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
  • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
  • C11D11/0088—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads 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
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
  • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
  • 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 low density 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.
• non-tower process One characteristic common to the existing process for producing modem 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 modem detergent compositions for flexibility in the ultimate density of the final composition, especially for the 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 agglomerated with a binder such as a nonionic or anionic surfactant, finally, various detergent components are dry mixed to produce detergent granules (e.g., tower process plus 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 Laid-open No.W093/23,523 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.
• This disclosure also describes a process by which the density of the final agglomerate can be adjusted by adjusting the amount of liquid binder added in the second mixer. It is not clear from the disclosure on what contributes to the density reduction.
• the process in Laid-open No. WO93/23,523 differs from the invention disclosed herein which will be apparent to those skilled in the art.
• the U. S. Patent No. 4,992,079 describes agglomeration process for low density non- phosphate detergents having increased resistance to non ionic bleeding.
• the first process step agglomerates detergent ingredients with non aqueous liquid surfactant.
• 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. It is not clear from the disclosure on what contributes to the low density. In addition, the disclosure does not include aqueous surfactants and phosphate containing detergents.
• the process in the U.S. patent No. 4,992,079 differs from the invention disclosed herein which will be apparent to those skilled in the art.
• the present invention meets the aforementioned needs in the art by providing a process which produces a low 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 of the proposed invention has capability of adjusting the density of the granules of the composition by controlling shape of the granules. Namely, the process of the present invention can be applied to obtain a granular detergent composition which has low density (e.g., irregular-shaped granules having a density from about 300 to about 600 g/1 ).
• agglomerates refers to particles formed by agglomerating raw materials with binder such as surfactants and or inorganic solutions / organic solvents and polymer solutions.
• the term "irregular-shaped granules" refers to particles wherein the shape of the granules having irregular shape in the case of low density formed by agglomerating starting detergent materials, fine powders and finely atomized liquid. 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 preferably from about 300 g/1 to 600 g/1.
• the process comprises the steps of: (a) (i) dispersing an aqueous or non-aqueous surfactant, and (ii) coating the surfactant with fine powders having a diameter from 0.1 to 500 microns, in a mixer which is operated under the following conditions to obtain granules:
• granular detergent compositions having a low density preferably from about 300 g/1 to about 600g/l, produced by any one of the process embodiments described herein.
• FIG.l is a photograph showing irregular-shaped agglomerates after the first step of the process of the present invention, having low density (about 475 - 530 g/1 ).
• FIG.2 is a photograph showing irregular-shaped agglomerates after the first and the second steps of the present invention, having low density (about 475 - 500 g/1).
• FIG.3 is a photograph showing irregular-shaped agglomerates after the first and the second steps of the present invention and drying and cooling process, having low density (about 475 - 500 g/1).
• FIG.4 is a photograph showing round-shaped agglomerates after agglomeration process for obtaining high density (about 700-800 g/1).
• the present invention is directed to a process which produces free flowing, granular detergent agglomerates having a low density of not less than about 300 g/1, preferably from about
• the process produces granular detergent agglomerates from an aqueous or non-aqueous surfactant which is then coated with fine powders having a diameter from 0.1 to
