CN1354784A - Detergent composition - Google Patents

Detergent composition Download PDF

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Publication number
CN1354784A
CN1354784A CN99811308.5A CN99811308A CN1354784A CN 1354784 A CN1354784 A CN 1354784A CN 99811308 A CN99811308 A CN 99811308A CN 1354784 A CN1354784 A CN 1354784A
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China
Prior art keywords
composition
weight
polymkeric substance
visbreaking
poly
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CN99811308.5A
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Chinese (zh)
Inventor
D·J·比克
J·C·范德帕斯
C·C·维尔博格
J·J·维尔哈根
P·维尔斯卢伊斯
P·C·维森博格
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Unilever NV
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Unilever NV
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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005Other compounding ingredients characterised by their effect
    • C11D3/0021Dye-stain or dye-transfer inhibiting compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005Other compounding ingredients characterised by their effect
    • C11D3/0036Soil deposition preventing compositions; Antiredeposition agents
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/38Products with no well-defined composition, e.g. natural products
    • C11D3/386Preparations containing enzymes, e.g. protease or amylase

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The present invention relates to a structured liquid detergent composition with(i)less than 10 % volume phase separation after 21 days at 25 DEG C from the time of preparation;(ii)a viscosity lower than 500 mPa.s at a shear rate of 21 s<-1>; and(iii)a Dissolution Time, as measured herein, of less than 120 seconds while being stable without deflocculating polymer. In addition a process is provided to clean laundry using said composition.

Description

Detergent composition
Technical field
The present invention relates to detergent composition, especially structured liquid detergent compositions.
Background and prior art
Liquid detergent composition has some advantage than granular detergent composition.For example, liquid composition is prepared burden easily and is made the human consumer not worry that fabric is impaired.This may be exactly why to introduce market since heavy duty type and the composite laundry detergent product of light-duty just to obtain the reason greatly popularized.
Have two classes common and independently liquid detergent composition, i.e. isotropy and structural liquid.Isotropic liquid is that wherein all components all is dissolved, and opposite with structural liquid, does not have structure to exist in isotropic liquid.
In structural liquid, can make structural contribution go out some character such as flowing property that the human consumer liked and/or muddy outward appearance.Many structural liquid granular solids that also can suspend.The example of structural liquid is at US-A-4244840, and EP-A-0160342 provides among EP-A-0038101 and the EP-A-0140452.Structural liquid can be " inner structure ", its structure is formed by initial component, preferably use surfactant material, and/or " outer structure ", its structure is to form by using three dimensional matrix (matrix) structure that auxiliary additive provided, additive preferred polymers, clay, silica and/or silicate material.Outer structure liquid can provide the high viscosity when storing.
Usually, the ordering degree that contains surfactant system increases with the increase of tensio-active agent and/or electrolyte concentration.When tensio-active agent and/or electrolytical concentration were extremely low, tensio-active agent can be used as molecular solution and exists, or existed as the solution of spherical micelle, and these two kinds of solution all are isotropic, and promptly they are amorphousness.Because tensio-active agent and/or electrolytical adding in addition, the structure of surfactant material can form.This structure has multi-form existence, as bilayer structure.They are called as with different terms, as rod-shaped micelle, and anisotropic surface promoting agent phase, plane laminate structure, stratiform droplet and mesomorphic phase.The various examples of the liquid with inner structure that formed by tensio-active agent are at H.A.Barnes, " Detergents (washing composition) ", chapter 2, K.walters (volume) " Rheometry:Industrial Applications (rheometry: industrial application) ", J.Wiley ﹠amp; Sons provides among the Letchworth 1980.Usually, different workers are actually identical structure with different term addresses.For example, in european patent application specification sheets EP-A-0151884, the stratiform droplet is called as spherocrystal.
