EP3102659A1 - Utilisation d'acides aminocarboxyliques pour la stabilisation des lessives ou détergents pauvres en eau - Google Patents

Utilisation d'acides aminocarboxyliques pour la stabilisation des lessives ou détergents pauvres en eau

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Publication number
EP3102659A1
EP3102659A1 EP15704267.2A EP15704267A EP3102659A1 EP 3102659 A1 EP3102659 A1 EP 3102659A1 EP 15704267 A EP15704267 A EP 15704267A EP 3102659 A1 EP3102659 A1 EP 3102659A1
Authority
EP
European Patent Office
Prior art keywords
weight
acid
water
preferred
liquid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP15704267.2A
Other languages
German (de)
English (en)
Other versions
EP3102659B1 (fr
Inventor
Ulrich Pegelow
Noelle Wrubbel
Martina Hutmacher
Matthias Sunder
Volker Blank
Klaus Dorra
Britta Strauss
Oliver Kurth
von den Karl-Josef DRIESCH
Friedhelm Siepmann
Mario Sturm
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
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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
    • C11D3/16—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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0004—Non aqueous liquid compositions comprising insoluble particles

Definitions

  • aminocarboxylic acids for the stabilization of low-water liquid washing or
  • the invention relates to the use of at least one aminocarboxylic acid for the stabilization of low-water, preferably substantially anhydrous liquid washing or
  • Detergents or hard surface cleaners such as dishwashing detergents, are available to the consumer in a variety of forms.
  • traditional solid agents are gaining increasingly increasingly flowable and especially liquid to gel detergent in importance.
  • the consumer especially appreciates the rapid solubility and the associated rapid availability of the ingredients in the cleaning liquor, especially in short-dishwashing programs and at low levels
  • compositions in which in particular the water content is reduced compared to conventional compositions, increases.
  • compositions whose water content is as low as possible are particularly desirable.
  • Disposable portions in particular water-soluble pouches or multi-chamber tablets made of water-soluble material, such as e.g. Containers made of PVA, produced by injection molding, enjoy the consumer not only because of increasing popularity, because the consumer with the chemical composition is no longer in contact, but not least because of the attractive appearance of the bag. For the consumer, it is therefore a nuisance if the bags lose their attractive appearance.
  • water-soluble pouches or multi-chamber tablets made of water-soluble material such as e.g. Containers made of PVA, produced by injection molding
  • the object was achieved by the use of at least one aminocarboxylic acid for the stabilization of low-water, preferably substantially anhydrous, liquid detergent or cleaner components.
  • Aminocarboxylic acids are here to be understood as meaning the aminocarboxylic acids themselves and / or their salts, for example nitrilotriacetic acid, in particular methylglycinediacetic acid (MGDA) or its salts and glutamic diacetic acid (GLDA) or its salts or ethylenediamine diacetic acid or its salts (EDDS). Also suitable are iminodisuccinic acid (IDS) and iminodiacetic acid (IDA). The aminodicarboxylic acids are preferably used. Particularly preferred representatives of this class are aminodiacetic acids,
  • the aminocarboxylic acid is selected from the group GLDA and MGDA, preferably MGDA.
  • the aminocarboxylic acid is present in amounts of from 2 to 25% by weight, in particular from 3 to 15% by weight, preferably from 4 to 10% by weight (based on the weight of the liquid washing or cleaning agent component) ,
  • aminodicarboxylic acids preferably in amounts of from 2 to 25% by weight, in particular from 3 to 15% by weight, preferably from 4 to 10% by weight (based on the weight of the liquid washing or cleaning agent component). contain.
  • aminocarboxylic acids are exclusively aminodicarboxylic acids, in particular in an amount of from 2 to 25% by weight, in particular from 3 to 15% by weight, preferably from 4 to 10% by weight (based on the weight of the liquid washing or
  • Detergent component is used.
  • low-water content means that a composition contains less than 20% by weight, in particular less than 15% by weight, preferably less than 13% by weight, particularly preferably less than 10% by weight of water.
  • substantially free of water means that a composition contains less than 7% by weight, in particular less than 5% by weight, preferably less than 3% by weight, more preferably less than 1% by weight.
  • the water content as defined herein refers to the water content determined by Karl Fischer titration.
  • the washing or cleaning agent is pre-portioned.
  • the disposable portion it is possible for the disposable portion to have one or more liquid phases which are located in a plurality of separate compartments.
  • an amino carboxylic acid in particular an amino dicarboxylic acid, in particular GLDA or MGDA, in particular MGDA, is then used in at least one, preferably in several, in particular in all liquid phases for phase stabilization.
  • the liquid phase is preferably "substantially free of water", this means that the liquid phase less than 7 wt .-%, in particular less than 5 wt .-%, preferably less than 3 wt .-%, more preferably less than
  • the water content as defined herein refers to the water content determined by Karl Fischer titration.
  • all liquid phases and all solid phases of the cleaning agent used according to the invention are "substantially free of water", ie each of the individual phases contains less than 7% by weight, in particular less than 5% by weight, preferably less than 3% by weight. -%, more preferably less than 1 wt .-% water (in each case based on the
  • Liquid as used herein with respect to the cleaning agent of the invention, includes all flowable compositions, and more particularly, includes gels and pasty compositions. In particular, the term also includes non-Newtonian
  • Liquids that have a yield point Liquids that have a yield point.
  • At least one as used herein means 1 or more, for example, 1, 2, 3, 4, 5, or more.
