CN1086258A - Prepare the method for high density granular detergent and the detergent composition for preparing by this method - Google Patents
Prepare the method for high density granular detergent and the detergent composition for preparing by this method Download PDFInfo
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- CN1086258A CN1086258A CN93118968A CN93118968A CN1086258A CN 1086258 A CN1086258 A CN 1086258A CN 93118968 A CN93118968 A CN 93118968A CN 93118968 A CN93118968 A CN 93118968A CN 1086258 A CN1086258 A CN 1086258A
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- detergent
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- mixing tank
- tap density
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/10—Carbonates ; Bicarbonates
-
- 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
- C11D3/1246—Silicates, e.g. diatomaceous earth
- C11D3/128—Aluminium silicates, e.g. zeolites
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents ; Methods for using cleaning compositions
- C11D11/0082—Special methods for preparing compositions containing mixtures of detergents ; Methods for using cleaning compositions one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
- C11D11/0088—Special methods for preparing compositions containing mixtures of detergents ; Methods for using cleaning compositions one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads the liquefied ingredients being sprayed or adsorbed onto solid particles
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- 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
Abstract
Improve the initial tap density method of the granulated detergent material tap density of 600g/l at least, by in one or more rotary drums or mixing tank with spray liquid on particle, and be sprinkled into fine powder, it is characterized in that initial average the degree of granulated detergent material greater than 400 microns and in preparation process the increased value of mean particle size be not more than 60%.The invention also discloses detergent composition with excellent distribution and dissolving properties.
Description
The trend that is tending towards high-bulk-density is arranged in commercially available granulated detergent now.This can bring the benefit of two aspects: the convenient and wrapping material minimizing of human consumer.
Run into low and form gel and the bad problem of dissolving properties that causes in the prior art by dissolution rate to many trials of this direction.The consequence that can produce thus in general washing process may be the distribution from the product difference of the gauger of placing washing clothes in the distributor disk of washing machine or the washing machine.The bad phenomenon of this distribution is often produced when contacting with water by the particle with high level of surfactant that gelation causes.Gelation has hindered a part of washing powder and has been dissolved in the washing water, thereby has reduced the efficient of washing powder.If washing powder can not dissolve fast, even it can well distribute and disperse also can produce other disadvantageous consequences.Have a limited time length wash(ing)cycle, washing composition can act on the clothing of washing in this time length.If owing to washing powder dissolves the clean effect that postponed lentamente, this also will limit the effectiveness of washing powder greatly.
Process engineer and preparation Shi Jingchang find that needing good distribution and needing good dissolution rate is a pair of conflicting requirement.Common solution is to find a balance that can provide sufficient distribution and suitable dissolution rate.For example, the high packing density of particles washing composition distributes that bad often to have a particle of high specific surface area relevant with tensio-active agent, and this is because its high porousness or owing to little granularity (particularly " molecule ").Yet, reduce porousness and/or increase mean particle size that dissolution rate is reduced.
The whole bag of tricks of increase tap density is existing in the prior art to be described-in many cases by using the method increase tap density of enrichment spray dried detergent.
EP 184794(1986 June 18 open (Henkel)) described adsorbing agent carrier has been added in the Loedige mixing tank to increase the method for tap density with nonionogenic tenside.Carrier is generally prepared by spraying drying.
EP 327963(1989 August 16 open (Henkel)) described alkaline back tower thickening method (basic post tower densification process), wherein pulverized before the reagglomeration of spray-dried component in granulation step.
Described two sections agglomeration methods EP 367339(1990 May 9 open (unilever).
Recently, developed certain methods, wherein the spraying drying step is eliminated fully.It is to comprise that by preparation the particle of tensio-active agent and washing assistant realizes, for example extruding or agglomeration viscosity lotion.
Yet, all art methods or suffer damage because of the existence of nano sized particles (particulate), these particles tend to gelation and cause bad distribution character, perhaps, big low porosity particulate suffers damage because of existing, these particles can overcome assignment problem, but the speed that is dissolved in washing process is slow.
The purpose of this invention is to provide detergent composition with three key property:
ⅰ) high-bulk-density
ⅱ) good distribution character
ⅲ) dissolving fast
This detergent composition is obtained by following method: at first most of in the dried particles shape finished product detergent composition (or all) components, then spraying liquid increases tap density in one or more rotary drums or mixing tank.
Major technique feature of the present invention is that initiating particle must be particle (not being powder), and they are without pulverising step.This is the key that obtains to distribute the properties benefit.
Another principal character of the present invention is that the mean particle size of finished particle should be greatly to dissolution rate is reduced.
By in one or more rotary drums or mixing tank with spray liquid on particle, and be sprinkled into fine powder and increase the method that initial tap density is at least the granulated detergent material tap density of 600g/L, it is characterized in that the initial mean particle size of washing composition material greater than 400 microns and in preparation process the increased value of mean particle size be not more than 60%.
The invention also discloses detergent composition with excellent distribution and dissolving properties.
The purpose of this invention is to provide detergent composition with three key property:
ⅰ) high-bulk-density
ⅱ) good distribution character
ⅲ) dissolving fast
This detergent composition is obtained by following method: the component in dry mixed major part (or all) the finished particle detergent composition at first, then spraying liquid increases tap density in one or more rotary drums or mixing tank.
The detergent component of required character most of by mixing (or all) granular powder form obtains, so that obtain having the composite grain material of the mean particle size and the tap density of regulation.And then increase tap density by following method: spraying liquid and be sprinkled into meticulous particle flow auxiliary agent in one or more rotary drums or mixing tank, so that partly make particle circular by filling orifice and surface imperfection.
Principal character of the present invention is that the powder at rotary drum/mixer entrance place is granular (almost not having molecule), is not ground into powder.This feature obtains distributing benefit (owing to there is not fine powder/powder, having avoided the generation of gel when contacting with water).
The preparation of grain fraction mixture
The grain fraction of using among the present invention is made up of the multiple various component that is used to wash, and prepares the teacher according to the needs of product and selects various components.Suitable component is described below:
Tensio-active agent
Tensio-active agent is selected from negatively charged ion, zwitter-ion, both sexes and cats product and its mixture.Anion surfactant preferably.The tensio-active agent that can be used among the present invention is listed in US 3,664,961(Norris, promulgation on May 23rd, 1972) and US 3,919, people such as 678(Laughlin, promulgation on December 30th, 1975) in.Useful cats product also is included in US 4,222,905(Cockrell, promulgation on September 16th, 1980) and US 4,239,659(Murphy, promulgation on December 16th, 1980) middle those cats products of describing., cats product generally is difficult for compatible with silico-aluminate of the present invention, therefore, if will use in composition of the present invention, preferably uses with low levels.Below tensio-active agent be the representational example of the tensio-active agent that uses in the present composition.
