CN1102954C - Percarbonate bleach particles coated with partially hydrated crystalline aluminosilicate flow aid - Google Patents
Percarbonate bleach particles coated with partially hydrated crystalline aluminosilicate flow aid Download PDFInfo
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- CN1102954C CN1102954C CN94193328A CN94193328A CN1102954C CN 1102954 C CN1102954 C CN 1102954C CN 94193328 A CN94193328 A CN 94193328A CN 94193328 A CN94193328 A CN 94193328A CN 1102954 C CN1102954 C CN 1102954C
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- percarbonate
- alkyl
- powder
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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
- C11D3/12—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
-
- 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
- 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3942—Inorganic per-compounds
Abstract
A process for making a granular detergent composition comprising the steps of adding to a detergent powder particles of percarbonate having a mean particle size in the range of from 250 to 900 micrometers and a powdery flow aid containing a partially hydrated crystalline sodium aluminosilicate having a moisture content of less than 15 %, preferably from 5 % to 12 %.
Description
Technical field
The present invention relates to contain the detergent composition of percarbonate bleach, it provides the method for compositions of making the best bleach stability of this generation.
Background of invention
The Sodium peroxoborate that very widely used inorganic persalt SYNTHETIC OPTICAL WHITNER is a hydration or four hydrated forms in laundry detergent composition.We increase the interest of other persalt at present, and wherein SPC-D is the easiest obtain a kind of.
The detergent composition that contains SPC-D is known in the industry altogether.For SPC-D, because it is dissolving easily in water, the weight efficiency height, and after emitting its available oxygen (available oxygen), the carbanion source that is useful on the washing purpose is provided, and is a kind of very attractive persalt that is used for detergent composition therefore.
In laundry detergent composition, comprise the restriction that percarbonate still is subjected to the unstable character of SYNTHETIC OPTICAL WHITNER so far.Can decompose rapidly when particularly percarbonate stores under moist and/or warm atmosphere.Yet know,, can protect carbonate, obtain acceptable storage characteristics by using crystallized product to carry out coating (coated) or during it is made, adding stablizer or use above-mentioned two kinds of methods simultaneously.Propose various suitable coating compounds agent, comprised the mixture of silicate and various mineral sulfates and carbonate.
In WO-92-06163, describe the various detergent composition that contain percarbonate, wherein required the various heavy metal ion of low equilibrium relative humidity and low levels.
Yet, also need the stability in storage of percarbonate bleach is improved, and require in various types of detergent composition, to comprise in the various compositions with various existing manufacturing process manufacturings reaching this point.
Yet, the applicant is surprised to find that, when using partially hydrated crystal aluminosilicate as the separant that is applied on the detergent composition particle that contains percarbonate bleach, in all types of compositions, the stability of percarbonate is significantly improved.
US4 has described a kind of method that improves detergent bar composition in 427,567, wherein detergent bar composition is crushed into powder, and described powder mixes with anhydrous zeolite/isolates.The content that described detergent composition is addressed restriction perborate and percarbonate is lower than 20w% (weight percentage, down together), preferably is lower than 10w%.
Disclosed JP61 069897 described silico-aluminate, silicon-dioxide, wilkinite and the carclazyte that average particle diameter is not more than 10 microns and can be used as surface-modifying agent on April 10th, 1986, and consumption is 0.5%-35%; In various bleaching components, only mention percarbonate.Preferred silico-aluminate is unformed, and not preferred anhydrous material.
The present invention's general introduction
Make the method for granular detergent composition, comprise that with average particle size at the percarbonate of 250-900 micrometer range with contain moisture content less than 15%, the powder flowbility auxiliary agent of the partially hydrated crystalline sodium aluminosilicate of preferred 5%-12% joins the step in the detergent powder particle.
Detailed description of the present invention
The feature of the inventive method is that percarbonate particles and powder flowbility auxiliary agent are joined in the detergent powder, and to produce detergent composition, the adding of two kinds of materials can be carried out with any order.
At this, detergent composition is meant that laundry detergent composition and automatic bowl are with composition or laundry additive.
Detergent powder
At this, detergent powder is made up of various granular detergent components, and every kind of one-component can be with agglomeration, press, micro encapsulation, pulverizing or the such method manufacturing of spraying drying, described each dry component is mixed obtaining detergent powder.
Various grain fractions can be by the method preparation and the mixing of any routine.Usually hybrid technique can carry out continuously, continuously various components is joined on the travelling belt by weight, and mixes in a rotary drum or mixing tank.
At this, percarbonate particles can add in any time in each component mixing process.
Preferred wherein do not contain by the spraying drying preparation and comprise the grain fraction of content greater than a kind of organic surface active agent of the 10w% of final product.Therefore, preferably use surfactant agglomerates (agglomerate); Having described a kind of highly active tensio-active agent cream in the common unsettled EP-A-92200993.1 of applicant adopts washing assistant and other powder to carry out agglomerant particularly preferred method.
More preferably wherein seldom or not by the various grain fractions of spraying drying preparation.
Among the present invention used various grain fractions by according to the product makers-up require selected the useful various components of its washing are made.Some suitable components are described below.
Anion surfactant
In preferred embodiments, when detergent composition was laundry detergent composition, composition of the present invention contained one or more anion surfactants as described below usually.
Alkyl sulfonate surfactants
At this, alkyl sulfonate surfactants comprises C
8-C
20The ol ester of carboxylic acid (being lipid acid), according to " The Journal of the American Oil ChemistsSociety " 52 (1975), the method that pp.323-329 introduces is used gas SO
3Sulfonation.Suitable parent material comprises the natural fat material derived from butter, palm wet goods.
Preferred alkyl sulfonate surfactants during especially for the laundry purposes, comprises alkyl ester sulfonate:
Wherein, R
3Be C
8-C
20Alkyl, preferred alkyl or its combination, R
4Be C
1-C
6Alkyl, preferred alkyl or its combination, M is the positively charged ion that forms water-soluble salt with the alkyl ester sulfonate radical.Suitable salt-forming cation comprises various metals, as sodium, potassium and lithium and ammonium ion that replace or non-replacement, as monoethanolamine, diethanolamine and trolamine.Preferred R
3Be C
10-C
16Alkyl, R
4Be methyl, ethyl or sec.-propyl.Especially preferably methyl ester sulfonate, wherein R
3Be C
14-C
16Alkyl.
