EP3628724A1 - Powder and granule, process for making such powder and granule, and use thereof - Google Patents

Powder and granule, process for making such powder and granule, and use thereof Download PDF

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Publication number
EP3628724A1
EP3628724A1 EP18196604.5A EP18196604A EP3628724A1 EP 3628724 A1 EP3628724 A1 EP 3628724A1 EP 18196604 A EP18196604 A EP 18196604A EP 3628724 A1 EP3628724 A1 EP 3628724A1
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EP
European Patent Office
Prior art keywords
copolymer
powder
granule
mole
formula
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP18196604.5A
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German (de)
French (fr)
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EP3628724B1 (en
Inventor
Roland Ettl
Frank Pirrung
Antje Gebert-Schwarzwaelder
Nadine BLUHM
Christa JUNKES
Daniela HERBST
Brigitte Giesen
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Henkel AG and Co KGaA
BASF SE
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Henkel AG and Co KGaA
BASF SE
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Application filed by Henkel AG and Co KGaA, BASF SE filed Critical Henkel AG and Co KGaA
Priority to EP18196604.5A priority Critical patent/EP3628724B1/en
Priority to PCT/EP2019/075395 priority patent/WO2020064570A1/en
Publication of EP3628724A1 publication Critical patent/EP3628724A1/en
Application granted granted Critical
Publication of EP3628724B1 publication Critical patent/EP3628724B1/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/02—Preparation in the form of powder by spray drying
    • 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
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3773—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines in liquid compositions

Definitions

  • the present invention is directed towards a process for making a powder or granule containing
  • Granules have the advantage of being highly concentrated, with a low amount of residual water. That means that in case of shipping, almost no water has to be shipped, and costs for extra weight can be avoided.
  • soil release agents based on (meth)acrylic esters for use preferably in liquid detergents are known from WO 2015/078736 .
  • Soil release agents known from WO 2015/078736 do not crystallize upon drying and therefore they cannot be transferred into granules or powders.
  • inventive process provides granules or powders, hereinafter also referred to as “inventive granules” or “inventive powders”, respectively.
  • Inventive powders and inventive granules can be manufactured according to the inventive process.
  • inventive powders are particulate materials that are solids at ambient temperature and that preferably have an average particle diameter in the range of from 0.001mm to less than 2.5 mm, preferably 0,1mm up to 1 mm.
  • the average particle diameter of inventive powders can be determined, e.g., by LASER diffraction methods, for example with Malvern apparatus, and refers to the volume average.
  • Inventive granules are particulate materials that are solids at ambient temperature and that preferably have an average particle diameter in the range of from 0.1 mm to 2 mm, more preferably between 0.45 mm to 1.00 mm.
  • the average particle diameter of inventive granules can be determined, e.g., by optical or preferably by sieving methods. Sieves employed may have a mesh in the range of from 60 to 1,250 ⁇ m.
  • inventive powders or inventive granules have a broad particle diameter distribution. In another embodiment of the present invention, inventive powders or inventive granules have a narrow particle diameter distribution.
  • the particle diameter distribution can be adjusted, if desired, by multiple sieving steps.
  • Granules and powders may contain residual moisture, moisture referring to water including water of crystallization and adsorbed water.
  • the amount of water may be in the range of from 0.1 to 20% by weight, preferably 1 to 15% by weight, referring to the total solids content of the respective powder or granule, and may be determined by Karl-Fischer-titration or by drying at 160°C to constant weight with infrared light.
  • Particles of inventive powders may have regular or irregular shape.
  • Preferred shapes of particles of inventive powders are spheroidal shapes.
  • Powders and granules made according to the inventive process contain
  • powders and granules made according to the inventive process contain
  • a copolymer (A) is obtainable by polymerization of at least one monomer according to formula (I): in an amount of 1 to 70 mole%, wherein n is ⁇ 3 and at least one monomer according to formula (II): in an amount of 30 to 99 mole%.
  • n of the monomer according to formula (I) is between 3 and 120, preferably between 5 and 50, more preferably between 5 and 46 and even more preferably between 5 and 23.
  • n of the monomer according to formula (I) is selected from the group consisting of 7, 23 and 46.
  • the monomer according to formula (I) is present in the amount of 5 to 70 mole% and the monomer according to formula (II) is present in the amount of 30 to 95 mole%. In a more preferred embodiment, the monomer according to formula (I) is present in the amount of 9 to 70 mole% and the monomer according to formula (II) is present in the amount of 30 to 91 mole%. In an even more preferred embodiment, the monomer according to formula (I) is present in the amount of 9 to 67 mole% and the monomer according to formula (II) is present in the amount of 33 to 91 mole%.
  • the monomer according to formula (I) is present in the amount of 5 to 60 mole% and the monomer according to formula (II) is present in the amount of 40 to 95 mole%. In a further preferred embodiment, the monomer according to formula (I) is present in the amount of 5 to 50 mole% and the monomer according to formula (II) is present in the amount of 50 to 95 mole%. In a further preferred embodiment, the monomer according to formula (I) is present in the amount of 1 to 67 mole% and the monomer according to formula (II) is present in the amount of 33 to 99 mole%
  • the copolymer (A) can be produced by polymerization. More precisely it can be prepared by using known polymerization methods as described, for example, in WO 2015/078736 or in US 4,170,582 , US 2009/0234062 or US 7,687,554 , as exemplified for emulsion and miniemulsion polymerizations, but without use of surfactants.
  • Polymer (B) is selected from homopolymers (B) of (meth)acrylic acid and of copolymers (B) of (meth)acrylic acid, preferably of acrylic acid, partially or fully neutralized with alkali.
  • copolymers (B) are those in which at least 50 mol-% of the comonomers are (meth)acrylic acid, preferably at least 75 mol-%, even more preferably 80 to 99 mol-%.
  • Suitable comonomers for copolymers (B) are ethylenically unsaturated compounds, such as styrene, isobutene, ethylene, ⁇ -olefins such as propylene, 1-butylene, 1-hexene, and ethylenically unsaturated dicarboxylic acids and their alkali metal salty and anhydrides such as but not limited to maleic acid, fumaric acid, itaconic acid disodium maleate, disodium fumarate, itaconic anhydride, and especially maleic anhydride.
  • Suitable comonomers are C 1 -C 4 -alkyl esters of (meth)acrylic acid, for example methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate.
  • polymer (B) is selected from copolymers of (meth)acrylic acid and a comonomer bearing at least one sulfonic acid group per molecule.
  • Comonomers bearing at least one sulfonic acid group per molecule may be incorporated into polymer (B) as free acid or least partially neutralized with alkali.
  • Particularly preferred sulfonic-acid-group-containing comonomers are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid (AMPS), 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,
  • Copolymers (B) may be selected from random copolymers, alternating copolymers, block copolymers and graft copolymers, alternating copolymers and especially random copolymers being preferred.
  • Useful copolymers (B) are, for example, copolymers of acrylic acid and methacrylic acid, copolymers of acrylic acid and maleic anhydride, ternary copolymers of acrylic acid, methacrylic acid and maleic anhydride, random or block copolymers of acrylic acid and styrene, copolymers of acrylic acid and methyl acrylate. More preferred are homopolymers of methacrylic acid. Even more preferred are homopolymers of acrylic acid.