The water-soluble salt of higher fatty acid, i.e. " soap " is the useful anion surfactant in the present composition.It comprises alkali metal soap, for example contains to have an appointment 8 to about 24 carbon atoms, preferred about 12 sodium salt, sylvite, ammonium salt and alkylammonium salts to the higher fatty acid of about 18 carbon atoms.Soap can prepare by the neutralization of fat and direct saponification of oil or free fatty acids.Useful especially is by Oleum Cocois and tallow deutero-mixing-in fat acid sodium-salt and sylvite, i.e. tallow sodium or potassium and coconut soap.
Useful anion surfactant also is included in to have in the molecular structure and contains about 10 water-soluble salts to the organosulfur reaction product of the alkyl of about 20 carbon atoms and sulfonic group or sulfate group, preferred as alkali salt, ammonium salt and alkylammonium salt.(is the moieties of acyl group comprising term " alkyl ").The example of this class synthetic tensio-active agent is sodium alkyl sulfate and magnesium, particularly by sulfation high fatty alcohol (C
8-C
18Carbon atom) tensio-active agent of Huo Deing for example passes through those tensio-active agents of the glyceryl ester preparation of reduction tallow or Oleum Cocois; Sodium alkyl benzene sulfonate and potassium, wherein alkyl contains and has an appointment 9 to about 15 carbon atoms, is the straight or branched structure, for example at US 2,220, those types of describing in 099 and 2,477,383.
Other anion surfactants are alkyl glycerylether sodium sulfonates, particularly by those ethers of tallow and Oleum Cocois deutero-higher alcohols; Coco-nut oil fatty acid direactive glyceride sulfonic acid and sodium sulfate; Alkylphenol ethylene oxide ether sodium sulfate or sylvite, wherein each molecule contains 1 to 10 ethylene oxide unit of having an appointment, and alkyl contains has an appointment 8 to about 12 carbon atoms; Alkyl ethylene oxide ether sodium sulfate or sylvite, wherein per molecule contains to have an appointment and 1 contains to about 10 ethylene oxide units and alkyl and to have an appointment 10 to about 20 carbon atoms.
Other useful anion surfactants comprise the water-soluble salt of α-sulfonated fatty acid ester among the present invention, and have an appointment 6 to about 20 carbon atoms wherein fatty acid-based containing, and ester group contains has an appointment 1 to about 10 carbon atoms; The water-soluble salt of 2-acetoxyl group-alkane-1-sulfonic acid, wherein acyl group contains 2 to 9 carbon atoms of having an appointment, and alkyl group partly contains has an appointment 9 to about 23 carbon atoms; Sulfated alkyl ether, wherein alkyl contains and has an appointment 10 to 20 carbon atoms and contain 1 to 30 mole ethylene oxide of having an appointment; The water-soluble salt of olefin sulfonic acid, wherein thiazolinyl contains 12 to 24 carbon atoms of having an appointment; β-alkoxyalkyl sulfonate, wherein alkyl contains 1 to 3 carbon atom of having an appointment, and alkane partly contains has an appointment 8 to about 20 carbon atoms.
The sulfonated products that contains the fatty acid methyl ester of the alkyl with 10 to 20 carbon atoms also is useful.C preferably
16-18Fatty acid methyl sulfonated ester (MES).
Water miscible nonionogenic tenside also can be used as second kind of tensio-active agent in the present composition.Such nonionic comprises by oxyalkylene compounds (being hydrophilic in nature) and hydrophobic in nature organic compound, can be the compound of aliphatic series or Alkylaromatics condensation prepared.Can easily regulate the length with the polyoxyalkylenes of any concrete hydrophobic group condensation, to obtain between hydrophilic unit and hydrophobic units, having the water-soluble cpds of required balance degree.
Suitable ionic surfactant pack is drawn together the condenses of polyoxyethylene and alkylphenol, for example has the alkylphenol that contains about 6 to 16 carbon atom straight chains or branched structure alkyl and the condensation product of about 5 to 25 mole ethylene oxides of per molecule alkylphenol.
Preferred nonionic is to contain the Fatty Alcohol(C12-C14 and C12-C18) of 8 to 22 carbon atom straight chains or branched structure and the condensation product of every mol of alcohol 4 to 25 mole ethylene oxides.Particularly preferably be and contain the alcohol with about 9 to 15 carbon atom alkyls and the condensation product of about 4 to 25 mole ethylene oxides of every mol of alcohol; The condensation product of propylene glycol and ethylene oxide.
Other useful nonionogenic tensides are with the reproducible resource of nature, as with glucose being base.Alkyl polyglucoside (APG) preferably contains 10 to 20 carbon atoms, on average contains 1 to 4 glucosyl.Glucamide also is useful for the nonionogenic tenside of base.Wherein contain alkyl, for example tallow N-methylglucosamine with 10 to 20 carbon atoms.
Polyhydroxy fatty acid amide can be by fatty acid ester and N-alkyl polyhydroxy amine prepared in reaction.The preferred amines of using among the present invention is N-(R
1)-CH
2(CH
2OH)
4-CH
2-OH and preferred ester are C
12-C
20Fatty acid methyl ester.Most preferably N-methylglucosamine and C
12-C
20The reaction product of fatty acid methyl ester.
The method for preparing polyhydroxy fatty acid amide is described among the disclosed WO 926073 on April 16th, 1992.This application has been described the method for preparing polyhydroxy fatty acid amide in the presence of solvent.At the present invention extremely N-methylglucosamine and C in the embodiment preferred
12-C
20The fatty acid methyl ester reaction.Preparation Shi Keneng discovery carrying out in the presence of the solvent easily amidate action that is to say granular detergent composition is very convenient, and solvent comprises oxyalkylated, particularly (E03-8) C of ethoxylation
12-C
18Alcohol (the 15th page, 22-27 is capable).This reaction directly produces preferred nonionic system among the present invention, and these systems comprise that N-methyl glucose amide and per molecule on average have the C of 3 oxyethyl groups
12-C
14Alcohol.
Semi-polar nonionic surfactants comprises water-soluble amine oxides, and it contains the moieties of about 10 to 18 carbon atoms and two and is selected from and contains 1 alkyl and hydroxyalkyl part to about 3 carbon atoms; The water soluble oxidized phosphine, it contains the moieties of about 10 to 18 carbon atoms and two and is selected from alkyl and the hydroxyalkyl part that contains 1 to 3 carbon atom of having an appointment; Water-soluble sulfoxide, it contains moieties and an alkyl and a hydroxyalkyl part that is selected from about 1 to 3 carbon atom of about 10 to 18 atoms.
