EP3426756B1 - Pourable detergent suspension comprising bleach catalyst granules - Google Patents

Pourable detergent suspension comprising bleach catalyst granules Download PDF

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Publication number
EP3426756B1
EP3426756B1 EP17709682.3A EP17709682A EP3426756B1 EP 3426756 B1 EP3426756 B1 EP 3426756B1 EP 17709682 A EP17709682 A EP 17709682A EP 3426756 B1 EP3426756 B1 EP 3426756B1
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EP
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Prior art keywords
water
suspension
detergent
coating
bleach catalyst
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EP17709682.3A
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German (de)
English (en)
French (fr)
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EP3426756A1 (en
Inventor
Pavle ANDRIC
Elena Maria Gabriella Barbuzzi
Maria Petra J VAN DEURZEN
Kaare Joergensen ENGSTED
Kees Bert Geerse
Robert Jan MOLL
Niels-Viktor Nielsen
Lei SHANG
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Unilever Global IP Ltd
Unilever IP Holdings BV
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Unilever PLC
Unilever NV
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3947—Liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2065—Polyhydric alcohols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3935—Bleach activators or bleach catalysts granulated, coated or protected

Definitions

  • the present invention relates to a pourable detergent suspension according to claim 1 comprising a bleaching agent and bleach catalyst. More particularly, the invention relates to a pourable detergent according to claim 1 comprising:
  • the detergent suspension of the present invention combines pourability with high stability, despite the presence of a bleach catalyst, bleaching agent and a substantial amount of water.
  • Detergent formulations typically contain a number of different active components, including surfactants, builders, enzymes and bleaching agents.
  • Bleaching agents are employed in detergent compositions to remove bleachable stains, such as those associated with tea, coffee, red wine, and various fruit and vegetable products, by oxidizing the components that make up these stains.
  • Typical bleaching agents for use in detergent formulations are chlorine- and peroxygen-based compounds, such as hypochlorite and percarbonate bleach, respectively.
  • Bleach catalysts are employed in detergent compositions to activate the bleaching agent, especially at lower temperatures.
  • Builders are incorporated in detergent formulations to complex magnesium and calcium ions as well as to maintain alkaline pH conditions.
  • Phosphorous based builders such as phosphates
  • Phosphorous based builders have been used for many years in a wide variety of detergent compositions.
  • alternative building agents have been developed and these alternative builders have found their way into commercial detergent products.
  • the aminocarboxylate chelant L-glutamic-N,N-diacetate is an example of an environmentally friendly builder that is used in commercial detergent products.
  • aminocarboxylate chelants are present in detergent formulations in the form of their (fully deprotonated) sodium salts.
  • Aqueous solutions of aminocarboxylate salts are alkaline.
  • Liquid detergent formulations have been developed as these products offer the advantage over powdered formulations that they are easy to dose, may contain higher concentrations of active ingredients, suffer less from moisture spoilage during storage and/or are more easily dispersed into aqueous cleaning liquid.
  • liquid detergent compositions that deliver cleaning, spotting and filming performance similar to that of a powdered formulation it is necessary to include components that remain undissolved in the liquid product matrix. These undissolved components need to be homogeneously suspended throughout the product to guarantee a constant, optimum cleaning result. Although this may be achieved by instructing the user to shake the product before use, it is clearly preferable to provide the liquid detergent formulation in the form of a suspension that remains stable during the lifecycle of the product. This objective, however, is very difficult to achieve as suspensions demix over time because suspended particles are subject to sedimentation and creaming/floating phenomena.
  • Bleaching agents are moisture-sensitive detergent ingredients that lose their activity over time if the water activity of a detergent composition is too high.
  • Detergent compositions containing bleaching agent in combination with bleach catalyst are particularly sensitive to moisture.
  • EP-A 1 129 160 describes liquid aqueous cleaning compositions containing water, glycerol, builder, enzyme and thickener.
  • WO 2013/092276 describes detergent formulations containing GLDA, water, citric acid, nonionic surfactant, coated spray-dried percarbonate, Mn catalyst granule and other ingredients.
  • WO 2014/107578 describes detergent compositions containing water, glycerol, polyaminocarboxylic acid (chelating agent), nonionic surfactant.
  • WO 2008/064935 describes a method for producing bleach catalyst granules comprising, relative to the total weight of the granules,
  • WO 2016/005392 describes a granule comprising
  • the present inventors have developed a pourable detergent suspension that is easy to manufacture and that exhibits good storage stability despite the fact that it contains bleaching agent, bleach catalyst and a significant amount of water.
  • the pourable detergent suspension of the present invention comprises:
  • the hygroscopic component is capable or reducing the water activity of the detergent suspension to very low levels, despite the presence of at least 8 wt.% water.
  • the detergent suspension contains a moisture sensitive bleaching system (bleaching agent and bleach catalyst)
  • the suspension is very stable. Further contributing to this stability are the special bleach catalyst granules that contain particles of manganese bleach catalyst that are separated from other components of the pourable detergent suspension by a matrix of water-soluble alkali metal sulfate salt.
  • the detergent compositions of the present invention further offer the advantage that a wide range of detergent ingredients can be incorporated therein in either dispersed or dissolved form.
  • the bleach catalyst granules are homogeneously dispersed throughout the detergents suspension.
  • the present invention provides a pourable detergent suspension comprising:
  • pourable refers to a composition that is able to flow under ambient conditions.
  • Thixotropic compositions that can be rendered pourable by shear thinning are also regarded as pourable.
  • thixotropic refers to compositions (e.g. gels or fluids) that are viscous under quiescent conditions and that become less viscous when shaken, agitated, or otherwise stressed. In thixotropic compositions, this so called “shear thinning effect" is reversible, i.e. the composition will return to a more viscous state once it is no longer subjected to shear stress.
