EP0929646A1 - Procede de production d'une composition de detergent de faible densite - Google Patents

Procede de production d'une composition de detergent de faible densite

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Publication number
EP0929646A1
EP0929646A1 EP96939442A EP96939442A EP0929646A1 EP 0929646 A1 EP0929646 A1 EP 0929646A1 EP 96939442 A EP96939442 A EP 96939442A EP 96939442 A EP96939442 A EP 96939442A EP 0929646 A1 EP0929646 A1 EP 0929646A1
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EP
European Patent Office
Prior art keywords
detergent
sodium
mixer
anionic surfactant
mixtures
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.)
Withdrawn
Application number
EP96939442A
Other languages
German (de)
English (en)
Inventor
Manivannan 5-11-501-2508 Koyo-cho Naka KANDASAMY
Yuji Mezon Flower 103 NAKAMURA
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble Co
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Procter and Gamble Co
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Publication date
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Publication of EP0929646A1 publication Critical patent/EP0929646A1/fr
Withdrawn legal-status Critical Current

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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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents ; Methods for using cleaning compositions
    • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents ; Methods for using cleaning compositions 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

Definitions

  • the present invention generally relates to a process for producing a low density detergent composition. More particularly, the invention is directed to a non-tower process during which low density detergent agglomerates are produced by hardening an aqueous surfactant paste by mixing said paste with a water absorbing material, and then mixing the hardened paste with other detergent ingredients so as to produce agglomerates.
  • the process produces a free flowing, low density detergent composition which can be commercially sold as a conventional non-compact detergent composition or used as an admix in a low dosage, "compact" detergent product.
  • non-tower process One characteristic common to the existing process for producing modern detergent composition by agglomeration, namely, non-tower process, is that the apparent density of the granules by such process is typically not less than 600 g/1. Consequently, there is a need in the art of agglomeration (e.g., non-tower process) to produce modern detergent compositions for flexibility in the ultimate density of the final composition, especially for low density (for example, the range of the density is from about 300g/l to about 600 g/1).
  • 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 agglo erated with a binder such as a nonionic or anionic surfactant, and finally, various detergent components are dry mixed to produce detergent granules (e.g., tower process plus 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., agglomeration process for high density detergent compositions).
  • a binder such as a nonionic or anionic surfactant
  • 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.
  • one attempt involves a batch process in which spray-dried or granulated detergent powders containing sodium tripolyphosphate and sodium sulfate are densified and spheronized in a Marumerizer®.
  • This apparatus comprises a substantially horizontal, roughened, rotatable table positioned within and at the base of a substantially vertical, smooth walled cylinder.
  • This process is essentially a batch process and is therefore less suitable for the large scale production of detergent powders.
  • More recently, other attempts have been made to provide continuous processes for increasing the density of "post-tower" or spray dried detergent granules.
  • Such processes require a first apparatus which pulverizes or grinds the granules and a second apparatus which increases the density of the pulverized granules by agglomeration. While these processes achieve the desired increase in density by treating or densifying "post tower” or spray dried granules, they are limited in their ability to go higher in surfactant active level without subsequent coating step. In addition, treating or densifying by "post tower” is not favourable in terms of economics (high capital cost) and complexity of operation. Moreover, all of the aforementioned processes are directed primarily for densifying or otherwise processing spray dried granules. Currently, the relative amounts and types of materials subjected to spray drying processes in the production of detergent granules has been limited.
  • the first step is, followed by a second agglomeration step where the surfactant loaded particles are dispersed into an inert gaseous medium, wetting the dispersed particles with atomized stream of aqueous sodium silicate or with separate atomized streams of water and concentrated sodium silicate to form the agglomerate detergent.
  • a second agglomeration step where the surfactant loaded particles are dispersed into an inert gaseous medium, wetting the dispersed particles with atomized stream of aqueous sodium silicate or with separate atomized streams of water and concentrated sodium silicate to form the agglomerate detergent.