• aqueous or non-aqueous surfactant(s) which is/are in the form of powder, paste or liquid, and fine powders having a diameter from 0.1 to 500 microns, preferably from about 1 to about 100 microns are fed into the mixer.
• 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 agglomeration, after which the mixed detergent materials are fed into the first step mixer as described herein for agglomeration.
• 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 10 m/s
• the energy per unit mass in the mixer is from about 0.15 kj/kg to about 4.20 kj/kg
• the mean residence time in the mixer is from about 10 to about 15 seconds and tip speed for the mixer is in range from about 6 m/s to about 8 m/s
• the energy per unit mass for the mixer is from about 0.15 kj/kg to about 2.5 kj/kg
• the mean residence time in the mixer is from about 10 to about 15 seconds and tip speed for the mixer is in range from about 6.5 m/s to about 7.5 m/s
• the energy per unit mass for the mixer is from about 0.15 kj/kg to about 1.30 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).
• L ⁇ dige CB Mixer manufactured by the L ⁇ dige company (Germany).
• Second Step the resultant product of the first step (granules and excess fine powders) is fed into a second mixer, and then finely atomized liquid is sprayed on the granules in the mixer.
• about 0-10% more preferably about 2-5% of powder detergent ingredients of the kind used in the first step and/or other detergent ingredients can be added to the second step.
• the mean residence time of the mixer for the second step is from about 0.2 to about 5 seconds and tip speed of the mixer for the second step is in range from about 10 m/s to about 23 m/s
• the energy per unit mass for the mixer (energy condition) for the second step is from about 0.15 kj/kg to about 2.9 kj/kg
• the mean residence time of the mixer is from about 0.5 to about 2 seconds and tip speed for the mixer is in range from about 13 m/s to about 20 m/s
• the energy per unit mass for the mixer from about 0.15 kj/kg to about 1.9 kj/kg
• the mean residence time in the mixer is from about 0.5 to about 2 seconds
• tip speed for the mixer is in range from about 15 m/s to about 17.5 m/s
• the energy per unit mass for the mixer is from about 0.15 kj/kg to about 1.0 kj/kg.
• 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 first step.
• An Example can be Flexomic Model manufactured by the Schugi company (Netherlands).
• granular detergent composition can be obtained (FIG. 2).
• the process in the present invention surprisingly reduce the amount of excess recycle fines from the second step, comparing 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.
• recycle fines from the second step will typically comprise from about 10 % to 40 % of the total amount of fine powders used in the first step.
• the total amount of the surfactants for 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 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.
• Detergent Surfactant (Aqueous /Non-aqueous.
• the amount of the aqueous or non-aqueous surfactant of the present process can be from about 5 % to about 60 %, more preferably from about 12% to about 40 %, more preferably, from about 15 to about 35%, in total amount of the final product obtained by the process of the present invention.
• the aqueous or non-aqueous 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 or pasted 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 J J -C J 8 alkyl benzene sulfonates ("LAS"), primary, branched-chain and random C ] Q-C20 alkyl sulfates (“AS”), the C J Q-C I S secondary (2,3) alkyl sulfates of the formula CH (CH 2 ) x (CHOS ⁇ 3 " M + ) CH 3 and CH 3 (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 Cjo-Cj g alkyl alkoxy sulfates ("AE X S”; especially EO 1-7 ethoxy sulfates).
• LAS C J J J -C J 8
• 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 .
• exemplary surfactants useful in the paste of the invention include CiQ-Cjs alkyl alkoxy carboxylates (especially the EO 1-5 ethoxycarboxylates), the C J Q. I S glycerol ethers, the Cjo-Cjg alkyl polyglycosides and the corresponding sulfated polyglycosides, and alpha-sulfonated fatty acid esters.
• the conventional nonionic and amphoteric surfactants such as the C ⁇ -C jg alkyl ethoxylates ("AE") including the so-called narrow peaked alkyl ethoxylates and Cg-C ⁇ alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), Cj Q -Ci g amine oxides, and the like, can also be included in the overall compositions.
