CN1139451A - Granular detergent composition comprising a low bulk density component - Google Patents
Granular detergent composition comprising a low bulk density component Download PDFInfo
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- CN1139451A CN1139451A CN 94194702 CN94194702A CN1139451A CN 1139451 A CN1139451 A CN 1139451A CN 94194702 CN94194702 CN 94194702 CN 94194702 A CN94194702 A CN 94194702A CN 1139451 A CN1139451 A CN 1139451A
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- weight
- granular detergent
- component
- anion surfactant
- acid
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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
- 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
- C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
Abstract
The present invention is concerned with a granular detergent component having a bulk density of less than 400 g/l comprising from 20 % to 50 % by weight of aluminosilicate; and optionally up to 50 % by weight of a co-filler; and 0.05 % to 2 % by weight of anionic surfactant, especially is C14-C20 alkyl sulphate. The low bulk density component is preferably mixed with other components such as percarbonate, silicate, layered silicate, carbonate, bicarbonate, sesquicarbonate, sulphate, citrate or mixtures of these.
Description
The present invention relates to the granular detergent component that apparent density is lower than 400g/l, it contains anion surfactant, zeolite and optional auxiliary packing.The invention still further relates to the granular laundry detergent composition, it contains the component of low bulk density, also contains high-density particulate component in addition, preferably contains percarbonate.
Use in the common process method of washing composition at the preparation granular laundry, use the spraying drying aqueous slurry to go to prepare the quite wide grain fraction of apparent density scope, apparent density depends on multiple factor, as is used for the components selection and the content of slurry, and the processing condition in the spray-drying tower.Yet spray-dired product itself does not have sufficiently high apparent density as current granulated detergent.
Found out that granular laundry is to improve the apparent density of finished product with the recent tendency of washing composition.This high apparent density is very convenient concerning the human consumer, and owing to for example reduced the packing needs, also has the benefit in the environmental protection.This density can reach by each detergent component that preparation and combination have high apparent density.
Spray-dired powder is a known technology with mixing of other grain fraction, hereinafter will quote some examples as proof.
The EPA289312 that announced on November 2nd, 1988 discloses the spray-dired method of aqueous slurry of a kind of carbonate containing and crystal growth modifier.Optional aftertreatment comprises with the nonionogenic tenside spraying and with other component that comprises SYNTHETIC OPTICAL WHITNER, bleach activator, enzyme etc. and mixing.Described component requires to have the organism of high level to exist, especially anion surfactant (in this application, the tensio-active agent weight content at least 5%).
The WO9303131 that on February 18th, 1993 announced discloses a kind of spray-dired component, and it comprises alkyl sulfuric ester (salt), silico-aluminate and silicate.Also describe some ratios and the processing conditions of component in detail.The component that spraying drying is crossed is mixed with SYNTHETIC OPTICAL WHITNER, bleach activator, froth suppressor, enzyme etc. again, and this application has been considered to replace linear alkylbenzene sulfonate (LAS) by the alkyl sulfuric ester of readily biodegradable (salt) more.Described component spraying drying be difficulty thereby require to quote special processing parameter such as low temperature spray drying.
The current desirable high apparent density component of granulated detergent as carbonate, percarbonate and silicate, can not make the detergent formulation teacher have very big handiness on the finished product apparent density.Yet the component that can cross with high apparent density component blended low bulk density spraying drying can show the handiness that improves greatly aspect the desired final product density reaching.This handiness results from the possibility that changes parameter, as the composition of aqueous slurry before the spraying drying, parameter and the low bulk density component of use and the ratio of high apparent density component of drying process with atomizing process.
The purpose of this invention is to provide the spray-dried component that a kind of apparent density is lower than 400g/l.It contains the organism of low levels.Organism helps to produce the spray-dried component with good physicals, and can make the component apparent density of making low but quality is reduced.Selection is used for the tensio-active agent that organism of the present invention is a low levels, and preferred weight content is at the anion surfactant of 0.05%-2%, at least 30 ℃ of its Kraft points (Krafft Point).
Second purpose of the present invention provides the final composition of the spray-dried component that contains low bulk density and other higher bulk density component.
The 3rd purpose of the present invention provides the low spray-dried component of water-content.And this component moisture absorption capacity height.Described component has the stability in storage of improved percarbonate when mixing with the particle percarbonate, especially under wet condition.Detailed Description Of The Invention
At first the present invention relates to the granular detergent component that apparent density is lower than 400g/l, it comprises the silico-aluminate and the optional auxiliary packing up to 50% weight of 20%-50% weight.Grain fraction of the present invention further comprises the anion surfactant of 0.05%-2% by weight.Anion surfactant can use individually, also can mix use with non-anion surfactant.Anion surfactant, or the mixture of negatively charged ion and non-anion surfactant (if there is), its Kraft point (Krafft Point) is greater than 30 ℃.Preferred anionic tensio-active agent amount is 1%-1.8%, and is C
14-C
20Alkyl sulfuric ester salt.
Preferred auxiliary packing is to be selected from carbonate, but supercarbonate, sesquicarbonate, vitriol, Citrate trianion or and the hydrated inorganic salt of mixture, and amount is counted 10-30% by the weight of low-density fraction.
Secondly, the component of low bulk density can be mixed with other component.This grain fraction preferably contains those components that is selected from silicate, layered silicate, carbonate, supercarbonate, sesquicarbonate, vitriol, Citrate trianion or its mixture.Preferably the content that exists in composition of spray-dried component is 10%-60% by weight, and exist the grain fraction that respectively has greater than 800g/l, when grain fraction mixed in composition, its content was by weight up to 50%, preferred 10-40%.