  • aminocarboxylate chelant refers to compounds containing one or more nitrogen atoms connected through carbon atoms to one or more carboxyl groups, which form strong complexes with metal ions by donation of electron pairs from the nitrogen and oxygen atoms to the metal ion to form multiple chelate rings.
  • water-soluble alkali metal sulfate salt refers to a alkali metal sulfate salt having a solubility in distilled water at 20°C of at least 10 g/l, preferably of at least 50 g/l.
  • particle size or “particle diameter”, unless indicated otherwise, it refers to particle diameter determined by laser diffraction using a system (such as a MastersizerTM 2000 available from Malvern Instruments Ltd) meeting the requirements set out in ISO 13320:2009.
  • water content includes unbound (free) as well as bound water.
  • a parameter such as a concentration or a ratio
  • a certain upper limit it should be understood that in the absence of a specified lower limit the lower limit for said parameter is 0.
  • the quantified amount or quantified concentration relates to said component per se, even though it may be common practice to add such a component in the form of a solution or of a blend with one or more other ingredients
  • the detergent suspension of the present invention is a homogenous product.
  • the non-dissolved components such as the bleach catalyst granules are evenly dispersed throughout the detergent suspension.
  • the detergent suspension preferably contains one or more aminocarboxylate chelants. More preferably, the detergent suspension contains water and the one or more aminocarboxylate chelants in a weight ratio of not more than 2:1, preferably of not more than 1.5:1, most preferably of not more than 1.2:1. Water and the one or more aminocarboxylate chelants are typically contained in the detergent suspension in a weight ratio of at least 1:3, more preferably of at least 1:2 and most preferably of at least 1:1.8.
  • the detergent suspension preferably contains glycerol.
  • Glycerol and water are preferably contained in the pourable detergent suspension in a weight ratio that lies within the range of 2:3 to 1:6, more preferably within the range of 1:2 to 1:5, most preferably within the range of 1:2.2 to 1:4.
  • the pourable detergent suspension preferably contains 20-75 wt.%, more preferably 30-60 wt.% and most preferably 35-55 wt.% glycerol.
  • the water content of the detergent suspension preferably is in the range of 10-22 wt.%, more preferably in the range of 11-20 wt.% and most preferably in the range of 12-18 wt.%.
  • the detergent suspension typically has a water activity of 0.2 to 0.6 at 20°C. More preferably, the water activity of the detergent suspension at 20°C is in the range of 0.3 to 0.5, most preferably of 0.35 to 0.45
  • the pourable detergent suspension preferably contains at least 8 wt.%, more preferably 10-40 wt.% and most preferably 12-30 wt.% of the one or more aminocarboxylate chelants.
  • the one or more aminocarboxylate chelants are selected from glutamic acid N,N-diacetic acid (GLDA), methylglycinediacetic acid (MGDA), iminodisuccinic acid (IDS), ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), hydroxyethyliminodiacetic acid (HEIDA), Nitrilotriacetic acid (NTA), aspartic acid diethoxysuccinic acid (AES), aspartic acid-N, -diacetic acid (ASDA), hydroxyethylenediaminetetraacetic acid (HEDTA), hydroxyethylethylenediaminetriacetic acid (HEEDTA), iminodifumaric (IDF), iminoditartaric acid (IDT), iminodimaleic acid (IDMAL), iminodimalic acid (IDM), ethylenediaminedifumaric acid (EDDF), ethylenedi
  • the one or more aminocarboxylate chelants are selected from GLDA, MGDA, IDS, HEIDA, EDDS and NTA, and their salts. In an even more preferred embodiment, the one or more aminocarboxylate chelants are selected from GLDA, MGDA, IDS and their salts. Most preferably, the the one or more aminocarboxylate chelants are selected from GLDA and salts thereof.
  • the GLDA employed in the present suspension preferably is an alkali metal salt of glutamic-N,N-diacetic acid. More preferably, the GLDA employed is a sodium salt of glutamic-N,N-diacetic acid. Most preferably, the GLDA employed is a tetra sodium salt of glutamic-N,N-diacetic acid.
  • the combination of glycerol, water and the one or more amincarboxylate chelants typically represent at least 45 wt.%, preferably at least 55 wt.% and most preferably at least 60 wt.% of the detergent suspension.
  • the present detergent suspension preferably contains at least 1.5 wt.%, more preferably 1.8-15 wt.% and most preferably 2-12 wt.% of bleaching agent.
  • the bleaching agent is preferably selected from peroxy compound bleaches, hydrogen peroxide liberating compounds, hydrogen peroxide generating systems, peroxyacids and their salts, peroxyacid bleach precursor systems and combinations thereof. Even more preferably, the bleaching agent is a hydrogen peroxide sources selected from alkali metal peroxides, organic peroxide bleaching compounds and inorganic persalt bleaching compounds and combinations thereof. Even more preferably, the bleaching agent is a peroxide.
  • peroxides are acids and corresponding salts of monopersulfate, perborate monohydrate, perborate tetrahydrate, and percarbonate.
  • Organic peracids useful herein include alkyl peroxy acids and aryl peroxyacids such as peroxybenzoic acid and ring substituted peroxybenzoic acids (e.g. peroxy-alpha- naphthoic acid), aliphatic and substituted aliphatic monoperoxy acids (e.g. peroxylauric acid and peroxystearic acid), and phthaloyl amido peroxy caproic acid (PAP).
