ES2954295T3 - Phosphate-free detergent composition for automatic dishwashers - Google Patents

Abstract

The 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 non-ionic surfactant; · 0-60% by weight of one or more detergent ingredients; wherein the graft copolymer and the adjuvant are present in a weight ratio of copolymer to adjuvant of 1:50 to 1:4; and wherein the builder contains at least 20% citrate by weight of the builder and at least 25% carbonate by weight of the builder, and the builder is composed of: a) no more than 70% by weight of a hydroxycarboxylate sequestering builder selected from citrate, tartrate, gluconate and combinations thereof; b) no more than 80% by weight of precipitation adjuvant selected from carbonate, silicate and combinations thereof; c) 0-25% by weight of one or more adjuvants; wherein the citrate and carbonate together constitute at least 50% by weight of the builder; and wherein the citrate and carbonate are present in a citrate:carbonate molar ratio of 0.1 to 1.0. The ADW detergent composition of the present invention produces very good cleaning results with minimal stain and film formation. The detergent composition also offers the advantage of being less likely to cause corrosion to glassware. (Automatic translation with Google Translate, without legal value)

Description

DESCRIPTION

Phosphate-free detergent composition for automatic dishwashers

Technical field of the invention

The present invention relates to a phosphate-free detergent composition for automatic dishwashers having an adjuvant, a 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 and optionally one or more other detergent components. The adjuvant component of the detergent composition is composed of:

• hydroxycarboxylate sequestration adjuvant selected from citrate, tartrate, gluconate and combinations thereof;

• precipitation aid selected from carbonate, silicate and combinations thereof; and • optionally one or more other adjuvants.

The automatic dishwasher detergent (ADW) composition of the present invention combines very good cleaning action with minimal drip marks and film formation. Additionally, the composition is less harmful to glassware compared to current high-performance ADW detergents.

Background of the invention

Automatic dishwasher detergents (ADW) constitute a distinct class of detergent compositions. Unlike most other detergents, ADW detergents should be low sudsing. Additionally, a drip-mark-free, film-free appearance of glasses and cutlery is the expected end result of every automatic dishwasher cycle.

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 can be caused by beverages such as coffee and tea or by plant soils such as carotenoid soils.

Drop marks and film formation on glassware are the main criteria by which the performance of a dishwasher formulation is judged. Drop marks are an obvious reference to discrete residues on glassware that form when water droplets evaporate and leave behind dissolved solids. Film formation refers to a more uniform deposition over a large, continuous portion of the glass surface. This film may sometimes be of organic origin (resulting from dirt in the washing liquid or organic components in the detergent), but is often also 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, antifouling agents, corrosion inhibitors, surfactants, antifoams, coating polymers and/or enzymes. Adjuvant materials are used to provide alkalinity and buffering capacity, maintain ionic strength, extract metals from dirt, and/or remove alkaline earth metal ions from wash solutions. Examples of adjuvant materials include alkali metal phosphates, 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 type silicas and mixtures thereof.

Sodium tripolyphosphate is among the best of a variety of adjuvant salts. However, the phosphate content of detergent compositions has been limited by law and regulations to minimize eutrophication of inland waters.

Therefore, phosphate-free detergents have been developed for ADW. US 5,898,025, for example, describes a slightly alkaline phosphate-free detergent composition for dishwashers containing:

• from 20 to 60% by weight of sodium citrate;

• from 5 to 50% by weight of alkali metal hydrogen carbonate;

• from 7 to 12 % by weight of alkali metal carbonate;

• from 2 to 20% by weight of a whitening agent;

• from 1 to 8% by weight of a whitening agent activator; and

• from 0.2 to 4% by weight of an enzyme,

wherein the composition in the form of a 1% by weight aqueous solution has a pH value of from about 8 to less than 10.