The third aspect, composition contain the apparent density particle percarbonate of 800g/l at least in addition.The content of percarbonate is preferably greater than 3% of final composition weight when it exists, and by more preferably 5%-50% of final composition weight.In the composition that contains a kind of like this percarbonate, handle spray-dired component in case make wherein total water and the ratio of sial salt be no more than 1: 3, preferably be no more than 1: 5.
Hereinafter will do more detailed the explanation to various detergent components.Tensio-active agent
As each component of low bulk density component of the present invention is that effective tensio-active agent is that those have Kraft point (Krafft) greater than 30 ℃ tensio-active agent.
The water-soluble salt of higher fatty acid, i.e. " soap class " is effective anion surfactant in the present composition.It comprises alkali metal soap such as sodium, potassium, ammonium and contains the alkylammonium salt of the higher fatty acid of about 24 carbon atoms of about 8-, about 18 carbon atoms of preferably about 12-.The soap class can be made by the direct saponification of fat and oil or by the neutralization of free fatty acids.Special sodium and the sylvite that effectively derives from the mixed fatty acid of Oleum Cocois and Tallow, beef, i.e. sodium or potassium Tallow, beef and Oleum Cocois soap.These soap classes with at least 12 carbon atoms of chain length are useful especially in the present invention, because their Kraft point (Krafft Point) is in the scope that requires.
Useful anion surfactant also comprises water-soluble salt, and the salt of preferred organic sulfating reaction product has alkyl and the sulfonic acid or the sulfate group of about 20 carbon atoms of about 10-, the salt of described salt preferred as alkali, ammonium and alkanol ammonium in the tool molecular structure.This synthetic surfactant example is sodium alkyl sulfate and potassium, especially by sulfation higher alcohols (C
8-C
18Carbon atom) higher alcohols that for example produces from the glyceryl ester of reduction Tallow, beef or Oleum Cocois.Alkyl sulfuric ester salt with at least 14 carbon atom chain lengths is useful especially in the present invention, because their Kraft point (Krafft) is in the scope that requires.
Other useful anion surfactant of the present invention comprises and contains 6-20 the carbon atom of having an appointment in the fatty acid group, and contains the water-soluble salt of the α-sulfonated fatty acid ester of 1-10 the carbon atom of having an appointment in the ester group; Contain the 10-20 that has an appointment, a particularly 16-20 carbon atom in the alkyl and contain the alkyl ether sulphate salts of the 1-30 moles of ethylene oxide of having an appointment.
Same effectively also have alkyl to have the sulfonated product of the fatty acid methyl ester of 10-20 carbon atom.C preferably
16-18Sulfonic acid methyl ester (MES).
The particularly preferred tensio-active agent of the present invention comprises: primary and secondary alkyl sulfuric ester salt; The coconut alkyl glyceryl ether sulfonate; Alkyl ether sulphate salts, wherein moieties contains about 16-18 carbon atom and the about 1-4 of average degree of ethoxylation wherein; The alkene or the alkane sulfonate that contain about 16 carbon atoms; And sulfonic acid methyl ester.
Preferred nonionic surfactants is the fatty alcohol that contains 8-22 carbon atom, or the straight or branched configuration, with the water-soluble condensation product of every mol of alcohol 4-25 moles of ethylene oxide.Particularly preferably be the alcohol with the alkyl that contains about 9-15 carbon atom and the condensation product of the about 4-25 moles of ethylene oxide of every mol of alcohol; And the condensation product of propylene glycol and oxyethane.
The nonionogenic tenside of an other class contains general formula
RO (C
nH
2nO)
tz
xThe alkyl polyglucoside compound, Z is the part from glucose in the formula; R is the saturated hydrophobic alkyl group that contains 12-18 carbon atom; T from 0 to 10 and n is 2 or 3; X is by 1.3 to 4, and this compound contains the alkyl polyglucoside that is lower than 10% unreacted Fatty Alcohol(C12-C14 and C12-C18) and is lower than 50% short chain.Such compound and the purposes in detergent composition thereof are described among the EP-B0070074,0070077,0075996 and 0094118.
Also have an other class nonionogenic tenside, comprise polyhydroxy fatty acid amide, it is produced by fatty acid ester and the reaction of N-alkyl polyhydroxy amine.Preferred amines is N-(R1)-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 of making polyhydroxy fatty acid amide is described among the WO926073 that announced on April 16th, 1992.This piece application has illustrated the preparation of polyhydroxy fatty acid amide in the presence of solvent.
The N-methylglucosamine is and C in the most preferred embodiment of the present invention
12-C
20The methyl ester reaction.
Be used for a class ionic surfactant pack of the present invention and draw together ethylene oxide condensate with hydrophobic part, it can make tensio-active agent have on average hydrophilic-oleophylic (HLB) equilibrium value (HLB) in the scope of 8-17, preferred 9.5-13.5, more preferably 10-12.5.Hydrophobic (oleophylic) part with regard to its character can be aliphatic series also can be aromatics and also be easy to be conditioned with the length of the polyoxyethylene group of any special hydrophobic grouping condensation and produce water-soluble cpds, it has the balanced degree between desired hydrophilic and hydrophobic part.
The particularly preferred nonionogenic tenside of this class is the C that every mol of alcohol contains the 3-9 moles of ethylene oxide
9-C
15The primary alconol b-oxide, particularly every mol of alcohol contains the C of 6-9 moles of ethylene oxide
13-C
15Primary alconol and every mol of alcohol contain the C of 3-5 moles of ethylene oxide
11-C
15Primary alconol.
Having Kraft point (Krafft Point) is lower than 30 ℃ tensio-active agent and is not excluded outside the present invention, but they should get up to use with the combinations-of surfactants of high Kraft point in the surfactant system of different grades, and the Kraft point that makes the total surfactant system thus is above 30 ℃.
