CN1352677A - Fabric softening component - Google Patents
Fabric softening component Download PDFInfo
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- CN1352677A CN1352677A CN00808082.8A CN00808082A CN1352677A CN 1352677 A CN1352677 A CN 1352677A CN 00808082 A CN00808082 A CN 00808082A CN 1352677 A CN1352677 A CN 1352677A
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-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0047—Detergents in the form of bars or tablets
- C11D17/0065—Solid detergents containing builders
- C11D17/0073—Tablets
-
- 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
- C11D17/0047—Detergents in the form of bars or tablets
- C11D17/0065—Solid detergents containing builders
-
- 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
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/001—Softening 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
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/10—Carbonates ; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
- C11D3/1246—Silicates, e.g. diatomaceous earth
- C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
- C11D3/126—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite in solid compositions
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- 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)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
The present invention relates to fabric softening component comprising a clay, a flocculating agent, a surfactant and a carrier material. The carrier material is preferably a powdered or granular builder or alkalinity source. The component is preferably a spray-dried particle, extrudate or an agglomerate. It preferably comprises at least a sulphate and/or sulphonate surfactant, a zeolite and/or phosphate builder and a carbonate salt. Highly preferred is that the component also comprises a brightener.
Description
Technical field
The present invention relates to the softening component as fabric softener, it comprises clay and flocculation agent, surfactant system and solid support material.Described component also can be used for detergent composition.
Background of the present invention
In the past few years thereby clay has been used to provide in the various washing composition fabric-softening effect of adopting described cleaning compositions.They be described to driedly to be added into other detergent particles or can with other composition blended material.The clay particle that EP-A-313146 has described 60%-99% clay and wetting agent joins in the detergent composition.
Known that in the past few years the clay flocculating agent can improve clay and transmit on fabric.EP-A-313146 has also described the washing composition that contains clay particle and has preferably included a kind of clay flocculating agent.
The inventor has now found that when clay and flocculation agent exist with the form of intimate mixture each other, can improve the sedimentation effect of clay.It has not only improved the sedimentation effect of clay, and clay that can also lower level reaches and transmits identical softening performance.
In the sedimentary while by using intimate mixture to improve clay, also finding to be in the suds effectively, the distribution flocculation agent also is important.The inventor has been found that the mixture by clay and flocculation agent mixes with tensio-active agent and can realize this point.But, find that also described transmission is further enhanced when Powdered or granular carrier mix with clay, flocculation agent and tensio-active agent.In addition, use tensio-active agent to improve the mixing of clay and flocculation agent, use described solid support material can form the mixture of non-sticky and easy hand washing (handable) simultaneously, it can be processed into its desired form easily.The mixture of also finding this form has better package stability, and this point is useful, because described mixture can store subsequently until last use, and it needn't be for further processing at once.
Highly preferred described solid support material comprises alkali source and/or washing assistant, because can obtain multi-functional softening component like this.This component can be used for several applications, comprises as the component of the component of detergent composition, fabric softener composition or self as washing and softening component, is particularly useful for hand-washing or the washing of washing of little load or non-heavy dirt load.
The present invention's summary
The present invention relates to a kind of solid fabric softening component, it comprises:
A) clay;
B) at least 5% surfactant system;
C) solid carrier material of at least 15% (weight);
D) flocculation agent.
Described component is preferably spray-dried granules, agglomerate or extrudate.But described component also can be processed into sheet form or bulk form.Any that can adopt these forms handled fabric, and perhaps it can be as a part of detergent composition or fabric softener composition.Described component can be used for the conditioning of washing automatically and hand washing (also comprising pre-treatment or immersion) or aftertreatment such as fabric.Softening component
Component of the present invention comprises at least a clay, a kind of flocculation agent, a kind of tensio-active agent and a kind of solid carrier material.
The aggregate level of the tensio-active agent in described component is preferably the 5-90% of described composition weight, more preferably 10-70% or even 60%, more preferably 15%-60% or even 50%.
Preferred described tensio-active agent contains at least a anion sulfate acid salt surfactant or anion sulfoacid salt surfactant.After this will be described preferred sulfonate and sulfate surfactant.
The level that exists of preferred described sulfonate or sulfate surfactant or its mixture is the 5-60% of described composition weight, more preferably the 10-60% of described composition weight or even 15-50%.
Can preferred described component contain nonionogenic tenside or its mixture, can be used as in the described component unique a kind of tensio-active agent or but also can with other combinations-of surfactants.The level that exists of preferred nonionic surfactants is the 2-60% of described composition weight, more preferably the 5-50% of described composition weight or even 10%-45%.