  • peroxybenzoic acid and ring substituted peroxybenzoic acids e.g. peroxy-alpha- naphthoic acid
  • aliphatic and substituted aliphatic monoperoxy acids e.g. peroxylauric acid and peroxystearic acid
  • PAP phthaloyl amido peroxy caproic acid
  • Typical diperoxy acids useful herein include alkyl diperoxy acids and aryldiperoxy acids, such as 1,12 di-peroxy-dodecanedioic acid (DPDA), 1,9 diperoxyazelaic acid, diperoxybrassylic acid, diperoxysebacic acid and diperoxy-isophthalic acid, and 2 decyldiperoxybutane 1,4 dioic acid.
  • DPDA 1,12 di-peroxy-dodecanedioic acid
  • 1,9 diperoxyazelaic acid diperoxybrassylic acid
  • diperoxysebacic acid and diperoxy-isophthalic acid diperoxy-isophthalic acid
  • 2 decyldiperoxybutane 1,4 dioic acid 2,4 di-diperoxybutane 1,4 dioic acid.
  • the bleaching agent is percarbonate.
  • the detergent suspension of the present invention preferably contains bleaching agent in the form of particles. More preferably, the suspension contains 1-15 wt.%, more preferably 2-12 wt.% of particles comprising bleaching agent. Preferably, these particles contain at least 10 wt.%, more preferably at least 30 wt.% and most preferably at least 50 wt.% of bleaching agent.
  • the particles of bleaching agent are coated particles comprising one or more core particles that contain the bleaching agent, which one or more core particles are enclosed by a water-soluble coating.
  • the water-soluble coating advantageously comprises a coating agent selected from alkali sulfate, alkali carbonate or alkali chloride and combinations thereof.
  • the particles of bleaching agent typically have a diameter in the range of 10-3000 ⁇ m, more preferably of 20-2000 ⁇ m and most preferably of 30-1500 ⁇ m.
  • the a volume weighted mean particle size of the particles of bleaching agent preferably is in the range of 10 to 3000 ⁇ m, more preferably of 100 to 1500 ⁇ m and most preferably of 200 to 1000 ⁇ m.
  • the pourable detergent suspension of the present invention typically contains 0.2-4 wt.%, more preferably 0.2-3 wt.% and most preferably 0.4-2.5 wt.% of the bleach catalyst granules.
  • the bleach catalyst granules typically contain at least 0.5 wt.%, more preferably 0.8-10 wt.% and most preferably 1-8 wt.% of the manganese bleach catalyst.
  • the bleach catalyst granules typically contain at least 40 wt.%, more preferably at least 50 wt.% and most preferably at least 60 wt.% of the water-soluble salt.
  • the bleach catalyst granules typically have a diameter of at least 50 ⁇ m, more preferably of 100-1500 ⁇ m, even more preferably of 250-1200 ⁇ m and most preferably of 350-1000 ⁇ m.
  • the bleach catalyst granules are preferably spherical particles.
  • the catalyst particles in the bleach catalyst granules typically contain at least 50 wt.%, more preferably at least 80 wt.% of manganese bleach catalyst.
  • the inventors have unexpectedly found that granules having particularly good stability can be prepared if the diameter of the catalyst particles is very small.
  • at least 90 wt.% of the catalyst particles have a diameter in the range of 0.2 to 25 ⁇ m, more preferably in the range of 0.4 to 20 ⁇ m, even more preferably in the range of 0.5 to 18 ⁇ m and most preferably in the range of 0.6 to 15 ⁇ m.
  • the catalyst particles have a volume weighted mean diameter in the range of 1-12 ⁇ m, most preferably of 1.5-10 ⁇ m.
  • the water-soluble alkali metal sulfate salt in the bleach catalyst granules preferably has a constant humidity at 2°C above 85%, particularly above 90%.
  • the water-soluble alkali metal sulfate salt may be in anhydrous form, or it may be a hydrated salt, i.e. a crystalline salt hydrate with bound water(s) of crystallization.
  • a specific example is anhydrous sodium sulfate (Na 2 SO 4 ).
  • the bleach catalyst granules preferably contain at least 35 wt.%, more preferably 40-80 wt.% wt.% and most preferably at least 45-75 wt.% of the one or more core particles.
  • the bleach catalyst granules contain one single core particle.
  • the one or more core particles in the bleach catalyst granules preferably have a diameter of 40-1500 ⁇ m, more preferably of 80-1200 ⁇ m, even more preferably of 200-1000 ⁇ m and most preferably of 300-900 ⁇ m..
  • the core particle may consist of inert carrier material.
  • the core may suitably contain functional detergent ingredient such as builders, bleach activators, dispersing polymers, silicates, anti-scaling agents, glass corrosion inhibitors, ant-tarnishing agents, surfactants and combinations thereof.
  • the core particles contain at least 50 wt.%, more preferably at least 80 wt.% and most preferably at least 90 wt.% of an inert carrier material selected from water-soluble salt (e.g. sulfate salt and/or carbonate salt), cellulose fibers, dextrin, disaccharides and combinations thereof.
  • the coating of the bleach catalyst granules preferably has a thickness in the range of 5 to 150 ⁇ m, more preferably in the range of 10 to 120 ⁇ m, even more preferably in the range of 12 to 80 ⁇ m and most preferably in the range of 15 to 50 ⁇ m.
  • the coating typically represents not more than 65 wt.%, more preferably 20-60 wt.% and most preferably 25-55 wt.% of the bleach catalyst granules.
  • the coating preferably contains 2-25%, more preferably 3-20% and most preferably 3.5-15% by weight of the coating of the catalyst particles comprising manganese bleach catalyst.
