EP1025196B1 - Verfahren zur herstellung einer waschmittelzusammensetzung durch zugabe von cotensiden - Google Patents

Verfahren zur herstellung einer waschmittelzusammensetzung durch zugabe von cotensiden Download PDF

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EP1025196B1
EP1025196B1 EP97907907A EP97907907A EP1025196B1 EP 1025196 B1 EP1025196 B1 EP 1025196B1 EP 97907907 A EP97907907 A EP 97907907A EP 97907907 A EP97907907 A EP 97907907A EP 1025196 B1 EP1025196 B1 EP 1025196B1
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Prior art keywords
detergent
anionic surfactant
crystalline
process according
surfactant paste
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French (fr)
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EP1025196A1 (de
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Manivannan Kandasamy
Kenji Naemura
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Procter and Gamble Co
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Procter and Gamble Co
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/37—Mixtures of compounds all of which are anionic
    • 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
    • C11D17/06—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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers

Definitions

  • the present invention generally relates to a process for producing a detergent composition. More particularly, the invention is directed to a non-tower process during which detergent granules are produced by adding co-surfactants. The process produces a free flowing, detergent composition whose density can be adjusted for wide range of consumer needs, and which can be commercially sold.
  • the first type of process involves spray-drying an aqueous detergent slurry in a spray-drying tower to produce highly porous detergent granules (e.g., tower process for low density detergent compositions).
  • the second type of process involves spray-drying an aqueous detergent slurry in a spray-drying tower as the first step, then, the resultant granules are agglomerated with a binder such as a nonionic or anionic surfactant, finally, various detergent components are dry mixed to produce detergent granules (e.g., tower process plus non-tower [agglomeration] process for high density detergent compositions)
  • the various detergent components are dry mixed after which they are agglomerated with a binder such as a nonionic or anionic surfactant, to produce high density detergent compositions (e.g., non-tower [agglomeration] process for high density detergent compositions).
  • the important factors which govern the density of the resulting detergent granules are the shape, porosity and particle size distribution of said granules, the density of the various starting materials, the shape of the various starting materials, and their respective chemical composition.
  • surfactants are typically prepared in the form of aqueous pastes (typically 25-70% active).
  • aqueous pastes typically 25-70% active.
  • surfactants in the form of paste are mixed so as to form a co-surfactant paste, followed by agglomerating the paste in a mixer, or in a series of mixers with dry ingredients such as builders (e.g. sodium tripolyphosphate), inorganic fillers (e g. sodium sulfate), bleaches, etc.
  • builders e.g. sodium tripolyphosphate
  • inorganic fillers e g. sodium sulfate
  • bleaches etc.
  • a non-crystalline surfactant paste i.e the paste of a type of surfactant which is typically sticky and difficult to be applied in an agglomeration process
  • a paste of a crystalline surfactant i.e.
  • Laid-open No H5-171199 (Lion), describes a high bulk density granular detergent composition comprising a fatty acid lower alkyl ester sulfonate ("Co-surfactant I") and an anionic surfactant other than Co-surfactant I, silicate, and carbonate. This composition is disclosed as preventing the hydrolysis of Co-surfactant I after long term shortage.
  • EP 560 001 relates to a process for making high active detergent agglomerates.
  • GB 2 289 687 relates to an agglomeration process for making anionic surfactant agglomerates having improved cold-water solubility.
  • WO94/24242 relates to a process for making secondary alkyl sulphate particles.
  • JP61/291693 relates to a detergent composition.
  • the present invention meets the aforementioned needs in the art by providing a non-tower process, especially agglomeration process, which produces a granular detergent composition having ultimate density of the final granular composition.
  • the present process is stable in terms of flow ability and cost effective, since the process reduces the level of undesirable oversized granules and/or the level of process flow aids. such as zeolites and/or silicates. that prevent over agglomeration. Consequently, the process of the present invention is more efficient, economical and flexible with regard to obtaining detergent compositions having less oversized granules (i.e., agglomerates).
  • the term “agglomerates” refers to particles formed by agglomerating raw materials with binder such as surfactants and or inorganic solutions / organic solvents and polymer solutions.
  • crystalline (anionic) surfactant paste refers to the (anionic) surfactant paste having crystalline structure, generally having about 50-100%, preferably about 65-100%, more preferably about 80-100% of crystallinity, measured by X-Ray Diffraction (XRD).
