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WO2014037255A1 - Particules, procédé de fabrication et utilisation - Google Patents

Particules, procédé de fabrication et utilisation Download PDF

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Publication number
WO2014037255A1
WO2014037255A1 PCT/EP2013/067774 EP2013067774W WO2014037255A1 WO 2014037255 A1 WO2014037255 A1 WO 2014037255A1 EP 2013067774 W EP2013067774 W EP 2013067774W WO 2014037255 A1 WO2014037255 A1 WO 2014037255A1
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WO
WIPO (PCT)
Prior art keywords
cationic
particles according
acid
polymer
compound
Prior art date
Application number
PCT/EP2013/067774
Other languages
German (de)
English (en)
Inventor
Stephan Hüffer
Alejandra Garcia Marcos
Frank-Peter Lang
Ralf Bohlander
Markus Hartmann
Original Assignee
Basf Se
Basf Schweiz Ag
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Basf Se, Basf Schweiz Ag filed Critical Basf Se
Publication of WO2014037255A1 publication Critical patent/WO2014037255A1/fr

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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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/08—Silicates
    • 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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
    • C11D11/0088—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads the liquefied ingredients being sprayed or adsorbed onto solid particles
    • 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
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/128—Aluminium silicates, e.g. zeolites
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3723—Polyamines or polyalkyleneimines
    • 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
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3753—Polyvinylalcohol; Ethers or esters thereof

Definitions

  • the present invention relates to particles containing
  • the present invention relates to a process for the preparation of particles of the invention and their use.
  • Modern dishwashing detergents have many requirements to fulfill. So they have to clean the dishes thoroughly, they should not leave any harmful or potentially harmful substances in the sewage, they should allow the draining and drying of the water from the dishes, and they should not cause problems when operating the dishwasher. Furthermore, they should remain well storable for a long time. This not only means that they do not attract much water during prolonged storage, but also should show no unwanted discolorations, in particular no unwanted yellowing.
  • Glass corrosion is caused not only by mechanical effects, for example, by juxtaposition of glasses or mechanical contact of the glasses with parts of the dishwasher, but is mainly promoted by chemical influences. For example, certain ions can be released from the glass by repeated mechanical cleaning, adversely altering the optical and thus the aesthetic properties.
  • EP 2 392 638 discloses that aminocarboxylates may be used in admixture with silicates or with a second aminocarboxylate to produce the less hygroscopic automatic dishwashing formulations.
  • glass corrosion can not be combated with sufficient efficiency in many cases.
  • silica or silicate in a concentration ranging from 50 to 99.9% by weight, based on the sum of compound (s) (a) and cationic (co) polymer (b).
  • particles of the invention may contain phosphate or polyphosphate.
  • inventive particles are free of phosphates and polyphosphates, wherein hydrogen phosphates are subsumed with, for example, free of trisodium phosphate, pentasodium tripolyphosphate and Hexanatri- ummetaphosphat.
  • "free from” is to be understood, in the context of phosphates and polyphosphates, as meaning that the content of phosphate and Polyphosphate in total in the range of 10 ppm to 0.2 wt .-%, determined by gravimetry.
  • particles according to the invention are free from those heavy metal compounds which do not act as bleach catalysts, in particular compounds of iron and bismuth. Under “free of” should be related to
  • heavy metal compounds are understood to mean that the content of heavy metal compounds which do not act as bleach catalysts is in the range from 0 to 100 ppm, determined by the Leach method and based on the solids content. Particles according to the invention preferably have a heavy metal content below 0.05 ppm.
  • heavy metals are all metals having a specific density of at least 6 g / cm 3.
  • heavy metals are noble metals and also zinc, bismuth, iron, copper, lead, tin, nickel, cadmium and chromium.
  • Particles according to the invention preferably contain no measurable proportions of zinc and bismuth compounds, that is, for example, less than 1 ppm.
  • Particulates according to the invention may have a regular or an irregular shape. Examples of regular shapes are balls and egg shapes, cuboids and cubes.
  • particles according to the invention may have substantially a spherical shape, which however is not uniform due to the presence of individual elevations or depressions and is therefore considered irregular in the context of the present invention.
  • Particles according to the invention preferably have a spherical shape or essentially a spherical shape, "substantially spherical shape” meaning that they are round particles whose diameters deviate by a maximum of 10% at the thickest point and at the thinnest point.
  • particles according to the invention have an average diameter in the range of 1 mm to 4 mm.
  • the mean diameter is to be understood as meaning both the average diameter of the individual particles and the average diameter of a representative sample of particles according to the invention, determined by sieve analysis.
  • particles according to the invention have a monomodal particle diameter distribution, the mean particle diameter being in the range from 0.1 mm to 4 mm, preferably 0.5 ⁇ m to 2 mm.
  • particles according to the invention have a bimodal particle diameter distribution which has a first fraction, the 5 to 35 wt .-% of the particles in question, which have a particle diameter in the range of 10 ⁇ to 0.5 mm, preferably 50 ⁇ to 0.25 mm, and a second fraction, the 65 to 95 wt .-% of the particles in question comprising a particle diameter of in the range of 0.5 to 4 mm, preferably 0.8 to 2 mm.
  • Bimodal particle diameter distributions can be adjusted, for example, by mixing different batches.
  • the sheath (A) is preferably thinner than the core (B) of particles according to the invention.
  • shell (A) has a thickness in the range of 2 to 25% (radial) of the total subject particle of the invention.
  • Sleeve (A) can completely encase core (B) or have gaps. It is preferred if shell (A) completely surrounds the core (B).
