composition for automatic dishwasher - Google Patents

Abstract

The present invention relates to a detergent composition for automatic dishwashers consisting of: * 20-80% by weight of adjuvant; * 5-25% by weight of bleaching component; * 1-10% by weight of a graft copolymer having a polysaccharide main chain and one or more side chains of one or more synthetic monomeric units; * 1-15% by weight of nonionic surfactant represented by the following formula: R1-O-(CH2CH2O)n-(CHR2CHR2'O)q-(CH2CH(OH)R3)s-R4 in which R1 is an agent linear or branched. a C8-C22 alkyl radical or a linear or branched C8-C22 alkylphenol radical; or R2 and R2' are independently selected from hydrogen and a C1-C5 alkyl radical, and where R2 or R2' is hydrogen; or R3 is a covalent bond or a linear aliphatic C2-C26 alkyl radical; or R4 is selected from hydrogen and an alkyl radical having 1 to 15 carbon atoms; or 5 <= n <= 30; or 0 <= q <= 3; 20 os = 1-5, said nonionic surfactant being selected from homopolymers, statistical copolymers, block copolymers and combinations thereof; and * 0-60% by weight of one or more different ingredients. The detergent composition of the present invention produces very good cleaning results with minimal staining and film formation. (Automatic translation with Google Translate, without legal value)

Description

DESCRIPTION

Detergent composition for automatic dishwasher

Technical field of the invention

The present invention relates to an automatic dishwasher detergent composition containing adjuvant, bleaching component, a graft copolymer having a polysaccharide backbone and one or more side chains of one or more synthetic monomeric units, a nonionic surfactant based in polyoxyethylene and optionally one or more other components.

The automatic dishwasher detergent (ADW) composition of the present invention combines very good cleaning action with minimal film formation and staining.

Background of the invention

Automatic dishwasher detergents (ADW) constitute a distinctive class of detergent compositions. Unlike most other detergents, ADW detergents must be low foaming. Furthermore, the expected end result of each automatic dishwashing series is a stain-free and film-free appearance of glassware and cutlery.

In general, ADW detergents are mixtures of components whose purpose, in combination, is to break down and remove food soils; inhibit foaming caused by certain food soiling; and remove stains that may be caused by beverages such as coffee and tea or by plant soil such as carotenoid soil.

Staining and filming of glassware are the main criteria by which the performance of a dishwasher formulation is assessed. Staining is an obvious reference to distinct residues on glassware that form when water droplets evaporate and leave behind dissolved solids. Film formation refers to a more uniform deposition along a large continuous portion of the glass surface. Sometimes this film can be of organic origin (resulting from dirt in the wash bath or organic components in the detergent) but it is also frequently inorganic in nature, due to the formation and deposition of some mineral precipitate.

ADW detergents may comprise a variety of detergent components, including alkalinity sources, adjuvants, bleaching systems, scale inhibitors, corrosion inhibitors, surfactants, defoamers, laminating polymers and/or enzymes. Adjuvant materials are used to provide alkalinity and buffering capacity, maintain ionic strength, extract metals from soils, and/or remove alkaline earth metal ions from wash solutions. Examples of adjuvant materials include phosphates, alkali metal citrates, carbonates and bicarbonates; and nitrilotriacetic acid (NTA) salts; methylglycine-diacetic acid (MGDA); glutaric-diacetic acid (GLDA), polycarboxylates such as polymaleates, polyacetates, polyhydroxyacrylates, polyacrylate/polymaleate and polyacrylate/polymethacrylate copolymers, as well as zeolites; stratified silicas and mixtures thereof.

Phosphate-free or low-phosphate compositions rely on non-phosphate adjuvants, such as citrate, carbonate, silicate, disilicate, bicarbonate, aminocarboxylates, and other salts, to sequester calcium and magnesium from hard water and, after drying, can leave a visible insoluble deposit. Polymers made from (meth)acrylic acid and maleic acid are known for use in inhibiting scale or other insoluble deposits produced from non-phosphate adjuvants.

Surfactants are amphiphilic compounds, that is, compounds that contain hydrophobic as well as hydrophilic groups, a property that allows them to mix hydrophobic dirt on dishes with rinse water. Nonionic surfactants are preferably used for dishwashing applications as they are known to produce low to moderate foaming, are gentle on human skin, and have superior performance in removing oily soils. Nonionic surfactants are additionally suitable for mixing with other materials contained in the detergent formulation since they are known to be chemically inert and stable against pH change. Nonionic surfactants typically have uncharged hydrophilic head groups and are usually based on polyoxyethylene or a glycoside.

Document US 2011/0028371 describes a hybrid copolymer comprising:

a synthetic polymer derived from at least one ethylenically unsaturated anionic monomer and a chain transfer agent containing naturally derived hydroxyl as a terminal group, wherein the chain transfer agent is present at from about 75% by weight to approximately 99% by weight, based on the total weight of the hybrid copolymer. Examples 24 and 28 describe formulations for phosphate-free automatic dishwashers containing the copolymer, adjuvant and bleach.

Document WO 2013/092276 describes a detergent composition comprising 20-99.7% by weight of a continuous phase containing glutamic compound-N,N-diacetate (GLDA), water and optionally other components; and 0.3-80% by weight of a dispersed phase comprising at least 0.3% bleach particles by weight of the composition. Dehypon™ Wet is mentioned as an example of a nonionic surfactant that can be applied in the detergent composition.

