WO1998014556A1 - Process for making a detergent composition by non-tower process - Google Patents
Process for making a detergent composition by non-tower process Download PDFInfo
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- WO1998014556A1 WO1998014556A1 PCT/US1997/009794 US9709794W WO9814556A1 WO 1998014556 A1 WO1998014556 A1 WO 1998014556A1 US 9709794 W US9709794 W US 9709794W WO 9814556 A1 WO9814556 A1 WO 9814556A1
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- surfactant
- detergent
- mixer
- agglomerates
- process according
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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
- C11D11/0088—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 the liquefied ingredients being sprayed or adsorbed onto solid particles
-
- 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
-
- 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
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents ; Methods for using cleaning compositions
- C11D11/02—Preparation in the form of powder by spray drying
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- 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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
- C11D17/065—High-density particulate detergent compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- 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 non-tower process for producing a particulate detergent composition. More particularly, the invention is directed to a continuous process during which detergent agglomerates are produced by feeding a surfactant and coating materials into a series of mixers. 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 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).
- 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.
- the Laid-open No.W093/23,523 (Henkel) describes the process comprising pre-agglomeration by a low speed mixer and further agglomeration step by high speed mixer for obtaining high density detergent composition with less than 25 wt% of the granules having a diameter over 2 mm.
- the U.S. Patent No. 4,427,417 (Korex) describes continuous process for agglomeration which reduces caking and oversized agglomerates. None of the existing art provides all of the advantages and benefits of the present invention.
- the present invention meets the aforementioned needs in the art by providing a process which produces a high density granular detergent composition.
- the present invention also meets the aforementioned needs in the art by providing a process which produces a granular detergent composition for flexibility in the ultimate density of the final composition from agglomeration (e.g., non-tower) process.
- 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 solutic.3.
- binder such as surfactants and or inorganic solutions / organic solvents and polymer solutic.3.
- a process for preparing a granular detergent composition having a density at least about 600 g/1 is provided.
- the process comprises the steps of:
- granular detergent compositions having a high density of at least 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 density of at least about 600 g/1.
- the process produces granular detergent agglomerates from an aqueous and/or non-aqueous surfactant which is then coated with fine powder having a diameter from 0.1 to 500 microns, in order to obtain low density granules.
- surfactant i.e., one or more of aqueous and/or non-aqueous surfactant(s), which is/are in the form of powder, paste and/or liquid , and fine powder having a diameter from 0.1 to 500 microns, preferably from about 1 to about 100 microns are fed into a mixer, so as to make agglomerates.
- a mixer so as to make agglomerates.
- an internal recycle stream of powder having a diameter of about 0.1 to about 300 microns generated from fluidizing apparatus which is described hereinafter in the second step, can be fed into the mixer in addition to the fine powder.
- the amount of such internal recycle stream of powder can be 0 to about 60 wt% of the final product from the process of the present invention.
- the surfactant(s) can be initially fed into a mixer or pre-mixer (e.g. a conventional screw extruder or other similar mixer) prior to the above, after which the mixed detergent materials are fed into the first step mixer as described herein for agglomeration.
- a mixer or pre-mixer e.g. a conventional screw extruder or other similar mixer
- the mean residence time of the mixer is in range from about 2 to about 50 seconds and tip speed of the mixer is in range from about 4 m/s to about 25 m/s
- the energy per unit mass of the mixer (energy condition) is in range from about 0.15 kj/kg to about 7 kj/kg
- the mean residence time of the mixer is in range from about 5 to about 30 seconds and tip speed of the mixer is in range from about 6 m/s to about 18 m/s
- the energy per unit mass of the mixer (energy condition) is in range from about 0.3 kj/kg to about 4 kj/kg
- the mean residence time of the mixer is in range from about 5 to about 20 seconds and tip speed of the mixer is in range from about 8 m/s to about 18 m/s
- the energy per unit mass of the mixer (energy condition) is from about 0.3 kj/kg to about 4 kj/kg.
- the examples of mixers for the first 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 first step.
- An Example can be L ⁇ dige CB Mixer manufactured by the L ⁇ dige company (Germany).
- resultant product agglomerates having fine powder on the surface of the agglomerates
- the resultant product of the first step (the agglomerates) is fed into a fluidized apparatus, such as fluidized bed, in order to enhance granulation for producing free flowing high density granules.