The feature of preferred laminate structure is the stratiform droplet of surfactant material at continuous aqueous phase, and wherein the dispersive structure generally is considered to be made up of the class onion configuration that contains the concentric bilayer surfactant molecule mutually, is sealing water up for safekeeping between bilayer, i.e. water.Liquid with stratiform droplet structure is preferred, because this droplet tightly packed provides the ideal structure of physical stability and useful flowing property in the system, promptly good pourability combines with enough stability.This class I liquid I is at for example A.Jurgews, Micro-Structure andViscosity of Liquid Detergent (microstructure of liquid washing agent and viscosity), Tenside Surfactant Detergents 26 (1989), 222 pages and J.C.Van dePas, Liquid Detergents, Tenside Surfactants Detergents28 (1991) states in 158 pages.The existence of surfactant structure system and characteristic can be measured with the known method of person skilled in the art in the liquid, optical technology for example, various rheological measurements, X ray or neutron diffraction and electron microscopy sometimes.
The feasible composition that is difficult to prepare chemistry and physically stable of a large amount of interactions in the liquid detergent composition between the component is particularly when storing.It is inhomogeneous that this detergent composition can become, and for example some components can be separated owing to crystallization or precipitation.Liquid washing agent be their solubility property on the other hand.So far, few people are put into attention on the solubility property of liquid washing agent.When using detergent composition, the user likes seeing its dissolving rapidly in water.It is active fully that this makes the user be sure of that detergent composition becomes very soon.Structured liquid detergent compositions dissolves rapidlyer than powder detergent.But for can be used for the hand washing operation, comprise the liquid detergent composition of laundry, need extremely excellent solubility property.Low viscosity liquid washing composition such as pure nonionogenic tenside demonstrate trouble and bad solubility property, and this is because the formation of intermediate phase.Another solvability can problematic example be under the situation of the laminate structure liquid washing agent of also being made up of intermediate phase also.Although we do not wish to be bound by any theory, we believe that the dissolving that contains the structured liquid detergent of stratiform droplet can be divided into two-phase.In first phase of dilution, droplet disperses, and in second phase decomposition.Yet dilute with water can cause the reduction of the outer salt concn of stratiform droplet.Because osmotic pressure is, this can cause the swelling of stratiform droplet.Such process can help to explain the bad solvency action of some structured liquid detergent.
Many structured liquid detergent compositions can suspended solids, as zeolite.Yet with regard to rheology and stability, such composition causes some problems deserving of attention, because solid should keep in week suspending at 1-3 at least, the while composition should keep pourability.Yet solid suspends and is not always required.So do not contain stable suspersion solid structured liquid detergent is preferred, because these compositions needn't satisfy such strict demand and thereby can be easier to preparation.Yet technology the earliest relates to have the structural liquid of stable suspersion solid.
EP-A-301882 discloses has the structured liquid detergent compositions of stable suspersion solid as 20% weight zeolite.The solubility property of these compositions is not open.EP-A-362916 relates to and mixes the high-content functional polymer, to suppress the effect of fabric softening clay.The composition that is exemplified can suspended solids.The solubility property of the composition that obtains is unclear.EP-A-829530 has described and has contained the structural hard surface detergent compositions of stable suspersion solid.Solubility property about the composition that exemplifies is not open.EP-A-74134 discloses has stable suspersion solid structured liquid detergent compositions.This patent is described, if use sodium xylene sulfonate or toluenesulfonic acid sodium salt to obtain suitable viscosity and satisfactory stability, then S-WAT can be used for having the composition of high-content Tri sodium Phosphate (25-26%).Solubility property about disclosed composition does not disclose therein yet.
Therefore, be still needs for not containing stable suspersion solid rock steady structure liquid detergent composition, it should have the good solubility energy, as not showing one or more shortcomings of pointing out above.
Astoundingly, we have now found that preparation rock steady structure liquid washing agent is possible, and it shows outstanding dissolution rate, if viscosity is 21S in shearing rate -1The time be lower than 500mPaS, said composition does not contain deflocculate polymkeric substance and stable suspersion solid substantially.