  • bleach catalyst granules contain a single core particle and the size of the core particle, the thickness of the coating and the size of the catalyst particles have been selected to provide an optimum combination of storage stability, suspension stability and delivery of the activity of the bleach catalyst during use. Accordingly, the bleach catalyst granules preferably contain one core particle having and meet the following specifications:
  • the bleach catalyst granules meet the following specifications:
  • the thickness of the coating exceeds the volume weighted average diameter of the catalyst particles by at least 50%, more preferably at least 100% and most preferably by at least 200%.
  • the coating of the bleach catalyst granules preferably contains 55-90 wt.%, more preferably 60-85 wt.% of the water-soluble salt.
  • the coating of the bleach catalyst granules comprises at least two coating layers, including (i) a first coating layer comprising 30-90 wt.% of the catalyst particles and 10-70 wt.% of a water-soluble binder, and (ii) a second layer that surrounds the first coating layer, said second coating layer comprising at least 60 wt.%, more preferably at least 70 wt.%, even more preferably at least 80 wt.% and most preferably at least 90 wt.% of the water-soluble salt.
  • the water-soluble binder is preferably selected from monosaccharides, disaccharides, trisaccharides, dextrin and combinations thereof. Most preferably, the water-soluble binder is selected from sucrose, lactose, dextrin and combinations thereof. Most preferably, the water-soluble binder is dextrin, e.g. maltodextrin.
  • the combination of catalyst particles, water-soluble salt and water-soluble binder typically constitutes at least 60 wt.%, more preferably at least 70 wt.% and most preferably at least 75 wt.% of the coating of the bleach catalyst granules.
  • the aforementioned first coating layer preferably has an average thickness of 2-50 ⁇ m, more preferably of 3-30 ⁇ m, even more preferably of 4-25 ⁇ m and most preferably of 5-20 ⁇ m.
  • the first coating layer typically comprises the catalyst particles in an amount of 2-15%, more preferably of 3-10% by weight of the core.
  • the first coating layer preferably contains the water-soluble binder in an amount of 1-20%, more preferably of 2-10% by weight of the core.
  • the second coating layer of the bleach catalyst granules typically represents at least 5%, more preferably at least 10% and most preferably at least 20% by weight of the core.
  • the second coating layer preferably represents at most 100%, more preferably at most 80%and most preferably at most 75% by weight of the core.
  • the second coating layer preferably has an average thickness of at least 3-100 ⁇ m, more preferably of 5-80 ⁇ m, even more preferably of 8-60 ⁇ m and most preferably of 10-40 ⁇ m.
  • the bleach catalyst granules may include an additional third coating layer that surrounds the second coating layer.
  • This third coating layer preferably contains at least 20 wt.%, more preferably at least 25 wt.% and most preferably at least 30 wt.% of a film forming component selected from polyethylene glycol (PEG), hydroxypropyl methyl cellulose (HPMC), polyvinyl alcohol (PVA) and combinations thereof.
  • the third coating layer has a thickness in the range of 1-50 ⁇ m, most preferably of 2-30 ⁇ m.
  • the manganese bleach catalyst in the coating of the bleach catalyst granules is represented by formula (I): [L n Mn m X p ] z Y q (I) wherein:
  • the coefficient p preferably is an integer from 3 to 6.
  • each Mn independently has an oxidation state selected from III and IV.
  • X in formula (I) preferably represents a coordination or bridging species selected from H 2 O, OH - , O 2- , S 2 - , HOO - , O 2 2- , O 2 1- , R-COO - , with R being H, alkyl, aryl, optionally substituted, NR 3 with R being H, alkyl, aryl, optionally substituted, Cl - , SCN - , N 3 - , etc. or a combination thereof.
  • X represents O 2- or (OAc) - , more preferably O 2- .
  • Ac signifies an acyl group.
  • Y is a counter-ion, the type of which is dependent upon the charge z of the complex which can be positive, zero or negative. If z is positive, Y is an anion, such as Cl - , Br - , I - , NO 3 - , ClO 4 - , NCS - , PF 6 - , RSO 4 - , OAc - , BPh 4 - , CF 3 SO 3 - , RSO 3 - , RSO 4 - , etc., where R represents alkyl, or aryl. Preferably, Y is PF 6 - or ClO 4 - . If z is negative, Y is a cation, such as an alkali metal, alkaline earth metal or (alkyl)ammonium cation, etc.
  • L in formula (I) is a ligand in the form of a macrocyclic organic molecule represented by general formula (II) wherein R 1 and R 2 can each be zero, H, alkyl or aryl; t and t' are each independent integers from 2 to 3; each D can independently be N, NR, PR, O, or S, wherein R is H, alkyl or aryl.
  • the coefficient s in formula (II) preferably is 2, 3, or 4, even more preferably s is 2.
  • Particularly preferred ligands are 1,4,7-trimethyl-1,4,7-triazacyclononane, coded as Me-TACN, 1,4,7-triazacyclononane, coded as TACN, 1,5,9-trimethyl-1,5,9-triazacyclododecane, coded as Me-TACD; 2-methyl-1,4,7-trimethyl-1,4,7-triazacyclononane, coded as Me/Me-TACN and 2-methyl-1,4,7-triazacyclononane, coded as Me/TACN.
  • Me-TACN and Me/Me-TACN are the most preferred.
  • Examples of suitable manganese bleach catalysts are provided in EP-A- 0 458 397 .
