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 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).
• a binder such as a nonionic or anionic surfactant
• the Laid-open No.W093/23,523 (Henkel) describes the process comprising pre-aggiomeration 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.
• 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 solutions.
• binder such as surfactants and or inorganic solutions / organic solvents and polymer solutions.
• a process for preparing a granular detergent composition having a density at least about 600 g/l is provided.
• the process comprises the steps of: (a) dispersing a surfactant, and coating the surfactant with fine powder having a diameter from 0.1 to 500 microns, in a mixer wherein conditions of the mixer include (i) from about 2 to about 50 seconds of mean residence time, (ii) from about 4 to about 25 m/s of tip speed, and (iii) from about 0.15 to about 7 kj/kg of energy condition, wherein first agglomerates are formed; (b) spraying finely atomized liquid onto the first agglomerates in a mixer wherein conditions of the mixer include (i) from about 0.2 to about 5 seconds of mean residence time, (ii) from about 10 to about 30 m/s of tip speed, and (iii) from about 0.15 to about 5 kj/kg of energy condition, wherein second agglomerates are formed; and
• conditions of the mixer include (i) from about 0.2 to about 5 seconds of mean residence time, (ii) from about 10 to about 30 m/s of tip speed, and (iii) from about 0.15 to about 5 kj/kg of energy condition, wherein second agglomerates are formed;
• each of the fluidizing apparatus includes (i) from about 1 to about 10 minutes of mean residence time, (ii) from about 100 to about 300 mm of depth of unfluidized bed, (iii) not more than about 50 micron of droplet spray size, (iv) from about 175 to about 250 mm of spray height, (v) from about 0.2 to about 1.4 m/s of fluidizing velocity and (vi) from about 12 to about 100 °C of bed temperature.
• granular detergent compositions having a high density of at least about 600g/l, produced by any one of the process embodiments described herein.
• FIG. 1 is a flow diagram of a process in accordance with one embodiment of the invention which includes the agglomeration process by the first mixer, followed by the second mixer, then fluidizing apparatus, to produce a granular detergent composition having a density of at least 600g/l.
• FIG. 2 is a flow diagram of a process in accordance with one embodiment of the invention which includes the agglomeration process by the first mixer, followed by the second mixer, then the third mixer, finally fluidizing apparatus, to produce a granular detergent composition having a density of at least 600g/l.
• FIG. 3 is a flow diagram of a process which is capable to conduct variety of agglomeration processes selected from the group consisting of the first mixer, the second mixer, the third mixer, fluidizing apparatus, and the combination thereof, to produce a granular detergent composition.
• the present invention is directed to a process which produces free flowing, granular detergent agglomerates having a density of at least about 600 g/l.
• 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.
• Fig.1 presents a flow chart illustrating an embodiment of the present invention, i.e., process comprising the first step, the second step (i) and the third step below
• Fig.2 presents a flow chart illustrating an embodiment of the present invention, i.e., process comprising the first step, the second steps (i) and (ii), and the third step below
• Fig.3 presents a flow chart illustrating various embodiments which include the present invention.
• surfactant 11 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
• fine powder 12 having a diameter from 0.1 to 500 microns, preferably from about 1 to about 100 microns are fed into a first mixer 13, so as to make agglomerates.
• an internal recycle stream of powder 30, having a diameter of about 0.1 to about 300 microns generated from fluidizing apparatus 27, which are described hereinafter in the step 3 can be fed into the mixer in addition to the fine powder.
• the amount of such internal recycle stream of powder 30 can be 0 to about 60 wt% of final product 29.
• the surfactant 11 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 first mixer is in range from about 2 to about 50 seconds and tip speed of the first mixer is in range from about 4 m/s to about 25 m/s
• the energy per unit mass of the first mixer (energy condition) is from about 0.15 kj/kg to about 7 kj/kg
• the mean residence time of the first mixer is in range from about 5 to about 30 seconds and tip speed of the first mixer is in range from about 6 m/s to about 18 m/s
• the energy per unit mass of the first mixer (energy condition) is in range from about 0.3 kj/kg to about 4 kj/kg
• the mean residence time of the first mixer is in range from about 5 to about 20 seconds and tip speed of the first mixer is in range from about 8 m/s to about 18 m/s
• the energy per unit mass of the first mixer (energy condition) is in range 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).
• the resultant product 16 (first agglomerates having fine powder on the surface of the agglomerates) is then obtained.
• second step (i) only, or second step (i) followed by second step (ii).
• the resultant product 16, i.e., the first agglomerates, is fed into a second mixer 17, and then finely atomized liquid 18 is sprayed on the first agglomerates in the mixer 17.
• excessive fine powder formed in the first step is added to the second step. If the excessive fine powder is added to the second step (i), spraying the finely atomized liquid is useful in order to bind the excessive fine powder onto the surface of agglomerates.