Alkyl sulfate surfactant
At this, alkyl sulfate surfactant is that structural formula is ROSO
3The water-soluble salt of M or acid, wherein R C preferably
10-C
24Alkyl, preferably contain C
10-C
20The alkyl of moieties or hydroxyalkyl, more preferably C
12-C
18Alkyl or hydroxyalkyl, M is hydrogen or positively charged ion, as alkali metal cation (as sodium, potassium and lithium), or ammonium ion or the ammonium ion of replacement are (as methyl, dimethyl and trimethyl ammonium positively charged ion or quaternary ammonium cation, as tetramethyl-ammonium and lupetidine positively charged ion, with derived from various alkylamines, as the quaternary ammonium cation of ethamine, diethylamine, triethylamine and its mixture, or the like).Generally speaking, for lower wash temperature (as being lower than about 50 ℃), preferred C
12-C
16Alkyl chain, and for higher wash temperature (as being higher than about 50 ℃), preferred C
16-C
18Alkyl chain.
Alkyl alkoxylated sulfate surfactant
At this, alkyl alkoxylated sulfate surfactant is that structural formula is: RO (A) mSO
3The water-soluble salt of M or acid, wherein R is the C of non-replacement
10-C
24Alkyl or moieties be C
10-C
24Hydroxyalkyl, preferred C
12-C
20Alkyl or hydroxyalkyl, more preferably C
12-C
18Alkyl or hydroxyalkyl, A is oxyethyl group or propoxy-unit, m is greater than 0, be generally about 0.5-about 6, the number of more preferably about 0.5-about 3, M are hydrogen or positively charged ion, as alkali metal cation (as sodium, potassium, lithium, calcium, magnesium etc.), ammonium or the ammonium cation of replacement.At this, the propenoxylated vitriol of the vitriol of alkyl ethoxylated and alkyl can.The specific examples of the ammonium cation that replaces is methyl, dimethyl and trimethyl ammonium and quaternary ammonium cation, as tetramethyl-ammonium, lupetidine with derived from various alkylamines, as the quaternary ammonium cation of ethamine, diethylamine, triethylamine and its mixture.The example of tensio-active agent is C
12-C
18Alkyl polyethoxye (1.0) vitriol, C
12-C
18E (1.0) M), C
12-C
18Alkyl polyethoxye (2.25) vitriol, C
12-C
18E (2.25) M), C
12-C
18Alkyl polyethoxye (3.0) vitriol, C
12-C
18E (3.0) M) and C
12-C
18Alkyl polyethoxye (4.0) vitriol, C
12-C
18E (4.0) M), wherein M is selected from sodium or potassium usually.
Other anion surfactants
Various other anion surfactants that can be used for washing purpose also can be included in the laundry detergent composition of the present invention.These tensio-active agents can comprise various soap salt (for example, comprise sodium, potassium, ammonium and the various ammonium salts that replace, as one, two and the salt of trolamine), C
9-C
20Linear alkyl benzene sulfonate, C
8-C
22Uncle or secondary alkyl sulfonate, C
8-C
24The sulfonation poly carboxylic acid of alkenyl sulphonate, the preparation of the pyrolysis product by sulfonation alkali earth salt, as british patent specification 1,082, those described in 179, C
8-C
24Alkyl polyglycol ether sulfate (containing 10mol oxyethane at the most); Fatty acyl group glycerol sulfonate, fatty oil acylglycerol vitriol, alkylphenol ethylene oxide ether sulfate, paraffin sulfonate, alkyl phosphonate, isethionate, as acyl-hydroxyethyl sulfonate, N-acyl taurine salt (taurate), amber alkyl amide salts and. the monoesters of sulfosuccinate, sulfosuccinate (particularly saturated and undersaturated C
12-C
18Monoesters) and the diester of sulfosuccinate (particularly saturated and undersaturated C
6-C
14Diester), the vitriol of fatty acyl group sarcosinate, alkyl polysaccharide, as alkyl polyglucoside vitriol (below will describe the compound of non-ionic non-sulfuric acidization), the primary alkyl sulphates of side chain, alkyl polyethoxye carboxylate salt, be RO (CH as structural formula
2CH
2O) kCH
2COO
-M
+Carboxylate salt, wherein R is C
8-C
22Alkyl, k is the integer of 0-10, M is the solubility salt-forming cation.Resinous acid and hydrogenated resin acid also are suitable for, as rosin, and staybelite and be present in or derived from the resinous acid and the hydrogenated resin acid of Yatall MA.Other example provides in " Surface Active Agents and Detergents " (Vol.I and II, bySchwartz, Perry and Berch) book.Various such tensio-active agents are at the USP3 of bulletin on December 30th, 1975, and the 23rd hurdle the 58th row among 929,678 people such as () Laughlin is described (being incorporated herein by reference document) in the 29th hurdle 23 row.
At this, when comprising this anion surfactant in the laundry detergent composition of the present invention, its content generally is that about l%-is about 40%, about 20% weight ratio of preferably about 3%-.
Nonionogenic tenside
Common any nonionogenic tenside may be used among the present invention, but finds that it is useful especially that two class nonionogenic tensides are arranged.Here it is based on the nonionogenic tenside of various oxyalkylated (particularly ethoxylation) alcohol with based on the nonionogenic tenside of the amidated products of fatty acid ester and N-alkyl polyhydroxy amine.At this, the amidated products of ester and amine is commonly referred to polyhydroxy fatty acid amide.Useful especially in the present invention is the mixture that comprises two kinds and two or more nonionogenic tensides, and wherein at least a nonionogenic tenside is selected from oxyalkylated pure and mild polyhydroxy fatty acid amide.
Suitable ionic surfactant pack is drawn together the compound that the organic hydrophobic compound condensation by alkylene oxide group (possess hydrophilic property) and aliphatics or alkyl aromatic is produced.Can regulate at an easy rate with the length of the polyoxyalkylenes of arbitrarily concrete hydrophobic group condensation, to obtain having the water-soluble cpds of desired hydrophile-lipophile balance value.
Being particularly preferred for of the present invention is the such nonionogenic tenside of alkylphenol polyethylene oxide condensation compound, for example contains the condensation product of oxyethane (every mole of alkylphenol) of alkylphenol and about 4-25 mole of the straight or branched alkyl of about 6-16 carbon atom.
