EP1141218B1 - Verfahren zur herstellung einer körnigen reinigungsmittelzusammensetzung - Google Patents
Verfahren zur herstellung einer körnigen reinigungsmittelzusammensetzung Download PDFInfo
- Publication number
- EP1141218B1 EP1141218B1 EP98965437A EP98965437A EP1141218B1 EP 1141218 B1 EP1141218 B1 EP 1141218B1 EP 98965437 A EP98965437 A EP 98965437A EP 98965437 A EP98965437 A EP 98965437A EP 1141218 B1 EP1141218 B1 EP 1141218B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- granules
- detergent
- spray
- surfactants
- aqueous solution
- 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.)
- Expired - Lifetime
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- 239000003599 detergent Substances 0.000 title claims description 90
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 239000008187 granular material Substances 0.000 claims description 43
- 238000000034 method Methods 0.000 claims description 43
- 230000008569 process Effects 0.000 claims description 39
- 239000002736 nonionic surfactant Substances 0.000 claims description 33
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 28
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- 238000000576 coating method Methods 0.000 claims description 14
- 238000001694 spray drying Methods 0.000 claims description 14
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- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 10
- 239000004115 Sodium Silicate Substances 0.000 claims description 7
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 7
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- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- DAPMZWDGZVFZMK-UHFFFAOYSA-N sodium;2-[2-[4-[4-[2-(2-sulfophenyl)ethenyl]phenyl]phenyl]ethenyl]benzenesulfonic acid Chemical group [Na].[Na].OS(=O)(=O)C1=CC=CC=C1C=CC1=CC=C(C=2C=CC(C=CC=3C(=CC=CC=3)S(O)(=O)=O)=CC=2)C=C1 DAPMZWDGZVFZMK-UHFFFAOYSA-N 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000001180 sulfating effect Effects 0.000 description 1
- 230000019635 sulfation Effects 0.000 description 1
- 238000005670 sulfation reaction Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- GTZCVFVGUGFEME-UHFFFAOYSA-N trans-aconitic acid Natural products OC(=O)CC(C(O)=O)=CC(O)=O GTZCVFVGUGFEME-UHFFFAOYSA-N 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
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
- 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
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents
- C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
Definitions
- the present invention relates to a process for preparing a detergent composition having improved solubility and improved physical properties.
- nonionic surfactants tend to stick together, resulting in the formation of large particles.
- the stickiness of nonionic surfactant may be caused by premature dissolution.
- the nonionic surfactants start to dissolve first, changing their form to that of a gel-like substance, and finally becoming sticky.
- the sticky, gel-like formation of the nonionic surfactants on the surface of granular detergent particles tends to perform masking/covering of the detergent particles to prevent dissolution of detergent particles, particularly to prevent the dissolution of detergent slurry located inside of the granular particles.
- the stickiness tends to proceed agglomeration of the particles, resulting in increased caking of the granular detergent composition during the remainder of processing, after preparing granules, and in storage.
- EP 353 976 and US 3 989 635 relate to a process for preparing a granular detergent composition.
- the present invention is directed to process for making a granular detergent composition comprising the steps of:
- mixtures is meant to include a simple combination of materials and any compounds that may result from their combination.
- cold water means water which has at a temperature of bellow 30° C.
- density means bulk density unless specifically stated otherwise.
- ingredients such as detersive surfactants and builders useful herein may be categorized or described by their benefit or their postulated mode of action. However, it is to be understood that the ingredients useful herein can, in some instances, provide more than one benefit or operate via more than one mode of action. Therefore, classifications herein are made for the sake of convenience and are not intended to limit an ingredient to the particularly stated application or applications listed.
- the present invention is directed to a process for preparing a granular detergent composition
- a process for preparing a granular detergent composition comprising the steps of: granulating a detersive material comprising a detergent surfactant and a builder; and coating an inorganic aqueous solution on the granules to substantially coat the granules, wherein the process further comprises the step of applying a zeolite shell to the coated granules obtained by step (b).
- the granular detergent composition prepared by the process of the present invention provides improved solubility of detergent compositions, e.g., by coating of the aqueous inorganic that prevents gel-like formation of particulate granules in the remainder of processing, after preparing granules, and in storage.