  • Polymer (B) may constitute straight-chain or branched molecules. Branching in this context will be when at least one repeating unit of such polymer (B) is not part of the main chain but forms a branch or part of a branch. Preferably, polymer (B) is not cross-linked.
  • polymer (B) has an average molecular weight M w in the range of from 1,200 to 30,000 g/mol, preferably from 2,500 to 15,000 g/mol and even more preferably from 3,000 to 10,000 g/mol, determined by gel permeation chromatography (GPC) and referring to the respective free acid.
  • M w average molecular weight
  • polymer (B) is at least partially neutralized with alkali, for example with lithium or potassium or sodium or combinations of at least two of the forgoing, especially with sodium.
  • alkali for example with lithium or potassium or sodium or combinations of at least two of the forgoing, especially with sodium.
  • polymer (B) is at least partially neutralized with alkali, especially with sodium.
  • polymer (B) is selected from per-sodium salts of polyacrylic acid, thus, polyacrylic acid, fully neutralized with sodium.
  • polymer (B) is selected from a combination of at least one polyacrylic acid and at least one copolymer of (meth)acrylic acid and a comonomer bearing at least one sulfonic acid group per molecule, both polymers being fully neutralized with alkali.
  • polymer (B) is selected from per-sodium salts of polyacrylic acid with an average molecular weight M w in the range of from 1,200 to 30,000 g/mol, preferably from 2,500 to 15,000 g/mol and even more preferably from 3,000 to 10,000 g/mol, determined by gel permeation chromatography (GPC) and referring to the respective free acid.
  • M w average molecular weight
  • the inventive process comprises two steps,
  • Step (a) and step (b) will be described in more detail below.
  • Mixing of copolymer (A) and polymer (B) is usually performed in the presence of water. Said mixing can be conducted in a way that an aqueous solution of polymer (B) and an aqueous solution of copolymer (A) are being combined in a vessel, preferably under stirring. It is also possible to combine an aqueous solution of polymer (B) and solid copolymer (A), or to combine an aqueous solution of copolymer (A) with solid polymer (B), or to combine aqueous slurries of copolymer (A) and polymer (B).
  • water is provided and subsequently, polymer (B) and then copolymer (A) are added.
  • a solution of copolymer (A) is provided that has a temperature of 35 to 75°C, and polymer (B) is being added, either in bulk or as solution, under stirring.
  • Step (a) can be performed at ambient temperature. In other embodiments, step (a) is being performed at 20° C or at elevated temperature, for example at a temperature in the range of from 25 to 90°C, preferably 40 to 75°C.
  • the water used in step (a) may be present in an amount that both copolymer (A) and polymer (B) are dissolved. However, it is also possible to use less amounts of water and mix copolymer (A) and polymer (B) in a way that a slurry is being formed. Solutions are preferred.
  • the total solids content of such solution or slurry formed as result of step (a) is in the range of from 20 to 75%, preferably 35 to 50%.
  • such solution or slurry has a pH value in the range of from 2.5 to 13, preferably from 4 to 11, and also preferably at least 5.
  • Mixing may be performed with mechanical support, for example shaking or stirring.
  • step (b) a spray-drying or spray granulation is performed, using a gas with an inlet temperature of at least 125°C.
  • Said gas hereinafter also being referred to as "hot gas”
  • hot gas may be nitrogen, a rare gas or preferably air.
  • most of the water used in step (a) will be removed, for example at least 55%, preferably at least 65% of the water. In one embodiment of the present invention, 99% of the water at most will be removed.
  • Spray-drying and spray granulation will be described in more detail below.
  • a drying vessel for example a spray chamber or a spray tower, is being used in which a spray-granulating process is being performed by using a fluidized bed.
  • a drying vessel is charged with a fluidized bed of a solid mixture of copolymer (A) and polymer (B), obtained by any drying method such as spray drying or evaporation crystallization, and a solution or slurry of solid mixture of copolymer (A) and polymer (B) is sprayed onto or into such fluidized bed together with a hot gas stream.
  • the hot gas inlet stream may have a temperature in the range of from 125 to 350°C, preferably 160 to 220°C.
  • the fluidized bed may have a temperature in the range of from 80 to 150°C, preferably 100 to 120°C.
  • Spraying is being performed through one or more nozzles per drying vessel.
  • Suitable nozzles are, for example, high-pressure rotary drum atomizers, rotary atomizers, single-fluid nozzles and two-fluid nozzles, two-fluid nozzles and rotary atomizers being preferred.
  • the first fluid is the solution or slurry obtained according to step (a)
  • the second fluid is compressed gas, for example with a pressure of 1.1 to 7 bar.
  • the droplets formed during the spray-granulating have an average diameter in the range of from 10 to 500 ⁇ m, preferably from 20 to 180 ⁇ m, even more preferably from 30 to 100 ⁇ m.
  • the off-gas departing the drying vessel may have a temperature in the range of from 40 to 140°C, preferably 80 to 110°C but in any way colder than the hot gas stream.
  • the temperature of the off-gas departing the drying vessel and the temperature of the solid product present in the drying vessel are identical.
  • spray-granulation is being performed by performing two or more consecutive spray-drying processes, for example in a cascade of at least two spray dryers, for example in a cascade of at least two consecutive spray towers or a combination of a spray tower and a spray chamber, said spray chamber containing a fluidized bed.
  • a spray-drying process is being performed in the way as follows.
  • Spray-drying may be preferred in a spray dryer, for example a spray chamber or a spray tower.
  • a solution or slurry obtained according to step (a) with a temperature preferably higher than ambient temperature, for example in the range of from 50 to 95°C, is introduced into the spray dryer through one or more spray nozzles into a hot gas inlet stream, for example nitrogen or air, the solution or slurry being converted into droplets and the water being vaporized.
  • the hot gas inlet stream may have a temperature in the range of from 125 to 350°C.
  • the second spray dryer is charged with a fluidized bed with solid from the first spray dryer and solution or slurry obtained according to the above step is sprayed onto or into the fluidized bed, together with a hot gas inlet stream.
  • the hot gas inlet stream may have a temperature in the range of from 125 to 350°C, preferably 160 to 220°C.
  • the average residence time of copolymer (A) and polymer (B), respectively, in step (b) is in the range of from 2 minutes to 4 hours, preferably from 30 minutes to 2 hours.
  • the average residence time of copolymer (A) and polymer (B), in step (b) is in the range of from 1 second to 1 minute, especially 2 to 20 seconds.
  • the pressure in the drying vessel in step (b) is normal pressure ⁇ 100 mbar, preferably normal pressure ⁇ 20 mbar, for example one mbar less than normal pressure.
  • one or more additives (C) can be added to the solution obtained according to step (a) before performing step (b), or one or more of such additives (C) can be added at any stage during step (a).
  • useful additives (C) are, for example, titanium dioxide, sugar, silica gel and polyvinyl alcohol.
  • Polyvinyl alcohol in the context of the present invention refers to completely or partially hydrolyzed polyvinyl acetate. In partially hydrolyzed polyvinyl acetate, at least 95 mol-%, preferably at least 96 mol-% of the acetate groups have been hydrolyzed.
  • polyvinyl alcohol has an average molecular weight M w in the range of from 22,500 to 115,000 g/mol, for example up to 40,000 g/mol.
  • polyvinyl alcohol has an average molecular weight M n in the range of from 2,000 to 40,000 g/mol.