Document US 2009/0186795 describes a dry detergent for automatic dishwashers comprising:

• 80-95% of a base that includes one or more of a sulfate, a carbonate, a citrate and a silicate, wherein 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 watermark reduction system that includes (i) a polyacrylate and (ii) a carboxymethyl inulin; and

• 0.1-3% of an enzyme system.

Document US 2011/0240063 describes a phosphate-free and bleach-free agent for automatic dishwashers that contains:

a) from 5 to 60% by weight of citrate;

b) (hydrogen)carbonate; and

c) from 2 to 40% by weight of ethylenediaminedisuccinic acid,

in which the weight ratio of components b) and c) is between 1:5 and 10:1.

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 occurring hydroxyl as an end group, wherein the chain transfer agent is present from about 75% by weight to about 99% by weight, based on the total weight of the hybrid copolymer. Examples 24 and 28 describe phosphate-free formulations for automatic dishwashers containing the copolymer, the adjuvant and the bleach.

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 occurring hydroxyl as an end 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 an end 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 occurring hydroxyl-containing chain transfer agent and M ^hsc 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 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 a carbonate inhibition 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 an automatic dishwasher detergent tablet that is made up of three different phases. The tablet contains adjuvant (sodium citrate.2H2O; sodium citrate anhydrous; citric acid; and Na2CO3), hybrid polymer, bleach and nonionic surfactant.

Summary of the invention

The inventors have developed a phosphate-free detergent composition for ADW that combines very good cleaning action with minimal bead marks, film formation and glassware corrosion. The phosphate-free detergent composition for ADW 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 non-ionic surfactant; wherein the nonionic surfactant is a polyoxyalkylene condensate, represented by the following formula: C _x H _2x+1 -O-[CH ₂ CH ₂ O] _n -CH ₂ CH(OH)C _y H _2y+1 , in which 4<x<22, 8<n<50, 4<y<22;

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

wherein the graft copolymer and the adjuvant are present in a weight ratio of copolymer to adjuvant of 1:50 to 1:4; and wherein the adjuvant contains at least 20% citrate by weight of the adjuvant and at least 25% carbonate by weight of the adjuvant, and the adjuvant is composed of:

a) not more than 70% by weight of hydroxycarboxylate sequestration adjuvant selected from citrate, tartrate, gluconate and combinations thereof;

b) not more than 80% by weight of precipitation aid selected from carbonate, silicate and combinations thereof;

c) 0-25% by weight of one or more other adjuvants;

wherein the citrate and carbonate together constitute at least 50% by weight of the adjuvant; and wherein the citrate and carbonate are present in a citrate:carbonate molar ratio of 0.1 to 1.0; wherein the terms citrate, tartrate, gluconate, carbonate and silicate encompass both acid and salt forms; and wherein the concentration of a salt or an acid refers to the equivalent concentration of the salt or acid in anhydrous form.

The ADW phosphate-free 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 component mainly consisting of hydroxycarboxylate adjuvant and precipitation adjuvant, nonionic surfactant and graft copolymer very effectively minimizes droplet marks and film formation. This is quite surprising since the detergent composition contains a substantial amount of precipitation aid which is traditionally believed to give rise to film formation problems. Finally, the ADW detergent composition offers the additional advantage of being less likely to cause corrosion of glassware.

Detailed description of the invention

A first aspect of the present invention relates to a phosphate-free 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; wherein the nonionic surfactant is a condensate of polyoxyalkylene, represented by the following formula: C ^x H ^{2x+ i} -O-[CH ² CH ² O] ⁿ -CH ² CH(OH)C ^y H ^{2 yi} , in which 4<x<22, 8<n< 50, 4<and<22;

