EP3138895B1 - Particules, leur utilisation comme detergent pour lave-vaisselle et leur fabrication - Google Patents

Particules, leur utilisation comme detergent pour lave-vaisselle et leur fabrication Download PDF

Info

Publication number
EP3138895B1
EP3138895B1 EP16185582.0A EP16185582A EP3138895B1 EP 3138895 B1 EP3138895 B1 EP 3138895B1 EP 16185582 A EP16185582 A EP 16185582A EP 3138895 B1 EP3138895 B1 EP 3138895B1
Authority
EP
European Patent Office
Prior art keywords
acid
particles
additive
range
weight
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.)
Not-in-force
Application number
EP16185582.0A
Other languages
German (de)
English (en)
Other versions
EP3138895A1 (fr
Inventor
Frank Jaekel
Markus Hartmann
Sven Bensmann
Frank-Peter Lang
Lothar Seidemann
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.)
BASF SE
Original Assignee
BASF SE
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 filed Critical BASF SE
Publication of EP3138895A1 publication Critical patent/EP3138895A1/fr
Application granted granted Critical
Publication of EP3138895B1 publication Critical patent/EP3138895B1/fr
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • 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
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • 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
    • C11D3/16—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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3245—Aminoacids

Definitions

  • the present invention relates to a process for the preparation of particles according to the invention and their use as or for the production of solid dishwashing detergents, in particular dishwasher detergents for automatic dishwashing.
  • aminopolycarboxylates and polyaminopolycarboxylates are recommended, for example the alkali metal salts of methylglycinediacetic acid (MGDA) or glutamic acid diacetic acid (GLDA).
  • MGDA methylglycinediacetic acid
  • GLDA glutamic acid diacetic acid
  • aminopolycarboxylates and polyaminopolycarboxylates, and in particular MGDA and GLDA are hygroscopic, the processing properties leave much to be desired. For example, many granules of MGDA are difficult to process into tablets.
  • aminopolycarboxylates and polyaminopolycarboxylates in application forms that can be tabletted particularly well.
  • a further object was to provide a process by which it is possible to obtain readily tablettable aminopolycarboxylates and polyaminopolycarboxylates, and there was also the object of providing use for the new uses of the aminopolycarboxylates and polyaminopolycarboxylates in question.
  • Particulates according to the invention can be present as powders, granules or pellets.
  • Particular preference is given to particles according to the invention as granules with an average particle diameter (D) in the range from 100 to 800 ⁇ m.
  • Such particles of the invention can be processed particularly well to tablets.
  • aminopolycarboxylates are z.
  • NTA nitrilotriacetic acid
  • EDTA ethylenediaminetetraacetic acid
  • DTPA
  • Preferred aminopolycarboxylates (A) are salts of MGDA and GLDA, very particularly preferred are salts of MGDA and even more preferably dialkali metal salts and trialkali metal salts of MGDA and mixtures of dialkali metal salts and trialkali metal salts of MGDA.
  • salts are the ammonium salts and the alkali metal salts, for example sodium salts and potassium salts, and mixtures of sodium and potassium salts.
  • Preferred alkali metal salts are each sodium salts.
  • aminopolycarboxylates (A) may contain small amounts of alkaline earth metal salts, for example Mg 2+ or Ca 2+ salts, or Fe 3+ salts or the respective complexes as impurities, for example 0.01 to 0.5, due to the production process mol%, based on the anion.
  • impurities for example 0.01 to 0.5, due to the production process mol%, based on the anion.
  • Such minor impurities are not explicitly mentioned in the context of the present invention.
  • aminopolycarboxylate (A) is used as the aminopolycarboxylic acid completely neutralized with alkali.
  • Preferred examples are the trisodium salt of MGDA and the tripotassium salt of MGDA, the tetrasodium salt of GLDA and the tetrapotassium salt of GLDA and mixed sodium potassium salts of MGDA and GLDA, in which the underlying aminopolycarboxylic acid is in each case completely neutralized.
  • aminopolycarboxylate (A) is used as a mixture of fully alkoxylated and partially alkali neutralized aminopolycarboxylic acid.
  • Preferred examples are mixtures of dialkali metal salt and trialkali metal salt of MGDA, for example in a molar ratio in the range of 1:10 to 10: 1, and mixtures of trialkali metal salt and tetraalkali metal salt of GLDA, for example in a molar ratio in the range of 1:10 to 10: 1.
  • amine polycarboxylates (A) are based on aminopolycarboxylic acids which may be present in the form of the racemate or as L- or D-enantiomer or in partially racemized form.
  • the aminopolycarboxylate (A) used is a racemic alkali metal salt of MGDA.
  • the aminopolycarboxylate (A) used is an alkali metal salt of MGDA-for example the trisodium salt or the tripotassium salt-in which predominantly the L-enantiomer is present, for example with an enantiomeric excess (ee) in the range from 5 to 75%. , preferably 10 to 50%.
  • the aminopolycarboxylate (A) used is an alkali metal salt of GLDA, for example the tetrantrium salt or the tetrapotassium salt, in which predominantly the L-enantiomer is present, for example with an enantiomeric excess (ee) in the range from 5 to 95%, preferably 50 to 90%.