- the second step can proceed in one or more than one fluidized apparatus (e.g., combining different kinds of fluidized apparatus such as fluid bed dryer and fluid bed cooler ).
- the resultant product from the first step is fluidized thoroughly so that the granules from the second step have a round shape.
- about 0 to about 10% , more preferably about 2-5% of powder detergent materials of the kind used in the first step and/or other detergent ingredients can be added to the second step.
- liquid detergent materials of the kind used in the first step and/or other detergent ingredients can be added to the step, for enhancing granulation and coating on the surface of the granules.
- condition of a fluidized apparatus can be; Mean residence time : from about 1 to about 10 minutes Depth of unfluidized bed : from about 100 to about 300 mm Droplet spray size : not more than about 50 micron Spray height: from about 175 to about 250 mm Fluidizing velocity : from about 0.2 to about 1.4 m/s Bed temperature : from about 12 to about 100 °C, more preferably; Mean residence time : from about 2 to about 6 minutes Depth of unfluidized bed : from about 100 to about 250 mm Droplet spray size : less than about 50 micron Spray height: from about 175 to about 200 mm Fluidizing velocity : from about 0.3 to about 1.0 m/s Bed temperature : from about 12 to about 80 °C.
- mean residence time of the second step in total can be from about 2 to about 20 minutes, more preferably, from about 2 to 12 minutes.
- a coating agent to improve flowability and/or minimize over agglomeration of the detergent composition can be added 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 fluid bed dryer and/or (2) the coating agent may be added between the fluid bed dryer and the fluid bed cooler.
- 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. 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 total amount of the surfactants in products made by the present invention, which are included in the following detergent materials, finely atomized liquid and adjunct detergent ingredients is generally from about 5% to about 60%, more preferably from about 12% to about 40%, more preferably, from about 15 to about 35%, in percentage ranges.
- the surfactants which are 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 and/or the second step of the present invention.
- Detergent Surfactant (Agueous /Non-aqueous)
- the amount of the surfactant of the present process can be from about
- the surfactant of the present process which is used as the above mentioned starting detergent materials in the first step, is in the form of powdered, pasted or liquid raw materials.
- 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 ⁇
- LAS C ⁇
- AS random C10-C20 a,kvl sulfates
- tne C10-C18 secondary (2,3) alkyl sulfates of the formula CH3(CH 2 ) x (CHOS ⁇ 3 " M + ) CH3 and CH3 (CH2)y(CHOS ⁇ 3 _ M + ) CH2CH3 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 a'M alkoxy sulfates ("AE X S"; especially EO 1-7 ethoxy sulfates).
- 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 .
- exemplary surfactants useful in the paste of the invention include C ⁇
- the conventional nonionic and amphoteric surfactants such as the C12-C18 alkyl ethoxylates ("AE") including the so-called narrow peaked alkyl ethoxylates and C6-C12 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), C-10-C18 amine oxides, and the like, can also be included in the overall compositions.
- AE C12-C18 alkyl ethoxylates
- C-10-C18 amine oxides and the like
- 8 N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include the C12-C18 N-methylglucamides. See WO 9,206,154.
- sugar- derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C-10-C18 N-(3-methoxypropyl) glucamide.
- 8 glucamides can be used for low sudsing.
- C10-C20 conventional soaps may also be used. If high sudsing is desired, the branched-chain C10-C16 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 C6-C16, preferably C6-C10 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; zwitte onic 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 )2N + R 2 COO-, wherein R is a C6-C18 hydrocarbyl group, preferably a C10- C16 alkyl group or C10-C16 acylamido alkyl group, each R 1 is typically C1-C3 alkyl, preferably methyl and R2 is a C1-C5 hydrocarbyl group, preferably
- betaines examples include coconut acylamidopropyldimethyl betaine; hexadecyl dimethyl betaine; C12-14 acylamidopropylbetaine; C8-14 acylamidohexyldiethyl betaine; 4[C ⁇
- Preferred betaines are C12-I8 dimethyl-ammonio hexanoate and the C10-I8 acylamidopropane (or ethane) dimethyl (or diethyl) betaines; and the sultaines having the formula (R(R 1 )2N + R 2 S03- wherein R is a C6-C18 hydrocarbyl group, preferably a C10- C16 alkyl group, more preferably a C12-C13 alkyl group, each R 1 is typically C1- C3 alkyl, preferably methyl, and R 2 is a C1-C6 hydrocarbyl group, preferably a C1-C3 alkylene or, preferably, hydroxyalkylene group.