Preferred nonionic is to contain the straight or branched Fatty Alcohol(C12-C14 and C12-C18) of 8-22 carbon atom and the water-soluble condensation product that average 25 moles oxyethane (every mole of Fatty Alcohol(C12-C14 and C12-C18)) condensation at the most obtains.Particularly preferably be the alcohol and the condensation product of the oxyethane (every mol of alcohol) of about 2-10 mole and the condensation product of propylene glycol and oxyethane that wherein contain the 9-15 carbon atom alkyl of having an appointment.The condensation product of the alcohol that most preferably wherein contains the 12-15 carbon atom alkyl of having an appointment and average about 3 moles oxyethane (every mol of alcohol).
This nonionic surfactant system also can comprise the polyhydroxy fatty acid amide component.
Polyhydroxy fatty acid amide can be by fatty acid ester and N-alkyl polyhydroxy amine prepared in reaction.Being used for preferred amine of the present invention is N-(R
1) CH
2(CH
2OH)
4-CH
2-OH, and preferred ester is C
12-C
20Fatty acid methyl ester.Most preferably N-methylglucosamine and C
12-C
20The reaction product of fatty acid methyl ester.
The whole bag of tricks of preparation polyhydroxy fatty acid amide has been described in the WO 92 6073 of bulletin on April 16th, 1992.This application has been described the method for preparing polyhydroxy fatty acid amide in the presence of solvent.A particularly preferred embodiment of this invention is N-methylglucosamine and C
12-C
20Fatty acid methyl ester reaction.The makers-up who also says granular detergent composition can find comprise oxyalkylated, (EO3-8) C of ethoxylation particularly
12-C
14Under the existence of alcoholic solvent, amidate action can carry out (the 15th page, 22-27 is capable) easily.Can directly obtain institute's preferred nonionic system in the present invention like this, as comprise the C of N-methyl glucose amide and 3 oxyethyl groups of per minute sub-band averaging
12-C
14The system of alcohol.
The granulated detergent of in the WO92 6160 of bulletin on April 16th, 1992, having described nonionic surfactant system and having made by this system.This application has been described by (embodiment 15) and carried out the granular detergent composition that fine dispersion is mixed with in Eirich RV02 mixing tank, wherein contains N-methylglucosamine (10%), nonionogenic tenside (10%).
The nonionic surfactant system preparation technology suitable with it all described in these two parts of patent applications, and these all are applicable to the present invention.
In the present composition, polyhydroxy fatty acid amide can scrubbed component or the 0-50w% of composition weight, preferred 5w%-40w%, and more preferably the amount of 10w%-30w% exists.
Other tensio-active agent
Laundry detergent composition of the present invention also can contain positively charged ion, both sexes, zwitter-ion and semi-polarity tensio-active agent, and the nonionogenic tenside except that described above, comprises the semi-polarity nonionic amine oxide that describes below.
The cationic detersive tensio-active agent that is applicable to laundry detergent composition of the present invention is those tensio-active agents with long chain hydrocarbon groups.The example of this cationoid tensio-active agent comprises ammonium class tensio-active agent, as the halogenide of alkyl dimethyl ammonium and those tensio-active agents with following structure:
[R
2(OR
3)
y] [R
4(OR
3)
y]
2R
5N
+X
-Wherein, R
2Be alkyl or the alkyl benzyl that contains about 18 carbon atoms of the 8-that has an appointment in the alkyl chain, each R
3Be selected from-CH
2CH
2-,-CH
2CH (CH
3)-,-CH
2CH (CH
2OH)-,-CH
2CH
2CH
2-, and composition thereof; Each R
4Be selected from C
1-C
4Alkyl, C
1-C
4Hydroxyalkyl, two R
4The benzyl ring structure that base connects into ,-CH
2COH-CHOHCOR
6CHOHCH
2OH, wherein, R
6Be any hexose or molecular weight less than about 1000 hexose polymkeric substance, when y is not equal to 0, R
6Can be hydrogen; R
5With R
4Identical or alkyl chain, wherein R
2With R
5The total number of carbon atoms be not more than about 18; Each y is that 0-is about 10, and the summation of y value is 0-about 15; X is any compatible negatively charged ion.
At this, other useful cats product is described among 228,044 (Cambre) at the USP4 of bulletin on October 14th, 1980, is incorporated herein by reference.
When laundry detergent composition of the present invention comprised above-mentioned cats product, typical content was the about 25w% of 0%-, the about 15w% of preferably about 3w%-.
Amphoterics also is applicable to laundry detergent composition of the present invention.These tensio-active agents can be described as the aliphatic derivatives of the second month in a season or tertiary amine widely, or the aliphatic derivatives of the heterocycle second month in a season or tertiary amine, and wherein fatty group can be a straight or branched.Aliphatic series one of substituting group contains at least 8 carbon atoms, is typically about 18 carbon atoms of about 8-, and at least one contains the water-soluble anionic group, as carboxyl, sulfonate radical, sulfate radical.Can be for the example of amphoterics with reference to the USP3 of bulletin on December 30th, 1975,929,678 people such as () Laughlin the 19th hurdle 18-35 capable (being incorporated herein by reference).
When laundry detergent composition of the present invention comprised above-mentioned amphoterics, typical content was the about 15w% of 0%-, the about 10w% of preferably about 1w%-.
Zwitterionics also is applicable to laundry detergent composition.These tensio-active agents can be described as the derivative of the second month in a season or tertiary amine widely, the derivative of the heterocycle second month in a season or tertiary amine, the derivative of quaternary ammonium, quaternary phosphine or uncle's sulfonium compound.Can be for the example of zwitterionics with reference to the USP3 of bulletin on December 30th, 1975,929,678 people such as () Laughlin the 19th hurdle the 38th row is to the 22nd hurdle the 48th row (being incorporated herein by reference document).
When laundry detergent composition of the present invention comprised above-mentioned zwitterionics, typical content was the about 15w% of 0%-, the about 10w% of preferably about 1w%-.
Semi-polar nonionic surfactants is the special nonionogenic tenside of a class, it comprises water miscible amine oxide, and amine oxide contains the moieties of about 18 carbon atoms of about 10-and two and is selected from containing and has an appointment 1 to the alkyl of about 3 carbon atoms and the part of hydroxyalkyl; Water miscible phosphine oxide, phosphine oxide contain the moieties of about 18 carbon atoms of about 10-and two and are selected from containing and have an appointment 1 to the alkyl of about 3 carbon atoms and the part of hydroxyalkyl.