  • Formulations used in the invention contain in the core (A)
  • aminocarboxylate at least one compound selected from aminocarboxylates, in the context of the present invention also briefly called aminocarboxylate (a) or compound (a), as well as their derivatives and preferably salts.
  • Compound (a) may be in the form of a free acid or preferably in partially or completely neutralized form, ie as a salt.
  • counterions for example inorganic cations, such as ammonium, alkali or alkaline earth metal are suitable, preferably Mg 2+, particularly preferably Na +, K +, or organic cations, preferably with one or more organic radicals, substituted ammonium, more particularly triethanolammonium, ⁇ , ⁇ - Diethanolammonium, N-mono-C 1 -C 4 -alkyldiethanolammonium, for example N-methyldiethanolammonium or Nn-butyldiethanolammonium, and N, N-di-C 1 -C 4 -alkylethanolammonium.
  • inorganic cations such as ammonium, alkali or alkaline earth metal are suitable, preferably Mg 2+, particularly preferably Na +, K +, or organic cations, preferably with one or more organic radicals, substitute
  • compound (a) is selected from derivatives of aminocarboxylates and, for example, methyl or ethyl esters.
  • aminocarboxylates (a) are understood as meaning nitrilotriacetic acid and those organic compounds which have a tertiary amino group which has one or two CH 2 -COOH groups which, as mentioned above, can be partially or completely neutralized
  • polyaminocarboxylates (a) are understood as meaning those organic compounds which have at least two tertiary amino groups which independently of one another each contain one or two
  • aminocarboxylates (a) are selected from those organic compounds having a secondary amino group having one or two CH (COOH) CH 2 -COOH group (s) partially or as previously mentioned can be completely neutralized or can.
  • polyaminocarboxylates (a) from such organic compounds having at least two secondary amino groups, each having a CH (COOH) CH2-COOH group, which - as mentioned above - may be partially or completely neutralized.
  • Preferred aminocarboxylates (a) are nitrilotriacetic acid and those organic compounds having an amino acid-based structure whose amino group (s) have one or two Ch-COOH groups and are tertiary amino groups. It is possible to select amino acids from L-amino acids, R-amino acids and mixtures of enantiomers of amino acids, for example the racemates.
  • compound (a) is selected from methylglycine diacetate (MGDA), iminodisuccinic acid (IDS) and glutamic acid diacetate (GLDA) as well as their derivatives and preferably their salts, in particular the sodium salts of MGDA, IDS and GLDA. Very particular preference is given to methylglycine diacetate and to the trisodium salt of MGDA.
  • Particulates according to the invention continue to be present in the core
  • cationic (co) polymer (b) in the context of the present invention also referred to as "cationic (co) polymer (b)" or cationic "(co) polymer (b)".
  • the presence of at least one (co) polymer (b) is preferred.
  • cationic (co) polymer (b) has a cationic charge density of at least 5 milliequivalents / gram.
  • Preferred (co) polymers (b) are selected from polyvinylamine and linear and branched homopolymers of alkyleneimine.
  • Particularly preferred (co) polymers (b) are selected from homopolymers and copolymers of ethyleneimine, also referred to as polyethylenimine (b) for short, and homopolymers and copolymers of propyleneimine, in short also called polypropyleneimine (b).
  • Cationic (co) polymers (c) in the context of the present invention are understood to mean those (co) polymers which have at least one of the following structural features:
  • Arylimidazolium groups tetra (2-aminoethyl) groups, tetra (2-iminoethyl) groups, N-pyridinium groups or ⁇ , ⁇ -dialkylimino groups, preferred are tri-C 1 -C 4-n-alkylammonium groups, 3-methylimidazolium groups, 3-phenylimidazolium groups and tetra (2-aminoethyl) groups, or
  • Examples are -NH 2 groups, -NH (C 1 -C 10 -alkyl) groups, -N (C 1 -C 10 -alkyl) 2 groups, -NH (C 2 -C 10 -alkylene) groups, - (CH 2 ) 2-N (CH 3 ) 2 groups, NH-CH 2 CH (C 1 -C 10 -alkyl) groups and - (C 2 -C 10 -alkylene) N (C 2 -C 10 -alkylene) - Groups, in particular CH 2 -CH 2 -NH-CH 2 -CH 2 -NH groups and CH 2 -CH 2 - NH- (CH 2 ) 3 -NH groups.
  • Cationic (co) polymer (b) may have, per molecule, at least two structural features (i), which may be the same or different, or at least two structural features (ii), which may be the same or different, or at least one structural feature (i ) and at least one structural feature (ii).
  • cationic (co) polymer per molecule (c) has at least five structural features (i), which may be the same or different, or at least five structural features (ii), which may be the same or different.
  • Cationic (co) polymer (b) can have as counter ions high molecular weight or low molecular weight anions, organic or preferably inorganic.
  • High molecular weight anions in the context of the present invention have an average molecular weight of 200 g / mol or more, for example up to 2500 g / mol
  • low molecular weight anions have a molecular weight of less than 200 g / mol, for example from 17 to 150 g / mol.
  • Examples of low molecular weight organic counterions are acetate, propionate and benzoate.
  • Examples of low molecular weight inorganic counterions are sulfate, chloride, bromide, hydroxide, carbonate, methanesulfonate and bicarbonate.
  • Cationic (co) polymers (b) have a cationic charge density of at least 5 milliequivalents / g, with the statement in g referring to cationic (co) polymer (b) without consideration of the counterions.
