WO2013092276A1 - Detergent composition comprising glutamic-n,n-diacetate, water and bleaching agent - Google Patents
Detergent composition comprising glutamic-n,n-diacetate, water and bleaching agent Download PDFInfo
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- WO2013092276A1 WO2013092276A1 PCT/EP2012/074947 EP2012074947W WO2013092276A1 WO 2013092276 A1 WO2013092276 A1 WO 2013092276A1 EP 2012074947 W EP2012074947 W EP 2012074947W WO 2013092276 A1 WO2013092276 A1 WO 2013092276A1
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- 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
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- 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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
- C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
- C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
- C11D17/043—Liquid or thixotropic (gel) compositions
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- 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
Definitions
- the present invention relates to a detergent composition comprising glutamic-N,N-diacetate (GLDA), water and a bleaching agent. More particularly, the present invention relates to a detergent composition comprising 20-99.7 wt.% of a continuous phase containing GLDA, water and optionally other components; and 0.3-80 wt.% of a dispersed phase comprising at least 0.3% of bleach particles by weight of the composition, said bleach particles having a particle size of at least 10 ⁇ , wherein the continuous phase contains at least 10 wt.% of GLDA and at least 10 wt.% water, and wherein the weight ratio of GLDA to water lies within the range of 5:6 to 5: 1.
- GLDA glutamic-N,N-diacetate
- composition of the present invention offers the advantage that the bleaching agent remains stable despite the fact that the composition contains a substantial amount of water.
- This detergent composition may suitably be provided in the form of a liquid, a gel or a paste.
- detergent compositions according to the present invention include dishwashing compositions, laundry detergents and hard surface cleaning compositions.
- Detergent formulations typically contain a number of different active components, including builders, surfactants, enzymes and bleaching agents.
- Liquid and gelled detergent formulations have been developed as these products offer the advantage that they are easy to dose and/or that they can easily be dispersed into aqueous cleaning liquid.
- bleaching agents such as percarbonates and peracids
- Bleaching agents are employed in detergent compositions to remove bleachable stains, e.g. tea stains.
- a problem associated with the use of bleaching agents in liquid, water-containing detergent formulations lies in the fact that most bleaching agents are not stable in an aqueous (alkaline) environment. Not only does this instability mean that bleaching activity is lost over time, but in addition this bleach instability also adversely affects the functionality of other detergent components, notably enzymes.
- Calcium and magnesium ions have a negative effect on the removal of soils by detergent compositions. In order to negate these negative effects so called 'builders' (complexing agents) are commonly applied in detergent compositions.
- Phosphorous based builders, such as phosphates have been used for many years in a wide variety of detergent compositions.
- Glutamic-N,N-diacetate (GLDA), methyl-glycine diacetate (MGDA) and citrate are examples of environmentally friendly builders that are used in commercial detergent products.
- WO 2007/141527 describes a detergent composition comprising an amino acid based builder, enzymes that are destabilized by the builder and a stabilization system for the enzymes that comprises one or more divalent metal compounds or salts and one or more non-ionic surfactants.
- the example of this patent application describes detergent pouches made of PVA that contain a bleach- free liquid dishwashing formulation comprising 58.7 wt.% water and 31.0 wt.% GLDA.
- WO 2009/123322 describes an automatic dishwasher composition comprising a builder and a malic acid based water-soluble sulphonated copolymer.
- Example 3 of this international patent application describes a bleach-free formulation comprising 53.4 wt.% water and 30.0 wt.% GLDA.
- One aspect of the invention relates to a detergent composition
- a detergent composition comprising 20-99.7 wt.% of a continuous phase containing GLDA, water and optionally other components; and 0.3-80 wt.% of a dispersed phase comprising at least 0.3% of bleach particles by weight of the composition, said bleach particles having a particle size of at least 10 ⁇ , wherein the continuous phase contains at least 10 wt.% of GLDA and at least 10 wt.% of water and wherein the weight ratio of GLDA to water lies within the range of 5:6 to 5: 1.
- Another aspect of the invention relates to a composition
- a composition comprising 20-99.7 wt.% of a continuous phase containing GLDA, water and optionally other components; and 0.3-80 wt.% of a dispersed phase comprising at least 0.3 wt.% of bleach particles by weight of the composition, said bleach particles having a particle size of at least 10 ⁇ , wherein the composition contains at least 10 wt.% water and has a water activity of not more than 0,7.
- the GLDA in the present composition binds the water contained therein so strongly that the water can no longer exert its destabilising effect on the bleaching agent.
- the present invention also provides a process of preparing a liquid base for a detergent composition comprising GLDA and water in a weight ratio of GLDA to water of 5:6 to 5: 1 , said process comprising combining 100 parts by weight of a liquid mixture of GLDA and water with 10-300 parts by weight of GLDA powder, said liquid mixture containing 20-50 wt.% of GLDA and 50-80 wt.% water and said GLDA powder containing at least 65 wt.% GLDA.