• 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 mixer 17.
• the mean residence time of the second mixer is in range from about 0.2 to about 5 seconds and tip speed of the mixer of the second mixer is in range from about 10 m/s to about 30 m/s
• the energy per unit mass of the second mixer (energy condition) of the second mixer is in range from about 0.15 kj/kg to about 5 kj/kg
• the mean residence time of the second mixer is in range from about 0.2 to about 5 seconds and tip speed of the second mixer is in range from about 10 m/s to about 30 m/s
• the energy per unit mass of the second mixer (energy condition) is in range from about 0.15 kj/kg to about 5 kj/kg
• the most preferably, the mean residence time of the second mixer is in range from about 0.2 to about 5 seconds
• tip speed of the second mixer is in range from about 15 m/s to about 26 m/s
• the energy per unit mass of the second mixer (energy condition) is from about 0.2 kj/kg to about 3 kj/kg.
• the examples of the second mixer 17 can be any types of mixer known to the skilled in the art, as long as the mixer can maintain the above mentioned condition for the second step (i).
• An Example can be Flexomic Model manufactured by the Schugi company (Netherlands).
• the resultant product 20 is then obtained.
• the resultant product 20 (second agglomerates) is then subjected to either the second step (ii) or the third step.
• the resultant product 20 (second agglomerates) of the second step (i) is fed into a third mixer 21.
• the resultant product from the second mixer is mixed and sheared thoroughly for rounding and growth of the agglomerates in the third mixer 21.
• about 0-10% , more preferably about 2-5% of powder detergent ingredients of the kind used in the first step and/or the second step (i), and/or other detergent ingredients can be added to the second step (ii).
• choppers which are attachable for the third mixer can be used to break up undesirable oversized agglomerates.
• the process including the third mixer 21 with choppers is useful in order to obtain reduced amount of oversized agglomerates as final products, and such process is one preferred embodiment of the present invention.
• the mean residence time of the third mixer is in range from about 0.5 to about 15 minutes and the energy per unit mass of the third mixer (energy condition) is in range from about 0.15 to about 7 kj/kg, more preferably, the mean residence time of the third mixer is from about 3 to about 6 minutes and the energy per unit mass of the third mixer (energy condition) is in range from about 0.15 to about 4kj/kg.
• the examples of the third mixer 21 can be any types of mixer known to the skilled in the art, as long as the mixer can maintain the above mentioned condition for the second step (ii).
• An Example can be Lodige KM Mixer manufactured by the L ⁇ dige company (Germany).
• the resultant product 24, i.e., granules with round shape is then obtained.
• the resultant product of the second step i.e., a resultant product 20 or a resultant product 24, is fed into a fluidized apparatus 27, such as fluidized bed, in order to enhance granulation for producing free flowing high density granules.
• the third 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 second step is fluidized thoroughly so that the granules from the third 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 third step.
• liquid detergent materials of the kind used in the first step, the second 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 third 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; (2) the coating agent may be added between the fluid bed dryer and the fluid bed cooler; and/or (3) the coating agent may be added directly to the third mixer 21 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. 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 of the present invention is carried out by using (1) CB mixer which has flexibility to inject at least two liquid ingredients; (2) Schugi Mixer which has flexibility to inject at least two liquid ingredients; (3) KM mixer which has flexibility to inject at least a liquid ingredient; (4) Fluidized (Fluid) Bed which has flexibility to inject at least two liquid ingredients, the process can inco ⁇ orate seven different kinds of liquid ingredients in the process. Therefore, the proposed process is beneficial for persons skilled in the art in order to incorporate into a granule making process starting detergent materials which are in liquid form and are rather expensive and sometimes more difficult in terms of handling and/or storage than solid materials.
• the proposed invention is also useful in view of industrial requirement, because the person skilled in the art can set a series of apparatuses (e.g., shown in the Fig. 3) in a plant, and by using divertors which are capable for connecting/disconnecting between each apparatus, so that the skilled in the art can select variations of the process to meet desired property (e.g., particle size, density, formula design) of the final product.
• desired property e.g., particle size, density, formula design
• 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, the second step and/or the third step of the present invention.
• Detergent Surfactant (Agueous /Non-agueous)
• the amount of the 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 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-j 1-C-
• LAS C-j 1-C-