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

wherein the graft copolymer and the adjuvant are present in a weight ratio of copolymer to adjuvant of 1:50 to 1:4; and wherein the adjuvant contains at least 20% citrate by weight of the adjuvant and at least 25% carbonate by weight of the adjuvant, and the adjuvant is composed of:

a) not more than 70% by weight of hydroxycarboxylate sequestration adjuvant selected from citrate, tartrate, gluconate and combinations thereof;

b) not more than 80% by weight of precipitation aid selected from carbonate, silicate and combinations thereof;

c) 0-25% by weight of one or more other adjuvants;

wherein the citrate and carbonate together constitute at least 50% by weight of the adjuvant; wherein the citrate and carbonate are present in a citrate:carbonate molar ratio of 0.1 to 1.0; wherein the terms citrate, tartrate, gluconate, carbonate and silicate encompass both acid and salt forms; and wherein the concentration of a salt or an acid refers to the equivalent concentration of the salt or acid in anhydrous form.

The term “phosphate-free detergent composition for ADW” as used herein refers to an ADW detergent composition containing less than 0.1% by weight of phosphate. In this case, the term "phosphate" refers to monophosphate salts, diphosphate salts, triphosphate salts and combinations thereof. The term “phosphate” does not include phosphonates.

The term "adjuvant" as used herein refers to a material that is capable of removing calcium ions from the aqueous solution by ion exchange, complexation, sequestration and/or precipitation.

Examples of adjuvant materials include alkali metal citrates, carbonates and bicarbonates; aminopolycarboxylates, polycarboxylates such as polymaleates, polyacetates, polyhydroxyacrylates, polyacrylate/polymaleate and polyacrylate/polymethacrylate copolymers, as well as zeolites; stratified type 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 are capable of removing 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 (2Na ₂ CO ₃ -3H ₂ O ₂ ).

The term "carbonate" as used herein refers to carbonic acid (H ₂ CO ₃ ) 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. The terms “tartrate”, “gluconate”, “silicate”, etc., should be interpreted accordingly.

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

The terminology “one or more other detergent components” as used herein refers to detergent components other than the adjuvant; the whitening component; the graft copolymer having a polysaccharide backbone and one or more side chains of one or more synthetic monomeric units; and the nonionic surfactant.

The term "one or more other adjuvants" refers to adjuvants other than citrate, tartrate, gluconate, carbonate and silicate.

The phosphate-free detergent composition for ADW of the present invention preferably contains less than 0.05% by weight of phosphate, more preferably less than 0.02% by weight of phosphate and most preferably less than 0.01% by weight of phosphate.

Expressed differently, the phosphate content of the ADW detergent composition is preferably less than 0.3% by weight of the adjuvant.

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 material composition or a solid article, for example, a tablet.

The combination of the adjuvant, the bleaching 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 hydroxycarboxylate adjuvant are preferably present in the detergent composition in a weight ratio of graft copolymer to hydroxycarboxylate adjuvant of at least 1:60, more preferably at least 1:50 and most preferably from 1:40 to 1:5.

The graft copolymer and citrate are preferably present in the detergent composition in a weight ratio of graft copolymer to citrate of at least 1:70, more preferably at least 1:50 and most preferably 1:40 at 1:5.

The graft copolymer and the nonionic surfactant are typically 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 of, calculated by weight of dry matter:

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 non-ionic surfactants;

and. 0.01-0.5% by weight enzymes;

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

The adjuvant contained in the detergent composition preferably comprises 25-65%, more preferably 30-60% by weight of the hydroxycarboxylate sequestration adjuvant by weight of the adjuvant. The adjuvant preferably comprises 30-75%, more preferably 40-70% by weight of precipitation aid by weight of the adjuvant.

According to a particularly preferred embodiment, the detergent composition contains no more than 70% citrate by weight of the adjuvant. More preferably, the detergent composition contains 25-65%, most preferably 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 alkali metal citrate, most preferably sodium citrate.

According to a particularly preferred embodiment, the 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 citrate and carbonate together constitute at least 30% by weight, more preferably 35-75% by weight 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 a particularly preferred embodiment, the detergent composition contains no more than 80% carbonate by weight of the adjuvant. More preferably, the detergent composition contains 30-75%, 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 disilicate, metasilicate and combinations thereof.