  • the manganese bleach catalyst comprises one or more from [Mn III 2 ( ⁇ -O) 1 ( ⁇ -OAc) 2 (Me-TACN) 2 ] (ClO 4 ) 2 , [Mn III Mn IV ( ⁇ -O) 1 ( ⁇ -OAc) 2 (Me-TACN) 2 ] (ClO 4 ) 3 , [Mn III 2 ( ⁇ -O) 1 ( ⁇ -OAc) 2 (Me-TACN) 2 ] (PF 6 ) 2 , [Mn III 2 ( ⁇ -O) 1 ( ⁇ -OAc) 2 (Me/Me-TACN) 2 ] (PF 6 ) 2 , [Mn IV 2 ( ⁇ -O) 3 (Me-TACN) 2 ] (PF 6 ) 2 , and [Mn IV 2 ( ⁇ -O) 3 (Me/Me-TACN) 2 ] (PF 6 ) 2 , and [Mn IV 2 (
  • the manganese bleach catalyst comprises one or more from [Mn IV 2 ( ⁇ -O) 3 (Me-TACN) 2 ] (PF 6 ) 2 , and [Mn IV 2 ( ⁇ -O) 3 (Me/Me-TACN) 2 ] (PF 6 ) 2 . It is still more preferred that the manganese bleach catalyst is [Mn IV 2 ( ⁇ -O) 3 (Me-TACN) 2 ] (PF 6 ) 2 .
  • the bleach catalyst granules of the present invention may suitably be produced by fluid bed coating.
  • the first coating layer is applied by spraying onto a fluidized bed of core particles an aqueous suspension of catalyst particles that contains dissolved binder.
  • the coated particles so obtained are coated with the second coating layer by means of fluid bed coating by spraying an aqueous salt solution onto a fluidized bed of the coated particles.
  • 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 can be named N,N,N',N'-tetraacetyl ethylene diamine (TAED), sodium nonanoyloxybenzene sulfonate (SNOBS), sodium benzoyloxybenzene sulfonate (SBOBS) and the cationic peroxyacid precursor (SPCC) as described in US-A-4,751 ,015 .
  • the present detergent suspension preferably contains one or more surfactants.
  • Surfactants within the invention, are components within the classification as described in " Surfactant Science Series", Vol.82, Handbook of detergents, part A: Properties, chapter 2 (Surfactants, classification), G. Broze (ed .).
  • the detergent composition contains 0.5-30 wt.%, preferably 1-20 wt.%,more preferably 1.3-10 wt.% of one or more surfactants.
  • the surfactants are selected from one or more non-ionic surfactants.
  • the composition contains 0.1-15 wt.%, more preferably 0.5-10 wt.% and most preferably 1-5 wt.% of a nonionic surfactant or a mixture of two or more non-ionic surfactants.
  • nonionic surfactants that may be employed in the present composition include the condensation products of hydrophobic alkyl, alkenyl, or alkyl aromatic compounds bearing functional groups having free reactive hydrogen available for condensation with hydrophilic alkylene oxide, such as ethylene oxide, propylene oxide, butylene oxide, polyethylene oxide or polyethylene glycol to form nonionic surfactants.
  • functional groups include hydroxy, carboxy, mercapto, amino or amido groups.
  • Examples of useful hydrophobes of commercial nonionic surfactants include C8-C18 alkyl fatty alcohols, C8-C14 alkyl phenols, C8-C18 alkyl fatty acids, C8-C18 alkyl mercaptans, C8-C18 alkyl fatty amines, C8-C18 alkyl amides and C8-C18 alkyl fatty alkanolamides.
  • suitable ethoxylated fatty alcohols may be chosen from ethoxylated cetyl alcohol, ethoxylated ketostearyl alcohol, ethoxylated isotridecyl alcohol, ethoxylated lauric alcohol, ethoxylated oleyl alcohol and mixtures thereof.
  • suitable nonionic surfactants for use in the invention are found in the low- to non-foaming ethoxylated/ propoxylated straight-chain alcohols of the PlurafacTM LF series, supplied by the BASF and the SynperonicTM NCA series supplied by Croda.
  • end-capped ethoxylated alcohols available as the SLF 18 series from BASF and the alkylpolyethylene glycol ethers made from a linear, saturated C16-C18 fatty alcohol of the LutensolTM AT series, supplied by BASF.
  • suitable nonionics to apply in the composition of the invention are modified fatty alcohol polyglycolethers available as DehyponTM 3697 GRA or DehyponTM Wet from BASF/Cognis.
  • nonionics from the LutensolTM TO series of BASF which are alkylpolyethylene glycol ethers made from a saturated iso-C13 alcohol.
  • Amineoxide surfactants may also be used in the present invention as anti- redeposition surfactant.
  • Suitable amineoxide surfactants are C10-C15 alkyl dimethylamine oxide and C10-C15 acylamido alkyl dimethylamine oxide.
  • the inventors have found that, a detergent composition that is not only chemically but also physically very stable can be produced if the nonionic surfactant employed is solid at ambient temperature.
  • the present composition contains 0.1 -30 wt.%, more preferably 0.5-20 wt.%, further preferred 1-10 wt.%, and most preferably 1 -5 wt.% of nonionic surfactant that is solid at 25°C.
  • the total amount present preferably is less than 5 wt.%, and more preferably not more than 2 wt.%. Furthermore, if an anionic surfactant is present, it is preferred that an antifoam agent to suppress foaming is present.
  • suitable anionic surfactants are methylester sulphonates or sodium lauryl sulphate. It is preferred that no anionic surfactant is present in the composition of the current invention.
  • Silicates may be added to the formulation.
  • Silicates can act as builder, buffering agent or article care agent.
  • Preferred silicates are sodium silicate such as sodium disillicate, sodium metasilicate and crystalline phyllosilicates and mixtures thereof.
  • Silicates are preferably used in the detergent suspension in a concentration of 0.5 to 8%, more preferably of 0.8 to 6% by weight of the suspension.
  • enzymes suitable for use in the cleaning suspensions of this invention include lipases, cellulases, peroxidases, proteases (proteolytic enzymes), amylases (amylolytic enzymes) and others which degrade, alter or facilitate the degradation or alteration of biochemical soils and stains encountered in cleansing situations so as to remove more easily the soil or stain from the object being washed to make the soil or stain more removable in a subsequent cleansing step. Both degradation and alteration can improve soil removal.