- the improved solubility can be detected by evidence of increased solubility of the surfactants in the washing solution, by the decreased amount of granular detergent left on laundered clothes, and/or by substantially no caking in the stored package.
- the composition prepared by the process herein can also provide good physical properties such as free flowability and high density to the granules. Improved free flowability can provide no caking and no lumps in product so as to be easy to use, e.g., to scoop and measure the detergent.
- the composition prepared by the present invention can provide increased bulk density, particularly increasing 50 to 70 g/l more (the range of conventional compact detergent is about 600 to 800g/l), resulting in producing more a compact detergent product to the consumer.
- the composition which is more compact but has no caking and good solubility can make use of the detergent easier for the consumers.
- surfactants particularly nonionic surfactants, contained in detersive materials, which change the form to gel when exposed to humidity or when contacted with water, tend to permeate coming out of the granules.
- the surfactant which coats the detergent beads may perform as well (binding detergent particles by gelled surfactants).
- the surfactant turned to gel-like formation makes each particulate stick together to form large agglomerates.
- gelled surfactants may mask the each particulate, e.g., substantially cover the detersive material, resulting in preventing dissolution of the detersive material.
- inorganic aqueous solutions used in the process of the present invention have good water solubility, therefore tending to smoothly dissolve when exposed to humidity and facilitating dissolution of the composition.
- the first step for preparing granular detergent composition of the present invention is granulating a detersive material comprising a detergent surfactant and a builder. Any known processes conventionally used for preparing granules, various means and equipment are available.
- the detersive material is applied by the form of an aqueous slurry.
- slurry refers to a mixture of a detergent surfactant and a builder, which is not substantially solid form.
- the slurry can also include other ingredients such as brighteners and buffers.
- Spray-drying for slurry mixtures preferably for aqueous slurry mixtures to form spray-dried granules, is preferable. More preferably, spray-drying in relatively tall spray drying towers is useful.
- the spray drying process useful herein includes dispersing an aqueous slurry or mixture under high pressure through nozzles down a spray drying tower through which hot gases are counter-currently flowing up the tower. This step can be carried out in conventional spray drying equipment such as the aforementioned towers as well as other spray drying apparatus.
- the spray-dried granules, that are subsequently used as part of the overall process then can be compacted by a compacting machine.
- the aqueous slurry used comprises the anionic surfactant, the builder, and no more than about 1.0%, preferably about 0%, by weight of nonionic surfactant.
- the amount of nonionic surfactant in the aqueous slurry is based on limitations concerning environmental and safety concerns (plume opacity, auto-oxidation) and limitations concerning the physical properties of the slurry used during the spray drying process.
- Spray-dried granules from a tower also can be densified further by loading a liquid such as water or a nonionic surfactant into the pores of the granules and/or subjecting them to one or more high speed mixer/densifiers.
- a suitable high speed mixer/densifier for this process is a device marketed under the tradename "Lödige CB 30" or “Lödige CB 30 Recycler” which comprises a static cylindrical mixing drum having a central rotating shaft with mixing/cutting blades mounted thereon. In use, the ingredients for the composition are introduced into the drum and the shaft/blade assembly is rotated at speeds in the range of 100-2500 rpm to provide thorough mixing/densification. See U.S.
- Other such apparatus includes the devices marketed under the tradename “Shugi Granulator” and under the tradename “Drais K-TTP 80".
- Another process step which can be used to further densify spray-dried granules involves treating the spray-dried granules in a moderate speed mixer/densifier.
- Equipment such as that marketed under the tradename "Lödige KM” (Series 300 or 600) or “Lödige Ploughshare” mixer/densifiers are suitable for this process step.
- Such equipment is typically operated at 40-160 rpm.
- the residence time of the detergent ingredients in the moderate speed mixer/densifier is from about 0.1 to 12 minutes conveniently measured by dividing the steady state mixer/densifier weight by the throughput ( e.g ., Kg/hr).
- the formulator can eliminate the spray-drying step by feeding, in either a continuous or batch mode, starting detergent ingredients directly into mixing equipment that is commercially available.
- One particularly preferred embodiment involves charging a surfactant paste and an anhydrous material into a high speed mixer/densifier (e.g. , Lödige CB) followed by a moderate speed mixer/densifier (e.g ., Lödige KM) to form high density detergent agglomerates.