- glutamic-N,N-diacetate or "GLDA” as used herein refers to glutamic-N,N-diacetic acid and salts thereof.
- bleach particles refers to particles comprising a bleaching agent that is capable of releasing peroxygen, chlorine- or bromine under conditions typically encountered during the cleansing process, especially if the present composition is diluted 10-1000 times with water having a temperature of 5-80°C.
- particles as used herein, unless indicated otherwise, refers to a solid material in the form of, for instance, particles, grains, granules or tablets.
- water soluble as used herein means a solubility in distilled water of 20°C of at least 0.01 mol/L, preferably of at least 0.1 mol/L.
- dispersed phase refers to any particulate matter that is contained in the present composition.
- This particulate matter may be solid, semi-solid or liquid. Particulate matter having a particle size of less than 100 nm is deemed to be part of the continuous phase.
- a water content unless indicated otherwise, said water content includes unbound (free) as well as bound water.
- a parameter such as a concentration or a ratio, is said to be less than 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.
- one aspect of the present invention relates to a composition
- a composition comprising 20-99.7 wt.% of a continuous phase containing GLDA, water and optionally other components; and 0.3-80 wt.% of a dispersed phase comprising at least 0.3% of bleach particles by weight of the composition, said bleach particles having a particle size of at least 10 ⁇ , wherein the continuous phase contains at least 10 wt.% of GLDA and at least 10 wt.% water and wherein the weight ratio of GLDA to water lies within the range of 5:6 to 5: 1.
- the water activity of the composition typically does not exceed 0.7. More preferably, the water activity of the composition lies within the range of 0.1-0.6, even more preferably 0.2-0.55, most preferably of 0.3-0.5
- the water activity of the composition may suitably be determined by a Novasina labmaster conditioned Aw measuring device that is set at 25 °C and measured until stable.
- compositions comprising 20-99.7 wt.% of a continuous phase containing GLDA, water and optionally other components; and 0.3-80 wt.% of a dispersed phase comprising at least 0.3 wt.% of bleach particles by weight of the composition, said bleach particles having a particle size of at least 10 ⁇ , wherein the composition contains at least 10 wt.% water and has a water activity of not more than 0.7.
- the water activity of the composition lies within the range of 0.1-0.6, even more preferably of 0.2-0.55 and most preferably of 0.3-0.5
- composition according to the latter embodiment preferably contains GLDA and water in weight ratio of GLDA to water that lies within the range of 5:6 to 5: 1.
- the continuous phase containing GLDA, water and optional other components and the dispersed phase comprising the bleach particles are present as distinct (separate) phases in the detergent composition of the present invention.
- the dispersed phase may contain additional solid or liquid component that are not soluble in the continuous phase.
- This detergent composition may suitably be provided in the form of a liquid, a gel or a paste.
- the composition is a liquid or a gel.
- the present composition contains 5-80 wt.%, more preferably 10-60 wt.% and most preferably 15-50 wt.% of GLDA.
- the present composition preferably contains 30-70% of GLDA by weight of the continuous phase. Even more preferably, the composition contains 35-65% and most preferably 40-60% of GLDA by weight of the continuous phase.
- the water content of the present composition preferably lies in the range of 10-50 wt.%, more preferably of 15-45 wt.% and most preferably of 20-35 wt.%.
- the water content of the present composition expressed by weight of the continuous phase preferably lies in the range of 6-55 wt.%, more preferably 15-50 wt.% and most preferably 25-48 wt.%.
- GLDA and water typically represent at least 60 wt.%, more preferably at least 70 wt.% and most preferably at least 80 wt.% of the continuous phase of the present composition.
- the stability of the bleaching agent in the present composition is dependent on the water/GLDA balance of the product.
- the present composition contains GLDA and water in a weight ratio of GLDA to water that lies within the range of 9:10 to 3:1 ; more preferably of 1 : 1 to 5:2; and most preferably of 5:4 to 5:3.
- the continuous phase of the present detergent composition preferably is a liquid, a paste or a gel. Even more preferably, the continuous phase of the detergent composition is a liquid or a gel.
- the one or more other component that are optionally present in the continuous phase include, for instance polyols (e.g. glycerol), acids (e.g. citric acid), viscosifiers, surfactants, perfume, preservatives and colorant.
- the one or more other components represent not more than 40 wt.% , more preferably not more than 30 wt.%, even more preferably not more than 20 wt.% and most preferably not more than 10 wt.% of the continuous phase.
- detergent compositions encompassed by the present invention include dishwashing compositions, laundry detergents, rim blocks and hard surface cleaning compositions. According to a particularly preferred embodiment, the detergent composition is a dishwashing composition, especially a machine dishwashing composition.
- the composition of the invention is a machine dishwashing composition which, when added to demineralised water having a temperature of 20°C in a concentration of 1 g per 100 ml of water, yields an aqueous solution having a pH of 7-13, preferably of 8-12, most preferably of 9-1 1.4.