  • the present invention meets the aforementioned needs in the art by providing a non- tower process which produces a low density granular detergent composition directly from an anionic surfactant paste and other conventional detergent ingredients.
  • the process of the proposed invention has capability of adjusting the density of the granules of the composition by controlled hardening of the anionic surfactant paste to a specified degree of hardness, as measured by penetration values.
  • the process does not use the conventional spray drying towers currently which is limited in producing high surfactant loading compositions.
  • the process of the present invention is more efficient, economical and flexible with regard to the variety of detergent compositions which can be produced in the process.
  • the process is more amenable to environmental concerns in that it does not use spray drying towers which typically emit particulates and volatile organic compounds into the atmosphere.
  • agglomerates refers to particles formed by agglomerating raw materials with binder such as surfactants and or inorganic solutions / organic solvents and polymer solutions. All percentages used herein are expressed as “percent-by-weight” unless indicated otherwise.
  • a process for preparing a granular detergent composition having a low density (less than about 600 g/1), preferably from about 300 g/1 to 600 g/1 comprises the steps of: (a) mixing an anionic surfactant paste comprising from about 35% to about 85% anionic surfactant and from about 15% to about 65% water with a sufficient amount of a particulate water absorbing material to form a solid mass having a penetration value of from about 75 gf to about 4,000 gf, then (b) agglomerating the solid mass from the step (a) and an amount of one or more other detergent ingredients in a mixer so as to produce agglomerates having an anionic surfactant content of from about 12 % to about 60%.
  • granular detergent compositions having a low density of less than about 600 g/1, preferably from about 300 g/1 to about 600g l, produced by any one of the process embodiments described herein.
  • the present invention is directed to a process which produces free flowing, granular detergent agglomerates having a low density of less than about 600 g/1, preferably from about 300 to about 600 g/1.
  • the process produces low density detergent agglomerates from an anionic surfactant paste having a water content, of typically at least about 15%, generally from about 15 to about 65 %, preferably from about 20 to about 60 %, more preferably from about 30 to about 50 %.
  • the detergent agglomerates can be used as a detergent or as a detergent additive. It should be understood that the process described herein can be continuous depending upon the desired application.
  • an anionic surfactant paste (aqueous or non-aqueous), comprising from about 35% to about 85% anionic surfactant and from about 15 % to about 65% water is mixed with sufficient amount of a particulate water absorbing material to form a solid mass having a penetration value of from about 75 gf to about 4,000 gf as measured according to a conventional penetrometer known to those skilled in the art (e.g., such as ASTM D 217-IP 50 or ISO 2137).
  • Forming a solid mass means not only making a mass of the anionic surfactant paste having a property of plastic solids or highly viscous fluids, but also means (i) increasing the anionic surfactant paste's apparent viscosity, (ii) increasing the anionic surfactant paste's effective melting point, (iii) increasing the "hardness" of the anionic surfactant paste.
  • the hardness of the anionic surfactant paste after the first step is expressed as penetration value.
  • the mixing of the First Step can be accomplished in any type of equipment suitable for kneading plastic solids or highly viscous fluids.
  • the penetration value which is given to the surfactant paste can be controlled by the equipment used for the mixing (e.g., the first step) and by the amount and the choice of water absorbing agent.
  • a twin screw extruder such as that used as a plodder in the manufacture of soap bars is particularly suitable.
  • Preferred examples of the twin screw extruder are: the CONTLNUA-83, manufactured by Werner and Pfleiderer, and other twin screw extruders manufactured by such as Kurimoto Compounder or Reico Teledyne Compounder.
  • the solid mass produced in the first step is sometimes referred to herein as "hardened paste".
  • the solid mass (hardened paste) obtained by the first step and other detergent ingredients are fed into a mixer which can be used for an agglomeration and is known to those skilled in the art for agglomeration, then the contents in the mixer are agglomerated so as to form detergent agglomerates having a density of less than about 600 g/1.