  • the aminopolycarboxylate used is a mixture of two different aminopolycarboxylates, for example alkali metal salts of MGDA and GLDA, for example in a molar ratio in the range from 50: 1 to 4: 1.
  • Particulates according to the invention also contain (B) at least one anionic homo- or copolymer.
  • anionic (co) polymers (B) are understood as meaning those organic homo- or copolymers which carry at least one carboxylic acid group or at least one sulfonic acid group per molecule.
  • Preferred anionic (co) polymers (B) are those which carry at least one carboxylic acid group or at least one sulfonic acid group per monomer unit.
  • the carboxylic acid group (s) or sulfonic acid group (s) may be present as free acids or preferably in partially or completely neutralized form with alkali or ammonium.
  • Preferred alkali for neutralization is sodium or potassium or mixtures of sodium and potassium.
  • anionic (co) polymer (B) is selected from poly (meth) acrylic acids which are partially or completely neutralized with alkali.
  • anionic copolymer (B) is selected from random or block copolymers of acrylic acid and maleic anhydride and random copolymers of (meth) acrylic acid with one or more radically polymerizable sulfonic acids, for example 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
  • anionic (co) polymer (B) has an average molecular weight M w in the range of 1,000 to 1,000,000 g / mol, preferably 2,000 to 50,000 g / mol.
  • the average molecular weight M w is based on the free acid.
  • Aminopolycarboxylat (A) and (co) polymer (B) are molecularly dispersed mixed together.
  • molecularly dispersedly mixed means that all or a majority of the particles, for example at least 80%, of a representative sample comprise at least 90% by weight of aminopolycarboxylate (A) and 0.01 to 2% by weight of (co) polymer (B). contain.
  • molecularly dispersed mixed with one another means that particles according to the invention have over their cross-section a substantially or even exactly uniform composition with respect to aminopolycarboxylate (A) and (co) polymer (B).
  • Particulates according to the invention furthermore have at least one additive (C), with additive (C) being predominantly on the outer surface of the particles according to the invention.
  • Mainly means that at least 75% of the additive (C) is on the outer surface of particles of the invention.
  • the remaining proportions of additive (C) can be present, for example, in particles according to the invention or as separate particles.
  • the morphology can be determined, for example, by light microscopy.
  • Particles of the invention with additive (C) are preferably completely or incompletely encased.
  • Additives (C) are selected from pyrogenic silicas and precipitated silicas.
  • Pyrogenic silicic acids are obtained by high-temperature flame hydrolysis of silicon tetrachloride in the oxyhydrogen flame.
  • Precipitated silicas are wet-chemically made from alkali silicate solutions obtained by addition of acids. Fumed silicas and precipitated silicas are not crystalline, but of amorphous structure.
  • Examples of pyrogenic silicic acids are the Aerosil brands® (from Evonik), in particular Aerosil® 200.
  • Examples of precipitated silicas are the Sipernat brands® (Evonik), in particular Sipernat® 320, Sipernat® 320 DS, Sipernat® 360, Sipernat® 500 LS, Sipernat® 2200, Sipernat® 22, Sipernat® 22 S, Sipernat® 22 LS, Sipernat® 50, Sipernat® 50 S, Sipernat® C 600, Sipernat® C 630, Sipernat® 820 A and Sipernat® 880 ,
  • the abovementioned silicic acids can be used as hydrophilic silicic acids or as hydrophobically modified silicic acids.
  • hydrophobically modified silicas are, for example, Sipernat® D 10, Sipernat® D 17 and Aerosil® R 812 and R 972.
  • Hydrophobically modified, precipitated silicas and hydrophobically modified fumed silicas are very particularly preferred additives (C).
  • Hydrophobically modified silicas are obtainable by aftertreatment of silicic acids with after-treatment agents such as silanes, for example trimethylchlorosilane or dimethyldichlorosilane, or with siloxanes.
  • after-treatment agents such as silanes, for example trimethylchlorosilane or dimethyldichlorosilane, or with siloxanes.
  • the aftertreatment agent is linked to the silica via a chemical bond.
  • additive (C) is selected from silicas having a specific surface area (BET) in the range of 30 to 800 m 2 / g.
  • Preferred precipitated silicas are characterized by a specific surface area of from 25 to 800 m 2 / g, preferably from 30 to 500 m 2 / g, particularly preferably from 150 to 450 m 2 / g, determined by means of the Areameter method, ISO 5794-1 , Annex D.
  • Hydrophobically modified precipitated silicas preferably have a specific surface area of 75 to 125 m 2 / g, Areameter method ISO 5794-1, Annex D.
  • the tamped density of precipitated silicas used is in the range from 50 to 300 g / l, preferably 75 to 200 g / l and very particularly preferably 90 to 150 g / l (determination according to DIN ISO 787/11).
  • additive (C) preferably has an average particle diameter in the range from 1 to 200 .mu.m, preferably from 5 to 150 .mu.m, more preferably from 6 to 120 .mu.m and most preferably from 8 to 20 .mu.m (D50), each determined by light scattering according to ISO13320-1: 1999.
  • Additive (C) in the form of fumed silicic acids preferably has a specific surface area in the range of 100 to 400 m 2 / g and average particle diameter of 1 nm to 50 nm, based on the primary particles.
  • Primary particles may be fused together or aggregates or agglomerates.
  • the tamped density of fumed silicas is preferably in the range of 50 to 150 g / l.