The anion surfactant of the low Kraft point that uses by this way comprises sodium alkyl benzene sulfonate and potassium, and wherein alkyl contains about 9 to about 15 carbon atoms, the straight or branched configuration, for example at US2,220,099 and 2,477, the tensio-active agent of type described in 383.Useful especially is the line style linear alkylbenzene sulfonate, wherein the about 11-13 of carbon atom mean number of alkyl, is called for short C
11-C
13LAS.
The tensio-active agent of other kind comprises as follows:
Effectively anion surfactant comprises R
4R
5R
6R
7N
+X
-The water-soluble quaternary ammonium compound of form, wherein R
4Carbonatoms is 10-20, preferred 12-18, and R
5, R
6And R
7Be respectively C
1-C
7Alkyl, preferable methyl; X
-Be negatively charged ion, muriate for example.The example of said trimethyl ammonium compound comprises C
12-C
14Alkyl trimethyl ammonium chloride and methylsulfuric acid ester coconut alkyl trimethyl ammonium.
Semi-polar nonionic surfactants comprises the water soluble oxidized scar, and it contains moieties and 2 hydroxyl alkyls that are selected from alkyl and contain about 3 carbon atoms of 1-of about 10-18 carbon atom; The water soluble oxidized phosphine, it contains moieties and 2 hydroxyalkyls that are selected from alkyl and contain about 1-3 carbon atom of about 10-18 carbon atom; And water-soluble sulfoxide, it contains the moieties of 10-18 the carbon atom of having an appointment and is selected from alkyl and the hydroxyalkyl part of 1-3 the carbon atom of having an appointment.
Amphoterics comprises the derivative of aliphatic derivatives aliphatic series or the heterocycle second month in a season and tertiary amine, aliphatic series part or straight chain or side chain in the amine, and a kind of aliphatic substituting group wherein contains about 8-18 carbon atom and at least a aliphatic substituting group contains anionic water-solubilizing group.
Zwitterionics comprises the derivative of aliphatic quaternary amine Phosphonium, and sulfonium compound, and wherein a kind of aliphatic substituting group contains about 8-18 carbon atom.
Low bulk density component of the present invention comprises other detergent component, and these components are selected from the general various possible component of cloth-washing detergent.Particle contains the silico-aluminate of 20-50% by weight, up to 50% by weight auxiliary packing, and other optional component; Preferred ingredient will be described below.
Although all can use in the silico-aluminate ion-exchange material scope, the preferably aluminosilicate natrolite, its unit structure cell general formula is
Na
z[(AlO
2)
z(SiO
2)
y] xH
2Z and y are at least 6 in the O formula; The mol ratio of z and y is that 1.0-0.5 and x are at least 5, preferred 7.5-276, more preferably 10-264.Alumino-silicate materials is xln hydrated form and preferred, and containing combination water is 10%-28%, more preferably 16%-22%.
Another feature of above-mentioned silico-aluminate ion conversion material is the particle size diameter of 0.1-10 micron, preferred 0.2-4 micron.Term " particle size diameter " represents in the present invention that analytical technology is routinely for example utilized the microscopic measurement method of scanning electronic microscope or by means of the mean particle diameter of laser degree instrumentation amount specify ion exchange material.Another feature of aluminosilicate ion exchange material is its calcium ion-exchanged capacity, presses moisture-free basis and calculates, and the silico-aluminate of 1g is equivalent to the CaCO of 200mg at least
3The water hardness is general in the scope of 300mg eq./g-352mg eg./g.Another feature of aluminosilicate ion exchange material of the present invention is that its calcium ion exchange rate is at least the normal CaCO of 130mg
3/ liter/minute/(g/l) [2 grain Ca of silico-aluminate (moisture-free basis)
++/ gpm/(gram/gallon)], generally be positioned at 130mg equivalent CaCO
3/ liter/minute/(grams per liter) [2 grains/gpm/(gram/gallon)]-normal CaCO of 390mg
3/ liter/minute/(grams per liter) [6 grains/gpm/(gram/gallon)], based on calcium ion hardness.
The calcium exchange velocity that is used for the best silico-aluminate demonstration of washing assistant is at least the normal CaCO of 260mg
3/ liter/minute/(grams per liter) [4 grains/gpm/(gram/gallon)].
That be used to implement aluminosilicate ion exchange material of the present invention and be bought from the market and can be the material of natural generation, but preferably obtain with synthetic method.The method of producing aluminosilicate ion exchange material is described in US3, in 985,669.The commercially available trade mark of preferred synthetic crystalline silica-aluminate ion-exchange material that the present invention is suitable for has zeolite A, zeolite B, X zeolite, zeolite HB, zeolite MAP and composition thereof.In optimum implementation, the crystalline silica-aluminate ion-exchange material is zeolite A and has general formula
Na
12[(AlO
2)
12(SiO
2)
12] .xH
2X is 20-30 in the O formula, especially 27.General formula Na
88[(AlO
2)
86(SiO
2)
10] 276H
2The X zeolite of O also is suitable, also has general formula Na
6[(AlO
2) (SiO
2)
6] 7.5H
2The zeolite HS of O.
Suitable auxiliary packing can include but not limited to the polycarboxylate of alkaline carbonate, supercarbonate, sesquicarbonate, vitriol, monomeric polycarboxylate, homopolymerization or copolymerization, wherein poly carboxylic acid comprises at least two kinds by being not more than two carboxyls that carbon atom is separated from one another, and organic phosphonate and amino alkylidenyl gather (alkylene phosphonic acids salt) and any aforesaid mixture thereof.
So-called " salt hydrate " means this salt is to exist with the state that absorbs additional water by hydration.That is to say this salt or exist or exist with the part hydrated form with anhydrous form.
Preferred builder system is that macromolecule organic no boron compound and any is preferably biodegradable.