  • XRD X-Ray Diffraction
  • non-crystalline (anionic) surfactant paste refers to the (anionic) surfactant paste which is not crystalline (anionic) surfactant paste defined as the above. All percentages used herein are expressed as "percent-by-weight" unless indicated otherwise.
  • the present invention provides a process for preparing a granular detergent composition, the process comprising: (a) thoroughly mixing a crystalline anionic surfactant paste with a sufficient amount of fine powders of starting detergent materials form a free flowing agglomerate; (b) thoroughly mixing a product of the step (a) with a non-crystalline anionic surfactant paste to form a free flowing agglomerate; is provided.
  • An agglomerate from the process of the present invention has a reduced level of resulting undesirable oversized granules.
  • the present invention is directed to a process which produces free flowing, granular detergent composition by controlling stickiness derived from a non-crystalline surfactant paste.
  • a crystalline anionic surfactant paste and finely powdered detergent ingredients (hereinafter, fine powders), such as builders, are fed into an mixing equipment and then are agglomerated by dispersing the surfactant paste onto the fine powders, so as to form a free flowing agglomerate.
  • fine powders such as builders
  • other starting detergent materials can be also fed into the equipment in this step.
  • the amount of fine powders required to the first step depends on the amount of the crystalline anionic surfactant paste and the water content of the paste.
  • the examples of the equipment for the first step can be any types of equipment for agglomeration known to those skilled in the art.
  • a suitable example can be a mixer, such as Lödige CB Mixer, Lödige KM Mixer, or Drais K-TTP.
  • Condition of agglomeration including time period for the first step depends on the type of equipment used for the first step, so as to produce an agglomerated homogeneous mixture. Such conditions can also be decided based on the design of final composition from the process of the present invention.
  • the resultant from the first step a non-crystalline anionic surfactant paste and fine powders are further mixed together so as to form a free flowing agglomerate.
  • other starting detergent materials can be also fed into the equipment in this step.
  • the amount of fine powders required to the second step depends on the amount of the anionic surfactant paste (i.e., unreacted paste in the first step and the non-crystalline anionic surfactant paste), and the water content in the paste.
  • fine powders can be added to the second process.
  • a non-crystalline anionic surfactant paste is added to a resultant from the first step, subsequently, the paste and the resultant are further agglomerated so as to form granulates/agglomerates.
  • fine powders either used in the first step or other fine powders, can be additionally added to the resultant.
  • the second step can be undertaken in the equipment for the first step or in another (second) equipment for agglomeration.
  • the examples of the equipment can be any types of mixers known to those skilled in the art.
  • a suitable example can be a mixer, such as Schugi Flexomic Model, Lödige CB Mixer, Lödige KM Mixer or Drais K-T
  • the process of the present invention allows the mixed crystalline anionic surfactant paste from the first step to stand for at least about 0.1 seconds prior to adding the non-crystalline anionic surfactant paste in the second step.
  • the agglomerated materials during the second step which includes the anionic crystalline surfactant paste and the anionic non-crystalline surfactant paste, has a nature similar to agglomerates formed from crystalline anionic surfactant paste, namely, less amount of over sized agglomerates than agglomerates formed from non-crystalline anionic surfactant paste or formed from a mixture of crystalline surfactant paste and morphous anionic surfactant paste. Consequently, the second step can be undertaken smoothly since the agglomerated material has less amount of over sized agglomerates.
  • the agglomerates from the present process include less than 20 % of particles whose diameter is larger than 1180 ⁇ m.
  • the agglomerates from the present process include less than 15 % of particles whose diameter is larger than 1180 ⁇ m. More preferably, the agglomerates from the present process include less than 10 % of particles having diameter larger than about 1180 ⁇ m.
  • the resultant from the second step can be processed for further agglomeration which is well known to those skilled in the art.
  • the amount (as an active weight ratio) of the fine powders to the amount of crystalline anionic surfactant in the paste can be from about 2.0 % to about 3.2 %, preferably, from about 2.4 % to about 2.8 %.
  • the amount (as an active weight ratio) of the crystalline anionic surfactant in the paste to the amount of the non-crystalline anionic surfactant in the paste can be from about 4 % to about 14 %, preferably, from about 6 % to about 12 %, more preferably, from about 8 % to about 10 %.
  • Starting detergent materials for granular detergent composition which is made according to the process of the present invention, except for crystalline anionic surfactant(s), non-crystalline anionic surfactant(s) and fine powders for the present invention, can be added anytime during or after the above two steps. Such other starting detergent materials fully described below.