  • Additive(s) (C) can amount to 0.1 to 5 % by weight, referring to the sum of copolymer (A) and polymer (B).
  • step (b) no additive (C) is being employed in step (b).
  • One or more additional steps (c) may be performed at any stage of the inventive proves, preferably after step (b). It is thus possible to perform a sieving step (c) to remove lumps from the powder or granule. Also, a post-drying step (c) is possible. Air classifying can be performed during or after step (b) to remove fines.
  • Fines especially those with a diameter of less than 50 ⁇ m, may deteriorate the flowing behavior of powders or granules obtained according to the inventive process.
  • amorphous or preferably crystalline fines may be returned to the spray vessel(s) as seed for crystallization.
  • Lumps may be removed and either re-dissolved in water or milled and used as seed for crystallization in the spray vessel(s).
  • the inventive process furnishes powders or granules containing copolymer (A) and polymer (B) and, optionally, one or more additives (C).
  • Such powders and granules exhibit overall advantageous properties including but not limited to an excellent yellowing behavior.
  • inventive powders or inventive granules are powders and granules, hereinafter also being referred to as inventive powders or inventive granules, respectively, containing
  • Copolymer (A) and polymer (B) have been defined above.
  • the term "in molecularly disperse form” implies that all or a vast majority, for example at least 80% of the particles of inventive powder and of inventive granules contain copolymer (A) and polymer (B).
  • inventive powders are selected from powders having an average particle diameter in the range of from 1 ⁇ m to less than 0.1 mm.
  • inventive granules are selected from granules with an average particle diameter in the range of from 0.1 mm to 2 mm, preferably 0.45 mm to 1.00 mm.
  • inventive powder or inventive granule contains in the range of from 20 - 80 % by weight copolymer (A) and 80 - 20 % by weight homo- or copolymer (B), percentages referring to the solids content of said powder or granule.
  • the term "in molecularly disperse form” also implies that essentially all particles of inventive powder or inventive granule contains in the range of from 40 - 75 % by weight copolymer (A) and 60 - 25 % by weight homo- or copolymer (B), percentages referring to the solids content of the respective powder or granule.
  • inventive powders and inventive granules are selected from those wherein polymer (B) has an average molecular weight M w in the range of from 1,200 to 30,000 g/mol, determined by gel permeation chromatography and referring to the respective free acid.
  • inventive powders and inventive granules are selected from those wherein copolymer (A) is a copolymer obtainable by polymerization of at least one monomer according to formula (I): in an amount of 1 to 70 mole%, wherein n is between 5 and 7 and at least one monomer according to formula (II): in an amount of 30 to 99 mole%.
  • inventive powders and inventive granules are selected from those wherein said homo- and copolymer (B) are selected from the per-sodium salts of polyacrylic acid.
  • inventive powders and inventive granules are selected from those wherein said polymer (B) is selected from copolymers of (meth)acrylic acid and a comonomer bearing at least one sulfonic acid group per molecule. Comonomers bearing at least one sulfonic acid group per molecule may be incorporated into polymer (B) as free acid or least partially neutralized with alkali.
  • Particularly preferred sulfonic-acid-group-containing comonomers are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid (AMPS), 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,
  • inventive powders and inventive granules are selected from those wherein said polymer (B) is selected from a combination of at least one polyacrylic acid and at least one copolymer of (meth)acrylic acid and a comonomer bearing at least one sulfonic acid group per molecule, both polymers being fully neutralized with alkali.
  • Inventive powders and inventive granules exhibit overall advantageous properties including but not limited to being stable under high alkaline conditions with no malodour formation and evolvement during storage conditions. They are therefore excellently suitable for the manufacture of cleaning agents.
  • Typical compact and powder detergents may for example comprise the following ingredients
  • the present invention is further illustrated by working examples .
  • NI Norm liter, liters under normal conditions
  • Nm 3 norm cubic meter, cubic meter under normal conditions
  • Example I Manufacture of inventive granules
  • a vessel was charged with 25kg of an aqueous solution of Sokalan® PA 30 CL PN (homopolymer (B)) and 13,3kg of an aqueous solution of Sokalan® SR400 (copolymer (A)).
  • the solution SL.1 so obtained was stirred, heated to 70°C and then subjected to spray granulation.
  • the solid ratio between Sokalan® PA 30 CL PN and Sokalan® SR400 is 3:1.
  • the granulation was carried out in a lab granulator (Glatt LabSystem with Vario 3 insert attached with a zig-zag air classifier).
  • the granulator was charged with 1,3kg of solid Sokalan® PA 30 CL PN spherical particles. An amount of 200 Nm3/h of air with a temperature of 166 to 173°C was blown from the bottom. A fluidized bed of Sokalan® Pa 30 CL PN particles was obtained.
  • the inventive solution SL.1 was introduced by spraying 7,3 kg of SL.1 (temperature of the solution: 70°C) per hour into the fluidized bed from the bottom through a two-fluid nozzle (parameters: absolute pressure in the nozzle: 5 bar). Granules were formed, and the bed temperature, which corresponds to the surface temperature of the solids in the fluidized bed, was 100°C.
  • hot air can be replaced by hot nitrogen having the same temperature of 166-173°C.
  • a vessel was charged with 16,67kg of an aqueous solution of Sokalan® CP 45 (Copolymer (B)) and 26,67kg of an aqueous solution of Sokalan® SR400 (copolymer (A)).
  • the solution SL.2 so obtained was stirred, heated to 70°C and then subjected to spray granulation.
  • the solid ratio between Sokalan® CP 45 and Sokalan® SR400 is 1:1.
  • a vessel was charged with 8,34kg of an aqueous solution of Sokalan® PA 30 CL PN (homopolymer (B)) and 13,34kg of an aqueous solution of Sokalan® SR400 (copolymer (A)).
  • the solution SL.3 so obtained was stirred, heated to 70°C and then subjected to spray granulation.
  • the solid ratio between Sokalan® PA 30 CL PN and Sokalan® SR400 is 1:1
  • a vessel was charged with 5,22kg of an aqueous solution of Sokalan® PA 30 CL PN (homopolymer (B)) and 16kg of an aqueous solution of Sokalan® SR400 (copolymer (A)).
  • the solution SL.4 so obtained was stirred, heated to 70°C and then subjected to spray granulation.
  • the solid ratio between Sokalan® PA 30 CL PN and Sokalan® SR400 is 1:2
  • a Sokalan® SR400 aqueous solution with a content of 31 % by weight was applied with a brush on a hot surface (150°C). After 10 minutes of drying time, the dried Sokalan® SR400 was still sticky and ruber-like. No powder or granules could be obtained even after prolonged drying.