  • a charge density in the range of 5 to 22 milliequivalents / g is preferred.
  • the cationic charge density can be determined, for example, by titration.
  • Cationic (co) polymers (b) may also contain one or more anionic comonomers copolymerized, for example (meth) acrylic acid.
  • cationic (co) polymer (b) does not incorporate anionic comonomers in copolymerized form.
  • cationic (co) polymers (b) are polyvinylamine-co-vinylformamide, preparable for example by partial hydrolysis of polyvinylformamide, furthermore polyvinylpyrrolidone, polyDADMAC (DADMAC: diallyldimethylammonium chloride), polyvinylpyrrolidone-co-vinyl-3-methylimidazolium, graft copolymers of 3 -Methyl-N-vinylimidazolium on polyethers such as polyethylene glycol or polypropylene glycol, graft copolymers of 3-methyl-N-vinylimidazolium and N-vinylpyrrolidone on polyethers such as polyethylene glycol or polypropylene glycol.
  • cationic (co) polymers (b) are copolymers of (meth) acrylates with N, N-dimethylaminoethyl (meth) acrylate and copolymers of (meth) acrylates with ⁇ , ⁇ , ⁇ -trimethylammoniumethyl (meth) acrylate.
  • Another example is cationically modified starch.
  • cationic (co) polymer (b) has an average molecular weight M n of from 500 g / mol to 125,000 g / mol, preferably from 750 g / mol to 100,000 g / mol.
  • cationic (co) polymer (b) has an average molecular weight M w in the range of 500 to 1,000,000 g / mol, preferably in the range of 600 to 75,000 g / mol, particularly preferably in the range of 800 to 25,000 g / mol, determinable for example by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • Preferred (co) polymers (b) are selected from polyvinylamines, also referred to as polyvinylamines (b) for short, and from linear and branched homopolymers of alkyleneimines, termed polyalkylenimine (b) for short, and in particular from linear and branched homopolymers of ethyleneimine and / or propyleneimine, polyethylenimine (b) or polypropyleneimine (b) for short.
  • polyvinylamines (b) are not only fully saponified polyvinylamides, for example fully saponified poly-N-vinylformamide, but also so-called hydrophobically modified polyvinylamines, for example by reaction with one or more linear carboxylic acids having 10 to 22 carbon atoms / molecule , preferably having 14 to 18 carbon atoms / molecule, for example capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid,
  • one or more linear or branched alkyl halides containing from 10 to 22 carbon atoms per molecule, preferably from 14 to 18 carbon atoms per molecule, for example n-tetradecyl chloride, n-hexadecyl chloride, n-octadecyl chloride,
  • alkyl epoxides having 10 to 22 carbon atoms / molecule, for example 1, 2-hexadecenyl oxide and 1, 2-octadecenyloxide,
  • Alkylketen dimers having 9 to 21 carbon atoms in the respective alkyl radical, preferably up to 18 carbon atoms, for example dimeric lauryl ketene, dimeric palmityl ketene, lower stearyl ketene and dimeric oleyl ketene, or mixtures thereof,
  • cyclic dicarboxylic acid anhydrides in particular alkyl-substituted succinic anhydrides having 10 to 22 carbon atoms in the alkyl radical, preferably having 14 to 18 carbon atoms in the alkyl radical, for example dodecenylsuccinic anhydride, tetradecylsuccinic anhydride, hexadecenylbernstenic anhydride, and mixtures thereof; Chloroformates of fatty alcohols having 10 to 22 carbon atoms in the alkyl radical, preferably having 14 to 18 carbon atoms in the alkyl radical,
  • Alkylene diisocyanates having 10 to 22 carbon atoms in the alkylene radical, preferably having 14 to 18 carbon atoms in the alkyl radical, for example OCN- (CH 2 ) i4-NCO, OCN- (CH 2 ) i6-NCO or OCN- (CH 2 ) i8-NCO or mixtures of at least two of the above
  • polyalkyleneimines (b) can be prepared not only by polymerization of alkyleneimine, but also, for example, by polycondensation of ⁇ , ⁇ -hydroxy-C 2 -C 10 -alkyleneamines, by polycondensation of ⁇ , ⁇ -C 2 -C 10 -alkylenediamines with a, (jo-hydroxy-C 2 -C 10 -alkylenediols or by polycondensation of ⁇ , oo-C 2 -C 10 -alkylenediamines
  • An example of the polycondensation of ⁇ 1 -C -hydroxy-C 2 -C 10 -alkyleneamines is the polycondensation of triethanolamine
  • polyethyleneimine (b) has an average molecular weight M w in the range of 600 to 75,000 g / mol, preferably in the range of 800 to 25,000 g / mol.
  • polyethyleneimines (b) are selected from highly branched polyethylenimines (b).
  • Highly branched polyethylenimines (b) are characterized by their high degree of branching (DB).
  • highly branched polyethyleneimines (b) are polyethyleneimines (b) having DB in the range from 0.1 to 0.95, preferably 0.25 to 0.90, more preferably in the range from 0.30 to 0.80 and most preferably at least 0.5.
  • polyethylenimines (b) with a structurally and molecularly uniform structure are considered.
  • polyethylenimine (b) is highly branched polyethyleneimines (homopolymers) having an average molecular weight M w in the range from 600 to 75,000 g / mol, preferably in the range from 800 to 25,000 g / mol.
  • polyethylenimine (b) is a highly branched polyethyleneimine (homopolymer) having an average molecular weight M n of from 500 g / mol to 125,000 g / mol, preferably from 750 g / mol to 100,000 g / mol be selected from dendrimers.
