EP0971023A1 - Tensidagglomerate - Google Patents

Tensidagglomerate Download PDF

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Publication number
EP0971023A1
EP0971023A1 EP99870092A EP99870092A EP0971023A1 EP 0971023 A1 EP0971023 A1 EP 0971023A1 EP 99870092 A EP99870092 A EP 99870092A EP 99870092 A EP99870092 A EP 99870092A EP 0971023 A1 EP0971023 A1 EP 0971023A1
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EP
European Patent Office
Prior art keywords
surfactant
agglomerate
acetate
alkyl
water
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
EP99870092A
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English (en)
French (fr)
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EP0971023B1 (de
Inventor
Lucas Goovaerts
Eric Tcheou
Jose Luis Vega
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Procter and Gamble Co
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Procter and Gamble Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to DE69926181T priority Critical patent/DE69926181T2/de
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to AT99870092T priority patent/ATE299928T1/de
Priority to ES99870092T priority patent/ES2245819T3/es
Priority to EP99870092A priority patent/EP0971023B1/de
Priority to ARP990103365A priority patent/AR027165A1/es
Priority to CA002333045A priority patent/CA2333045A1/en
Priority to CZ20004890A priority patent/CZ20004890A3/cs
Priority to MA25674A priority patent/MA24925A1/fr
Priority to AU49847/99A priority patent/AU4984799A/en
Priority to JP2000559211A priority patent/JP2002520445A/ja
Priority to PCT/US1999/015667 priority patent/WO2000002989A1/en
Priority to BR9912006-2A priority patent/BR9912006A/pt
Priority to KR1020007014086A priority patent/KR20010052780A/ko
Priority to CN99808437A priority patent/CN1308666A/zh
Publication of EP0971023A1 publication Critical patent/EP0971023A1/de
Priority to US10/303,388 priority patent/US20030171245A1/en
Application granted granted Critical
Publication of EP0971023B1 publication Critical patent/EP0971023B1/de
Anticipated expiration legal-status Critical
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    • 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
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • 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
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/128—Aluminium silicates, e.g. zeolites
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • 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

Definitions

  • X can be a nonionic group selected from hydrogen (H), C 1 -C 4 alkyl or hydroxyalkyl ester or ether groups, or mixtures thereof.
  • Preferred esters or ethers are the acetate ester and methyl ether, respectively.
  • the particularly preferred nonionic groups are H and the methyl ether.
  • Preferred ethoxylated cationic monoamines and diamines have the formula: wherein X and n are defined as before, a is from 0 to 4 (e.g. ethylene, propylene, hexamethylene) b is 1 or 0.
  • a is from 0 to 4 (e.g. ethylene, propylene, hexamethylene) b is 1 or 0.
  • n is preferably at least about 12, with a typical range of from about 15 to about 35.
  • n is at least about 12 with a typical range of from about 12 to about 42.
  • R 4 (linear, branched, or cyclic) is preferably a substituted C 3 -C 6 alkyl, hydroxyalkyl or aryl group;
  • a 1 is preferably n is preferably at least about 12, with a typical range of from about 12 to about 42;
  • p is preferably from 3 to 6.
  • q is preferably 1 and R 5 is preferably C 2 -C 3 alkylene.
  • ethoxylated cationic polyamines can be derived from polyamino amides such as: These ethoxylated cationic polyamines can also be derived from polyaminopropyleneoxide derivatives such as: wherein each c is a number from 2 to about 20.
  • Cationic amines of the present invention can be prepared according to the following scheme: The synthesis of one such cationic amine is described as follows:
  • the ethoxylated compound (0.03 moles) from step 1 is mixed with 1,6-dibromohexane (0.015 moles).
  • the reaction mixture is mixed, sealed in a jar, and heated to 80°C for ten days to provide crude quaternized 1,6-bis[(-N-morpholiniopolyethoxylate (11)]-hexane dibromide.
  • TEA Dried triethanolamine
  • EO Ethylene oxide
  • PEI 17 The ethoxylated TEA (PEI 17) was a light brown waxy solid.
  • attachment to means that the group is pendent from the polymer backbone, examples of which are represented by the following general structures A and B:
  • integral with means that the group forms part of the polymer backbone, examples of which are represented by the following general structures C and D:
  • M can be any compatible cationic group which comprises an N + (quaternary), positively charged center.
  • the quaternary positively charged center can be represented by the following general structures E and F: Particularly preferred M groups are those containing a quaternary center represented by general structure E.
  • the cationic group is preferably positioned close to or integral with the polymer backbone.
  • the cationic polymers of the present invention normally have a ratio of cationic groups M to nonionic groups X of from about 1:1 to about 1:2.
  • the ratio of cationic groups M to nonionic groups X can be varied.
  • the ratio of groups M to groups X can usually range from about 2:1 to about 1:10.
  • the ratio is from about 1:1 to about 1:5.
  • the polymers formed from such copolymerization are typically random, i.e. the cationic, nonionic, and mixed cationic/nonionic monomers copolymerize in a nonrepeating sequence.
  • the units which contain groups M and groups L-X can comprise 100% of the cationic polymers of the present invention.
  • inclusion of other units (preferably nonionic) in the polymers is also permissible.
  • other units include acrylamides, vinyl ethers, and those containing unquaternized tertiary amine groups (M 1 ) containing an N center.
  • M 1 unquaternized tertiary amine groups
  • These other units can comprise from 0 to about 90% of the polymer (from about 10 to 100% of the polymer being units containing M and L-X groups, including M 1 -L-X groups).
  • these other units comprise from 0 to about 50% of the polymer (from about 50 to 100% of the polymer being units containing M and L-X groups).
  • a plurality (2 or more) of moieties -L-X can also be hooked together and attached to group M or to the polymer backbone, examples of which are represented by the following general structures G and H:
  • Structures such as G and H can be formed, for example, by reacting glycidol with group M or with the polymer backbone, and ethoxylating the subsequently formed hydroxy groups.