• 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 ⁇ n-C-i ⁇ alkyl alkoxy carboxylates (especially the EO 1-5 ethoxycarboxylates), the C-JQ-18 glycerol ethers, the CIQ-C-JS alkyl polyglycosides and the corresponding sulfated polyglycosides, and C12-C18 alpha-sulfonated fatty acid esters.
• the conventional nonionic and amphoteric surfactants such as the C-12-C18 a ' k y' ethoxylates ("AE") including the so-called narrow peaked alkyl ethoxylates and C6-C12 al yi phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), Cin-C-is amine oxides, and the like, can also be included in the overall compositions.
• the C ⁇ n- C-J8 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 C10-C18 N-(3-methoxypropyl) glucamide.
• 8 glucamides can be used for low sudsing.
• C-J0-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; zwitterionic surfactants which include derivatives of aliphatic quaternary ammonium, phosphonium and sulfonium compounds; water-soluble salts of esters of alpha-sulfonated fatty acids; alkyl ether sulfates; water-soluble salts of olefin sulfonates; beta-alkyloxy alkane sulfonates; betaines having the formula R(R 1 )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 R1 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; C 12-14 acylamidopropylbetaine; C8-14 acylamidohexyldiethyl betaine; 4[C14-16 acylmethylamidodiethylammonio]-1-carboxybutane; Ci6-18 acylamidodimethylbetaine; C12-I6 acylamidopentanediethylbetaine; and [C12-16 acylmethylamidodimethylbetaine.
• 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 S ⁇ 3 " 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 C ⁇
• 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 C12-14 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 aluminosiiicate 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 aluminosiiicate ion exchange material is produced. In that regard, the aluminosiiicate ion exchange materials used herein are preferably produced in accordance with Corkill et al, U.S. Patent No.
• the aluminosiiicate ion exchange material is in "sodium" form since the potassium and hydrogen forms of the instant aluminosiiicate do not exhibit as high of an exchange rate and capacity as provided by the sodium form.
• the aluminosiiicate ion exchange material preferably is in over dried form so as to facilitate production of crisp detergent agglomerates as described herein.
• the aluminosiiicate 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 aluminosiiicate 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 aluminosiiicate 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 aluminosiiicate ion exchange material has the formula
• the aluminosiiicate has the formula Na 12 [(Al ⁇ 2)i2 (Si ⁇ 2)l2]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.
• the aluminosilicates used herein are further characterized by their ion exchange capacity which is at least about 200 mg equivalent of CaC03 hardness/gram, calculated on an anhydrous basis, and which is preferably in a range from about 300 to 352 mg equivalent of CaCO3 hardness/gram. Additionally, the instant aluminosiiicate ion exchange materials are still further characterized by their calcium ion exchange rate which is at least about 2 grains Ca ++ /galion/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.
• 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 Ce-C-jo N-alkyl or alkenyl ammonium surfactants wherein remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.
• suitable quaternary ammonium surfactants are selected from mono C6-C16, preferably Ce-C-jo 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, C3-C12 hydroxyaikylene, C4-C12 dihydroxy- alkylene, C8-C12 dialkylarylene, -(R 1 0) X R1-, -(R 1 0) x R5(OR 1 ) ⁇ -, -(CH2CH(OR2)CH 2 O) z (R 1 0)yRl(OCH2CH(OR2)CH2) -.
• R1 is C2- CQ alkylene and mixtures thereof;
• R is hydrogen, -(Rl ⁇ ) x B, and mixtures thereof;
• R 3 is C-I-C-J S alkyl, C7-C12 arylalkyl, C7-C-J2 a
• R 4 is C-1-C12 alkylene, C4-C12 alkenylene, C8- C12 arylalkylene, C ⁇ -C-io arylene, and mixtures thereof;
• R 5 is C1-C12 alkylene, C3-C12 hydroxyaikylene, C4-C12 dihydroxy-alkylene, C8-C12 dialkylarylene, -C(O)-, -C(0)NHR6NHC(0)-, -R1(0R1)
• polyethyleneimines a polyethyleneimine having a molecular weight of 1800 which is further modified by ethoxylation to a degree of approximately 7 ethyleneoxy residues per nitrogen (PEI 1800, E7). It is preferable for the above polymer solution to be pre-complex with anionic surfactant such as NaLAS.
• Unsaturated monomeric acids that can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid.
• 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 4000, such as described next are preferred.
• Particularly suitable homo- polymeric polycarboxylates can be derived from acrylic acid.
• acrylic acid- based polymers which are useful herein are the water-soluble salts of polymerized acrylic acid.
• the average molecular weight of such polymers in the acid form preferably ranges from above 4,000 to 10,000, preferably from above 4,000 to 7,000, and most preferably from above 4,000 to 5,000.
• Water-soluble salts of such acrylic acid polymers can include, for example, the alkali metal, ammonium and substituted ammonium salts.
• Co-polymeric polycarboxylates such as a Acrylic/maleic-based copolymers may also be used.
• Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid.
• the average molecular weight of such copolymers in the acid form preferably ranges from about 2,000 to 100,000, more preferably from about 5,000 to 75,000, most preferably from about 7,000 to 65,000.
• the ratio of acrylate to maleate segments in such copolymers will generally range from about 30:1 to about 1:1, more preferably from about 10:1 to 2:1.
• Water-soluble salts of such acrylic acid/maleic acid copolymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. It is preferable for the above polymer solution to be pre-complexed with anionic surfactant such as LAS .