  • polyethylenimine (b) is a polyethylenimine modified with carboxylate groups or alkoxylate groups, in particular a polyethylenimine modified with ethoxylate, propoxylate or acetate by Michael addition of acrylic acid.
  • Shell (B) of particles according to the invention contains
  • the respective compound (s) (a) and cationic (co) polymer (b) correspond to core (A), of the particular particle according to the invention, as well as
  • Shell (B) also contains silicic acid, called silica for short (c), or at least one silicate, also called silicate (c) for short, selected from sodium silicates, potassium silicates and aluminosilicates. Examples are in particular sodium disilicate and sodium metasilicate, aluminosilicates (zeolites) and phyllosilicates.
  • silicic acid (c) is selected from monokeryic acid, diclilic acid, trisilicic acid, metasilicic acid, cyclotric acid and cyclotetraceric acid and mixtures of at least two of the abovementioned silicic acids (d).
  • silicate (c) is selected from those of the formal composition
  • M is selected from potassium, sodium or mixtures of potassium and preferably sodium and x is in the range of 1 to 3.5, preferably in the range of 1, 6 to 2.6 and particularly preferably in the Range from 1.8 to 2.2.
  • silicates of the formula a-Na 2 Si 2 O 5 , ⁇ -Na 2 Si 2 O 5 , and 5-Na 2 Si 2 O 5 .
  • silicate (c) is selected from hydrous silicates wherein water may be physisorbed or chemically bound.
  • silicate (c) in combination with cationic (co) polymer (b) may have a zeta potential> zero.
  • silicate (c) has a zeta potential -i null. In a preferred embodiment of the present invention, silicate (c) in combination with cationic (co) polymer (b) has a zero zeta potential.
  • silicate (c) or silica (c) has a mean primary particle diameter (number average) in the range from 10 to 200 nm, preferably 50 to 100 nm, determinable, for example, by image analysis with the aid of electron microscopy.
  • silicate (c) in the formulation according to the invention is composed of agglomerates of silicate primary particles.
  • the agglomerates mentioned may have a mean diameter (number average) in the range from 0.5 to 100 ⁇ m, preferably from 1 to 20 ⁇ m (determinable, for example, by electron microscopy).
  • core (A) contains neither silica (c) nor silicate (c).
  • core (A) may contain silica (c) or at least one silicate (c), but in significantly less than shell (B), for example in proportions of 10% by weight or less, based on Sum of compound (s) (a) and cationic (co) polymer (b).
  • shell (B) of particles according to the invention comprises polyvinyl alcohol (d), where polyvinyl alcohol in the context of the present invention comprises completely hydrolyzed polyvinyl acetate and substantially, for example at least 95, preferably at least 96, mol% hydrolyzed polyvinyl acetate ,
  • shell (B) of particles according to the invention may contain polyvinyl alcohol (d), for example 0.5 to 5% by weight, based on the solids content of the formulation used according to the invention.
  • polyvinyl alcohol (d) has an average molecular weight M n in the range of 22,500 to 15,000 g / mol, for example up to 40,000 g / mol. In one embodiment of the present invention, polyvinyl alcohol (d) has an average molecular weight M w in the range from 2,000 to 40,000 g / mol. In one embodiment of the present invention, particles according to the invention have a water content in the range from 0.1 to 25% by weight, preferably from 1 to 15% by weight.
  • particles according to the invention on shell (B) are additionally coated with silica (c) or silicate (c), the relevant silica (c) or silicate (c) having an average particle diameter in the range from 1 to 200 ⁇ m, preferably 5 to 150 ⁇ , more preferably 6 to 120 ⁇ and most preferably from 8 to 20 ⁇ (d50), each determined by light scattering according to IS013320-1.
  • Silica (c) is selected from precipitated silicas and fumed silicas.
  • Silica gel (c) is preferably selected from hydrophobized silicic acids, for example from silicic acids which have been rendered hydrophobic by thermal treatment, and from silicas which have been rendered hydrophobic by aftertreatment with aftertreatment agents such as silanes, for example trimethylchlorosilane or dimethyldichlorosilane, or siloxanes which have been rendered hydrophobic.
  • aftertreatment agents such as silanes, for example trimethylchlorosilane or dimethyldichlorosilane, or siloxanes which have been rendered hydrophobic.
  • the after-treatment agent is linked to the silica via at least one chemical bond.
  • silicic acid (c) or silicate (c) is selected from silicas or silicates having a specific surface area (BET) in the range from 30 to 800 m 2 / g.
  • Preferred silica (c) is characterized by a specific surface area of from 25 to 800 m 2 / g, preferably 30-500 m 2 / g, particularly preferably from 150 to 450 m 2 / g (Areameter method ISO 5794-1, Annex D). Hydrophobised silica (c) may have a specific surface area of preferably 75 to 125 m 2 / g, Areameter method ISO 5794-1, Annex D.
  • the tamped density of silica (c) is in the range of 50 to 300 g / l, preferably 75 to 200 g / l and most preferably 90 to 150 g / l (determined according to DIN ISO 787 / 1 1).
  • Silica (c) has the task of at least partially enveloping or at least partially covering particles according to the invention.
  • Particles according to the invention are excellently suited for rinsing dishes and / or kitchen utensils, preferably to rinse them by machine (automatically). Another object of the present invention is therefore the use of particles according to the invention for rinsing dishes and kitchen utensils. Another object of the present invention is the use of particles according to the invention for rinsing articles which have at least one surface made of glass. Particulates according to the invention have a good ability to eliminate water hardness and only a slight tendency to yellow. Furthermore, one observes a very good flowability and a very low tendency to form unwanted particulate matter.