• the Cj ⁇ -C j g N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include the C ⁇ -Cjg N-methylglucamides. See WO 9,206,154.
• sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as Ci ⁇ -C j g N-(3-methoxypropyl) glucamide.
• the N-propyl through N-hexyl Ci ⁇ -Cjg glucamides can be used for low sudsing.
• C10-C20 conventional soaps may also be used. If high sudsing is desired, the branched-chain Cjo-Cjg 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 C ⁇ -C ⁇ Q N-alkyl or alkenyl ammonium surfactants wherein remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.
• Ampholytic surfactants can also be used as a detergent surfactant herein, which include aliphatic derivatives of heterocyclic secondary and tertiary amines; zwitterionic surfactants which include derivatives of aliphatic quaternary ammonium, phosphonium and sulfonium compounds; water-soluble salts of esters of alpha-sulfonated fatty acids; alkyl ether sulfates; water-soluble salts of olefin sulfonates; beta-alkyloxy alkane sulfonates; betaines having the formula R(R1 )2N + R2COO " , wherein R is a C6-C18 hydrocarbyl group, preferably a C 10-C 16 alkyl group or C 10-C 16 acylamido alkyl group, each R 1 is typically C ⁇ -C 3 alkyl, preferably methyl and R2 is a C 1-C5 hydrocarbyl group, preferably a C _
• betaines examples include coconut acylamidopropyldimethyl betaine; hexadecyl dimethyl betaine; CJ2-14 acylamidopropylbetaine; C8-14 acylamidohexyldiethyl betaine; 4[Ci4_ _ 6 acylmethylamidodiethylammonio]- 1 -carboxybutane; C16-I8 acylamidodimethylbetaine; C12-I6 acylamidopentanediethylbetaine; and
• Preferred betaines are C 12-18 dimethyl-ammonio hexanoate and the C 10- 18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines; and the sultaines having the formula (R(R1 )2N + R2S0 3 " wherein R is a C6-C18 hydrocarbyl group, preferably a Cj o-Ci ⁇ alkyl group, more preferably a C _2-C _ 3 alkyl group, each R is typically C _-C 3 alkyl, preferably methyl, and R ⁇ is a Cj-C ⁇ hydrocarbyl group, preferably a C ⁇ -C 3 alkylene or, preferably, hydroxyalkylene group.
• Suitable sultaines include C12- 14 dimethylammonio-2-hydroxypropyl sulfonate, C12-C14 amido propyl ammonio-2- hydroxypropyl sultaine, C12-C14 dihydroxyethylammonio propane sulfonate, and C16-I 8 dimethylammonio hexane sulfonate, with CJ2-14 amido propyl ammonio-2-hydroxypropyl sultaine being preferred.
• the amount of the fine powders 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 powders of the present process preferably selected from the group consisting of ground soda ash, powdered sodium tripolyphosphate (STPP), hydrated tripolyphosphate, ground sodium sulphates, aluminosilicates, crystalline layered silicates, nitrilotriacetates (NTA), phosphates, precipitated silicates, polymers, carbonates, citrates, powdered surfactants (such as powdered alkane sulfonic acids) and recycle fines occurring from the process of the present invention, wherein the average diameter of the powder is from 0.1 to 500 microns, preferably from 1 to 300 microns, more preferably from 5 to 100 microns.
• the aluminosilicate ion exchange materials used herein as a detergent builder preferably have both a high calcium ion exchange capacity and a high exchange rate. Without intending to be limited by theory, it is believed that such high calcium ion exchange rate and capacity are a function of several interrelated factors which derive from the method by which the aluminosilicate ion exchange material is produced. In that regard, the aluminosilicate ion exchange materials used herein are preferably produced in accordance with Corkill et al, U.S. Patent No. 4,605,509 (Procter & Gamble), the disclosure of which is incorporated herein by reference.
• the aluminosilicate ion exchange material is in "sodium" form since the potassium and hydrogen forms of the instant aluminosilicate do not exhibit as high of an exchange rate and capacity as provided by the sodium form.
• the aluminosilicate ion exchange material preferably is in over dried form so as to facilitate production of crisp detergent agglomerates as described herein.
• the aluminosilicate ion exchange materials used herein preferably have particle size diameters which optimize their effectiveness as detergent builders.
• particle size diameter represents the average particle size diameter of a given aluminosilicate ion exchange material as determined by conventional analytical techniques, such as microscopic determination and scanning electron microscope (SEM).