  • cationic polymers of the present invention are as follows:
  • a 1 is preferably A 2 is preferably -O-; x is preferably 1; and R is preferably H.
  • R 1 can be linear (e.g. -CH 2 -CH 2 -CH 2 -, or branched alkylene, hydroxyalkylene, alkenylene, cycloalkylene, alkarylene or oxyalkylene; when R 1 is a C 2 -C 3 oxyalkylene moiety, the number of oxyalkylene units is preferably from about 2 to about 12; R 1 is preferably C 2 -C 6 alkylene or phenylene, and most preferably C 2 -C 6 alkylene (e.g. ethylene, propylene, hexamethylene).
  • R 2 is preferably -OR 5 - or -(OR 8 ) y -; R 3 is preferably -R 5 O- or -(R 8 O) y -; R 4 and R 6 are preferably methyl.
  • R 5 can be linear or branched, and is preferably C 2 -C 3 alkylene; R 7 is preferably H or C 1 -C 3 alkyl; R 8 is preferably ethylene; R 9 is preferably methyl; X is preferably H or methyl; k is preferably 0; m is preferably 0; r and s are each preferably 2; y is preferably from 2 to about 12.
  • n is preferably at least about 6 when the number of N + centers and X groups is 2 or 3; n is most preferably at least about 12, with a typical range of from about 12 to about 42 for all ranges of u + v + w.
  • u is preferably from about 3 to about 40, and is most preferably from about 3 to about 20.
  • v and w are each preferably from about 3 to about 40.
  • Suitable cationic polymers are derived from polyacrylates, polyacrylamides, polyvinylethers and the like. These polymers comprise units selected from those having formulas IV, V and VI: wherein A 1 is -O-, R is H or C 1 -C 4 alkyl or hydroxyalkyl ; R 1 is substituted C 2 -C 12 alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene, or C 2 -C 3 oxyalkylene; each R 2 is C 1 -C 12 alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene; each R 3 is C 1 -C 4 alkyl or hydroxyalkyl, the moiety -(R 2 ) k -[(C 3 H 6 O) m (CH 2 CH 2 O) n ]-X, or together form the moiety -(CH 2 ) r -A 2 -(CH 2 ) s -, wherein A 2
  • n, u, v and w can be varied according to the n, u, v and w for the polyurethane and like polymers.
  • Suitable cationic polymers are derived from polyalkyleneamines, polyalkyleneimines and the like. These polymers comprise units selected from those having formulas VII and VIII and IX : wherein R 1 is C 2 - C 12 alkylene, hydroxyalkylene, alkenylene, cycloalkylene, arylene or alkarylene, or a C 2 -C 3 oxyalkylene moiety having from 2 to about 20 oxyalkylene units provided that no O-N bonds are formed; each R 2 is C 1 -C 4 alkyl or hydroxyalkyl, or the moiety - (R 3 ) k -[(C 3 H 6 O) m (CH 2 CH 2 O) n ]-X; R 3 is C 1 -C 12 alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene; M' is an N + or N center; X is H, -R 4 or mixture thereof, wherein R 4 is C 1 -C 4
  • R 1 can be varied like R 1 of the polyurethane and like polymers; each R 2 is preferably methyl or the moiety -(R 3 ) k -[(C 3 H 6 O) m (CH 2 CH 2 O) n ]-X; R3 is preferably C 2 -C 3 alkylene; R 4 is preferably methyl; X is preferably H; k is preferably 0; m is preferably 0.
  • n is preferably at least about 6 when the number of M' and X groups is 2 or 3; n is most preferably at least about 12, with a typical range of from about 12 to about 42 for all ranges of x + y + z.
  • x + y + z is from 2 to about 40, and preferably from 2 to about 20.
  • x + y + z can range from 2 to 9 with from 2 to 9 N+ centers and from 2 to 11 X groups.
  • x + y + z is at least 10, with a preferred range of from 10 to about 42.
  • the M' groups are typically a mixture of from about 50 to 100% N + centers and from 0 to about 50% N centers.
  • Preferred cationic polymers within this class are derived from the C 2 -C 3 polyalkyleneamines (x + y + z is from 2 to 9) and polyalkyleneimines (x + y + z is at least 10, preferably from 10 to about 42).
  • Particularly preferred cationic polyalkyleneamines and polyalkyleneimines are the cationic polyethyleneamines (PEAs) and polyethyleneimines (PEIs).
  • PDAs polyethyleneamines
  • PEIs polyethyleneimines
  • These preferred cationic polymers comprise units having the general formula: wherein R 2 (preferably methyl), M', X, d, x, y, z and n are defined as before; a is 1 or 0.
  • the PEAs used in preparing cationic polymers of the present invention have the following general formula: wherein x + y + z is from 2 to 9, and a is 0 or 1 (molecular weight of from about 100 to about 400). Each hydrogen atom attached to each nitrogen atom represents an active site for subsequent ethoxylation.
  • x + y + z is from about 3 to about 7 (molecular weight of from about 140 to about 310)
  • TETA triethylenetetramine
  • TEPA tetraethylenepentamine
  • the cogenerically derived mixture does not appear to separate by distillation and can include other materials such as cyclic amines and particularly piperazines. There can also be present cyclic amines with side chains in which nitrogen atoms appear. See U.S. Patent 2,792,372 to Dickson, issued May 14, 1957, which describes the preparation of PEAs.
  • n is at least about 6.
  • y + z is from 4 to 9
  • suitable benefits are achieved when n is at least about 3.
  • n is at least about 12, with a typical range of from about 12 to about 42.
  • the PEIs used in preparing the polymers of the present invention have a molecular weight of at least about 440 prior to ethoxylation, which represents at least about 10 units.
  • Preferred PEIs used in preparing these polymers have a molecular weight of from about 600 to about 1800.