  • hydrophobically modified pyrogenic silicas having a specific surface area in the range of 100 to 400 m 2 / g and an average particle diameter of 1 nm to 50 nm are selected.
  • additive (C) has a pH in the range of 3 to 7.
  • the pH of additive (C) can be determined, for example, analogously to ISO 787-9: 1981.
  • Additive (C) may contain metal ions such as Ca 2+ , Mg 2+ , Al 3+ or Fe 3+ in very small amounts, for example in each case ⁇ 6, preferably ⁇ 5% by weight, preferably less than 3% by weight, especially preferably less than 2 wt .-% and particularly preferably less than 1.5 wt .-% based on the total weight of the respective silica and determined as the oxide. In one embodiment, at least 0.001% by weight each of the above-mentioned metal ions, based on the total weight of the respective silica and determined as oxide, may be present.
  • metal ions such as Ca 2+ , Mg 2+ , Al 3+ or Fe 3+ in very small amounts, for example in each case ⁇ 6, preferably ⁇ 5% by weight, preferably less than 3% by weight, especially preferably less than 2 wt .-% and particularly preferably less than 1.5 wt .-% based on the total weight of the respective silica and determined as the oxide.
  • additive (C) is selected from fumed silicas
  • the content of metal ions such as Ca 2+ , Mg 2+ , Al 3+ or Fe 3+ , at max. 0.05 wt .-%, based on the total weight of the respective silica and determined as the oxide, and in the case of precipitated silicas at max. 1% by weight (calcined substance, 2 hours at 1000 ° C.).
  • metal ions such as Ca 2+ , Mg 2+ , Al 3+ or Fe 3+
  • the Na content determined as Na 2 O (ISO 3262-18), at ⁇ 1.5 wt .-%. Crystalline silicates, phyllosilicates and zeolites are not among the preferred additives (C).
  • Contain particles according to the invention at least 90% by weight of complexing agent (A), preferably 94.5 to 97.95% by weight, 0.1 to 9 wt .-% of anionic homo- or copolymer (B), and particularly preferably 1 to 5 wt .-%, and in the range from 1 to 10% by weight of additive (C), preferably from 2 to 5% by weight, in each case based on the active ingredient content of total particles.
  • A complexing agent
  • B anionic homo- or copolymer
  • additive additive
  • Particulates according to the invention may contain water, for example residual moisture and, in particular, water of crystallization of complexing agent (A). Such water is not taken into account in the determination of the ingredients. Particulates according to the invention can furthermore contain impurities which originate from the synthesis of complexing agent (A). Such impurities are also not taken into account in the determination of the ingredients.
  • Particulates according to the invention can be processed very well to form solid dishwashing detergents, for example to powders and in particular to those which are present in the form of so-called unit doses, for example in the form of tablets.
  • Another aspect of the present invention therefore relates to the use of particles according to the invention for the production of solid dishwashing detergents.
  • a further aspect of the present invention relates to a process, also called formulation process according to the invention in the context of the present invention, for the production of solid dishwashing detergents, for example tablets, using particles according to the invention.
  • a further aspect of the present invention relates to solid dishwashing detergents, in the context of the present invention also dishwasher detergents according to the invention, comprising particles according to the invention and preferably at least one nonionic surfactant.
  • dishwashing compositions according to the invention are designed as tablets.
  • solid is understood to mean “solid at room temperature”.
  • Tablets within the scope of the present invention may be from 5 to 50 g, preferably from 10 to 25 g, and more preferably from 15 to 22.5 g.
  • Tablets generally have a base which may be triangular, quadrangular, in particular rectangular or square, pentagonal or hexagonal, or which is oval or preferably circular, or which may be angular with rounded corners. Tablets have different thicknesses at different locations, or preferably the same at all points. For example, tablets may have a recess in one location and a compartment fitted into the recess containing ingredients to be separated from the other ingredients during storage.
  • Dishwashing agents according to the invention are preferably free of phosphates and polyphosphates, with hydrogen phosphates being subsumed, for example free from trisodium phosphate, pentasodium tripolyphosphate and hexasodium metaphosphate.
  • "free from”, in the context of phosphates and polyphosphates is understood to mean that the total content of phosphate and polyphosphate ranges from 10 ppm to 2% by weight, preferably to 0.2% by weight. lies, determined by gravimetry.
  • Dishwashing agents according to the invention may contain further constituents. Examples include zinc salts, bismuth salts, builders, bleach, or other ingredients.
  • Zinc salts can be selected from water-soluble and non-water-soluble zinc salts.
  • zinc salts which are not water-soluble and which have a solubility of 0.1 g / l or less in distilled water at 25 ° C. Accordingly, zinc salts which have a higher water solubility are referred to in the context of the present invention as water-soluble zinc salts.
  • zinc salt is selected from zinc benzoate, zinc gluconate, zinc lactate, zinc formate, ZnCl 2 , ZnSO 4 , zinc acetate, zinc citrate, Zn (NO 3 ) 2 , Zn (CH 3 SO 3 ) 2 and zinc gallate, ZnCl 2 , ZnSO 4 , zinc acetate, zinc citrate, Zn (NO 3 ) 2 , Zn (CH 3 SO 3 ) 2 and zinc gallate are preferred.