  • particles according to the invention are used for the automatic cleaning of dishes and kitchen utensils, namely they can be used alone or together with other substances, for example together with one or more excipients (f).
  • kitchen utensils are in the context of the present invention, for example, pots, pans and casserole to call, also metal objects such as slotted spoons, roasting and garlic presses.
  • a surface of glass is to be understood as meaning that the object in question has at least one piece of glass which comes into contact with the ambient air and can be contaminated when the object is used.
  • the objects in question may be those which are essentially glassware such as drinking glasses or glass bowls. But it can also be, for example, cover that have individual components of a different material, such as pot lid with edging and handle made of metal or ceramic.
  • Ceramic or preferably glass surface may be decorated, for example colored or printed, or not decorated.
  • glass includes any glass, for example lead glass and in particular soda lime glass, crystal glass and borosilicate glasses.
  • Mechanical cleaning preferably involves rinsing with a dishwashing machine (English: automatic dishwashing).
  • particles according to the invention are used for the automated cleaning of drinking glasses, glass vases and glass vessels for cooking.
  • water having a hardness in the range from 1 to 30 ° dH, preferably from 2 to 25 ° dH, is used for cleaning, German hardness being taken to mean in particular the calcium hardness.
  • particles according to the invention are used for machine cleaning, then, in particular if they have at least one cationic (co) polymer (b), only a very small amount is obtained even with repeated mechanical cleaning of objects which have at least one surface made of glass Tendency to glass corrosion, and even if you clean objects that have at least one glass surface together with heavily soiled cutlery or dishes.
  • the at least one cationic (co) polymer (b) only a very small amount is obtained even with repeated mechanical cleaning of objects which have at least one surface made of glass Tendency to glass corrosion, and even if you clean objects that have at least one glass surface together with heavily soiled cutlery or dishes.
  • the at least one cationic (co) polymer (b) only a very small amount is obtained even with repeated mechanical cleaning of objects which have at least one surface made of glass Tendency to glass corrosion, and even if you clean objects that have at least one glass surface together with heavily soiled cutlery or dishes.
  • particles according to the invention are part of a dishwashing agent, for example a constituent of an automatic dishwashing agent.
  • dishwashing detergents are likewise the subject matter of the present invention.
  • Dishwashing agents according to the invention are preferably solid at room temperature, dishwashing agents according to the invention can be present, for example, as a powder, as tablets or tablets.
  • dishwashing agents according to the invention contain at least one cationic (co) polymer (b), as a constituent of particles according to the invention or as an other constituent.
  • Dishwashing agents according to the invention preferably comprise at least one cationic (co) polymer (b), either as a constituent of particles according to the invention or as an other constituent.
  • dishwashing agents according to the invention contain in the range from 1 to 60% by weight of particles according to the invention, based on the solids content of dishwasher detergent according to the invention, preferably from 5 to 50% by weight.
  • dishwashing agents according to the invention contain a total of from zero to 5% by weight of cationic (co) polymer (b), based on the solids content of dishwashing detergent according to the invention, preferably from 0.001 to 3% by weight, more preferably from 0.01 to 0.5 Weight%.
  • dishwashing agents according to the invention may contain at least one adjuvant (s), for example one or more surfactants, one or more enzymes, one or more builders, in particular phosphorus-free builders, one or more cobuilders, sodium citrate, one or more one or more bleach activators, one or more bleach stabilizers, one or more defoamers, one or more corrosion inhibitors, one or more builders, buffers, dyes, one or more perfumes, one or more organic solvents, one or more tabletting aids, one or more disintegrating agents, one or more thickeners, or one or more solubilizing agents.
  • adjuvant for example one or more surfactants, one or more enzymes, one or more builders, in particular phosphorus-free builders, one or more cobuilders, sodium citrate, one or more one or more bleach activators, one or more bleach stabilizers, one or more defoamers, one or more corrosion inhibitors, one or more builders, buffers, dyes, one or more perfumes, one or more organic solvents, one or
  • surfactants are, in particular, nonionic surfactants and mixtures of anionic or zwitterionic surfactants with nonionic surfactants.
  • Preferred nonionic surfactants are alkoxylated alcohols and alkoxylated fatty alcohols, di- and multiblock copolymers. sate of ethylene oxide and propylene oxide and reaction products of sorbitan with ethylene oxide or propylene oxide, alkyl glycosides and so-called amine oxides.
  • alkoxylated alcohols and alkoxylated fatty alcohols are, for example, compounds of the general formula (I)
  • R 1 is identical or different and selected from linear C 1 -C 10 -alkyl, preferably in each case identical and ethyl and particularly preferably methyl,
  • R 2 selected from Cs-C22-alkyl, for example nC & Hn, n-doFi, n-Ci2H25, nC-uF s), n-Ci6H33
  • R 3 is selected from C 1 -C 10 -alkyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec.
  • neo-pentyl 1, 2-dimethylpropyl, iso-amyl, n-hexyl, iso -hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl or iso-decyl
  • m and n are in the range of zero to 300, the sum of n and m being at least one.
  • m is in the range of 1 to 100 and n is in the range of 0 to 30.
  • Compounds of the general formula (I) may be block copolymers or random copolymers, preference being given to block copolymers.