Amphoterics comprises the aliphatic derivatives of aliphatic derivatives or the heterocycle second month in a season or tertiary amine, wherein the aliphatic series part can be a straight or branched, aliphatic series one of substituting group contains have an appointment 8 to 18 carbon atoms and at least one aliphatic substituting group and contains anionic water dissolving base.
Zwitterionics comprises aliphatic quaternary ammonium, the derivative of Phosphonium and sulfonium compound, and wherein one of aliphatic substituting group contains 8 to 18 carbon atoms of having an appointment.
Particularly preferred tensio-active agent comprises tallow alkyl sulfate among the present invention; Coconut alkyl glycerol sulphur hard and infertile hydrochlorate; Sulfated alkyl ether, wherein to contain have an appointment 14 to 18 carbon atoms and average degree of ethoxylation be about 1 to 4 to moieties; The thiazolinyl or the alkylsulfonate that contain 14 to 16 carbon atoms of having an appointment; Alkyl dimethyl amine oxide, wherein alkyl contains 11 to 16 carbon atoms of having an appointment; Alkyl dimethyl amino propane sulfonic acid salt and alkyl dimethyl hydroxy amino propane sulfonate, wherein alkyl contains 14 to 18 carbon atoms of having an appointment; The soap that contains 12 to 18 the carbon atom higher fatty acid of having an appointment; C
9-C
15The condensation product of pure and about 3 to 8 mole ethylene oxides; With its mixture.
Useful cats product comprises water miscible formula R
4R
5R
6R
7N
+X
-Quaternary ammonium compound, R in the formula
4Be to have 10 to 18 carbon atoms, the alkyl of preferred 12 to 20 carbon atoms, R
5, R
6And R
7Be respectively C
1To C
7Alkyl, preferably methyl; X
-Be negatively charged ion, chlorine for example.Such trimethyl ammonium examples for compounds comprises C
12-14Alkyl trimethyl ammonium chloride and coconut alkyl trimethyl methylsulfuric acid ammonium.
The concrete preferred surfactant that uses among the present invention comprises: α-Xi Jihuangsuanyan; Triethanol ammonium C
11-C
13Alkylbenzene sulfonate; Alkyl-sulphate, (tallow, coconut, palm, synthetic source are as C
45Deng); Sodium alkyl sulfate; Methylmesylate; Coconut alkyl glycerylether sodium sulfonate; The sodium salt of the sulfation condensation product of tallow alcohol and about 4 mole ethylene oxides; The condensation product of coconut Fatty Alcohol(C12-C14 and C12-C18) and about 6 mole ethylene oxides; The condensation product of beef fat fat alcohol and about 11 mole ethylene oxides; Contain and have an appointment 14 to the Fatty Alcohol(C12-C14 and C12-C18) of about 15 carbon atoms and the condensation product of about 7 mole ethylene oxides; C
12-13The condensation product of Fatty Alcohol(C12-C14 and C12-C18) and about 3 mole ethylene oxides; 3-(N, N-dimethyl-N-coconut alkylamino)-2-hydroxy propane-1-sulfonate; 3-(N, N-dimethyl-N-coconut alkylamino)-propane-1-sulfonate; 6-(N-dodecylbenzyl-N, the N-dimethylamino) hexanoate; Dimethyl dodecyl amine oxide; The coconut alkyl dimethyl amine oxide; The water miscible sodium and the sylvite of coconut fatty acid and tallow fatty acids.
Washing auxiliary detergent
Any compatible washing auxiliary detergent or the composition of auxiliary agent or powder all can be used in the method and composition of the present invention.
Detergent composition of the present invention can contain the crystal aluminosilicate ion exchange material of following formula:
Z and y are at least about 6 in the formula, and the mol ratio of z and y about 1.0 is to about 0.4, and z is about 10 to about 264.The amorphous hydrated aluminosilicate material that the present invention uses has following empirical formula:
M is the ammonium of sodium, potassium, ammonium or replacement in the formula, and Z is about 0.5 to about 2, and Y is 1.The magnesium ion exchange capacity that the above-mentioned substance thing has is that the anhydrous silico-aluminate of every gram is at least about 50 milligramequivalent CaCO
3Hardness.It is preferred that granularity is about 1 to 10 micron hydration natrolite A.
Silico-aluminate ion-exchange builder material among the present invention is a hydrated form, if crystalline then contains and has an appointment 10% to about 28% water (weight), if amorphous, then may contain even more high-load water.Extremely preferred crystal aluminosilicate ion exchange material contains 18% to about 22% the water of having an appointment in its crystalline matrix.Crystal aluminosilicate ion-exchange thing another feature is that granularity is about 0.1 micron to about 10 microns.Amorphous substance often is less, for example less than about 0.01 micron.About 0.2 micron to about 4 microns of the granularity of preferred ion exchange material.The mean particle size of the ion exchange material of the given weight of term herein " granularity " expression.The granularity common analysis is for example measured with the measurement microscope method of scanning electronic microscope.Usually, another feature of crystal aluminosilicate ion exchange material is its calcium ion exchange capacity, is at least about 200mg equivalent CaCO
3The water hardness/g silico-aluminate (pressing moisture-free basis calculates) generally is that about 300mg eq/g is to about 352mg eq/g.Another feature of silico-aluminate ion exchange material is its calcium ion exchange rate, is benchmark with calcium ion hardness, is about 2 grain Ca at least
++/ gpm/gram/gallon silico-aluminate (moisture-free basis) generally is that about 2 grains/gpm/gram/gallon is to about 6 grains/gpm/gram/gallon.
The calcium ion exchange rate that best silico-aluminate washing assistant shows is at least about 4 grains/gpm/gram/gallon.
Usually, amorphous silicon aluminate ion exchange material has M
++Exchange capacity is at least about 50mg equivalent CaCO
3/ g(12mg Mg
++/ g) and Mg
++Exchange velocity is at least about 1 grain/gpm/gram/gallon.Amorphous substance does not demonstrate observable diffraction pattern when with Cu radiation (1.54 atomic meter) check.