- a high speed mixer/densifier e.g. , Lödige CB
- a moderate speed mixer/densifier e.g ., Lödige KM
- Patent 5,486,303, Capeci et al issued January 23, 1996 .
- the liquid/solids ratio of the starting detergent ingredients in such a process can be selected to obtain high density agglomerates that are more free flowing and crisp. See U.S. Patent 5,565,137, Capeci et al, issued October 15, 1996 .
- the process may include one or more recycle streams of undersized particles produced by the process which are fed back to the mixer/densifiers for further agglomeration or build-up.
- the oversized particles produced by this process can be sent to grinding apparatus and then fed back to the mixing/densifying equipment.
- These additional recycle process steps facilitate build-up agglomeration of the starting detergent ingredients resulting in a finished composition having a uniform distribution of the desired particle size (400-700 microns) and density (> 550 g/l). See U.S. Patent 5,516,448, Capeci et al, issued May 14, 1996 and U.S. Patent 5,489,392, Capeci et al, issued February 6, 1996 .
- a high density detergent composition using a fluidized bed mixer.
- the various ingredients of the finished composition are combined in an aqueous slurry (typically 80% solids content) and sprayed into a fluidized bed to provide the finished detergent granules.
- this process can optionally include the step of mixing the slurry using the aforementioned Lödige CB mixer/densifier or a "Flexomix 160" mixer/densifier, available from Shugi. Fluidized bed or moving beds of the type available under the tradename "Escher Wyss" can be used in such processes.
- Another suitable process which can be used herein involves feeding a liquid acid precursor of an anionic surfactant, an alkaline inorganic material (e.g. , sodium carbonate) and optionally other detergent ingredients into a high speed mixer/densifier so as to form particles containing a partially or totally neutralized anionic surfactant salt and the other starting detergent ingredients.
- a high speed mixer/densifier e.g. , Lödige KM
- the contents in the high speed mixer/densifier can be sent to a moderate speed mixer/densifier (e.g. , Lödige KM) for further mixing resulting in the finished high density detergent composition. See U.S. Patent 5,164,108, Appel et al, issued November 17, 1992 .
- high density detergent compositions according to the invention can be produced by blending conventional or densified spray-dried detergent granules with detergent agglomerates in various proportions (e.g ., a 60:40 weight ratio of granules to agglomerates) produced by one or a combination of the processes discussed herein. See U.S. Patent 5,569,645, Dinniwell et al, issued October 29, 1996 . Additional adjunct ingredients such as enzymes, perfumes, brighteners and the like can be sprayed or admixed with the agglomerates, granules or mixtures thereof produced by the processes discussed herein.
- the granular detergent compositions produced by the process of the present invention useful herein comprise from about 5% to about 80%, more preferably from about 10% to about 70%, most preferably from about 15% to about 40%, by weight of the composition, of detergent surfactant.
- the detergent surfactant can be selected from the group consisting of anionic surfactants, nonionic surfactants, zwitterionic surfactants, ampholytic surfactants, cationic surfactants, and mixtures thereof; more preferably anionic surfactants, nonionic surfactants and mixtures thereof.
- the granular detergent compositions of the present invention comprise from about 5% to about 80% of anionic surfactant, preferably from about 10% to about 70%, most preferably 15% to about 40% by weight.
- Water-soluble salts of the higher fatty acids are useful anionic surfactants in the compositions herein.
- Such salts include alkali metal soaps such as the sodium, potassium, ammonium, and alkylolammonium salts of higher fatty acids containing from about 8 to about 24 carbon atoms, and preferably from about 12 to about 18 carbon atoms. Soaps can be made by direct saponification of fats and oils or by the neutralization of free fatty acids.
- Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap.
- Useful anionic surfactants also include the water-soluble salts, preferably the alkali metal, ammonium and alkylolammonium salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 10 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group.
- alkyl is the alkyl portion of acyl groups.
- this group of synthetic surfactants are the sodium and potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols (C 12-18 carbon atoms) such as those produced by reducing the glycerides of tallow or coconut oil; and the sodium and potassium alkylbenzene sulfonates in which the alkyl group contains from about 10 to about 16 carbon atoms, in straight chain or branched chain configuration. See U.S. Patent No. 2,220,099 and 2,477,383 .