Explanation of the present invention
The present invention relates to a kind of stable structure liquid detergent composition, it is characterized by:
(i) at 25 ℃ of these polymkeric substance after 21 days generation is lower than being separated of 10% volume from when preparation; With
Be 21 S (ii) in shearing rate -1The time viscosity be lower than 500mPaS; With
(iii) when the 10ml said composition being dissolved in 2.51 25 ℃ and 4 H water, dissolution time as measuring, is less than 120 seconds here; With
If (iv) said composition contains the polymkeric substance of visbreaking, then the visbreaking polymkeric substance is not single by dextran, and dextran sulfonate or polyoxyethylene glycol are formed; As long as when composition contains 10.4% weight Sodium dodecylbenzene sulfonate, 6.7% weight C 12-13Every mole on average by the oxyalkylated Fatty Alcohol(C12-C14 and C12-C18) of 7mol oxyethane, 4.6% weight sodium-chlor, so said composition contain at least a single be that the sodium polyacrylate of 1200-8000 is formed by weight-average molecular weight; Said composition is substantially free of deflocculate polymkeric substance and stable suspersion solid.
In this article, contain stable suspersion solid composition and be situation about can be under normal pressure not showing in the composition in 25 ℃ of 20% 3 weeks of weight zeolite 4A that suspended greater than top layer 2%, the contained zeolite in upper strata is less than bottom.
And another specific embodiments provides the method for a usefulness liquid detergent composition cleaning clothes of the present invention.
Detailed description of the present invention
The dissolution rate that the water-bearing structure liquid detergent composition is lower may be the main drawback that the user perceives.High dissolution rate makes the user be sure of that liquid detergent composition is consoluet and thereby is active fully.This point is applicable to all liquid detergent composition usually, but especially for the liquid detergent composition that is fit to the hand washing operation.Favourable dissolution rate is to be less than 120 seconds when dissolution time (as measuring below), preferably is less than 100 seconds, more preferably less than 90 seconds, more preferably less than 80 seconds, when most preferably being less than 60 seconds.According to the present invention, the 10ml liquid washing agent is added in the 3L beaker (diameter 14cm) that fills 2.5L4 H water (at 25 ℃) through a syringe with common flow.(the long 6cm of rod) stirs the water in the beaker with magnetic stirrer, and the mode of stirring should make beaker central authorities form the vortex of 1cm.Liquid washing agent is added in the outside of vortex.The record specific conductivity is as the function of time, from walls of beaker 1cm, until reading constant (all liquid washing composition all dissolves).By the gained data make even the weighing apparatus electric conductivity value reach 90% Time Calculation dissolution time, promptly when 90% weight combinations thing dissolves.
We find, when preparation has the liquid detergent composition of favourable dissolution rate, are wonderful big factors with viscosity limitation to the specific level of liquid detergent composition.
Visbreaking
The viscosity of the present composition can be controlled with known the whole bag of tricks in the present technique.In a preferred embodiment, a composition contains just like the visbreaking polymkeric substance described in the EP-A-0301882.This visbreaking polymkeric substance is compared with the same composition that is removed except all these base polymers and can be reduced the viscosity of composition that (in shearing rate is 21S more than 5% -1Under when measuring).A large amount of different polymkeric substance can be used, as long as the requirement of electrolytic resistance and vapour pressure is satisfied.The former is that conduct is that the amount that reaches the necessary sodium nitrilo triacetate of cloud point (NaNTA) of the solution of 100ml 5% polymkeric substance in 25 ℃ of water is measured, and the pH of regulation system is neutral simultaneously, promptly is about 7 and preferably reaches this purpose with sodium hydroxide.Most preferred electrolytic resistance is 10g NaNTA, especially 15g.The requirement of vapour pressure shows that vapour pressure will be hanged down is enough to have tangible water binding ability, as what illustrate among the GB-A-2053249.Thereby the vapour pressure of polymkeric substance 20% aqueous solution preferably is equal to or less than the vapour pressure that molecular-weight average is 10% weightaqueous solution of 6000 polyoxyethylene glycol.It is emphasized that with the present invention to differ widely that EP-A-0301882 discloses and how to have removed to improve the pourability (page 2,43 row) of liquid and not point out may influence solubility property with the visbreaking polymkeric substance.In a preferred embodiment, composition of the present invention contains greater than 0.01%, is preferably greater than 0.05%, more preferably greater than 0.1% with less than 10%, preferably less than 5%, is more preferably less than the visbreaking polymkeric substance of 2.5% weight.Content is higher than these numerals and can causes instability in many compositions (but not being whole).