Available on the silico-aluminate ion exchange material market of using in the invention process.The silico-aluminate that uses among the present invention can be crystalline or amorphous structure, can be naturally occurring or synthetic.The method for preparing the silico-aluminate ion exchange material is at US 3,985, and people such as 669(Krummel issued on October 12nd, 1976) the middle detailed description in detail, this patent is quoted with reference at this.The preferred synthetic crystal aluminosilicate ion exchange material that the present invention uses can title zeolite A, zeolite B and X zeolite bought.In particularly preferred embodiments, the crystal aluminosilicate ion exchange material has following empirical formula:
X is about 20 to about 30 in the formula, especially is about 27, and its granularity is generally less than about 5 microns.
Granulated detergent of the present invention can contain neutrality or basic salt, and its PH in solution is 7 or bigger, can be organic or inorganic in nature.The tap density of the detergent particles that builder salt assists to provide required.Because some salt are inert, so the many salt in them also play the washing auxiliary detergent material in washing soln.
The example of neutral water-soluble salt comprises basic metal, muriate, fluorochemical and the vitriol of ammonium or replacement ammonium.Above-mentioned an alkali metal salt, particularly sodium salt is preferred.General sodium sulfate is used for detergent particles, and it is particularly preferred salt.Citric acid and other general any organic or inorganic acid can be mixed in the granulated detergent of the present invention, as long as all the other components of itself and agglomerant composition chemically are being compatible.
Other water-soluble salts comprise the known compound that can be used as the washing auxiliary detergent material.Washing assistant generally is selected from various water-soluble alkalis, ammonium or replaces phosphoric acid salt, polyphosphate, phosphonate, polyphosphonic acid salt, carbonate, silicate, borate and the polyhydroxy sulfonate of ammonium.Preferably an alkali metal salt, particularly sodium salt in the above-mentioned salt.
The specific examples of inorganic phosphate builders is the tri-polyphosphate of sodium and potassium, pyrophosphate salt, and the polymerization degree is about polymetaphosphate of 6 to 21, and orthophosphoric acid salt.The example of polyphosphonic acid salt washing assistant is the sodium salt of ethylidene diphosphonic acid and sylvite, ethane-1-hydroxyl-1, the sodium salt of 1-di 2 ethylhexyl phosphonic acid and sylvite and ethane-1,1, the sodium salt of 2-tri methylene phosphonic acid and sylvite.Other phosphorus washing-aid compounds are disclosed in US 3,159,581; 3,213,030; 3,422,021; 3,422,137; In 3,400,176 and 3,400,148, these patents are quoted with reference at this.
The example of without phosphorus inorganic builders is carbonate, supercarbonate, letter half carbonate, the tetraborate decahydrate of sodium and potassium, and silicate, wherein SiO
2With the mol ratio of alkalimetal oxide be about 0.5 to about 4.0, preferably about 1.0 to about 2.4.
Multilayer silicate (Frankfurt, Germany Hoechst AG makes, and sells with trade(brand)name SKS-6) also is useful in the present invention.
As mentioned above, the chemical composition that generally is used for washing composition, for example zeolite, carbonate, silicon-dioxide, silicate, Citrate trianion, phosphoric acid salt, perborate, percarbonate etc. and processing aid such as starch can be used in the embodiment preferred of the present invention.
Polymkeric substance
Various organic polymers also are useful, and some of them also can be used as auxiliary agent to improve scourability.Be included in these polymkeric substance can be carboxyl low-grade alkyl sodium cellulosate, low alkyl group sodium cellulosate and hydroxyl low-grade alkyl sodium cellulosate, for example Xylo-Mucine, sodium carboxymethylcellulose pyce and HPMC, polyvinyl alcohol (also often comprising some polyvinyl acetate), polyacrylamide, polyacrylate and various multipolymer, for example toxilic acid and acrylic acid multipolymer.The molecular weight of above-mentioned polymkeric substance can change in very wide scope, but maximum in 2,000 to 100,000 scopes.
The polycarboxylate washing assistant is at US 3,308, and 067(Diehl issued on March 7th, 1967) middle statement.These materials comprise the aliphatic carboxylic acid for example homopolymer of toxilic acid, methylene-succinic acid, methylfumaric acid, fumaric acid, aconic acid, citraconic acid and methylene radical propanedioic acid and the water-soluble salt of multipolymer.
Component arbitrarily
Other components that are generally used in the detergent composition can be included in the composition of the present invention.These components comprise glidant, the agent of color spot decorations, SYNTHETIC OPTICAL WHITNER, bleach-activating agent, suds booster or suds suppressor, anti-tarnishing agent and sanitas, outstanding dirty agent, stain remover, mild clay, dyestuff, weighting material, fluorescent bleaches, sterilant, PH conditioning agent, non-washing assistant alkaline source, hydrotropic agent, enzyme, enzyme stabilizers, sequestrant and spices.
Fluorescent bleaches can directly add in (or a plurality of) particle combination, perhaps in the rotary drum or mixing tank that the solution or the slip of fluorescent bleaches can be sprayed into the inventive method.
Concrete suds suppressor can be sneaked in the final product composition having with blending means of the present invention.These particles preferably press down the bubble activity and are based on lipid acid or siloxanes.
Mix
Grain fraction can and be mixed with any universal method preparation.Generally, mixing process can be by in each component and in rotary drum or mixing tank each component is mixed and carry out continuously by weight on the travelling belt.The mean particle size of blended grain fraction must be greater than 400 microns. and tap density must be greater than 600g/L.
For these physicalies and the maintenance distribution benefit of the present invention that obtain the grain fraction mixture, preferably by the method except that spraying drying, methods such as for example agglomeration, compression, encapsulate prepare each grain fraction.The method of particularly preferred agglomeration high active surfactant paste and washing assistant and other powder is open October 28 at the Europe of the applicant's unexamined application EP-A-510746(1992) in description.Preferably almost there is not grain fraction to contain the pulp preparation of organic surface active agent with spraying drying.In order to prepare the component of high-bulk-density, such spray-dried component generally needs pulverising step.The component of spraying drying preparation preferably of no use, this component comprises organic surface active agent, its content is greater than 10% of finished product product weight.
Rotary drum/mixing tank operation
Method of the present invention is carried out in one or more rotary drums or mixing tank, and wherein the tap density of product obtains increasing, and does not lose good distribution character and rapidly-soluble benefit.
Do not wish bound by theory, the hygrometric state particle rolls in rotary drum/mixing tank, makes its globulate and especially regular shape (promptly spherical) and granularity.The result forms final product composition having, and its density is 750g/L at least, preferably greater than 800g/L.
Suitable device comprises various rotary drums or the mixing tank of turning axle is arranged, for example ribbon blender or low shear mixer they by Germany, Paderborn, Lodige Machinenbau GmbH is provided by (particularly those mixing tanks that provide with trade mark Loeding KM).Low shear mixer like this comprises the mixing equipment of " ploughshare " type that is assemblied in usually on the turning axle.If with low shear mixer, the speed of rotation of axle should be less than 250rmp.