  • zinc salt is selected from ZnO, ZnO ⁇ aq, Zn (OH) 2 and ZnCO 3 .
  • ZnO ⁇ aq is preferred.
  • zinc salt is selected from zinc oxides having an average particle diameter (weight average) in the range of 10 nm to 100 ⁇ m.
  • the cation in zinc salt can be complexed, for example, complexed with ammonia ligands or water ligands, and in particular be present hydrated.
  • ligands are usually omitted in the context of the present invention, if they are water ligands.
  • zinc salt can be converted.
  • Zinc salt is present in dishwashing compositions according to the invention preferably in the form of particles which have, for example, a mean diameter (number average) in the range from 10 nm to 100 .mu.m, preferably 100 nm to 5 .mu.m, determined for example by X-ray scattering.
  • dishwashing detergent according to the invention contains one or more bleaching agents (D), for example one or more oxygen bleaching agents or one or more chlorine-containing bleaching agents.
  • D bleaching agents
  • formulations according to the invention may contain from 0.5 to 15% by weight of bleach (D).
  • oxygen bleaching agents are sodium perborate, anhydrous or, for example, as monohydrate or as tetrahydrate or so-called dihydrate, sodium percarbonate, 2Na 2 CO 3 .3H 2 O 2 , anhydrous or, for example, as monohydrate, hydrogen peroxide, persulphates, organic peracids such as peroxylauric acid, peroxystearic acid, Peroxy- ⁇ -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.
  • organic peracids such as peroxylauric acid, peroxystearic acid, Peroxy- ⁇ -naphthoic acid, 1,12-diperoxyd
  • Dishwashing agents according to the invention may contain, for example, in the range from 0.5 to 15% by weight of oxygen bleach.
  • Suitable chlorine-containing bleaching agents are, for example, 1,3-dichloro-5,5-dimethylhydantoin, 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. Because of corrosion problems dishwashing agents according to the invention preferably contain sodium percarbonate, but no chlorine bleach.
  • dishwashing detergent according to the invention may comprise further ingredients (E), for example one or more surfactants, one or more enzymes, one or more builders, in particular phosphorus-free builders, one or more cobuilders, one or more alkali carriers, one or more alkali carriers a plurality of bleach catalysts, 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 tableting aids, one or more several disintegrating agents, one or more thickeners, or one or more solubilizing agents.
  • surfactants for example one or more surfactants, one or more enzymes, one or more builders, in particular phosphorus-free builders, one or more cobuilders, one or more alkali carriers, one or more alkali carriers a plurality of bleach catalysts, one or more bleach activators, one or more bleach stabilizers, one or more defoamers, 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 of ethylene oxide and propylene oxide and reaction products of sorbitan with ethylene oxide or propylene oxide, alkyl glycosides and so-called amine oxides.
  • these may be block copolymers or random copolymers, preference being given to block copolymers.
  • These compounds of the general formula (III) may be block copolymers or random copolymers, block copolymers are preferred.
  • (AO) x is (CH 2 CH 2 O) x1 , where x1 is in the range of 1 to 50.
  • (AO) x is selected from - (CH 2 CH 2 O) x2 - (CH 2 CH (CH 3) -O) x3, and - (CH 2 CH 2 O) x2 - (CH (CH 3 ) CH 2 -O) x 3 where x 2 and x 3 may be the same or different and range from 1 to 30.
  • (AO) x is selected from - (CH 2 CH 2 O) x4 where x4 is in the range of 10 to 50, AO is EO, and R 6 and R 7 are independently selected from C 8 -C 14 alkyl.
  • x or x1 or x2 and x3 or x4 stands for average values, with a number average being preferred. Accordingly, x or x1 or x2 or x3 or x4, if present, may be a non-integer, although of course in a particular molecule only whole AO units may be.
  • 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.
  • 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.
  • dishwashing detergent 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, pectinases, lactases and peroxidases.
  • Dishwashing agents according to the invention may contain, for example, up to 5% by weight of enzyme, preferably from 0.1 to 3% by weight, based in each case on the total solids content of the dishwashing detergent according to the invention.
  • Dishwashing agents according to the invention may contain one or more builders, in particular phosphate-free builders.
  • suitable builders are silicates, in particular sodium disilicate and sodium metasilicate, zeolites, sheet silicates, especially those of the formula ⁇ -Na 2 Si 2 O 5 , ⁇ -Na 2 Si 2 O 5 , and ⁇ -Na 2 Si 2 O 5 , furthermore citric acid and their alkali metal salts, succinic acid and its alkali metal salts, 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 such as polycarboxylates and polyaspartic acid.
  • builders of polycarboxylates are selected, for example, alkali metal salts of (meth) acrylic acid homo- or (meth) acrylic acid copolymers.
  • Suitable comonomers 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.
  • 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-hexadecene and 1-octadecene.
  • Suitable hydrophilic monomers are monomers having sulfonate or phosphonate groups, as well as nonionic monomers having hydroxy function or alkylene oxide groups. Examples include: allyl alcohol, isoprenol, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, methoxypolybutylene glycol (meth) acrylate, methoxypoly (propylene oxide-coethylene oxide) (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, ethoxypolypropylene glycol (meth) acrylate, ethoxypolybutylene glycol (meth) acrylate and ethoxypoly (propylene oxide-co-ethylene oxide) (meth) acrylate.