  • other detergent ingredients refers to ingredients selected from fine powders typically having an average diameter from 0.1 to 500 microns, preferably from about 1 to about 100 microns, or selected from the mixtures of the fine powders and optional ingredients selected from the group comprising such as (i) other surfactants, (ii) adjunct detergent ingredients and (iii) the mixtures thereof.
  • the mean residence time in the mixer is from about 5 to about 30 seconds and tip speed for the mixer is in range from about 5 m/s to about 22 m/s
  • the energy per unit mass in the mixer is from about 0.15 kj/kg to about 12 kj/kg
  • the mean residence time in the mixer is from about 5 to about 15 seconds and tip speed for the mixer is in range from about 6 m/s to about 20 m/s
  • the energy per unit mass for the mixer is from about 0.15 kj/kg to about 8 kj/kg
  • the mean residence time in the mixer is from about 5 to about 10 seconds and tip speed for the mixer is in range from about 6 m/s to about 18 m/s
  • the energy per unit mass for the mixer is from about 0.15 kj/kg to about 4.5 kj/kg.
  • the examples of mixers for the second step can be any types of mixer known to the skilled in the art, as long as the mixer can maintain the above mentioned condition for the second step.
  • An Example can be L ⁇ dige CB Mixer manufactured by the L ⁇ dige company (Germany).
  • the detergent agglomerates produced by the process preferably have an anionic surfactant level of from about 12% to about 60%, more preferably from about 25% to about 55%, i.e. they comprise up to about 88% other detergent ingredients (including the ingredient used for paste hardening).
  • the agglomerates are irregular in shape and have a relatively high degree of intraparticle voids, both of which characteristics contribute to low density.
  • the present process typically provides detergent agglomerates having a mean particle size of from about 200 microns to about 800 microns, and more preferably from about 300 microns to about 650 microns.
  • mean particle size refers to average size of all particles that make up the agglomerate.
  • the agglomerates having desired mean particle size can be obtained by screening the agglomeration from the second step, since the agglomerates from the second step may contain a relatively large amount of fines that have to be recycled, further agglomeration (i.e., an additional mixing step) can be optionally used.
  • the agglomerates and other liquid components can be added to the contents in one or more mixers (e.g., the second mixer, or the series of the second mixers) then the contents in this mixer are agglomerated so as to form detergent agglomerates having a density of less than about 600 g/1.
  • the examples of mixers for the second mixer can be any types of mixer for agglomeration which are known to those skilled in the art.
  • An example can be L ⁇ dige KM Mixer manufactured by the L ⁇ dige company (Germany) or Schugi Flexomic Model manufactured by the Schugi company (Netherlands).
  • the process includes the second mixer, it surprisingly reduces the amount of excess recycle fines from the second step, compared to the amount of excess recycle fines due to common agglomeration processes known to the skilled in the art.
  • the existence of excess fines leads to excessive recycle streams which disrupt the process and are therefore not economically favourable.
  • the total amount of the surfactants for the present invention, which are included in the following detergent surfactants, other liquid compositions and adjunct detergent ingredients is generally from about 5 % to about 60 %, more preferably from about 12% to about 55 %, more preferably, from about 15 % to about 45%, in total amount of the final product obtained by the process of the present invention.
  • the surfactants which should be included in the above can be from any part of the process of the present invention., e.g., from either one of the first step or the second step, or both steps of the present invention.
  • the amount of anionic surfactant in paste form can be from about 5 % to about 60 %
  • active more preferably from about 12 % to about 60 % (active), more preferably, from about 25% to about 55% (active), in total amount of the final product obtained by the process of the present invention.
  • One or more various aqueous pastes of the salts of anionic surfactant is preferred for use in the present invention, including the water-soluble salts, preferably the alkali metal, ammonium and alkylolammonium salts of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 10 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group. (Included in the term "alkyl” is the alkyl portion of acyl groups.).
  • the water in the surfactant paste is as low as possible, while maintaining paste fluidity, since low moisture reads to a higher concentration of the surfactant in the finished agglomerates.