  • the total amount of detergent surfactant i e., crystalline anionic surfactant(s), non-crystalline anionic surfactant(s) and other surfactants for the final product from the present invention
  • the total amount of detergent surfactant i e., crystalline anionic surfactant(s), non-crystalline anionic surfactant(s) and other surfactants for the final product from the present invention
  • the total amount of detergent surfactant can be from about 5 % to about 60 %, more preferably from about 12% to about 40 %, more preferably, from about 15% to about 35%, in total amount of the final product obtained by the process of the present invention.
  • the surfactant itself is preferably selected from anionic, nonionic, zwitterionic, ampholytic and cationic classes and compatible mixtures thereof.
  • Detergent surfactants useful herein are described in U.S. Patent 3,664,961, Norris, issued May 23, 1972, and in U.S. Patent 3,929,678, Laughlin et al., issued December 30, 1975, both of which are incorporated herein by reference.
  • Useful cationic surfactants also include those described in U.S. Patent 4,222,905, Cockrell, issued September 16, 1980. and in U.S. Patent 4,239,659, Murphy, issued December 16, 1980, both of which are also incorporated herein by reference.
  • anionics and nonionics are preferred and anionics are most preferred.
  • Nonlimiting examples of the preferred anionic surfactants useful in the present invention include the conventional C 11 -C 18 alkyl benzene sulfonates ("LAS"), primary, branched-chain and random C 10 -C 20 alkyl sulfates (“AS”), the C 10 -C 18 secondary (2,3) alkyl sulfates of the formula CH 3 (CH 2 ) x (CHOSO 3 - M + )CH 3 and CH 3 (CH 2 ) y (CHOSO 3 - M + )CH 2 CH 3 where x and (y + 1) are integers of at least about 7, preferably at least about 9, and M is a water-solubilizing cation, especially sodium, unsaturated sulfates such as oleyl sulfate, and the C 10 -C 18 alkyl alkoxy sulfates ("AE x S"; especially EO 1-7 ethoxy sulfates).
  • LAS C 11 -C 18 alkyl benzene
  • Useful anionic surfactants also include water-soluble salts of 2-acyloxy-alkane-1-sulfonic acids containing from about 2 to 9 carbon atoms in the acyl group and from about 9 to about 23 carbon atoms in the alkane moiety; water-soluble salts of olefin sulfonates containing from about 12 to 24 carbon atoms; and beta-alkyloxy alkane sulfonates containing from about 1 to 3 carbon atoms in the alkyl group and from about 8 to 20 carbon atoms in the alkane moiety.
  • the preferable examples as crystalline anionic surfactant paste(s) of the present invention include; either natural or synthetic alkyl sulfates, preferably, C 12 -C 18 coconut fatty alcohol sulfates or C 14 -C 15 synthetic alkyl sulfates.
  • the preferable examples as non-crystalline anionic surfactant paste(s) of the present invention include; alkyl alkoxy sulfates (AE x S), alkyl benzene sulfonates (LAS).
  • exemplary surfactants useful in the paste of the invention include C 10 -C 18 alkyl alkoxy carboxylates (especially the EO 1-5 ethoxycarboxylates), the C 10-18 glycerol ethers, the C 10 -C 18 alkyl polyglycosides and the corresponding sulfated polyglycosides, and C 12 -C 18 alpha-sulfonated fatty acid esters.
  • the conventional nonionic and amphoteric surfactants such as the C 12 -C 18 alkyl ethoxylates ("AE") including the so-called narrow peaked alkyl ethoxylates and C 6 -C 12 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), C 10 -C 18 amine oxides, and the like, can also be included in the overall compositions.
  • the C 10 -C 18 N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include the C 12 -C 18 N-methylglucamides. See WO 9,206,154.
  • sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C 10 -C 18 N-(3-methoxypropyl) glucamide.
  • the N-propyl through N-hexyl C 12 -C 18 glucamides can be used for low sudsing.
  • C 10 -C 20 conventional soaps may also be used. If high sudsing is desired, the branched-chain C 10 -C 16 soaps may be used. Mixtures of anionic and nonionic surfactants are especially useful. Other conventional useful surfactants are listed in standard texts.
  • Cationic surfactants can also be used as a detergent surfactant herein and suitable quaternary ammonium surfactants are selected from mono C 6 -C 16 , preferably C 6 -C 10 N-alkyl or alkenyl ammonium surfactants wherein remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.