  • alkoxylated alcohols and alkoxylated fatty alcohols are, for example, compounds of the general formula (II) in which the variables are defined as follows: identical or different and selected from linear C 1 -C 10 -alkyl, preferably in each case identical and ethyl and particularly preferably methyl, R 4 is selected from C 6 -C 20 -alkyl, in particular n-CsH-i, n-doH-i, n-C 12 H 25, n-Ci4H29, n-C 16 H 33, n-
  • a is a number ranging from 1 to 6
  • b is a number ranging from 4 to 20
  • d is a number ranging from 4 to 25.
  • Compounds of general formula (II) may be block or random copolymers , preferred are block copolymers.
  • suitable nonionic surfactants are selected from di- and multiblock copolymers, composed of ethylene oxide and propylene oxide.
  • suitable nonionic surfactants are selected from ethoxylated or propoxylated sorbitan esters.
  • amine oxides or alkyl glycosides are also suitable. An overview of suitable further nonionic surfactants can be found in EP-A 0 851 023 and in DE-A 198 19 187.
  • anionic surfactants are C 8 -C 20 -alkyl sulfates, C 8 -C 20 -alkyl sulfonates and C 8 -C 20 -alkyl ether sulfates having one to six ethylene oxide units per molecule.
  • the formulation used according to the invention may contain in the range from 3 to 20% by weight of surfactant.
  • Dishwashing agents according to the invention may contain one or more enzymes.
  • enzymes are lipases, hydrolases, amylases, proteases, cellulases, esterases, pectins, lactases and peroxidases.
  • Dishwashing agents according to the invention may contain, for example, up to 5% by weight of enzyme, preferably 0.1 to 3% by weight, in each case based on the total solids content of the formulation according to the invention.
  • Dishwashing agents according to the invention may comprise, in addition to sodium citrate, one or more builders, in particular phosphate-free builders.
  • Suitable builders are citric acid and its alkali metal salts, in particular sodium citrate, fatty acid sulfonates, ⁇ -hydroxypropionic acid, alkali malonates, fatty acid sulfonates, alkyl and alkenyl disuccinates, tartaric acid diacetate, tartaric acid monoacetate, oxidized starch, and polymeric builders, for example polycarboxylates and polyaspartic acid , Particularly preferred is sodium citrate.
  • builders of polycarboxylates for example, alkali metal salts of (meth) acrylic acid homo- or
  • (Meth) acrylic acid copolymers are monoethylenically unsaturated dicarboxylic acids such as maleic acid, fumaric acid, maleic anhydride, itaconic acid and citraconic acid.
  • a suitable polymer is in particular polyacrylic acid, which preferably has an average molecular weight M w in the range from 2000 to 40,000 g / mol, preferably 2,000 to 10,000 g / mol, in particular 3,000 to 8,000 g / mol.
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid and / or fumaric acid.
  • monomers selected from the group consisting of monoethylenically unsaturated C 3 -C 10 -mono- or C 4 -C 10 -dicarboxylic acids or their anhydrides such as maleic acid, maleic anhydride, acrylic acid, methacrylic acid, fumaric acid, itaconic acid and citraconic acid with at least a hydrophilic or hydrophobically modified monomer as enumerated below.
  • Suitable hydrophobic monomers are, for example, isobutene, diisobutene, butene, pentene, hexene and styrene, olefins having 10 or more carbon atoms or mixtures thereof, for example 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1 - Eicosene, 1-docoses, 1-tetracoses and 1-hexacoses, C22- ⁇ -olefin, a mixture of C2o-C24- ⁇ -olefins and polyisobutene having an average of 12 to 100 carbon atoms per molecule.
  • Suitable hydrophilic monomers are monomers having sulfonate or phosphonate groups, as well as nonionic monomers having hydroxy function or alkylene oxide groups. Examples which may be mentioned are: allyl alcohol, isoprenol, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, methoxypolybutylene glycol (meth) acrylate, methoxypoly (propylene oxide-co-ethylene oxide) (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, ethoxypolypropylene glycol (meth) acrylate, ethoxypolybutylene glycol (meth) acrylate and ethoxypoly (propylene oxide-co-ethylene oxide) (meth) acrylate.
  • Polyalkylene glycols may contain 3 to 50, in particular 5 to 40 and especially 10 to 30 alkylene oxide units per molecule.
  • Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 3-methacrylamido-2- hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 2-sulfoethyl methacrylate, 3-sulfopropyl methacrylate , Sulfomethacrylamide, sulfomethylmethacrylamide
  • amphoteric polymers may also be present as builders.
  • Dishwashing agents according to the invention may contain, for example, in the range from 10 to 50% by weight, preferably up to 20% by weight, of builder.
  • dishwashing agents according to the invention may contain one or more cobuilders.
  • cobuilders are phosphonates, for example hydroxyalkanephosphonates and aminoalkanephosphonates.
  • hydroxyalkane phosphonates the 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a cobuilder.
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • Preferred aminoalkanephosphonates are ethylenediaminetetra-methylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of the neutral reacting sodium salts, e.g. as hexasodium salt of EDTMP or as hepta- and octa-sodium salt of DTPMP used.
  • Dishwashing agents according to the invention may contain sodium citrate.
  • sodium citrate includes the mono-, the disodium salt, but most preferably designates the trisodium salt.
  • Sodium citrate can be used as anhydrous salt or as a hydrate, for example as a dihydrate.
  • Dishwashing agents according to the invention may contain one or more alkali carriers.
  • Alkaline carriers for example, provide the pH of at least 9 when an alkaline pH is desired.