  • Table 1 composition of laundry detergents (weight-%) W1 W2 W3 inventive granule 1 - 0,25 - inventive granule 3 - - 0,25 Carboxymethylcellulose 3 3 3 HEDP-Na4 1 1 1 Polyacrylate 3 3 3 Sodium silicate 7 7 7 7 Sodium carbonate 21 21 21 Defoamer 0,1 0,1 0,1 Sodium hydrogen carbonate 10 10 10 Sodium percarbonate 12 12 12 TAED 4 4 4 4 Enzyme 0,8 0,8 0,8 Perfume 0,3 0,3 0,3 Alkyl Benzene Sulfonic Acid, Na-salt 13 13 13 13 Fatty Alcohol Sulfate-Na 3 3 3 3 Soap 0,1 0,1 0,1 Optical brightener 0,2 0,2 0,2 Water, Sodium Sulfate, other Polymers Ad 100 Ad 100 Ad 100 Ad 100 Ad 100 Ad 100 Ad 100 Ad 100 Ad 100 Ad 100 Ad 100 Ad 100 Ad 100 Ad 100 Ad 100 Ad 100 Ad 100 Ad 100 Ad 100 Ad 100 Ad 100 Ad 100 Ad 100 Ad 100 Ad 100 Ad 100 Ad

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Abstract

The present invention is directed towards a process for making a powder or granule containing(A) at least one copolymer obtainable by polymerization of at least one monomer according to formula (I):in an amount of 1 to 70 mole%,wherein n is ≥ 3andat least one monomer according to formula (II):in an amount of 30 to 99 mole%,(B) at least one homo- or copolymer of (meth)acrylic acid, partially or fully neutralized with alkali,said process comprising the steps of(a) mixing the at least one copolymer (A) and the at least one homo- or copolymer (B) in the presence of water,(b) removing most of said water by spray-drying or spray granulation using a gas with an inlet temperature of at least 125°C.

Description

  • The present invention is directed towards a process for making a powder or granule containing
    1. (A) at least one copolymer obtainable by polymerization of at least one monomer according to formula (I):
      Figure imgb0001
       in an amount of 1 to 70 mole%,
      wherein n is ≥ 3
      and
      at least one monomer according to formula (II):
      Figure imgb0002
       in an amount of 30 to 99 mole%,
    2. (B) at least one homo- or copolymer of (meth)acrylic acid, partially or fully neutralized with alkali,
      wherein the weight ratio of (A) to (B) is from 20:80 to 80:20,
      said process comprising the steps of
      1. (a) mixing the at least one copolymer (A) and the at least one homo- or copolymer in the presence of water,
      2. (b) removing most of said water by spray-drying or spray granulation using a gas with an inlet temperature of at least 125°C.
  • Granules have the advantage of being highly concentrated, with a low amount of residual water. That means that in case of shipping, almost no water has to be shipped, and costs for extra weight can be avoided.
  • The soil release agents based on (meth)acrylic esters for use preferably in liquid detergents are known from WO 2015/078736 .
  • Soil release agents known from WO 2015/078736 do not crystallize upon drying and therefore they cannot be transferred into granules or powders.
  • It was an objective of the present invention to provide a copolymer in form of a powder or of a granule for powder detergents, stable under high alkaline conditions with no malodour formation and evolvement during storage conditions. It was further an objective to provide a process for making a copolymer in form of a powder or of a granule, such powder or granule stable under high alkaline conditions with no malodour formation and evolvement during storage conditions.
  • Accordingly, the process defined at the outset has been found, hereinafter also being referred to as "inventive process" or as "process according to the (present) invention".
  • The inventive process provides granules or powders, hereinafter also referred to as "inventive granules" or "inventive powders", respectively. Inventive powders and inventive granules can be manufactured according to the inventive process.
  • In the course of the present invention, inventive powders are particulate materials that are solids at ambient temperature and that preferably have an average particle diameter in the range of from 0.001mm to less than 2.5 mm, preferably 0,1mm up to 1 mm. The average particle diameter of inventive powders can be determined, e.g., by LASER diffraction methods, for example with Malvern apparatus, and refers to the volume average. Inventive granules are particulate materials that are solids at ambient temperature and that preferably have an average particle diameter in the range of from 0.1 mm to 2 mm, more preferably between 0.45 mm to 1.00 mm. The average particle diameter of inventive granules can be determined, e.g., by optical or preferably by sieving methods. Sieves employed may have a mesh in the range of from 60 to 1,250 µm.
  • In one embodiment of the present invention, inventive powders or inventive granules have a broad particle diameter distribution. In another embodiment of the present invention, inventive powders or inventive granules have a narrow particle diameter distribution. The particle diameter distribution can be adjusted, if desired, by multiple sieving steps.
  • Granules and powders may contain residual moisture, moisture referring to water including water of crystallization and adsorbed water. The amount of water may be in the range of from 0.1 to 20% by weight, preferably 1 to 15% by weight, referring to the total solids content of the respective powder or granule, and may be determined by Karl-Fischer-titration or by drying at 160°C to constant weight with infrared light.
  • Particles of inventive powders may have regular or irregular shape. Preferred shapes of particles of inventive powders are spheroidal shapes.
  • Powders and granules made according to the inventive process contain
    1. (A) at least one copolymer obtainable by polymerization of at least one monomer according to formula (I):
      Figure imgb0003
       in an amount of 1 to 70 mole%,
      wherein n is ≥ 3
      and
      at least one monomer according to formula (II):
      Figure imgb0004
       in an amount of 30 to 99 mole%, also being referred to as "copolymer (A)",
    2. (B) at least one homo- or copolymer of (meth)acrylic acid, partially or fully neutralized with alkali, hereinafter also referred to as "polymer (B)". Polymers (B) that are homopolymers are also being referred to as "homopolymers (B)", and polymers (B) that are copolymers are also being referred to as "copolymers (B)",
      wherein the weight ratio of (A) to (B) is from 20:80 to 80:20.
  • Another aspect of the present invention, powders and granules made according to the inventive process contain
    1. (A) in the range of from 40 - 75 % by weight of at least one copolymer obtainable by polymerization of at least one monomer according to formula (I):
      Figure imgb0005
       in an amount of 1 to 70 mole%,
      wherein n is ≥ 3
      and
      at least one monomer according to formula (II):
      Figure imgb0006
       in an amount of 30 to 99 mole%,
    2. (B) in the range of from 60 - 25 % by weight of at least one homo- or copolymer of (meth)acrylic acid, partially or fully neutralized with alkali,
      percentages referring to the solids content of said powder or granule.
  • In the context of the present invention, a copolymer (A) is obtainable by polymerization of at least one monomer according to formula (I):
    Figure imgb0007
     in an amount of 1 to 70 mole%,
    wherein n is ≥ 3
    and
    at least one monomer according to formula (II):
    Figure imgb0008
     in an amount of 30 to 99 mole%.
  • In a preferred embodiment, n of the monomer according to formula (I) is between 3 and 120, preferably between 5 and 50, more preferably between 5 and 46 and even more preferably between 5 and 23.
  • In another preferred embodiment, n of the monomer according to formula (I) is selected from the group consisting of 7, 23 and 46.
  • In a further preferred embodiment, the monomer according to formula (I) is present in the amount of 5 to 70 mole% and the monomer according to formula (II) is present in the amount of 30 to 95 mole%. In a more preferred embodiment, the monomer according to formula (I) is present in the amount of 9 to 70 mole% and the monomer according to formula (II) is present in the amount of 30 to 91 mole%. In an even more preferred embodiment, the monomer according to formula (I) is present in the amount of 9 to 67 mole% and the monomer according to formula (II) is present in the amount of 33 to 91 mole%. In another preferred embodiment, the monomer according to formula (I) is present in the amount of 5 to 60 mole% and the monomer according to formula (II) is present in the amount of 40 to 95 mole%. In a further preferred embodiment, the monomer according to formula (I) is present in the amount of 5 to 50 mole% and the monomer according to formula (II) is present in the amount of 50 to 95 mole%. In a further preferred embodiment, the monomer according to formula (I) is present in the amount of 1 to 67 mole% and the monomer according to formula (II) is present in the amount of 33 to 99 mole%
  • The copolymer (A) can be produced by polymerization. More precisely it can be prepared by using known polymerization methods as described, for example, in WO 2015/078736 or in US 4,170,582 , US 2009/0234062 or US 7,687,554 , as exemplified for emulsion and miniemulsion polymerizations, but without use of surfactants.