  • Solid as used herein in reference to the detergent used in the invention includes all solid compositions, and includes in particular powdered, granular, amorphous, compressed, in particular pressed, tabletted compositions Powdered compositions may also contain, in addition to pulverulent constituents, some of the granules ,
  • the cleaning agent is preferably present in a water-soluble packaging.
  • the water-soluble packaging allows a portioning of the detergent.
  • the amount of detergent in the sachet is preferably 5 to 50 g, more preferably 10 to 30 g, especially 15 to 25 g.
  • the detergent is preferably in an amount sufficient to carry out the cleaning, in machine dishwashing detergents in particular a cycle or a complete program run one
  • the water-soluble packaging in this case has at least two or more spatially separated compartments (chambers), in which spatially separated at least one solid, preferably pulverulent, and at least one liquid phase are filled.
  • two-chamber bags or two-chamber tablets which contain a solid and a liquid phase in separate compartments.
  • multi-chamber packages multi-chamber bags or multi-chamber shaped bodies
  • a phase is here understood to mean a detergent (partial) composition which, in combination with the other phase (s), results in a cleaning agent, in particular a machine dishwashing detergent.
  • the cleaning agent used according to the invention in particular machine dishwashing detergent, can also be present in a water-soluble packaging which contains in particular more than two, for example three, four, five or six compartments.
  • the package contains two, three or more chambers (compartments), wherein one, two or more of these chambers are filled with liquid phases, which are preferably different from each other, and in particular one or more mutually different ingredients.
  • liquid phases which are preferably different from each other, and in particular one or more mutually different ingredients.
  • pre-portioned detergents in which the water-soluble package has one, two or more chambers in addition to one, two or more liquid phases
  • Solid phases with solid phases.
  • two or more solid phases it is preferred that they be of different composition and / or have a different solid form.
  • pre-portioned cleaning compositions which have at least one solid, preferably at least one pulverulent phase and at least one liquid phase in separate compartments.
  • pre-portioned detergents containing at least one solid, preferably at least one compressed phase and one liquid phase in separate
  • the pre-portioned cleaning agent may also be preferable for the pre-portioned cleaning agent to have two or more solid phases, of which at least one powdery and at least one compressed and at least one, also two, three or more liquid phases are in each case separate compartments.
  • the pre-portioned detergent in particular the
  • Multi-chamber bag containing a solid, one of them different powdery and two liquid phases in each separate compartments.
  • the pre-portioned detergents according to the invention in particular machine dishwashing detergents, preferably comprise in the liquid phase, in one of the liquid phases, in particular in all liquid phases,
  • R is selected from -H, -CH 3 , straight-chain or branched, saturated or mono- or polyunsaturated, C2-24-alkyl or alkenyl radical;
  • R 2 , R 3 , R 4 , R 5 are each independently selected from -H, -CH 3 , -
  • R 6 is selected from -H, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -CH 2 -CH 2 -
  • R 7 represents a straight-chain or branched, saturated or mono- or polyunsaturated C 6-26-alkyl or alkenyl radical
  • the liquid phase or the liquid phases of the cleaning agents according to the invention contain at least one component according to a).
  • the liquid phase or contain the liquid phases of the cleaning agent according to the invention at least one component according to a), which is selected from the
  • Formula (I) are also a large part of the nonionic surfactants to grasp. Preference is given to weakly foaming alkoxylated nonionic surfactants, in particular ethoxylated,
  • the automatic dishwashing agents contain nonionic surfactants from the group of alkoxylated alcohols.
  • the water-poor, preferably substantially anhydrous, liquid washing or cleaning agent components comprise one or more nonionic surfactants in an amount of from 15 to 60% by weight, preferably from 20 to 50% by weight, in particular from 30 to 40% by weight. % (based on the weight of the liquid detergent or cleaner component).
  • surfactants come from the groups of alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures of these surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants).
  • Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.
  • nonionic surfactants used are low-foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units.
  • surfactants with EO-AO-EO-AO blocks are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows.
  • R-O- (CH 2 -CH (R 2 ) -O) w- (CH 2 -CH (R 3 ) -O) x- (CH 2 -CH (R 4 ) -O) y - (CH 2 -CH (R 5 ) -0) zR 6 in which R is a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24-alkyl or alkenyl radical; R 2 , R 4 , R 6 each -H; each group R 3 or R 5 is independently selected from -Chta, -CH 2 CH 3, -CH 2 CH 2 -CH 3, CH (CH 3) 2 and the indices w, x, y, z independently represent integers from 1 to 6.
  • nonionic surfactants having a C9-alkyl group with 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units, followed by 1 to 4
  • nonionic surfactants are those of the general formula
  • R is H or a linear or branched hydrocarbon radical having 2 to 26 carbon atoms
  • R 2 , R 3 , R 4 , R 5 are each independently selected from -H, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , CH (CH 3 ) 2, preferably -H or -CH 3 ;
  • R 6 is selected from -CH 2 CH (OH) R 7
  • R 7 for a straight-chain or branched, saturated or on or
  • w, x, y and z are values between 1 and 120, where x, y and / or z can also be 0.
  • nonionic surfactants of the general formula (I) have proven to be particularly effective.
  • R is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms
  • R 6 is selected from -CH 2 CH (OH) R 7 with R 7 for a straight-chain or branched, saturated or on or
  • nonionic surfactants include, for example, the C4-22 fatty alcohol (EO) io-so-2-hydroxyalkyl ethers, in particular also the C8-12 fatty alcohol (EO) 22-2-hydroxydecyl ethers and the C4-22 fatty alcohol (EO) 4o 8o-2-hydroxyalkyl ethers.