- Machine dishwash detergent compositions according to the invention may suitably be dosed at levels of 5 to 40 grams per wash, more preferably at 10 to 30 grams per wash.
- the stability of the bleaching agent in the present composition is further improved if the composition contains 0.1-10%, preferably 0.5-4% by weight of the continuous phase of dissolved acid.
- the acid is selected from sulphuric acid, citric acid and combinations thereof.
- the incorporation of dissolved acid in the specified amounts enables the preparation of stable bleach-containing detergent compositions having a water activity in the range of, for instance, 0.4-0.7, especially of 0.45-0.65.
- the bleach particles in the detergent composition contain at least 20 wt.%, more preferably at least 40 wt.% and most preferably at least 70 wt.% of bleaching agent.
- the bleach particles contained in the present composition may be contained therein in suspended and/or sedimented form. Preferably, the particles are suspended in the continuous phase.
- the bleach particles contained in the present composition preferably have a volume weighted mean particle size of 10-3000 ⁇ , more preferably of 100-1500 ⁇ and most preferably of 200-1000 ⁇ .
- the particle size of particles may suitably be determined by a Malvern particle size analyzer based on laser differentiation.
- the amount of bleach particles contained in the present composition typically lies in the range of 0.5- 25 wt.%. More preferably the bleach particles content is in the range of 1-20 wt.%, most preferably of 3-18 wt.%.
- the bleach particles of the present composition may suitably comprise a chlorine-, or bromine- releasing agent or a peroxygen compound.
- the bleach particles of the present composition may comprise a bleaching agent selected from peroxides, organic peracids, salts of organic peracids and combinations thereof.
- peroxides examples include acids and corresponding salts of monopersulphate, perborate
- 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).
- 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
- 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 12-di-peroxy-dodecanedioic acid
- DPDA 12-di-peroxy-dodecanedioic acid
- 1 DPDA 1- ,9-diperoxyazelaic acid
- diperoxybrassylic acid diperoxysebacic acid and diperoxy-isophthalic acid
- 2-decyldiperoxybutane-1 ,4-dioic acid 2-decyldiperoxybutane-1 ,4-dioic acid.
- the bleach particles of the present composition comprise a bleaching agent selected from peroxides (including peroxide salts such as sodium percarbonate), organic peracids, salts of organic peracids and combinations thereof. More preferably, the bleaching agent is a peroxide. Most preferably, the bleaching agent is a percarbonate.
- the present composition comprises coated bleach particles.
- substantially all bleach particles are coated bleach particles.
- the coated bleach particles comprise a water-soluble coating.
- the water-soluble coating advantageously comprises a coating agent selected from alkali sulphate, alkali carbonate or alkali chloride and combinations thereof.
- the coating of the bleaching agent can be done by, for example, crystallisation or by spray granulation. Suitable coated bleaching agents are described in, for example, EP-A 0 891 417, EP-A 0 136 580 and EP-A 0 863 842. The use of spray granulated coated percarbonate is most preferred.
- the present detergent composition offers the advantage that despite the high water content, the bleach particles remain very stable.
- bleach activity of a freshly prepared composition according to the present invention decreases by not more than 70%, more preferably by not more than 50% and most preferably by not more than 20% when the composition is stored in a closed container for 8 weeks at 20 °C.
- Bleach activity may suitably be determined by iodometric titration. In this titration a suitable amount of detergent sample is dissolved in acidified water containing a molybdate catalyst. Subsequently potassium iodide is added to an aliquot of the solution.
- 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 ⁇ , ⁇ , ⁇ ', ⁇ '-tetraacetyl ethylene diamine (TAED), sodium nonanoyloxybenzene sulphonate (SNOBS), sodium benzoyloxybenzene sulphonate (SBOBS) and the cationic peroxyacid precursor (SPCC) as described in US-A-4,751 ,015.
- a bleach catalyst such as the manganese complex, e.g. Mn-Me TACN, as described in EP-A-0458397, or the sulphonimines of US-A-5,041 ,232 and US-A-5,047, 163, can be incorporated.
- This bleach catalyst may suitably be present in the composition in the form of a encapsulate, notably an encapsulate that is separate from the bleach particles (to avoid premature bleach activation).
- Cobalt or iron catalysts can also be used.
- the high stability of the bleaching agent in the present composition makes it possible to include enzymes in the formulation as the enzymes are not immediately deactivated by the bleaching agent.
- enzymes suitable for use in the cleaning compositions 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.
- proteases are proteases, amylases, cellulases, peroxidases, mannanases, pectate lyases and lipases and combinations thereof.
- the enzymes most commonly used in detergent compositions are proteolytic and amylolytic enzymes.
- Enzymes may be added in liquid or in encapsulated form. In a preferred embodiment of this invention the enzymes are present in encapsulated form.
- Well know enzyme stabilizers such as
- proteolytic enzymes in this invention include metalloproteases 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.