The visbreaking polymkeric substance is optional from polyacrylic ester, polysaccharide, modified polysaccharide, polyalkylene oxide, Polyvinylpyrolidone (PVP), multipolymer is as gathering (acrylate-be total to-maleic acid ester), poly-(acrylate-be total to-vinylbenzene) and poly-(ethylene terephthalate-be total to-oxyethane) and their mixture.The example of suitable polymers comprises: Sokalan PA50 TM, Sokalan CP5 TM(the two is available from BASF), Narlex LD 31 TMWith Narlex H1200 TM(the two is available from NationalStarch), Alcosperse 725 TM(available from National Starch), Xylo-Mucine, O14-Methyldelectine, PEG 1500 and Aquaperle (available from ICI).
In addition, the preparation of the method for composition of the present invention visbreaking routinely comprises any combination of following selection or following various selections:
(i) increase electrolytical content in the prescription.A possible shortcoming is that too high electrolyte content can cause physical instability, causes finally genetic horizon separation when storing.There is some method can correct this physical instability, these methods comprise the adding molten ionogen of salt (for example EP-A-0079646), add salt tolerant and analyse tensio-active agent (for example EP-A-0328177) and add deflocculate polymkeric substance (for example EP-A-0346995 and EP-A-0623670).
(ii) reduce surfactant content.
(iii) change the tensio-active agent ratio.For example, in the composition that contains negatively charged ion and nonionogenic tenside, can come visbreaking by the ratio that reduces or increase the anionic/nonionic tensio-active agent.This will depend on the composition situation of prescription, and the best way should be to produce viscosity by aforesaid method to lower.The person skilled in the art can find that adopting the aforesaid method visbreaking is best practical approach with simple experiment.
(iv) change cationic ratio.Usually positively charged ion is sodium and potassium, be three sometimes-or-thanomin.Change positively charged ion, for example increase potassium/sodium ratio, can cause the increase (when the part electrolysis is when existing with crystal) of electrolyte dissolution concentration.This can be by method (i) and/or amount (when dissolving takes place crystal) or visbreaking by reducing solid particulate.
(v) add a small amount of hydrotropic agent, comprise (for example, EP-A-0491 723) such as sodium xylene sulfonate, ethanol, propylene glycol.Hydrotropic amount is too high scarcely, otherwise physical instability will take place product.It is believed that and lower through the viscosity of this method that the flexible increase that is by laminar bilayer causes, this causes the increase of stratiform droplet deformability.Yet, when the amount that hydrotropic agent adds is too many, double-deck integrity forfeiture, the stratiform droplet damages and produces physical instability as a result.
Surfactant material
Liquid detergent composition of the present invention contains surfactant material, and preferred content is at least 1% of composition weight, and more preferably at least 5% weight most preferably is at least 10% of composition weight; With preferred content 80% weight at the most, more preferably at the most 40%, 35% weight at the most most preferably.
Under the wideest definition, the activated detergent material generally can contain one or more tensio-active agents and can be selected from negatively charged ion, positively charged ion, nonionic, zwitter-ion and amphoterics and their mixture (so long as hold mutually).For example they can be selected from the Vol.1 at ' Surface Active Agents (tensio-active agent) ', Schwartz ﹠amp; Perry, Interscience 1949 and ' Surface Active Agents ' Vol.II, Schwartz, Perry ﹠amp; Among the Berch (Interscience 1958), the current edition of publishing by McCutcheon division of Manufacturing Confectioners Company " McCutcheon ' s Emulsifiers ﹠amp; Detergents " in and at ' Tensid-Taschenbuch ', H.Stache, second edition, Carl HanserVerlag, M ü nchen ﹠amp; Wien, 1981 or US-A-5750733 described in any class, subclass and certain material.