Carboxylate salt washing assistant suitable water-soluble monomer or oligomeric comprises lactic acid, ethanol grandson (glycolic acid) and as belgian patent number 831,368,821,369 and 821,370 described ether derivants.The polycarboxylate that contains two kinds of carboxyls comprises the water-soluble salt of Succinic Acid, propanedioic acid, (ethylenedioxy) oxalic acid, toxilic acid, diglycollic acid, Tartaric acid, tartronic acid and fumaric acid; and German prospectus 2446686 and 2; 446678 and U.S3; 935,257 ether carboxylates of describing and the belgian patent number 840623 sulfinyl carboxylate salts of describing.The polycarboxylate that contains three kinds of carboxyls is particularly including water-soluble citrate, aconitate (aconitrate) and citraconate and succinate such as English Patent 1,379,241 described carboxymethoxyl succinates, English Patent 1,389,732 described newborn oxygen base succinates (lactoxysuccinates) and Holland's application 7205873 described amino-succinic acid salt, and oxidation polycarboxylate material such as English Patent 1,387,447 described 2-oxa-s-1,1,3-tricarballylic acid salt.
The polycarboxylate that contains 4 carboxyls comprises English Patent 1,261,829 described oxidation disuccinates, 1,1,2,2-ethane tetracarboxylic acid hydrochlorate, 1,1,3,3-propane tetracarboxylic acid salt and 1,1,2,3-propane tetracarboxylic acid salt.Contain the substituent polycarboxylate of sulfo group and comprise English Patent 1,398,421,1,398,422 and the U.S patent No. 3,936,448 described sulfosuccinates, and British Patent No. 1,439,000 described sulfonation pyrolysis Citrate trianion.
Preferably poly-in addition carboxylic acyl salt washing assistant is ethylene diamine-N, N
1The ammonium salt of-two butyric acid (EDDS) or its basic metal, alkaline-earth metal, ammonium or its replacement or its mixture.
Alicyclic ring and heterocycle polycarboxylate comprise that pentamethylene one is suitable, suitable, suitable-the tetracarboxylic acid hydrochlorate, cyclopentadiene thing pentacarboxylic acid salt, 2,3,4,5-tetrahydrofuran (THF)-suitable, suitable, along 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 such as sorbyl alcohol, mannitol and Xylitol.The aromatics polycarboxylate comprises mellitic acid, 1,2,4,5-pyromellitic acid and British Patent No. 1,425,343 disclosed phthalic acid derivatives.
From the above mentioned, preferred polycarboxylate is the highest hydroxycarboxylate who contains three carboxyls of per molecule, and reasonable is Citrate trianion.
The mixture of female acid of monomer or oligomeric polycarboxylate sequestrant or its and its salt, for example citric acid or Citrate trianion/citric acid mixture can consider that equally excellent is the component of the builder system of detergent composition of the present invention.
Other suitable water-soluble organic salt is the poly carboxylic acid or its esters of homopolymerization or copolymerization, and wherein poly carboxylic acid comprises at least two kinds of carboxyls that are not more than two carbon atoms separated from one another.The polymkeric substance of back one type is disclosed in GB-A-1, in 596,756.The example of described salt be MWt 2000-5000 polyacrylate and with the multipolymer of maleic anhydride, the molecular weight of described multipolymer is 20,000-70,000, especially about 40,000.This washing assistant macromolecular material is identical with the macromolecular material of making adhesive material and coated material as mentioned above.The normally used content of these materials is counted 0.5-10% by composition weight, more preferably 0.75%-8%, most preferably 1%-6%.
Organic phosphonate and amino alkylidenyl poly-(alkylene phosphonic acids salt) comprise basic metal ethane 1-alkyl diphosphonate, nitrilo trimethylene phosphonic salt, ethylene diamine tetramethylene phosphonic acid salt and diethylenetriamine, methylene phosphonic acid salt, though these materials are more not preferred at the phosphorus compound that requires composition during for mnm..
The apparent density of the component that the present invention is main is lower than 400g/l and preferred by spray drying method for preparation, and the technology of powder also can be used though other preparation low density flows.Following spraying drying route, preparation contains the solid aqueous slurry.Make slurry under high pressure send drying tower with pump to through atomizing nozzle then, superfluous water is excluded in drying tower, produces flowable powder.Cross spray resulting powder, especially nonionogenic tenside with liquid ingredient again, described powder had the capacity of high this tensio-active agent of absorption before it loses good flowability.
Can use and can mix the example of other component in the low bulk density component in the washing composition of laundry usefulness will be hereinafter illustrated in " other optional components ".Percarbonate bleach
In Cui embodiment of the present invention, composition will comprise percarbonate bleach, normally with the form of sodium salt, in washings as the source of alkaline hydrogen peroxide.The content that this percarbonate mixes is usually counted 3%-50% by the weight of total composition, comparative optimization be 5%-30%, 8%-25% most preferably.
SPC-D is a kind of 2Na of being equivalent to that has
2CO
33H
2O
2The addition compound of general formula can be used as crystal and has bought from the market.Amount heavy metal chelant such as EDTA are hanged down in all containing that great majority have been bought from the market, 1-hydroxy ethylene 1, and 1-di 2 ethylhexyl phosphonic acid (HEDP) or amino-phosphonate, sequestrant adds in process for making.For detergent composition of the present invention, percarbonate is added in the detergent composition and not protection in addition, but make the coated form that this composition preferably utilizes material.Preferred coating is the mixing salt of alkali metal sulfates and carbonate.This coating and coating processes had before had been described in 1977 the 3 bright GB-1 that licensed to Interox on the 9th, in 466,799.The weight ratio of mixing salt coated material and carbonate places 1: 200-1: in 4 the scope, reasonable is 1: 99-1: 9, preferably 1: 49-1: 19.Preferred version is, mixing salt is sodium sulfate and yellow soda ash, and its general formula is Na
2SO
4.n.Na
2CO
3, wherein n is 0.1-3, preferred n is 0.3-1.0, most preferably is 0.2-0.5.Preferred coating materials is a Citrate trianion in addition, or the mixture of Citrate trianion and vitriol or carbonate.The water soluble surfactant active also can be used as coated material and uses.