  • nonionic surfactants include, for example, the C2-26 fatty alcohol (PO) i- (EO) is-4o-2-hydroxyalkyl ethers, in particular the coco fatty alcohol (PO) i (EO) 22-2-hydroxydecyl ethers ,
  • R 7 represents a straight-chain or branched, saturated or mono- or polyunsaturated C 6-26-alkyl or alkenyl radical
  • At least one, preferably at least two, in particular at least three of the components according to a) has a melting point (at 1 bar) of ⁇ 30 ° C., preferably ⁇ 25 ° C., in particular ⁇ 20 ° C.
  • polyethylene glycols having an average molecular weight of from 180 to 600 and also nonionic surfactants of the general formula (I)
  • the cleaning agent in particular machine dishwashing detergent in the liquid phase as one of the component according to a) at least one polyalkylene glycol, preferably at least one polyethylene glycol or at least one polypropylene glycol, in particular at least one polyethylene glycol, with a middle
  • Molecular weight between 180 and 6000, preferably 200 to 5000, in particular between 300 and 4000 is included.
  • Polyalkylene glycol preferably at least one polyethylene glycol, which is a middle
  • the liquid phase (at least one of the liquid phases, preferably the liquid phases) is a component according to a) at least one further polyalkylene glycol, preferably at least one polyethylene glycol (PEG), which has an average molecular weight between 2000 and 6000 g / mol, preferably an average molecular weight between 3500 to 4500, in particular about 4000, (INCI: PEG 4000).
  • PEG polyethylene glycol
  • the liquid phase (s) comprises a PEG having an average molecular weight of about 400 (INCI: PEG 400) and a PEG having a middle molecular weight
  • the liquid phase or the at least one liquid phase or the liquid phases of the cleaning agent according to the invention preferably additionally contain at least one nonionic surfactant, preferably one which also represents a component according to a) according to formula I.
  • R is selected from straight-chain or branched, saturated Ce-alkyl radicals
  • R 2 and R 4 are -H
  • R 3 and R 5 are -CH 3
  • R 6 is selected from -H, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -CH 2 -CH 2 -
  • w 1 to 6, preferably 1, 5 to 4.5, in particular 2 to 3;
  • x 1 to 6, preferably 1, 5 to 4.5, in particular 2 to 3;
  • y 0 to 6, preferably 1, 5 to 4.5, 2 to 3;
  • z 0 to 6, preferably 1, 5 to 4.5, 2 to 3, included.
  • components according to a) are particularly advantageous, as they may optionally provide a basis for the liquid phase in addition to the liquid polyalkylene glycols, without causing organic components, in particular organic solvents, which
  • At least one polyalkylene glycol preferably at least one polyethylene glycol having an average molecular weight between about 300 and about 5000, in particular approx 4000 g / mol is used.
  • the liquid phase (at least one of the liquid phases, preferably the liquid phases) additionally contains as a further component according to a) at least one further polyalkylene glycol, preferably at least one polyethylene glycol (PEG) which has an average molecular weight between 2000 and 6000 g / mol, in particular a PEG having an average molecular weight between 3500 to 4500, in particular about 4000 has.
  • PEG polyethylene glycol
  • the liquid phase (s) comprises a PEG having an average molecular weight of about 400 (INCI: PEG 400) and a PEG having a middle molecular weight
  • Components used as further component according to a) is at least one ethoxylated hydroxy mixed ether of the formula (I)
  • R is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms
  • R 6 is selected from -CH 2 CH (OH) R 7
  • R 7 for a straight-chain or branched, saturated or on or
  • C 4-22 fatty alcohol (EO) io-8o-2-hydroxyalkyl ethers particularly preferred are in particular also the C 8-12 fatty alcohol (EO) 22-2-hydroxydecyl ethers and the C 4-22 fatty alcohol (EO) 4-oxyalkyl ethers. 8o-2-hydroxyalkyl ethers.