  • the anionic surfactant paste comprises from about 35 % to about 85 % anionic surfactant, and from about 15 % to about 65 % water.
  • Nonlimiting examples of the preferred anionic surfactants useful in the present invention include the conventional C j i -Ci alkyl benzene sulfonates ("LAS"), primary, branched-chain and random C10-C20 alkyl sulfates (“AS”), the Ci ⁇ -Ci g secondary (2,3) alkyl sulfates of the formula CH3(CH 2 ) x (CHOS0 3 " M + ) CH and CH (CH 2 ) y (CHOS0 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 I Q-C I g alkyl alkoxy sulfates ("AE X S”; especially EO 1-7 ethoxy sulfates).
  • LAS C j i -Ci al
  • Useful anionic surfactants also include water-soluble salts of 2-acyloxy-alkane-l- 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 .
  • other exemplary surfactants useful in the paste of the invention include
  • the conventional nonionic and amphoteric surfactants such as the C j 2-Cj 8 alkyl ethoxylates ("AE") including the so-called narrow peaked alkyl ethoxylates and Cg-Cj2 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), Cj -Cjg amine oxides, and the like, can also be included in the overall compositions.
  • the C I -C J N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include the C12-C1 N-methylglucamides. See WO 9,206,154.
  • sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C iQ-Cj g N-(3-methoxypropyl) glucamide.
  • the N-propyl through N-hexyl C12-C18 glucamides can be used for low sudsing.
  • C10-C20 conventional soaps may also be used. If high sudsing is desired, the branched-chain C j Q-Ci g soaps may be used. Mixtures of anionic and nonionic surfactants are especially useful. Other conventional useful surfactants are listed in standard texts.
  • anionic surfactant paste can be selected from the group consisting of alkyl benzene sulfonates, alkyl alkoxy sulfates, alkyl ethoxylates, alkyl sulfates, coconut fatty alcohol sulfates and mixtures thereof.
  • Secondary Surfactants The secondary surfactant(s) which can be optionally applied for the second step of the present invention is/are 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.
  • anionics and nonionics are preferred and anionics are most preferred.
  • the examples of the anionic surfactants described in the above (a) can also be used for the secondary surfactant.
  • Cationic surfactants can also be used as a detergent surfactant herein and suitable quaternary ammonium surfactants are selected from mono C6-C i6, preferably C6-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 wherein R is a C6-C18 hydrocarbyl group, preferably a C10-C16 alkyl group or C 10-C16 acylamido alkyl group, each R* is typically C ⁇ -C 3 alkyl, preferably methyl and R2 is a C1-C5 hydrocarbyl group, preferably a C1-C3 alkylene group, more preferably a C
  • betaines examples include coconut acylamidopropyldimethyl betaine; hexadecyl dimethyl betaine; CJ2-14 acylamidopropylbetaine; C8-14 acylamidohexyldiethyl betaine; 4[Ci4_i6 acylmethylamidodiethylammonio]-l-carboxybutane; C16-I 8 acylamidodimethylbetaine; C12-16 acylamidopentanediethylbetaine; and
  • betaines are C 12-18 dimethyl-ammonio hexanoate and the C10-I8 acylamidopropane (or ethane) dimethyl (or diethyl) betaines; and the sultaines having the formula (R(R ⁇ )2N + R ⁇ S0 3 " wherein R is a C6-C18 hydrocarbyl group, preferably a C10-C16 alkyl group, more preferably a C12- 3 alkyl group, each R ⁇ is typically Cj-C 3 alkyl, preferably methyl, and R ⁇ is a Cj-C ⁇ hydrocarbyl group, preferably a C 1 -C3 alkylene or, preferably, hydroxyalkylene group.
  • Suitable sultaines include Cl2-Cl4 dimethylammonio-2-hydroxypropyl sulfonate, C12-C14 amido propyl ammonio-2- hydroxypropyl sultaine, C12-C14 dihydroxyethylammonio propane sulfonate, and C 16- 18 dimethylammonio hexane sulfonate, with CJ2-14 amido propyl ammonio-2-hydroxypropyl sultaine being preferred.