Suitable ionic surfactant pack is drawn together, and especially, has the product of the compound of hydrophobic group and reactive hydrogen atom, for example the reaction product of fatty alcohol, acid, acid amides or alkylphenol and alkylene oxide, particularly oxyethane or propylene oxide.Specific nonionic detergent compounds is the alkyl (C that has oxyethane 6-C 18) uncle or the alcohol of secondary line style or branching and the product that obtains by oxyethane and propylene oxide and the condensation of 1 reaction product.Other so-called nonionic detergent compounds comprise the long-chain tertiary amine oxide, long-chain oxidation tertiary phosphine, alkyl polysaccharide and dialkyl sulphoxide.By the weight of composition, the content of nonionogenic tenside material preferably at least 1%, more preferably at least 2%, even more preferably at least 5%, most preferably at least 10% and at the most 80%, more preferably at the most 50%, more preferably at the most 30%.
The anion surfactant that is fit to is generally has about 8 water-soluble alkali metal salts to the alkyl organo-sulfate or the organic sulfonic acid ester of about 22 carbon atoms, and used term alkyl comprises the moieties of senior acyl group.The example of suitable synthetic anionic detergent compound is alkyl sulfuric ester sodium and potassium, especially senior (the C that is for example produced by butter or Oleum Cocois by sulfation 8-C 18) alcohol resulting those, alkyl (C 9-C 20) the secondary alkyl (C of benzene sulfonate sodium and potassium, especially line style 10-C 15) benzene sulfonate sodium; The alkyl glycerol ether sodium sulfovinate is especially derived from the higher alcohols of butter and Oleum Cocois with derived from the ether of the synthol of oil; Ether carboxylate, Oleum Cocois aliphatic series glycerine Monosulfate (and sulphonate) sodium; Senior (C 8-C 18) fatty alcohol-alkylene oxide especially sodium and the sylvite of the sulfuric ester of oxirane reaction product; The reaction product of lipid acid, as with the isethionic acid esterification and with sodium hydroxide neutral cocoanut fatty acid; The sodium salt of the fatty acid amide of N-methyltaurine and sylvite; The alkane monosulfonate is as passing through alpha-olefin (C 8-20) obtain with sodium bisulfite reaction those and by paraffin and SO 2And Cl 2Reaction produces those that random sulfonate obtains with basic hydrolysis then; And ethylenic sulfonate, this term is used for describing by alkene, especially C 10-C 20Alpha-olefin and SO 3Reaction and neutralization and hydrolysis reaction product and the material that makes then.The preferred anionic surfactants detergent compound is (C 11-C 15) benzene sulfonamide acid esters sodium and (C 16-C 18) alkyl sulfuric ester sodium.The content of common above-mentioned non-soap anionic surfactant is at least 1%, more preferably at least 2%, more preferably at least 5%, more preferably at least 8%, most preferably at least 10% and at the most 80%, more preferably at the most 40%, more preferably at the most 25%, all by the weight of composition.
Some or all these washing composition active materials also may be stabilized surfactant, and it has greater than the mean alkyl chain length of 6 carbon atoms and its resistance of saltouing more than or equal to 6.4.These stabilized surfactant are disclosed among our European patent application EP-A-328177.The example of these materials is the poly-alkoxide carbonyl hydrochlorates of alkyl, and alkyl gathers alkoxide phosphoric acid salt, and alkyl gathers the alkoxide sulfosuccinate; Dialkyl group phenyl ether stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate; Alkyl polysaccharide and their mixture.
Also possible and preferred sometimes, comprise long-chain list-or dicarboxylic acid, for example have the alkali metal soap of the carboxylic acid of 12-18 carbon atom.Typical this class acid is oleic acid, ricinolic acid and derived from the lipid acid of Viscotrol C, rape seed oil, peanut oil, Oleum Cocois, palm-kernel oil or their mixture.Sodium that these are sour or potash soap can be used.The preferred content of soap is at least 1%, more preferably at least 5% and at the most 35%, preferably at the most 25%, and all by the weight of composition.
Electrolyte
Composition of the present invention can contain electrolyte, their the part or all can be the washing assistant material.Should be noted that for purpose of the present invention, the term ionogen can comprise the washing assistant material.