The semi-polarity nonionic detergent comprises the amine oxide surfactant with following structure with tensio-active agent:
Washing assistant
Compositions herein preferably comprises washing assistant, more preferably comprises nonphosphate builders.These can comprise alkaline carbonate, supercarbonate, silicate, silico-aluminate, carboxylate salt and their any mixture, but are not limited only to this.The content of builder system is the 25w%-80w% of composition, more preferably 30w%-60w%.
Suitable silicate is SiO
2: Na
2The O ratio is at the product of 1.6-3.4 scope, preferably SiO
2: Na
2O is than the product of the so-called amorphous silicic salt in the 2.0-2.8 scope.
In silicates, particularly preferred material is the crystalline layered sodium silicate of following general formula:
NaMSi
xO
2x+1YH
2O wherein, M is sodium or hydrogen, x is the number of 1.9-4, y is the number of 0-20.This crystalline layered sodium silicate is described in EP-A-0164514, and has described their preparation method in DE-A-3417649 and DE-A-3742043.For the purposes of the present invention, the x in the general formula has numerical value 2,3 or 4 in the above, and is preferably 2.More preferably M is a sodium, and y is 0, and the preferred example of this structural formula comprises Na
2Si
2O
5These materials can obtain with the title of NaSKS-5, NaSKS-7, NaSKS-11 and NaSKS-6 respectively from Hoechst AG FRG.Crystalline layered silicate adds wherein with the agglomerant solid ingredient of other component as doing mixed solid or conduct.
Can use a large amount of aluminosilicate ion exchange materials, but the sodium silicoaluminate zeolite of preferred following cell configuration formula:
Na
z[(AlO
2)
z(SiO
2)
y] xH
2O wherein z and y is at least approximately 6, and the mol ratio of z and y is about 0.4 for about 1.0-, and z is about 10-about 264.Unformed hydrated aluminosilicate material with following empirical formula is useful:
Mz (zAlO2.ySiO
2) wherein, M is the ammonium of sodium, potassium, ammonium or replacement, z is about 2 for about 0.5-, and y is 1, and described material has and is at least about 50 millinormal CaCO
3The magnesium ion exchange capacity of hardness/(restraining anhydrous silico-aluminate).The preferred particle size is the hydration sodium type Zeolite A zeolite of about 1-10 micron.
The silico-aluminate ion-exchange here helps washes material and is in hydration status, and for crystal type, contains the water from about 10w% to about 28w%, for unformed body, contains the more water of volume.Preferred crystal aluminosilicate ion-exchange material contains 18% to about 22% the water of having an appointment in its crystal matrix (crystal matrix).The further feature of this crystal aluminosilicate ion-exchange material is that particle dia is from about 0.1 micron to about 10 microns.Amorphous material is littler usually, as less than about 0.01 micron.Preferred its size of particles diameter of ion-exchange material is from about 0.2 micron to about 4 microns.Determine the weighted average size of particles diameter of the ion-exchange material that provides as usefulness " the micro-mensuration of scanning electronic microscope " with common analytical technology in this term " size of particles diameter " expression.
The aluminosilicate ion exchange material that can be used for practice of the present invention is an available product on the market.What can be used for silico-aluminate of the present invention and structurally can be crystal type also can be unformed, can be natural formation also can be synthetic.A kind of method of producing aluminosilicate ion exchange material is at the USP3 of bulletin on October 12nd, 1976, is described among 985,669 people such as () Krummel, is incorporated herein by reference.The preferred synthetic crystallization aluminosilicate ion exchange material that can be used for this can obtain with the trade mark of Zeolite A, Zeohite B, Zeolite X, P and MAP, and the latter has description in EPA384070.In particularly preferred embodiments, the crystal aluminosilicate ion-exchange material is the Zeolite A with following structural formula:
Na
12[(AlO
2)
12(SiO
2)
12] xH
2O wherein, x is from about 20 to about 30, and is particularly about 27, and size of particles is usually less than about 5 microns.
The suitable carboxylate salt washing assistant that contains a carboxyl comprises lactic acid, oxyacetic acid and their ether derivant, and as at belgian patent No831,368,821,369 and 821,370 is described.The multi-carboxylate of containing two carboxyls comprises the water-soluble salt of following acid: Succinic Acid, propanedioic acid, (ethylenedioxy) oxalic acid, toxilic acid, diethyl alkyd, tartrate, tartronic acid and fumaric acid; and at German Offenlegenschrift 2; 446; 686 and 2,446,687 and USP3; 935; ether carboxylate of describing in 257 and the sulfinyl carboxylate salt of in belgian patent 840,623, describing.The multi-carboxylate of containing three carboxyls particularly comprises water miscible Citrate trianion, aconate, citraconate and succinate derivative, as in English Patent 1,379, the carboxy methoxy-succinic acid salt of describing in 241, newborn oxygen base succinate and the oxygen Quito carboxylate salt material in Netherlands patent applications 7205873, described, as in English Patent 1,387, the 2-oxa-of describing in 447-1,1,3 tricarballylic acid's salt.
The multi-carboxylate of containing four carboxyls comprises English Patent 1,261, the oxygen base disuccinate of describing in 829,1 and 1,2,2-ethane tetracarboxylic acid hydrochlorate, 1,1,3,3 ,-propane tetracarboxylic acid salt and 1,1,2,3-propane tetracarboxylic acid salt.Contain the substituent multi-carboxylate of sulfo group and comprise English Patent 1,398,421 and 1,398, the sulfo-succinic acid salt derivative of describing in 422 and USP3,936,448, with English Patent 1,082, the 179 sulfonated pyrolysis Citrate trianion of describing contains phosphorous substituent multi-carboxylate in English Patent 1, be described in 439,000.