  • Polymer (B) is selected from homopolymers (B) of (meth)acrylic acid and of copolymers (B) of (meth)acrylic acid, preferably of acrylic acid, partially or fully neutralized with alkali. In the context of the present invention, copolymers (B) are those in which at least 50 mol-% of the comonomers are (meth)acrylic acid, preferably at least 75 mol-%, even more preferably 80 to 99 mol-%.
  • Suitable comonomers for copolymers (B) are ethylenically unsaturated compounds, such as styrene, isobutene, ethylene, α-olefins such as propylene, 1-butylene, 1-hexene, and ethylenically unsaturated dicarboxylic acids and their alkali metal salty and anhydrides such as but not limited to maleic acid, fumaric acid, itaconic acid disodium maleate, disodium fumarate, itaconic anhydride, and especially maleic anhydride. Further examples of suitable comonomers are C1-C4-alkyl esters of (meth)acrylic acid, for example methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate.
  • In one embodiment of the present invention, polymer (B) is selected from copolymers of (meth)acrylic acid and a comonomer bearing at least one sulfonic acid group per molecule. Comonomers bearing at least one sulfonic acid group per molecule may be incorporated into polymer (B) as free acid or least partially neutralized with alkali. Particularly preferred sulfonic-acid-group-containing comonomers are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid (AMPS), 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 salts of said acids, such as the sodium salts, potassium salts or ammonium salts thereof.
  • Copolymers (B) may be selected from random copolymers, alternating copolymers, block copolymers and graft copolymers, alternating copolymers and especially random copolymers being preferred.
  • Useful copolymers (B) are, for example, copolymers of acrylic acid and methacrylic acid, copolymers of acrylic acid and maleic anhydride, ternary copolymers of acrylic acid, methacrylic acid and maleic anhydride, random or block copolymers of acrylic acid and styrene, copolymers of acrylic acid and methyl acrylate. More preferred are homopolymers of methacrylic acid. Even more preferred are homopolymers of acrylic acid.
  • Polymer (B) may constitute straight-chain or branched molecules. Branching in this context will be when at least one repeating unit of such polymer (B) is not part of the main chain but forms a branch or part of a branch. Preferably, polymer (B) is not cross-linked.
  • In one embodiment of the present invention, polymer (B) has an average molecular weight Mw in the range of from 1,200 to 30,000 g/mol, preferably from 2,500 to 15,000 g/mol and even more preferably from 3,000 to 10,000 g/mol, determined by gel permeation chromatography (GPC) and referring to the respective free acid.
  • In one embodiment of the present invention, polymer (B) is at least partially neutralized with alkali, for example with lithium or potassium or sodium or combinations of at least two of the forgoing, especially with sodium. For example, in the range of from 10 to 100 mol-% of the carboxyl groups of polymer (B) may be neutralized with alkali, especially with sodium.
  • In one embodiment of the present invention, polymer (B) is selected from per-sodium salts of polyacrylic acid, thus, polyacrylic acid, fully neutralized with sodium.
    In one embodiment of the present invention, polymer (B) is selected from a combination of at least one polyacrylic acid and at least one copolymer of (meth)acrylic acid and a comonomer bearing at least one sulfonic acid group per molecule, both polymers being fully neutralized with alkali.
  • In one embodiment of the present invention, polymer (B) is selected from per-sodium salts of polyacrylic acid with an average molecular weight Mw in the range of from 1,200 to 30,000 g/mol, preferably from 2,500 to 15,000 g/mol and even more preferably from 3,000 to 10,000 g/mol, determined by gel permeation chromatography (GPC) and referring to the respective free acid.
  • The inventive process comprises two steps,
    1. (a) mixing the at least one copolymer (A) and the at least one homo- or copolymer (B) in the presence of water,
    2. (b) removing most of said water by spray-drying or spray granulation,
    hereinafter also referred to as step (a) and step (b). Usually, step (b) is performed after step (a).
  • Step (a) and step (b) will be described in more detail below.
    Mixing of copolymer (A) and polymer (B) is usually performed in the presence of water. Said mixing can be conducted in a way that an aqueous solution of polymer (B) and an aqueous solution of copolymer (A) are being combined in a vessel, preferably under stirring. It is also possible to combine an aqueous solution of polymer (B) and solid copolymer (A), or to combine an aqueous solution of copolymer (A) with solid polymer (B), or to combine aqueous slurries of copolymer (A) and polymer (B). In an alternative embodiment, water is provided and subsequently, polymer (B) and then copolymer (A) are added. In a preferred embodiment, a solution of copolymer (A) is provided that has a temperature of 35 to 75°C, and polymer (B) is being added, either in bulk or as solution, under stirring.
  • Step (a) can be performed at ambient temperature. In other embodiments, step (a) is being performed at 20° C or at elevated temperature, for example at a temperature in the range of from 25 to 90°C, preferably 40 to 75°C.
  • The water used in step (a) may be present in an amount that both copolymer (A) and polymer (B) are dissolved. However, it is also possible to use less amounts of water and mix copolymer (A) and polymer (B) in a way that a slurry is being formed. Solutions are preferred.
  • In one embodiment of the present invention, the total solids content of such solution or slurry formed as result of step (a) is in the range of from 20 to 75%, preferably 35 to 50%.
  • In one embodiment of the present invention, such solution or slurry has a pH value in the range of from 2.5 to 13, preferably from 4 to 11, and also preferably at least 5.
  • Mixing may be performed with mechanical support, for example shaking or stirring.
  • In step (b), a spray-drying or spray granulation is performed, using a gas with an inlet temperature of at least 125°C. Said gas, hereinafter also being referred to as "hot gas", may be nitrogen, a rare gas or preferably air. In the course of step (b), most of the water used in step (a) will be removed, for example at least 55%, preferably at least 65% of the water. In one embodiment of the present invention, 99% of the water at most will be removed.
  • Spray-drying and spray granulation will be described in more detail below.
  • In one embodiment of the present invention, a drying vessel, for example a spray chamber or a spray tower, is being used in which a spray-granulating process is being performed by using a fluidized bed. Such a drying vessel is charged with a fluidized bed of a solid mixture of copolymer (A) and polymer (B), obtained by any drying method such as spray drying or evaporation crystallization, and a solution or slurry of solid mixture of copolymer (A) and polymer (B) is sprayed onto or into such fluidized bed together with a hot gas stream. The hot gas inlet stream may have a temperature in the range of from 125 to 350°C, preferably 160 to 220°C.
  • In one embodiment of the present invention, the fluidized bed may have a temperature in the range of from 80 to 150°C, preferably 100 to 120°C.
  • Spraying is being performed through one or more nozzles per drying vessel. Suitable nozzles are, for example, high-pressure rotary drum atomizers, rotary atomizers, single-fluid nozzles and two-fluid nozzles, two-fluid nozzles and rotary atomizers being preferred. The first fluid is the solution or slurry obtained according to step (a), the second fluid is compressed gas, for example with a pressure of 1.1 to 7 bar.