• the preferred particle size diameter of the aluminosilicate is from about 0.1 micron to about 10 microns, more preferably from about 0.5 microns to about 9 microns. Most preferably, the particle size diameter is from about 1 microns to about 8 microns.
• the aluminosilicate ion exchange material has the formula Na z [(A10 2 ) z .(Si0 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 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 finely atomized liquid of the present process, which is used in the second step, 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-C]6, 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:
• 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-C 12 alkylene, C4-C12 alkenylene, C 3 -Cj2 hydroxyalkylene, C4-C12 dihydroxy-alkylene, Cg-C ⁇ dialkylarylene, -(R ⁇ R 1 -, -(R ⁇ R ⁇ OR 1 )*-'
• R 1 is C -C 6 alkylene and mixtures thereof
• R 2 is hydrogen, -(Rl ⁇ ) x B, and mixtures thereof
• R.3 is C I -C J S alkyl, C7-C12 arylalkyl, C7-C12 a l substituted aryl, Cg-C ⁇ aryl, and mixtures thereof
• R 4 is C1 -C12 alkylene, C4-C 12 alkenylene, Cg-C ⁇ .2 arylalkylene, Cg-C jo arylene, and mixtures thereof
• R ⁇ is C]-C i2 alkylene, C 3 -Ci2 hydroxyalkylene, C4-C12 dihydroxy-alkylene, Cg-Ci2 dialkylarylene, -C(O)-, -C(0)NHR 6 NHC(0)-,
• B is hydrogen, C j-C 6 alkyl, -(CH 2 ) q S0 3 M, -(CH 2 ) p C0 2 M, -(CH 2 ) q (CHS0 3 M)CH 2 S0 3 M, - (CH2) q -(CHS0 2 M)CH 2 S0 3 M, -(CH 2 ) p P0 M, -P0 3 M, 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
• 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.
• aqueous or non-aqueous polymer solutions which can be used as the finely atomized liquid in the present inventions are polymeric polycarboxylate dispersants which can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid form.
• Unsaturated monomeric acids that can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid.
• the presence in the polymeric polycarboxylates herein of monomeric segments, containing no carboxylate radicals such as vinylmethyl ether, styrene, ethylene, etc. is suitable provided that such segments do not constitute more than about 40% by weight.
• homo-polymeric polycarboxylates which have molecular weights above 4000, such as described next are preferred.
• Particularly suitable homo-polymeric polycarboxylates can be derived from acrylic acid.
• acrylic acid-based polymers which are useful herein are the water-soluble salts of polymerized acrylic acid.
• the average molecular weight of such polymers in the acid form preferably ranges from above 4,000 to 10,000, preferably from above 4,000 to
• 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/maieic 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 ammoni
• 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-tamish 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 O- 18 f attv ac '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
• the crystalline layered sodium silicate has the formula
• NaMS.2O5.yH2O wherein M is sodium or hydrogen, and y is from about 0 to about 20.
• 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-l, 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 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.
• FIG. 4 a photograph of high density agglomerates (an average density is about 700 - 800g/l) obtained by a series of the mixers operated under different conditions from the present invention is shown as FIG. 4.
• L ⁇ dige CB mixer CB-30, operated at 550 RPM
• Schugi Flexomic mixer operated at 2800RPM
• L ⁇ dige KM mixer KM-600, operated at 100 RPM with normal plows
• the material used for obtaining agglomerates of FIG.4 is the same as Example 2, filly described in the "EXAMPLES”.
• 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 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 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 moderate speed mixer for agglomeration which is commonly known to the skilled in the art ; and/or (4) the coating agent may be added directly to a moderate speed mixer for agglomeration which is commonly known to the skilled in the art and the fluid bed dryer.
• the coating agent is preferably selected from the group consisting of aluminosilicates, silicates, carbonates and mixtures thereof.
• the coating agent not only enhances the free flowability of the resulting detergent composition which is desirable by consumers in that it permits easy scooping for detergent during use, but also serves to control agglomeration by preventing or minimizing over agglomeration, especially when added directly to the moderate speed mixer. As those skilled in the art are well aware, over agglomeration can lead to very undesirable flow properties and aesthetics of the final detergent product.