In addition a kind of, SiO
2: Na
2O ratio is 1.6: 1-3.4: 1, preferred 2.8: although 1 water glass is a preferred coating materials not too, can be used as the aqueous solution and use, the content that can obtain silicate solid by percarbonate weight is 2%-10%, (being generally 3%-5%).Magnesium Silicate q-agent also can be included in the coating.But silicate can not be as main coating-forming agent, in order that keep good disperse properties.If present, the content of silicate in coating should be lower than 3% by percarbonate weight.
The particle size range of crystal percarbonate is at 150 microns-1500 microns, and preferably at 250 microns-1000 microns, its median size is at 500 microns-700 microns.
Can control by the sequestrant that contains in the reaction mixture although be used for making the heavy metal that the yellow soda ash of percarbonate exists, percarbonate needs still to prevent that heavy metal from existing as impurity in other component of product.The particle water glass
Suitable silicate is that those have SiO
2: Na
2The O ratio range is at the silicate of 1.6-3.4, so-called SiO
2: Na
2O ratio is that the amorphous silicate of 2.0-2.8 is preferred.These materials can add on the each point in production process, as with the form of the aqueous solution condensing agent as other solid ingredient, perhaps when silicate itself is particle state, just are added in other particle component of composition as solid.
In the silicate scope, best material is the crystal lamina sodium silicate, and its general formula is
NaMSi
xO2
X+1YH
2M is sodium or hydrogen in the O formula, and x is 1.9-4-individual numerical value, and y is the numerical value of 0-20.The lamellated water glass of such crystal has been disclosed among the EP-A-0164514, and its preparation method is disclosed among DE-A-3417649 and the DE-A-3742043.For the present invention, in above-mentioned general formula the value of x 2,3 and 4, preferred 2.Preferred M be sodium and y be 0 and the preferred embodiment of this general formula comprise the Na of α, β, γ and δ type
2Si
2O
5These materials can have been bought as NaSKS-11 and NASKS-6 respectively from Hoechst AG FRG.Most preferred material is δ-Na
2Si
2O
5, (NaSKS-6).Crystal stratiform carbonate both can have been done also can the condense solid ingredient form of other component of mixed solid form and add.
By other component in the dry type adding composition, comprise carbonate, supercarbonate, sesquicarbonate, vitriol, Citrate trianion or all mixtures described above with particle form.In addition, the form that some components can partic acid adds, for example citric acid.Being appreciated that such particle can be made of a kind of component separately, also can be the composite particles (co-granulates) of two kinds of components in the various ingredients.The component that contains additional surfactants
But the grain fraction that contains the significant quantity tensio-active agent also dry type adds in the final composition.The desirable sheet of this class surfactant granules form of the present invention, coccoid, marume, slice, bandlet shape, the preferred particulates shape.Producing this particulate optimal way and be with high active surfactant cream goes the particle diameter of the agglomerate that agglomerating powder (aforesaid, as silico-aluminate, carbonate) and control generated in the qualification of regulation.A kind of method like this comprises mixes with high active surfactant cream the powder of significant quantity in one or more machines (agglomerator); as disc type granule machine, Z-blade mixer or be more preferably single stirrer; as Holland; Lelystad, Schugi (Holland) BV, 29 Chroomstraat, 8211 AS produce; and the Gebruder Lodige Maschinenbau GmbH of Germany; D-4790Paderborn l, Elsenerstrasse7-9, Postfach 2050.Most preferably use high-shear impeller, as Lodige CB (trade mark).
Can use by tensio-active agent weight to contain 50%-100% the high active surfactant cream of preferred 70%-85%.Surfactant system can contain any one group of negatively charged ion, nonionic, positively charged ion, both sexes and zwitterionics, or its mixture.Make paste under sufficiently high temperature to keep pumpable viscosity, be evacuated in the machine with pump, but low temperature to be enough to avoid the degraded of used anion surfactant.50 ℃-80 ℃ paste service temperature is typical.
Made the specially suitable method of surfactant granules describes fully in the EP510746 that announced on October 28th, 1992 by high active surfactant cream.
Term median size by the present invention's definition is to be screened into many grades (5 grades typically) by the sample that makes composition on a series of Tyler meshs to calculate.The weight grade that obtains is thus mapped to the aperture of sieve.Measure median size and be the aperture that has 50% by weight sample to pass through.The particle median size that contains tensio-active agent for the present invention is lower than 480 microns, preferably is lower than 400 microns, most preferably is lower than 350 microns.Other optional components
Detergent composition of the present invention can comprise anti redeposition agent and soil-suspending agent, bleach activator, white dyes, stain remover, froth suppressor, enzyme, fabric softener, spices and dyestuff arbitrarily, and other known in cloth-washing detergent effective component.
Suitable antiredeposition of the present invention and soil-suspending agent comprise fiber derivative and methylcellulose gum, the poly carboxylic acid of carboxymethyl cellulose and Natvosol and homopolymerization or copolymerization or its salt.Such polymkeric substance comprises the multipolymer of maleic anhydride and ethene, methylvinylether or methacrylic acid, and maleic anhydride constitutes multipolymer and is at least 20% mole.The use content of common this material is counted 0.5%-10% by the weight of composition, comparative optimization 0.75%-8%, most preferably 1%-6%.
Other useful macromolecular material is polyoxyethylene glycol, and particularly those molecular weight are 1000-10000, more preferably 2000-8000 and most preferably about 4000 polyoxyethylene glycol.Used content is 0.20%-5% by weight, is more preferably 0.25%-2.5%.These polymkeric substance and above-mentioned homopolymerization and copolymerization polycarboxylate are effective for the maintenance, the deposition of fibrous residue and the detergency ability of clay that improve whiteness, protein and the oxidable dirt in the presence of transition metal impurity.