- Preferred levels of protease in the present composition are from 0.1 to 10, more preferably from 0.2 to 5, most preferably 0.4 to about 4 mg active protease per gram of composition.
- 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 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.
- Preferred levels of amylase in the present composition are from 0.01 to 5, more preferably from 0.02 to 2, most preferably from 0.05 to about 1 mg active amylase per gram of composition.
- the enzymes may suitably be incorporated in the detergent composition in liquid or in encapsulated form.
- the composition has a pH of 9.0 and more it is preferred to employ enzymes in encapsulated form.
- encapsulated forms are enzyme granule types D, E and HS by Genencor and granule types , T, GT, TXT and EvityTM of Novozymes.
- the composition contains active protease and the protease activity of the freshly prepared composition decreases by not more than 70%, more preferably by not more than 50% and most preferably by not more than 20% when the composition is stored in a closed container for 8 weeks at 20 °C.
- the present detergent composition 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 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.
- functional groups include hydroxy, carboxy, mercapto, amino or amido groups.
- Examples of useful hydrophobes of commercial nonionic surfactants include C8-C18 alkyl fatty alcohols, C 8 -Ci4 alkyl phenols, C 8 -Ci 8 alkyl fatty acids, C 8 -Ci 8 alkyl mercaptans, C 8 -Ci 8 alkyl fatty amines, C 8 -Ci 8 alkyl amides and C 8 -Ci 8 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.
- 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. Also of interest are the end-capped ethoxylated alcohols available as the SLF 18 series from BASF and the alkylpolyethylene glycol ethers made from a linear, saturated Ci 6 -Ci 8 fatty alcohol of the LutensolTM AT series, supplied by BASF.
- 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. Also suitable for use herein are nonionics from the LutensolTM TO series of BASF, which are alkylpolyethylene glycol ethers made from a saturated iso-d 3 alcohol.
- Amineoxide surfactants may also be used in the present invention as anti-redeposition surfactant.
- suitable amineoxide surfactants are Ci 0 -Ci 8 alkyl dimethylamine oxide and Ci 0 -Ci 8 acylamido alkyl dimethylamine oxide.
- the present composition contains 0.1-15 wt.%, more preferably 0.5-10 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.%.
- an anionic surfactant it is preferred that an antifoam agent to suppress foaming is present.
- suitable anionic surfactants are methylester sulphonates or sodium lauryl sulphate.
- the GLDA contained in the present composition 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.
- Compositions according to the present invention may, next to GLDA, also contain additional water- softening builders.
- phosphorous based builders such as phosphates have been used as builders, but due to environmental pressures other builders are preferred.
- organic builders such as citrate, MGDA (methyl-glycine diacetate) and inorganic builders such as carbonates, in particular sodium carbonate.
- 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 composition in a concentration of 1 to 20%, more preferably of 2 to 10% by weight of the composition.
- the detergent composition furthermore comprises at least one dispersing polymer.
- 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.
- suitable anti-scaling agents include organic phosphonates, amino carboxylates, polyfunctionally-substituted compounds, and mixtures thereof.
- Particularly preferred anti-scaling agents are organic phosphonates such as a-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 a-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 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 sulphonated polymers as described in EP 851 022.
- Polymers of this type include polyacrylate with methyl methacrylate, sodium methallyl sulphonate and sulphophenol methallyl ether such as AlcosperseTM 240 supplied (AkzoNobel).
- terpolymer containing polyacrylate with 2-acrylamido-2 methylpropane sulphonic 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 homo-polymeric 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.
- 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.
- Anti-scaling agents may also be used. Particularly useful is a mixture of organic phosphonates and polymers of acrylic acid.
- the level of dispersing polymers ranges from 0.2 to 10 wt.% of the total composition, 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 composition 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 composition are 0.01-2 wt.%, more preferably 10.01- 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 composition.
- Other anti-tarnishing 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 are in the oxidation state of II, II, IV V or VI.
- the present composition may suitably contain a non-surfactant, water-soluble, liquid binder, e.g. in a concentration of 0-50% by weight of the continuous phase.
- a non-surfactant, water-soluble, liquid binder e.g. in a concentration of 0-50% by weight of the continuous phase.
- liquid binders include polyethylene glycols, polypropylene glycols, glycerol, glycerol carbonate, ethylene glycol, propylene gylcol and propylene carbonate.
- the continuous phase of the detergent composition preferably contains a viscosifier.
- a viscosifier By increasing the viscosity of the continuous phase through the addition of a viscosifier a stable suspension of the particles in the continuous phase can be produced.
- the continuous phase contains 0.5-10 wt.% of a viscosifier.
- compositions such as perfume, colorant or preservatives.
- the desired viscosity profile of the detergent composition 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 composition as defined herein before.
- the inventors have found that the detergent composition of the present invention, despite the fact that it contains a substantial amount of water, can be packaged in a water-soluble sachet.