  • In one embodiment of the present invention, the droplets formed during the spray-granulating have an average diameter in the range of from 10 to 500 µm, preferably from 20 to 180 µm, even more preferably from 30 to 100 µm.
  • In one embodiment of the present invention, the off-gas departing the drying vessel may have a temperature in the range of from 40 to 140°C, preferably 80 to 110°C but in any way colder than the hot gas stream. Preferably, the temperature of the off-gas departing the drying vessel and the temperature of the solid product present in the drying vessel are identical.
  • In another embodiment of the present invention, spray-granulation is being performed by performing two or more consecutive spray-drying processes, for example in a cascade of at least two spray dryers, for example in a cascade of at least two consecutive spray towers or a combination of a spray tower and a spray chamber, said spray chamber containing a fluidized bed. In the first dryer, a spray-drying process is being performed in the way as follows.
  • Spray-drying may be preferred in a spray dryer, for example a spray chamber or a spray tower. A solution or slurry obtained according to step (a) with a temperature preferably higher than ambient temperature, for example in the range of from 50 to 95°C, is introduced into the spray dryer through one or more spray nozzles into a hot gas inlet stream, for example nitrogen or air, the solution or slurry being converted into droplets and the water being vaporized. The hot gas inlet stream may have a temperature in the range of from 125 to 350°C.
  • The second spray dryer is charged with a fluidized bed with solid from the first spray dryer and solution or slurry obtained according to the above step is sprayed onto or into the fluidized bed, together with a hot gas inlet stream. The hot gas inlet stream may have a temperature in the range of from 125 to 350°C, preferably 160 to 220°C.
  • In one embodiment of the present invention, especially in a process for making an inventive granule, the average residence time of copolymer (A) and polymer (B), respectively, in step (b) is in the range of from 2 minutes to 4 hours, preferably from 30 minutes to 2 hours.
  • In another embodiment, especially in a process for making an inventive powder, the average residence time of copolymer (A) and polymer (B), in step (b) is in the range of from 1 second to 1 minute, especially 2 to 20 seconds.
  • In one embodiment of the present invention, the pressure in the drying vessel in step (b) is normal pressure ± 100 mbar, preferably normal pressure ± 20 mbar, for example one mbar less than normal pressure.
  • In one embodiment of the present invention, one or more additives (C) can be added to the solution obtained according to step (a) before performing step (b), or one or more of such additives (C) can be added at any stage during step (a). Examples of useful additives (C) are, for example, titanium dioxide, sugar, silica gel and polyvinyl alcohol. Polyvinyl alcohol in the context of the present invention refers to completely or partially hydrolyzed polyvinyl acetate. In partially hydrolyzed polyvinyl acetate, at least 95 mol-%, preferably at least 96 mol-% of the acetate groups have been hydrolyzed.
  • In one embodiment of the present invention polyvinyl alcohol has an average molecular weight Mw in the range of from 22,500 to 115,000 g/mol, for example up to 40,000 g/mol.
  • In one embodiment of the present invention polyvinyl alcohol has an average molecular weight Mn in the range of from 2,000 to 40,000 g/mol.
  • Additive(s) (C) can amount to 0.1 to 5 % by weight, referring to the sum of copolymer (A) and polymer (B).
  • Preferably, no additive (C) is being employed in step (b).
    One or more additional steps (c) may be performed at any stage of the inventive proves, preferably after step (b). It is thus possible to perform a sieving step (c) to remove lumps from the powder or granule. Also, a post-drying step (c) is possible. Air classifying can be performed during or after step (b) to remove fines.
  • Fines, especially those with a diameter of less than 50 µm, may deteriorate the flowing behavior of powders or granules obtained according to the inventive process. However, amorphous or preferably crystalline fines may be returned to the spray vessel(s) as seed for crystallization. Lumps may be removed and either re-dissolved in water or milled and used as seed for crystallization in the spray vessel(s).
  • The inventive process furnishes powders or granules containing copolymer (A) and polymer (B) and, optionally, one or more additives (C). Such powders and granules exhibit overall advantageous properties including but not limited to an excellent yellowing behavior.
  • Another aspect of the present invention are powders and granules, hereinafter also being referred to as inventive powders or inventive granules, respectively, containing
    1. (A) at least one copolymer obtainable by polymerization of at least one monomer according to formula (I):
      Figure imgb0009
       in an amount of 1 to 70 mole%,
      wherein n is ≥ 3
      and
      at least one monomer according to formula (II):
      Figure imgb0010
       in an amount of 30 to 99 mole%,
    2. (B) at least one homo- or copolymer of (meth)acrylic acid, partially or fully neutralized with alkali,
      wherein the weight ratio of (A) to (B) is from 20:80 to 80:20
      in molecularly disperse form.
    A further aspect of the present invention are powders and granules, hereinafter also being referred to as inventive powders or inventive granules, respectively, containing
    1. (A) in the range of from 40 - 75 % by weight of at least one copolymer obtainable by polymerization of at least one monomer according to formula (I):
      Figure imgb0011
       in an amount of 1 to 70 mole%,
      wherein n is ≥ 3
      and
      at least one monomer according to formula (II):
      Figure imgb0012
       in an amount of 30 to 99 mole%,
    2. (B) in the range of from 60 - 25 % by weight of at least one homo- or copolymer of (meth)acrylic acid, partially or fully neutralized with alkali, in molecularly disperse form, percentages referring to the solids content of said powder or granule.
  • Copolymer (A) and polymer (B) have been defined above.
  • In the context of the present invention, the term "in molecularly disperse form" implies that all or a vast majority, for example at least 80% of the particles of inventive powder and of inventive granules contain copolymer (A) and polymer (B).
  • In one embodiment of the present invention, inventive powders are selected from powders having an average particle diameter in the range of from 1 µm to less than 0.1 mm.
  • In one embodiment of the present invention, inventive granules are selected from granules with an average particle diameter in the range of from 0.1 mm to 2 mm, preferably 0.45 mm to 1.00 mm.
  • In one embodiment of the present invention, inventive powder or inventive granule contains in the range of from 20 - 80 % by weight copolymer (A) and 80 - 20 % by weight homo- or copolymer (B), percentages referring to the solids content of said powder or granule.
  • In a preferred embodiment of the present invention, the term "in molecularly disperse form" also implies that essentially all particles of inventive powder or inventive granule contains in the range of from 40 - 75 % by weight copolymer (A) and 60 - 25 % by weight homo- or copolymer (B), percentages referring to the solids content of the respective powder or granule.
  • In one embodiment of the present invention, inventive powders and inventive granules are selected from those wherein polymer (B) has an average molecular weight Mw in the range of from 1,200 to 30,000 g/mol, determined by gel permeation chromatography and referring to the respective free acid.
  • In one embodiment of the present invention, inventive powders and inventive granules are selected from those wherein copolymer (A) is a copolymer obtainable by polymerization of at least one monomer according to formula (I):
    Figure imgb0013
     in an amount of 1 to 70 mole%,
    wherein n is between 5 and 7
    and
    at least one monomer according to formula (II):
    Figure imgb0014
     in an amount of 30 to 99 mole%.