- Especially valuable are linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from about 11 to 14, abbreviated as C 11-14 LAS.
- C 11-16 preferably C 11-13 linear alkylbenzene sulfonates and C 12-18 (preferably C 14-16 ) alkyl sulfates. These are preferably present in a weight ratio of between 4:1 and 1:4, preferably about 3:1 to 1:3, alkylbenzene sulfonate: alkyl sulfate.
- Sodium salts of the above are preferred.
- anionic surfactants useful herein are the sodium alkyl glyceryl ether sulfonates and water-soluble salts of esters of alpha-sulfonated fatty acids. Examples of these anionic surfactants are set forth in U.S. Patent 5,565,422, Del Greco, issued October 15, 1996 .
- the granular detergent compositions of the present invention useful herein may also comprise nonionic surfactant.
- the nonionic surfactant can be incorporated into the composition as an integral part of the spray dried granule and/or via the spraying step of the process herein. A portion of the nonionic surfactant can also be incorporated after mixing and/or grinding the granules.
- Water-soluble nonionic surfactants are used in the instant detergent compositions.
- Such nonionic materials include compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature.
- the length of the polyoxyalkylene group which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
- Suitable nonionic surfactants include the polyethylene oxide condensates of alkyl phenols, e.g. , the condensation products of alkyl phenols having an alkyl group containing from about 6 to 15 carbon atoms, in either a straight chain or branched chain configuration, with from about 3 to 80 moles of ethylene oxide per mole of alkyl phenol.
- water-soluble and water-dispersible condensation products of aliphatic alcohols containing from 8 to 22 carbon atoms, in either straight chain or branched configuration, with from 3 to 12 moles of ethylene oxide per mole of alcohol.
- Semi-polar nonionic surfactants include water-soluble amine oxides containing one alkyl moiety of from abut 10 to 18 carbon atoms and two moieties selected from the group of alkyl and hydroxyalkyl moieties of from about 1 to about 3 carbon atoms; water-soluble phosphine oxides containing one alkyl moiety of about 10 to 18 carbon atoms and two moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of from about 10 to 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from about 1 to 3 carbon atoms.
- Preferred nonionic surfactants are of the formula R 1 (OC 2 H 4 )OH, wherein R 1 is a C 10-16 alkyl group or a C 8-12 alkyl phenyl group, and n is from 3 to about 80.
- condensation products of alcohols with from about 5 to about 20 moles of ethylene oxide per mole of alcohol, e.g., C 12-13 alcohol condensed with about 6.5 moles of ethylene oxide per mole of alcohol.
- the nonionic surfactant is an ethoxylated surfactant derived from the reaction of a monohydroxy alcohol or alkylphenol containing from about 8 to about 20 carbon atoms, excluding cyclic carbon atoms, with from about 6 to about 15 moles of ethylene oxide per mole of alcohol or alkyl phenol on an average basis.
- a particularly preferred ethoxylated nonionic surfactant is derived from a straight chain fatty alcohol containing from about 16 to about 20 carbon atoms (C 16-20 alcohol), preferably a C 18 alcohol, condensed with an average of from about 6 to about 15 moles, preferably from about 7 to about 12 moles, and most preferably from about 7 to about 9 moles of ethylene oxide per mole of alcohol.
- the ethoxylated nonionic surfactant so derived has a narrow ethoxylate distribution relative to the average.
- the ethoxylated nonionic surfactant can optionally contain propylene oxide in an amount up to about 15% by weight of the surfactant and retain the advantages hereinafter described.
- Preferred surfactants of the invention can be prepared by the processes described in US Patent 4,223,163, Builloty, issued September 16, 1980 .
- a highly preferred composition contains the ethoxylated monohydroxyalcohol or alkyl phenol and additionally comprises a polyoxyethylene, polyoxypropylene block polymeric compound; the ethoxylated monohydroxy alcohol or alkyl phenol nonionic surfactant comprising from about 20% to about 80%, preferably from about 30% to about 70%, of the total surfactant composition by weight.
- Suitable block polyoxyethylene-polyoxypropylene polymeric compounds that meet the requirements described hereinbefore include those based on ethylene glycol, propylene glycol, glycerol, trimethylolpropane and ethylenediamine as the initiator reactive hydrogen compound.