Alicyclic ring and heterocyclic multi-carboxylate comprise pentamethylene-suitable, suitable, suitable-tetracarboxylic acid hydrochlorate, cyclopentadiene pentacarboxylic acid salt, 2,3,4,5-tetrahydrofuran (THF)-suitable, suitable, suitable-the tetracarboxylic acid hydrochlorate, 2,5-tetrahydrofuran (THF)-suitable-dicarboxylate, 2,2,5,5-tetrahydrofuran (THF)-tetracarboxylic acid hydrochlorate, 1,2,3,4,5, the carboxymethyl derivant of 6-hexane hexacarboxylic acid salt and polyhydroxy-alcohol (as sorbyl alcohol, mannitol and Xylitol).Aromatic multi-carboxy acid's salt comprises English Patent 1,425, the mellitic acid of describing in 343,1,2,4,5-benzene tetracarboxylic acid and phthalic acid derivatives.
In above-mentioned multi-carboxylate, preferred multi-carboxylate is contained the hydroxycarboxylate of three carboxyls, particularly Citrate trianion at the most in the per molecule.
The mixture of the parent acid of monomer or oligomeric multi-carboxylate's sequestrant or they and its salt, for example citric acid or Citrate trianion/citric acid mixture also can be used as builder system component useful among the present invention.
In another embodiment of the invention, provide
The automatic bowl composition:
Automatic bowl usually except containing percarbonate and partially hydrated zeolite of the present invention, also comprises washing assistant with composition, material and alkali source as described above, and as silicate or carbonate, these components account for 70% of finished product preparation at the most.Optional component comprises various polymkeric substance and various enzyme.
In another embodiment of the invention, provide
Laundry additive composition:
This composition also comprises washing assistant and alkali source usually except containing percarbonate and partially hydrated zeolite of the present invention.
Optional components
Other various components that become known for detergent composition within the scope of the invention also can be as the optional components of detergent powder of the present invention, as activator of bleaching agent, other SYNTHETIC OPTICAL WHITNER, polymkeric substance, enzyme, froth suppressor and dyestuff, filler, white dyes, PH conditioning agent, non-soda source, enzyme stabilizers, hydrotropic solvent, the spices of helping.
Preferred its composition also contains the peroxyacid bleach activator of composition weight 1%-20%, preferred 2%-15%, more preferably 3-10%.
According to the present invention, peroxyacid bleach activator (bleach precursor) can be selected widely as additional bleaching component, and preferably contains the material of one or more N-or O-acyl group.
Suitable kind comprises the acylated derivatives of acid anhydrides, ester, acid amides and imidazoles and oxime, has described the various examples of material useful in these kinds in GB-A-1586789.Most preferred kind is as GB-A-836,988,864,798,1,147,871 and 2,143, and the ester described in 231 and as the acid amides described in GB-A-855 735 and 1 246 338.
According to the present invention, as additional bleaching component, particularly preferred activator of bleaching agent compound is N, N, and N ', N ' tetrem acylated compounds, structural formula is:
Wherein, x is 0 or the integer of 1-6.
Various examples comprise tetra-acetylated methylene diamine (TAMD), wherein x=1, tetra-acetylated ethylene diamine (TAED), wherein x=2 and tetra-acetylated hexamethylenediamine (TAHD), wherein x=6.These compounds and homologue thereof have been described in GB-A-907 356.As additional bleaching component, most preferred peroxyacid bleach activator is TAED.
Another kind of preferred peroxy acid bleach immunomodulator compounds is to have the compound that following general formula acid amides replaces:
Wherein, R
1Be aryl or the alkaryl that contains about 14 carbon atoms of the 1-that has an appointment, R
2Be alkylidene group, arylidene and the alkarylene that contains about 14 carbon atoms of the 1-that has an appointment, R
5Be hydrogen or alkyl, the aryl that contains 1-10 carbon atom, alkaryl, L are actually any leavings group.R
1Preferably contain 6-12 the carbon atom of having an appointment.R
2Preferably contain 4-8 the carbon atom of having an appointment.R
1Can be straight or branched alkyl, contain side chain, substituting group or contain side chain simultaneously and substituent substituted aryl or alkaryl, they can come from synthetic source or natural origin, as shea butter.Similarly structural changes is for R
2Also be applicatory.Substituting group also can comprise alkyl, aryl, fontanel element, nitrogen, sulphur and other typical substituting group or organic compound.R
5Be preferably hydrogen or methyl.R
1And R
5Contained the total number of carbon atoms should be greater than 18.The activator of bleaching agent compound that this class acid amides replaces has description in EP-A-0170386.
Except percarbonate, the composition here can also contain other bleach system, as perborate and activator, or preformed organic peroxide acid or mistake imino-acid, as O-phthalic amido peroxide caproic acid, 2-carboxyl-O-phthalic amido peroxide caproic acid, N, N-O-phthalic amido peroxide valeric acid, peroxide hexanodioic acid pelargonamide, 1,12-diperoxy dodecanedioic acid, benzoyl hydroperoxide and cyclosubstituted benzoyl hydroperoxide, a peroxide phthalic acid (magnesium salts, hexahydrate), diperoxy undecane dicarboxylic acid.
Percarbonate particles
As previously mentioned, other grain fraction of percarbonate particles and detergent powder is done mixed.
At this, composition contains 1w%-40w%, preferred 3w%-30w%, and more preferably 5w%-25w%, median size is the 250-900 micron, the alkali metal percarbonate SYNTHETIC OPTICAL WHITNER of preferred 500-700 micron.
When said composition was laundry additive, the content of percarbonate was generally 20w%-80w%.
The alkali metal percarbonate SYNTHETIC OPTICAL WHITNER is the form of sodium salt normally.SPC-D is an adducts, and its corresponding structure formula is: 2Na
2CO
33H
2O
2, for the stability that stores, percarbonate bleach can be with the mixing salt coating of other alkali metal sulfates and carbonate.The method of this coating and coating thereof is at GB-1, existingly in 466,799 describes (authorizing Interox on March 9th, 1977).The weight ratio of mixing salt coated material and percarbonate is 1: 20 00-1: 4, more preferably 1: 99-1: 9, most preferably 1: 49-1: 19.Preferred mixing salt is sodium sulfate and yellow soda ash, and general formula is Na
2SO
4.n.Na
2CO
3, wherein n is 0.1-3, preferred 0.3-1, most preferably 0.2-0.5.
Other coated material that is suitable for is a water glass, its SiO
2: Na
2The O ratio is 1.6: 1-2.8: 1, and Magnesium Silicate q-agent.