In the preferred embodiment of the invention, composition contains peroxyacid bleach precursor.Solid peroxygen acid blanching agent precursor of the present invention comprises the precursor that contains one or more N-or O-acyl group, and this precursor can be selected from very wide classification.
Suitable classification comprises the derivative of the acrylated of acid anhydrides, ester, imide and imidazoles and oxime, and the example of useful matter is disclosed among the GB-A-1586789 in these class scopes.Most preferred kind is as disclosed ester class among the GB-A-836988,864,978,1147871 and 2,143231 with as GB-A-855735 and 1246338 disclosed imides.
Particularly preferred precursor compound is a general formula
N, N, N
1, N
1The compound of tetra-acetylatedization, x is an integer between 0 or 1 and 6 in the formula.
Example comprises the tetra-acetylated methylene diamine (TAMD) of x=1, the tetra-acetylated ethylene diamine (TAED) of x=2 and the tetra-acetylated hexamethylenediamine (TAHD) of x=6.These and similar compound are described among the GB-A-907356.Most preferred peroxyacid bleach precursor is TAED.
Other activator is a peroxybenzoic acid precursors, as benzoyloxy benzene sulfonate (BOBS) and benzoyl caprolactam.
Most preferably the content of peroxyacid bleach precursor existence is pressed composition weight meter at least 0.5%.Preferred 100 microns-1500 microns of the grain diameter of peroxyacid bleach precursor.
These peroxyacid bleach precursors can part be crossed acid substitution by ready-formed, as N, the nonyl acid amides (NAPAA) of N-phthalyl amido peroxyacid (PAP), peroxide hexanodioic acid, 1,2 diperoxy dodecandioic acid (DPDA) and TMA (TriMethylAmine) propenyl imino-peroxide mellitic acid (TAPIMA).Other bleach precursor comprises glycolate (describing) in EP507475; 4h-3,1-benzoxazine-4-ketone; Cation precursor (in EP458396 and EP464880, describing); Carbonic ether activator (in EP475511, describing), NOBS, different-NOBS.
Preferred white dyes is anionic in nature, and the example is 4,4
1-two-(2-diethanolamino-4-anilino-S-triazine-6-base is amino) stilbene-2:2
1Disulfonic acid disodium, 4,4
1-two-(2-morpholino-4-anilino-2-triazine-6-base is amino) stilbene-2:2
1-disulfonic acid disodium, 4,4
1-two-(2,4-hexichol amido-S-triazine-6-base is amino) stilbene-2:2
1-disulfonic acid disodium, 4
1, 4
11-two-(2,4-hexichol amido-S-triazine-6-base is amino) stilbene-2-sulfonic acid list sodium, 4,4
1-two-(2-anilino-4-(N-methyl-N-2-hydroxyethylamino)-2-triazine-6-base is amino) stilbene-2,2
1-disulfonic acid disodium, 4,4
1-two-(4-phenyl-2,1,3-triazole-2-yl) stilbene-2,2 ' disulfonic acid disodium, 4,4
1-two-(2-anilino-4-(1-methyl-2-hydroxyethylamino)-S-triazine-6-base is amino) stilbene-2,2
1Disulfonic acid disodium and 2-(Stilbyl-4
11-(bitter edible plant is also-1
1, 2
1: 4,5)-1,2,3-triazoles-2
11-sodium sulfonate.
Useful stain remover is conventional terephthalic acid and ethylene glycol and/or propylene glycol unit multipolymer or the terpolymer with the various forms arrangement in the present composition.The example of this base polymer be disclosed in common transfer US4116885 and 4711730 and European publication application number 0272033 in.Polymkeric substance by EP-A-0272033 the best has general formula
(CH
3(PEG)
43)
0.75(POH)
0.25(T-PO)
2.8(T-PEG)
0.4] T (PO-H)
0.25((PEG)
43CH
3)
0.75Wherein PEG is-(OC
2H
4) O-, PO is (OC
3H
6O) and T be (pCOC
6H
4CO).
Some macromolecular material such as common MWt5000-20000, the polyvinylpyrrolidone of preferred 10000-15000 can form useful reagent aspect the transfer that prevents unsettled dyestuff between fabric in washing process.
Ren Xuan detergent composition component is a froth suppressor in addition, and the mixture of lifting siloxanes and silicon-dioxide-siloxanes is the example explanation.Siloxanes is generally represented with alkylating polysiloxane, and silicon-dioxide generally uses with powder type; Enumerate various types of silicon-dioxide aerosols and xerogel and hydrophobic silicon-dioxide and do the example explanation.These materials are added into as particle, but wherein froth suppressor is preferably introduced with delivery mode in the impermeable carrier of water-soluble or water-dispersion, essentially no surface-active washing composition.Use another kind of method, froth suppressor can be dissolved or be dispersed in the liquid vehicle and sprays application on one or more other the component by spraying.
As noted above, effectively silicone foam control agent can comprise and is included into above the alkylation siloxanes and the solid silica of type.Such mixture is by preparing on the surface that siloxanes is appended to solid silica.Preferred silicone foam control agent with particle size range at 10 nanometers-20 nanometer and specific surface at 50m
2(most preferably trimethyl silicone hydride) silicon-dioxide of hydrophobic silaneization that/g is above is represented, and with molecular weight ranges at about 500-about 200,000 dimethyl silicone fluids is mixed fully, the weight ratio of siloxanes and silanized silica about 1: 1-1: 2.
Preferred silicone foam control agent is disclosed among people's such as Bartollota the U.S 3,933,672.Other effective especially froth suppressor is a self-emulsifying siloxane foams inhibitor, is described among the German patent application DTOS 2,646,126 that announced on April 28th, 1977.A kind of like this examples for compounds is DC0544, can buy from Dow Corning, and it is a kind of multipolymer of siloxanes/dibasic alcohol.