  • Suitable examples are alkali metal carbonates, alkali metal hydrogencarbonates, alkali metal hydroxides and alkali metal metasilicates.
  • Preferred alkali metal is in each case potassium, particularly preferred is sodium.
  • Dishwashing agents according to the invention may contain one or more bleaching agents.
  • Bleaching agents can be selected from chlorine-free bleaches, also called oxygen bleaches, and chlorine-containing bleaches.
  • oxygen bleaching agents sodium perborate, anhydrous or, for example, as monohydrate or as tetrahydrate or so-called dihydrate, sodium percarbonate, anhydrous or, for example, as monohydrate, furthermore hydrogen peroxide, persulfates, organic chlorine-free peracids such as peroxylauric acid, peroxystearic acid, peroxy-o
  • Naphthoic acid 1, 12-diperoxydodecanedioic acid, perbenzoic acid, peroxylauric acid, 1, 9- Diperoxyazelaic acid, diperoxyisophthalic acid, in each case as the free acid or as the alkali metal salt, in particular as the sodium salt, furthermore sulfonyl peroxyacids and cationic peroxyacids.
  • formulations according to the invention may contain in the range of 0.5 to 15% by weight of oxygen bleach.
  • Chlorine-free bleaching agents are preferably selected from alkali metal percarbonate, alkali metal perborate and alkali metal persulfate.
  • Preferred chlorine-free bleaching agents are selected from sodium perborate, anhydrous or, for example, as monohydrate or as tetrahydrate or so-called dihydrate, sodium percarbonate, anhydrous or, for example, as monohydrate, and sodium persulphate, the term "persulphate" in each case denoting peroxodisulphate
  • Each of the alkali metal salts may also be alkali metal hydrogencarbonate, alkali metal hydrogen perborate and alkali metal hydrogen persulphate, however, the dialkali metal salts are preferred.
  • Suitable chlorine-containing bleaching agents are, for example, 1,3-dichloro-5,5-dimethylhydantoin, N-N-chlorosulfamide, chloramine T, chloramine B, sodium hypochlorite, calcium hypochlorite, magnesium hypochlorite, potassium hypochlorite, potassium dichloroisocyanurate and sodium dichloroisocyanurate.
  • Dishwashing agents according to the invention may contain, for example, in the range from 3 to 10% by weight of chlorine-containing bleach.
  • Dishwashing agents according to the invention may contain one or more bleach catalysts.
  • Bleach catalysts can be selected from bleach-enhancing transition metal salts or transition metal complexes such as manganese, iron, cobalt, ruthenium or molybdenum-salene complexes or carbonyl complexes. Also, manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod
  • Ligands as well as cobalt, iron, copper and ruthenium amine complexes are useful as bleach catalysts.
  • Dishwashing agents according to the invention may contain one or more bleach activators, for example N-methylmorpholinium acetonitrile salts ("MMA salts”), trimethylammonium acetonitrile salts, N-acylimides such as N-nonanoylsuccinimide "1, 5-diacetyl-2,2-dioxo - hexahydro-1,3,5-triazine ("DADHT”) or nitrile quats (trimethylammonium acetonitrile salts).
  • MMA salts N-methylmorpholinium acetonitrile salts
  • DADHT 5-diacetyl-2,2-dioxo - hexahydro-1,3,5-triazine
  • nitrile quats trimethylammonium acetonitrile salts
  • TAED tetraacetylethylenediamine
  • TAED tetraacetylhexylenediamine
  • Dishwashing agents according to the invention may contain one or more corrosion inhibitors.
  • corrosion inhibitors such compounds that inhibit the corrosion of metal.
  • suitable corrosion inhibitors are triazoles, in particular benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles, furthermore phenol derivatives such as, for example, hydroquinone, catechol, hydroxyhydroquinone, gallic acid, phloroglucinol or pyrogallol.
  • dishwashing agents according to the invention contain a total of from 0.1 to 1.5% by weight of corrosion inhibitor.
  • Dishwashing agents according to the invention may contain one or more builders, for example sodium sulphate.
  • Dishwashing agents according to the invention may contain one or more defoamers selected, for example, from silicone oils and paraffin oils.
  • dishwashing agents according to the invention contain a total of from 0.05 to 0.5% by weight defoamer.
  • Dishwashing agents according to the invention may contain phosphonic acid or one or more phosphonic acid derivatives, for example hydroxyethane-1,1-diphosphonic acid.
  • a further subject of the present invention is a process for the production of particles according to the invention, in short also called production process according to the invention.
  • To carry out the preparation process according to the invention it is preferably possible to proceed in such a way that
  • polyvinyl alcohol (d) for example from 0.5 to 5% by weight, based on the solids content of the relevant formulation.
  • Semi-finished products may have a residual moisture in the range of 2 to 20 wt .-%, preferably 2.5 to 10 wt .-%.
  • Semifinished products may, for example, have an average particle diameter (volume average) in the range from 0.1 to 4 mm, preferably 0.5 to 2 mm, particularly preferably 0.8 to 1.6 mm.
  • the semi-finished product (s) are treated with an aqueous solution of silica (c) or silicate (c).
  • an aqueous solution of silicate (c) or silica (c) or, for example, a solution of water glass can be carried out in equipment such as stirrers or mixers.
  • a fluidized bed apparatus for example by introducing compound (a) as granules - with or without (co) polymer (b) - and simultaneously from above with an aqueous solution of silicate (c) or of silica (c) or apply a solution of sodium silicate.
  • aqueous solution of silicate (c) or of silica (c) or apply a solution of sodium silicate.