- Certain of the block polymer surfactant compounds designated PLURONIC and TETRONIC by the BASF-Wyandotte Corp., Wyandotte, Mich., are suitable in the surfactant compositions of the invention.
- a particularly preferred embodiment contains from about 40% to about 70% of a polyoxypropylene, polyoxyethylene block polymer blend comprising about 75%, by weight of the blend, of a reverse block co-polymer of polyoxyethylene and polyoxypropylene containing 17 moles of ethylene oxide and 44 moles of propylene oxide; and about 25%, by weight of the blend, of a block co-polymer of polyoxyethylene and polyoxypropylene, initiated with trimethylol propane, containing 99 moles of propylene oxide and 24 moles of ethylene oxide per mole of trimethylol propane.
- the compounds are suitable for use in the surfactant compositions of the invention and have relatively low cloud points.
- Cloud points of 1% solutions in water are typically below about 32 degC and preferably from about 15 degC to about 30 degC for optimum control of sudsing throughout a full range of water temperatures and water hardnesses.
- the detergent compositions may also contain surfactants selected from the group of ampholytic, zwitterinoic, cationic surfactants and mixtures thereof.
- Ampholytic surfactants include derivatives of aliphatic or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic moiety can be straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and at least one aliphatic substituent contains an anionic water-solubilizing group.
- Zwitterionic surfactants include derivatives of aliphatic, quaternary, ammonium, phosphonium, and sulfonium compounds in which one of the aliphatic substituents contains from about 8 to 18 carbon atoms.
- Cationic surfactants can also be included in the present detergent granules.
- Cationic surfactants comprise a wide variety of compounds characterized by one or more organic hydrophobic groups in the cation and generally by a quaternary nitrogen associated with an acid radical.
- Pentavalent nitrogen ring compounds are also considered quaternary nitrogen compounds. Halides, methyl sulfate and hydroxide are suitable.
- Tertiary amines can have characteristics similar to cationic surfactants at washing solution pH values less than about 8.5.
- a more complete disclosure of these and other cationic surfactants useful herein can be found in US Patent 4,228,044, Cambre, issued Oct. 14, 1980 .
- Cationic surfactants are often used in detergent compositions to provide fabric softening and/or antistatic benefits.
- Antistatic agents which provide some softening benefit and which are preferred herein are the quaternary ammonium salts described in US Patent 3,936,537, Baskerville, Jr. et al., issued February 3, 1976 .
- Useful cationic surfactants also include those described in US Patent 4,222,905, Cockrell, issued September 16, 1980 , and in US Patent 4,239,659, Murphy, issued December 16, 1980 .
- Builders are typically employed to sequester hardness ions and to help adjust the pH of the laundering liquid. Such builders present in the compositions up to about 85%, preferably from about 5% to about 50%, most preferably from about 10% to about 30% to provide their builder and pH-controlling functions.
- the builders herein include any of the conventional inorganic and organic water-soluble builder salts.
- Such builders include water-soluble salts of phosphates, e.g., such as tripolyphosphates, pyrophosphates, orthophosphates, higher polyphosphates, other carbonates, silicates, and organic polycarboxylates.
- phosphates e.g., such as tripolyphosphates, pyrophosphates, orthophosphates, higher polyphosphates, other carbonates, silicates, and organic polycarboxylates.
- Specific preferred examples of inorganic phosphate builders include sodium and potassium tripolyphosphates and pyrophosphates.
- Nonphosphorus-containing material may also be selected.
- Specific examples of nonphosphorus, inorganic detergent builder ingredients include water-soluble bicarbonate, and silicate salts.
- the alkali metal, e.g., sodium and potassium, bicarbonates, and silicates are particularly useful herein.
- Aluminosilicate ion exchange materials useful in the practice of this invention are commercially available.
- the aluminosilicates useful in this invention can be crystalline or amorphous in structure and can be naturally-occurring aluminosilicates or synthetically derived.
- a method for producing aluminosilicate ion exchange materials is discussed in Krummel et al, US Patent 3,985,669, issued October 12, 1976 .
- Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite B, and Zeolite X.