  • the amount of all the components mentioned in accordance with a) in the liquid phase is between 10 to 80 wt .-%, preferably between 20 to 70 wt .-% (each based on the total weight of the liquid phase) ,
  • the liquid phase (at least one of the liquid phase, if appropriate all liquid phases) in each case based on the respective
  • R is selected from straight-chain or branched, saturated Ce-alkyl radicals
  • R 2 and R 4 are -H
  • R 3 and R 5 are -CH 3
  • R 6 is selected from -H, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -CH 2 -CH 2 -
  • w 1 to 6, preferably 1, 5 to 4.5, in particular 2 to 3;
  • x 1 to 6, preferably 1, 5 to 4.5, in particular 2 to 3;
  • R is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms
  • R 6 is selected from -CH 2 CH (OH) R 7
  • R 7 for a straight-chain or branched, saturated or on or
  • the amount of all of the components referred to as preferred according to a) in the liquid phase is between 10 to 80 wt .-%, preferably between 20 to 70 wt .-% (each based on the total weight of the liquid phase) ,
  • the liquid phase (at least one of the liquid phase, if appropriate all liquid phases) in each case based on the respective
  • R is selected from straight-chain or branched, saturated Ce-alkyl radicals
  • R 2 and R 4 are -H
  • R 3 and R 5 are -CH 3
  • R 6 is selected from -H, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -CH 2 -CH 2 -
  • w 1 to 6, preferably 1, 5 to 4.5, in particular 2 to 3;
  • x 1 to 6, preferably 1, 5 to 4.5, in particular 2 to 3;
  • y 0 to 6, preferably 1, 5 to 4.5, 2 to 3;
  • z 0 to 6, preferably 1, 5 to 4.5, 2 to 3, is contained,
  • R 6 is selected from -CH 2 CH (OH) R 7
  • R 7 for a straight-chain or branched, saturated or on or
  • the amount of all of the components referred to as preferred according to a) in the liquid phase is between 15 to 80 wt .-%, preferably between 20 to 70 wt .-% (each based on the total weight of the liquid phase) ,
  • the liquid phase (at least one of the liquid phase, if appropriate all liquid phases) in each case based on the respective
  • R is selected from straight-chain or branched, saturated Ce-alkyl radicals
  • R 2 and R 4 are -H
  • R 3 and R 5 are -CH 3
  • R 6 is selected from -H, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -CH 2 -CH 2 -
  • w 1 to 6, preferably 1, 5 to 4.5, in particular 2 to 3;
  • x 1 to 6, preferably 1, 5 to 4.5, in particular 2 to 3;
  • y 0 to 6, preferably 1, 5 to 4.5, 2 to 3;
  • z 0 to 6, preferably 1, 5 to 4.5, 2 to 3, is contained,
  • R is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms
  • R 6 is selected from -CH 2 CH (OH) R 7 with R 7 for a straight-chain or branched, saturated or on or
  • Polyethylene glycols having an average molecular weight between 300 and 600 g / mol and
  • polyethylene glycols having a molecular weight between 2000 and 6000
  • the amount of all of the components referred to as preferred according to a) in the liquid phase is between 10 to 80 wt .-%, preferably between 20 to 70 wt .-% (each based on the total weight of the liquid phase) ,
  • the amount of all components mentioned as being preferred according to a) in the liquid phase is between 10 to 80% by weight, preferably between 20 and 70% by weight (in each case based on the total weight of the liquid phase) ,
  • liquid phase in the liquid phase (the liquid phases) additionally a end-capped nonionic surfactant according to formula I I
  • poly (oxyalkylated) nonionic surfactants of the formula I I
  • R 8 and R 0 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms
  • R 9 is H or a methyl, ethyl, n-propyl, iso-propyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical
  • h are values between 1 and 30
  • k and j are values between 1 and 12, preferably between 1 and 5. If the value h> 2, then any R 9 in the formula above can
  • R 8 0 [CH 2 CH (R 9 ) 0] h [CH 2 ] kCH (OH) [CH 2] jOR ° be different.
  • R 8 and R 0 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic
  • Hydrocarbon radicals having 6 to 22 carbon atoms with radicals having 8 to 18 carbon atoms being particularly preferred.
  • R 9 H, -Chta or -CH 2 CH 3 are particularly preferred.
  • Particularly preferred values for h are in the range from 1 to 20, in particular from 6 to 15.
  • each R 9 in the above formula may be different if h> 2.
  • the alkylene oxide unit in the square bracket can be varied.
  • the value 3 for h has been chosen here as an example and may be larger, with the range of variation increasing with increasing h values and including, for example, a large number of (EO) groups combined with a small number (PO) groups, or vice versa.
  • R 8 0 [CH 2 CH (R 9 ) 0] hCH 2 CH (OH) CH 2 OR ° simplified.
  • R 8 , R 0 and R 9 are as defined above and x is from 1 to 30, preferably from 1 to 20 and especially from 6 to 18.
  • Particularly preferred are surfactants in which the radicals R 8 and R 0 have 9 to 14 C atoms, R 9 is H and h assumes values of 6 to 15.
  • the amount of all components according to a) in the liquid phase is between 10 and 80% by weight, preferably between 20 and 70% by weight (in each case based on the total weight of the liquid phase).
  • the ratio of the weight of one or more solid phases (of which preferably at least one solid phase is powdery, (in the case of several solid / powder phases the total weight of all solid and powder phases) to the weight of one or more liquid phases (in the case of several liquid phases preferably from 1:10 to 10: 1, particularly preferably from 1: 5 to 5: 1, very particularly preferably from 4: 1 to 1: 2.
  • the cleaning agent in particular
  • Machine dishwashing detergents essentially free of anionic surfactants
  • Substantially free of anionic surfactants as used herein means that a composition is less than 7% by weight, preferably less than 5% by weight, more preferably less than 3% by weight, most preferably less than 1% by weight. -%, particularly preferably less than 0.1 wt .-% anionic surfactant (based on the total weight of the composition). This preferably applies to all, in particular also the combinations according to the invention explicitly mentioned as preferred above.
  • the water-soluble coating of the cleaning agent, the packaging is preferably formed from a water-soluble film material selected from the group consisting of polymers or polymer blends.
  • the wrapper may be formed of one or two or more layers of the water-soluble film material.
  • the water-soluble film material of the first layer and the further layers, if present, may be the same or different. Particularly preferred are films which, for example, can be glued and / or sealed to packages such as hoses or cushions after being filled with an agent. It is preferred that the water-soluble coating be polyvinyl alcohol or a
  • Water-soluble coatings containing polyvinyl alcohol or a polyvinyl alcohol copolymer have a good stability with a sufficiently high water solubility, in particular cold water solubility on.