  • the one or more active enzymes contained in the present suspension are selected from protease, amylase, cellulase, peroxidase, mannanase, pectate lyase and lipase.
  • the active enzyme is selected from protease, amylase and combinations thereof.
  • the suspension of the present invention typically contains at least 10 mg/kg, more preferably at least 20 mg/kg, even more preferably at least 50 mg/kg and most preferably at least 100 mg/kg of active enzyme.
  • the concentration of active enzyme preferably does not exceed 50 g/kg, more preferably it does not exceed 40 g/kg and most preferably it does not exceed 30 g/kg.
  • the suspension contains at least 10 mg/kg, more preferably at least 20 mg/kg and most preferably at least 50 mg/kg of active amylase.
  • the suspension 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 may be added in liquid or in encapsulated form.
  • encapsulated enzymes are enzyme granule types D, E and HS by Genencor and granule types , T, GT, TXT and EvityTM of Novozymes.
  • proteolytic enzymes in this invention include metal loproteases and serine proteases, including neutral or alkaline microbial serine protease, such as subtilisins (EC 3.4.21 .62).
  • the proteolytic enzymes for use in the present invention can be those derived from bacteria of 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 most preferred.
  • proteolytic enzymes are ExcellaseTM, ProperaseTM, PurafectTM, PurafectTM Prime, PurafectTM Ox by Genencor; and those sold under the trade names BlazeTM, OvozymeTM, SavinaseTM, AlcalaseTM, EverlaseTM, EsperaseTM, RelaseTM, PolarzymeTM, LiquinaseTM and CoronaseTM by Novozymes.
  • amylolytic enzymes for use in the present invention can be those derived from bacteria or fungi. Chemically or genetically modified mutants (variants) are included.
  • 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 of StainzymeTM, StainzymeTM Plus, TermamylTM, NatalaseTM and DuramylTM by Novozymes; as well as PoweraseTM, PurastarTM, PurastarTM Oxam by Genencor. StainzymeTM, StainzymeTM Plus and PoweraseTM are the preferred amylases.
  • the suspension contains active protease and the protease activity of the freshly prepared suspension decreases by not more than 70%, more preferably by not more than 50% and most preferably by not more than 20% when the suspension is stored in a closed container for 8 weeks at 20 °C.
  • Well known enzyme stabilizers such as polyalcohols/borax, calcium, formate or protease inhibitors like 4-formylphenyl boronic acid may also be present in the suspension.
  • the detergent suspension may suitably contain one or more dispersing polymers.
  • Dispersing polymers as referred to in this invention are chosen from the group of anti-spotting agents and/or anti-scaling agents.
  • suitable anti-spotting polymeric agents include hydrophobically modified polycarboxylic acids such as AcusolTM 460 ND (ex Dow) and AlcosperseTM 747 by AkzoNobel, whereas also synthetic clays, and preferably those synthetic clays which have a high surface area are very useful to prevent spots, in particular those formed where soil and dispersed remnants are present at places where the water collects on the glass and spots formed when the water subsequently evaporates.
  • hydrophobically modified polycarboxylic acids such as AcusolTM 460 ND (ex Dow) and AlcosperseTM 747 by AkzoNobel
  • synthetic clays and preferably those synthetic clays which have a high surface area are very useful to prevent spots, in particular those formed where soil and dispersed remnants are present at places where the water collects on the glass and spots formed when the water subsequently evaporates.
  • Suitable anti-scaling agents include organic phosphonates, amino carboxylates, polyfunctionally-substituted compounds, and mixtures thereof.
  • anti-scaling agents are organic phosphonates such as alpha-hydroxy-2 phenyl ethyl diphosphonate, ethylene diphosphonate, hydroxy 1 ,1 - hexylidene, vinylidene 1 ,1 -diphosphonate, 1 ,2-dihydroxyethane 1 ,1 -diphosphonate and hydroxy-ethylene 1 ,1 - diphosphonate.
  • organic phosphonates such as alpha-hydroxy-2 phenyl ethyl diphosphonate, ethylene diphosphonate, hydroxy 1 ,1 - hexylidene, vinylidene 1 ,1 -diphosphonate, 1 ,2-dihydroxyethane 1 ,1 -diphosphonate and hydroxy-ethylene 1 ,1 - diphosphonate.
  • EDHP hydroxy-ethylene 1 ,1 - diphosphonate
  • 2-phosphono-butane 1 ,2,4-tricarboxylic acid
  • Suitable anti-scaling agents are water soluble dispersing polymers prepared from an allyloxybenzenesulfonic acid monomer, a methallyl sulfonic acid monomer, a copolymerizable nonionic monomer and a copolymerizable olefinically unsaturated carboxylic acid monomer as described in US 5 547 612 or known as acrylic sulfonated polymers as described in EP 851 022 .
  • Polymers of this type include polyacrylate with methyl methacrylate, sodium methallyl sulfonate and sulfophenol methallyl ether such as AlcosperseTM 240 supplied (AkzoNobel).
  • terpolymer containing polyacrylate with 2-acrylamido-2 methylpropane sulfonic acid such as Acumer 3100 supplied by Dow.
  • polymers and co-polymers of acrylic acid having a molecular weight between 500 and 20,000 can also be used, such as homopolymeric polycarboxylic acid compounds with acrylic acid as the monomeric unit.
  • the average weight of such homo-polymers in the acid form preferably ranges from 1,000 to 100,000 particularly from 3,000 to 10,000 e.g. SokolanTM PA 25 from BASF or AcusolTM 425 from Dow.