Liquid detergent compositions of the present invention preferably contains the lyotrope value less than 9.5 with preferably less than 9.0 salting-out electrolyte.Salting-out electrolyte has the connotation described in the EP-A-0079646.Preferred salting-out electrolyte be selected from phosphoric acid (comprise Jiao, just, Tripyrophosphoric acid), silicic acid, boric acid, carbonic acid, sulfuric acid, citric acid, an alkali metal salt of NTA and succsinic acid and ammonium salt.This liquid composition preferably contains at least 1% weight salting-out electrolyte, and more preferably at least 2%, most preferably at least 5% weight and 30% weight at the most, more preferably 20% weight salting-out electrolyte at the most.Randomly, the molten ionogen of some salt (as defined in the specification sheets in the back) also can be included.
Electrolytical total content is preferably at least 1%, and more preferably at least 5%, most preferably at least 10% and at the most 60%, more preferably at the most 45%, 30% weight at the most most preferably.
Under any circumstance, preferred composition of the present invention comprises the washing assistant material, their part or all can be that ionogen should be noted that some surfactant material in this article, and for example soap also has the washing assistant performance.The washing assistant material is preferably from soap and non-soap washing assistant material.Composition of the present invention is formed.Preferred always to help the content of washing material be the 0.1-60% of composition weight, and the 0.5-50% of composition weight more preferably most preferably is the 2-30% of composition weight, and preferred washing assistant material is water miscible.
Non-soap washing assistant material is for example phosphorous or phosphorated inorganic builders not.The example of inorganic phosphor-contained washing assistant comprises water-soluble salt, particularly alkali metal pyrophosphate, orthophosphoric acid salt, polyphosphate and phosphoric acid salt.The example of phosphorated inorganic builders when existing, does not comprise water soluble alkali metal carbonate, supercarbonate, silicate and crystallization and amorphous aluminosilicate.The example of organic washing-assisting detergent when existing, comprises alkaline-earth metal, the poly-acetate of ammonium and replacement ammonium, carboxylate salt, polycarboxylate, poly-ethanoyl carboxylate salt and polyhydroxy sulfonate.
Preferably, when composition contained washing assistant, washing assistant is single to be that the sodium polyacrylate of 1200-8000 is formed by weight-average molecular weight.
The content of non-soap washing assistant material is preferably the 1-40% of composition weight, and more preferably 3% of composition weight to being lower than 24%.
The application of deflocculate polymkeric substance (being called stablizer sometimes) is described in front, for example at WO 91/06622, WO 91/06623, GB-A-2237813, WO 91/09109, among PCT application No.EP/93/01882 and/or the EP-A-0346995, comprise end-blocking deflocculate polymkeric substance, as at EP-A-0623670, US-A-5489397 is described in EP-A-691399 and/or the GB application No.9711849.1.Liquid detergent composition of the present invention is substantially free of the deflocculate polymkeric substance.This means that general said composition comprises is less than 0.01%, more preferably less than 0.001% with even more preferably less than this deflocculate polymkeric substance of 0.0001% weight.
Preferred composition of the present invention is an inner structure, and more preferably composition contains the stratiform droplet in the surfactant material of continuous aqueous phase.
Optional components
Except that each component of having pointed out, also can there be many optional components, profoamer for example, froth suppressor, oxygen release SYNTHETIC OPTICAL WHITNER such as Sodium peroxoborate and SPC-D, peracid bleach precursor, release chlorine bleach such as TCCA (Trichloroisocyanuric acid), inorganic salt such as S-WAT and common with the indivisible white dyes that exists, spices, enzyme, as proteolytic enzyme, amylase, cellulase and lipase (comprising Lipolase (trade mark)), enzyme stabilizers available from Novo, anti redeposition agent, the dirt remover, anti-dye-transfer, sterilant and tinting material.
Although we would rather not have fabric-softening, swelling clay to exist, if be included in few 5% weight, material then argillaceous can be any this material that the fabric-softening benefit can be provided.Usually these materials are materials that contain three layers of swellable smectic type clay of natural origin, it is desirable to calcium and/or sodium montmorillonite class.Be preferably in before the granulating and during, use yellow soda ash that the natural calcium clay is become na form, as described in the GB-A-2138037 (Colgate).The argillaceous material depends on the content of smectic type clay especially as the effectiveness of fabric softener.Impurity such as calcite, feldspar and silica exist through regular meeting.More impure clay can use, and wants these impurity to allow in composition to the greatest extent.