  • In one embodiment of the present invention, inventive powders and inventive granules are selected from those wherein said homo- and copolymer (B) are selected from the per-sodium salts of polyacrylic acid.
  • In one embodiment of the present invention, inventive powders and inventive granules are selected from those wherein said polymer (B) is selected from copolymers of (meth)acrylic acid and a comonomer bearing at least one sulfonic acid group per molecule. Comonomers bearing at least one sulfonic acid group per molecule may be incorporated into polymer (B) as free acid or least partially neutralized with alkali. Particularly preferred sulfonic-acid-group-containing comonomers are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid (AMPS), 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 salts of said acids, such as the sodium salts, potassium salts or ammonium salts thereof.
  • In one embodiment of the present invention, inventive powders and inventive granules are selected from those wherein said polymer (B) is selected from a combination of at least one polyacrylic acid and at least one copolymer of (meth)acrylic acid and a comonomer bearing at least one sulfonic acid group per molecule, both polymers being fully neutralized with alkali.
  • Inventive powders and inventive granules exhibit overall advantageous properties including but not limited to being stable under high alkaline conditions with no malodour formation and evolvement during storage conditions. They are therefore excellently suitable for the manufacture of cleaning agents.
  • Typical compact and powder detergents may for example comprise the following ingredients
    Figure imgb0015
  • The present invention is further illustrated by working examples.
  • General remarks: NI: Norm liter, liters under normal conditions; Nm3: norm cubic meter, cubic meter under normal conditions
    • Example I: Manufacture of inventive granules 1.1 Manufacture of spray solution SL.1
  • A vessel was charged with 25kg of an aqueous solution of Sokalan® PA 30 CL PN (homopolymer (B)) and 13,3kg of an aqueous solution of Sokalan® SR400 (copolymer (A)). The solution SL.1 so obtained was stirred, heated to 70°C and then subjected to spray granulation. The solid ratio between Sokalan® PA 30 CL PN and Sokalan® SR400 is 3:1.
    • 1.2 Spray granulation of Spray Solution SL.1
  • The granulation was carried out in a lab granulator (Glatt LabSystem with Vario 3 insert attached with a zig-zag air classifier).
  • At the beginning, the granulator was charged with 1,3kg of solid Sokalan® PA 30 CL PN spherical particles. An amount of 200 Nm3/h of air with a temperature of 166 to 173°C was blown from the bottom. A fluidized bed of Sokalan® Pa 30 CL PN particles was obtained. The inventive solution SL.1 was introduced by spraying 7,3 kg of SL.1 (temperature of the solution: 70°C) per hour into the fluidized bed from the bottom through a two-fluid nozzle (parameters: absolute pressure in the nozzle: 5 bar). Granules were formed, and the bed temperature, which corresponds to the surface temperature of the solids in the fluidized bed, was 100°C.
  • Continuously, particles, which are large (heavy) enough fall through the zigzag air classifier (operated at 0,5 to 0,7 bar relative pressure) into a sample bottle. The smaller (lighter) granules were blown through the recycle back into the fluidized bed by the air classifier.
  • When about 1-2L of granules were collected in the sample bottle, the bottle is replaced by a new sample bottle. The collected granules were subjected to a sieving step. The mesh size of the sieve is 1mm. Two fractions were obtained: coarse particles (diameter > 1mm) and value fraction (<1mm). Coarse particles (diameter > 1mm), were milled using a hammer mill (Kinetatica Polymix PX-MFL 90D) at 4000 rpm (rounds per minute), 2 mm mesh. The powder so obtained was returned into the fluidized bed.
  • After 10kg of sprayed liquid a steady state was reached. The fraction <1 mm was collected as inventive granule Gran 1.
  • In the above example, hot air can be replaced by hot nitrogen having the same temperature of 166-173°C.
    • II. Manufacture of further spray solutions and spray granulation thereof 11.1 Manufacture of spray solution SL.2 and spray granulation
  • A vessel was charged with 16,67kg of an aqueous solution of Sokalan® CP 45 (Copolymer (B)) and 26,67kg of an aqueous solution of Sokalan® SR400 (copolymer (A)). The solution SL.2 so obtained was stirred, heated to 70°C and then subjected to spray granulation. The solid ratio between Sokalan® CP 45 and Sokalan® SR400 is 1:1.
  • For spray granulation, the protocol according to 1.2 was followed but with spraying of SL.2 instead of SL.1. Inventive granule Gran 2 was obtained.
    • 11.2 Manufacture of spray solution SL.3 and spray granulation
  • A vessel was charged with 8,34kg of an aqueous solution of Sokalan® PA 30 CL PN (homopolymer (B)) and 13,34kg of an aqueous solution of Sokalan® SR400 (copolymer (A)). The solution SL.3 so obtained was stirred, heated to 70°C and then subjected to spray granulation. The solid ratio between Sokalan® PA 30 CL PN and Sokalan® SR400 is 1:1
  • For spray granulation, the protocol according to 1.2 was followed but with spraying of SL.3 instead of SL.1. Inventive granule Gran 3 was obtained.
    • II.3 Manufacture of spray solution SL.4 and spray granulation
  • A vessel was charged with 5,22kg of an aqueous solution of Sokalan® PA 30 CL PN (homopolymer (B)) and 16kg of an aqueous solution of Sokalan® SR400 (copolymer (A)). The solution SL.4 so obtained was stirred, heated to 70°C and then subjected to spray granulation. The solid ratio between Sokalan® PA 30 CL PN and Sokalan® SR400 is 1:2
  • For spray granulation, the protocol according to 1.2 was followed but with spraying of SL.4 instead of SL.1. Inventive granule Gr.4 was obtained.
    • III.1: Comparative example: Manufacture of a comparative spray drying of copolymer (A)
  • A Sokalan® SR400 aqueous solution with a content of 31 % by weight was applied with a brush on a hot surface (150°C). After 10 minutes of drying time, the dried Sokalan® SR400 was still sticky and ruber-like. No powder or granules could be obtained even after prolonged drying.
  • Storage tests:
    A standard powder detergent was mixed with the inventive granules by a dry mixing equipment. The resulting products were stored and subjected to an olfactory assessment up to 12 weeks. The result is given as "pass" or "no pass".