  • the polymer backbone of these PEIs can be represented by the general formula: wherein the sum of x, y and z represents a number of sufficient magnitude to yield a polymer having the molecular weights previously specified. Although linear polymer backbones are possible, branch chains can also occur.
  • the relative proportions of primary, secondary and tertiary amine groups present in the polymer can vary, depending on the manner of preparation. The distribution of amine groups is typically as follows:
  • n is at least about 3 for the cationic PEIs.
  • the minimum degree of ethoxylation required for suitable clay soil removal/anti-redeposition performance can increase as the molecular weight of the PEI increases, especially much beyond about 1800.
  • the degree of ethoxylation for preferred polymers increases as the molecular weight of the PEI increases.
  • n is preferably at least about 12, with a typical range of from about 12 to about 42.
  • n is preferably at least about 24, with a typical range of from about 24 to about 42.
  • Suitable cationic polymers are those derived from the diallylamines. These polymers comprise units selected from those having formulas X and XI: wherein R 1 is C 1 -C 4 alkyl or hydroxyalkyl, or the moiety - (R 2 ) k -[(C 3 H 6 O) m (CH 2 CH 2 O) n ]-X; R 2 is C 1 -C 12 alkylene, hydroxylakylene, alkylene, arylene or alkarylene; each R 3 is C 1 -C 4 alkyl or hydroxyalkyl, or together form the moiety -(CH 2 ) r -A-(CH 2 ) s -, wherein A is -O- or -CH 2 -; X is H, -R 4 or mixture thereof, wherein R 4 is C 1 -C 4 alkyl or hydroxyalkyl; k is 1 or 0; m and n are numbers such that the moiety -(CH 2
  • A is preferably -O-;
  • R 1 is preferably methyl ;
  • each R 2 is preferably C 2 -C 3 alkylene;
  • each R 3 is preferably methyl;
  • R 4 is preferably methyl;
  • X is preferably H;
  • k is preferably 0;
  • m is preferably 0;
  • r and s are each preferably 2.
  • polyurethane versions of the present invention can be prepared according to the following general scheme.
  • the ethoxylated compound from step 1 is dissolved in 1000 ml. of acetonitrile and then cooled to about 10°C. To this solution is added 2.67 moles of tosyl chloride dissolved in 500 ml. of acetonitrile and cooled to 10°C and then 2.9 moles of triethylamine is added. After the reaction is complete, H 2 O is added to decompose the remaining tosyl chloride.
  • step 3 To the reaction mixture from step 3 is added 3.4 moles of diethanolamine. After heating for 18 hrs. at 80°C, the reaction mixture is cooled and carefully acidified with HCl to a pH just above 7 and then extracted with ether. The aqueous phase is then extracted with a mixture of ether:acetonitrile (ratio of about 5:2) twice. The aqueous phase is separated and then made basic with 50% NaOH. This aqueous phase is extracted with dichloromethane (2000 ml.). The lower layer is separated and then extracted 3 times with 2000 ml. portions of 1/4 saturated NaCl solution while adding enough 50% NaOH to make the aqueous phase strongly basic (pH of about 11). The lower organic layer is stripped to give the desired aminated compound. Toluene (200 ml.) is added and the mixture stripped again to give the desired aminated monomer.
  • the polymer from step 4 is dissolved in methanol and an excess of methyl bromide is passed in. After about 5 hours, the pH is adjusted to about 4 with aqueous HCl and is then allowed to stand overnight to solvolyze the tetrahydropyranyl protecting group. The solution is then neutralized with NaOH and stripped to give the crude polyurethane. This crude polyurethane is dissolved in chloroform and filtered to remove any salts. The chloroform is stripped away to give the desired, largely salt-free polymer.
  • the random copolymer versions of the present invention can be prepared according to the following general scheme: The synthesis of one such random copolymer is described as follows:
  • Decaethylene glycol monomethacrylate monomer (0.008 moles) and N-(3-dimethylaminopropyl)-methacrylamide monomer (0.011 moles) are dissolved in 40 ml. of acetonitrile.
  • the reaction mixture is purged of oxygen by bubbling argon through it.
  • a 0.23 g. portion of benzoyl peroxide is separately dissolved in 10 ml. of acetonitrile and similarly purged.
  • the reaction mixture is heated to reflux and the benzoyl peroxide solution then added dropwise over 0.5 hours.
  • 0.28 g. of azobisisobutyronitrile in 5 ml. of acetonitrile is added to the reaction mixture and heating continued overnight.
  • a stream of methyl bromide is then passed through the reaction mixture which is then warmed slightly for 1 hour.
  • the desired random copolymer is isolated by stripping off the solvent.
  • Quaternized polyethyleneamines and polyethyleneimines can be prepared using standard methods for ethoxylating amines, with subsequent quaternization. Representatiave syntheses of such polyethyleneamines and polyethyleneimines are as follows:
  • Tetraethylenepentamine (M.W. 189, 13.5 g., 0.071 moles) was placed in a nominally dry flask and dried by stirring for 0.5 hrs. at 110°-120°C under vacuum (pressure less than 1 mm Hg.). The vacuum was released by drawing ethylene oxide (EO) from a prepurged trap connected to a supply tank. Once the flask was filled with EO, an outlet stopcock was carefully opened to a trap connected to an exhaust bubbler. After 3 hrs. stirring at 115°-125°C, H-NMR analysis indicated the degree of ethoxylation of 1 per reactive site. The reaction mixture was cooled while being swept with argon and 0.5 g.
  • EO ethylene oxide
  • Diallylamine polymer versions of the present invention can be prepared according to the following general scheme: The synthesis of one such polymer is described as follows:
  • Diallylamine (1.7 moles) is dissolved in methanol (160 ml.) under argon and then heated to 45°C. Ethylene oxide is then added for 2.5 hours. Methanol is then removed by heating the reaction mixture to 100°C in vacuo. To the residue is added sodium hydride in mineral oil (6.6 g., 0.165 moles) with stirring until the evolution of hydrogen has ceased. Ethylene oxide is then added until the degree of ethoxylation (n) is about 7.