The consumption that above-described froth suppressor is general is counted 0.001%-0.5% by composition weight, preferably is 0.01%-0.1% by weight.
The preferred method that adds comprises or sprays application to the froth suppressor that uses liquid form on one or more main ingredients of composition by spraying, perhaps use another method, froth suppressor is made dispersed particles, and these particles can mix with other solid ingredient of composition then again.Foam properties-correcting agent adds the foam control material that also can comprise other as dispersed particles, as C
20-C
24The high MWt multipolymer of lipid acid, microcrystalline wax and oxyethane and propylene oxide, described in other cases multipolymer will exert an adverse impact for the dispersiveness of matrix.The technology of making this foam modified particles is disclosed among the people's such as Bartolotta that mention previously the US 3,933,672.
Being used for other optional components of the present invention is one or more enzymes.
Preferred enzyme comprises amylase, neutrality and Sumizyme MP, lipase, esterase and the cellulase of having bought from the market, with ordinary method they is added in the composition of washing composition.Suitable enzyme is described in US3, in 519,570 and 3,533,139
Fabric softener also can be added in the detergent composition of the present invention.The kind of these reagent can be inorganic also can be organic.Unit's machine softening agent is with being disclosed in GB-A-1, and the smectic clays in 400,898 illustrates.The organic fabric softening agent comprises as disclosed water-fast tertiary amine among GB-A-1514276 and the E P-B-0011340.
They and single C
12-C
14The combination of quaternary amine is disclosed in EP-B-0026527 and 528.Other useful organic fabric softening agent is as disclosed two long (dilong) chain acid amides among the EP-B-0242919.The additional organic constituent of fabric sofetening system comprises as EP-A-0299575 and the high polyethylene oxide material of 0313146 disclosed molecular weight.
Smectic clays with as do mixing the material that component is added to the prescription remainder-rise, common content range is 5%-15%, even more preferably 8%-12% by weight.The content that organic fabric softening agent such as water-insoluble tertiary amine or two long-chain acid amides material add is 0.5%-5% by weight, usually 1%-3% by weight, and high polyethylene oxide material and the water-soluble cationic material of molecular weight adds content 0.1%-2% by weight, is generally 0.15%-1.5%.When part composition during by spraying drying, can be added to these materials in the aqueous slurry of sending into spray-drying tower, but the dried mixed particle of conduct is more more convenient with their addings in some cases, or as melt liquid it is sprayed application on other solid ingredient of composition.
Embodiment
All in these embodiments per-cent all is weight percent.
Embodiment 1 embodiment 2C16/18 alkyl sulfate salt 1.9 1.6 Wessalith CSs, (moisture-free basis) 40.0 29.5 acrylic acid-maleic acid 10.0 8.5 sodium carbonate 31.0 46.8DTPMP 3.0 2.5 fluorescent whitening agents 0.7 0.6 solvent naphthas 5.3 4.5 water, (being combined with zeolite) 8.0 5.9 water, (free) 0.1 0.1, (DTPMP=diethylenetriamine pentamethylenophosphonic acid salt)
Embodiment 3 embodiment 4 embodiment, 5 spray-dried powders 25.9-26.3 (from embodiment 1) spray-dried powders-30.9-(from embodiment 2) SPC-D
*17.5 13.0 16.3 enzyme granulates
*1.9 0.7 1.0 layered silicates, 12.4 8.0 8.8 (SKS-6
Ex Hoechst)
*Bleach-activating agent (TAED) 6.0 2.7 2.8 particle sodium bicarbonates
*4.5 5.8 4.0 anion surfactants, 25.0 20.7 23.4 particles
1Froth suppressor 0.9 0.8 0.8 particulate zeolites A 1.3 3.0 3.0 nonionogenic tenside 4.6 4.6 4.6 (spraying) sodium sulfate
*-9.8 9.0
Usefulness asterisk in embodiment 3-5 (
*) grain fraction that marks has the apparent density greater than 800g/l.
Anionic surfactant granules among the embodiment 3-5 (as
1Shown in) comprising 35% by weight anion surfactant, 26% zeolite A, 28% yellow soda ash, 5% carboxymethyl cellulose by weight, remainder is a water.
Claims (10)
1. an apparent density is lower than the granular detergent component of 400g/l, comprises
20%-50% silico-aluminate by weight,
Be up to 50% by weight auxiliary packing; Be characterised in that it and also contain 0.05%-2% anion surfactant by weight, non-anion surfactant with choosing other wantonly has the mixture of Kraft point (Krafft Point) greater than 30 ℃ negatively charged ion and non--anion surfactant.
2. according to the granular detergent component of claim 1, comprise 1%-1.8% anion surfactant by weight, this anion surfactant is C
14-C
20Alkyl sulfuric ester salt.
3. according to the granular detergent component of claim 1, comprise 10-30% auxiliary packing by weight, this auxiliary packing is salt hydrate or is neutralized the acid that forms salt hydrate.
4. according to the granular detergent component of claim 3, described auxiliary packing is selected from salt, organic phosphonate, amino alkylidenyl poly-(alkylene phosphonic acids salt) or their mixture of the poly carboxylic acid of carbonate, supercarbonate, sesquicarbonate, vitriol, monomeric polycarboxylates, homopolymerization or copolymerization.
5. granular detergent composition comprises:
(i) apparent density is lower than the laundry granular detergent component of 400g/l, comprises
20%-50% silico-aluminate by weight,
Be up to 50% by weight auxiliary packing; With 0.05%-2% anion surfactant and optional other non-anion surfactant by weight, Kraft point (Krafft Point) is greater than 30 ℃ the negatively charged ion and the mixture of non-anion surfactant
The (ii) apparent density other granular detergent component of 0%-50% of 800g/l at least.