The percarbonate bleach of the carbonate/sulfate coating that can buy can comprise the heavy metal chelant of low levels such as EDTA, 1-hydroxy ethylene-1,1-di 2 ethylhexyl phosphonic acid (HEDP) or amino phosphonates do, and these compounds add wherein in preparation process.
As mentioned above, the preferred heavy metal chelant that uses includes organic phosphonates and amino alkylidenyl many (alkylene phosphonic acids salt), as basic metal ethane-1-hydroxyl di 2 ethylhexyl phosphonic acid, nitrilo trimethylene phosphonic salt, ethylene diamine tetramethylene phosphonic acid salt and diethylenetriamine pentamethylenophosphonic acid(DTPP) salt.
Particularly when making laundry detergent composition, preferably its tap density contains the detergent powder of percarbonate more than 650g/l.
Another feature of the inventive method is before or after adding percarbonate, adds the powder flowbility auxiliary agent in detergent powder.
Flow aids
Mixing process can be carried out in any suitable mixing equipment, comprise thermopnore and one or more various rotary drum or mixing tank that rotation axis is housed, as by LodigeMachinenbau GmbH, ribbon blender that Paderborn, Germany provide or low shear mixer (the particularly mixing tank of commodity Loedige KM by name).This low shear mixer comprises mixing tool, normally is contained in " ploughshare " type device on the rotation axis.If use low shear mixer, the velocity of rotation of rotation axis should be less than 250rpm.
In preferred embodiments, with before flow aids mixes, at first nonionogenic tenside is sprayed onto in the detergent powder that contains percarbonate.The tap density that can make the composition that finally obtains like this is 800g/l, or higher.
The liquid that is sprayed onto on the grain fraction mixture preferably comprises nonionogenic tenside.The nonionogenic tenside that is suitable for is described in the above.Particularly preferably be the condensation product of alcohol with the alkyl that contains 9-15 the carbon atom of having an appointment and about 4-25 mole ethylene glycol or propylene glycol and oxyethane.
Other liquid ingredient also can be sprayed onto on the mixture of grain fraction after the independent respectively or first pre-mixing.
Usually, the soup compound of spices and white dyes also can spray into.Although any white dyes can add by this way, find that Colour IndexFluorescent Brightener number 351 (announcing as The Society of Dryers andColourists and the American Association of Textile Chemists andColourists) can provide good especially colour stability.
Key of the present invention is that flow aids contains partially hydrated silico-aluminate or is made up of partially hydrated silico-aluminate.
The aluminosilicate ion exchange material that can be used in the practice of the present invention all is an available material on the market.Useful in the present invention silico-aluminate is the crystalline texture and the material of synthetic preferably.Produce the USP3 of the method for aluminosilicate ion exchange material, be described among 985,669 (Krummel etc.), as a reference at this at bulletin on October 12nd, 1976.
Preferred this synthetic crystallization aluminosilicate ion exchange material is for can ZeoliteA and the zeolite that obtains of the trade mark of Zeolite X and Zeolite P and Zeolite MAP, and description is arranged in EP-A-0170386.In an especially preferred embodiment, crystal aluminosilicate ion-exchange material of the present invention is derived from Zeolite A, and its structural formula is:
Na
12[(AlO
2)
12(SiO
2)
12] xH
2O wherein x is about 30 for about 20-, and its particle dia is generally less than 5 microns.
The feature of necessity of the present invention is that described crystal aluminosilicate is in partially hydrated form, and so-called partially hydrated form is meant dewaters above-mentioned crystal aluminosilicate material, so that its water-content is in the useful scope that the present invention found.
This water-content should not be higher than 15% of alumino-silicate materials weight, and can hang down to 1.5%, and this water-content is corresponding to substantially anhydrous form.
Find that preferred water-content is in the scope of 5%-12%.
Dehydration is known in the industry, comprises the high temperature dehydration process, and this process produces water-content usually and is lower than 5% roasting material, and is generally used for preparing A type zeolite crystal, as catalyst for cracking.
Yet, if the high temperature dehydration process was interrupted before dehydration is finished, or the high temperature of the zeolite dehydration that is used for dewatering is lower, then can obtain the zeolite of partially hydrated state, and can adjust moisture content to this process to obtain requiring, for example, the level of 5-12% preferred for this invention can also be adsorbed at least 10% moisture (in moisture-free basis).
Except partially hydrated silico-aluminate, the powder flowbility auxiliary agent also can contain hydrophobic silicon oxide, and content is at most 30% of flow aids weight.
Silicon oxide is the amorphous silica of high dispersing.On market, can obtain in a variety of forms.The most common silicon oxide has the tap density of 50-120g/l.The particulate specific surface area is 25-800m
2/ g.
Chemically modified can be carried out in the surface of silicon oxide particle, to change its behavior to water.For example, silicon oxide particle can be handled with organosilane, so that particle mainly is hydrophobic.Find that also silicon oxide must carry out hydrophobization to be applicable to the present invention.
In industrial practice, silicon oxide is usually by a kind of preparation the in two kinds of technology: or by the precipitator method or by thermal-flame hydrolysis (high temperature flamehydrolysis) method.Sedimentary silicon oxide has the cohesive size of 3-100 micron usually, and the system of forging (fumed) silicon oxide (by the flame hydrolysis preparation) has the primary particle of ball-type usually, and its mean diameter is 7-40nm.The fumed silica that the preferred primary particle mean diameter of the present invention is 7-25nm.
The example of useful especially silicon oxide comprises the AG by Degussa in the present invention, the silicon oxide of the commodity that Frankfurt, Germany provide " Aerosil " by name.Find that Aerosil R972 is useful especially.This silicon oxide is hydrophobic fumed silica, and its specific surface area is about 110m
2/ g, average primary particle dia are 16nm.
Powder flowbility auxiliary agent of the present invention can also comprise Wessalith Day, Hydrotalcit, and talcum powder or fusing point are higher than 40 ℃ wax.