- the sachet comprises 5-40 ml, more preferably 10-30 ml and most preferably 15-25 ml of the detergent composition.
- the water-soluble sachet is advantageously made of a polymer selected from polyvinyl alcohol, cellulose ethers, polyethylene oxide, starch, polyvinylpyrrolidone, polyacrylamide, polyvinyl methyl ether-maleic anhydride, polymaleic anhydride, styrene maleic anhydride, hydroxyethylcellulose, methylcellulose, polyethylene glycols, carboxymethylcelluloseose, polyacrylic acid salts, alginates, acrylamide copolymers, guar gum, casein, ethylene-maleic anhydride resin series, polyethylene imine, ethyl hydroxyethylcellulose, ethyl methylcellulose, hydroxyethyl methylcellulose and combinations thereof.
- the water-soluble sachet is made of polyvinyl alcohol, polyethelene oxide, polyvinylpyrrolidone and combinations thereof. Most preferably, the water-soluble sachet is made of polyvinyl alcohol, a copolymer of polyvinyl alcohol and combinations thereof. Polyvinyl alcohols preferred have a weight average molecular weight between 1 ,000 and 300,000, more preferably, between 2,000 and 150,000, and most preferably, between 3,000 and 100,000.
- Yet another aspect of the invention relates to a process of preparing a liquid base for a detergent composition
- a process of preparing a liquid base for a detergent composition comprising GLDA and water in a weight ratio of GLDA to water of 5:6 to 5: 1 , said process comprising combining 100 parts by weight of a liquid mixture of GLDA and water withl 0-300 parts by weight, preferably 20-100 parts by weight of GLDA powder, said liquid mixture containing 20-50 wt.% of GLDA and 50-80 wt.% water and said GLDA powder containing at least 65 wt.% GLDA.
- the inventors have found that the detergent composition described herein before can suitably be produced by first producing a liquid base by combining a GLDA water mixture and GLDA powder, followed by the addition of other detergent components.
- the liquid base that is obtained in the present method comprises GLDA and water in a weight ratio of GLDA to water that lies within the range of 9:10 to 3: 1 ; more preferably of 1 : 1 to 5:2; and most preferably of 5:4 to 5:3
- the liquid base that is obtained in the present process preferably contains 50-70 wt.%, more preferably 53-68 wt. and most preferably 55-65 wt.% GLDA.
- the water content of the liquid mixture preferably is in the range of 30-50 wt.%, more preferably 32-47 wt.% and most preferably 35-45wt.%.
- the liquid mixture of GLDA and water that is employed in the present process typically contains 30-50 wt.% of GLDA and 50-70 wt.% water.
- the GLDA powder preferably contains at least 70 wt.% of GLDA.
- GLDA and water typically represent at least 90 wt.%, more preferably at least 95 wt.% and most preferably at least 98 wt.% of the liquid mixture.
- GLDA and water together also represent preferably at least 90 wt.%, more preferably at least 95 wt.% and most preferably at least 98 wt.% of the GLDA powder.
- the liquid mixture of GLDA and water has a temperature of at least 5°C, more preferably of 10-80°C and most preferably of 15-70°C when it is combined with the GLDA powder in order to ensure that a fully liquid base can be obtained without difficulty.
- an acid component as defined herein before is present in the liquid base, most preferably said acid component is added in protonated, i.e. acid form.
- the acid component is added in an amount of 0.1-10%, more preferably of 1-7% and most preferably 3-5% by weight of the total amount of GLDA in the liquid base.
- the acid component may suitably be added to the continuous phase before addition of the bleach particles.
- the aforementioned process for preparing a liquid base is followed by further manufacturing steps to create a detergent composition from that liquid base, preferably a storage stable bleach-containing detergent composition as described herein before.
- these further manufacturing steps include the addition to the liquid base of the bleach particles as defined herein before.
- these bleach particles are added in an amount of at least 0.3%, more preferably of 0.3-50%, even more preferably of 0.5-30% by weight of the liquid base.
- a viscosifier as defined herein before is incorporated in the liquid base, typically in an amount of 0.5-10% by weight of the liquid base.
- a detergent composition according to the present invention was prepared on the basis of the formulation presented in table 1. Table 1
- a liquid premix base was prepared by adding DissolvineTM PD-S to DissolvineTM GL 47-S at ambient temperature. Subsequently citric acid was admixed to the DissolvineTM solution under stirring. The water content of the liquid premix so obtained was approximately 40 wt.%. Next, the remaining ingredients were added under stirring to produce a homogeneous suspension. The water content of the total composition was approximately 31 %. The measured A w (water activity) of the composition was 0.48.
- the detergent composition was stored in a closed container for 2 weeks at 37°C. After this storage period the residual bleach activity was measured to be 80%.
- Example 3 The detergent composition of Example 1 was filled into transparent pouches made of polyvinyl alcohol. Each pouch contained about 20 ml of the detergent composition. The appearance of these pouches did not change when the pouches were stored for several weeks under ambient conditions.