Preferred described solid support material is particle or powder type.Preferred described solid support material is alkali source and/or washing assistant.Preferred alkali source is an inorganic carbonate.Preferred washing assistant (also being alkali usually) is silico-aluminate, crystalline silicate, amorphous silicate, crystalline layered silicate, phosphoric acid salt, carboxylic acid or its salt.But can also use other inorganic salt such as vitriol.Preferred the above-mentioned type salt is sodium salt.Can exist with form by preferred at least a sylvite with the clay intimate mixture.
The level that exists of preferred described solid support material is 20-95% (weight), more preferably 25% to 90% (weight) or even to 80% (weight), even more preferably 30-70% (weight).
Therefore can preferred described inorganic carbonate exist level be described composition weight at least 10% or even 15%, preferred highest level is 60% or even 50% or even 40%.
Highly preferably there are at least a phosphoric acid salt or silico-aluminate washing assistant herein.Therefore can preferred described washing assistant (preferably phosphate and/or silico-aluminate washing assistant) exist level be described composition weight at least 10% or even 15%, preferred highest level is 60% or even 50% or even 40%.
Because silicate is suitable for and even be preferred for herein, except at least a other washing assistant or alkali source, also preferably use silicate.
The level that exists of preferred described clay is at least 1% of a described composition weight, and more preferably its level is 2-60%, more preferably 5-40% or even 5-30% or even 7-25%.
Prepare described component by mixed clay, flocculation agent, solid support material and tensio-active agent.Therefore these materials closely mix each other.This can be undertaken by any hybrid system known in the art or comminution granulation.But the last performance of the described component of blended order possibility remarkably influenced.Preferred blending means is as follows:
-in one embodiment, clay and flocculation agent are intimate mixtures (obtaining by mixed clay and flocculation agent) each other, it is dispersed to the intimate mixture of surfactant system, solid support material or tensio-active agent and solid support material subsequently or disperses with above-mentioned substance.
-in another highly preferred embodiment, at first tight mixed flocculation agent and surfactant system or its part, perhaps solid support material or its part, but preferred surfactant system and solid support material or its part are mixed this mixture subsequently or are disperseed with clay.Choose wantonly and subsequently remaining solid support material and/or tensio-active agent are mixed with the mixture that obtains.
-in a further preferred embodiment, at first clay and solid support material or its part are carried out intimate mixing, after this this mixture and flocculation agent and tensio-active agent and optional remaining solid support material are disperseed or mix.The part of option list surface-active agent can be in first step be mixed with clay and solid support material or its part.
The weight ratio of preferably clay and flocculant polymer is 1000: 1-1: 1, more preferably 500: 1-1: 1, most preferably be 300: 1-1: 1, perhaps even more preferably 80: 1-10: and 1, perhaps in some applications even be 60: 1-20: 1.
The weight ratio of preferably clay and solid support material is 1: 30-5: 1, more preferably 1: 20-3: 1, even more preferably 1: 15-1: 1 or even be 1: 10-1: 2.The weight ratio of preferred surfactant and clay is 1: 30-10: 1, more preferably 1: 15-5: 1, even more preferably 1: 10-3: 1 or even be 1: 5-1: 1.
Highly preferably there is whitening agent, fabric brightness and whiteness not only are provided, also improve the outward appearance of described component.The level that exists of preferred described whitening agent is at least 0.05% of a described composition weight, more preferably at least 0.1% or even 0.15% or even 0.2%.
Described component also can comprise free water content, preferably is not more than 30% of described composition weight, more preferably the 0.5-20% of described composition weight or even 1% to 15% or even at least 5%.But can preferably exist the composition of water sensitive such as effervescent system, enzyme, SYNTHETIC OPTICAL WHITNER, spices, in this case preferably the level of free-water less than above-mentioned level, as as described in being lower than composition weight 12%, more preferably less than 6% or even 5%, most preferably be lower than 4% or even 3%.
In a preferred embodiment, described component comprises organic acid or mineral acid (especially when having carbonate) thereby provides effervescent effect with carbonate.Preferred acid comprises citric acid, tartrate, lactic acid, toxilic acid, oxysuccinic acid, pentanedioic acid, hexanodioic acid, acetate and amino acid.
Described component also can comprise other fabric care agent such as soil release polymer, cellulose polymer compound, dye transfer inhibitor, cationic softening agent or its mixture.Also can there be perfume composition (highly preferred) and enzyme or sequestrant.