  • the crude ethoxylated diallylamine from step 1 is dissolved in about an equal volume of 1N methanolic NaOH and then methyl bromide is added. This methyl bromide addition is continued until H-NMR analysis shows complete disappearance of the methylene hydrogens adjacent to the tertiary nitrogen. Additional portions of 1 N methanolic NaOH are added as needed to maintain the pH of the reaction mixture at about 9. The methanol is removed, yielding a damp mass. This damp mass is washed with several portions of dichloromethane. The combined washes are concentrated to yield the desired quaternized compound.
  • the quaternized monomer from step 2 is mixed with D 2 O (20 ml.) and heated to 95°C under argon for 1 hour. Tertbutylhydroperoxide (25 drops) is then added and the reaction continued at 90°C for 18 hours. Then 20 more drops of the hydroperoxide is added. After heating 3 more days, water is then removed in vacuo (50°-60°C at pressure of 0.1 mm) to yield the crude polymer.
  • the cationic compounds for use herein are water-soluble.
  • water-soluble preferably means that at least 30g of compound is soluble in 100g of water, at 20°C.
  • a water-soluble cationic compound allows to formulate agglomerates which are much more active, i.e. which comprise a greater amount of surfactant, without any significant impact on the solubility of the agglomerate in water, or without increasing its tendency to gel upon contact with water. It is believed that premixing the compound and the surfactant causes to structure the surfactant paste so as to form a dough of a higher viscosity and reduced stickiness. This, in turn allows for the use of a lesser amount of the carrier, and the overall result is an agglomerate of higher activity.
  • the agglomerates of the present invention comprise from 10% to 50% by weight of the agglomerate of a surfactant, preferably from 20% to 40%, most preferably from 25% to 35%.
  • the agglomerates of the present invention comprise from 10% to 50% by weight of the agglomerate of a carrier, preferably from 20% to 40%, most preferably from 25% to 35%.
  • the agglomerates of the present invention comprise from 10% to 50% by weight of the agglomerate of acetate, preferably from 20% to 40%, most preferably from 25% to 35%.
  • the agglomerates of the present invention comprise from 0% to 40% by weight of the agglomerate of water soluble cationic compound, preferably from 2% to 30%, most preferably from 3% to 15%.
  • a preferred optional ingredient for the surfactant agglomerate is a polymer having a melting point of more than 35°C, preferably of more than 45°C, more preferably of more than 55°C, and most preferably of more than 60°C, including PEGs (poly-ethylene-glycol) for example, most preferred being PEG 4000.
  • the agglomerate comprises a surfactant, more preferably a nonionic surfactant, having a melting temperature of less than 35°C, whereby this surfactant having a melting temperature of less than 35°C is likely to melt when the agglomerate is placed in high temperature environment, in which case the addition of the polymer having a melting point of more than 35°C will allow to increase the melting point of the mixture, thus avoiding formation of a liquid phase.
  • This polymer is preferably treated during the process for making the agglomerate at the same time as the surfactant, and is preferably present in proportions of at least 3% and up to 20% by weight of the agglomerate, more preferably in proportions of at least 4 and up to 6%.
  • Another preferred optional ingredient is a water-soluble salt of citrate so as to further improve the dissolution profile of the agglomerates herein.
  • a water-soluble salt of citrate is commercially available and can be used in the present invention. Mixtures of different salts can also be used. It is undesirable that the citrate should introduce any water into the agglomerate, and so a preferred form of the citrate salt is the anhydrous form.
  • citrate should be in the closest possible proximity with the surfactant.
  • citrate especially in its anhydrous form
  • citrate is a hygroscopic material which therefore has a strong tendency to cake, even when packed in moisture protected packages.
  • the problem is particularly acute with fine materials which are preferred for use herein.
  • zeolites also referred to as zeolites, particularly overdried zeolites.
  • the result is a powdery mixture of a water-soluble salt of citrate salt and zeolite, suitable for the manufacture of the agglomerate of the present invention.
  • the powdery mixture has improved flowing properties, without significant negatives on the dissolution profile of citrate.
  • the powdery mixture can comprise from 1 % to 30% by weight of the mixture of zeolite, and the remainder citrate, or acetate, or a mixture of both. Generally, an amount of 1% to 10% zeolite is sufficient to achieve the desired result.
  • These materials can be mixed together with any suitable equipment, and it is preferred to mix these ingredients, i.e. acetate and/or citrate and zeolite at temperature ranging from 10 to 50, preferably from 15 to 30. Indeed, the use of such lower temperature prevents or reduces moisture pick up.
  • the citrate has a function in wash as it acts as a builder.
  • the agglomerate comprises a mixture of acetate and citrate instead of acetate alone.
  • the mixture of citrate and acetate may comprise from 1 up to 100% by weight of citrate, and more preferably from 40 up to 60% by weight of citrate.
  • the critical aspect of the process according to the invention is that it must ensure that the acetate is in close proximity with the surfactant in the agglomerate. Such close proximity could not be achieved through dry addition of the acetate with the agglomerate so as to form a final composition. Rather, such close proximity can be achieved by a variety of means which include the two following embodiments.
  • the acetate, or a portion thereof is intimately mixed with the surfactant before it is agglomerated with the carrier.
  • the acetate is intimately mixed with the carrier before the surfactant is agglomerated with it.
  • the surfactant and the carrier are pre-agglomerated, and the acetate is sprayed onto the pre-agglomerate so as to form the final agglomerate.
  • Both embodiments can be combined in that a portion only of the acetate can be intimately mixed with the surfactant or the carrier. Then, the surfactant and the carrier and the portion of the acetate are pre-agglomerated, and the remainder of the acetate is finally sprayed onto the pre-agglomerate so as to form the final agglomerate.