- Example 3 The detergent composition of Example 1 was filled into transparent pouches made of polyvinyl alcohol. Each pouch contained about 20 ml of the detergent composition. The appearance of these pouches did not change when the pouches were stored for several weeks under ambient conditions.
- a detergent composition according to the present invention was prepared on the basis of the formulation presented in table 2.
- a liquid premix base was prepared by adding DissolvineTM PD-S to DissolvineTM GL 47-S at ambient temperature under stirring.
- the water content of the liquid premix so obtained was approximately 42% wt.%.
- the remaining ingredients were added under stirring to produce a homogeneous suspension.
- the water content of the total composition was approximately 29%.
- the measured A w (water activity) of the composition was 0.46.
- the detergent composition was stored in a closed container for 2 weeks at 37°C. After this storage period the residual bleach activity was measured to be 76%. 20 g of the detergent composition was used in a machine dishwasher. The composition showed excellent cleaning performance.
- a detergent composition according to the present invention was prepared on the basis of the formulation presented in table 3. Table 3
- the pH of the formulation was 6.5.
- the water content of the total composition was approximately 39%.
- the A w (water activity) of the composition was ⁇ 0.5.
- the detergent formulation was found to retain its stability for over 7 months at ambient temperature.
- a detergent composition according to the present invention was prepared on the basis of the formulation presented in table 4. Table 4
- a liquid premix base was prepared by adding TrilonTM M granule to TrilonTM M liquid at ambient temperature. Subsequently citric acid was admixed to the TrilonTM M solution under stirring. The water content of the liquid premix so obtained was approximately 44 wt.%. Next, the remaining ingredients were added under stirring to produce a homogeneous suspension. The water content of the total composition was approximately 32%. The measured A w (water activity) of the composition was 0.64. The detergent composition was stored in a closed container for 2 weeks at 37°C. After this storage period the residual bleach activity was measured to be 2%. Comparative Example B
- a detergent composition was prepared on the basis of the formulation presented in table 5.
- the water content of the total composition was approximately 47%.
- the measured A w (water activity) of the composition was 0.72.
- the detergent composition was stored in a closed container for 2 weeks at 37°C. After this storage period the residual bleach activity was measured to be 2%.
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BR112014014717A BR112014014717A8 (en) | 2011-12-22 | 2012-12-10 | water-soluble sachet and process of preparing a liquid base for a detergent composition |
EP12809160.0A EP2794836B1 (en) | 2011-12-22 | 2012-12-10 | Detergent composition comprising glutamic-n,n-diacetate, water and bleaching agent |
CA2859297A CA2859297A1 (en) | 2011-12-22 | 2012-12-10 | Detergent composition comprising glutamic-n,n-diacetate, water and bleaching agent |
EA201400745A EA026023B9 (en) | 2011-12-22 | 2012-12-10 | Detergent composition comprising glutamic-n,n-diacetate, water and bleaching agent |
ZA2014/04543A ZA201404543B (en) | 2011-12-22 | 2014-06-20 | Detergent composition comprising glutamic-n,n-diacetate, water and bleaching agent |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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EP11195076.2 | 2011-12-22 | ||
EP11195076 | 2011-12-22 |
Publications (1)
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WO2013092276A1 true WO2013092276A1 (en) | 2013-06-27 |
Family
ID=47471726
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/EP2012/074947 WO2013092276A1 (en) | 2011-12-22 | 2012-12-10 | Detergent composition comprising glutamic-n,n-diacetate, water and bleaching agent |
Country Status (10)
Country | Link |
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EP (1) | EP2794836B1 (en) |
AR (1) | AR089399A1 (en) |
BR (1) | BR112014014717A8 (en) |
CA (1) | CA2859297A1 (en) |
CL (1) | CL2014001642A1 (en) |
EA (1) | EA026023B9 (en) |
PL (1) | PL2794836T3 (en) |
PT (1) | PT2794836T (en) |
WO (1) | WO2013092276A1 (en) |
ZA (1) | ZA201404543B (en) |