US 2016/0348036 describes a phosphate-free dishwashing composition in unit dose format comprising

to. non-phosphate adjuvant;

b. alkaline percarbonate;

c. one or more polycarboxylate polymers;

d. alkali carbonate, alkali silicates or mixtures thereof;

and. one or more nonionic surfactants; and

F. a manganese bleaching catalyst.

The dishwasher composition may include a nonionic surfactant of the formula R<3>-(PO)<x>(EO)<y>-CH<2>CH(OH)-R<4>; where R<3>is C<5>-C<15>; R<5>is C<4>-C<10>, and x is an integer in the range 0-10, and y is an integer in the range 3-30. Suitable nonionic compounds of this type include modified fatty alcohol polyglycol ethers available as Dehypon® 3697 GRA or Dehypon® Wet from BASF.

US 2011/0118168 describes hard surface cleaning compositions comprising a hybrid copolymer and a surfactant. Non-ionic surfactants with the structure R<1>-O-(CH<2>CH<2>O)<n>-(CH<2>CHCH<3>O)<q>-(CH<2>) are mentioned. CH(OH))-R<4>. In the examples, hybrid copolymers that are prepared from maltodextrin and acrylic acid/propylmethacrylamide are described.

WO 2014/021902 describes a detergent composition for ADW containing a hybrid copolymer that is based on maltodextrin and (among other things) methacrylate. The examples describe compositions containing approximately 6% by weight of hybrid copolymer and 3.7% by weight of Dehypon LS-36 (an ethylene oxide/propylene oxide fatty alcohol).

WO 2013/022762 describes detergent compositions for ADW containing a hybrid copolymer based on maltodextrin and acrylic acid in a ratio of 1:1 w/w. In the examples, compositions containing 2-6% by weight of this hybrid copolymer and 1.7% by weight of Pluronic N-3 (an ethylene oxide/propylene oxide block copolymer) are described.

WO 2011/014783 describes ADW detergents containing a hybrid copolymer based on maltodextrin and acrylic acid/2-acrylamido-2-methylpropanesulfonic acid, adjuvant and nonionic surfactant.

US 2009/0186795 describes a dry automatic dishwasher detergent comprising: • 80-95% of a base including one or more of a sulfate, a carbonate, a citrate and a silicate, in which the carbonate is present in an amount of less than about 25% of the composition;

• 0.1-10% of a non-ionic surfactant;

• 0.55-4% of a stain reduction system that includes (i) a polyacrylate and (ii) a carboxymethyl-inulin; and,

• 0.1-3% of an enzyme system.

WO 2011/014783 describes a scale inhibition composition for aqueous systems, comprising an anionic hybrid copolymer composition wherein said copolymer comprises:

• at least one ethylenically unsaturated anionic monomer and a chain transfer agent containing naturally derived hydroxyl as a terminal group; and

• a hybrid synthetic copolymer comprising one or more synthetic polymers derived from at least one ethylenically unsaturated anionic monomer with at least one initiator fragment as a terminal group, said hybrid synthetic copolymer having the structure:

I-(-M<hsc>-)-H

wherein I is the initiator fragment, H is a proton extracted from the naturally derived hydroxyl-containing chain transfer agent and M is a synthetic portion of the hybrid synthetic copolymer derived from the at least one ethylenically unsaturated anionic monomer; and

wherein the chain transfer agent is present in amounts of greater than 75% by weight to about 99% by weight, based on the total weight of the hybrid copolymer, wherein the scale inhibition composition has an inhibition of carbonate of more than 80% at a dosage level of 100 ppm of the anionic hybrid copolymer composition in an aqueous system.

WO 2015/169793 describes detergent compositions containing a combination of protease and hybrid polymer. Example 1 describes a detergent tablet for automatic dishwashers that is composed of three different phases. The tablet contains adjuvant, hybrid polymer, bleach and nonionic surfactant.

Summary of the invention

The inventors have developed a detergent composition for ADW that combines very good cleaning action with minimal film formation and staining.

The ADW detergent composition of the present invention consists of:

• 20-80% by weight of adjuvant;

• 5-25% by weight of bleaching component;

• 1-10% by weight of a graft copolymer having a polysaccharide backbone and one or more side chains of one or more synthetic monomeric units;

• 1-15% by weight of non-ionic surfactant represented by the following formula:

R<1>-O-(CH<2>CH<2>O)<n>-(CHR<2>CHR<2'>O)<q>-(CH<2>CH(OH)R<3 >)<s>-R<4>

in which

or R<1>is a linear or branched C<8>-C<22>alkyl radical or a linear or branched C<8>-C<22>alkylphenol radical;

or R<2>and R<2'>are independently selected from hydrogen and a C<1>-C<5>alkyl radical, and wherein either R<2>or R<2'>is hydrogen;

or R<3>is a covalent bond or a linear C<2>-C<26>alkyl radical;

or R<4>is selected from hydrogen and an alkyl radical having 1-15 carbon atoms;

or 5 < n < 30;

or 0 < q < 3;

or s=1-5,

said nonionic surfactant being selected from homopolymers, statistical copolymers, block copolymers and combinations thereof; and

• 0-60% by weight of one or more other components.