  • the polyalkylene glycols contain 3 to 50, in particular 5 to 40 and especially 10 to 30 alkylene oxide units.
  • Particularly preferred sulfonic acid-containing monomers 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 and salt
  • Particularly preferred phosphonate group-containing monomers are the vinylphosphonic acid and its salts.
  • amphoteric polymers can also be used 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 compositions according to the invention may contain one or more co-builders.
  • co-builders are phosphonates, for example hydroxyalkane phosphonates and aminoalkane phosphonates.
  • hydroxyalkane phosphonates 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder.
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • Preferred aminoalkanephosphonates are ethylenediaminetetra-methylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably used in the form of the neutrally reacting sodium salts, for example as the hexasodium salt of EDTMP or as the hepta- and octa-sodium salt of DTPMP.
  • 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 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 manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes.
  • Manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands and cobalt, iron, copper and ruthenium-amine complexes can also be used 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-nonanoyl succinimide, 1,5-diacetyl-2,2-dioxohexahydro-1,3 , 5-triazine (“DADHT”) or nitrile quats (trimethylammonium acetonitrile salts).
  • MMA salts N-methylmorpholinium acetonitrile salts
  • DADHT 1,5-diacetyl-2,2-dioxohexahydro-1,3
  • DADHT 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 comprise one or more acids, for example methanesulfonic acid.
  • Dishwashing agents according to the invention show very good rinsing properties.
  • the production process according to the invention comprises several steps.
  • a first step complexing agent (A) and (co) polymer (B) are mixed together. You can mix complexing agent (A) and (co) polymer (B) dry together.
  • Mixing sets the desired ratio of complexing agent (A) and (co) polymer (B). For example, one can use a weight ratio of complexing agent (A) to (co) polymer (B) in the range of 45: 1 to 9900 to 1.
  • water is removed by spray drying, in another by spray granulation.
  • an aqueous suspension or, preferably, an aqueous solution of complexing agent (A) and (co) polymer (B) can be fed into a spray tower with a hot gas stream, for example hot nitrogen or preferably hot air, and thereby sprayed into droplets
  • "Hot" means at least 120 ° C, preferably at least 125 ° C.
  • the hot gas stream should not exceed a temperature of 450 ° C, preferably at most 220 ° C, measured in each case at the beginning of the spray drying, ie at the inlet.
  • the droplets thus produced preferably have an average diameter in the range of 10 to 550 ⁇ m, preferably 20 to 180 ⁇ m, and more preferably 30 to 100 ⁇ m.
  • an aqueous suspension or preferably an aqueous solution of complexing agent (A) and (co) polymer (B) with a hot gas stream for example with hot nitrogen or preferably with hot air, on a fluidized bed of particles, such as complexing agent (A) or of complexing agent (A) and (co) polymer (B), spray.
  • a hot gas stream for example with hot nitrogen or preferably with hot air
  • the hot gas stream should not exceed a temperature of 350 ° C, preferably at most 220 ° C, measured at the beginning of the spray granulation, ie at the inlet.
  • the droplets thus produced preferably have an average diameter in the range of 10 to 550 ⁇ m, preferably 20 to 180 ⁇ m, and more preferably 30 to 100 ⁇ m.
  • water evaporates.
  • the droplets containing complexing agent (A) and (co) polymer (B) allow the solid, ie molecularly disperse mixture of complexing agent (A) and (co) polymer (B), to grow on particles already present in the granulator.
  • water as it was present when mixing complexing agent (A) and (co) polymer (B), is largely removed.
  • substantially removed is meant that one obtains particles which may have a residual moisture, for example in the range of 1 to 20 wt .-%, but preferably not more.
  • the particles - ie powder or granules or pellets - are free-flowing powders that leave a dry impression on the unaided eye.
  • the particles thus obtainable are mixed with additive (C), in the dry state.
  • the mixing process can be used in the usual mixing units, such.
  • drum mixer V-Blender, tumble or Turbula mixer
  • cone mixer eg Nauta mixer
  • PflugscharMischer Liödige mixer
  • high-shear mixer Diosna mixer
  • intensive mixer fast mixer Esirich Mixer
  • the mixing process takes place in mixers that exert low shear forces on the mix, such.
  • tumble mixer cone mixer and ploughshare mixer.
  • particles of complexing agent (A) and (co) polymer (B) are added and then additive (C) is added followed by mixing.
  • additive (C) is added followed by mixing.
  • So z For example, for the production of 100 g of the particles according to the invention in a Turbula mixer, a mixing time of 3 minutes is completely sufficient.
  • additive (C) can advantageously be obtained separately from the aqueous solution of complexing agent (A) and (co) polymer (B) directly meter into the spray tower.
  • Possible locations for metering are the upper end of the spray dryer, a metering connection via a sight glass or metering via the hot gas stream. The same applies in principle for a spray granulation.