    product intial 4 weeks RT 8 weeks RT 12 weeks RT
    Standard powder detergent pass pass pass pass
    Standard powder detergent plus + inventive granule 3 pass pass pass pass
    Standard powder detergent plus + inventive granule 4 pass pass pass pass
    • Performance Tests:
  • Textile sheets made of cotton and polyester, previously equipped with altogether 60 standardised stains, were laundered in the laundry machine at 30 °C with wash fleets each containing 3.8 g/l of a laundry detergent W1, W2 and W3 of the composition as described in table1, and subsequently dried. The resulting brightness values (Y values) were determined. The laundry detergent containing an inventive combination of agents were superior to the laundry detergents without the inventive combination. Table 1: composition of laundry detergents (weight-%)
    W1 W2 W3
    inventive granule 1 - 0,25 -
    inventive granule 3 - - 0,25
    Carboxymethylcellulose 3 3 3
    HEDP-Na4 1 1 1
    Polyacrylate 3 3 3
    Sodium silicate 7 7 7
    Sodium carbonate 21 21 21
    Defoamer 0,1 0,1 0,1
    Sodium hydrogen carbonate 10 10 10
    Sodium percarbonate 12 12 12
    TAED 4 4 4
    Enzyme 0,8 0,8 0,8
    Perfume 0,3 0,3 0,3
    Alkyl Benzene Sulfonic Acid, Na-salt 13 13 13
    Fatty Alcohol Sulfate-Na 3 3 3
    Soap 0,1 0,1 0,1
    Optical brightener 0,2 0,2 0,2
    Water, Sodium Sulfate, other Polymers Ad 100 Ad 100 Ad 100
    Table 2: number of stains on which improved removal of stains was detected, compared to W1:
    Fat containing stains on polyester Fat containing stains on cotton
    W2 6 5
    W3 8 9

Claims (15)

  1. Process for making a powder or granule containing
    (A) at least one copolymer obtainable by polymerization of at least one monomer according to formula (I):
    Figure imgb0016
     in an amount of 1 to 70 mole%,
    wherein n is ≥ 3
    and
    at least one monomer according to formula (II):
    Figure imgb0017
     in an amount of 30 to 99 mole%,
    (B) at least one homo- or copolymer of (meth)acrylic acid, partially or fully neutralized with alkali,
    wherein the weight ratio of (A) to (B) is from 20:80 to 80:20,
    said process comprising the steps of
    (a) mixing the at least one copolymer (A) and the at least one homo- or copolymer (B) in the presence of water,
    (b) removing most of said water by spray-drying or spray granulation using a gas with an inlet temperature of at least 125°C.
  2. Process according to claim 1, wherein said powder or granule contains in the range of from 40 - 75 % by weight copolymer (A) and 60 - 25 % by weight homo- or copolymer (B), percentages referring to the solids content of said powder or granule.
  3. Process according to claim 1 or 2, wherein the copolymer (A) is selected from random copolymer obtainable by polymerization of at least one monomer according to formula (I):
    Figure imgb0018
     in an amount of 1 to 67 mole%,
    wherein n is between 5 and 7 and
    at least one monomer according to formula (II):
    Figure imgb0019
     in an amount of 30 to 99 mole%.
  4. Process according to any of the preceding claims, wherein said homo- and copolymer (B) is selected from the per-sodium salts of polyacrylic acid.
  5. Process according to any of the preceding claims, wherein said homo- or copolymer (B) has an average molecular weight Mw in the range of from 1,200 to 30,000 g/mol, determined by gel permeation chromatography and referring to the respective free acid.
  6. Process according to any of the preceding claims wherein said homo- and copolymers (B) are selected from copolymers of (meth)acrylic acid and a comonomer bearing at least one sulfonic acid group per molecule.
  7. Powder or granule containing
    (A) at least one copolymer obtainable by polymerization of at least one monomer according to formula (I):
    Figure imgb0020
     in an amount of 1 to 70 mole%,
    wherein n is ≥ 3
    and
    at least one monomer according to formula (II):
    Figure imgb0021
     in an amount of 30 to 99 mole%,
    (B) at least one homo- or copolymer of (meth)acrylic acid, partially or fully neutralized with alkali,
    wherein the weight ratio of (A) to (B) is from 20:80 to 80:20
  8. Powder or granule according to claim 7, said powder or granule containing
    (A) in the range of from 40 - 75 % by weight of at least one copolymer obtainable by polymerization of at least one monomer according to formula (I):
    Figure imgb0022
     in an amount of 1 to 70 mole%,
    wherein n is ≥ 3
    and
    at least one monomer according to formula (II):
    Figure imgb0023
     in an amount of 30 to 99 mole%,
    (B) in the range of from 60 - 25 % by weight of at least one homo- or copolymer of (meth)acrylic acid, partially or fully neutralized with alkali,
    in molecularly disperse form, percentages referring to the solids content of said powder or granule.
  9. Powder or granule according to claim 7 or 8 having a residual moisture content in the range of from 1 to 20 % by weight.
  10. Powder or granule according to any of claims 7 to 9 having an average diameter in the range of from powders with an average particle diameter in the range of from 1 µm to less than 0.1 mm and from granules with an average particle diameter in the range of from 0.1 mm to 2 mm.
  11. Powder or granule according to any of claims 7 to 10 wherein said homo- or copolymer (B) has an average molecular weight Mw in the range of from 1,200 to 30,000 g/mol, determined by gel permeation chromatography and referring to the respective free acid.
  12. Powder or granule according to any of claims 7 to 11 wherein copolymer (A) is selected from a random copolymer obtainable by polymerization of at least one monomer according to formula (I):
    Figure imgb0024
     in an amount of 1 to 67 mole%,
    wherein n is between 5 and 7 and
    at least one monomer according to formula (II):
    Figure imgb0025
     in an amount of 30 to 99 mole%.
  13. Powder or granule according to any of claims 7 to 12 wherein said homo- and copolymer (B) is selected from the per-sodium salts of polyacrylic acid.
  14. Powder or granule according to any of claims 7 to 13 wherein said homo- and copolymers (B) are selected from copolymers of (meth)acrylic acid and a comonomer bearing at least one sulfonic acid group per molecule.
  15. Cleaning agent, containing at least one powder or granule according to any of claims 7 to 14.
EP18196604.5A 2018-09-25 2018-09-25 Powder and granule, process for making such powder and granule, and use thereof Active EP3628724B1 (en)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4170582A (en) 1976-08-03 1979-10-09 Dainippon Ink And Chemicals, Inc. Process for preparing a polymer resin aqueous dispersion
US20090234062A1 (en) 2002-11-20 2009-09-17 Harm-Jan Kok Aqueous emulsion polymer as dispersant
US7687554B2 (en) 2003-09-11 2010-03-30 Ciba Specialty Chemicals Corporation Water based concentrated product forms of light stabilizers made by a heterophase polymerization technique
WO2015078736A1 (en) 2013-11-27 2015-06-04 Basf Se Random copolymers as soil release agents in laundry processes
WO2016049456A1 (en) * 2014-09-26 2016-03-31 International Flavors & Fragrances Inc. Capsule aggregates
EP3196284A1 (en) * 2016-01-21 2017-07-26 Henkel AG & Co. KGaA Removal of anti-transpirant contamination
WO2018028935A1 (en) * 2016-08-08 2018-02-15 Henkel Ag & Co. Kgaa Stable liquid detergent comprising soil release polymer

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4170582A (en) 1976-08-03 1979-10-09 Dainippon Ink And Chemicals, Inc. Process for preparing a polymer resin aqueous dispersion
US20090234062A1 (en) 2002-11-20 2009-09-17 Harm-Jan Kok Aqueous emulsion polymer as dispersant
US7687554B2 (en) 2003-09-11 2010-03-30 Ciba Specialty Chemicals Corporation Water based concentrated product forms of light stabilizers made by a heterophase polymerization technique
WO2015078736A1 (en) 2013-11-27 2015-06-04 Basf Se Random copolymers as soil release agents in laundry processes
WO2016049456A1 (en) * 2014-09-26 2016-03-31 International Flavors & Fragrances Inc. Capsule aggregates
EP3196284A1 (en) * 2016-01-21 2017-07-26 Henkel AG & Co. KGaA Removal of anti-transpirant contamination
WO2018028935A1 (en) * 2016-08-08 2018-02-15 Henkel Ag & Co. Kgaa Stable liquid detergent comprising soil release polymer

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WO2020064570A1 (en) 2020-04-02

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