Preferred described component is spray-dried granules or agglomerated particle, perhaps can be processed into sheet form or bulk form for extrudate or thin slice or it.These particles can be by known granulation, spraying drying, agglomeration, extrude or pressed disc method prepares, and described method relates to the various compositions of intimate mixing, optional entry or other solvent and the optionally drying of adding.Clay
Clay can be for providing any clay of fabric-softening effect herein.For the sake of clarity, it should be noted that term clay used herein does not comprise sodium silicoaluminate zeolite builders compound, but this zeolite builders can be included in the component of the present invention as solid support material or its part.
The mixture that can preferred described component comprises a kind of clay.
A kind of preferred clay can be wilkinite.Highly preferred smectite-type clay, its example are disclosed in U.S. Patent number 3862058,3948790,3954632 and 4062647 and european patent number EP-A-299575 and EP-A-313146 (all from Procter and GambleCompany).
The term smectite-type clay comprises that aluminum oxide is present in clay in the lattice silicate and magnesium oxide and is present in clay in the lattice silicate herein.Typical smectite-type clay compound comprises that general formula is Al
2(Si
2O
5)
2(OH)
2.nH
2The compound of O and general formula are Mg
3(Si
2O
5)
2(OH)
2.nH
2The compound of O.Smectite-type clay tends to adopt expandable tripartile structure.
The object lesson of suitable smectite-type clay comprises and is selected from montmorillonite, hectorite, volchonskonite, nontronite, saponite and sauconite particularly have those clays of basic metal or alkaline-earth metal ions in the crystal lattice structure.Especially preferred sodium montmorillonite or Ca-montmorillonite.
Suitable smectite-type clay, especially polynite is provided by different suppliers, and these suppliers comprise English China Clays, Laviosa, Georgia Kaolin and Colin StewartMinerals.
The maximum particle diameter of preferred clay used herein is 0.01 micron to 800 microns, more preferably 1 millimeter to 400 millimeters, most preferably is 5 millimeters to 200 millimeters.
The particle of clay mineral compound can be included in the agglomerated particle that contains other detergent compound as its component.When having these components, " maximum particle size " of term clay mineral compound is meant the clay mineral compound rather than refers to do the overall dimension of as a whole agglomerated particle.
Usually can in the crystal lattice structure of smectite-type clay, carry out the replacement of small cation such as proton, sodium ion, potassium ion, magnesium ion and calcium ion and the replacement that comprises some organic molecule of positively charged functional group.Can select a kind of positively charged ion is had the clay of preferential absorption ability, this ability is evaluated by measuring relative loading capacity.The smectite-type clay of Shi Yonging has the cation exchange capacity of 50meq/100g at least usually herein.U.S. Patent number 3954632 has been described a kind of method of measuring cation exchange capacity.
The crystal lattice structure of clay mineral compound can have the cationic fabric softener (preferred example) that wherein replaces.The clay of this replacement is called " hydrophobic activity " clay.Usually cationic fabric softener to have weight ratio (with cationic fabric softener to clay) be 1: 200 to 1: 10, preferred 1: 100 to 1: 20.Suitable cationic fabric softener comprises water-insoluble tertiary amine or the two long-chain acid amides materials that are disclosed in GB-A-1154276 and EP-B-0011340.
Preferably " hydrophobic activated clay " commodity are the wilkinite that contains the dimethyl ditallow quaternary ammonium salt of 40% (weight) of having an appointment, and it is sold with the trade(brand)name of Claytone EM by English China Clays International.
Also can use organophilic clay herein.They are the clay of hydrophobically modified, and it has the organic ion by ion exchange method displacement inorganic metal ion known in the art.This class clay easily mixes with organic solvent and absorbs organic solvent at interlayer.The suitable example that is applicable to organophilic clay of the present invention is from Rheox of Highstown, Bentone SD-1, SD-2 and the SD-3 of N.j..
Can choose described clay wantonly is present in a kind of mixture with wax and structural agent and also optional flocculating polymer.Flocculation agent
Described component of the present invention can contain a kind of clay flocculating agent, preferably its to have level be the 0.005-10% of described composition weight, more preferably 0.05-5%, most preferably 0.1-2%.
The function of clay flocculating agent is in washing soln the clay compound particle to be combined and therefore help them to be deposited on the fabric face of washing.Therefore this functional requirement is different from common adding clothes washing composition and helps to remove clay soil and can make them be dispersed in clay dispersion compound the washing soln from fabric.