The ADW detergent composition of the present invention produces very good cleaning results for china, glassware, metal as well as plastic. Furthermore, the inventors have discovered that the combination of adjuvant, graft copolymer and nonionic surfactant represented by the formula described above very effectively minimizes film formation and staining.

Detailed description of the invention

A first aspect of the present invention relates to a detergent composition for ADW consisting of:

• 20-80% by weight of adjuvant;

• 5-25% by weight of bleaching component;

• 1-10% by weight of a graft copolymer having a polysaccharide backbone and one or more side chains of one or more synthetic monomeric units;

• 1-15% by weight of non-ionic surfactant represented by the following formula:

R<1>-O-(CH<2>CH<2>O)<n>-(CHR<2>CHR<2'>O)<q>-(CH<2>CH(OH)R<3 >)<s>-R<4>

in which

or R<1>is a linear or branched C<8>-C<22>alkyl radical or a linear or branched C<8>-C<22>alkylphenol radical;

or R<2>and R<2'>are independently selected from hydrogen and a C<1>-C<5>alkyl radical, and wherein either R<2>or R<2'>is hydrogen;

or R<3>is a covalent bond or a linear C<2>-C<26>alkyl radical;

or R<4>is selected from hydrogen and an alkyl radical having 1-15 carbon atoms;

or 5 < n < 30;

or 0 < q < 3;

or s=1 -5,

said nonionic surfactant being selected from homopolymers, statistical copolymers, block copolymers and combinations thereof; and

• 0-60% by weight of one or more other components.

The term "adjuvant" as used herein refers to a material that can remove calcium ions from an aqueous solution by ion exchange, complexation, sequestration and/or precipitation. Examples of adjuvant materials include phosphates, alkali metal citrates, carbonates and bicarbonates; aminopolycarboxylates, polycarboxylates such as polymaleates, polyacetates, polyhydroxyacrylates, polyacrylate/polymaleate and polyacrylate/polymethacrylate copolymers, as well as zeolites; stratified silicas and mixtures thereof.

The term “surfactant” as used herein refers to components within the classification described in “Surfactant Science Series”, vol. 82, (1999) Handbook of detergents, part A: Properties, chapter 2 (Surfactants, classification), G. Broze (ed.).

The term “bleaching component” as used herein refers to substances that can remove color stains by oxidizing or reducing the color components of the stain. Examples of oxidizing bleach components include peroxides, such as hydrogen peroxide, sodium percarbonate and sodium perborate. Examples of reducing bleach components include sodium dithionite, sodium borohydride, and sodium sulfite. In addition to the bleach component, the detergent composition may suitably contain bleach activators and/or bleach catalysts.

The term "percarbonate" as used herein refers to an adduct of alkali metal carbonate and hydrogen peroxide (a perhydrate), such as sodium percarbonate (2Na2CO3-3H2O2).

The term "carbonate" as used herein refers to carbonic acid (H2CO23) and salts thereof. The term “carbonate” as used herein does not encompass percarbonates.

The term "citrate" as used herein refers to citric acid and salts thereof. Likewise, the term "silicate" as used herein refers to silicic acid and salts thereof.

The term “polysaccharide” as used herein refers to a polymeric carbohydrate molecule composed of a chain of at least 5 monosaccharide units linked together by glycosidic bonds.

The term "one or more other components" as used herein refers to components other than adjuvant; bleaching component; graft copolymer having a polysaccharide backbone and one or more side chains of one or more synthetic monomeric units; and nonionic surfactant.

Whenever reference is made herein to the concentration of a salt or acid, unless otherwise indicated, such concentration refers to the equivalent concentration of the salt or acid in anhydrous form.

Detergent composition

The ADW detergent composition of the present invention is preferably a particulate composition or a solid article. Accordingly, the detergent composition is preferably a powder or a tablet.

The combination of the adjuvant, the bleach component, the graft copolymer and the nonionic surfactant typically represents at least 40%, more preferably at least 50% and most preferably at least 60% by weight of the detergent composition.

The detergent composition of the present invention preferably contains the graft copolymer and the adjuvant in a weight ratio of at least 1:50, more preferably 1:40 to 1:8 and most preferably 1:30 to 1:10 .

The graft copolymer and the nonionic surfactant are normally present in the detergent composition in a weight ratio of 1:4 to 3:1, more preferably 1:3 to 5:2 and most preferably 1:2.2 at 2:1. According to a particularly preferred embodiment, the ADW detergent composition of the present invention consists, calculated by dry matter weight, of:

to. 30-70% by weight of the adjuvant;

b. 5-25% by weight of the bleaching component;

c. 1-8% by weight of the graft copolymer;

d. 1-10% by weight of the non-ionic surfactant;

and. 0.01-0.5 wt% enzymes;

F. 0-60% by weight of one or more additives selected from bleach catalysts, alkaline carriers, corrosion inhibitors, colorants, fragrances and fillers.

Adjuvant

The detergent composition typically contains at least 30% by weight of adjuvant, more preferably 35-70% by weight of adjuvant and most preferably 40-65% by weight of adjuvant.