- Suitable sultaines include C12-C14 dimethylammonio-2-hydroxypropyl sulfonate, C12- C14 amido propyl ammonio-2-hydroxypropyl sultaine, C12-C14 dihydroxyethylammonio propane sulfonate, and C16-I8 dimethylammonio hexane sulfonate, with C-J2-14 amido propyl ammonio-2-hydroxypropyl sultaine being preferred.
- Fine Powder The amount of the fine powder of the present process, which is used in the first step, can be from about 94% to 30%, preferably from 86% to 54%, in total amount of starting material for the first step .
- the starting fine powder 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 internal recycle stream of powder 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 [(Al ⁇ 2)z (Si ⁇ 2)y]xH 2 0 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 [(Al ⁇ 2)i2 (Si ⁇ 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 CaC ⁇ 3 hardness/gram, calculated on an anhydrous basis, and which is preferably in a range from about 300 to 352 mg equivalent of CaC03 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 ++ /gallon/minute/ -gram/gallon. Finely Atomized Liquid
- the amount of the finely atomized liquid of the present process can be from about 1% to 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 finely atomized liquid of the present process can be selected from the group consisting of liquid silicate, anionic or cationic surfactants which are in liquid form, aqueous or non-aqueous polymer solutions, water and mixtures thereof.
- Other optional examples for the finely atomized liquid 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 finely atomized liquid 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.
- Cationic surfactants can also be used as finely atomized liquid 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 finely atomized liquid in the present inventions are modified polyamines which comprise a polyamine backbone corresponding to the formula: H I
- polyamine backbone prior to modification having a modified polyamine formula ( n _k+-
- V units are terminal units having the formula:
- W units are backbone units having the formula:
- Y units are branching units having the formula:
- Z units are terminal units having the formula: X "
- backbone linking R units are selected from the group consisting of C2- C12 alkylene, C4-C12 alkenylene, C3-C12 hydroxyalkylene, C4-C12 dihydroxy- alkylene, C8-C12 dialkylarylene, -(R 1 0) X R1-, -(Rl ⁇ ) x R5(ORl) ⁇ -, -(CH 2 CH(OR2)CH 2 0) Z (R10) y Rl (OCH 2 CH(OR 2 )CH2)w-,
- R 1 is C2- CQ alkylene and mixtures thereof
- R 2 is hydrogen, -(R 1 0) x B, and mixtures thereof
- R 3 is C ⁇
- R 4 is C1-C12 alkylene, C4-C12 alkenylene, Cs- C ⁇
- R5 is C- ⁇ -C-12 alkylene, C3-C-12 hydroxyalkylene, C4-C12 dihydroxy-alkylene, C8-C12 dialkylarylene, -C(O)-, -C(0)NHR 6 NHC(0)-, -R 1 (OR 1
- B is hydrogen, C-i-C ⁇ alkyl, -(CH2) q S ⁇ 3M, -(CH2) p C ⁇ 2M, -(CH2) q (CHS03M)CH2S03M, -(CH2) q -(CHS02M)CH2S03M, -(CH2) p P03M, -PO3M, and mixtures thereof;
- M is hydrogen or a water soluble cation in sufficient amount to satisfy charge balance;
- X is a water soluble anion;
- m has the value from 4 to about 400;
- n has the value from 0 to about 200;
- p has the value from 1 to 6,
- q has the value from 0 to 6;
- r has the value of 0 or 1 ;
- w has the value 0 or 1 ;
- x has the value from 1 to 100;
- y has the value from 0 to 100;
- z has the value 0 or 1.
- 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.
- anionic surfactant such as NaLAS.
- polymeric polycarboxylate dispersants which can be prepared by poiymerizing 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 of the polymer.
- Homo-polymeric polycarboxylates which have molecular weights above
- 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 .
- Adiunct Detergent Ingredients can include, for example, the alkali metal, ammonium and substituted ammonium salts
- 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.
- the alkali metal especially sodium, salts of the above.
- Preferred for use herein are the phosphates, carbonates, C-
- 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. Such crystalline layered sodium silicates are discussed in Corkill et al, U.S. Patent No. 4,605,509, previously incorporated herein by reference.
- 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 Si0 2 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 polycarboxyiic 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.