• the process can comprise the step of spraying an additional binder in one or both of the first and second mixers for the present invention or fluid bed dryers and/or fluid bed coolers.
• a binder is added for purposes of enhancing agglomeration by providing a "binding" or "sticking" age t 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.
• Other 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 other essential step in the process involves high active paste structuring process, e.g., hardening an aqueous anionic surfactant paste by incorporating a paste-hardening material by using an extruder, prior to the process of the present invention.
• high active paste structuring process e.g., hardening an aqueous anionic surfactant paste by incorporating a paste-hardening material by using an extruder.
• the details of the high active paste structuring process is disclosed co-application No. JA162F (filed 04 October, 1996) which was filed on the same day as the present invention.
• Example 1 (Irregular-shaped agglomerates after the first step of the present invention)
• the 259 kg/hr of aqueous coconut fatty alcohol sulfate surfactant paste (71.5% active) is dispersed by the pin tools of a CB-30 mixer along with the 217 kg/hr of powder STPP (mean particle size of 40 - 75 microns), the 169 kg/hr of micronized soda ash (mean particle size of
• the surfactant paste is fed at about 40 to 55°C, and the powders are fed at room temperature.
• the condition of the CB-30 mixer is as follows: Mean residence time : 14-20 seconds Tip speed : 6.5 to 7.0 m/s
• Example 2 (Irregular-shaped agglomerates obtained after the first and second steps of the present invention)
• the agglomerates from the CB-30 mixer are fed to the Schugi Flexomic mixer.
• the 30 kg/hr of HLAS is atomized and sprayed in the Schugi Flexomic mixer.
• the condition of the Schugi mixer is as follows:
• Mean residence time 0.5 to 2 seconds
• Example 3 (Irregular-shaped agglomerates obtained from the process of the present invention) The following is an example for obtaining agglomerates using L ⁇ dige CB mixer (CB-
• the surfactant is fed at about 40 to 55°C, and the powders are fed at room temperature.
• the condition of the CB-30 mixer is as follows: Mean residence time : 10 - 18 seconds Tip speed : 6 to 13 m/s Energy condition : 0.15 to 3.5 kj/kg
• the agglomerates from the CB-30 mixer are fed to the Schugi Flexomic mixer.
• the 30 kg/hr of HLAS is atomized and sprayed in the Schugi Flexomic mixer and 20 kg/hr of carbonate is added to the Schugi mixer.
• the condition of the Schugi mixer is as follows: Mean residence time : 0.5 to 2 seconds Tip speed : 15 to 18 m/s Energy condition : 0.15 to 1.0 kj/kg
• Resulting granules after Schugi mixer and after sizing and grinding have the density of 500 - 550 g/1.
• Example 4 (Irregular-shaped agglomerates obtained from the process of the present invention) The following is an example for obtaining agglomerates using L ⁇ dige CB mixer (CB- 30), then L ⁇ dige KM mixer (KM-600) and Schugi Flexomic mixer, followed by fluid bed cooler (FBC), then sizing and grinding
• the 220 kg/hr of non aqueous Linear alkyl Benzene Sulfonic acid (94 - 96% active) is dispersed by the pin tools of a CB-30 mixer along with 300 kg/hr of powder STPP (Mean particle size of 40 - 75 microns), 230 kg/hr of micronized soda ash (5 - 30 microns), 100 kg/hr of micronized sulfate (5 - 30 microns), 90 kg/hr of Zeolite and fines recycle of 100 kg/hr.
• the surfactant is fed at about 40 to 55C, and the powders are fed at room temperature.
• the condition of the CB-30 mixer is as follows: Mean residence time : 10 - 18 seconds
• the agglomerates from the CB mixer is charged to a KM-Mixer where a retention is about 40 - 60 kgs.
• the plow RPM is 100 and chopper RPM is 1300 (three choppers are on the mixer).
• the agglomerates from the KM-Mixer have the density of 750 - 800 g/1.
• the agglomerates from the KM-Mixer are fed to a Schugi Flexomix (FX-160) mixer.
• the 30 kg/hr of HLAS is atomized and sprayed in the Schugi Flexomic mixer and 20 kg/hr of carbonate is added to the Schugi mixer.
• the condition of the Schugi mixer is as follows: Mean residence time : 0.5 to 2 seconds Tip speed : 15 to 18 m/s
• Resulting granules after Schugi mixer and after sizing and grinding have the density of about 600 g/1.