  • Ampholytic surfactants can also be used as a detergent surfactant herein, which include aliphatic derivatives of heterocyclic secondary and tertiary amines; zwitterionic surfactants which include derivatives of aliphatic quaternary ammonium, phosphonium and sulfonium compounds; water-soluble salts of esters of alpha-sulfonated fatty acids; alkyl ether sulfates; water-soluble salts of olefin sulfonates; beta-alkyloxy alkane sulfonates; betaines having the formula R(R 1 ) 2 N + R 2 COO - , wherein R is a C 6 -C 18 hydrocarbyl group, preferably a C 10 -C 16 alkyl group or C 10 -C 16 acylamido alkyl group, each R 1 is typically C 1 -C 3 alkyl, preferably methyl and R 2 is a C 1 -C 5 hydrocarbyl
  • betaines examples include coconut acylamidopropyldimethyl betaine; hexadecyl dimethyl betaine; C 12-14 acylamidopropylbetaine; C 8-14 acylamidohexyldiethyl betaine; 4[C 14-16 acylmethylamidodiethylammonio]-1-carboxybutane; C 16-18 acylamidodimethylbetaine; C 12-16 acylamidopentanediethylbetaine; and C 12-16 acylmethylamidodimethylbetaine.
  • Preferred betaines are C 12-18 dimethylammonio hexanoate and the C 10-18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines; and the sultaines having the formula (R(R 1 ) 2 N + R 2 SO 3 - wherein R is a C 6 -C 18 hydrocarbyl group, preferably a C 10 -C 16 alkyl group, more preferably a C 12 -C 13 alkyl group, each R 1 is typically C 1 -C 3 alkyl, preferably methyl, and R 2 is a C 1 -C 6 hydrocarbyl group, preferably a C 1 -C 3 alkylene or, preferably, hydroxyalkylene group.
  • Suitable sultaines include C 12 -C 14 dimethylammonro-2-hydroxypropyl sulfonate, C 12 -C 14 amido propyl ammonio-2-hydroxypropyl sultaine, C 12 -C 14 dihydroxyethylammonio propane sulfonate, and C 16-18 dimethylammonio hexane sulfonate, with C 12-14 amido propyl ammonio-2-hydroxypropyl sultaine being preferred.
  • the fine powders of the present process preferably selected from the group consisting of ground soda ash, powdered sodium tripolyphosphate (STPP), hydrated tripolyphosphate, ground sodium sulphates, aluminosilicates, crystalline layered silicates, nitrilotriacetates (NTA), phosphates, precipitated silicates, polymers, carbonates, citrates, powdered surfactants (such as powdered alkane sulfonic acids) and recycle fines occurring from the process of the present invention, wherein the average diameter of the powder is from 0 1 to 500 microns, preferably from 1 to 300 microns, more preferably from 5 to 100 microns.
  • the aluminosilicate ion exchange materials used herein as a detergent builder preferably have both a high calcium ion exchange capacity and a high exchange rate. Without intending to be limited by theory, it is believed that such high calcium ion exchange rate and capacity are a function of several interrelated factors which derive from the method by which the aluminosilicate ion exchange material is produced. In that regard, the aluminosilicate ion exchange materials used herein are preferably produced in accordance with Corkill et al, U.S. Patent No. 4,605,509 (Procter & Gamble), the disclosure of which is incorporated herein by reference.
  • the aluminosilicate ion exchange material is in "sodium" form since the potassium and hydrogen forms of the instant aluminosilicate do not exhibit as high of an exchange rate and capacity as provided by the sodium form.
  • the aluminosilicate ion exchange material preferably is in over dried form so as to facilitate production of crisp detergent agglomerates as described herein.
  • the aluminosilicate ion exchange materials used herein preferably have particle size diameters which optimize their effectiveness as detergent builders.
  • particle size diameter represents the average particle size diameter of a given aluminosilicate ion exchange material as determined by conventional analytical techniques, such as microscopic determination and scanning electron microscope (SEM).
  • the preferred particle size diameter of the aluminosilicate is from about 0.1 micron to about 10 microns, more preferably from about 0.5 microns to about 9 microns. Most preferably, the particle size diameter is from about 1 microns to about 8 microns.
  • the aluminosilicate ion exchange material has the formula Na z [(AlO 2 ) z .(SiO 2 ) y ]xH 2 O wherein z and y are integers of at least 6, the molar ratio of z to y is from about 1 to about 5 and x is from about 10 to about 264. More preferably, the aluminosilicate has the formula Na 12 [(AlO 2 ) 12 .(SiO 2 ) 12 ]xH 2 O wherein x is from about 20 to about 30, preferably about 27.