According to a preferred embodiment, the adjuvant contained in the detergent composition according to the invention comprises 20-80% precipitation adjuvant by weight of the adjuvant, said precipitation adjuvant being selected from carbonate, silicate and combinations thereof. More preferably, the detergent composition contains 25-75% precipitation adjuvant by weight of the adjuvant, even more preferably 30-72% and most preferably 40-70% precipitation adjuvant by weight of the adjuvant.

According to a particularly preferred embodiment, the detergent composition contains 20-80% carbonate by weight of the adjuvant. More preferably, the detergent composition contains 25-75%, even more preferably 30-72% and most preferably 40-70% carbonate by weight of the adjuvant. As explained above, these concentrations refer to the equivalent concentration of the carbonate in anhydrous form.

Preferably, the carbonate is alkali metal carbonate, most preferably sodium carbonate.

The silicate content of the adjuvant component of the detergent composition is preferably 0-20% by weight of the adjuvant. More preferably, the detergent composition contains 1-10% silicate, most preferably 1.5-6% silicate by weight of the adjuvant. As explained above, these concentrations refer to the equivalent concentration of the silicate in anhydrous form.

Preferably, the silicate is an alkali metal silicate, most preferably sodium silicate. Examples of silicates that may be applied include disilicate, metasilicate and crystalline phyllosilicates and mixtures thereof. Most preferably, the silicate is selected from sodium disilicate, sodium metasilicate and combinations thereof.

Preferably, the adjuvant contained in the detergent composition according to the invention comprises 20-70% citrate by weight of the adjuvant. More preferably, the detergent composition contains 25-65% citrate by weight of the adjuvant. Even more preferably, the detergent composition contains 30-60% citrate by weight of the adjuvant. As explained above, these concentrations refer to the equivalent concentration of citrate in anhydrous form. Preferably, the citrate is an alkali metal citrate, most preferably sodium citrate.

According to a particularly preferred embodiment, citrate and carbonate together constitute at least 60% by weight, more preferably at least 70% by weight and most preferably at least 80% by weight of the adjuvant.

In a further preferred embodiment of the present invention, the composition comprises citrate and carbonate, wherein the citrate and carbonate together constitute at least 30% by weight, more preferably at least 35% by weight of the detergent composition. Even more preferably, the citrate and carbonate together constitute 35-75% by weight of the detergent composition and most preferably 40-70% by weight of the detergent composition.

Preferably, the citrate and carbonate are present in the detergent composition in a citrate:carbonate molar ratio of 0.15 to 0.9, more preferably 0.2-0.8 and most preferably 0.25 to 0. ,6.

According to another embodiment, the adjuvant comprises less than 25% by weight of the adjuvant of adjuvant components other than citrate, carbonate and silicate, more preferably the adjuvant comprises less than 15%, even more preferably less than 10% by weight of the adjuvant of adjuvant components other than citrate, carbonate and silicate.

The phosphate content of the ADW detergent composition is preferably less than 10%, more preferably less than 3% and most preferably less than 1% by weight of the adjuvant.

The inventors have found that the inclusion of even small amounts of aminocarboxylate chelator can adversely affect the cleaning properties of the present detergent composition. Accordingly, in a preferred embodiment the detergent composition contains less than 3% by weight, more preferably less than 2% by weight and most preferably less than 1% by weight of aminopolycarboxylate chelator. Examples of aminocarboxylate chelator include MGDA (methyl-glycinediacetic acid), GLDA (glutamic-N,N-diacetic acid), iminodisuccinic acid (lDS), aspartic acid-N-monoacetic acid (ASMA), aspartic acid-N,N -diacetic acid (ASDA), aspartic acid-N-monopropionic acid (ASMP), iminodisuccinic acid (IDA), N-(2-sulfomethyl)-aspartic acid (SMAS), N-(2-sulfoethyl)-aspartic acid (SEAS) ), N-(2-sulfomethyl)-glutamic acid (SMGL), N-(2-sulfoethyl)-glutamic acid (SEGL), iminodiacetic acid and salts and derivatives thereof.

Bleach

The detergent composition of the present invention preferably comprises 7-22% by weight, more preferably 8-20% by weight and most preferably 9-18% by weight of bleach component. The bleach component used in the present detergent composition is preferably an oxidizing bleach component. The oxidative bleach component may suitably comprise a chlorine or bromine releasing agent or a peroxygen compound. Preferably, the bleach component is selected from peroxides (including peroxide salts such as sodium percarbonate), organic peracids, salts of organic peracids and combinations thereof. More preferably, the bleaching component is a peroxide. Examples of peroxides are acids and corresponding salts of monopersulfate, perborate monohydrate, perborate tetrahydrate and percarbonate. Most preferably, the bleach component is a percarbonate, notably sodium percarbonate.

Organic peracids useful herein include alkyl peroxyacids and aryl peroxyacids such as peroxybenzoic acid and ring-substituted peroxybenzoic acids (e.g., peroxy-alphanaphthoic acid), aliphatic monoperoxyacids and substituted aliphatics (e.g., peroxylauric acid and peroxystearic acid) and phthaloyl-amido-peroxycaproic acid (PAP).

Typical diperoxy acids useful herein include alkyl diperoxy acids and aryl diperoxy acids, such as 1,12-di-peroxy-dodecanedioic acid (DPDA), 1,9-diperoxyazelaic acid, diperoxybrasilic acid, diperoxysebacic acid and diperoxy-isophthalic acid , and 2-decyldiperoxybutane-1,4-dioic acid.