  • the water absorbing agent mixed with the anionic surfactant paste in the first step of the process can be any granular material which is capable of absorbing water, modifying crystal structures of the selected anionic surfactant paste, providing elastic properties to the selected anionic surfactant paste, and which is suitable for use in detergent compositions.
  • hydrophilic precipitated silica aluminosilicates which are fully described in the below section of "Fine Powders”
  • hydratable salts such as sodium carbonate, sodium sulfate, sodium citrate, trisodium phosphate, sodium tripolyphosphate (STPP), tetrasodium tripolyphosphate, soda ash, sodium carboxy methyl cellulose, and quaternary ammonium compounds.
  • Co-polymeric polycarboxylates such as a Acrylic/maleic-based copolymers may also be used as water absorbing agent of the present invention .
  • 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.
  • the amount of water absorbing material used is that which is sufficient to produce a hardened paste which has a penetration value in the range of from about 100 to about 4,000 gf, preferably from about 1000 to about 3,000 gf. This amount, of course, will be dependent upon the water content of the paste and the water absorbing capacity of the water absorbent material.
  • the amount of any particular water absorbing material required for any particular surfactant paste can be determined by routine experimentation.
  • the amount of the fine powders of the present process, which is used in the second step, can be from about 94% to 30%, preferably from 86% to 54%, in total amount of starting material for the second step .
  • 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 water absorbing agent for the first step of the present invention may suitable as fine powders for the second step of the present invention.
  • STPP which is hydrated to a level of not less than 50% is preferable.
  • 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.
  • 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 [(Al0 2 ) z .(Si ⁇ 2)y]xH2 ⁇ 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 [(A10 2 ) 12 .(Si0 2 )i2]xH 2 0 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.
  • Naturally-occurring or synthetically derived aluminosilicate ion exchange materials suitable for use herein can be made as described in Krummel et al, U.S. Patent No. 3,985,669, the disclosure of which is incorporated herein by reference.
  • the aluminosilicates used herein are further characterized by their ion exchange capacity which is at least about 200 mg equivalent of CaC0 3 hardness/gram, calculated on an anhydrous basis, and which is preferably in a range from about 300 to 352 mg equivalent of CaC0 3 hardness/gram. Additionally, the instant aluminosilicate ion exchange materials are still further characterized by their calcium ion exchange rate which is at least about 2 grains Ca ++ /gallon/minute/-gram/gallon, and more preferably in a range from about 2 grains Ca ++ /gallon/minute/-gram/gallon to about 6 grains Ca "H 7gallon/minute/-gram/gallon.
  • the amount of the other liquid components (aqueous or non aqueous) which can be additionally used for the present process can be from less than about 10% (active basis), preferably from 2% to about 6% (active basis) in total amount of the final product obtained by the process of the present invention.
  • the other liquid components of the present process can be selected from the group consisting of liquid silicate, liquid solutions of anionic or cationic surfactants, aqueous or non-aqueous polymer solutions, water and mixtures thereof.
  • Other examples for the other liquid compositions of the present invention can be sodium carboxy methyl cellulose solution, polyethylene glycol (PEG), and solutions of dimethylene triamine pentamethyl phosphonic acid (DETMP),
  • anionic surfactant solutions which can be used as the other liquid compositions in the present inventions are about 88 - 97% active HLAS, about 30 - 50% active NaLAS, about 28% active AE3S solution, about 40-50% active liquid silicate, and so on.
  • Liquid solution of cationic surfactants can also be used as other liquid compositions herein and suitable quaternary ammonium surfactants are selected from mono C6-C16, preferably C6-C10 N-alkyl or alkenyl ammonium surfactants wherein remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.