• Adjunct Detergent Ingredients can include, for example, the alkali metal, ammonium and substituted ammonium salts.
• the starting detergent material in the present process can include additional detergent ingredients and/or, any number of additional ingredients can be inco ⁇ orated 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, antitamish 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., inco ⁇ orated herein by reference.
• Other builders can be generally selected from the various water-soluble, alkali metal, ammonium or substituted ammonium phosphates, polyphosphates, phosphonates, polyphosphonates, carbonates, borates, polyhydroxy sulfonates, polyacetates, carboxylates, and polycarboxylates.
• alkali metal especially sodium, salts of the above.
• Preferred for use herein are the phosphates, carbonates, C ⁇ O-18 fatty acids, 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 ail of the "hardness" is removed from the wash water.
• These crystalline layered sodium silicates are generally more expensive than amo ⁇ hous 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 inco ⁇ orated 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 Si ⁇ 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 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 inco ⁇ orated 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 inco ⁇ orated herein by reference.
• These polyacetal carboxylates can be prepared by bringing together under polymerization condition 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 inco ⁇ orated herein by reference. Bleaching agents and activators are described in U.S. Patent 4,412,934,
• 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 one or more than one of the first, second and/or the third mixers for the present invention.
• a binder is added for pu ⁇ oses 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 inco ⁇ orated 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.
• the details of the surfactant paste structuring process are disclosed co-application No. PCT/US96/15960 (filed October 4, 1996) . ln order to make the present invention more readily understood, reference is made to the following examples, which are intended to be illustrative only and not intended to be limiting in scope.
• Step 1 250 - 270 kg/hr of aqueous coconut fatty alcohol sulfate surfactant paste (C-j2-Ci8 > 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 (i) The agglomerates from the CB-30 mixer are fed to the Schugi FX-160 mixer.
• 30 kg/hr of HLAS an acid precursor of C11-C18 alkyl benzene sulfonate; 94 - 97% active
• HLAS an acid precursor of C11-C18 alkyl benzene sulfonate; 94 - 97% active
• soda ash an acid precursor of C11-C18 alkyl benzene sulfonate
• soda ash mean particle size of about 10 - 20 microns
• Step 2 (ii) The agglomerates from the Schugi mixer are fed to the KM- 600 mixer for further agglomeration, rounding and growth of agglomerates. 30 kg/hr of Zeolite is also added in the KM mixer. Choppers for the KM mixer can be used to reduce the amount of oversized agglomerates.
• the condition of the KM mixer is as follows:
• Step 3 The agglomerates from the KM 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:
• Droplet spray size less than 50 micron Spray height: 175 - 250 mm (above distributor plate)
• the resulting granules from the step 3 has a density of about 700 g/l, and can be optionally subjected to the optional process of cooling, sizing and/or grinding.
• Example 2
• Step 1 15 kg/hr - 30kg/hr of HLAS (an acid precursor of C ⁇ n-C-
• HLAS an acid precursor of C ⁇ n-C-
• 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 (i) The agglomerates from the CB-30 mixer are fed to the Schugi FX-160 mixer. 35 kg/hr of neutralized AE3S liquid (28% active) is dispersed as finely atomized liquid in the Schugi mixer at about 30-40°C. 20-80 kg/hr of soda ash is added in the Schugi mixer.
• the condition of the Schugi mixer is as follows:
• KM mixer KM mixer.
• Choppers for the KM mixer can be used to reduce the amount of oversized agglomerates.
• the condition of the KM mixer is as follows:
• Step 3 The agglomerates from the KM 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)
• Fluidizing velocity 0.4 - 0.8 m/s
• Bed temperature 40 - 70 °C
• the condition of the fluid bed cooling apparatus is as follows:
• the resulting granules from the step 3 has a density of about 700 g/l, and can be optionally subjected to the optional process of sizing an/or grinding.
• 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 (i) The agglomerates from the CB-30 mixer are fed to the Schugi
• HLAS an acid precursor of C11-C18 alkyl benzene sulfonate; 94 - 97% active
• HLAS an acid precursor of C11-C18 alkyl benzene sulfonate; 94 - 97% active
• the condition of the Schugi mixer is as follows:
• Step 3 The agglomerates from the Schugi 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: Mean residence time : 2- 4 minutes Depth of unfluidized bed : 200 mm
• Spray height 175 - 250 mm (above distributor plate)
• the resulting granules from the step 3 has a density of about 600 g/l and, can be optionally subjected to the optional process of cooling, sizing an/or grinding.

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 (3)

Publications (1)

Family

ID=22255901

Family Applications (9)

Family Applications Before (4)

Family Applications After (4)

Country Status (12)

Families Citing this family (23)

Family Cites Families (13)

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

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events