  • a sieving step can be connected to remove coarse agglomerated particles containing complexing agent (A) and (co) polymer (B) and additive (C) or coarse particles derived from additive (C).
  • a sieve with a mesh size of 1200 to 2100 ⁇ m, preferably 1300 to 1500 ⁇ m. They can be processed excellently to solid dishwashing detergents and in particular to solid dishwashing detergents in the form of tablets.
  • a further aspect of the present invention relates to a process for the preparation of solid dishwashing detergents in the form of tablets, also referred to in the context of the present invention as tabletting process according to the invention.
  • the tabletting process according to the invention can be carried out by mixing particles according to the invention with at least one nonionic surfactant and optionally one or more further substances and then compressing them into tablets.
  • suitable nonionic surfactants and other substances such as builders, enzymes are enumerated above.
  • Particularly preferred examples of nonionic surfactants are hydroxy mixed ethers, for example hydroxy mixed ethers of the general formula (IV).
  • the tabletting process according to the invention can be carried out as a direct tabletting process, that is to say without tabletting excipients, or with the aid of one or more tabletting excipients. It is preferred to carry out the tabletting process according to the invention in rooms which have a suitably low relative humidity, for example up to 50%.
  • these conditions may be necessary or advantageous, for example, in the case of high air humidity of the outside air or high hygroscopicity of individual components
  • the tableting process according to the invention is preferably carried out with a tablet press.
  • Small quantities of tablets can be produced by means of a manually operated tablet press.
  • Tablet presses suitable for large numbers are rotary tablet presses, roller tablet presses and eccentric presses.
  • first portioned according to the invention dishwashing detergent and then pressed it.
  • suitable are contact pressures in the range of 50 to 500 MPa.
  • Tablets prepared according to the invention have little tendency for tablet errors such as sticking or lidding.
  • the term "gluing” generally refers to the gluing of the tablet mass to the pressing surfaces of the punches and not to the gluing of the tablet to the die wall, i. the adhesion outweighs the cohesion.
  • lidding dissolves after compaction still in the die or after or at the ejection of the compact from the fracture point convexly curved cover layer. It can even split the whole tablet in layers.
  • causes of capping are radial pressures acting on the tablet by the die, an inhomogeneous distribution of porosity and residual stresses in the tablet, and the elastic retraction of the particles and the entire tablet during ejection.
  • tablets prepared according to the invention rapidly dissolve in water.
  • the spray granulator used for laboratory purposes was a cylindrical vessel with perforated base plate, diameter 148 mm, upper base area: 0.017 m 2 , height 40 cm, with a conical insert, inner surface 0.000785 m 2 .
  • 1 kg granules of MGDA trisodium salt were placed, diameters ranging from 350 ⁇ m to 1.2 mm.
  • a fluidized bed was created by passing nitrogen at a temperature of 150 ° C through the bottom plate, amount: 42 Nm 3 nitrogen / h.
  • Nl, Nm 3 standard liter or standard cubic meter, liter or cubic meter at 1 bar and 20 ° C
  • the coarse fraction was ground using a hammer mill (Kinetatica Polymix PX-MFL 90D) at 4000 rpm (revolutions per minute), 2 mm mesh
  • the resulting powder was mixed with the fines and then returned to the spray granulator
  • the stationary state was reached for 2 hours and the granules had a residual moisture content of 10.5 to 11%.
  • All percentages are by weight and refer to solids content. All particles (according to the invention or comparison particles) each had a mean diameter of 600 microns. Fines and chunks were removed by sieving, as described above. The residual moisture was 13% each, determined one hour after production.
  • a total of 470 grams of base mix 1 or 2 were placed in a laboratory mixer Somakon MP-M Somakon and premixed dry at a temperature of 60 ° C with a mixer speed of 600 rev / min and with a mixing time of 10 minutes.
  • a mixing element was a mixing tool on the container bottom. Through the use of the counter-rotating tool on the container lid and by a scraping plate on the container wall, the required mixing quality was achieved.
  • Table 4 Composition of dishwashing compositions according to the invention and comparative dishwashing detergents
  • Dishwashing detergent according to Table 3 was tabletted as follows. For each dishwashing detergent, 10 tablets each were measured with respect to their height and breaking strength using the tablet tester WHT 2 from Pharmatest, Hainburg. The average tablet height was 5 mm each. As observed by visual inspection, in the case of using base mixtures containing particles of the present invention, good tablet strength was achieved and there were no tabletting errors. When using base blends containing comparative particles, the number of tableting errors was significantly higher.
  • the dissolution time was determined as follows: A tablet was placed in a container having a diameter of 65 mm and a volume of 800 ml and dissolved in 600 ml of water with the aid of a propeller stirrer at a constant rotational speed. The time was measured until the refractive index of the solution became constant and visually no solid particles were visible.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)