  • aqueous or non-aqueous polymer solutions which can be used as the other liquid components in the present inventions are modified polyamines which comprise a polyamine backbone corresponding to the formula:
  • V units are terminal units having the formula:
  • W units are backbone units having the formula:
  • Y units are branching units having the formula:
  • backbone linking R units are selected from the group consisting of C2-C12 alkylene, C4-C12 alkenylene, C 3 -Ci 2 hydroxyalkylene, C4-C12 dihydroxy-alkylene, C8-Cj2 dialkylarylene, -(R'O ⁇ R 1 -, -(R 1 0) x R 5 (OR 1 ) x -,
  • R 1 is C 2 -C 6 alkylene and mixtures thereof
  • R 2 is hydrogen, -(R ⁇ O) x B, and mixtures thereof
  • R ⁇ is C ] -C i 8 alkyl, C -C12 arylalkyl, C7-C J2 alkyl substituted aryl, Cg-C ]2 aryl, and mixtures thereof
  • R 4 is C1 -C12 alkylene, C4-C J2 alkenylene, C8-C j 2 arylalkylene, Cg-Cjo arylene, and mixtures thereof
  • R ⁇ is C j-C ⁇ alkylene, C 3 -C ⁇ 2 hydroxyalkylene, C4-C12 dihydroxy-alkylene, C8-C 12 dialkylarylene, -C(O)-, -C(0)NHR6NHC(0)-
  • polyethyleneimines a polyethyleneimine having a molecular weight of 1800 which is further modified by ethoxylation to a degree of approximately 7 ethyleneoxy residues per nitrogen (PEI 1800, E7). It is preferable for the above polymer solution to be pre-complex with anionic surfactant such as NaLAS.
  • 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 a 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 .
  • Adjunct Detergent Ingredients 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 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.
  • the alkali metal especially sodium, salts of the above.
  • Preferred for use herein are the phosphates, carbonates, C j Q- 18 f attv a 'ds, polycarboxylates, and mixtures thereof. More preferred are sodium tripolyphosphate, tetrasodium pyrophosphate, citrate, tartrate mono- and di-succinates, and mixtures thereof (see below).
  • crystalline layered sodium silicates exhibit a clearly increased calcium and magnesium ion exchange capacity.
  • the layered sodium silicates prefer magnesium ions over calcium ions, a feature necessary to insure that substantially all of the "hardness" is removed from the wash water.
  • These crystalline layered sodium silicates are generally more expensive than amorphous silicates as well as other builders. Accordingly, in order to provide an economically feasible laundry detergent, the proportion of crystalline layered sodium silicates used must be determined judiciously.
  • the crystalline layered sodium silicates suitable for use herein preferably have the formula NaMSi x 0 2x+1 .yH 2 0 wherein M is sodium or hydrogen, x is from about 1.9 to about 4 and y is from about 0 to about 20. More preferably, the crystalline layered sodium silicate has the formula
  • inorganic phosphate builders are sodium and potassium tripolyphosphate, pyrophosphate, polymeric metaphosphate having a degree of polymerization of from about 6 to 21, and orthophosphates.
  • polyphosphonate builders are the sodium and potassium salts of ethylene diphosphonic acid, the sodium and potassium salts of ethane 1 -hydroxy- 1, 1 -diphosphonic acid and the sodium and potassium salts of ethane, 1,1,2-triphosphonic acid.
  • Other phosphorus builder compounds are disclosed in U.S. Patents 3,159,581; 3,213,030; 3,422,021; 3,422,137; 3,400,176 and 3,400,148, all of which are incorporated herein by reference.
  • nonphosphorus, inorganic builders are tetraborate decahydrate and silicates having a weight ratio of SiO- to alkali metal oxide of from about 0.5 to about 4.0, preferably from about 1.0 to about 2.4.
  • Water-soluble, nonphosphorus organic builders useful herein include the various alkali metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates and polyhydroxy sulfonates.
  • polyacetate and polycarboxylate builders are the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylene diamine tetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, and citric acid.
  • Polymeric polycarboxylate builders are set forth in U.S. Patent 3,308,067, Diehl, issued March 7, 1967, the disclosure of which is incorporated herein by reference.