Embodiment
Dummy suffix notation below using in these embodiments:
C45AS:C
14-C
15Sodium alkyl sulfate
C35AE3S:C
13-C
15Sulfated alkyl ether, every mole on average contains three moles of oxyethyl groups
CMC: Xylo-Mucine
C25E3: with the C of average 3 moles of ethylene oxide condensations
12-C
15Primary alconol
C45E7: with the C of average 7 moles of ethylene oxide condensations
14-C
15Primary alconol
TAED: tetra acetyl ethylene diamine
Polymkeric substance: 1: 4 toxilic acid/polymerizing acrylic acid thing, average MW=80,000
Example I prepares following granular laundry detergent compositions
Silicate presses particle to % by weight anionic surfactant agglomerate * 30 stratiforms (layered) (is provided by Hoechst; Trade name SKS-6) 18 percarbonate (being provided by Interox) * * 25TAED agglomerate, 9 foam in hibitors agglomerates, 2 flavor capsules, 0.2 particle heavy ash, 8.4 particle acrylic acid-maleic acids, 3.2 enzymes, 3.6 particulate stain removal agent polymer 0.6* anionic surfactant agglomerate are made by 78% active surfactant cream, comprise 80: 20 C45AS/C35AE3S. According to the method for describing among the EPA510746 with the powdered mixture agglomeration of this cream.It consists of 30% C45AS, 7.5% C35AE3S, 24% zeolite, 20% carbonate, 2.5% CMC, 12% the vinylformic acid-maleic acid and the moisture of surplus the anionic surfactant granules that obtains.The * percarbonate is with, 2.5% carbonate/sulfate coating, and average particulate size is 500 microns.Top listed granular detergent composition is packed in 140 liters the rotary drum, and velocity of rotation is 25rpm.Under the situation that rotary drum rotates, be sprayed onto on the particulate composition with the mixture of 14:1 ratios 20% aqueous solution of nonionogenic tenside (C25E3) and white dyes, make its content reach 7% of particulate composition weight.The about 1-2 of spray time minute.Under the situation that rotary drum rotates, then spices is sprayed into then, its content reaches 0.5% of particulate composition weight.Then, do not stop the rotation of rotary drum, flow aids is slowly added in the mixing tank, about 30 seconds of time spent.In the composition of embodiments of the invention I, the type of used flow aids is the A type zeolite (water-content is 6%) of dehydration, and addition is 8%.In case flow aids adds, mixing tank is rotated further about 1 minute, stops then.Final product is taken out from rotary drum.
In Comparative composition A, the type of used flow aids is the zeolite of hydration (water-content is 16%, is provided by Degus sa), and addition is 8%.In case flow aids adds, mixing tank is rotated further about 1 minute, stops then.Final product is taken out from rotary drum.
Respectively 2kg embodiment 1 and composition A product are packed in the carton of sealing, under 35 ℃/80%eRH (equilibrium relative humidity) atmosphere, store.
The rate of recovery (recovery) of measuring percarbonate is as follows:
Condition of storage embodiment 1 composition A
In 2 weeks, 35 ℃/80%eRH 73% 68%
In 3 weeks, 35 ℃/80%eRH 67% 58%
In 4 weeks, 35 ℃/80%eRH 60% 47%
Top result has shown that use has the zeolite of water-content of the present invention to improving the importance of percarbonate stability in the product.
Example II
Prepare laundry detergent composition (its percentage ratio is the percentage ratio of composition total weight) according to following processing step:
Spray-dired powder (54%) carries out enrichment (densified) with C25E3 tensio-active agent (5%) in high-shear mixer, humidity is 6%.
Sodium percarbonate granules (17%), TAED particle (5%), water glass (4%) and enzyme granulate (1.5%) mix in rotary drum with above-mentioned powder.
C25E3 tensio-active agent (3%), froth suppressor (1%) and spices (0.5%) are sprayed in the rotary drum, and 3% moisture content is that 6% dehydration A type zeolite adds in the rotary drum as mobile agent.
EXAMPLE III
Prepare laundry detergent composition (its percentage ratio is the percentage ratio of composition total weight) according to following processing step:
Spray-dired powder (45%), nonionic carrier granule (20%), tensio-active agent cream (8%) and water (2%) mix in twin screw extruder together and extrude.
In thermopnore be that 10% dehydration A type zeolite adds in the extrudate with moisture content.
Then, sodium percarbonate granules (15%), enzyme granulate (1.5%) and TAED particle (4%) are done in rotary drum and mixed, and be last, and C45E7 nonionogenic tenside (3%), froth suppressor (1%) and spices (0.5%) are sprayed in rotary drum.
EXAMPLE IV
Prepare automatic bowl with detergent composition (its percentage ratio is the percentage ratio of composition total weight) according to following processing step:
Yellow soda ash (5%), water glass (16%), Trisodium Citrate (42%), polymkeric substance (4%), TAED (3%), sodium percarbonate granules (10%), enzyme granulate (2%) and sodium sulfate (13%) mix in rotary drum.
Nonionogenic tenside (1%) is sprayed onto in the rotary drum.Dehydration A type zeolite (moisture content is 10%) adds in the rotary drum as flow aids.
EXAMPLE V
Prepare following laundry detergent composition:
Surfactant agglomerates
％
A type zeolite 16
MAP type zeolite 16
C24AS5 5
C24E5 10
Moisture 3
Do and mix
％
Percarbonate 18
TAED 5
Water glass 5
Yellow soda ash 5
Complexing agent 0.5
Enzyme 3
Whitening agent 0.2
Suds suppressor 3
Spraying
％
C24 5
Spices 0.3
Dusting (dusting) (flow aids)
％
MAP type zeolite 5
(moisture content is 5%)
Prepare surfactant agglomerates by in Eirich mixing tank RV02, anion surfactant cream, alcohol ethoxylate and detergent powder being mixed and carry out agglomeration.The agglomerate process screening that obtains, and directly mix in rotary drum with other exsiccant component, wherein nonionogenic tenside sprays into spices.Then the product that obtains is sent in the Loedige FM Ploughshare mixing tank, carried out dusting at this with MAP type zeolite and isolate (dust).
Claims (7)
1. the preparation method of granular detergent composition, comprise size of particles at the percarbonate of 250-900 micrometer range with will contain moisture content and join step in the detergent powder particle, the wherein essentially no various grain fractions of granular detergent composition by the spraying drying preparation less than the powder flowbility auxiliary agent of 15% partially hydrated crystalline sodium aluminosilicate.
2. according to the process of claim 1 wherein that described silico-aluminate is selected from A type zeolite or X type zeolite, and moisture content is 5%-12%.
3. according to the process of claim 1 wherein that described percarbonate particles used the inorganic salt material coating before adding composition.