  • Optional ingredients in the agglomerate can be formulated in a variety of ways, with the exception of the water-soluble cationic compound which must be mixed with the surfactant before the surfactant is mixed with the carrier. If the acetate is also mixed with the surfactant, it is preferred to first mix the surfactant and the water-soluble cationic compound, then the acetate, then to agglomerate that mix with the carrier.
  • the process herein includes mixing a fluid (the surfactant) with powders (the acetate, the carrier), a fluid (the surfactant) with a fluid (the water-soluble cationic compound), a powder (the acetate) with a powder (the carrier), and those can be performed by any means which are well know to the skilled person.
  • Suitable pieces of equipment to perform those steps include : mixers of the Fukae R FS-G series manufactured by Fukae Powtech Kogyo Co., Japan; this apparatus is essentially in the form of a bowl-shaped vessel accessible via a top port, provided near its base with a stirrer having a substantially vertical axis, and a cutter positioned on a side wall.
  • the stirrer and cutter may be operated independently of one another and at separately variable speeds.
  • the vessel can be fitted with a cooling jacket or, if necessary, a cryogenic unit.
  • mixers found to be suitable for use in the process of the invention include Diosna R V series ex Dierks & Söhne, Germany; and the Pharma Matrix R ex T K Fielder Ltd., England.
  • Other mixers believed to be suitable for use in the process of the invention are the Fuji R VG-C series ex Fuji Sangyo Co., Japan; and the Roto R ex Zanchetta & Co srl, Italy.
  • Other preferred suitable equipment can include Eirich R , series RV, manufactured by Gustau Eirich Hardheim, Germany; Lödige R , series FM for batch mixing, series Baud KM for continuous mixing/agglomeration, manufactured by Lödige Machinenbau GmbH, Paderborn Germany; Drais R T160 series, manufactured by Drais Werke GmbH, Mannheim Germany; and Winkworth R RT 25 series, manufactured by Winkworth Machinery Ltd., Berkshire, England.
  • the Littleford Mixer, Model #FM-130-D-12, with internal chopping blades and the Cuisinart Food Processor, Model #DCX-Plus, with 7.75 inch (19.7 cm) blades are two examples of suitable mixers. Any other mixer with fine dispersion mixing and granulation capability and having a residence time in the order of 0.1 to 10 minutes can be used.
  • the "turbine-type" impeller mixer, having several blades on an axis of rotation, is preferred.
  • the invention can be practiced as a batch or a continuous process.
  • acetate is sprayed onto a pre-agglomerate of the surfactant and the carrier (and optionally the water-soluble cationic compound)
  • Suitable sprayable solutions comprise 30g/l to 60g/l of acetate, preferably 40g/l to 50g/l of acetate.
  • the acetate can be dissolved in a variety of liquid carriers, including water and polyethylene glycol.
  • any spraying equipment can be used, and it is preferred that the agglomerate is dried after it has been sprayed with the solution of acetate. Again, any conventional drying equipment can be used for this purpose.
  • the surfactant agglomerate Once the surfactant agglomerate has been formed, it can be desirable to subject it to a heating and/or drying step, followed by a cooling step. This will enable the removal of excess moisture.
  • the surfactant - or surfactant/water-soluble cationic compound premix - is mixed with the carrier, it is desirable to bring the surfactant - or surfactant/water-soluble cationic compound premix - to a viscosity of about 15000 to 35000 cps, preferably 20000 to 25000 cps. This can be achieved by controlling the temperature of the surfactant or surfactant/water-soluble cationic compound premix. This will enable a more convenient mixing of the surfactant or surfactant/polymer premix with the carrier.
  • the dissolution profile of the surfactant agglomerate can be measured as follows :
  • compositions in which the agglomerate can be formulated
  • the agglomerates according to the present invention can be formulated in granular or tablet detergent compositions.
  • these detergent compositions can comprise a variety of ingredients including but not limited to other surfactants, builders, chelants, bleaches, bleach activators, soil release polymers, suds controlling or boosting agents, pH adjusting agents, enzymes, enzyme stabilizers, perfumes, brighteners, dye transfer inhibiting agents, and the like.
  • At least 40%, preferably at least 60%, most preferably at least 90% of the surfactant is incorporated by means of the agglomerate.
  • the surfactant agglomerates can be simply mixed with the rest of the ingredients that are in particulate form or in turn may be subjected to further process steps of spraying liquids and coating with fine powders.
  • the modular approach is based on the manufacturing of particles highly specific in one or at most two ingredients of the formulation which are then mixed at the desired ratios to form the finished products.
  • These particles being highly specific in the ingredient they are to deliver, can be used in a wide range of products without need to be modified.
  • These particles can be prepared with an optimal combination of ingredients that maximize their properties independently of full finished product formulations.
  • Detergent tablets can be prepared simply by mixing the solid ingredients together and compressing the mixture in a conventional tablet press as used, for example, in the pharmaceutical industry.
  • the detergent tablets can be made in any size or shape and can, if desired, be coated.
  • the particulate materials (other than the agglomerates of the invention) used for making the tablet can be made by any particulation or granulation process.
  • An example of such a process is spray drying (in a co-current or counter current spray drying tower) which typically gives low bulk densities 600g/l or lower.
  • Particulate materials of higher density can be prepared by granulation and densification in a high shear batch mixer/granulator or by a continuous granulation and densification process (e.g. using Lodige® CB and/or Lodige® KM mixers).
  • Other suitable processes include fluid bed processes, compaction processes (e.g. roll compaction), extrusion, as well as any particulate material made by any chemical process like flocculation, crystallisation sentering, etc.
  • Individual particles can also be any other particle, granule, sphere or grain.
  • the particulate materials may be mixed together by any conventional means. Batch is suitable in, for example, a concrete mixer, Nauta mixer, ribbon mixer or any other. Alternatively the mixing process may be carried out continuously by metering each component by weight on to a moving belt, and blending them in one or more drum(s) or mixer(s).
  • a non-gelling binder can be sprayed on to the mix of some, or all of, the particulate materials.