  • These preferred aluminosilicates are available commercially, for example under designations Zeolite A, Zeolite B and Zeolite X.
  • aluminosilicates used herein are further characterized by their ion exchange capacity which is at least about 200 mg equivalent of CaCO 3 hardness/gram, calculated on an anhydrous basis, and which is preferably in a range from about 300 to 352 mg equivalent of CaCO 3 hardness/gram.
  • the instant aluminosilicate ion exchange materials are still further characterized by their calcium ion exchange rate which is at least about 0.26 g Ca 2 ⁇ /L/min/-g/L (2 grains Ca ++ /gallon/minute/-gram/gallon), and more preferably in a range from about 0.26 g Ca 2 ⁇ /L/min/-g/L (2 grains Ca ++ /gallon/minute/-gram/gallon) to about 0.78 g Ca 2 ⁇ /L/min/-g/L (6 grains Ca ++ /gallon/minute/-gram/gallon).
  • the starting detergent material for the present process can include liquid polymers.
  • the liquid polymers can be selected from aqueous or non-aqueous polymer solutions, water and mixtures thereof.
  • the amount of liquid polymers of the present process can be lower than about 10% (active basis), preferably lower than about 6% (active basis) in total amount of the final product obtained by the process of the present invention.
  • aqueous or non-aqueous polymer solutions which can be used in the present inventions are modified polyamines which comprise a polyamine backbone corresponding to the formula: having a modified polyamine formula V (n+1) W m Y n Z or a polyamine backbone corresponding to the formula: having a modified polyamine formula V (n-k+1) W m Y n Y' k Z, wherein k is less than or equal to n, said polyamine backbone prior to modification has a molecular weight greater than about 200 daltons, wherein
  • aqueous or non-aqueous polymer solutions which can be used as liquid polymers in the present inventions are polymeric polycarboxylate dispersants which can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid form.
  • Unsaturated monomeric acids that can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid.
  • the presence in the polymeric polycarboxylates herein of monomeric segments, containing no carboxylate radicals such as vinylmethyl ether, styrene, ethylene, etc. is suitable provided that such segments do not constitute more than about 40% by weight.
  • homo-polymeric polycarboxylates which have molecular weights above 4000, such as described next are preferred.
  • Particularly suitable homo-polymeric polycarboxylates can be derived from acrylic acid
  • acrylic acid-based polymers which are useful herein are the water-soluble salts of polymerized acrylic acid.
  • the average molecular weight of such polymers in the acid form preferably ranges from above 4,000 to 10,000, preferably from above 4,000 to 7,000, and most preferably from above 4,000 to 5,000.
  • Water-soluble salts of such acrylic acid polymers can include, for example, the alkali metal, ammonium and substituted ammonium salts.
  • Co-polymeric polycarboxylates such as an acrylic/maleic-based copolymers may also be used.
  • Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid.
  • the average molecular weight of such copolymers in the acid form preferably ranges from about 2,000 to 100,000, more preferably from about 5,000 to 75,000, most preferably from about 7,000 to 65,000.
  • the ratio of acrylate to maleate segments in such copolymers will generally range from about 30:1 to about 1:1, more preferably from about 10:1 to 2:1.
  • Water-soluble salts of such acrylic acid/maleic acid copolymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. It is preferable for the above polymer solution to be pre-complexed with anionic surfactant such as LAS
  • the starting detergent material in the present process can include additional detergent ingredients and/or, any number of additional ingredients can be incorporated in the detergent composition during subsequent steps of the present process.
  • adjunct ingredients include other detergency builders, bleaches, 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, chelating agents, smectite clays, enzymes, enzyme-stabilizing agents and perfumes. See U.S. Patent 3,936,537, issued February 3, 1976 to Baskerville, Jr. et al., incorporated herein by reference.
  • Other builders can be generally selected from the various water-soluble, alkali metal, ammonium or substituted ammonium phosphates, polyphosphates, phosphonates, polyphosphonates, carbonates, borates, polyhydroxy sulfonates, polyacetates, carboxylates, and polycarboxylates.
  • alkali metal especially sodium, salts of the above.