  • the air stream may, for example, have a temperature in the range of 70 to 150 ° C, preferably 75 to 100 ° C.
  • Particles according to the invention which can be post-processed, for example with the aid of a cyclone to separate fine dust, or with the aid of a sieve or more sieves to separate agglomerates and / or fine dust.
  • Dishwashing agents according to the invention can be produced using particles according to the invention by mixing particles according to the invention with at least one adjuvant (s) and optionally carrying out a shaping step, for example pressing or tableting.
  • a shaping step for example pressing or tableting.
  • Semi-finished products were prepared by spray-drying in each case compound (a.1) or (a.2).
  • the supply air temperature was 185 ° C.
  • spray granules with a mean diameter (volume average) of 1, 0 mm which were used as semifinished products. They had a residual moisture of 10 wt .-%.
  • the semifinished product in question was placed in a fluidized bed apparatus and charged at a supply air temperature of 90 ° C with a 25 wt .-% water glass solution with a SiO 2 module (molar ratio of Na 2 O 5 SiO 2) according to Table 1.
  • the water content in Table 1 refers to particles according to the invention.
  • the storage stability test was carried out as follows: 5.0 g ( ⁇ 0.1 mg) were weighed into Petri dishes and placed in a climatic chamber (HSK 359/20 (Heraeus), adjusted to 37 ° C., 78 % relative humidity After a certain time interval (see Table 2), one Petri dish was taken and the weight was determined to determine the weight gain (room temperature, current humidity) After the weight had been determined, the Petri dish was immediately returned to the climatic chamber.
  • HSK 359/20 Heraeus
  • Table 2 The values in Table 2 are based on duplicate determinations. These differed by less than 0.5 wt .-% from each other.
  • Mi weight of powder in g
  • the storage test with sodium percarbonate was carried out as follows: each weighed 5.0 g ( ⁇ 0.01 g) of the sample to be tested and 2.5 g of sodium percarbonate (2 Na2C03-3 H2O2) in plastic cups, this locked with Screw caps and homogenized by shaking for several minutes.

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Abstract

L'invention concerne des particules contenant (A) un noyau renfermant (a) au moins un composé choisi parmi aminocarboxylates et polyaminocarboxylates, (b) au moins un (co)polymère cationique, (B) une enveloppe renfermant (a) au moins un composé (a), (b) au moins un (co)polymère cationique correspondant respectivement au composé (a) et au (co)polymère cationique (b) du noyau (A), et (c) de l'acide silicique ou du silicate dans une concentration de 50 à 99,9 % en poids par rapport à la somme du ou des composé(s) (a) et du (co)polymère (b).
PCT/EP2013/067774 2012-09-07 2013-08-28 Particules, procédé de fabrication et utilisation WO2014037255A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020200836A1 (fr) * 2019-04-01 2020-10-08 Basf Se Procédé pour la fabrication d'un granulé ou d'une poudre
CN112654693A (zh) * 2018-09-14 2021-04-13 雷克特本克斯尔菲尼施公司 用于洗涤剂组合物的颗粒物

Citations (5)

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Publication number Priority date Publication date Assignee Title
EP0851023A2 (fr) 1996-12-23 1998-07-01 Unilever N.V. Tablettes pour machine à laver la vaisselle contenant un peracide
DE19819187A1 (de) 1998-04-30 1999-11-11 Henkel Kgaa Festes maschinelles Geschirrspülmittel mit Phosphat und kristallinen schichtförmigen Silikaten
WO2010020765A1 (fr) 2008-08-16 2010-02-25 Reckitt Benckiser N.V. Composition
EP2392638A1 (fr) 2010-06-04 2011-12-07 Dalli-Werke GmbH & Co. KG Composition particulaire faiblement hygroscopique comprenant un ou plusieurs composés chélateurs d'aminopolycarboxylate
WO2012000915A1 (fr) * 2010-06-28 2012-01-05 Akzo Nobel Chemicals International B.V. Particules revêtues contenant un agent chélatant à base de n,n-diacétate d'acide glutamique

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0851023A2 (fr) 1996-12-23 1998-07-01 Unilever N.V. Tablettes pour machine à laver la vaisselle contenant un peracide
DE19819187A1 (de) 1998-04-30 1999-11-11 Henkel Kgaa Festes maschinelles Geschirrspülmittel mit Phosphat und kristallinen schichtförmigen Silikaten
WO2010020765A1 (fr) 2008-08-16 2010-02-25 Reckitt Benckiser N.V. Composition
EP2392638A1 (fr) 2010-06-04 2011-12-07 Dalli-Werke GmbH & Co. KG Composition particulaire faiblement hygroscopique comprenant un ou plusieurs composés chélateurs d'aminopolycarboxylate
WO2012000915A1 (fr) * 2010-06-28 2012-01-05 Akzo Nobel Chemicals International B.V. Particules revêtues contenant un agent chélatant à base de n,n-diacétate d'acide glutamique

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112654693A (zh) * 2018-09-14 2021-04-13 雷克特本克斯尔菲尼施公司 用于洗涤剂组合物的颗粒物
US11746311B2 (en) 2018-09-14 2023-09-05 Reckitt Benckiser Finish B.V. Granulate for detergent composition comprising nitrogen-containing builders
WO2020200836A1 (fr) * 2019-04-01 2020-10-08 Basf Se Procédé pour la fabrication d'un granulé ou d'une poudre
CN113710789A (zh) * 2019-04-01 2021-11-26 巴斯夫欧洲公司 制造颗粒或粉末的方法

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