6. according to the granular detergent composition of claim 5, described granular detergent component (ii) is selected from silicate, layered silicate, carbonate, supercarbonate, sesquicarbonate, vitriol, Citrate trianion, citric acid, bleach activator, tensio-active agent or their mixture.
7. according to claim 5 or 6 each granular detergent compositions, also comprise and be at least 3% the apparent density particle percarbonate of 800g/l at least by weight.
8. according to the granular detergent composition of claim 7, comprise 5%-30% percarbonate by weight, percarbonate is a SPC-D.
9. according to each granular detergent composition of claim 5-8, the ratio that wherein total water and apparent density are lower than the anhydrous silico-aluminate in the granular detergent component of 400g/l is no more than 1: 3.
10. according to the granular detergent composition of claim 9, the ratio of wherein total water and anhydrous silico-aluminate is no more than 1: 5.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP93309042.5 | 1993-11-11 | ||
| EP93309042A EP0653481A1 (en) | 1993-11-11 | 1993-11-11 | Granular detergent composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1139451A true CN1139451A (en) | 1997-01-01 |
| CN1047792C CN1047792C (en) | 1999-12-29 |
Family
ID=8214603
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94194702A Expired - Fee Related CN1047792C (en) | 1993-11-11 | 1994-10-11 | Granular detergent composition comprising a low bulk density component |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0653481A1 (en) |
| JP (1) | JPH09505097A (en) |
| CN (1) | CN1047792C (en) |
| AU (1) | AU1039395A (en) |
| BR (1) | BR9408033A (en) |
| CA (1) | CA2174721C (en) |
| WO (1) | WO1995013344A1 (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4424005A1 (en) * | 1994-07-07 | 1996-01-11 | Henkel Kgaa | Powdery bleach and detergent |
| US5958871A (en) * | 1995-09-26 | 1999-09-28 | The Procter & Gamble Company | Detergent composition based on zeolite-bicarbonate builder mixture |
| GB9519607D0 (en) * | 1995-09-26 | 1995-11-29 | Procter & Gamble | Detergent composition |
| US5665691A (en) * | 1995-10-04 | 1997-09-09 | The Procter & Gamble Company | Process for making a low density detergent composition by agglomeration with a hydrated salt |
| US5576285A (en) * | 1995-10-04 | 1996-11-19 | The Procter & Gamble Company | Process for making a low density detergent composition by agglomeration with an inorganic double salt |
| EP0912717B1 (en) * | 1996-05-14 | 2002-12-11 | The Procter & Gamble Company | Process for making a low density detergent composition by agglomeration followed by dielectric heating |
| GB9711356D0 (en) | 1997-05-30 | 1997-07-30 | Unilever Plc | Particulate detergent composition |
| GB9711350D0 (en) * | 1997-05-30 | 1997-07-30 | Unilever Plc | Granular detergent compositions and their production |
| GB9711359D0 (en) * | 1997-05-30 | 1997-07-30 | Unilever Plc | Detergent powder composition |
| WO1998054289A1 (en) | 1997-05-30 | 1998-12-03 | Unilever Plc | Free-flowing particulate detergent compositions |
| GB2356201A (en) * | 1999-11-13 | 2001-05-16 | Procter & Gamble | Detergent compositions |
| JP4509741B2 (en) * | 2004-11-02 | 2010-07-21 | 花王株式会社 | Pollen adhesion preventive for textile products |
| EP1918362A1 (en) * | 2006-10-16 | 2008-05-07 | The Procter & Gamble Company | Low builder, highly water-soluble, low-density solid laundry detergent composition |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1538607A (en) * | 1976-11-26 | 1979-01-24 | Unilever Ltd | Process for manufacture of detergent powders |
| JPS57192499A (en) * | 1981-05-20 | 1982-11-26 | Lion Corp | Manufacture of granular detergent |
| GB8328017D0 (en) * | 1983-10-19 | 1983-11-23 | Unilever Plc | Detergent powders |
| DE3424987A1 (en) * | 1984-07-06 | 1986-02-06 | Unilever N.V., Rotterdam | METHOD FOR PRODUCING A POWDERED DETERGENT WITH INCREASED SHOULDER WEIGHT |
| DE3534888A1 (en) * | 1984-10-02 | 1986-04-10 | Toyo Soda Manufacturing Co., Ltd., Shinnanyo, Yamaguchi | Granular zeolite composition as builder, and detergent containing it |
| GB8609044D0 (en) * | 1986-04-14 | 1986-05-21 | Unilever Plc | Detergent powders |
| GB8626082D0 (en) * | 1986-10-31 | 1986-12-03 | Unilever Plc | Detergent powders |
-
1993
- 1993-11-11 EP EP93309042A patent/EP0653481A1/en not_active Withdrawn
-
1994
- 1994-10-11 AU AU10393/95A patent/AU1039395A/en not_active Abandoned
- 1994-10-11 JP JP7513824A patent/JPH09505097A/en active Pending
- 1994-10-11 WO PCT/US1994/011511 patent/WO1995013344A1/en active Application Filing
- 1994-10-11 CN CN94194702A patent/CN1047792C/en not_active Expired - Fee Related
- 1994-10-11 BR BR9408033A patent/BR9408033A/en not_active Application Discontinuation
- 1994-10-11 CA CA002174721A patent/CA2174721C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH09505097A (en) | 1997-05-20 |
| BR9408033A (en) | 1996-12-17 |
| CN1047792C (en) | 1999-12-29 |
| CA2174721C (en) | 1999-12-14 |
| WO1995013344A1 (en) | 1995-05-18 |
| AU1039395A (en) | 1995-05-29 |
| CA2174721A1 (en) | 1995-05-18 |
| EP0653481A1 (en) | 1995-05-17 |
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