In addition to the hydroxycarboxylate adjuvant and the precipitation adjuvant, the adjuvant preferably comprises less than 15%, more preferably less than 10% of the one or more other adjuvants, calculated 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 (IDS), aspartic acid-N-monoacetic acid (ASMA), aspartic acid-N-acid, 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 contains 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 oxidant bleach component may suitably comprise a chlorine or bromine releasing compound or a peroxygen compound. Preferably, the bleaching 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 the corresponding salts of monopersulfate, perborate monohydrate, perborate tetrahydrate and percarbonate. Most preferably, the bleaching component is a percarbonate, in particular 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 phthaloylamidoperoxycaproic 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-diperoxyzelaic 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, N,N,N',N'-tetraacetylethylenediamine (TAED), sodium nonanoyloxybenzenesulfonate (SNOBS), sodium benzoyloxybenzenesulfonate (SBOBS) and the peroxyacid cationic precursor (SPCC) as described in the document can be named. US-A-4,751,015.

If desired, a bleach 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, in particular an encapsulated material that is separated from the bleach particles (to prevent premature activation of the bleach). 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 used 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 monomer units are preferably selected from carboxylate monomers; sulfonate monomers; olefinically unsaturated phosphonate monomers and combinations thereof. More preferably, the one or more synthetic monomer units are selected from carboxylate monomers; olefinically unsaturated 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, pmethyl-acrylic acid (crotonic acid), a -phenylacrylic acid, p -acryloxypropionic acid, sorbic acid, a-chlorosorbic acid, angelic acid, cinnamic acid, p-chlorocinnamic acid, p-styrylacrylic acid, (1-carboxy-4-phenylbutadiene-1,3)-itaconic 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 that can be derivatized to an acid-containing group may also be used. 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 styrenesulfonic acid, sulfoalkyl esters of (meth)acrylic acid, sulfoalkyl esters of itaconic acid, preferably in each case as C ¹ -alkyl esters. C ⁶ , vinylsulfonic acid and the alkali metal, alkaline earth metal and/or ammonium salts thereof. Monomers containing a (meth)acrylate, a (meth)acrylamide and/or a vinyl group are preferred, in particular 2-acrylamido-2-methylpropanesulfonic acid (AMPS), styrenesulfonic acid, sulfopropyl ester of acrylic acid, sulfopropyl ester of acrylic acid itaconic, 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, through treatment with propylene oxide, ethylene oxide, 2,3-epoxypropyltrimethylammonium chloride), esterification (for example, through reaction with acetic anhydride, octenylsuccinic anhydride (“OSA”)), acid hydrolysis, dextrinization, oxidation (e.g., oxidized starch) or enzyme 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 the hydrolysis of starch and have units of D-glucose linked primarily by -1,4 bonds and a dextrose equivalent of less than about 20. Dextrose equivalent (DE) is a measure of the extent 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, which represents 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 some 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 used according to the present invention is Alcoguard® H 5240, which is commercially available from AkzoNobel®.

Surfactants

Examples of nonionic surfactants include the condensation products of hydrophobic alkyl, alkenyl or alkylaromatic compounds bearing functional groups having free reactive hydrogen available for condensation with hydrophilic alkylene oxide, such as ethylene oxide, propylene oxide, oxide of butylene, poly(ethylene oxide) or polyethylene glycol to form nonionic surfactants. Examples of such functional groups include hydroxyl, carboxyl, mercapto, amino or amido groups.