Claims (12)

  1. Particules, contenant :
    (A) au total au moins 90 % en poids de complexants, choisis parmi les aminopolycarboxylates,
    (B) au total dans la plage allant de 0,1 à 9 % en poids d'au moins un homo- ou copolymère anionique et
    (C) au total dans la plage allant de 1 à 10 % en poids d'au moins un additif, choisi parmi les silices précipitées et les silices pyrogénées,
    à chaque fois par rapport à la teneur en agents actifs de la particule totale,
    le (co)polymère (B) et l'aminopolycarboxylate (A) étant mélangés l'un avec l'autre sous forme dispersée moléculairement et l'additif (C) se trouvant essentiellement sur la surface extérieure des particules.
  2. Particules selon la revendication 1, caractérisées en ce que l'homo- ou copolymère anionique est choisi parmi les acides poly(méth)acryliques, qui sont neutralisés en partie ou en totalité avec un métal alcalin.
  3. Particules selon la revendication 1 ou 2, caractérisées en ce que les complexants (A) sont choisis parmi le diacétate de méthylglycine (MGDA) et le diacétate de l'acide glutamique, ainsi que leurs sels de métaux alcalins.
  4. Particules selon l'une quelconque des revendications 1 à 3, caractérisées en ce qu'elles présentent un diamètre de particule moyen (D50) dans la plage allant de 100 à 800 µm.
  5. Particules selon l'une quelconque des revendications 1 à 4, caractérisées en ce qu'elles sont enrobées en totalité ou non en totalité avec l'additif (C) .
  6. Particules selon l'une quelconque des revendications 1 à 5, caractérisées en ce que l'additif (C) est une silice pyrogénée ayant un diamètre de particule moyen dans la plage allant de 1 nm à 50 µm.
  7. Utilisation de particules selon l'une quelconque des revendications 1 à 6 pour la fabrication d'agents de lavage de la vaisselle solides.
  8. Agent de lavage de la vaisselle solide, contenant des particules selon l'une quelconque des revendications 1 à 6 et au moins un tensioactif non ionique.
  9. Agent de lavage de la vaisselle selon la revendication 8, caractérisé en ce que le tensioactif non ionique est un éther mixte d'hydroxyalkyle.
  10. Procédé de fabrication de particules selon l'une quelconque des revendications 1 à 6, caractérisé en ce que
    (A) au moins un complexant, choisi parmi les aminopolycarboxylates, et
    (B) au moins un homo- ou copolymère anionique sont mélangés l'un avec l'autre éventuellement en présence d'eau, l'eau éventuellement présente est essentiellement éliminée, puis
    (C) au moins un additif, choisi parmi les silices précipitées et les silices pyrogénées,
    est mélangé à l'état sec.
  11. Procédé selon la revendication 10, caractérisé en ce que l'eau est éliminée par séchage par pulvérisation ou granulation par pulvérisation.
  12. Procédé de fabrication d'agents de lavage de la vaisselle solides sous la forme de tablettes, caractérisé en ce que des particules selon l'une quelconque des revendications 1 à 6 sont mélangées avec au moins un tensioactif non ionique et éventuellement une ou plusieurs autres substances, puis comprimées en tablettes.
EP16185582.0A 2015-09-02 2016-08-25 Particules, leur utilisation comme detergent pour lave-vaisselle et leur fabrication Not-in-force EP3138895B1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP15183468 2015-09-02