4. according to the method for one of claim 1-3, the detergent powder of wherein said adding percarbonate particles and flow aids mixes by doing, agglomeration, press, the combination of micro encapsulation, extruding, grinding or described the whole bag of tricks is prepared.
5. according to the method for claim 4, comprising step:
A) the preparation tap density is at least the granulated detergent powder that contains percarbonate of 650g/l;
B) nonionogenic tenside is sprayed onto on the described particle powder;
C) product of step b) is mixed with the powder flowbility auxiliary agent that contains described partially hydrated crystalline zeolite.
6. according to the process of claim 1 wherein that the powder flowbility auxiliary agent also contains hydrophobic silicon oxide in addition.
7. according to the method for claim 6, wherein hydrophobic silicon oxide is that average primary particle size is the fumed silica of 7-25 millimicron.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP93870140 | 1993-07-14 | ||
| EP93870140.6 | 1993-07-14 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1130920A CN1130920A (en) | 1996-09-11 |
| CN1102954C true CN1102954C (en) | 2003-03-12 |
Family
ID=8215369
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94193328A Expired - Fee Related CN1102954C (en) | 1993-07-14 | 1994-07-13 | Percarbonate bleach particles coated with partially hydrated crystalline aluminosilicate flow aid |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0708818A4 (en) |
| JP (1) | JPH09500171A (en) |
| CN (1) | CN1102954C (en) |
| AU (1) | AU7361594A (en) |
| BR (1) | BR9407276A (en) |
| CA (1) | CA2167161C (en) |
| WO (1) | WO1995002672A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023028824A1 (en) | 2021-08-31 | 2023-03-09 | 万华化学集团股份有限公司 | Polymer composite, preparation method therefor and application thereof |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9317180D0 (en) * | 1993-08-18 | 1993-10-06 | Unilever Plc | Granular detergent compositions containing zeolite and process for their preparation |
| GB9504912D0 (en) * | 1995-03-10 | 1995-04-26 | Ind Zeolite Uk Ltd | Zeolites |
| DE19541755A1 (en) * | 1995-11-09 | 1997-05-15 | Henkel Kgaa | Detergent containing amorphous alkali silicates and peroxy bleach |
| DE19600018A1 (en) | 1996-01-03 | 1997-07-10 | Henkel Kgaa | Detergent with certain oxidized oligosaccharides |
| DE19701896A1 (en) * | 1997-01-21 | 1998-07-23 | Clariant Gmbh | Granular secondary alkane sulfonate |
| CA2838224A1 (en) * | 2011-06-29 | 2013-01-03 | Basf Se | Modified aminocarboxylates with improved storage stability and processability |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4329244A (en) * | 1979-06-21 | 1982-05-11 | Interox (Societe Anonyme) | Particles of stabilized peroxygenated compounds, process for their manufacture, and composition containing such particles |
| US4391727A (en) * | 1975-12-15 | 1983-07-05 | Colgate Palmolive Company | Non-caking bleach containing molecular sieve zeolite |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3951838A (en) * | 1973-10-10 | 1976-04-20 | E. I. Du Pont De Nemours And Company | Silica sol stabilizers for improving the stability of sodium percarbonate in solid bleaches and detergents |
| US4274975A (en) * | 1974-03-11 | 1981-06-23 | The Procter & Gamble Company | Detergent composition |
| US4055505A (en) * | 1974-07-12 | 1977-10-25 | Colgate-Palmolive Company | Activated percompound bleaching compositions |
| ZA767170B (en) * | 1975-12-15 | 1978-07-26 | Colgate Palmolive Co | Detergent composition and method for use |
| DE2652488C3 (en) * | 1976-11-18 | 1983-03-10 | Kali-Chemie Ag, 3000 Hannover | Process for the production of granules from zeolites and oxygen-releasing compounds |
| AT352241B (en) * | 1977-04-22 | 1979-09-10 | Henkel Kgaa | POWDERED, PHOSPHATE-FREE TEXTILE DETERGENT |
| DE2902236A1 (en) * | 1978-01-25 | 1979-07-26 | Kao Corp | BLEACHING AGENT |
| US4215990A (en) * | 1978-04-14 | 1980-08-05 | Purex Corporation | Peroxygen bleaching and laundering compositions |
| IE51848B1 (en) * | 1980-11-06 | 1987-04-15 | Procter & Gamble | Bleach activator compositions,preparation thereof and use in granular detergent compositions |
| GB9007999D0 (en) * | 1990-04-09 | 1990-06-06 | Unilever Plc | Particulate bleaching detergent composition |
| GB9113674D0 (en) * | 1991-06-25 | 1991-08-14 | Unilever Plc | Detergent compositions |
-
1994
- 1994-07-13 CA CA002167161A patent/CA2167161C/en not_active Expired - Fee Related
- 1994-07-13 BR BR9407276A patent/BR9407276A/en not_active IP Right Cessation
- 1994-07-13 CN CN94193328A patent/CN1102954C/en not_active Expired - Fee Related
- 1994-07-13 AU AU73615/94A patent/AU7361594A/en not_active Abandoned
- 1994-07-13 JP JP7504699A patent/JPH09500171A/en not_active Ceased
- 1994-07-13 EP EP94922546A patent/EP0708818A4/en not_active Withdrawn
- 1994-07-13 WO PCT/US1994/007876 patent/WO1995002672A1/en not_active Application Discontinuation
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4391727A (en) * | 1975-12-15 | 1983-07-05 | Colgate Palmolive Company | Non-caking bleach containing molecular sieve zeolite |
| US4329244A (en) * | 1979-06-21 | 1982-05-11 | Interox (Societe Anonyme) | Particles of stabilized peroxygenated compounds, process for their manufacture, and composition containing such particles |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023028824A1 (en) | 2021-08-31 | 2023-03-09 | 万华化学集团股份有限公司 | Polymer composite, preparation method therefor and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0708818A1 (en) | 1996-05-01 |
| JPH09500171A (en) | 1997-01-07 |
| WO1995002672A1 (en) | 1995-01-26 |
| AU7361594A (en) | 1995-02-13 |
| CN1130920A (en) | 1996-09-11 |
| CA2167161C (en) | 1999-11-09 |
| EP0708818A4 (en) | 1997-05-14 |
| CA2167161A1 (en) | 1995-01-26 |
| BR9407276A (en) | 1996-10-01 |
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