Preferred herein clay flocculating agent is an organic polymer material, and its molecular weight is 100,000-10, and 000,000, preferred 150,000-5,000,000, more preferably 200,000-2,000,000.
Suitable organic polymer material comprises some homopolymer or multipolymer, and it contains the monomeric unit that is selected from alkylene oxide (especially oxyethane), acrylamide, vinylformic acid, vinyl alcohol, V-Pyrol RC and ethyleneimine.Especially optimization ethylene oxide, acrylamide and acrylic acid homopolymer.
The european patent number EP-A-299 of Procter and Gamble Company, 575 and EP-A-313,146 have described the organic polymer clay flocculating agent that preferably is used for herein.
The inorganic clay flocculation agent also is applicable to this, and exemplary comprises lime and alum.Carbonate
Basic metal of Shi Heing and/or alkaline-earth metal inorganic carbonate comprise carbonate and the supercarbonate and the percarbonate of potassium, lithium, sodium etc. herein, wherein preferred yellow soda ash and salt of wormwood.The supercarbonate that is applicable to this comprises any an alkali metal salt such as lithium, sodium and the sylvite of supercarbonate, wherein preferred sodium bicarbonate and saleratus.But, be dissolved in the required pH value of water medium wherein according to described dry effervescent granule, can select carbonate or supercarbonate or its mixture in the dry effervescent granule, wherein.For example when needing the water medium of higher pH (as being higher than pH9.5), can preferably use carbonate separately or be used in combination carbonate and supercarbonate (wherein the level of carbonate is higher than the level of supercarbonate).The inorganic base metal of preferred component of the present invention and/or sylvite or the preferred sodium salt that alkaline earth salt comprises carbonate and/or supercarbonate.Preferred carbonate comprises yellow soda ash, the optional sodium bicarbonate that also comprises.
In one embodiment of the invention, have a kind of effervesce source, preferably it comprises organic acid (as carboxylic acid or amino acid) and carbonate.Then can be preferably herein carbonate partly or entirely and organic acid carry out pre-mixing, and exist with grain fraction independently thus.
Described carbonate can have any particle size.In one embodiment, especially when carbonate is present in the particle or be not during as the compound that adds separately, the volume medium of preferred described carbonate is the 5-375 micron, thus preferably at least 60%, preferably at least 70% (volume) or even at least 80% or even at least 90% particle diameter be the 1-425 micron.More preferably the volume medium of carbon dioxide source is 10-250, thus preferably at least 60%, or even at least 70% or even at least 80% or even the particle diameter of at least 90% (volume) be the 1-375 micron; Perhaps in addition the preferred volume median particle diameter be the 10-200 micron, thus preferably at least 60%, preferably at least 70% or even at least 80% or even the particle diameter of at least 90% (volume) be the 1-250 micron.The washing assistant material
Preferred washing assistant material is alumino-silicate materials such as zeolite and/or phosphoric acid salt.
The suitable example of water-soluble phosphate washing assistant is sodium salt, sylvite and the ammonium salt of alkali-metal tri-polyphosphate, tetra-sodium, sodium salt and sylvite, the sodium salt (wherein polymerization degree scope is about 6-21) of poly-metaphosphoric acid/phosphoric acid and the salt of phytic acid of orthophosphoric acid salt.Most preferably the phosphate builders material comprises tetrasodium pyrophosphate or more preferably anhydrous sodium tripolyphosphate.
The unit cell formula of suitable aluminosilicate zeolite is Na
z[(AlO
2)
z(SiO
2)
y] .xH
2O, wherein z and y are at least 6; The mol ratio of z and y is 1.0-0.5, and x is at least 5, preferred 7.5-276, most preferably 10-264.Alumino-silicate materials is a hydrated form, is preferably crystal, and it contains 10-28%, more preferably the combination water of 18-22%.
Described aluminosilicate zeolite can be the natural material that exists, but is preferably synthetic materials.The commodity of synthetic crystal aluminosilicate ion-exchange material are Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS and composition thereof.Zeolite A has following formula:
Na
12[(AlO
2)
12(SiO
2)
12].xH
2O
X is 20-30 in the formula, especially is 27.ZeoliteX has formula Na
86[(AlO
2)
86(SiO
2)
106] .276H
2O.