  • Suitable water-soluble films for producing the water-soluble coating are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer whose
  • Molecular weight in the range of 10,000 to 1,000,000 gmol "1 , preferably from 20,000 to 500,000 gmol, more preferably from 30,000 to 100,000 gmol " 1 and in particular from 40,000 to 80,000 gmol 1 .
  • polyvinyl alcohol is usually carried out by hydrolysis of polyvinyl acetate, since the direct synthesis route is not possible.
  • polyvinyl alcohol copolymers which are prepared from correspondingly polyvinyl acetate copolymers. It is preferred if at least one layer of the water-soluble coating comprises a polyvinyl alcohol whose degree of hydrolysis makes up 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.
  • a polymer selected from the group comprising a polyvinyl alcohol-containing sheet material suitable for producing the water-soluble sheath is selected from the group comprising a polyvinyl alcohol-containing sheet material suitable for producing the water-soluble sheath
  • (Meth) acrylic acid-containing (co) polymers polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers, polylactic acid or mixtures of the above polymers may be added.
  • a preferred additional polymer is polylactic acids.
  • Preferred polyvinyl alcohol copolymers include, in addition to vinyl alcohol, dicarboxylic acids as further monomers.
  • Suitable dicarboxylic acids are itaconic acid, malonic acid, succinic acid and
  • polyvinyl alcohol copolymers include, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt or its esters.
  • Such polyvinyl alcohol copolymers particularly preferably contain, in addition to vinyl alcohol, acrylic acid, methacrylic acid, acrylates, methacrylates or mixtures thereof.
  • the film material contains further additives.
  • the film material may include, for example, plasticizers such as dipropylene glycol, ethylene glycol, diethylene glycol,
  • Additives include, for example, release aids, fillers, crosslinking agents, surfactants, antioxidants, UV absorbers, antiblocking agents, detackifiers, or mixtures thereof.
  • Suitable water-soluble films for use in the water-soluble casings of the water-soluble packaging according to the invention are films sold by the company MonoSol LLC, for example under the designation M8630, C8400 or M8900.
  • Other suitable films include films named Solublon® PT, Solublon® GA, Solublon® KC or Solublon® KL from Aicello Chemical Europe GmbH or the films VF-HP from Kuraray.
  • the cleaning agents used according to the invention can be used as dishwashing agents, in particular automatic dishwasher detergents.
  • the corresponding use is also the subject of the invention.
  • the invention likewise relates to a dishwashing process, in particular a machine dishwashing process, in which a cleaning agent according to the invention is used.
  • the particular embodiments described above are for use as well as the method.
  • the cleaning agents used according to the invention are preferably a dishwashing detergent, in particular a machine dishwashing detergent.
  • the pre-portioned cleaning agent used according to the invention in particular machine dishwashing detergent, is essentially free of phosphates. This preferably applies to all, in particular also the combinations according to the invention explicitly mentioned as preferred above.
  • Substantially free of phosphates means that the total cleaning agent resulting from the addition of all phases (or all ingredients of all compartments) is preferably substantially free of phosphate-containing components. As phosphates or too
  • Phosphate-containing components in the context of the present invention are, in particular, phosphates, polyphosphates and pyrophosphates. However, phosphonates or hexafluorophosphate are not covered by this term.
  • the total detergent thus contains less than 1% by weight, preferably 0.5% by weight, of phosphates, based on the total weight of the detergent (i.e., the total weight of all phases (i.e., all liquid and solid phases).
  • the detergents used according to the invention in particular machine dishwashing detergents, contain builders, such as zeolites, silicates, carbonates, in particular the
  • Alkali carbonates for example sodium carbonate, sodium bicarbonate or sodium sesquicarbonate, and organic cobuilders.
  • silicates are, in particular crystalline layered silicates of general formula NaMSix02x + i ⁇ y H2O wherein M is sodium or hydrogen, x is a number from 1, 9 to 22, preferably from 1: 9 to 4, particularly preferred values for x being 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20, into consideration.
  • amorphous sodium silicates having a modulus Na 2 O: SiO 2 of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which are preferably delayed in dissolution and secondary wash properties.
  • the content of silicates based on the total weight of the cleaning agent, to amounts below 10 wt .-%, preferably below 5 wt .-%.
  • organic co-builders are polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, further organic cobuilders and phosphonates. These classes of substances are described below.
  • Useful organic builders are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function.
  • these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid,
  • NTA nitrilotriacetic acid
  • Acidification and thus also serve to set a lower and milder pH of the automatic dishwashing detergent.
  • citric acid here are citric acid,
  • Succinic acid glutaric acid, adipic acid, gluconic acid and any mixtures thereof.
  • polymeric polycarboxylates for example the alkali metal salts of polyacrylic acid or of polymethacrylic acid, for example those having a relative molecular mass of from 500 to 70,000 g / mol.
  • the polyacrylate or the polyacrylates are used here in particular in a dried, more preferably in a dried and granulated (solid) form, which optionally may additionally be ground.
  • Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of about 1000 to 20,000, in particular 2,000 to 20,000 g / mol. Because of their superior solubility, this group can again be the short chain polyacrylates, the molecular weights of 2000 to 10000 g / mol, and more preferably from 3000 to 5000 g / mol, be preferred.
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Their relative molecular weight, based on free acids is generally from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.
  • the detergents may contain, in particular, phosphonates as builder.
  • the phosphonate compound used is preferably a hydroxyalkane and / or aminoalkane phosphonate.
  • hydroxyalkane phosphonates 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance.