Nonionic surfactants are found in the low to no foaming ethoxylated/propoxylated straight chain alcohols of the Plurafac™ LF series provided by BASF and the Synperonic™ NCA series provided by Croda. Other nonionic surfactants are ethoxylated alcohols with occupied ends available as the SLF 18 series from BASF and alkylpolyethylene glycol ethers made from a saturated linear C6-Cs fatty alcohol from the Lutensol™ AT series provided by BASF. Other nonionic surfactants suitable for application in the composition of the invention are polyglycol ethers of modified fatty alcohols available as Dehypon™ GRA or Dehypon™ Wet from BASF/Cognis. Other nonionic surfactants are from BASF's Lutensol™ TO series, which are alkyl polyethylene glycol ethers made from a saturated iso-d3 alcohol.

The nonionic surfactant is a polyoxyalkylene condensate, represented by the following formula: C _x H _2x+1 -O-[CH ² CH ² O]n-CH ² CH(OH)CyH ² y+ ¹ , in which 4<x<22,8<n<50,4<y<22.

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 nonionic surfactant used in the present detergent composition is preferably a low foaming nonionic surfactant. The term “low foaming nonionic surfactant” as used herein document relates to a nonionic surfactant which at a concentration of 1 % by weight in distilled water and a temperature of 50 °C has an initial foam height 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 D1173-07 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 can be produced that is not only chemically but also physically very stable if the nonionic surfactant used is solid at all temperatures that are relevant in the logistics chain. Therefore, it is preferred that the nonionic surfactant be solid below 45°C.

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.

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 (amylolytic enzymes) and others that degrade, alter or facilitate the degradation or alteration of stains and soils. biochemicals found in cleaning situations to more easily remove the dirt or stain from the object being washed to make the dirt or stain more 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 enzyme granules of types D, E and HS from Genencor and granules of types T, GT, TXT and Evity™ 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 B. lentus and B. gibsonii are the most preferred. Examples of such proteolytic enzymes are Excellase™, Properase™, Purafect™, Purafect™ Prime, Purafect™ Ox from Genencor; and those sold under the trade names BlazeTM, Ovozyme™, Savinase™, Alcalase™, Everlase™, Esperase™, Relase™, Polarzyme™, Liquinase™ and Coronase™ from Novozymes.

Amylolytic enzymes for use in the present invention may be those derived from bacteria or fungi. Chemically or genetically modified mutants (variants) are included. The preferred amylolytic enzyme is an alpha-amylase derived from a strain of Bacillus, such as B. subtilis, B. licheniformis, B. amyloliquefaciens or B. stearothermophilus. Examples of such amylolytic 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-formylphenylboronic 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 detergent 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, methylbenzotriazole 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 Il, Il, IV , V or VI.

The detergent composition of the present invention may include one or more water conditioning agents. For example, phosphonates in the form of water-soluble acid salts, particularly alkali metal salts, such as sodium or potassium, may suitably be used; ammonium salts; or alkylamine salts where the alkylol has 2 to 3 carbon atoms, such as mono-, di- or triethanolamine salts. Preferred phosphonates include organic phosphonates. Preferred organic phosphonates include phosphonobutanetricarboxylic acid (PBTC) and hydroxylethylidene diphosphonic acid (HEDP). Preferably, the composition contains 0-10% by weight of organic phosphonate, more preferably 0.2-5% by weight of organic phosphonate, even more preferably 0.3-2% by weight of organic phosphonate and most preferably 0.4 1.5% by weight of organic phosphonate.

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

Another aspect of the invention relates to the use of a detergent composition as defined herein above 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 monomeric side chains from Akzo Nobel

2 Dehypon WET, a 90% solution of low-foaming polyglycol ether fatty alcohols with the typical molecular formula C ₁ H ₂₃ -O-(CH ₂ CH ₂ O) ₂₀ -(CH ₂ CH(OH))-C _{BASF 8H17}

3 Dequest 2016, Monsanto HEDP

Detergent compositions for ADW 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 sprayed evenly over the powder bed. The resulting powder was subsequently compressed to give monolayer tablets. The combined weight of the tablet and Alcoguard H5240 was 18 grams.