Landscapes

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

Applications Claiming Priority (1)

Publications (1)

Family

ID=22255901

Family Applications (9)

Family Applications After (8)

Country Status (12)

Families Citing this family (23)

Family Cites Families (13)

• 1996
  • 1996-10-04 MX MX9903193A patent/MX219076B/es not_active IP Right Cessation
  • 1996-10-04 WO PCT/US1996/015881 patent/WO1998014549A1/en not_active Application Discontinuation
  • 1996-10-04 AU AU73881/96A patent/AU7388196A/en not_active Abandoned
  • 1996-10-04 BR BR9612732A patent/BR9612732A/pt not_active IP Right Cessation
  • 1996-10-04 EP EP96936168A patent/EP0929645A1/de not_active Withdrawn
  • 1996-10-04 MX MX9903195A patent/MX219077B/es not_active IP Right Cessation
  • 1996-10-04 JP JP53523397A patent/JP3305327B2/ja not_active Expired - Fee Related
  • 1996-10-04 CA CA002267291A patent/CA2267291C/en not_active Expired - Fee Related
• 1997
  • 1997-06-05 BR BR9711865A patent/BR9711865A/pt not_active IP Right Cessation
  • 1997-06-05 EP EP97929815A patent/EP0929650B1/de not_active Expired - Lifetime
  • 1997-06-05 EP EP97928871A patent/EP0929648B1/de not_active Expired - Lifetime
  • 1997-06-05 JP JP51649098A patent/JP3299982B2/ja not_active Expired - Fee Related
  • 1997-06-05 WO PCT/US1997/009794 patent/WO1998014556A1/en active IP Right Grant
  • 1997-06-05 EP EP97931058A patent/EP0929653B1/de not_active Expired - Lifetime
  • 1997-06-05 BR BR9713249-7A patent/BR9713249A/pt not_active Application Discontinuation
  • 1997-06-05 AU AU34785/97A patent/AU3478597A/en not_active Abandoned
  • 1997-06-05 BR BR9713246-2A patent/BR9713246A/pt not_active IP Right Cessation
  • 1997-06-05 AU AU33031/97A patent/AU3303197A/en not_active Abandoned
  • 1997-06-05 JP JP51649698A patent/JP3299987B2/ja not_active Expired - Fee Related
  • 1997-06-05 CA CA002268063A patent/CA2268063C/en not_active Expired - Fee Related
  • 1997-06-05 AT AT97931058T patent/ATE238409T1/de not_active IP Right Cessation
  • 1997-06-05 JP JP51649398A patent/JP3299984B2/ja not_active Expired - Fee Related
  • 1997-06-05 CN CNB971802971A patent/CN1156563C/zh not_active Expired - Fee Related
  • 1997-06-05 BR BR9712492-3A patent/BR9712492A/pt not_active IP Right Cessation
  • 1997-06-05 WO PCT/US1997/009795 patent/WO1998014557A1/en active IP Right Grant
  • 1997-06-05 AU AU34784/97A patent/AU3478497A/en not_active Abandoned
  • 1997-06-05 CN CNB971802785A patent/CN1133738C/zh not_active Expired - Fee Related
  • 1997-06-05 EP EP97931057A patent/EP0929652A1/de not_active Ceased
  • 1997-06-05 CN CNB971802807A patent/CN1156561C/zh not_active Expired - Fee Related
  • 1997-06-05 WO PCT/US1997/009790 patent/WO1998014552A1/en active IP Right Grant
  • 1997-06-05 CN CNB971802939A patent/CN1133739C/zh not_active Expired - Fee Related
  • 1997-06-05 EP EP97931056A patent/EP0929651B1/de not_active Expired - Lifetime
  • 1997-06-05 WO PCT/US1997/009796 patent/WO1998014558A1/en active Application Filing
  • 1997-06-05 WO PCT/US1997/009789 patent/WO1998014551A1/en active IP Right Grant
  • 1997-06-05 BR BR9712490-7A patent/BR9712490A/pt not_active IP Right Cessation
  • 1997-06-05 JP JP51649198A patent/JP3299983B2/ja not_active Expired - Fee Related
  • 1997-06-05 ES ES97928871T patent/ES2178778T3/es not_active Expired - Lifetime
  • 1997-06-05 AT AT97931056T patent/ATE255160T1/de not_active IP Right Cessation
  • 1997-06-05 JP JP51649598A patent/JP3299986B2/ja not_active Expired - Fee Related