  • Aminoalkanphosphonate are preferably
  • ETMP Ethylenediaminetetramethylenephosphonate
  • DTPMP Diethylentriaminpentamethylenphosphonat
  • Phosphonate-containing components are contained in the compositions preferably in amounts of 0, 1 to 10 wt .-%, in particular in amounts of 0.5 to 8 wt .-%, each based on the total weight of the cleaning agent.
  • Aminoalkan portion contain the compositions according to the invention from 0.01 to 25% by weight, preferably 5 to 20 wt .-%, 8 to 15 wt .-% phosphonate (each based on the
  • the phosphonates are preferably contained in the solid phase (s).
  • the cleaning agents used according to the invention may further comprise a sulfopolymer.
  • the proportion by weight of the sulfopolymer in the total weight of the cleaning agent used according to the invention is preferably from 0.1 to 20 wt .-%, in particular from 0.5 to 18 wt .-%, particularly preferably 1, 0 to 15 wt .-%, most preferably 2.0 to 14 wt .-%, in particular from 4 to 14 wt .-%, especially from 4.5 to 12 wt .-%.
  • the sulfopolymer is used here in particular in a dried, particularly preferably in a dried and granulated (solid) form, which optionally may additionally be ground.
  • the sulfopolymer used is preferably a copolymeric polysulfonate, preferably a hydrophobically modified copolymeric polysulfonate.
  • the copolymers may have two, three, four or more different monomer units.
  • Preferred copolymeric polysulfonates contain sulfonic acid group-containing (s)
  • Monomer (s) at least one monomer from the group of unsaturated carboxylic acids.
  • unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, alpha-chloroacrylic acid, alpha-cyanoacrylic acid, crotonic acid, alpha-phenyl-acrylic acid,
  • Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3 Methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propenylsulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfo - Propylmethacrylat, sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of said acids or their water-
  • the sulfonic acid groups may be wholly or partially in neutralized form, i. the acidic acid of the sulfonic acid group in some or all sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions.
  • metal ions preferably alkali metal ions and in particular for sodium ions.
  • Sulfonic acid-containing copolymers is inventively preferred.
  • the monomer distribution of the copolymers preferably used according to the invention in the case of copolymers containing only monomers containing carboxylic acid groups and monomers containing sulfonic acid groups is preferably from 5 to 95% by weight, more preferably from 50 to 90% by weight of the sulfonic acid group-containing monomer. % and the share of
  • the molar mass of the sulfo copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired end use.
  • Preferred cleaning agents are characterized in that the copolymers have molecular weights of 2000 to 200,000 gmol -1 , preferably from 4000 to 25,000 gmol and in particular from 5000 to 15,000 gmol -1 .
  • the copolymers include besides
  • Carboxyl-containing monomer and sulfonic acid-containing monomer further at least one nonionic, preferably hydrophobic monomer.
  • the use of these hydrophobically modified polymers has made it possible in particular to improve the rinse aid performance of automatic dishwashing detergents according to the invention.
  • Anionic copolymers comprising monomers containing carboxylic acid groups, monomers containing sulfonic acid groups and nonionic monomers, in particular hydrophobic monomers, are therefore preferred according to the invention.
  • nonionic monomers are preferably monomers of the general formula
  • nonionic monomers are butene, isobutene, pentene, 3-methylbutene, 2-methylbutene, cyclopentene, hexene, hexene-1, 2-methylpentene-1, 3-methylpentene-1, cyclohexene, methylcyclopentene, cycloheptene, methylcyclohexene, 2,4 , 4-trimethylpentene-1, 2,4,4-trimethylpentene-2,3,3-dimethylhexene-1, 2,4-dimethylhexene-1, 2,5-dimethlyhexene-1,3,5-dimethylhexene-1,4 , 4-dimethylhexane-1, ethylcyclohexyne, 1-octene, alpha-olefins having 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and
  • the monomer distribution of the hydrophobically modified copolymers preferably used according to the invention is preferably in each case from 5 to 80% by weight, with respect to the sulfonic acid group-containing monomer, the hydrophobic monomer and the carboxylic acid group-containing monomer, the proportion of the sulfonic acid group-containing monomer and of the each hydrophobic monomer 5 to 30 wt .-% and the proportion of the carboxylic acid group-containing monomer 60 to 80 wt .-%, the monomers are in this case preferably selected from the aforementioned.
  • the agents used according to the invention preferably contain at least one further constituent, preferably selected from the group consisting of cationic and amorphous surfactants, bleaching agents, bleach activators, bleach catalysts, enzymes, thickeners, sequestering agents, electrolytes, corrosion inhibitors, in particular silver protectants, glass corrosion inhibitors, foam inhibitors, dyes, fragrances, bitter substances, and antimicrobial agents.
  • at least one further constituent preferably selected from the group consisting of cationic and amorphous surfactants, bleaching agents, bleach activators, bleach catalysts, enzymes, thickeners, sequestering agents, electrolytes, corrosion inhibitors, in particular silver protectants, glass corrosion inhibitors, foam inhibitors, dyes, fragrances, bitter substances, and antimicrobial agents.
  • detergents preferably dishwashing detergents, in particular machine
  • Dishwashing agents can also be used bleaching agents.