The liquid that preferably is sprayed on the grain fraction mixture comprises nonionogenic tenside.Useful nonionogenic tenside is described hereinbefore.Particularly preferably be to contain and have an appointment 9 to the alcohol of about 15 carbon atom alkyls and the condensation product of about 4 to 25 mole ethylene oxides of every mol of alcohol; The condensation product of propylene glycol and ethylene oxide.
Other liquid ingredients also can respectively or be sprayed on after the pre-mixing in the mixture of grain fraction.Generally, the slip of spices and fluorescent bleaches can spray into.Though any fluorescent bleaches can add by this way, but have been found that color index is that 351 fluorescent bleaches (as disclosed among Sociecy of Dyers and Colourists and the American Association of Texeile Chemists and Colourists) obtains special colour stable benefit.
High speed stapling machine or knife mill can still should be avoided the fragmentation (may take place) of powder expediently in order to prevent the generation of big ball product under hygrometric state when the grain end is dry.High speed stapling machine or knife mill can be assemblied on the axle with respect to the mixer wall radial location, and this is preferably with greater than the rotation of the speed of 1000rpm.
The inventive method is different with more general agglomeration method.This can be clear that by the raising that begins to observe to the end mean particle size from present method.The increased value of mean particle size is not more than the about 60% of initial mean particle size in the present invention, and preferred increased value is not more than 40% of initial mean particle size, and preferred increased value is not more than 20% of initial mean particle size.
The term mean particle size that defines among the present invention is by sieving into several fractions (general 5 fractions) with Tyler mesh with the composition sample.The weight fraction that obtains is thus mapped to aperture size.Mean particle size is a 50%(weight) the theoretical aperture size that passes through of sample.
According to the present invention, pulverizing glidant (for example zeolite, carbonate, silicate, silicon-dioxide) adds in the mixture of grain fraction, preferably adds near end of processing the time.These separants only are the components that adds with powder type.Therefore, the glidant of particularly importantly selecting can gel (gel can take place the silicate of some pulverizing forms) when contacting with water.The glidant of the fine dispersion of this careful selection can make tap density further improve and not lose the benefit of good distribution character.
Final product composition having
The invention provides preparing washing agent method for compositions, said composition has very high tap density, good distribution character and quick dissolving properties.This method is very flexibly for preparation that can be processed.Certainly, all available method defined above of any chemical that can add in the particle adds in the composition of high-bulk-density.
Particularly preferred embodiment of the present invention is to have tap density 750g/L at least, the preferred composition of 800g/L at least, and it comprises:
A) 5% to 20% organic surface active agent;
B) 5% to 20% sodium silicoaluminate
The distribution residuum of composition is less than 30%:150g detergent composition sample and pours Zanussi(TM in following test) in the box of spraying type divider, 20 ℃ of temperature with 4 premium on currency from the nozzle of divider with 2 liters/minute speed by said box, the left that part of detergent composition in above-mentioned distributor disk of weighing then, the weight that obtains is represented with the percentage ratio of initial 150g sample, calculate the mean value of at least 5 revision tests, the percentage ratio that obtains is the percentage ratio that distributes residuum;
When being dissolved in 1 liter of Sotax cup 20 ℃ of temperature, the 10g sample (Sotax agitating auger collection is housed 3990-2 number, it is the speed rotation with 200rpm in Z-axis week, during 33mm place, top at the bottom of the bottom of said agitating auger slurry is arranged in glass) 1 liter of distilled water, the dissolution rate of detergent composition is to have at least 50% sulfates/sulfonates to enter in the solution being less than in 3 minutes.
The test method of recommending is described in detail in B and partly provides.
Most preferred composition comprises that Krafft temperature is lower than 40 ℃ mixed anion surfactant system, so that obtain good dissolution rate when mean particle size 550-750 micron.
In addition, because environment reason, most preferred composition is no phosphoric acid salt and no linear alkylbenzene sulfonate (no LAS).
Embodiment
The embodiment I
Mixture according to following formulation particulate material:
Weight %
Cats product agglomerate 30.0
Multilayer silicate compressing grains 17.7
Percarbonate 24.7
TAED agglomerate 9.2
Suds suppressor agglomerate 2.2
Spices seals 0.2
Particulate state soil release polymer 0.6
Particulate state heavy soda ash 8.6
Particulate state vinylformic acid-maleic acid 3.2
Enzyme 3.6
100
Anionic surfactant agglomerate is prepared by following method: be zeolite/carbonate/MgSO of 17/13/1/1 containing proportional in high-shear mixer
4Agglomeration 79% active C45AS/C35 A on the powdered mixture of/CMC
380: 20 lotions of S and phosphonate solution (35%).
44 parts of lotion/phosphonates are mixed with 66 parts of powdered mixture.
Wet agglomerate is dried to equilibrium relative humidity about 12% in 20 ℃ in fluidized-bed.Final agglomerate contains 30% anion surfactant and 2% phosphonate, the about 500mm of mean particle size, and 5% the amount of being less than is by No. 65 Tyler meshs.The tap density of agglomerate is 750g/L.
The tap density of the mixture of grain fraction is 780g/L, and size-grade distribution is as follows:
The product weight % of Taylor's screen size micron on sieve
14??1180??2
20??850??13
35??425??68
65??212??97
100??150??99
The mean particle size of thick component mixture is about 525 microns.
Above-mentioned grain fraction mixture is put into the rotary drum of 600L with rotating speed 15rpm operation.Nonionogenic tenside (C25E3) and 20% fluorescent bleaches (trade(brand)name Pinopal CBS-X, by Ciba-Geigy produce) are sprayed onto in the rotary drum operation with the mixture of 14: 1 ratios and make its amount reach 7% on the granular mixture.Spraying time is about 7 minutes.
After this, in the rotation rotary drum, spray spices at once with content 5%.Ceaselessly rotate rotary drum then, zeolite is added in the mixing tank lentamente, be about 8% to its content, carried out about 2 minutes.The mixing tank rotation was stopped after 30 seconds.Open valve also rotates rotary drum again and took out product in about 10 seconds.
Wearing out, product density is 910g/L after 2 days.Size-grade distribution is as follows:
The product weight % of Taylor's screen size micron on sieve
14??1180??2
20??850??23
35??425??87
65??212??99
100??150??99.5
About 640 microns of the mean particle size of product.Its expression mean particle size has increased by 22%.