  • Preferred for use herein are the phosphates, carbonates, C 10-18 fatty acids, polycarboxylates, and mixtures thereof. More preferred are sodium tripolyphosphate, tetrasodium pyrophosphate, citrate, tartrate mono- and di-succinates, and mixtures thereof
  • Bleaching agents and activators are described in U.S. Patent 4,412,934, Chung et al., issued November 1, 1983, and in U.S. Patent 4,483.781, Hartman, issued November 20, 1984, both of which are incorporated herein by reference.
  • Chelating agents are also described in U.S. Patent 4,663,071, Bush et al., from Column 17, line 54 through Column 18, line 68, incorporated herein by reference
  • Suds modifiers are also optional ingredients and are described in U.S. Patents 3,933,672, issued January 20, 1976 to Bartoletta et al., and 4,136,045, issued January 23, 1979 to Gault et al., both incorporated herein by reference.
  • Suitable smectite clays for use herein are described in U.S. Patent 4,762,645, Tucker et al, issued August 9, 1988, Column 6, line 3 through Column 7, line 24, incorporated herein by reference.
  • Suitable additional detergency builders for use herein are enumerated in the Baskerville patent, Column 13, line 54 through Column 16, line 16, and in U.S. Patent 4,663,071, Bush et al, issued May 5, 1987, both incorporated herein by reference.
  • One optional step after the second step of the present invention is an additional agglomeration process.
  • the examples which can be used as the additional process are described in such as USP-5,486,303, USP-5,516,448, USP-5,554,587 and USP-5,574,005.
  • drying if it is desired to reduce level of moisture from the present process.
  • This can be accomplished by a variety of apparatus, well known to these skilled in the art. Fluid bed apparatus is preferred, and will be referred to in the discussion which follows.
  • the detergent granules exiting the fluid bed dryer are further conditioned by additional cooling in cooling apparatus
  • the preferred apparatus is a fluid bed.
  • Another optional process step involves adding a coating agent to improve flowability in one or more of the following locations of the instant process.
  • the coating agent is preferably selected from the group consisting of aluminosilicates, silicates. carbonates and mixtures thereof.
  • the coating agent not only enhances the free flowability of the resulting detergent composition which is desirable by consumers in that it permits easy scooping for detergent during use, but also serves to control agglomeration by preventing or minimizing over agglomeration, especially when added directly to the moderate speed mixer. As those skilled in the art are well aware, over agglomeration can lead to very undesirable flow properties and aesthetics of the final detergent product.
  • the process can comprise the step of spraying an additional binder in the process for the present invention or fluid bed dryers and/or fluid bed coolers.
  • a binder is added for purposes of enhancing agglomeration by providing a "binding" or "sticking" agent for the detergent components.
  • the binder is preferably selected from the group consisting of water, anionic surfactants, nonionic surfactants, liquid silicates, polyethylene glycol, polyvinyl pyrrolidone polyacrylates, citric acid and mixtures thereof.
  • suitable binder materials including those listed herein are described in Beerse et al, U.S. Patent No 5,108,646 (Procter & Gamble Co.), the disclosure of which is incorporated herein by reference.
  • Another optional step of the instant process entails finishing the resulting detergent agglomerates by a variety of processes including spraying and/or admixing other conventional detergent ingredients.
  • the finishing step encompasses spraying perfumes, brighteners and enzymes onto the finished agglomerates to provide a more complete detergent composition.
  • Such techniques and ingredients are well known in the art.
  • the other optional step in the process involves high active paste structuring process, e.g., hardening an aqueous anionic surfactant paste by incorporating a paste-hardening material by using an extruder, prior to the process of the present invention.
  • high active paste structuring process e.g., hardening an aqueous anionic surfactant paste by incorporating a paste-hardening material by using an extruder.
  • the details of the high active paste structuring process is disclosed in WO 98/14550 (application No. PCT/ US 96/ 15960) (filed October 4, 1996).
  • CB mixer Lödige CB mixer
  • CFAS coconut fatty alcohol sulfate, C12-C18 paste (72 % active) is dispersed by the pin tools of a CB mixer for 7.25 seconds, along with 179g of powdered STPP (mean particle size of 40 - 75 microns). 119 of ground soda ash (mean particle size of 10-20 microns), 92g of sodium sulfate (mean particle size of 70-120 microns), 37 of zeolite and 140 of recycle fines. After a short interval (1-2 seconds).
  • the condition of the CB mixer is as follows:
  • the agglomerate from the CB mixer has free-flowing, density of 640-700 g/l.
  • the agglomerates includes only 5.2 % of oversized (i.e., larger than 1180 ⁇ m) granules.