- the crystalline aluminosilicate ion exchange material in Zeolite A has the formula Na 12 [(AlO 2 ) 12 (SiO 2 ) 12 ] ⁇ H 2 O wherein x is from about 20 to about 30, especially about 27.
- Other preferred builder include a mixture of a water-insoluble aluminosilicate builder such as zeolite A or of a layered silicate ( e.g. , SKS-6), and a water-soluble carboxylate chelating agent such as citric acid.
- Still other preferred builder include a mixture of a water-insoluble aluminosilicate builder such as zeolite A, and a watersoluble carboxylate chelating agent such as citric acid.
- Preferred builder systems for use in liquid detergent compositions of the present invention are soaps and polycarboxylates.
- Water-soluble, organic builders are also useful herein.
- the alkali metal, polycarboxylates are useful in the present compositions.
- Specific examples of the polycarboxylate builder salts include sodium and potassium, salts of ethylenediaminetetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acid, polyacrylic acid, and polymaleic acid.
- polycarboxylate builders are the builders set forth in Diehl, US Patent 3,308,067 , Examples of such materials include the water-soluble salts of homo- and co-polymers of aliphatic carboxylic acids such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid, and methylenemalonic acid.
- polyacetal carboxylates are the polyacetal carboxylates described in Crutchfield et al, U.S. Patent 4,144,226, issued March 13, 1979 , and U.S. Patent 4,246,495, issued March 27, 1979 .
- These polyacetal carboxylates can be prepared by bringing together under polymerization conditions an ester of glyoxylic acid and a polymerization initiator. The resulting polyacetal carboxylate ester is then attached to chemically stable end groups to stabilize the polyacetal carboxylate against rapid depolymerization in alkaline solution, converted to the corresponding salt, and added to a surfactant.
- compositions herein preferably contain little (e.g., less than 10%, preferably less than 5%, by weight) or no phosphate builder materials.
- the presence of higher levels of tripolyphosphate improves solubility of the compositions to the point where hydrophobic amorphous silicate provides little or no additional improvements.
- sodium pyrophosphate reduces solubility so that the benefit provided by the hydrophobic amorphous silicate is greater in granular compositions containing pyrophosphate.
- the second step for making a granular detergent composition of the present invention is applying an inorganic aqueous solution on the granules to substantially coat the granule obtained by the first step of the process.
- surfactants particularly nonionic surfactants, contained in detersive materials, tend to change to gel-like formation when exposed to humidity or when contacted with water in the washing solution. If the nonionic surfactant becomes gel-like, it may permeate coming out of the granule particles during processing of detergent compositions. If such gelled nonionic surfactants are coated to detesive material granular, the coating of gelled nonionic surfactants may perform as well (coating/masking the particles). Such gel-like formation which turns to a hard coating and covers the detersive material, may inhibit preventing the dissolution of the detersive material.
- the gel-like formation makes the particles stick together to form large agglomerates.
- Such large agglomeration may also make difficulty of the dissolution of detergent particles.
- the inorganic aqueous solution used in the present invention do not become gel-like when exposed to humidity, are not sticky and have good dissolution/dispersion property, therefore tending to smoothly dissolve when exposed in humidity, and overall facilitating dissolution the composition.
- the inorganic aqueous solution is applied by spraying on the surface of the granules prepared by the granulating step.
- the concentration of the inorganic solution is from about 0.5% to about 95%, preferably from 1.0% to about 50%.
- the inorganic aqueous solution is prepared by mixing one or more ingredients selected from the group consisting of sodium carbonate, sodium sulfate, potassium carbonate, potassium sulfate, sodium silicate, sodium hydroxide, potassium hydroxide, and mixtures thereof.
- the ingredient useful herein could be used as the builder described above.
- the inorganic aqueous solution useful herein is applied in an amount of from about 0.5% to about 6.0% by the total weight of detergent components, preferably from about 1.0% to about 4.5%.
- the temperature of inorganic aqueous solution during coating step is from about 10°C to about 100°C, preferably from about 30°C to about 70°C.
- the process for preparing a granular detergent composition further comprises the step of applying a shell to the surface of the inorganic coated detergent granules.
- shell means a material which covers the granules of detersive material to preventing agglomeration of the particles.