This product distribution residual content of method of partly describing according to B is:
Distribute residual content (%)
2L/min??24
3L/min??2
The solubility curve of the anion surfactant that the method for partly describing according to B is measured shows that the time of dissolving 50% anion surfactant is 1.8 minutes.
The embodiment II
Mixture according to following formulation particulate material:
Weight %
Anionic surfactant agglomerate 53.3
Particulate Si hydrochlorate 3.2
Particulate state heavy soda ash 11.0
Particulate state Trisodium Citrate 18.1
Particulate state vinylformic acid-maleic acid 7.9
Suds suppressor agglomerate 2.0
Enzyme 4.5
100
Through 78% active LAS/TAS/C in high-shear mixer
35E
374: 24: 2 lotion of S prepares anionic surfactant agglomerate in the agglomeration that contains on the powdered mixture of zeolite/carbonate/CMC of proportional 20/10/1.Wet agglomerate is dried to equilibrium relative humidity about 12% in 20 ℃ in fluidized-bed.Final agglomerate contains 35% anion surfactant, and 600 microns of mean particle sizes, 8% particulate granularity are less than 212 microns, and tap density is 740g/L.
The tap density of grain fraction mixture is 740g/L, and the distribution of granularity is as follows:
The product weight % of Taylor's screen size micron on sieve
14??1180??5
20??850??17
35??425??66
65??212??97
100??150??99
The mean particle size of grain fraction mixture is about 525 microns.
(50kg) puts into Lodige FM130D with said mixture.Axle is with the speed rotation of about 160rpm, and the speed of knife mill is 3000rpm.In the running of axle and knife mill, the aqueous solution of nonionogenic tenside (C45E7) and the 20% fluorescent bleaches ratio with 14: 1 is sprayed on the powdered mixture.In 1.5 minutes, add total 5.2Kg liquid mixture.Spray 0.3Kg spices then at once.The zeolite that in mixing tank, adds the 5Kg fine dispersion.About 2 minutes of joining day.Operating equipment half a minute again after the adding, and knife mill does not turn round in this half a minute.By emitting product at the mixing tank bottom opening.
The density of product is 897g/L two days later.Size-grade distribution is as follows:
The product weight % of Taylor's screen size micron on sieve
14??1180??17
20??850??41
35??425??78
65??212??94
100??150??98
About 740 microns of the mean particle size of product.The expression mean particle size has increased by 40%.
According to this product distribution residual content of method of describing in the B part be:
Distribute residual content (%)
2L/min??14
3L/min??0
The solubility curve of the anion surfactant that the method for partly describing according to B is measured shows that the dissolution time of 50% anion surfactant is 1.0 minutes.
The comparing embodiment III
Mixture according to following formulation particulate material:
Weight %
Anionic surfactant agglomerate 12.0
Blowing powder 49.2
Silicate 3.2
Particulate state heavy soda ash 11.0
Particulate state Trisodium Citrate 18.1
Suds suppressor agglomerate 2.0
Enzyme 4.5
100
By dry neutralizing acid LAS prepares anionic surfactant agglomerate on the powdered mixture of zeolite/carbonate of proportional 1/1 containing in high-shear mixer.The mean particle size that contains the agglomerate of 30% anion surfactant is 500 microns, and 16% particulate granularity is less than 212 microns, and tap density is 740g/L.
The blowing powder contains the mixture preparation of following component by spraying drying:
Weight %
Anion surfactant lotion 40.0
Zeolite 44.0
Vinylformic acid-maleic acid 16.0
Wherein the anion surfactant lotion is 50% tensio-active agent, contains LAS and TAS, and its ratio is 2.4: 1.
It is 670g/L that the feed composition mixture has tap density, and size-grade distribution is as follows:
The product weight % of Taylor's screen size micron on sieve
14??1180??4
20??850??11
35??425??33
65??212??64
100??150??86
The mean particle size of component mixture is to be about 370 microns.
(50kg) puts into Lodige FM130D with said mixture.Axle is with the speed rotation of about 160rpm, and chopper speed is 3000rpm.Mixture with the aqueous solution of 14: 1 nonionogenic tenside of ratio (C45E7) and 20% fluorescent bleaches when the running of axle and knife mill is sprayed on the powdered mixture.
In about 1.5 minutes, add total 5.2Kg liquid mixture.Spray 0.3Kg spices then at once.The zeolite that then in mixing tank, adds fine dispersion.About 2 minutes of joining day.Adding back equipment and knife mill rerunned 3 minutes.Opening by the mixing tank bottom is emitted product.
The density of product is 847g/L after 2 days.Size-grade distribution is as follows:
The product weight % of Taylor's screen size micron on sieve
14??1180??7
20??850??13
35??425??47
65??212??75
100??150??88
About 400 microns of the mean particle size of product.
This product distribution of the method result who partly describes according to B is:
Distribute residual content (%)
2L/min??102
3L/min??84
The solubility curve of the anion surfactant that the method for partly describing according to B is measured shows that the time of dissolving 50% anion surfactant is 0.8 minute.
B part-test method
Anion surfactant under the stress condition
Dissolution rate (Sotax method)
Equipment
1) Sotax cup (1L)
2) distilled water
3) the electric beater motor of variable-ratio (IKA-MerK RM 20 DZM)
4) stainless steel propeller mixer (No. 39902, Sotax)
5) 6 disposable strainer kind equipments, pore size are 0.22 micron (diameter 25mm, Millex No.SLGS025NB millipore filter)
6) plastic injector (2ml) and disposable use syringe needle (21 * 1 1/2)
7) sample collector (15ml Glass tubing)
8) a cover Tyler mesh and a screening plant (Rotap)
9) thermostatic bath
Specimen preparation
Get representational 10g detergent composition sample.
Testing sequence
1) there is the cup of 1L water (or the solution that needs) be placed in the temperature required bath in the step.Make the temperature of water reach the temperature of bath.
2) impeller agitator is contained in glass at the bottom of 33mm place, top.
3) preparation 5 has only the syringe of strainer and syringe needle.Preparing 1 has only syringe needle not have the syringe of strainer.
4) speed of mixing tank is transferred to 200rpm.
5) add the 10g test products fast.Start stopwatch.
6) in pitch time accurately: 10 seconds, 30 seconds, 1 minute, 2.5 minutes and 5 minutes, get about 2ml sample with syringe.For sampling is met the demands, syringe needle must be at 4cm place under the liquid level.
7) after getting 5 minutes sample, make the speed of impeller agitator rise to 300rpm.
8) after 10 minutes, get another sample by strainer.