  • CFAS coconut fatty alcohol sulfate, C 12 -C 18 paste (72 % active) is dispersed by the pin tools of a CB mixer for 7.5 seconds, along with 197g of powdered STPP (mean particle size of about 40 - 75 microns), 152g of ground soda ash (mean particle size of about 10-20 microns), 66g of sodium sulfate (mean particle size of about 10 -20 microns) and 136g of recycle fines.
  • the contents in the CB mixer are mixed for about 4 seconds in order to obtain free-flowing agglomerates.
  • the conditions of the CB-30 mixers are as follows. Mixer speed : 800 rpm Paste temperature : 45 - 47°C Jacket temperature : 30°C Pin length : 18.9 cm Diameter of the mixer : 20 cm
  • 750g of the agglomerates from the CB mixer is added to the KM mixer.
  • 8 g of zeolite (mean particle size of about 4 - 7 microns) and 50 g of ground soda ash (mean particle size of about 10 -20 microns) is added.
  • the contents are mixed in the KM mixer for 4-5 seconds, for the purpose of particle growth.
  • one or more conventional choppers can be attached into the KM mixer.
  • the conditions of the KM mixer are as follows:
  • the agglomerates obtained from the KM mixer are dried in a batch scale fluid bed dryer at 95°C for 3 minutes, and subsequently cooled in a batch scale fluid bed cooler.
  • the agglomerates from the cooler are free-flowing with a cake strength of about 0.7 kgf, and has density of 750 - 800 g/l.
  • the mean particle size of agglomerates is about 400 - 500 ⁇ m.
  • the agglomerates includes about 20 % of unacceptable oversized (i.e., larger than 1180 ⁇ m) agglomerates.
  • CB mixer Lödige CB-30 mixer
  • KM mixer Lödige KM-600 mixer
  • CFAS coconut fatty alcohol sulfate, C 12 -C 18 paste (72 % active) is dispersed by the pin tools of a CB mixer along with 250 kg/hr of powdered STPP (mean particle size of about 40 - 75 microns), 185 kg/hr of ground soda ash (mean particle size of about 10-20 microns), 195 kg/hr of ground sulfate (mean particle size of about 10 -20 microns), 200 kg/hr of recycle fines and 11 kg/hr of zeolite.
  • the conditions of the CB-30 mixer are as follows.
  • the agglomerates from the CB mixer is added to the KM mixer.
  • 37 kg/hr of AE 3 S (alkyl ethoxy sulfate, C12-C15) paste (70% active) is dispersed to KM mixer by the pin tools of the CB mixer.
  • 5 -10 kg/hr of Zeolite is added to the KM mixer.
  • conventional choppers (4 numbers of "Christmas Tree Choppers" can be attached into the KM mixer.
  • the conditions of the KM mixer are as follows:
  • the agglomerates obtained from the KM mixer has only about 2 - 10 % of unacceptable oversized (i.e., larger than 1180 ⁇ m) agglomerates.
  • the agglomerates from the KM mixer (having diameter not larger than 1180 ⁇ m) are dried in a fluid bed dryer at 95°C, and subsequently cooled at 10-12 °C in a fluid bed cooler.
  • the agglomerates from the cooler are free-flowing, and has density of 750 - 850 g/l.
  • the mean particle size of agglomerates is about 500 - 650 ⁇ m

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

Claims (10)

  1. Nichtturm-Verfahren zur Herstellung einer granulären Detergenszusammensetzung, wobei das Verfahren umfasst:
    (a) gründliches Mischen einer kristallinen anionischen Tensidpaste mit einer ausreichenden Menge feiner Pulver aus Ausgangsdetergensmaterialien zur Bildung eines freifließenden Agglomerats;
    (b) gründliches Mischen eines Produkts aus Schritt (a) mit einer nichtkristallinen anionischen Tensidpaste zur Bildung eines freifließenden Agglomerats.
  2. Verfahren nach Anspruch 1, wobei ein oder mehrere Ausgangsdetergensmaterialien, gewählt aus der Gruppe, bestehend aus Detergenstensiden, flüssigen Polymeren und Zusatzdetergensbestandteilen, während des Schritts (a) zugegeben werden.
  3. Verfahren nach Anspruch 1, wobei ein oder mehrere Ausgangsdetergensmaterialien, gewählt aus der Gruppe, bestehend aus Detergenstensiden, feinen Pulvern, flüssigen Polymeren und Zusatzdetergensbestandteilen, während des Schritts (b) zugegeben werden.