  • bleaching agents include sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Further useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and peroxygenic salts or peracids which yield H2O2, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. It is also possible to use all other inorganic or organic agents known to the person skilled in the art
  • bleaching agent As a bleaching agent and chlorine or bromine releasing substances can be used. Examples of suitable chlorine or bromine releasing materials
  • heterocyclic N-bromo- and N-chloroamides for example trichloroisocyanuric acid
  • Tribromoisocyanuric acid Tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium into consideration.
  • DICA dichloroisocyanuric acid
  • Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.
  • cleaning agents preferably dishwashing detergents, in particular machine
  • Dishwashing agents which contain 1 to 35% by weight, preferably 2.5 to 30% by weight, particularly preferably 3.5 to 25% by weight, very particularly preferably 4.0 to 20% by weight and in particular 5 to 18% by weight (based on the total weight of the cleaning agent) of bleaching agent, preferably sodium percarbonate.
  • the cleaning agents may contain bleach catalysts.
  • Useful bleach catalysts include, but are not limited to, the group of bleach-enhancing transition metal salts and transition metal complexes, preferably Mn, Fe, Co, Ru or Mo complexes, more preferably from the group of manganese and / or cobalt salts and / or or complexes, in particular the cobalt (ammin) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, the manganese sulfate and the complexes of manganese with 1, 4,7- trimethyl-1, 4,7-triazacyclononane (Mm-TACN) or 1, 2,4,7-tetramethyl-1, 4,7-triazacyclononane (Mm-TACN).
  • Mm-TACN 4,7- trimethyl-1, 4,7-triazacyclononane
  • Mm-TACN 2,4,7-tetramethyl-1, 4,7-tri
  • detergents preferably dishwashing agents, in particular automatic dishwasher detergents which contain from 0.001 to 1% by weight, preferably from 0.01 to 0.1% by weight (based in each case on the total weight of the cleaning agent) of bleach catalyst, preferably a Mn complex.
  • the cleaning agents preferably dishwashing agents, in particular automatic dishwasher detergents, additionally comprise at least one bleach activator.
  • bleach activators it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
  • acylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT) Glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS) are particularly preferably used.
  • TAED tetraacetylethylenediamine
  • DADHT 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine
  • Glycolurils in particular tetraacety
  • Combinations of conventional bleach activators can also be used. These bleach activators are preferably used in amounts of up to 10% by weight, in particular 0.1% to 8% by weight, especially 2 to 8% by weight and more preferably 2 to 6% by weight, based in each case on the total weight of the detergents used.
  • the bleaching agent and also bleach catalysts and / or bleach activators are preferably contained in the solid phase (s).
  • Suitable amphoteric surfactants are, for example, betaines of the formula (R iii) (R iv) (R v) N + CH2COO _ in which R i is an optionally interrupted by hetero atoms or hetero atom groups alkyl radical having 8 to 25, preferably 10 to 21 carbon atoms, and R IV and R v are identical or different alkyl radicals having 1 to 3 carbon atoms, in particular Cio-Cis-alkyl dimethylcarboxymethylbetain and Cn-Ci7-alkylamidopropyl-dimethylcarboxymethylbetain.
  • Suitable cationic surfactants are i.a. the quaternary ammonium compounds of the formula
  • R VI (R VI ) (R vii ) (R viii ) (R ix ) N + X "
  • R vi to R ix for four identical or different, in particular two long and two short-chain, alkyl radicals and X " for an anion , in particular a halide ion, for example, didecyl-dimethyl-ammonium chloride, alkyl-benzyl-didecyl-ammonium chloride and mixtures thereof.
  • Further suitable cationic surfactants are the quaternary surface-active compounds, in particular having a sulfonium, phosphonium, iodonium or arsonium group, which are also known as antimicrobial agents.
  • the agent can be designed with an antimicrobial effect or its possibly existing antimicrobial effect due to other ingredients can be improved.
  • the enzymes include in particular proteases, amylases, lipases, hemicellulases,
  • Cellulases perhydrolases or oxidoreductases, and preferably mixtures thereof. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents, which are preferably used accordingly.
  • Detergents used according to the invention preferably contain enzymes in total amounts of from 1 ⁇ 10 -6 to 5% by weight, based on active protein. The protein concentration can be determined by known methods, for example the BCA method or the biuret method.
  • subtilisin type those of the subtilisin type are preferable.
  • these are the subtilisins BPN 'and Carlsberg and their further developed forms, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase which can no longer be assigned to the subtilisins in the narrower sense, Proteinase K and the proteases TW3 and TW7.
  • amylases which can be used according to the invention are the ⁇ -amylases from Bacillus licheniformis, from B. amyloliquefaciens, from B. stearothermophilus, from Aspergillus niger and A. oryzae as well as the further developments of the aforementioned amylases which are improved for use in cleaning agents. Furthermore, for this purpose, the ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and cyclodextrin glucanotransferase (CGTase) from B. agaradherens
  • lipases or cutinases are also usable according to the invention.
  • lipases or cutinases in particular because of their triglyceride-splitting activities, but also in order to generate in situ peracids from suitable precursors.
  • lipases or cutinases include, for example, those originally from Humicola lanuginosa
  • Thermomyces lanuginosus or in particular those with one or more of the following amino acid exchanges starting from said lipase in positions D96L, T213R and / or N233R, more preferably all of the exchanges D96L, T213R and N233R.
  • enzymes can be used which are termed hemicellulases
  • Oxidoreductases for example oxidases, oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can be used according to the invention to increase the bleaching effect.