9) get liquid sample with the syringe of no strainer.The indicated number that is not both the solubleness of under this temperature, estimating between this result and the previous result different.Because high degree of agitation, at this moment between in system temperature is not improved.
10) carry out the assay determination (CatSO3 analyze or similar approach) of active component content.When representing to be used for titration, because the existence of insolubles must be noted that for not influence of filtered sample than turbid terminal point.
11) with unfiltered sample as 100%, calculate the percentage ratio (analyze with CatS03, even not molten tensio-active agent being also titrated) of each sample dissolution.
12) will dissolve time (up to the 5 minute) mapping of percentage ratio to the cycle very first time.The dissolving percentage ratio of the filtered sample that calculating is taken out 10 minutes the time under test conditions.
Distribution under stress condition (Zanussi(TM) method)
Equipment
1) divider Zanussi spray-type divider.Use main chamber wash.
2) waterside town city water
3) water temp is 20 ± 1 ℃
4) water flow velocity is per 60 ± 1 seconds, 2 ± 0.05L
Test was carried out 2 minutes.Demarcate water flow velocity with graduated cylinder or similar receptor.
5) sample material 150 ± 0.5g test products
Testing sequence
1) equipment under the calibration aforesaid operations condition.Guarantee that all testing installations all are level not have obstruction with nozzle divider.
2) test products of weighing requirement in cup.Guarantee that sample is representational in all prods (in adding cup time avoid disassociation).
3) the divider basin of after guaranteeing complete drying, weighing.
4) master who the sieve of vertically orient is placed on divider washes part, so that be blocked in the width of a 12.5cm place box of water out box farthest.Product is poured in the divider between that of the sieve of vertically orient and dried up outlet box farthest.Powder should with keep powder surface as far as possible the mode of level pour into.Remove sieve.
5) box of divider is put into groove lentamente, in place fully to guarantee it.
6) add water with the flow velocity of demarcating.Guarantee that water flows into the main part of washing fully.
7) stop to add entry after 2 minutes, stop fully up to the water of from box, discharging.
8) from groove, take out box, discharge any excessive water with shaking box slightly.Guaranteeing not have any product falls from box.Any other part at box should be anhydrous.If find some water, system must reexamine, and all flows into the main part of washing to guarantee all water.
9) the divider box of weighing and containing whole residuums.
10) replication is at least 5 times.
11) ask the mean value of wet residuum.The result represents with the weight percentage of initial dryed product amount.
Accuracy and evaluation
When average residuum percentage ratio differs 10% or more for a long time, can evaluate that there were significant differences between product.If under 2L/min the stress test residuum be lower than 30%(and/or under 3L/min residuum be lower than 10%), think that product shows good distribution.
Claims (9)
1, improves the initial tap density method of the granulated detergent material tap density of 600g/L at least, it by in one or more rotary drums or mixing tank with spray liquid on particle, and be sprinkled into fine powder, it is characterized in that the initial mean particle size of granulated detergent material greater than 400 microns and in preparation process the increased value of mean particle size be not more than 60%.
2, according to the process of claim 1 wherein that the final bulk density of granulated detergent material greater than 750g/L, is preferably greater than 800g/L.
3, according to the process of claim 1 wherein that primary particles washing composition material comprises the organic detergent material, it is processed into particle with the method except that spraying drying.
4, according to the method for claim 2, wherein primary particles washing composition material comprises the organic detergent material, and it is processed into particle with the method except that spraying drying.
5, according to the process of claim 1 wherein that the liquid that is sprayed on the particle contains nonionogenic tenside, its content is up to the 10%(weight of final product).
6, according to the method for claim 2, the liquid that wherein is sprayed on the particle contains nonionogenic tenside, and its content is up to the 10%(weight of final product).
7, according to the process of claim 1 wherein that at least one mixing tank is that level is columnar, it comprises that along the axle of cylinder axis rotation this drives mixing apparatus and rotates with the speed less than 250rpm.
8, according to the method for claim 7, wherein mixing tank also comprises the stapling machine that is assemblied on one or more axles, and to assembling, it is with the speed rotation greater than 1000rpm at the mixing tank barrel bore for said axle.
9, detergent composition, its tap density is 750g/L at least, preferred 800g/L at least, it comprises:
A) 5% to 20% organic surface active agent
B) 5% to 20% sodium silicoaluminate
It is characterized in that in following process distributing residuum: pour 150g detergent composition sample into Zanussi(TM less than 30%) in the box of spraying type divider, 20 ℃ of temperature with 4 premium on currency from the nozzle of divider with 2 liters/minute speed by said box, the left that part of cleaning composition in above-mentioned distributor disk of weighing then, the weight that obtains is represented with the percentage ratio of initial 150g sample, calculate the mean value of at least 5 revision tests, the percentage ratio that obtains is the percentage ratio that distributes residuum;
When being dissolved at 1 liter of Sotax cup 20 ℃ of temperature, the 10g sample (Sotax agitating auger slurry is housed 3990-2 number, its speed with 200rpm around Z-axis is rotated, during 33mm place, top at the bottom of the bottom of said agitating auger slurry is arranged in glass) 1 liter of distilled water, the dissolution rate of detergent composition is to have at least 50% sulfates/sulfonates to enter in the solution in 3 minutes being less than.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP92870138.2 | 1992-09-01 | ||