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WO2014206781A1 (en) * | 2013-06-25 | 2014-12-31 | Unilever N.V. | Hygroscopic detergent formulation comprising water, aminocarboxylate chelant and moisture-sensitive ingredients |
WO2014206780A1 (en) * | 2013-06-25 | 2014-12-31 | Unilever N.V. | Composition comprising glutamic-n,n-diacetate (glda), water and enzyme |
EP2821471A1 (en) * | 2013-07-02 | 2015-01-07 | Basf Se | Aqueous solutions containing a complexing agent in high concentration |
WO2016058872A1 (en) * | 2014-10-17 | 2016-04-21 | Basf Se | Container comprising a detergent composition containing glda |
EP3124586A1 (en) * | 2015-07-29 | 2017-02-01 | The Procter and Gamble Company | Process for reducing malodour in a pack |
EP3004316B1 (en) | 2013-05-27 | 2017-03-22 | Basf Se | Aqueous solutions containing a complexing agent in high concentration |
EP3178917A1 (en) * | 2015-12-08 | 2017-06-14 | The Procter and Gamble Company | Cleaning pouch |
WO2017097637A1 (en) * | 2015-12-08 | 2017-06-15 | Basf Se | Aqueous solution containing a complexing agent in high concentrations |
EP3181670A1 (en) * | 2015-12-17 | 2017-06-21 | The Procter and Gamble Company | Automatic dishwashing detergent composition |
WO2017148985A1 (en) | 2016-03-02 | 2017-09-08 | Unilever N.V. | Pourable detergent composition |
WO2017148990A1 (en) | 2016-03-02 | 2017-09-08 | Unilever N.V. | Detergent composition in the form of a suspension |
WO2017148989A1 (en) | 2016-03-02 | 2017-09-08 | Unilever N.V. | Pourable detergent suspension comprising a dyed fluid phase and suspended particles |
WO2017153528A1 (en) | 2016-03-11 | 2017-09-14 | Unilever N.V. | Pourable detergent suspension comprising bleach catalyst granules |
JP2018505941A (en) * | 2015-02-02 | 2018-03-01 | ザ プロクター アンド ギャンブル カンパニー | Detergent composition |
EP3026100B1 (en) | 2014-11-26 | 2018-07-25 | The Procter and Gamble Company | Cleaning pouch |
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US10421927B2 (en) | 2015-12-17 | 2019-09-24 | The Procter & Gamble Company | Automatic dishwashing detergent composition comprising benzotriazole and nonionic surfactant mixture |
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WO2019144244A1 (en) * | 2018-01-29 | 2019-08-01 | Jempak Corporation | Multi-chamber unit dose detergent products, and machines and methods for manufacturing same |
WO2020030623A1 (en) * | 2018-08-10 | 2020-02-13 | Basf Se | Packaging unit comprising a detergent composition containing an enzyme and at least one chelating agent |
WO2021032816A1 (en) * | 2019-08-21 | 2021-02-25 | Unilever Ip Holdings B.V. | Detergent solid composition |
Citations (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0136580A2 (en) | 1983-10-06 | 1985-04-10 | Süddeutsche Kühlerfabrik Julius Fr. Behr GmbH & Co. KG | Fluid friction coupling |
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 |
US5041232A (en) | 1990-03-16 | 1991-08-20 | Lever Brothers Company, Division Of Conopco, Inc. | Sulfonimines as bleach catalysts |
US5047163A (en) | 1990-03-16 | 1991-09-10 | Lever Brothers Company, Division Of Conopco, Inc. | Activation of bleach precursors with sulfonimines |
EP0458397A2 (en) | 1990-05-21 | 1991-11-27 | Unilever N.V. | Bleach activation |
WO1994026860A1 (en) | 1993-05-08 | 1994-11-24 | Henkel Kommanditgesellschaft Auf Aktien | Silver-corrosion protection agent (ii) |
WO1994026859A1 (en) | 1993-05-08 | 1994-11-24 | Henkel Kommanditgesellschaft Auf Aktien | Silver-corrosion protection agent (i) |
EP0723577A1 (en) | 1993-10-14 | 1996-07-31 | Unilever N.V. | 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 |
EP0851022A2 (en) | 1996-12-23 | 1998-07-01 | Unilever N.V. | Rinse aid compositions containing scale inhibiting polymers |
DE19702734A1 (en) * | 1997-01-27 | 1998-07-30 | Basf Ag | Detergent and cleaning agent formulation with a bleaching system and a mixture of amines and complexing agents |
EP0863842A1 (en) | 1995-11-28 | 1998-09-16 | Degussa Aktiengesellschaft | Coated sodium percarbonate particles, process for the production thereof and use thereof |
EP0891417A1 (en) | 1996-03-27 | 1999-01-20 | SOLVAY INTEROX (Société Anonyme) | Compositions containing sodium percarbonate |
JPH11302694A (en) * | 1998-04-17 | 1999-11-02 | Kao Corp | Solid detergent composition for hard surface |
WO2007141527A1 (en) | 2006-06-07 | 2007-12-13 | Reckitt Benckiser N. V. | Detergent composition |
WO2009123322A1 (en) | 2008-03-31 | 2009-10-08 | Nippon Shokubai Co., Ltd. | Automatic dishwashing composition containing a sulfonated copolymer |