Publications (2)

Publication Number Publication Date
EP3138895A1 EP3138895A1 (fr) 2017-03-08
EP3138895B1 true EP3138895B1 (fr) 2018-10-17

Family

ID=54065706

Family Applications (1)

Application Number Title Priority Date Filing Date
EP16185582.0A Not-in-force EP3138895B1 (fr) 2015-09-02 2016-08-25 Particules, leur utilisation comme detergent pour lave-vaisselle et leur fabrication

Country Status (1)

Country Link
EP (1) EP3138895B1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111770984B (zh) 2018-02-23 2022-05-27 联合利华知识产权控股有限公司 具有热塑性固体部分的单位剂量洗涤剂产品
CN112074593B (zh) * 2018-05-04 2022-08-30 巴斯夫欧洲公司 颗粒或粉末及其制备方法
DE102022206583A1 (de) 2022-06-29 2024-01-04 Henkel Ag & Co. Kgaa Reinigungsmittel

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2134695A1 (de) * 1971-07-12 1973-01-25 Henkel & Cie Gmbh Streufaehige, als komplexbildner geeignete stoffgemische und diese enthaltende wasch-, waschhilfs-, bleich- und reinigungsmittel
US5837663A (en) 1996-12-23 1998-11-17 Lever Brothers Company, Division Of Conopco, Inc. Machine dishwashing tablets containing a peracid
DE19819187A1 (de) 1998-04-30 1999-11-11 Henkel Kgaa Festes maschinelles Geschirrspülmittel mit Phosphat und kristallinen schichtförmigen Silikaten
US20120225450A1 (en) * 2011-03-01 2012-09-06 Basf Se Carboxyl-containing polymers with improved storage stability and processability
RU2608221C2 (ru) 2011-06-29 2017-01-17 Басф Се Модифицированные аминокарбоксилаты с повышенной стабильностью при хранении и улучшенными технологическими свойствами

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
EP3138895A1 (fr) 2017-03-08

Similar Documents

Publication Publication Date Title
DE69108927T2 (de) Verfahren zur herstellung von sauerstoff-bleichsysteme enthaltende phosphatfreie geschirrspülmittelzusammensetzungen.
EP1004656B1 (fr) Granulé densifié, procédé pour sa fabrication et son utilisation comme désintégrant dans des corps formés par compactage
EP0579659B1 (fr) Procede de production de pastilles de detergent pour machines a laver la vaisselle
EP0663946B1 (fr) Produits d'interet et melanges de produits d'interet pour agents mouillants, detergents et/ou nettoyants sous une nouvelle forme de preparation
DE4228786A1 (de) Geschirrspülmittel mit ausgewähltem Builder-System
DE202014011351U1 (de) Mischungen von Enantiomeren und Reinigungsmittelzusammensetzungen
WO1993000419A1 (fr) Procede de fabrication de produits de lavage en comprimes pour le lavage de la vaisselle en machine
EP3138895B1 (fr) Particules, leur utilisation comme detergent pour lave-vaisselle et leur fabrication
EP0648259B1 (fr) Preparation detergente solide ayant un meilleur comportement au rin age
AT394864B (de) Im wesentlichen wasserfreies, fluessiges grobwaschmittel und verfahren zu seiner herstellung
EP0523095B1 (fr) Comprimes detergents stables, bifonctionnels et sans phosphate pour lave-vaisselle
DE3024912A1 (de) Teilchenfoermige bleichmittel
EP2726442B2 (fr) Aminocarboxylates modifiés ayant une meilleure stabilité à l'entreposage et une meilleure ouvrabilité
DE60210079T2 (de) Teilchenförmiges waschmittel mit zeolith
CN112771143A (zh) 制备颗粒或粉末的方法
CH619488A5 (en) Process for the production of a detergent, and product produced by the process
EP0612347A1 (fr) Procede de fabrication de produits pour machine lave-vaisselle faiblement alcalins, exempts de chlore actif et de phosphate, sous forme de granules lourds
DE10123621A1 (de) Verfahren zur Herstellung einer Wasserenthärtertablette
EP0848750B1 (fr) Procede de preparation de produits granules precurseurs de detergents de faible alcalinite
EP1416039B1 (fr) Utilisation d'agents builders hydrosolubles de granulométries spécifiques dans des compositions détergentes sans agent de blanchiment
DE60009745T2 (de) Waschmittelzusammensetzungen
EP1235896B1 (fr) Procede de production de particules comprimees
EP1489160B1 (fr) Corps moules a action detergente ou nettoyante a usage menager
WO2000071654A1 (fr) Procede de preparation de granulat de tensio-actifs
WO2000071657A1 (fr) Procede de preparation de granulat de tensio-actifs

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN PUBLISHED

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20170908

RBV Designated contracting states (corrected)

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20180515

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 502016002245

Country of ref document: DE

Ref country code: AT

Ref legal event code: REF

Ref document number: 1054035

Country of ref document: AT

Kind code of ref document: T

Effective date: 20181115

REG Reference to a national code

Ref country code: SE

Ref legal event code: TRGR

REG Reference to a national code

Ref country code: NL

Ref legal event code: FP

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190217

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181017

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190117

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181017

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181017

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181017

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190117

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181017

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181017

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181017

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190118

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181017

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190217

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 502016002245

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181017

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181017

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181017

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181017

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181017

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181017

26N No opposition filed

Effective date: 20190718

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181017

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20190831

Year of fee payment: 4

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 502016002245

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181017

REG Reference to a national code

Ref country code: NL

Ref legal event code: MM

Effective date: 20190901

REG Reference to a national code

Ref country code: SE

Ref legal event code: EUG

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190826

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190825

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181017

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190831

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190831

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20190831

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200303

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190901

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190831

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190825

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190831

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20200825

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181017

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200825

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20160825

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181017

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200825

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181017

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 1054035

Country of ref document: AT

Kind code of ref document: T

Effective date: 20210825

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210825