  • Other liquid ingredients may also be sprayed on to the mix of particulate materials either separately or premixed. For example perfume and slurries of optical brighteners may be sprayed.
  • a finely divided flow aid dustting agent such as zeolites, carbonates, silicas
  • the tablets may be manufactured by using any compacting process, such as tabletting, briquetting, or extrusion, preferably tabletting.
  • Suitable equipment includes a standard single stroke or a rotary press (such as Courtoy®, Korch®, Manesty®, or Bonals®).
  • Tablets prepared should preferably have a diameter of between 40mm and 60mm, and a weight between 25 and 100 g.
  • the ratio of height to diameter (or width) of the tablets is preferably greater than 1:3, more preferably greater than 1:2.
  • the compaction pressure used for preparing these tablets need not exceed 5000 kN/m 2 , preferably not exceed 3000 kN/m 2 , and most preferably not exceed 1000 kN/m 2 .
  • Suitable non-gelling binders include synthetic organic polymers such as polyethylene glycols, polyvinylpyrrolidones, polyacrylates and water-soluble acrylate copolymers.
  • the handbook of Pharmaceutical Excipients second edition has the following binders classification: Acacia, Alginic Acid, Carbomer, Carboxymethylcellulose sodium, Dextrin, Ethylcellulose, Gelatin, Guar gum, Hydrogenated vegetable oil type I, Hydroxyethyl cellulose, Hydroxypropyl methylcellulose, Liquid glucose, Magnesium aluminum silicate, Maltodextrin, Methylcellulose, polymethacrylates, povidone, sodium alginate, starch and zein.
  • binders also have an active cleaning function in the laundry wash such as cationic polymers, i.e. ethoxylated hexamethylene diamine quaternary compounds, bishexamethylene triamines, or others such as pentaamines, ethoxylated polyethylene amines, maleic acrylic polymers.
  • cationic polymers i.e. ethoxylated hexamethylene diamine quaternary compounds, bishexamethylene triamines, or others such as pentaamines, ethoxylated polyethylene amines, maleic acrylic polymers.
  • the non-gelling binder materials are preferably sprayed on and hence have an appropriate melting point temperature below 70°C and preferably below 50°C so as not to damage or degrade the other active ingredients in the matrix.
  • Most preferred are non-aqueous liquid binders (i.e. not in aqueous solution) which may be sprayed in molten form.
  • they may also be solid binders incorporated into the matrix by dry addition but which have binding properties within the tablet.
  • the non-gelling binder materials are preferably used in an amount within the range from 0.1 to 15% of the composition, more preferably below 5% and especially if it is a non laundry active material below 2% by weight of the tablet.
  • the tablets may be coated so that the tablet does not absorb moisture, or absorbs moisture at only a very slow rate.
  • the coating is also strong so that moderate mechanical shocks to which the tablets are subjected during handling, packing and shipping result in no more than very low levels of breakage or attrition.
  • the coating is preferably brittle so that the tablet breaks up when subjected to stronger mechanical shock.
  • the coating material is dissolved under alkaline conditions, or is readily emulsified by surfactants. This contributes to avoiding the problem of visible residue in the window of a front-loading washing machine during the wash cycle, and also avoids deposition of undissolved particles or lumps of coating material on the laundry load.
  • Water solubility is measured following the test protocol of ASTM E1148-87 entitled, "Standard Test Method for Measurements of Aqueous Solubility".
  • Suitable coating materials are dicarboxylic acids.
  • Particularly suitable dicarboxylic acids are selected from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid and mixtures thereof.
  • the coating material has a melting point preferably of from 40 °C to 200 °C.
  • the coating can be applied in a number of ways. Two preferred coating methods are a) coating with a molten material and b) coating with a solution of the material. In a), the coating material is applied at a temperature above its melting point, and solidifies on the tablet. In b), the coating is applied as a solution, the solvent being dried to leave a coherent coating.
  • the substantially insoluble material can be applied to the tablet by, for example, spraying or dipping. Normally when the molten material is sprayed on to the tablet, it will rapidly solidify to form a coherent coating. When tablets are dipped into the molten material and then removed, the rapid cooling again causes rapid solidification of the coating material.
  • substantially insoluble materials having a melting point below 40 °C are not sufficiently solid at ambient temperatures and it has been found that materials having a melting point above about 200 °C are not practicable to use.
  • the materials melt in the range from 60 °C to 160 °C, more preferably from 70 °C to 120 °C.
  • melting point is meant the temperature at which the material when heated slowly in, for example, a capillary tube becomes a clear liquid.
  • a coating of any desired thickness can be applied according to the present invention.
  • the coating forms from 1% to 10%, preferably from 1.5% to 5%, of the tablet weight.
  • Such tablet coatings are very hard and provide extra strength to the tablet.
  • the fracture of the coating in the wash is improved by adding a disintegrant in the coating.
  • This disintegrant will swell once in contact with water and break the coating in small pieces. This will improve the dissolution of the coating in the wash solution.
  • the disintegrant is suspended in the coating melt at a level of up to 30%, preferably between 5% and 20%, most preferably between 5 and 10% by weight. Possible disintegrants are described in Handbook of Pharmaceutical Excipients (1986).
  • Suitable disintegrants include starch: natural, modified or pregelatinized starch, sodium starch gluconate; gum: agar gum, guar gum, locust bean gum, karaya gum, pectin gum, tragacanth gum; croscarmylose Sodium, crospovidone, cellulose, carboxymethyl cellulose, algenic acid and its salts including sodium alginate, silicone dioxide, clay, polyvinylpyrrolidone, soy polysacharides, ion exchange resins and mixtures thereof.
  • the used compaction force will be adjusted to not affect the strength (Diametral Fracture Stress), and the disintegration time in the washing machine.
  • This process may be used to prepare homogenous or layered tablets of any size or shape.
  • the tablets further comprises an effervescent.