WO2011145420A1 (en) * | 2010-05-21 | 2011-11-24 | ライオン株式会社 | Disinfectant composition for hard article, and method for disinfection of surface of hard article |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5200236A (en) | 1989-11-15 | 1993-04-06 | Lever Brothers Company, Division Of Conopco, Inc. | Method for wax encapsulating particles |
US6475977B1 (en) | 2001-03-16 | 2002-11-05 | Unilever Home & Personal Care Usa, Division Of Conopco, Inc. | Water soluble sachet with a dishwasher composition |
ES2274296T3 (en) | 2002-12-20 | 2007-05-16 | Degussa Gmbh | LIQUID COMPOSITION OF DETERGENT AND CLEANING AGENT. |
GB2417250A (en) | 2004-08-20 | 2006-02-22 | Reckitt Benckiser Nv | Multi-chamber bottle containg a liquid detergent composition |
-
2012
- 2012-12-10 EA EA201400745A patent/EA026023B9/en not_active IP Right Cessation
- 2012-12-10 PT PT128091600T patent/PT2794836T/en unknown
- 2012-12-10 PL PL12809160.0T patent/PL2794836T3/en unknown
- 2012-12-10 EP EP12809160.0A patent/EP2794836B1/en active Active
- 2012-12-10 CA CA2859297A patent/CA2859297A1/en not_active Abandoned
- 2012-12-10 BR BR112014014717A patent/BR112014014717A8/en not_active Application Discontinuation
- 2012-12-10 WO PCT/EP2012/074947 patent/WO2013092276A1/en active Application Filing
- 2012-12-21 AR ARP120104903 patent/AR089399A1/en not_active Application Discontinuation
-
2014
- 2014-06-19 CL CL2014001642A patent/CL2014001642A1/en unknown
- 2014-06-20 ZA ZA2014/04543A patent/ZA201404543B/en unknown
Patent Citations (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0136580A2 (en) | 1983-10-06 | 1985-04-10 | Süddeutsche Kühlerfabrik Julius Fr. Behr GmbH & Co. KG | Fluid friction coupling |
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 |
US5041232A (en) | 1990-03-16 | 1991-08-20 | Lever Brothers Company, Division Of Conopco, Inc. | Sulfonimines as bleach catalysts |
US5047163A (en) | 1990-03-16 | 1991-09-10 | Lever Brothers Company, Division Of Conopco, Inc. | Activation of bleach precursors with sulfonimines |
EP0458397A2 (en) | 1990-05-21 | 1991-11-27 | Unilever N.V. | Bleach activation |
WO1994026860A1 (en) | 1993-05-08 | 1994-11-24 | Henkel Kommanditgesellschaft Auf Aktien | Silver-corrosion protection agent (ii) |
WO1994026859A1 (en) | 1993-05-08 | 1994-11-24 | Henkel Kommanditgesellschaft Auf Aktien | Silver-corrosion protection agent (i) |
EP0723577A1 (en) | 1993-10-14 | 1996-07-31 | Unilever N.V. | 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 |
EP0863842A1 (en) | 1995-11-28 | 1998-09-16 | Degussa Aktiengesellschaft | Coated sodium percarbonate particles, process for the production thereof and use thereof |
EP0891417A1 (en) | 1996-03-27 | 1999-01-20 | SOLVAY INTEROX (Société Anonyme) | Compositions containing sodium percarbonate |
EP0851022A2 (en) | 1996-12-23 | 1998-07-01 | Unilever N.V. | Rinse aid compositions containing scale inhibiting polymers |
DE19702734A1 (en) * | 1997-01-27 | 1998-07-30 | Basf Ag | Detergent and cleaning agent formulation with a bleaching system and a mixture of amines and complexing agents |
JPH11302694A (en) * | 1998-04-17 | 1999-11-02 | Kao Corp | Solid detergent composition for hard surface |
WO2007141527A1 (en) | 2006-06-07 | 2007-12-13 | Reckitt Benckiser N. V. | Detergent composition |
WO2009123322A1 (en) | 2008-03-31 | 2009-10-08 | Nippon Shokubai Co., Ltd. | Automatic dishwashing composition containing a sulfonated copolymer |
WO2011145420A1 (en) * | 2010-05-21 | 2011-11-24 | ライオン株式会社 | Disinfectant composition for hard article, and method for disinfection of surface of hard article |
Non-Patent Citations (3)
Title |
---|
"Handbook of detergents, part A: Properties", vol. 82, article "Surfactant Science Series" |
DATABASE WPI Week 200003, Derwent World Patents Index; AN 2000-033795, XP002675669 * |
DATABASE WPI Week 201180, Derwent World Patents Index; AN 2011-P45328, XP002675668 * |
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Also Published As
Publication number | Publication date |
---|---|
PL2794836T3 (en) | 2016-12-30 |
CL2014001642A1 (en) | 2015-02-27 |
PT2794836T (en) | 2016-07-25 |
ZA201404543B (en) | 2015-09-30 |
CA2859297A1 (en) | 2013-06-27 |
BR112014014717A2 (en) | 2017-06-13 |
EA201400745A1 (en) | 2014-11-28 |
EP2794836A1 (en) | 2014-10-29 |
BR112014014717A8 (en) | 2017-07-04 |
AR089399A1 (en) | 2014-08-20 |
EP2794836B1 (en) | 2016-06-01 |
EA026023B1 (en) | 2017-02-28 |
EA026023B9 (en) | 2017-04-28 |
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