  • 1997-06-05 AU AU34783/97A patent/AU3478397A/en not_active Abandoned
  • 1997-06-05 ES ES97928872T patent/ES2212109T3/es not_active Expired - Lifetime
  • 1997-06-05 AU AU35683/97A patent/AU3568397A/en not_active Abandoned
  • 1997-06-05 EP EP97928872A patent/EP0929649B1/de not_active Expired - Lifetime
  • 1997-06-05 CA CA002268060A patent/CA2268060C/en not_active Expired - Fee Related
  • 1997-06-05 WO PCT/US1997/009792 patent/WO1998014554A1/en not_active Application Discontinuation
  • 1997-06-05 WO PCT/US1997/009791 patent/WO1998014553A1/en active IP Right Grant
  • 1997-06-05 AT AT97929815T patent/ATE246726T1/de not_active IP Right Cessation
  • 1997-06-05 BR BR9711861A patent/BR9711861A/pt not_active Application Discontinuation
  • 1997-06-05 ES ES97931056T patent/ES2210544T3/es not_active Expired - Lifetime
  • 1997-06-05 JP JP51648998A patent/JP3299981B2/ja not_active Expired - Fee Related
  • 1997-06-05 DE DE69723986T patent/DE69723986T2/de not_active Expired - Fee Related
  • 1997-06-05 AU AU33030/97A patent/AU3303097A/en not_active Abandoned
  • 1997-06-05 AT AT97928872T patent/ATE255159T1/de not_active IP Right Cessation
  • 1997-06-05 WO PCT/US1997/009793 patent/WO1998014555A1/en not_active Application Discontinuation
  • 1997-06-05 DE DE69726440T patent/DE69726440T2/de not_active Expired - Fee Related
  • 1997-06-05 DE DE69726439T patent/DE69726439T2/de not_active Expired - Fee Related
  • 1997-06-05 CA CA002268055A patent/CA2268055C/en not_active Expired - Fee Related
  • 1997-06-05 CA CA002268067A patent/CA2268067C/en not_active Expired - Fee Related
  • 1997-06-05 AT AT97928871T patent/ATE223476T1/de not_active IP Right Cessation
  • 1997-06-05 CN CNB971802963A patent/CN1156562C/zh not_active Expired - Fee Related
  • 1997-06-05 EP EP97931059A patent/EP0929654A1/de not_active Withdrawn
  • 1997-06-05 ES ES97931058T patent/ES2193386T3/es not_active Expired - Lifetime
  • 1997-06-05 JP JP51649298A patent/JP3345022B2/ja not_active Expired - Fee Related
  • 1997-06-05 AU AU34782/97A patent/AU3478297A/en not_active Abandoned
  • 1997-06-05 JP JP51649498A patent/JP3299985B2/ja not_active Expired - Fee Related
  • 1997-06-05 CA CA002268062A patent/CA2268062C/en not_active Expired - Fee Related
  • 1997-06-05 EP EP97932153A patent/EP0929655A1/de not_active Ceased
  • 1997-06-05 CA CA002268068A patent/CA2268068C/en not_active Expired - Fee Related
  • 1997-06-05 DE DE69715224T patent/DE69715224T2/de not_active Expired - Fee Related
  • 1997-06-05 DE DE69721287T patent/DE69721287T2/de not_active Expired - Fee Related
  • 1997-06-05 CN CN97180294.7A patent/CN1239992A/zh active Pending
  • 1997-06-05 CA CA002268052A patent/CA2268052C/en not_active Expired - Fee Related
  • 1997-06-05 CN CN97180298.XA patent/CN1239995A/zh active Pending
  • 1997-06-05 AU AU33785/97A patent/AU3378597A/en not_active Abandoned
  • 1997-06-05 CA CA002267424A patent/CA2267424C/en not_active Expired - Fee Related
  • 1997-06-05 CN CNB971802793A patent/CN1156560C/zh not_active Expired - Fee Related
  • 1997-06-05 ES ES97929815T patent/ES2201305T3/es not_active Expired - Lifetime
  • 1997-10-03 AR ARP970104576A patent/AR010509A1/es unknown
  • 1997-10-03 AR ARP970104575A patent/AR010508A1/es unknown
  • 1997-10-03 AR ARP970104579A patent/AR010511A1/es unknown
  • 1997-10-03 AR ARP970104578A patent/AR010510A1/es unknown
  • 1997-10-03 AR ARP970104574A patent/AR010507A1/es unknown
  • 1997-10-03 AR ARP970104577A patent/AR010729A1/es unknown

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events