  4. Verfahren nach Anspruch 1, wobei die kristalline anionische Tensidpaste ein Alkylsulfat oder eine Mischung von Alkylsulfaten ist, gewählt aus der Gruppe, bestehend aus C12-C18-Kokosnussfettalkoholsulfaten, synthetischen C14-C15-Alkylsulfaten und Mischungen hiervon.
  5. Verfahren nach Anspruch 1, wobei die nichtkristalline anionische Tensidpaste aus der Gruppe gewählt ist, bestehend aus Alkylethoxysulfaten, Alkylbenzolsulfonaten und Mischungen hiervon.
  6. Verfahren nach Anspruch 1, wobei die feinen Pulver aus der Gruppe gewählt sind, bestehend aus Sodaasche, pulverisiertem Natriumtripolyphosphat, hydatisiertem Tripolyphosphat, Natriumsulfaten, Aluminiumsilicaten, kristallinen Schichtsilicaten, Phosphaten, ausgefällten Silicaten, Polymeren, Carbonaten, Citraten, Nitrilotriacetaten (NTA), puverisierten Tensiden, recyclierten Feinteilen aus Schritt (b) und Mischungen hiervon.
  7. Verfahren nach Anspruch 1, wobei das Agglomerat aus Schritt (b) weniger als etwa 20% Granulate mit einem Durchmesser von größer als 1180 µm beinhaltet.
  8. Verfahren nach Anspruch 1, wobei ein Aktivgewichtsverhältnis der kristallinen anionischen Tensidpaste zu den feinen Pulvern in Schritt (a) etwa 2,0 bis etwa 3,2 beträgt.
  9. Verfahren nach Anspruch 1, wobei ein Aktivgewichtsverhältnis der kristallinen anionischen Tensidpaste in Schritt (a) zu der nichtkristallinen anionischen Tensidpaste in Schritt (b) etwa 4% bis etwa 14% beträgt.
  10. Granuläre Detergenszusammensetzung, hergestellt gemäß dem Verfahren nach Anspruch 1.
EP97907907A 1997-02-27 1997-02-27 Verfahren zur herstellung einer waschmittelzusammensetzung durch zugabe von cotensiden Expired - Lifetime EP1025196B1 (de)

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JP (1) JP3105266B2 (de)
AR (1) AR011693A1 (de)
AT (1) ATE271601T1 (de)
AU (1) AU1978997A (de)
CA (1) CA2280898C (de)
DE (1) DE69729964T2 (de)
ES (1) ES2225955T3 (de)
MA (1) MA24478A1 (de)
MX (1) MX208228B (de)
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Publication number Priority date Publication date Assignee Title
US6576605B1 (en) 1998-10-28 2003-06-10 The Procter & Gamble Company Process for making a free flowing detergent composition
AU1581999A (en) * 1998-10-28 2000-05-15 Procter & Gamble Company, The Process for making a free flowing detergent composition

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH072955B2 (ja) * 1985-06-17 1995-01-18 花王株式会社 洗浄剤組成物
JPH05171199A (ja) * 1991-12-25 1993-07-09 Lion Corp 高嵩密度粒状洗剤組成物
ATE180273T1 (de) * 1992-03-10 1999-06-15 Procter & Gamble Hochaktive tensidpasten
CN1124498A (zh) * 1993-04-08 1996-06-12 普罗格特-甘布尔公司 在混合表面活性剂颗粒中的仲(2，3)烷基硫酸盐表面活性剂
GB2289687A (en) * 1994-04-11 1995-11-29 Procter & Gamble Agglomerated Detergent Composition Containing High Levels Of Anionic Surfactants And Potassium Salt For Improved Solubility In Cold Temperature Laundering Sol

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WO1998038279A1 (en) 1998-09-03
DE69729964D1 (de) 2004-08-26
DE69729964T2 (de) 2005-08-25
AR011693A1 (es) 2000-08-30
JPH11506498A (ja) 1999-06-08
MX208228B (en) 2002-06-05
EP1025196A1 (de) 2000-08-09
MA24478A1 (fr) 1998-10-01
JP3105266B2 (ja) 2000-10-30
AU1978997A (en) 1998-09-18
ES2225955T3 (es) 2005-03-16
ATE271601T1 (de) 2004-08-15
CA2280898C (en) 2003-04-01
PH11998000411B1 (en) 2002-05-07
CA2280898A1 (en) 1998-09-03
MX9907936A (en) 1999-12-31

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