- polyacetal carboxylates for use herein are the polyacetal carboxylates described in U.S. Patent 4,144,226, issued March 13, 1979 to Crutchfield et al, and U.S. Patent 4,246,495, issued March 27, 1979 to Crutchfield et al, both of which are incorporated herein by reference.
- 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 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.
- the process can comprise the step of spraying an additional binder in the mixer for the present invention.
- 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.
- surfactant 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.
- surfactant 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 surfactant paste structuring process are disclosed co-application No. PCT/US96/15960 (filed October 4, 1996) .
- Step 1 250 - 270 kg/hr of aqueous coconut fatty alcohol sulfate surfactant paste (C12-C18. 71.5% active) is dispersed by the pin tools of a CB- 30 mixer along with 220 kg/hr of powdered STPP (mean particle size of 40 - 75 microns), 160 - 200 kg/hr of ground soda ash (mean particle size of 15 microns), 80- 120 kg/hr of ground sodium sulfate (mean particle size of 15 microns), and the 200 kg/hr of internal recycle stream of powder.
- the surfactant paste is fed at about 40 to 52°C, and the powders are fed at room temperature.
- the condition of the CB-30 mixer is as follows:
- Step 2 The agglomerates from the CB mixer are fed to a fluid bed drying apparatus for drying, rounding and growth of agglomerates. 20 - 120 kg/hr of liquid silicate (43% solids, 2. OR) can be also added in the fluid bed drying apparatus at 35°C.
- the condition of the fluid bed drying apparatus is as follows:
- Spray height 175 - 250 mm (above distributor plate)
- the resulting granules from the step 2 have a density of about 600 g/l, and can be optionally subjected to the optional process of cooling, sizing and/or grinding.
- Step 1 15 kg/hr - 30kg/hr of HLAS (an acid precursor of C11-C18 alkyl benzene sulfonate; 95% active) at about 50 °C, and 20 kg/hr of AE3S liquid (C-10-C18 a "*y' alkoxy sulfates, EO-3; 28% active) is dispersed by the pin tools of a CB-30 mixer along with 220 kg/hr of powdered STPP (mean particle size of 40 - 75 microns), 160 - 200 kg/hr of ground soda ash (mean particle size of 15 microns), 80- 120 kg/hr of ground sodium sulfate (mean particle size of 15 microns), and the 200 kg/hr of internal recycle stream of powder.
- the surfactant paste is
- Step 2 The agglomerates from the CB-30 mixer are fed to a fluid bed drying apparatus for drying, rounding and growth of agglomerates. 20 - 80 kg/hr of liquid silicate (43% solids, 2.0 R) can be also added in the fluid bed drying apparatus at 35°C.
- the condition of the fluid bed drying apparatus is as follows:
- Step 1 15 kg/hr - 30kg/hr of HLAS (an acid precursor of C ⁇
- the surfactant paste is fed at about 40 to 52°C, and the powders are fed at room temperature.
- the condition of the CB-30 mixer is as follows: Mean residence time : 10
- Step 2 The agglomerates from the CB-30 mixer are fed to a fluid bed drying apparatus for drying, rounding and growth of agglomerates. 20 - 80 kg/hr of liquid silicate (43% solids, 2.0 R) can be also added in the fluid bed drying apparatus at 35°C.
- the condition of the fluid bed drying apparatus is as follows:
- Spray height 175 - 250 mm (above distributor plate)
- Bed temperature 40 - 70 °C
- the condition of the fluid bed cooling apparatus is as follows:
- the resulting granules from the step 2 has a density of about 600 g/l, and can be optionally subjected to the optional process of sizing an/or grinding.