The product form
Liquid composition of the present invention is 21s preceding cutting speed preferably -1The time have viscosity less than 500mPas, be more preferably less than 450mPas, most preferably less than 400mPas with preferably at 21s -1The time greater than 10mPas, more preferably greater than 50mPas.Liquid detergent composition of the present invention is stable, be that said composition is lower than 10% with generation, preferably be lower than 5%, most preferably be lower than being separated of 2% volume, as when composition at 25 ℃, after the preparation time stores 21 days, occur 2 or more separate phase and confirmed.
Preferably the pH that offers washing lotion with a kind of liquid is at least 6, more preferably at least 6.5, most preferably at least 7.Preferred pH is 12 to the maximum, more preferably is at most 11, more preferably is at most 10, most preferably is at most 9.
Preferred liquid composition water content of the present invention is at least 10% of a composition weight, more preferably at least 20%, most preferably at least 30%.Preferred liquid composition water content of the present invention is at the most 80% of a compound weight, more preferably at the most 70%, most preferably at the most 60%.Preferred this liquid is spissated.
Method of washing clothes
Another embodiment comprises with liquid detergent composition method of washing clothes of the present invention.Preferred washing clothes by hand in the method.
Except in example, or the place of pointing out in addition, used here expression amounts of components and all numerals of reaction conditions all are interpreted as modifying with " approximately " speech at all occasions.Similarly, all percentage number averages by weight, except as otherwise noted." comprising " speech meaning is to have unfixed feature, if promptly composition comprises X, then except that X, other components (a kind of or several) existence can be arranged also in the composition.
Following example is to further specify of the present invention.
Example
Component % weight
LAS-acid KOH LES STP Na 2SO 4Propane diols borax fluorescent whitening agent protease spices preservatives, dyes Sokalan PA50TM(mPa.s is at 21 s for water stability viscosity -1) dissolution time (s is during 90% dissolving) Example 1 12 Example 2 12 Example 3 12 Example 4 *??12
To pH 8
??4 ??5 ??11 ??2.5 ??2.5 ??0.05 ??0.25 ??0.22 ??0.016 ??0.004 ??0.15 ??4 ??5 ??11 ??2.5 ??2.5 ??0.05 ??0.25 ??0.22 ??0.016 ??0.004 ??0.12 ??4 ??5 ??11 ??2.5 ??2.5 ??0.05 ??0.25 ??0.22 ??0.016 ??0.004 ??0.10 ??4 ??5 ??11 ??2.5 ??2.5 ??0.05 ??0.25 ??0.22 ??0.016 ??0.004
Up to 100%
260 32 330 44 400 72 1,510 198
*The approximate C of (case of comparative examples) raw material LAS-acid 12Alkyl benzene sulphonate (ABS) (is purchased H ü ls or Industrial
Gessy Lever Ltd, Brazil) LES lauryl ether (about 3 oxyethane) sodium sulfate, Manro
Bes 70 is available from Hickson Manro or Genapol LRO
B. (available from Clariant) S.A., (Brazil) STP three (gathering) sodium phosphate, Thermphos NW, available from
Knapsack or available from Copebras S.A. (Brazil) Sokalan PA50 TMSodium polyacrylate, available from BASF sodium sulfate available from Crimidesa S.A. (Spain) propylene glycol available from Dow Quimica S.A (Brazil) borax available from Merck

Claims (13)

1. stable structure liquid detergent composition is characterized by:
(i) said composition will produce less than 10% volume in 25 ℃ after 21 days preparation time
Be separated; With
(ii) its viscosity is 21s in shearing rate -1The time be lower than 500mPas; With
When (iii) said composition 10ml dissolves in 2.51 25 ℃ and 4 H water, during dissolving
Between, as here measuring, less than 120 seconds; With
If (iv) said composition contains the visbreaking polymkeric substance, then the visbreaking polymkeric substance is not single
By dextran, asuro or polyoxyethylene glycol are formed; As long as when composition contains
10.4% weight Sodium dodecylbenzene sulfonate is arranged, the C of 6.7% weight 12-13whenever rub
You are on average by the oxyalkylated Fatty Alcohol(C12-C14 and C12-C18) of 7mol oxyethane, 4.6% weight chlorination
Sodium, then said composition contain at least a single be 1200-by weight-average molecular weight
8000 sodium polyacrylate is formed; Said composition do not contain substantially the deflocculate polymkeric substance and
The stable suspersion solid.