  • Effervescency as defined herein means the evolution of bubbles of gas from a liquid, as the result of a chemical reaction between a soluble acid source and an alkali metal carbonate, to produce carbon dioxide gas, i.e. C 6 H 8 O 7 + 3NaHCO 3 ⁇ Na 3 C 6 H 5 O 7 + 3CO 2 ⁇ + 3H 2 O
  • Tablets can also be used in a method of washing which comprises the preparation of an aqueous solution of a laundry detergent for use in a front-loading washing machine, the front-loading washing machine having a dispensing drawer and a washing drum, wherein the aqueous solution of laundry detergent is formed by the tablet which is placed in the dispensing drawer before water is passed through the dispensing drawer so that the tablet is dispensed as an aqueous solution of a laundry detergent, the aqueous solution subsequently being passed in the washing drum.
  • the surfactant agglomerate comprises an anionic surfactant together with an acetate in combination with any other structurant, whereby these components are brought in close proximity by use of a process producing a high shear force such as extrusion.
  • a surfactant agglomerate has a high activity, while having satisfactory processability, such satisfactory processability being provided by hardness and low stickiness of the paste obtained.
  • the structurant used may for example be zeolite, silicate, or a mixture of these. It should be noted that satisfactory processability is obtained with surprisingly low levels of acetate, preferably anhydrous sodium acetate, preferably less than 10% per weight of the agglomerate.
  • the agglomerate also preferably comprises more than 40% per weight of anionic surfactant, more preferably more than 50 % per weight.
  • the surfactant particle of composition given in table 1 was prepared as follows:
  • the surfactant particle of composition given in table 2 was prepared as follows:
  • example A The process used in example A was repeated using composition given in table 3.
  • the anhydrous acetate powder of example A was replaced by a premix of anhydrous acetate powder and overdried zeolite in a ratio of 9 parts anhydrous acetate powder for 1 part of overdried zeolite.
  • Composition by weight Anhydrous sodium acetate/zeolite premix 40 Sodium Carbonate 20
  • Nonionic surfactant C45 AE7)
  • Lutensit KHD96 6
  • Example C The process of example C was repeated replacing anhydrous sodium acetate with anhydrous magnesium acetate or sodium acetate trihydrate powder.
  • the magnesium acetate-zeolite premix here comprised 1 part anhydrous magnesium acetate powder for 9 parts of overdried zeolite.
  • Example D weight %
  • Example E weight %
  • Anhydrous magnesium acetate/zeolite premix 40 Sodium acetate trihydrate 40 Sodium Carbonate 20 36
  • Nonionic surfactant (C45 AE7) 26 13 Lutensit KHD96 6 3 Flow aid (Zeolite) 8 8
  • Example A The process of example A was repeated replacing surfactant C45 AE7 with various other surfactants as indicated in table 5.
  • Surfactant LAS is Linear alkylbenzene sulphonate
  • Surfactant AS is a C12-C15 alkyl sulphate.
  • Example F Composition by weight
  • Example G Composition by weight Anhydrous Sodium acetate 30 30 Sodium Carbonate 25 20 LAS paste 35 - AS paste - 40 Flow aid (Zeolite) 10 10
  • Example A was repeated using a different particle making process. The process allowed to increase the particle activity without the use of a cationic polymer:
  • the agglomerate after-drying had the composition indicated in table 7 Composition by weight Sodium Carbonate 30 Zeolite 25 LAS powder 20 Sodium acetate 50% solution 10 Water 4 Flow aid (Zeolite) 11
  • a detergent base powder of a finished laundry detergent was put together by blending the following components as shown in table 8, except the polyethylene Glycol and perfume which was sprayed-on.
  • Component Example J (wt %) Nonionic surfactant agglomerate of example B 9.9 Anionic surfactant agglomerate 28.1 Layered silicate compacted granule 9.0 Granular carbonate 13.4 Granular percarbonate 14.2 Anhydrous citric acid 7.0 Suds suppressor agglomerate 1.9 Soap powder 1.4 Granular soil release polymer 4.5 Bleach activator agglomerate 5.5 Miscellaneous 1.1 Enzymes 2.2 Sodium sulphate _ Polyethylene Glycol spray-on 1.3 Perfume spray-on 0.5
  • Anionic agglomerates comprise 38% anionic surfactant, 22% zeolite and 40% carbonate Bleach activator agglomerates comprise 81% TAED (Tetraacethylethylene diamine), 17% acrylic/maleic copolymer (acid form) and 2% water.
  • Zinc phthalocyanine sulphonate encapsulates are 10% active.
  • Suds suppressor agglomerate comprises 11.5% silicone oil (ex. Dow Corning) and 88.5 starch.
  • Layered silicate compacted granule comprises 78% SKS-6, ex Hoechst, 22% citric acid.
  • the tablet were dipped in a bath comprising 90 parts of dodecandioic acid mixed with 10 parts of Nymcel zsb16 heated at 140C. The time the tablet was dipped in the heated bath was adjusted to allow application of 5g of the described mixture on it. The tablet was then left to cool at room temperature of 25C for 24 hours.
  • Anionic agglomerates 1 comprise of 40% anionic surfactant, 27% zeolite and 33% carbonate
  • Anionic agglomerates 2 comprise of 40% anionic surfactant, 28% zeolite and 32% carbonate
  • Nonionic agglomerate comprise 26% nonionic surfactant, 6% Lutensit K-HD 96, 40% Sodium acetate anhydrous, 20% carbonate and 8% zeolite.
  • Cationic agglomerates comprise of 20% cationic surfactant, 56% zeolite and 24% sulphate
  • Layered silicate comprises of 95% SKS 6 and 5% silicate
  • Bleach activator agglomerates comprise of 81% TAED, 17% acrylic/maleic copolymer (acid form) and 2% water.
  • Ethylene diamine N,N-disuccinic acid sodium salt/Sulphate particle comprise of 58% of Ethylene diamine N,N-disuccinic acid sodium salt, 23% of sulphate and 19% water.