- the detergent granules covered by shell can provide increased bulk density and reduced friction between particles; thus, the volume of the product can be reduced, providing a more compact product to the consumer.
- the concentration of the shell is from about 2% to about 15%, preferably from about 3.0% to about 7.0%.
- the shell herein is Zeolite.
- the ratio of the inorganic aqueous solution to the shell is from about 0.2 to about 7.0.
- Bleaching agents and activators additionally useful herein are described in U.S. Patent 4,412,934, Chung et al., issued November 1, 1983 ; U.S. Patent 4,483,781, Hartman, issued November 20, 1984 ; U.S. Patent 4,634,551, Burns et al, issued January 6, 1987 ; and U.S. Patent 4,909,953, Sadlowski et al, issued March 20, 1990 .
- Chelating agents are described in U.S. Patent 4,663,071, Bush et al.
- Suds modifiers are also optional ingredients and are described in U.S. Patent 3,933,672, Bartoletta et al., issued January 20, 1976 ; and U.S. Patent 4,136,045, Gault et al., issued January 23, 1979 .
- Suitable smectite clays for use herein are described in U.S. Patent 4,762,645, Tucker et al, issued August 9, 1988 .
- Suitable additional detergency builders for use herein are enumerated in U.S. Patent 3,936,537, Baskerville, Jr. et al., issued February 3, 1976 , and in U.S. Patent 4,663,071, Bush et al, issued May 5, 1987 .
- ingredients suitable for inclusion in a granular detergent composition can be added to the present compositions. These include bleach activators, suds boosters or suds suppressors, anti-tarnish and anticorrosion agents, soil suspending agents, soil release agents, germicides, pH adjusting agents, non-builder alkalinity sources, enzymes, enzyme-stabilizing agents and perfumes. Such ingredients are described in the Baskerville, Jr's U.S. Patent referred to the above.
- the detergent ingredients are expressed by weight of the total compositions.
- the abbreviated component identifications therein have the following meanings:
- compositions are suitably made as follows:
- composition prepared by the present invention have improved water solubility in many conditions and improved physical properties such as flowability and high bulk density.
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Claims (8)
- Verfahren zum Herstellen einer granulären Detergenszusammensetzung, die folgenden Schritte umfassend:(a) Granulieren eines reinigungsaktiven Materials, das ein reinigungsaktives Tensid und einen Gerüststoff umfasst; und(b) Beschichten der Granalien mit einer anorganischen wässrigen Lösung, um die Granalien damit im Wesentlichen zu überziehen, wobei das Verfahren zum Herstellen der granulären Detergenszusammensetzung ferner den Schritt des Aufbringens einer Zeolith-Hülle auf die in Schritt (b) erhaltenen beschichteten Granalien umfasst.
- Verfahren nach Anspruch 1, wobei Schritt (b) das Sprühen der anorganischen wässrigen Lösung auf die Granalien von Schritt (a) umfasst.
- Verfahren nach einem der vorstehenden Ansprüche, wobei die Konzentration der anorganischen wässrigen Lösung bei 0,5 bis 95 % liegt.
- Verfahren nach einem der vorstehenden Ansprüche, wobei die anorganische wässrige Lösung ausgewählt ist aus der Gruppe bestehend aus Natriumcarbonat, Natriumsulfat, Kaliumcarbonat, Kaliumsulfat, Natriumsilikat, Natriumhydroxid, Kaliumhydroxid und deren Mischungen.
- Verfahren nach einem der vorangehenden Ansprüche, wobei die anorganische wässrige Lösung 0,5 bis 6 Gew.-% der Zusammensetzung ausmacht.
- Verfahren nach einem der vorstehenden Ansprüche, wobei die Detergenszusammensetzung ausgewählt ist aus der Gruppe bestehend aus anionischen Tensiden, nichtionischen Tensiden, zwitterionischen Tensiden, ampholytischen Tensiden, kationischen Tensiden und deren Mischungen und von ungefähr 5 bis 80 % der Zusammensetzung umfasst.
- Verfahren nach einem der vorstehenden Ansprüche, wobei Schritt (a) das Sprühtrocknen des reinigungsaktiven Materials, um sprühgetrocknete Granalien zu bilden, und das Beschleifen der sprühgetrockneten Granalien umfasst.