| EP92870138 | 1992-09-01 | ||
| EP93200460.9 | 1993-02-18 | ||
| EP93200460 | 1993-02-18 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1086258A true CN1086258A (en) | 1994-05-04 |
| CN1061369C CN1061369C (en) | 2001-01-31 |
Family
ID=26132630
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN93118968A Expired - Fee Related CN1061369C (en) | 1992-09-01 | 1993-09-01 | Process for making high density granular detergent and compositions made by the process |
Country Status (18)
| Country | Link |
|---|---|
| JP (1) | JP4056557B2 (en) |
| KR (1) | KR950703050A (en) |
| CN (1) | CN1061369C (en) |
| AT (1) | ATE201900T1 (en) |
| AU (1) | AU677238B2 (en) |
| CA (1) | CA2143628C (en) |
| DE (1) | DE69330311T3 (en) |
| DK (1) | DK0660873T3 (en) |
| EG (1) | EG20394A (en) |
| ES (1) | ES2157223T5 (en) |
| FI (1) | FI950913A0 (en) |
| IN (1) | IN188571B (en) |
| MA (1) | MA22965A1 (en) |
| MX (1) | MX9305352A (en) |
| NO (1) | NO950768L (en) |
| PT (1) | PT660873E (en) |
| TR (1) | TR27586A (en) |
| WO (1) | WO1994005761A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1119406C (en) * | 1996-08-26 | 2003-08-27 | 花王株式会社 | Method for producing high-bulk density tetergent composition |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| USH1604H (en) * | 1993-06-25 | 1996-11-05 | Welch; Robert G. | Process for continuous production of high density detergent agglomerates in a single mixer/densifier |
| EP0709449A1 (en) * | 1994-10-28 | 1996-05-01 | The Procter & Gamble Company | Non-aqueous compositions comprising polyhydroxy fatty acid amides |
| DE19538028A1 (en) * | 1995-10-12 | 1997-04-17 | Sued Chemie Ag | detergent additive |
| EP0816485B1 (en) * | 1996-07-04 | 2005-12-14 | The Procter & Gamble Company | Process for making detergent compositions |
| US6211138B1 (en) * | 1996-10-04 | 2001-04-03 | The Procter & Gamble Company | Process for making a detergent composition by non-tower process |
| US6211137B1 (en) * | 1996-10-04 | 2001-04-03 | The Procter & Gamble Company | Process for making a detergent composition by non-tower process |
| CN1175099C (en) * | 1998-10-16 | 2004-11-10 | 花王株式会社 | Process for producing detergent particles |
| US6602846B1 (en) | 1999-06-14 | 2003-08-05 | Kao Corporation | Method for producing single nucleus detergent particles |
| US6706931B2 (en) | 2000-12-21 | 2004-03-16 | Shell Oil Company | Branched primary alcohol compositions and derivatives thereof |
| DE102006035746A1 (en) * | 2006-07-28 | 2008-01-31 | Henkel Kgaa | liquid carrier |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4411809A (en) * | 1976-12-02 | 1983-10-25 | Colgate Palmolive Company | Concentrated heavy duty particulate laundry detergent |
| US4666740A (en) * | 1976-12-02 | 1987-05-19 | The Colgate-Palmolive Co. | Phosphate-free concentrated particulate heavy duty laundry detergent |
| DE3424987A1 (en) * | 1984-07-06 | 1986-02-06 | Unilever N.V., Rotterdam | METHOD FOR PRODUCING A POWDERED DETERGENT WITH INCREASED SHOULDER WEIGHT |
| US4970017A (en) * | 1985-04-25 | 1990-11-13 | Lion Corporation | Process for production of granular detergent composition having high bulk density |
| DE3812530A1 (en) * | 1988-04-15 | 1989-10-26 | Henkel Kgaa | PROCESS FOR INCREASING THE DENSITY OF SPREADY DRY, PHOSPHATE-REDUCED DETERGENT |
| GB8810821D0 (en) * | 1988-05-06 | 1988-06-08 | Unilever Plc | Detergent compositions & process for preparing them |
| CA2001535C (en) * | 1988-11-02 | 1995-01-31 | Peter Willem Appel | Process for preparing a high bulk density granular detergent composition |
| GB8907187D0 (en) * | 1989-03-30 | 1989-05-10 | Unilever Plc | Detergent compositions and process for preparing them |
| GB8922018D0 (en) * | 1989-09-29 | 1989-11-15 | Unilever Plc | Detergent compositions and process for preparing them |
| CZ280524B6 (en) * | 1992-01-17 | 1996-02-14 | Unilever Nv | Particulate bleaching detergent mixture and the use of map zeolite in the mixture |
-
1993
- 1993-08-26 TR TR00729/93A patent/TR27586A/en unknown
- 1993-08-29 EG EG55693A patent/EG20394A/en active
- 1993-08-30 PT PT93922135T patent/PT660873E/en unknown
- 1993-08-30 AT AT93922135T patent/ATE201900T1/en not_active IP Right Cessation
- 1993-08-30 DE DE69330311T patent/DE69330311T3/en not_active Expired - Lifetime
- 1993-08-30 ES ES93922135T patent/ES2157223T5/en not_active Expired - Lifetime
- 1993-08-30 DK DK93922135T patent/DK0660873T3/en active
- 1993-08-30 JP JP50737094A patent/JP4056557B2/en not_active Expired - Fee Related
- 1993-08-30 WO PCT/US1993/008151 patent/WO1994005761A1/en active IP Right Grant
- 1993-08-30 KR KR1019950700779A patent/KR950703050A/en not_active Application Discontinuation
- 1993-08-30 AU AU51245/93A patent/AU677238B2/en not_active Ceased
- 1993-08-30 CA CA002143628A patent/CA2143628C/en not_active Expired - Fee Related
- 1993-08-31 MA MA23274A patent/MA22965A1/en unknown
- 1993-09-01 IN IN951DE1993 patent/IN188571B/en unknown
- 1993-09-01 MX MX9305352A patent/MX9305352A/en unknown
- 1993-09-01 CN CN93118968A patent/CN1061369C/en not_active Expired - Fee Related
-
1995
- 1995-02-28 FI FI950913A patent/FI950913A0/en unknown
- 1995-02-28 NO NO950768A patent/NO950768L/en not_active Application Discontinuation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1119406C (en) * | 1996-08-26 | 2003-08-27 | 花王株式会社 | Method for producing high-bulk density tetergent composition |
Also Published As
| Publication number | Publication date |
|---|---|
| PT660873E (en) | 2001-10-31 |
| DE69330311T3 (en) | 2006-11-30 |
| ES2157223T5 (en) | 2007-03-01 |
| IN188571B (en) | 2002-10-19 |
| MA22965A1 (en) | 1994-04-01 |
| CA2143628C (en) | 1999-01-12 |
| CN1061369C (en) | 2001-01-31 |
| NO950768D0 (en) | 1995-02-28 |
| JP4056557B2 (en) | 2008-03-05 |
| FI950913A (en) | 1995-02-28 |
| NO950768L (en) | 1995-04-28 |
| TR27586A (en) | 1995-06-13 |
| KR950703050A (en) | 1995-08-23 |
| EG20394A (en) | 1999-02-28 |
| ES2157223T3 (en) | 2001-08-16 |
| JPH08500631A (en) | 1996-01-23 |
| ATE201900T1 (en) | 2001-06-15 |
| AU5124593A (en) | 1994-03-29 |
| DE69330311D1 (en) | 2001-07-12 |
| AU677238B2 (en) | 1997-04-17 |
| MX9305352A (en) | 1994-04-29 |
| CA2143628A1 (en) | 1994-03-17 |
| FI950913A0 (en) | 1995-02-28 |
| DK0660873T3 (en) | 2001-08-27 |
| DE69330311T2 (en) | 2002-03-14 |
| WO1994005761A1 (en) | 1994-03-17 |
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