Abstract
Description
Claims
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/269,850 US6211137B1 (en) | 1996-10-04 | 1997-06-05 | Process for making a detergent composition by non-tower process |
BR9713246-2A BR9713246A (en) | 1996-10-04 | 1997-06-05 | Process for obtaining a detergent composition because it can be a tower |
DE69721287T DE69721287T2 (en) | 1996-10-04 | 1997-06-05 | METHOD FOR PRODUCING A DETERGENT COMPOSITION BY A NO-TOWER PROCESS |
AT97931058T ATE238409T1 (en) | 1996-10-04 | 1997-06-05 | METHOD FOR PRODUCING A DETERGENT COMPOSITION BY A TOWER-FREE METHOD |
AU34784/97A AU3478497A (en) | 1996-10-04 | 1997-06-05 | Process for making a detergent composition by non-tower process |
EP97931058A EP0929653B1 (en) | 1996-10-04 | 1997-06-05 | Process for making a detergent composition by non-tower process |
JP51649498A JP3299985B2 (en) | 1996-10-04 | 1997-06-05 | Method for producing detergent composition by non-tower process |
CA002268067A CA2268067C (en) | 1996-10-04 | 1997-06-05 | Process for making a detergent composition by non-tower process |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
USPCT/US96/15881 | 1996-10-04 | ||
PCT/US1996/015881 WO1998014549A1 (en) | 1996-10-04 | 1996-10-04 | Process for making a low density detergent composition by non-tower process |
Publications (1)
Publication Number | Publication Date |
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WO1998014556A1 true WO1998014556A1 (en) | 1998-04-09 |
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Family Applications (9)
Application Number | Title | Priority Date | Filing Date |
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PCT/US1996/015881 WO1998014549A1 (en) | 1996-10-04 | 1996-10-04 | Process for making a low density detergent composition by non-tower process |
PCT/US1997/009795 WO1998014557A1 (en) | 1996-01-05 | 1997-06-05 | Process for making a detergent composition by non-tower process |
PCT/US1997/009792 WO1998014554A1 (en) | 1996-10-04 | 1997-06-05 | Process for making a detergent composition by non-tower process |
PCT/US1997/009791 WO1998014553A1 (en) | 1996-10-04 | 1997-06-05 | Process for making a detergent composition by non-tower process |
PCT/US1997/009790 WO1998014552A1 (en) | 1996-10-04 | 1997-06-05 | Process for making a detergent composition by non-tower process |
PCT/US1997/009793 WO1998014555A1 (en) | 1996-01-05 | 1997-06-05 | Process for making a detergent composition by non-tower process |
PCT/US1997/009794 WO1998014556A1 (en) | 1996-10-04 | 1997-06-05 | Process for making a detergent composition by non-tower process |
PCT/US1997/009796 WO1998014558A1 (en) | 1996-10-04 | 1997-06-05 | Process for making a detergent composition by non-tower process |
PCT/US1997/009789 WO1998014551A1 (en) | 1996-10-04 | 1997-06-05 | Process for making a detergent composition by non-tower process |
Family Applications Before (6)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1996/015881 WO1998014549A1 (en) | 1996-10-04 | 1996-10-04 | Process for making a low density detergent composition by non-tower process |
PCT/US1997/009795 WO1998014557A1 (en) | 1996-01-05 | 1997-06-05 | Process for making a detergent composition by non-tower process |
PCT/US1997/009792 WO1998014554A1 (en) | 1996-10-04 | 1997-06-05 | Process for making a detergent composition by non-tower process |
PCT/US1997/009791 WO1998014553A1 (en) | 1996-10-04 | 1997-06-05 | Process for making a detergent composition by non-tower process |
PCT/US1997/009790 WO1998014552A1 (en) | 1996-10-04 | 1997-06-05 | Process for making a detergent composition by non-tower process |
PCT/US1997/009793 WO1998014555A1 (en) | 1996-01-05 | 1997-06-05 | Process for making a detergent composition by non-tower process |
Family Applications After (2)
Application Number | Title | Priority Date | Filing Date |
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PCT/US1997/009796 WO1998014558A1 (en) | 1996-10-04 | 1997-06-05 | Process for making a detergent composition by non-tower process |
PCT/US1997/009789 WO1998014551A1 (en) | 1996-10-04 | 1997-06-05 | Process for making a detergent composition by non-tower process |
Country Status (12)
Country | Link |
---|---|
EP (9) | EP0929645A1 (en) |
JP (9) | JP3305327B2 (en) |
CN (8) | CN1239995A (en) |