  • Such materials include the water-soluble salts of homo- and copolymers of aliphatic carboxylic acids such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid and methylene malonic acid.
  • Some of these materials are useful as the water-soluble anionic polymer as hereinafter described, but only if in intimate admixture with the non-soap anionic surfactant.
  • Other suitable polycarboxylates for use herein are the polyacetal carboxylates described in U.S.
  • These polyacetal carboxylates can be prepared by bringing together under polymerization conditions an ester of glyoxylic acid and a polymerization initiator. The resulting polyacetal carboxylate ester is then attached to chemically stable end groups to stabilize the polyacetal carboxylate against rapid depolymerization in alkaline solution, converted to the corresponding salt, and added to a detergent composition.
  • Particularly preferred polycarboxylate builders are the ether carboxylate builder compositions comprising a combination of tartrate monosuccinate and tartrate disuccinate described in U.S. Patent 4,663,071, Bush et al., issued May 5, 1987, the disclosure of which is incorporated herein by reference.
  • 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
  • One optional step in the process is drying, if it is desired to reduce level of moisture in the agglomerates from the second step. 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 as the dryer in the discussion which follows.
  • the detergent agglomerates exiting the fluid bed dryer are further conditioned by additional cooling in cooling apparatus.
  • the preferred apparatus for cooling is a fluid bed.
  • Another optional process step involves adding a coating agent to improve flowability and/or minimize over-agglomeration of the detergent composition in one or more of the following locations of the instant process: (1) the coating agent can be added directly after the fluid bed cooler or dryer; (2) the coating agent may be added between the fluid bed dryer and the fluid bed cooler; (3) the coating agent may be added between the fluid bed dryer and a mixer for agglomeration (i.e., the first mixer or the second mixer in the second step) which is commonly known to those skilled in the art ; and/or (4) the coating agent may be added directly to a mixer for agglomeration (i.e., the first mixer or the second mixer in the second step) which is commonly known to those skilled in the art and the fluid bed dryer.
  • the coating agent may be added directly after the fluid bed cooler or dryer; (2) the coating agent may be added between the fluid bed dryer and the fluid bed cooler; (3) the coating agent may be added between the fluid bed dryer and a mixer for agglomeration (i.e., the first mixer or the second mixer in
  • 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 mixer for agglomeration. 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 mixer(s) in the second step of 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.
  • optional steps contemplated by the present process include screening the oversized detergent agglomerates in a screening apparatus which can take a variety of forms including but not limited to conventional screens chosen for the desired particle size of the finished detergent product.
  • Other optional steps include conditioning of the detergent agglomerates by subjecting the agglomerates to additional drying by way of apparatus discussed previously.
  • 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 representative examples of the series of mixers to make granular detergent compositions according to the process of the present invention plus optional processes are as follows: A. (a) Paste hardening by Twin Screw Extruder, then (b) agglomeration in (1) L ⁇ dige CB Model (the first mixer)-- (2) Schugi Flexomic Model (the second mixer) ⁇ (3) sizing in a Mogensens sizer to remove particles over 4.5 mm —(4) drying in a Fluid Bed Dryer --(5) cooling in a Fluid Bed Cooler —(6) sizing in a Mogensen sizer to remove over 1.2 mm —(7) grinding to reduce over size agglomerates from the sizers— and (8) feeding ground agglomerates back to the fluid bed dryer or fluid bed cooler or Lodigie CB mixer; B.
  • Example 1 The following is an example for obtaining agglomerates using Twin Screw Extruder
  • TSE L ⁇ dige CB mixer
  • CB-30 L ⁇ dige CB mixer
  • FBC fluid bed cooler
  • aqueous coconut fatty alcohol sulfate surfactant paste 72 % active
  • 5 g hydrophilic silica in Twin Screw Extruder (S2 KRC Krimoto Kneader).
  • the 200 g of the solid mass is added by the pin tools of a CB-30 mixer along with the 203 g of light granular STPP, the 224 g of ground soda ash (mean particle size of 10 -20 microns), and the 250 g of recycle fines.