2. the composition of claim 1, its medium viscosity is 21s in shearing rate -1The time be lower than 450mPas, preferably be lower than 400mPas.
3. by the composition of the arbitrary claim in front, wherein dissolution time as measuring, is lower than 100 seconds here, preferably is lower than 80 seconds.
4. by the composition of any claim in front, wherein composition contains the visbreaking polymkeric substance, and this polymkeric substance has described electrolytic resistance of specification sheets and vapour pressure.
5. the composition of claim 4, wherein composition contains more than 0.01% and is less than 10%, preferably more than 0.05% be less than the visbreaking polymkeric substance of 5% composition weight.
6. claim 4 or 5 composition, wherein the visbreaking polymkeric substance is to be selected from polyacrylic ester, polysaccharide, modified polysaccharide, polyalkylene oxide, Polyvinylpyrolidone (PVP), multipolymer, as gathering (acrylate-be total to-maleic acid ester), poly-(acrylate-be total to-vinylbenzene) and poly-(ethylene terephthalate-be total to-oxyethane) and their mixture.
7. the composition of claim 1, wherein liquid detergent composition is an inner structure.
8. the composition of claim 7, wherein liquid detergent composition contains at the stratiform droplet of the surfactant material of aqueous phase continuously.
9. the composition of any claim in front is characterized in that said composition contains the washing assistant material that is selected from soap and non-soap washing assistant material, presses composition weight meter, and its content is 0.1-60%.
10. by the composition of aforementioned any claim, it is characterized in that said composition contains by composition weight meter 8% and 25% non-soap anionic surfactant material at the most at least.
11., it is characterized by said composition and contain according to the composition of claim 1
A) be selected from the washing assistant of soap and non-soap washing assistant material by composition weight meter 0.1-60%
Material,
B) press composition weight meter at least 8% and 25% non-soap anionic surfactant at the most
Material,
C) contain by composition weight meter greater than 0.01% be less than 10% visbreaking polymerization
Thing, this polymkeric substance preferably is selected from polyacrylic ester, polysaccharide, modified polysaccharide, poly-epoxy
Alkane, Polyvinylpyrolidone (PVP), multipolymer is as poly-(acrylate-be total to-Malaysia
Acid esters), poly-(acrylate-be total to-vinylbenzene) and poly-(ethylene terephthalate
-altogether-oxyethane) and their mixture.
12. liquid detergent composition method of washing clothes with aforementioned arbitrary claim
13. the method for claim 12 wherein is a washing clothes by hand.
CN99811308.5A 1998-09-25 1999-09-08 Detergent composition Pending CN1354784A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP98203232.8 1998-09-25
EP98203232 1998-09-25

Publications (1)

Publication Number Publication Date
CN1354784A true CN1354784A (en) 2002-06-19

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AT (1) ATE284949T1 (en)
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CA (1) CA2345644A1 (en)
DE (1) DE69922672T2 (en)
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TR (1) TR200100847T2 (en)
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DE69922672T2 (en) 2005-12-22
WO2000018868A1 (en) 2000-04-06
CA2345644A1 (en) 2000-04-06
TR200100847T2 (en) 2002-02-21
DE69922672D1 (en) 2005-01-20
ES2230892T3 (en) 2005-05-01
BR9913923A (en) 2001-06-19
AU6080699A (en) 2000-04-17
EP1115833B1 (en) 2004-12-15
ATE284949T1 (en) 2005-01-15
EP1115833A1 (en) 2001-07-18

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