AR (6) | AR010729A1 (en) |
AT (5) | ATE238409T1 (en) |
AU (9) | AU7388196A (en) |
BR (7) | BR9612732A (en) |
CA (9) | CA2267291C (en) |
DE (5) | DE69721287T2 (en) |
ES (5) | ES2212109T3 (en) |
MX (2) | MX219076B (en) |
WO (9) | WO1998014549A1 (en) |
Cited By (11)
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US6056905A (en) * | 1997-06-16 | 2000-05-02 | Lever Brothers Company Division Of Conopco, Inc. | Production of detergent granulates |
US6077820A (en) * | 1995-12-20 | 2000-06-20 | Lever Brothers Company Division Of Conopco, Inc. | Process for preparing a granular detergent |
US6133223A (en) * | 1997-06-27 | 2000-10-17 | Lever Brothers Company, Division Of Conopco, Inc. | Production of detergent granulates |
US6258773B1 (en) | 1997-07-14 | 2001-07-10 | The Procter & Gamble Company | Process for making a low density detergent composition by controlling agglomeration via particle size |
US6274544B1 (en) | 1997-06-16 | 2001-08-14 | Lever Brothers Company, Division Of Conopco, Inc. | Production of detergent granulates |
US6440342B1 (en) | 1998-07-08 | 2002-08-27 | The Procter & Gamble Company | Process for making a low density detergent composition by controlling nozzle height in a fluid bed dryer |
US6455490B1 (en) | 1999-06-10 | 2002-09-24 | Unilever Home & Personal Care Usa Division Of Conopco, In.C | Granular detergent component containing zeolite map and laundry detergent compositions |
US6492319B1 (en) | 1998-08-20 | 2002-12-10 | The Procter & Gamble Company | High density detergent-making process involving a moderate speed mixer/densifier |
US6555514B1 (en) | 1998-10-26 | 2003-04-29 | The Procter & Gamble Company | Processes for making granular detergent composition having improved appearance and solubility |
EP1274827B2 (en) † | 2000-04-20 | 2016-11-02 | Unilever PLC | Granular detergent component and process for its preparation |
US11655436B2 (en) | 2018-01-26 | 2023-05-23 | Ecolab Usa Inc. | Solidifying liquid amine oxide, betaine, and/or sultaine surfactants with a binder and optional carrier |
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WO1996031510A1 (en) * | 1995-04-03 | 1996-10-10 | Novartis Ag | Pyrazole derivatives and processes for the preparation thereof |
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EP1002044B1 (en) | 1997-07-15 | 2004-05-06 | The Procter & Gamble Company | Process for making high-active detergent agglomerates by multi-stage surfactant paste injection |
US6794354B1 (en) * | 1998-09-18 | 2004-09-21 | The Procter & Gamble Company | Continuous process for making detergent composition |
GB9825558D0 (en) * | 1998-11-20 | 1999-01-13 | Unilever Plc | Granular detergent components and particulate detergent compositions containing them |
US6894018B1 (en) | 1999-06-21 | 2005-05-17 | The Procter & Gamble Company | Process for making granular detergent in a fluidized bed granulator having recycling of improperly sized particles |
CN1200999C (en) * | 1999-06-21 | 2005-05-11 | 宝洁公司 | Process for making granular detergent compsn. |
EP2123742A1 (en) | 2008-05-14 | 2009-11-25 | The Procter and Gamble Company | A solid laundry detergent composition comprising light density silicate salt |
WO2011061045A1 (en) | 2009-11-20 | 2011-05-26 | Unilever Nv | Detergent granule and its manufacture |
CN114774206A (en) | 2014-04-10 | 2022-07-22 | 宝洁公司 | Composite detergent particles and laundry detergent composition comprising the same |
KR20200110683A (en) | 2018-01-26 | 2020-09-24 | 에코랍 유에스에이 인코퍼레이티드 | Solidification of liquid amine oxides, betaines, and/or sultaines surfactants using carriers |
CA3089557A1 (en) * | 2018-01-26 | 2019-08-01 | Ecolab Usa Inc. | Solidifying liquid anionic surfactants |
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US4992079A (en) * | 1986-11-07 | 1991-02-12 | Fmc Corporation | Process for preparing a nonphosphate laundry detergent |
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US5489392A (en) * | 1994-09-20 | 1996-02-06 | The Procter & Gamble Company | Process for making a high density detergent composition in a single mixer/densifier with selected recycle streams for improved agglomerate properties |
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-
1996
- 1996-10-04 MX MX9903193A patent/MX219076B/en not_active IP Right Cessation