  • the solid mass is fed at about 56°C, and the powders are fed at room temperature.
  • the condition of the CB-30 mixer is as follows:
  • the resulting granules have density of about 490 g/1.
  • TSE Twin Screw Extruder
  • CB-30 L ⁇ dige CB mixer
  • FBC fluid bed cooler
  • aqueous coconut fatty alcohol sulfate surfactant paste 72 % active
  • 10 g hydrophilic silica in Twin Screw Extruder ( S2 KRC Kurimoto Kneader).
  • the 250 g of the solid mass is added by the pin tools of a CB-30 mixer along with the 203 g of light granular STPP , the 224 g of ground soda ash (mean particle size of 10-20 microns), and the 250 g of recycle fines.
  • the solid mass is fed at about 48°C, and the powders were fed at room temperature.
  • the condition of the CB-30 mixer is as follows: Residence time : 12 seconds Tip speed : 8 to 10 m/s Energy condition : 1.78 kj/kg After the agglomeration, bed temperature of the FBD is maintained between 40 - 60 °C and bed temperature of the FBC is maintained between 15 - 30 °C.
  • the resulting agglomerates are sized in a rotap to remove the particles which are over 1.18 mm or less than 150 ⁇ m.
  • the resulting granules have density of about 450 g/1.

Abstract

L'invention concerne un procédé de préparation sans colonne d'une composition de détergent granulaire présentant une faible densité, inférieure à 600 g/l. Le procédé comprend les étapes consistant: (a) à mélanger une pâte de tensioactif anionique comprenant environ 35 % à environ 85 % d'un tensioactif anionique et environ 15 % à environ 65 % d'eau avec une quantité suffisante d'une matière particulaire absorbant l'eau afin de former une masse solide ayant une valeur de pénétration comprise entre environ 75 gf et environ 4 000 gf, ensuite (b) à agglomérer la masse solide de l'étape (a) et une quantité d'un ou de plusieurs autres ingrédients de détergent dans un mélangeur afin de produire des agglomérats ayant une teneur en tensioactif anionique comprise entre environ 12 % et environ 60 %.
EP96939442A 1996-10-04 1996-10-04 Procede de production d'une composition de detergent de faible densite Withdrawn EP0929646A1 (fr)

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GB9526097D0 (en) * 1995-12-20 1996-02-21 Unilever Plc Process
GB9712583D0 (en) 1997-06-16 1997-08-20 Unilever Plc Production of detergent granulates
GB9712580D0 (en) * 1997-06-16 1997-08-20 Unilever Plc Production of detergent granulates
GB9713748D0 (en) * 1997-06-27 1997-09-03 Unilever Plc Production of detergent granulates
JP2002530518A (ja) * 1998-11-25 2002-09-17 ザ、プロクター、エンド、ギャンブル、カンパニー 凝集粒子の製法
US6514929B1 (en) 1998-11-25 2003-02-04 The Procter & Gamble Company Process for forming an agglomerated particle
WO2000037605A1 (fr) * 1998-12-22 2000-06-29 The Procter & Gamble Company Procede de preparation d'une composition detergente a faible masse volumique apparente par agglomeration
EP2123742A1 (fr) 2008-05-14 2009-11-25 The Procter and Gamble Company Compositions de détergent solide pour lessive comprenant du sel de silicate à faible densité

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US5108646A (en) * 1990-10-26 1992-04-28 The Procter & Gamble Company Process for agglomerating aluminosilicate or layered silicate detergent builders
US5366652A (en) * 1993-08-27 1994-11-22 The Procter & Gamble Company Process for making high density detergent agglomerates using an anhydrous powder additive
US5574005A (en) * 1995-03-07 1996-11-12 The Procter & Gamble Company Process for producing detergent agglomerates from high active surfactant pastes having non-linear viscoelastic properties

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AR010236A1 (es) 2000-06-07
CA2268057C (fr) 2002-12-10

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