The detergent composition may contain one or more bleach activators such as peroxyacid bleach precursors. Peroxyacid bleach precursors are well known in the art. As non-limiting examples, there may be mentioned N,N,N',N'-tetraacetyl-ethylenediamine (TAED), sodium nonanoyloxybenzenesulfonate (SNOBS), sodium benzoyloxybenzenesulfonate (SBOBS) and the peroxyacid cationic precursor (SPCC) as described in document US-A-4,751,015.

If desirable, a bleaching catalyst may be incorporated, such as a manganese complex, for example Mn-Me TACN, as described in EP-A-0458397, or the sulfonimines of US-A-5,041. .232 and US-A-5,047,163. This bleach catalyst may suitably be present in the composition in the form of an encapsulated material, notably an encapsulated material that is independent of the bleach particles (to avoid premature bleach activation). Cobalt or iron catalysts can also be used.

graft copolymer

The graft copolymer used according to the present invention has a polysaccharide backbone and one or more side chains of one or more synthetic monomeric units. Preferably, the graft copolymer contains one or more side chains of two or more, even more preferably three or more synthetic monomeric units.

The graft copolymer employed in the detergent composition typically has a molecular weight of at least 4,000 g/mol, more preferably at least 8,000 g/mol and most preferably at least 15,000 g/mol.

The one or more synthetic monomeric units are preferably selected from olefinically unsaturated carboxylate monomers; sulfonate monomers; phosphonate monomers and combinations thereof. More preferably, the one or more synthetic monomeric units are selected from olefinically unsaturated carboxylate monomers; sulfonate monomers and combinations thereof. Most preferably, the synthetic monomeric units are olefinically unsaturated carboxylate monomers. Olefinically unsaturated carboxylate monomers include, for example, aliphatic, branched or cyclic mono- or dicarboxylic acids, the alkali or alkaline earth metal or ammonium salts thereof and the anhydrides thereof. Examples of such olefinically unsaturated carboxylic acid monomers include acrylic acid, methacrylic acid, ethacrylic acid, a-chloro-acrylic acid, a-cyano-acrylic acid, bmethyl-acrylic acid (crotonic acid), a-phenyl-acrylic acid, p-acryloxypropionic acid, sorbic acid, a-chlorosorbic acid, angelic acid, cinnamic acid, p-chloro-cinnamic acid, p-styryl-acrylic acid (1-carboxy-4-phenylbutadiene-1,3), itaconic acid, acid maleic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, fumaric acid, tricarboxyethylene and 2-acryloxypropionic acid. Moieties such as maleic anhydride or acrylamide can also be used which can be derivatized to give an acid-containing group. Additionally, combinations of olefinically unsaturated carboxylic acid monomers can be used. In a preferred embodiment, the olefinically unsaturated carboxylic acid monomer is selected from acrylic acid, maleic acid, itaconic acid or methacrylic acid and combinations thereof.

Examples of the sulfonate monomers include 2-acrylamido-2-methylpropanesulfonic acid (AMPS), as well as styrene sulfonic acid, sulfoalkyl esters of (meth-)acrylic acid, sulfoalkyl esters of itaconic acid, preferably in each case as alkyl esters C<1>-C<5>, vinylsulfonic acid and the alkali, alkaline earth and/or ammonium salts thereof. Preferred are monomers containing a (meth)acrylate, (meth)acrylamide and/or vinyl group, in particular 2-acrylamido-2-methylpropanesulfonic acid (AMPS), styrenesulfonic acid, sulfopropyl ester of acrylic acid, sulfopropyl ester of itaconic acid, vinylsulfonic acid, as well as in each case the ammonium, sodium, potassium and/or calcium salts.

The polysaccharide forming the main structure of the graft copolymer is preferably selected from starch, maltodextrin, cellulose, gums (for example, gum arabic, guar and xanthan), alginates, pectin and gellan gum. More preferably, the polysaccharide is selected from starch and maltodextrin. The polysaccharides used in the graft copolymer can be modified or derivatized by etherification (for example, by treatment with propylene oxide, ethylene oxide, 2,3-epoxypropyl-trimethyl-ammonium chloride), esterification (for example, by reaction with acetic anhydride, octenyl succinic anhydride (“OSA”), acid hydrolysis, dextrinization, oxidation (e.g., oxidized starch) or enzymatic treatment, or various combinations of these treatments.

According to a particularly preferred embodiment, the polysaccharide of the copolymer is maltodextrin. Maltodextrins are polymers that can be produced by hydrolysis of starch and have Dglucose units linked primarily by α-1,4 bonds and a dextrose equivalent of less than about 20. Dextrose equivalent (DE) is a measure of the degree of starch hydrolysis. It is determined by measuring the amount of reducing sugars in a sample relative to dextrose (glucose). The DE of dextrose is 100, representing 100% hydrolysis.

The polysaccharide in the backbone of the graft copolymer preferably contains a chain of at least 8, more preferably at least 10 monosaccharide units linked together by glycosidic bonds.

The graft copolymer preferably has a high degree of polysaccharide. Typically, the polysaccharide represents at least 50% by weight, more preferably at least 60% by weight, even more preferably at least 70% by weight and most preferably at least 80% by weight of the graft copolymer.