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- 1997-06-05 ES ES97929815T patent/ES2201305T3/en not_active Expired - Lifetime
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- 1997-06-05 CA CA002267424A patent/CA2267424C/en not_active Expired - Fee Related
- 1997-06-05 JP JP51649698A patent/JP3299987B2/en not_active Expired - Fee Related
- 1997-06-05 CN CNB971802785A patent/CN1133738C/en not_active Expired - Fee Related
- 1997-06-05 DE DE69715224T patent/DE69715224T2/en not_active Expired - Fee Related
- 1997-06-05 EP EP97929815A patent/EP0929650B1/en not_active Expired - Lifetime
- 1997-06-05 ES ES97928871T patent/ES2178778T3/en not_active Expired - Lifetime
- 1997-06-05 AU AU33785/97A patent/AU3378597A/en not_active Abandoned
- 1997-06-05 AU AU35683/97A patent/AU3568397A/en not_active Abandoned
- 1997-06-05 BR BR9711865A patent/BR9711865A/en not_active IP Right Cessation
- 1997-06-05 EP EP97931058A patent/EP0929653B1/en not_active Expired - Lifetime
- 1997-06-05 BR BR9713249-7A patent/BR9713249A/en not_active Application Discontinuation
- 1997-06-05 CN CNB971802963A patent/CN1156562C/en not_active Expired - Fee Related
- 1997-06-05 AU AU33031/97A patent/AU3303197A/en not_active Abandoned
- 1997-10-03 AR ARP970104577A patent/AR010729A1/en unknown
- 1997-10-03 AR ARP970104576A patent/AR010509A1/en unknown
- 1997-10-03 AR ARP970104579A patent/AR010511A1/en unknown
- 1997-10-03 AR ARP970104575A patent/AR010508A1/en unknown
- 1997-10-03 AR ARP970104578A patent/AR010510A1/en unknown
- 1997-10-03 AR ARP970104574A patent/AR010507A1/en unknown
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WO1993025378A1 (en) * | 1992-06-15 | 1993-12-23 | The Procter & Gamble Company | Process for making compact detergent compositions |
WO1995012659A1 (en) * | 1993-11-02 | 1995-05-11 | Unilever Plc | Process for the production of a detergent composition |
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Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6077820A (en) * | 1995-12-20 | 2000-06-20 | Lever Brothers Company Division Of Conopco, Inc. | Process for preparing a granular detergent |
US6056905A (en) * | 1997-06-16 | 2000-05-02 | Lever Brothers Company Division Of Conopco, Inc. | Production of detergent granulates |
US6274544B1 (en) | 1997-06-16 | 2001-08-14 | Lever Brothers Company, Division Of Conopco, Inc. | Production of detergent granulates |
US6429184B1 (en) | 1997-06-16 | 2002-08-06 | Lever & Brothers Company, Division Of Conopco, Inc. | Production of detergent granulates |
US6133223A (en) * | 1997-06-27 | 2000-10-17 | Lever Brothers Company, Division Of Conopco, Inc. | Production of detergent granulates |
US6258773B1 (en) | 1997-07-14 | 2001-07-10 | The Procter & Gamble Company | Process for making a low density detergent composition by controlling agglomeration via particle size |
US6440342B1 (en) | 1998-07-08 | 2002-08-27 | The Procter & Gamble Company | Process for making a low density detergent composition by controlling nozzle height in a fluid bed dryer |
US6492319B1 (en) | 1998-08-20 | 2002-12-10 | The Procter & Gamble Company | High density detergent-making process involving a moderate speed mixer/densifier |
US6555514B1 (en) | 1998-10-26 | 2003-04-29 | The Procter & Gamble Company | Processes for making granular detergent composition having improved appearance and solubility |
US6784151B2 (en) * | 1998-10-26 | 2004-08-31 | The Procter & Gamble Company | Processes for making granular detergent composition having improved appearance and solubility |
US6455490B1 (en) | 1999-06-10 | 2002-09-24 | Unilever Home & Personal Care Usa Division Of Conopco, In.C | Granular detergent component containing zeolite map and laundry detergent compositions |
EP1274827B2 (en) † | 2000-04-20 | 2016-11-02 | Unilever PLC | Granular detergent component and process for its preparation |
US11655436B2 (en) | 2018-01-26 | 2023-05-23 | Ecolab Usa Inc. | Solidifying liquid amine oxide, betaine, and/or sultaine surfactants with a binder and optional carrier |
US11976255B2 (en) | 2018-01-26 | 2024-05-07 | Ecolab Usa Inc. | Solidifying liquid amine oxide, betaine, and/or sultaine surfactants with a binder and optional carrier |
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