  • Zinc phthalocyanine sulphonate encapsulates are 10% active.
  • Suds suppressor comprises of 11.5% silicone oil (ex Dow Corning); 59% of zeolite and 29.5% of water.
  • Binder spray-on system comprises of 0.5 parts of Lutensit K-HD 96 and 2.5 parts of PEGs

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EP99870092A 1998-07-10 1999-04-30 Tensidagglomerate Expired - Lifetime EP0971023B1 (de)

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Application Number Priority Date Filing Date Title
AT99870092T ATE299928T1 (de) 1998-07-10 1999-04-30 Tensidagglomerate
ES99870092T ES2245819T3 (es) 1998-07-10 1999-04-30 Aglomerados de tensioactivo.
EP99870092A EP0971023B1 (de) 1998-07-10 1999-04-30 Tensidagglomerate
DE69926181T DE69926181T2 (de) 1998-07-10 1999-04-30 Tensidagglomerate
BR9912006-2A BR9912006A (pt) 1998-07-10 1999-07-12 Aglomerados tensoativos
CZ20004890A CZ20004890A3 (cs) 1998-07-10 1999-07-12 Povrchově aktivní aglomerát
MA25674A MA24925A1 (fr) 1998-07-10 1999-07-12 Agglomerats d'agent (s) tensioactif (s)
AU49847/99A AU4984799A (en) 1998-07-10 1999-07-12 Surfactant agglomerates
ARP990103365A AR027165A1 (es) 1998-07-10 1999-07-12 Aglomerado de detergente tensoactivo que comprende un agente tensoactivo y un portador; proceso para fabricarlo; composicion detergente granular; composicion detergente en tabletas y mezcla polvorienta de una sal soluble en agua de sal de acetato y zeolita para fabricar dicho aglomerado
PCT/US1999/015667 WO2000002989A1 (en) 1998-07-10 1999-07-12 Surfactant agglomerates
CA002333045A CA2333045A1 (en) 1998-07-10 1999-07-12 Surfactant agglomerates
KR1020007014086A KR20010052780A (ko) 1998-07-10 1999-07-12 계면 활성제 응집물
CN99808437A CN1308666A (zh) 1998-07-10 1999-07-12 表面活性剂附聚物
JP2000559211A JP2002520445A (ja) 1998-07-10 1999-07-12 界面活性剤凝集体
US10/303,388 US20030171245A1 (en) 1998-07-10 2002-11-25 Surfactant agglomerates

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WO2000027985A1 (de) * 1998-11-09 2000-05-18 Henkel Kommanditgesellschaft Auf Aktien Wasch- und reinigungsmittelformkörper mit feinteiligen lösungsvermittlern
DE19948669A1 (de) * 1999-10-08 2001-04-19 Cognis Deutschland Gmbh Waschmitteltabletten
EP1384772A1 (de) * 2002-07-17 2004-01-28 Unilever N.V. Waschmitteltablette
EP1326929B2 (de) † 2000-09-27 2011-08-03 Unilever PLC Verfahren zur beschichtung von wasserlöslicher verpackung und beschichtete verpackung

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DE10160993A1 (de) 2001-12-12 2003-06-18 Basf Ag Stickstoffhaltige Polymere umfassende Reinigungsmittelzusammensetzungen
US20050187131A1 (en) * 2004-02-23 2005-08-25 The Procter & Gamble Company Granular laundry detergent composition comprising a ternary detersive surfactant system and low levels of, or no, zeolite builders and phosphate builders
WO2009050684A2 (en) * 2007-10-18 2009-04-23 Ecolab Inc. Pressed, waxy, solid cleaning compositions and methods of making them
CN108559679B (zh) * 2011-05-13 2021-03-26 Lg生活健康株式会社 用于洗涤的片
WO2016196021A1 (en) * 2015-06-01 2016-12-08 E I Du Pont De Nemours And Company Structured liquid compositions comprising colloidal dispersions of poly alpha-1,3-glucan

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JPH06122900A (ja) * 1992-10-13 1994-05-06 Kao Corp 錠剤型洗浄剤組成物
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US4180485A (en) * 1977-11-02 1979-12-25 The Procter & Gamble Company Spray-dried detergent compositions
US4169806A (en) * 1978-08-09 1979-10-02 The Procter & Gamble Company Agglomeration process for making granular detergents
US4524013A (en) * 1984-04-06 1985-06-18 Lever Brothers Company Powdered nonionic-based detergent compositions containing sodium acetate trihydrate
EP0403084A2 (de) * 1989-06-16 1990-12-19 The Clorox Company Zeolith-Agglomerierverfahren und -Produkt
JPH06122900A (ja) * 1992-10-13 1994-05-06 Kao Corp 錠剤型洗浄剤組成物
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000027985A1 (de) * 1998-11-09 2000-05-18 Henkel Kommanditgesellschaft Auf Aktien Wasch- und reinigungsmittelformkörper mit feinteiligen lösungsvermittlern
DE19948669A1 (de) * 1999-10-08 2001-04-19 Cognis Deutschland Gmbh Waschmitteltabletten
EP1326929B2 (de) † 2000-09-27 2011-08-03 Unilever PLC Verfahren zur beschichtung von wasserlöslicher verpackung und beschichtete verpackung
EP1384772A1 (de) * 2002-07-17 2004-01-28 Unilever N.V. Waschmitteltablette

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CA2333045A1 (en) 2000-01-20
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KR20010052780A (ko) 2001-06-25
ATE299928T1 (de) 2005-08-15
AR027165A1 (es) 2003-03-19
JP2002520445A (ja) 2002-07-09
WO2000002989A1 (en) 2000-01-20
DE69926181D1 (de) 2005-08-25
BR9912006A (pt) 2001-04-10
CZ20004890A3 (cs) 2001-12-12
MA24925A1 (fr) 2000-04-01
AU4984799A (en) 2000-02-01
DE69926181T2 (de) 2006-05-24

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