The chemical structure of an exemplary embodiment of the hybrid polymer is shown below.

An example of a graft copolymer that can be suitably employed according to the present invention is Alcoguard® H 5240, which is commercially available from AkzoNobel®.

Surfactants

The nonionic surfactant employed in the present detergent composition is a polyoxyalkylene condensate represented by the formula described hereinabove: R<1>-O-(CH<2>CH<2>O)<n>(CHR< 2>CHR<2'>O)<q>-(CH<2>CH(OH)R<3>)<s>-R<4>

According to a preferred embodiment R<2>or R<2'>in the aforementioned formula is selected from methyl or ethyl, most preferably R<2>or R<2'>is methyl.

In another preferred embodiment, the nonionic surfactant is represented by the aforementioned formula with q=0-2, more preferably q is 0 or 1. Most preferably, q is equal to 0.

In yet another preferred embodiment, the nonionic surfactant is represented by the aforementioned formula, and s=1-3, more preferably s=1-2 and most preferably s=1.

More particularly, the detergent composition according to the present invention contains a nonionic surfactant which is represented by the following formula:

R<1>-O-(CH<2>CH<2>O)<n>-(CHR<2>CHR<2'>O)<q>-(CH<2>CH(OH)R<3 >)<s>-R<4>

in which:

• R<2>is hydrogen and R<2’>is methyl;

• R<3>is a covalent bond;

• q is 0 or 1; and

• s is 1.

The nonionic surfactant used in the present detergent composition is preferably a low foaming nonionic surfactant. The term “low foaming nonionic surfactant” as used herein refers to a nonionic surfactant that, at a concentration of 1% by weight in distilled water and at a temperature of 50 ° C has a foam height initial of less than 50 mm, a foam height of less than 5 mm after 1 minute, and a foam height of less than 1 mm after 5 minutes in the ASTM 01173-07 test.

The nonionic surfactant used normally has a cloud point of at least 25 °C. More preferably the nonionic surfactant has a cloud point of 27-60°C, most preferably a cloud point of 28-50°C. The term "cloud point" as used herein refers to the temperature at which the nonionic surfactant begins to precipitate from an aqueous solution.

The inventors have found that a detergent composition, which is not only chemically but also physically very stable, can be produced if the non-ionic surfactant used is solid at all temperatures that are relevant in the logistics chain. Therefore, it is preferred that the nonionic surfactant solidify below 45°C.

According to a preferred embodiment, the detergent composition contains 1.5-10%, more preferably 2-8% of the nonionic surfactant by weight of the composition.

The detergent composition may contain another surfactant in addition to the nonionic surfactant. If an anionic surfactant is used, the total amount present is preferably less than 5% by weight, more preferably less than 2% by weight, even more preferably less than 1% by weight and most preferably less than 0.5% by weight. weight.

Enzymes

The detergent composition preferably contains at least 0.03% by weight, more preferably at least 0.05% by weight and most preferably 0.07-3% by weight of one or more enzymes.

Examples of enzymes suitable for use in the cleaning compositions of this invention include lipases, cellulases, peroxidases, proteases (proteolytic enzymes), amylases (amyolytic enzymes) and others that degrade, alter or facilitate the degradation or alteration of soils and stains. biochemicals found in cleaning situations to more easily remove dirt or stain from the object being washed to make the dirt or stain better removable in a later cleaning step. Both degradation and alteration can improve soil removal.

Preferably, the one or more active enzymes contained in the present composition are selected from protease, amylase, cellulase, peroxidase, mannanase, pectate, lyase and lipase. Most preferably, the active enzyme is selected from protease, amylase and combinations thereof.

According to a particularly preferred embodiment, the composition contains at least 10 mg/kg, more preferably at least 20 mg/kg and most preferably at least 50 mg/kg of active amylase.

According to another especially preferred embodiment, the composition contains at least 100 mg/kg, more preferably at least 200 mg/kg and most preferably at least 400 mg/kg of active protease.

Enzymes can be added in liquid or encapsulated form. Examples of encapsulated enzymes are type D, E and HS enzyme granules from Genencor and type T, GT, TXT and Evity™ granules from Novozymes.

Proteolytic enzymes in this invention include metalloproteases and serine proteases, including neutral or alkaline microbial serine proteases, such as subtilisins (EC 3.4.21.62). Proteolytic enzymes for use in the present invention may be those derived from bacteria or fungi. Chemically or genetically modified mutants (variants) are included. Preferred proteolytic enzymes are those derived from Bacillus, such as B. lentus, B. gibsonii, B. subtilis, B. licheniformis, B. alkalophilus, B. amyloliquefaciens and Bacillus pumilus, of which the most preferred are B. lentusyB. gibsonii.Examples of such proteolytic enzymes are Excellase™, Properase™, Purafect™, Purafect™ Prime, Purafect™ Ox from Genencor; and those marketed under the trade names BlazeTM, Ovozyme™, Savinase™, Alcalase™, Everlase™, Esperase™, Relase™, Polarzyme™, Liquinase™ and Coronase™ from Novozymes.

Amyolytic enzymes for use in the present invention may be those derived from bacteria or fungi.