  • polycarboxylates co-polymers derived from monomers of acrylic acid and maleic acid such as CP 5 from BASF.
  • the average molecular weight of these polymers in the acid form preferably ranges from 4,000 to 70,000.
  • Modified polycarboxylates like SokalanTMCP42, SokalanTM CP50 from BASF or AlcoguardTM 4160 from AkzoNobel may also be used.
  • Mixture of anti-scaling agents may also be used. Particularly useful is a mixture of organic phosphonates and polymers of acrylic acid. It is preferable if the level of dispersing polymers ranges from 0.2 to 10 wt.% of the total suspension, preferably from 0.5 to 8 wt.%, and further preferred from 1 to 6 wt.%.
  • Glass corrosion inhibitors can prevent the irreversible corrosion and iridescence of glass surfaces in machine dishwash detergents.
  • the claimed suspension may suitably contain glass corrosion inhibitors.
  • Suitable glass corrosion agents can be selected from the group 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 salts of bismuth, magnesium or zinc or combinations thereof.
  • Preferred levels of glass corrosion inhibitors in the present suspension are 0.01 -2 wt.%, more preferably 0.01 - 0.5 wt.%.
  • Anti-tarnishing agents may prevent or reduce the tarnishing, corrosion or oxidation of metals such as silver, copper, aluminium and stainless steel.
  • Anti-tarnishing agents such as benzotriazole or bis-benzotriazole and substituted or substituted derivatives thereof and those described in EP 723 577 (Unilever) may also be included in the suspension.
  • Other anti-tarnishing agents that may be included in the detergent suspension 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 are in the oxidation state of II, II, IV V or VI.
  • the desired viscosity profile of the detergent suspension depends on the end use of the product. It may be a liquid, gel or a paste depending on the application.
  • Another aspect of the present invention relates to a water-soluble sachet that is filled with a suspension as defined herein before.
  • the detergent suspension is a thixotropic suspension.
  • thixotropic means that the product is viscous under quiescent conditions and become less viscous when shaken, agitated, or otherwise stressed. In thixotropic suspensions, this so called “shear thinning effect" is reversible, i.e. the suspension will return to a more viscous state once it is no longer subjected to shear stress. This thixotropic behavior of the detergent suspension can be demonstrated by measuring the storage modulus (G') and the loss modulus (G") of the product as a function of angular frequency ( ⁇ ) on a rheometer in oscillatory mode.
  • G' and G" of the fluid product increase as a function of angular frequency ( ⁇ ), be it that G" increases at a faster rate than G'.
  • angular frequency ( ⁇ ) G" of the fluid product is lower than G', but at an ⁇ in the range of 0.05-50 rad/s G" surpasses G'.
  • Both the storage modulus (G') and the loss modulus (G") of the fluid product are determined at 20°C using Anton Paar® MCR 302 rheometer, using plate-plate geometry, spindle PP50/S (sandblasted) and a gap size of 3mm.
  • the program settings applied are as follows:
  • oscillatory rheology it is possible to quantify both the viscous-like and the elastic-like properties of a material at different time scales.
  • the basic principle of an oscillatory rheometer is to induce a sinusoidal shear deformation in the sample and measure the resultant stress response; the time scale probed is determined by the frequency of oscillation, ⁇ , of the shear deformation.
  • the stress in the sample is proportional to the rate of strain deformation, where the proportionality constant is the viscosity of the fluid.
  • Viscoelastic materials show a response that contains both in-phase and out-of-phase contributions. These contributions reveal the extents of solid-like and liquid-like behavior. As a consequence, the total stress response shows a phase shift ⁇ with respect to the applied strain deformation that lies between that of solids and liquids, 0 ⁇ /2.
  • the viscoelastic behaviour of the system at ⁇ is characterised by the storage modulus, G'( ⁇ ), and the loss modulus, G"( ⁇ ), which respectively characterise the solid-like and fluid-like contributions to the measured stress response.
  • the fluid product of the present invention has a loss modulus that is lower than the storage modulus, indicating solid-like behavior, while at the highest frequencies accessed the loss modulus dominates the response, indicating viscous-like behavior.
  • the detergent suspension is a thixotropic suspension having a storage modulus at 20°C (G'( ⁇ )) and a loss modulus at 20°C (G" ( ⁇ )), both moduli measured as a function of angular frequency ( ⁇ ) on a rheometer in oscillatory mode operating at a strain of 0.1%, wherein:
  • a detergent suspension having a storage modulus (G') and a loss modulus (G") that meet at least one of the following conditions:
  • the pourable detergent suspension typically has a storage modulus (G') at 0.2 rad/s in the range of 1 to 100 Pa, more preferably in the range of 8 to 30 Pa, most preferably in the range of 10 to 20 Pa.
  • G' storage modulus
  • the loss modulus (G) of the pourable detergent suspension at 0.2 rad/s preferably is in the range of 1 to 100 Pa, more preferably in the range of 3 to 60 Pa, most preferably in the range of 8 to 30 Pa.
  • a pourable, thixotropic machine dishwashing product was prepared on the basis of the recipe that is shown in Table 1.
  • Table 1 Ingredients Wt.% Glycerol 48.67 Citric Acid (50%) 1.43 DissolvineTM GL 47-S 1 9.40 DissolvineTM PD-S 2 2 18.40 Process water 7.99 Xanthan Gum 0.21 Carbonate ash light 12.05 Percarbonate 3 1.10 Bleach catalyst granulate 1.2 LutensolTM AT80 (nonionic surfactant) 1.87 1 Contains appr. 48 wt.% GLDA and 45 wt.% water 2 Contains appr. 85 wt.% GLDA and 9 wt.% water 3 Coated percarbonate, 98 wt.% between 0.2 mm and 1.4 mm
  • the bleach catalyst granulate had been prepared as follows:
  • the composition of the bleach catalyst granulate is summarized in Table 2.