- Verfahren nach einem der vorstehenden Ansprüche, wobei das Verfahren die folgenden Schritte umfasst:(a) Sprühtrocknen einer wässrigen Aufschlämmung, die ein anionisches Tensid und einen Gerüststoff umfasst, um sprühgetrocknete Agglomerate zu bilden;(b) Sprühen einer anorganischen wässrigen Lösung auf die sprühgetrockneten Agglomerate, um die Granalien im Wesentlichen zu überziehen.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/US1998/027271 WO2000037604A1 (en) | 1998-12-22 | 1998-12-22 | Process for preparing a granular detergent composition |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1141218A1 EP1141218A1 (de) | 2001-10-10 |
EP1141218B1 true EP1141218B1 (de) | 2008-09-24 |
Family
ID=22268527
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP98965437A Expired - Lifetime EP1141218B1 (de) | 1998-12-22 | 1998-12-22 | Verfahren zur herstellung einer körnigen reinigungsmittelzusammensetzung |
Country Status (10)
Country | Link |
---|---|
EP (1) | EP1141218B1 (de) |
JP (1) | JP2002533531A (de) |
CN (1) | CN1206336C (de) |
AR (1) | AR021976A1 (de) |
AT (1) | ATE409219T1 (de) |
AU (1) | AU2090399A (de) |
BR (1) | BR9816110A (de) |
CA (1) | CA2352431A1 (de) |
DE (1) | DE69840054D1 (de) |
WO (1) | WO2000037604A1 (de) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
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JP6168339B2 (ja) * | 2013-02-22 | 2017-07-26 | ライオンハイジーン株式会社 | 連続式洗濯機及びこれを用いた洗濯方法 |
CN111893008B (zh) * | 2020-08-10 | 2022-09-20 | 纳爱斯集团有限公司 | 一种洗涤制剂及其制备方法 |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5335568B2 (de) * | 1973-09-10 | 1978-09-28 | ||
EP0057611A3 (de) * | 1981-02-04 | 1982-08-25 | Unilever Plc | Seifenpulver und Verfahren zu dessen Herstellung |
GB8818613D0 (en) * | 1988-08-05 | 1988-09-07 | Paterson Zochonis Uk Ltd | Detergents |
JPH0691153A (ja) * | 1992-05-19 | 1994-04-05 | Hoechst Ag | 粉立ちの少ない顆粒の製法 |
CA2160900A1 (en) * | 1993-04-19 | 1994-10-27 | Cornelis Marinus Van't Land | Fluidized bed coated amidoperozyacid bleach composition |
-
1998
- 1998-12-22 AT AT98965437T patent/ATE409219T1/de not_active IP Right Cessation
- 1998-12-22 CA CA002352431A patent/CA2352431A1/en not_active Abandoned
- 1998-12-22 DE DE69840054T patent/DE69840054D1/de not_active Expired - Fee Related
- 1998-12-22 EP EP98965437A patent/EP1141218B1/de not_active Expired - Lifetime
- 1998-12-22 CN CN98814372.0A patent/CN1206336C/zh not_active Expired - Fee Related
- 1998-12-22 AU AU20903/99A patent/AU2090399A/en not_active Abandoned
- 1998-12-22 BR BR9816110-5A patent/BR9816110A/pt not_active IP Right Cessation
- 1998-12-22 JP JP2000589660A patent/JP2002533531A/ja active Pending
- 1998-12-22 WO PCT/US1998/027271 patent/WO2000037604A1/en active Application Filing
-
1999
- 1999-12-22 AR ARP990106663A patent/AR021976A1/es active IP Right Grant
Also Published As
Publication number | Publication date |
---|---|
BR9816110A (pt) | 2001-09-04 |
JP2002533531A (ja) | 2002-10-08 |
EP1141218A1 (de) | 2001-10-10 |
WO2000037604A1 (en) | 2000-06-29 |
ATE409219T1 (de) | 2008-10-15 |
DE69840054D1 (de) | 2008-11-06 |
AR021976A1 (es) | 2002-09-04 |
CN1354783A (zh) | 2002-06-19 |
CN1206336C (zh) | 2005-06-15 |
CA2352431A1 (en) | 2000-06-29 |
AU2090399A (en) | 2000-07-12 |
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