Chemically or genetically modified mutants (variants) are included. A preferred amyolytic enzyme is an alpha-amylase derived from a Bacillus strain, such as B. subtilis, B. licheniformis, B. amyloliquefaciensoB. stearothermophilus.Examples of such amyolytic enzymes are produced and distributed under the trade name Stainzyme™, Stainzyme™ Plus, Termamyl™, Natalase™ and Duramyl™ from Novozymes; as well as Powerase™, Purastar™, Purastar™ Oxam from Genencor. Stainzyme™, Stainzyme™ Plus and Powerase™ are the preferred amylases.

Well-known enzyme stabilizers such as polyalcohols/borax, calcium, formate or protease inhibitors such as 4-formylphenyl boronic acid may also be present in the composition.

Burden

The detergent composition may suitably contain up to 70% by weight of a load. More preferably, the composition contains no more than 60% by weight filler, most preferably 10-50% by weight filler.

Preferably, the filler used is a metal sulfate, for example sodium sulfate.

Other components

Glass corrosion inhibitors can prevent irreversible corrosion and iridescence of glass surfaces in automatic dishwasher detergents. The claimed composition may suitably contain glass corrosion inhibitors. Suitable glass corrosion agents may be selected from the group consisting of salts of zinc, bismuth, aluminum, tin, magnesium, calcium, strontium, titanium, zirconium, manganese, lanthanum, mixtures thereof and precursors thereof. Most preferred are bismuth, magnesium or zinc salts or combinations thereof.

Anti-tarnish agents can prevent or reduce tarnishing, corrosion or oxidation of metals such as silver, copper, aluminum and stainless steel. Anti-tarnish agents such as benzotriazole, methyl-benzotriazole or bis-benzotriazole and substituted or substituted derivatives thereof and those described in EP 723 577 (Unilever) may also be included in the composition. Other anti-tarnish agents that may be included in the detergent composition are mentioned in WO 94/26860 and WO 94/26859. Suitable redox active agents are, for example, complexes chosen from the group of cerium, cobalt, hafnium, gallium, manganese, titanium, vanadium, zinc or zirconium, in which the metal is in the oxidation state of II, II, IV , V or VI.

Optionally, other components can be added to the formulation such as perfume, coloring or preservatives.

Accordingly, in a preferred embodiment of the detergent composition according to the present invention, the other components are selected from enzymes, dispersant polymers, bleaches, bleach activators, bleach catalysts, alkaline carriers, corrosion inhibitors, colorants, fragrances and fillers. .

Another aspect of the invention relates to the use of a detergent composition as hereinbefore defined as a detergent in an automatic dishwashing appliance.

The invention is further illustrated by the following non-limiting examples.

Examples

Example 1

Compositions for automatic dishwashers were prepared based on the formulations shown in Table 1.

Table 1

1 Alcoguard H5240, a 45% solution of a graft copolymer consisting of a polysaccharide backbone and synthetic side chains from Akzo Nobel

2 Dehypon WET, a 90% solution of low foaming fatty alcohol polyglycol ether with typical molecular formula CnH23-O-(CH2CH2O)20-(CH2CH(OH))-C8H17 from BASF

3 Dequest 2016, Monsanto HEDP

The aforementioned ADW detergent compositions were prepared as follows: All solid components (i.e., all components in Table 1 except Alcoguard H5240 and Dehypon WET) were introduced into a powder mixer and mixed thoroughly. While mixing, Dehypon WET was carefully sprayed onto the powder in such a way that it was evenly dispersed over the powder bed. The resulting powder was then pressed to give monolayer tablets. The combined weight of the tablet and Alcoguard H5240 was 18 grams.

In the dishwashing tests described below, the tablet and Alcoguard H5240 were placed separately in the dishwasher. The pill was inserted into the dispenser before putting the machine into operation. Alcoguard H5240 was dispensed by putting the correct amount into a cup and manually adding the cup when the dispenser was opened.

The performance of the ADW detergent compositions was evaluated using the following test procedure:

A representative set of dishes consisting of crockery, glassware, metal and plastics is washed 30 consecutive times in a Miele 1222GSL dishwasher using the 65°C program. Detergent is dispensed into the dispenser before each wash. A cup containing 50 grams of Stiwa frozen mess is manually dispensed (for example, by opening the dishwasher and placing the cup upside down on the top rack) when the dispenser is opened.

After each wash, open the dishwasher and let the dishes dry completely and cool to room temperature. After 30 washes, the dishes are evaluated. Aesthetic scores are obtained by placing the dishes 115 cm from a gray wall (RAL 7030) and 45 to 50 cm from the ceiling of the room. The tableware is illuminated with 4 Philips master TL-D 36 W / 8652M type light sources, 120 cm long and evaluated with respect to the overall appearance, that is, taking into account stains, film, etc. A scale is used that goes from 1 to 10, with 10 corresponding to a perfect dish.

The results of these tests are summarized in table 2.

Table 2

Example 2

Compositions for automatic dishwashers were prepared in the same manner as described in Example 1 based on the formulations shown in Table 3.

Table 3

1 Mixture of 80% Plurafac LF 301 (fatty alcohol alkoxylate from BASF) and 20% benzotriazole fine grade from Helm AG

The performance of the ADW detergent compositions was evaluated using the same test procedure as in Example 1.

The results of these tests are summarized in table 4.

Table 4

These results demonstrate that the performance of detergent composition A that did not contain citrate was inferior to that of detergent compositions that did contain citrate.