  • the machine dishwashing product was prepared as follows. A liquid premix was made by mixing glycerol and xanthan gum to a homogeneous suspension. Next, water was added under constant stirring. After that DissolvineTM GL 47-S and citric acid were dosed at ambient temperature. Next, the DissolvineTM PD-S was mixed in. Finally the remaining ingredients were added to the mix under stirring. All ingredients were mixed in under vacuum to minimize formation of air bubbles.
  • the detergent product so obtained was a stable suspension that did not suffer from phase separation or sedimentation when stored under ambient conditions. Bleach activity of the product did not significantly decrease during normal storage. The product was quite viscous but could be poured from a bottle without any problems.
  • a pourable detergent suspension according to the present invention was compared with a pourable detergent composition that was identical, except that a different bleach catalyst granulate was used.
  • This bleach catalyst granulate A was prepared on the basis of the formulation shown in Table 3.
  • Table 3 Wt.% ManCat (MN-TACN crystals) Mncat 1033 4 Sodium carbonate (ash light monohydrate) 46.5 Sodium silicate (Britesil H20) 46.5 Polyacrylate (binder) (50% solution Pa 25 CL pH >8) 3
  • Bleach catalyst granulate A was prepared as follows: Carbonate and silicate were put in a ploughshare mixer together with the ManCat crystals. While mixing 3% of binder was sprayed onto the powder bed with a single phase nozzle in 3 minutes. Mixing was continued for 10 minutes after the spray on was complete. Next, the granulate was discharged and sieved on a sieve deck 710 - 255 micron. The fraction >255 microns and ⁇ 710 microns was used for the experiment.
  • the detergent suspension were prepared in batches of 3 kg in a Unimix (ex Haagen & Rinau) mixer, that was operated under vacuum at 70 rpm, whilst keeping the temperature of the mixer contents at 20°C.
  • the mixing procedure used was as follows:
  • suspension A contained oxidized catalyst particles and that the percarbonate in suspension A was prematurely decomposed, probably due to interaction with the manganese catalyst.

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EP17709682.3A 2016-03-11 2017-03-09 Pourable detergent suspension comprising bleach catalyst granules Active EP3426756B1 (en)

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GB2568867A (en) * 2017-10-31 2019-06-05 Mcbride Sa Dishwashing detergent gel comprising bleach
GB201814981D0 (en) 2018-09-14 2018-10-31 Reckitt Benckiser Finish Bv Granulate
EP3967742A1 (en) 2020-09-15 2022-03-16 WeylChem Performance Products GmbH Compositions comprising bleaching catalyst, manufacturing process thereof, and bleaching and cleaning agent comprising same

Citations (3)

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Publication number Priority date Publication date Assignee Title
WO2013092276A1 (en) 2011-12-22 2013-06-27 Unilever N.V. Detergent composition comprising glutamic-n,n-diacetate, water and bleaching agent
WO2014107578A1 (en) 2013-01-03 2014-07-10 Basf Corporation Homogeneous detergent composition
WO2016005392A1 (en) 2014-07-08 2016-01-14 Novozymes A/S Co-granulate of enzyme and bleach catalyst

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US4751015A (en) 1987-03-17 1988-06-14 Lever Brothers Company Quaternary ammonium or phosphonium substituted peroxy carbonic acid precursors and their use in detergent bleach compositions
EP0458398B1 (en) 1990-05-21 1997-03-26 Unilever N.V. Bleach activation
DK0697036T3 (da) 1993-05-08 2000-01-31 Henkel Kgaa Sølvkorrosionsbeskyttelsesmiddel II
CZ286401B6 (en) 1993-05-08 2000-04-12 Henkel Kgaa Use of inorganic redox-active substances
AU7812494A (en) 1993-10-14 1995-05-04 Unilever Plc Detergent compositions containing silver anti-tarnishing agents
US5547612A (en) 1995-02-17 1996-08-20 National Starch And Chemical Investment Holding Corporation Compositions of water soluble polymers containing allyloxybenzenesulfonic acid monomer and methallyl sulfonic acid monomer and methods for use in aqueous systems
US6210600B1 (en) 1996-12-23 2001-04-03 Lever Brothers Company, Division Of Conopco, Inc. Rinse aid compositions containing scale inhibiting polymers
DE19852135A1 (de) * 1998-11-12 2000-05-18 Henkel Kgaa Wäßrige Geschirreinigungsmittel
DE102005035916A1 (de) * 2005-07-28 2007-02-01 Clariant Produkte (Deutschland) Gmbh Verfahren zur Herstellung von Bleichkatalysator-Granulaten
DE102007039651A1 (de) * 2006-11-27 2009-02-26 Henkel Ag & Co. Kgaa Bleichkatalysatorgranulat

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Publication number Priority date Publication date Assignee Title
WO2013092276A1 (en) 2011-12-22 2013-06-27 Unilever N.V. Detergent composition comprising glutamic-n,n-diacetate, water and bleaching agent
WO2014107578A1 (en) 2013-01-03 2014-07-10 Basf Corporation Homogeneous detergent composition
WO2016005392A1 (en) 2014-07-08 2016-01-14 Novozymes A/S Co-granulate of enzyme and bleach catalyst

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JP2019507808A (ja) 2019-03-22
EP3426756A1 (en) 2019-01-16
CN109312267B (zh) 2021-02-05
CN109312267A (zh) 2019-02-05
PL3426756T3 (pl) 2020-01-31

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