In the dishwasher tests described below, the tablet and Alcoguard H5240 were placed independently in the dishwasher. The pill was inserted into the dispenser before starting the machine. Alcoguard H5240 was dispensed by putting the correct amount into a cup and adding the cup manually 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 frozen Stiwa dirt 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 were 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 dishes are illuminated with 4 Philips master TL-D 36 W / 8652M type light sources, 120 cm long, and the overall appearance is evaluated, 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 Plurafac LF 301 80 % (fatty alcohol alkoxylate from BASF) and benzotriazole 20 % 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 the remaining tests are summarized in table 4.

Table 4

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

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 polyglycol ether of fatty alcohols from Clariant

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 outperformed reference detergent compositions A and B containing a synthetic polymer, even though 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 by 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

These results demonstrate that the addition of aminocarboxylate adjuvants has an adverse impact on the performance of the detergent composition.

Example 5

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

Table 9

0,4

0,4

^Dye

0.4

0.4

1 Lutensol AT 25, fatty alcohol alkoxylate with molecular formula C ¹⁶ - ¹⁸ EO ²⁵ from BASF

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

The performance of the detergent compositions for ADW 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 only to drop marks and the total number of washes. It was limited to 10.

The results of these tests are summarized in table 10.

Table 10

Claims (14)

1. Phosphate-free 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; wherein the nonionic surfactant is a polyoxyalkylene condensate, represented by the following formula: C _x H _2x+1 -O-[CH ₂ CH ₂ O]n-CH ₂ CH(OH)CyH _2y+1 , in which that 4<x<22, 8<n<50, 4<y<22; • 0-60% by weight of one or more other detergent components; wherein the graft copolymer and the adjuvant are present in a weight ratio of copolymer to adjuvant of 1:50 to 1:4; and wherein the adjuvant contains at least 20% citrate by weight of the adjuvant and at least 25% carbonate by weight of the adjuvant, and the adjuvant is composed of: to. no more than 70% by weight of hydroxycarboxylate sequestration adjuvant selected from citrate, tartrate, gluconate and combinations thereof; b. not more than 80% by weight of precipitation aid selected from carbonate, silicate and combinations thereof; c. 0-25% by weight of one or more other adjuvants; wherein the citrate and carbonate together constitute at least 50% by weight of the adjuvant; wherein the citrate and carbonate are present in a citrate:carbonate molar ratio of 0.1 to 1.0; wherein the terms citrate, tartrate, gluconate, carbonate and silicate encompass both acid and salt forms; and wherein the concentration of a salt or an acid refers to the equivalent concentration of the salt or acid in anhydrous form. 2. Detergent composition according to claim 1, wherein the composition contains at least 30% by weight of adjuvant. 3. Detergent composition according to claim 1 or 2, wherein the citrate and carbonate are present in the detergent composition in a citrate:carbonate molar ratio of 0.15 to 0.9. 4. Detergent composition according to any one of the preceding claims, wherein the composition comprises at least 25% citrate by weight of the adjuvant. 5. Detergent composition according to any one of the preceding claims, wherein the composition comprises at least 30% carbonate by weight of the adjuvant. 6. Detergent composition according to any one of the preceding claims, wherein the adjuvant comprises less than 15% by weight of one or more other adjuvants. 7. Detergent composition according to any one of the preceding claims, wherein the bleaching component is percarbonate. 8. Detergent composition according to any one of the preceding claims, wherein the graft copolymer and the nonionic surfactant are present in a weight ratio of 1:4 to 3:1. 9. 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. 10. Detergent composition according to claim 9, wherein the polysaccharide is maltodextrin. 11. 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. 12. Detergent composition according to any one of the preceding claims, wherein the combination of the adjuvant, the bleaching component, the graft copolymer and the nonionic surfactant represents at least 50% by weight of the detergent composition. 13. Detergent composition according to any one of the preceding claims, wherein the composition is a particulate product or a solid article. 14. Use of a detergent composition according to any one of the preceding claims as a detergent in an automatic dishwasher.