Example 3

Compositions for automatic dishwashers were prepared in the same manner as described in Example 1 based on the formulations shown in Table 5. Compositions A and B are reference examples. Table 5

1 Alcoguard 4160G, maleic acid/acrylic acid/methyl methacrylate/2-acrylamido-2-methylpropanesulfonic acid copolymer as sodium salt from Akzo Nobel

2 Sokalan CP50, acrylic acid/AMPS copolymer from BASF

3 Genapol EC50, a low-foaming fatty alcohol polyglycol ether from BASF

The performance of the ADW detergent compositions was evaluated using the same test procedure as in Example 1.

The results of these tests are summarized in table 6.

Table 6

These results demonstrate that detergent compositions 1 and 2 containing a hybrid copolymer having a polysaccharide backbone and one or more synthetic side chains performed better than detergent compositions A and B containing a synthetic polymer, although the latter compositions They contained substantially more polymer (7% by weight versus 3% by weight).

Example 4

Compositions for automatic dishwashers were prepared in the same manner as described in Example 1 based on the formulations shown in Table 7.

Table 7

1 MGDA granules prepared according to document EP 2257522

2 Dissolvine GL-PD-S, 80% Glutamic Diacetic Acid (GLDA) Powder from AKZO

The performance of the ADW detergent compositions was evaluated using the same test procedure as in Example 1.

The results of these tests are summarized in table 8.

Table 8

Example 5

Compositions for automatic dishwashers were prepared in the same manner as described in Example 1, but without pilling, based on the formulations shown in Table 9. Composition A is a reference example.

Table 9

1 Lutensol AT 25, fatty alcohol alkoxylate with molecular formula C16-18EO25 from BASF

2 Acusol 460, copolymer of diisobutylene and maleic acid, 15,000 MW, from the Dow chemical company.

The performance of the ADW detergent compositions was evaluated using the same test procedure as in Example 1, except that another set of items was cleaned in the dishwasher, the evaluation was limited to stains only, and the total number of washes was limited. to 10.

The results of these tests are summarized in table 10.

Table 10

Claims (15)

1. Detergent composition consisting of: • 20-80% by weight of adjuvant; • 5-25% by weight of bleaching component; • 1-10% by weight of a graft copolymer having a polysaccharide backbone and one or more side chains of one or more synthetic monomeric units; • 1-15% by weight of non-ionic surfactant represented by the following formula: R<1>-O-(CH<2>CH<2>O)<n>-(CHR<2>CHR<2'>O)<q>-(CH<2>CH(OH)R<3 >)<s>-R<4> in which or R<1>is a linear or branched C<8>-C<22>alkyl radical or a linear or branched C<8>-C<22>alkylphenol radical; or R<2>and R<2'>are independently selected from hydrogen and a C<1>-C<5>alkyl radical, and wherein either R<2>or R<2'>is hydrogen; or R<3>is a covalent bond or a linear C<2>-C<26>alkyl radical; or R<4>is selected from hydrogen and an alkyl radical having 1-15 carbon atoms; or 5 < n < 30; or 0 < q < 3; or s=1 -5, said nonionic surfactant being selected from homopolymers, statistical copolymers, block copolymers and combinations thereof; and • 0-60% by weight of one or more other components. 2. Detergent composition according to claim 1, wherein the adjuvant comprises 25-80% precipitation adjuvant by weight of the adjuvant, said precipitation adjuvant being selected from carbonate, silicate and combinations thereof. 3. Detergent composition according to claim 1 or 2, wherein the adjuvant comprises 20-70% citrate by weight of the adjuvant. 4. Detergent composition according to any one of the preceding claims, wherein the polysaccharide in the graft copolymer is selected from starch, maltodextrin, cellulose, gums, alginates, pectin and gellan gum. 5. Detergent composition according to claim 4, wherein the polysaccharide is maltodextrin. 6. Detergent composition according to any one of the preceding claims, wherein the one or more synthetic monomeric units in the graft copolymer are selected from acrylic acid, maleic acid, itaconic acid or methacrylic acid and combinations thereof. 7. Detergent composition according to any one of the preceding claims, wherein the composition contains 5-25% by weight of bleaching component. 8. Detergent composition according to claim 7, wherein the bleach component is percarbonate. 9. Detergent composition according to any one of the preceding claims, wherein R2 or R2' is methyl. 10. Detergent composition according to any one of the preceding claims, wherein q is 0 or 1. 11. Detergent composition according to any one of the preceding claims, wherein s=1. 12. Detergent composition according to any one of the preceding claims, wherein the nonionic surfactant is represented by the following formula: R<1>-O-(CH<2>CH<2>O)<n>-(CHR<2>CHR<2'>O)<q>-(CH<2>CH(OH)R<3 >)<s>-R<4> in which: • R<2>is hydrogen and R<2'>is methyl; • R<3>is a covalent bond; • q is 0 or 1; and • s is 1. 13. Detergent composition according to any one of the preceding claims, wherein the composition contains 1.5-10% of the nonionic surfactant by weight of the composition. 14. Detergent composition according to any one of the preceding claims, wherein the composition is a powder or a tablet. 15. Use of a detergent composition according to any one of the preceding claims as a detergent in an automatic dishwasher.