  • organic, more preferably aromatic, enzyme-interacting compounds to enhance the activity of the respective oxidoreductases (enhancers) or to react at greatly varying redox potentials between the oxidizing enzymes and the
  • a protein and / or enzyme may be particularly protected during storage against damage such as inactivation, denaturation or degradation, such as by physical influences, oxidation or proteolytic cleavage.
  • damage such as inactivation, denaturation or degradation, such as by physical influences, oxidation or proteolytic cleavage.
  • inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases.
  • Detergents may contain stabilizers for this purpose; the provision of such means constitutes a preferred embodiment of the present invention.
  • Cleaning-active proteases and amylases are generally not provided in the form of the pure protein but rather in the form of stabilized, storage and transportable preparations.
  • Such prefabricated preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel-form detergents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or added with stabilizers or further auxiliaries.
  • the enzymes may be encapsulated for both the solid and liquid dosage forms, for example by spray-drying or extruding the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core with a water, air and / or
  • Chemical-impermeable protective layer is coated.
  • further active ingredients for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied.
  • Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes.
  • such granules for example by applying polymeric
  • Film former low-dust and storage-stable due to the coating. Furthermore, it is possible to assemble two or more enzymes together so that a single granule has several enzyme activities.
  • Protease and amylase preparations preferably used according to the invention contain between 0.1 and 40% by weight, preferably between 0.2 and 30% by weight, more preferably between 0.4 and 20% by weight and
  • Total weight 0, 1 to 12 wt .-%, preferably 0.2 to 10 wt .-% and in particular 0.5 to 8 wt .-% enzyme preparations.
  • the enzymes in particular the amylase (s) and / or protease (s), are preferably present in (one) of the solid phase (s), preferably as granules or granules.
  • Glass corrosion inhibitors used are metal salts, in particular zinc salts or bismuth salts, preferably zinc salts, in particular zinc acetate. Also preferred as glass corrosion inhibitors are polyethyleneimines and polyvinylamines, for example those obtainable under the name Lupasol® or Lupamin® from BASF, in particular nonalkoxylated
  • Glass corrosion inhibitors are preferably present in compositions according to the invention in an amount of from 0.05 to 5% by weight, in particular in an amount of from 0.1 to 2% by weight.
  • the cleaning agents used according to the invention are characterized in that they are stable on storage and even after a prolonged period, no phase separation occurs.
  • a further subject of the present invention is also a machine dishwashing process in which a cleaning agent according to the invention is used.
  • the invention also relates to the use of the cleaning agent according to the invention as a dishwashing detergent, in particular machine
  • Comparative formulation V1 shows visible phase separation on storage at 40 ° C., 1 bar within 4 weeks, while example E1 according to the invention had no visible phase separation under these conditions.

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Abstract

L'invention concerne l'utilisation d'au moins un acide aminocarboxylique pour la stabilisation de composants de lessive ou de détergent liquides pauvres en eau, de préférence sensiblement exempts d'eau.
EP15704267.2A 2014-02-06 2015-02-04 Utilisation d'acides aminocarboxyliques pour la stabilisation des lessives ou détergents pauvres en eau Active EP3102659B1 (fr)

Applications Claiming Priority (2)

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DE102014202223.1A DE102014202223A1 (de) 2014-02-06 2014-02-06 Verwendung von Aminocarbonsäuren zur Stabilisierung von wasserarmen flüssigen Wasch- oder Reinigungsmittelkomponenten
PCT/EP2015/052295 WO2015118008A1 (fr) 2014-02-06 2015-02-04 Utilisation d'acides aminocarboxyliques pour la stabilisation des lessives ou détergents pauvres en eau

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Publication number Priority date Publication date Assignee Title
AT291414B (de) 1967-01-27 1971-07-12 Unilever Nv Wasch- und Reinigungsmitell
DK129804A (fr) 1969-01-17
US4769168A (en) 1985-08-05 1988-09-06 Colgate-Palmolive Company Low phosphate or phosphate free nonaqueous liquid nonionic laundry detergent composition and method of use
GB8625974D0 (en) 1986-10-30 1986-12-03 Unilever Plc Non-aqueous liquid detergent
CA2295233A1 (fr) * 1997-06-27 1999-01-07 Lorenzo Matteo Pierre Gualco Compositions detergentes liquides non aqueuses contenant des particules enzymatiques
FR2818150B1 (fr) * 2000-12-15 2004-04-30 Anios Lab Sarl Composition pour le traitement d'objets destines a etre desinfectes
DE10153553A1 (de) * 2001-07-07 2003-06-12 Henkel Kgaa Nichtwäßrige "3in1"-Geschirrspülmittel II
AU2009235093A1 (en) 2008-04-07 2009-10-15 Ecolab Inc. Ultra-concentrated liquid degreaser composition
DE102008034231A1 (de) * 2008-07-23 2010-01-28 Cht R. Beitlich Gmbh Katalysierte Peroxidbleiche ("Katalysator-Bleiche-Variante 3: All-in-one")
JP2010077428A (ja) 2008-09-01 2010-04-08 Nippon Shokubai Co Ltd ポリオキシアルキレン系重合体組成物およびその製造方法
US8629093B2 (en) 2010-09-01 2014-01-14 The Procter & Gamble Company Detergent composition comprising mixture of chelants
GB201216028D0 (en) * 2012-09-07 2012-10-24 Reckitt Benckiser Nv Detergent formulation
PT3008159T (pt) * 2013-06-12 2017-02-10 Unilever Nv Composição detergente passível de ser vertida compreendendo partículas suspensas

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