Another kind of preferred aluminosilicate zeolite is a zeolite MAP builder.Zeolite MAP is described in EP384070-A.It is defined as silica alumina ratio and is not more than 1.33, preferably at the more preferably alkali metal aluminosilicate of the zeolite P type in the 0.9-1.2 scope of 0.9-1.33 scope.
What be even more important is zeolite MAP, and its silica alumina ratio is not more than 1.15, more preferably no more than 1.07.
One preferred aspect, the particle diameter of zeolite MAP builder is (with d
50Expression) be the 1.0-10.0 micron, more preferably 2.0-7.0 micron, most preferably 2.5-5.0 micron.
d
50The particle grain size of value representation 50% (weight) is worth less than this.Described particle diameter is passable, especially measures as the employing scanning electronic microscope or by the microscopic measurement of laser particle diameter instrument by the routine analysis technology.Determine d
50Other method of value is disclosed in EP384070A.
Also preferably can and also have amorphous silicate, preferred 1.6 or the water glass of 2 ratios for crystallizing layer type silicate material such as SKS-6 (selling) by Clariant.It can for low density as the powdered material that is lower than 40 grams per liters or with the dense material that obtains by roll-in (as density greater than 400 grams per liters).It also can be each other mixture, perhaps the form with the mixture of other washing assistant material or inorganic salt exists.
Described component also preferably includes the polycarboxylic acid of water-soluble mono build polycarboxylate or their acid type, homopolymerization or copolymerization or the mixture of their salt (wherein polycarboxylate comprises at least two carboxyls that separated by no more than 2 carbon atoms each other), borate and aforementioned substances.
Carboxylate salt or polycarboxylate washing assistant can be monomer or oligomeric-type, but because price and performance, preferred monomers polycarboxylate usually.
The carboxylate salt that is fit to that contains a carboxyl comprises the water-soluble salt of lactic acid, oxyacetic acid and ether derivant thereof.The polycarboxylate that contains two carboxyls comprises water-soluble salt and the ether carboxylate and the sulfinyl carboxylate salt of Succinic Acid, propanedioic acid, (ethylene dioxy) oxalic acid, toxilic acid, diglycollic acid, tartrate, tartronic acid and fumaric acid.The polycarboxylate or their acid that contain three carboxyls especially comprise water-soluble citrate, aconitate and citraconate and butanedioic acid derivative such as British Patent No. 1,379, carboxymethyl oxygen succinate described in 241, British Patent No. 1,389, amino-succinic acid described in lactoxy succinate described in 732 and the Netherlands patent applications 7205873 and oxygen PC material are as being described in British Patent No. 1,387, the 2-oxa--1 described in 447,1,3-propane trisalt.The most preferred polycarboxylic acid that contains three carboxyls is a citric acid, preferably its to have level be the 0.1-15% of described composition weight, more preferably 0.5-8%.
The polycarboxylate that contains four carboxyls comprises and is disclosed in British Patent No. 1,261, oxygen two butyratess in 829,1,1,2,2-ethane tetracid salt, 1,1,3,3-propane tetracid salt and 1,1,2,3-propane tetracid salt.Contain the substituent polycarboxylate of sulfo group and comprise and be disclosed in British Patent No. 1,398,421 and 1,398,422 and U.S. Patent number 3,936,448 in the sulfonation butanedioic acid derivative and be described in British Patent No. 1,439, the sulfonation pyrolysis Citrate trianion in 000.Preferred polycarboxylate contains hydroxycarboxylate up to three carboxyls, more preferably Citrate trianion for each molecule.
The mixture of the polycarboxylate sequestrant of monomer or oligopolymer or itself and their salt (as citric acid or Citrate trianion/citric acid mixture) also is suitable for and makes builder component.
Borate washing assistant and to contain the washing assistant that can generate boratory formation borate material under wash conditions also be useful herein water soluble detergency promoter.Surfactant system
Described component comprises a kind of surfactant system.Described surfactant system can contain any tensio-active agent such as anion surfactant, nonionogenic tenside, cats product, amphoterics, zwitterionics or its mixture that is usually used in the detergent composition.As mentioned above, preferably there are at least a anion sulfate and/or sulfosalt surfactant.Also be preferably nonionogenic tenside.
When having cats product, zwitterionics or amphoterics, can also preferably there be at least a anion surfactant or nonionogenic tenside.Anion surfactant
Any anion surfactant that is used for the decontamination purpose all is suitable.They can comprise anion sulfate, sulfonate, carboxylate salt and sarcosinate surfactant various salt (comprise as sodium, potassium, ammonium and substituted ammonium salt as single-, two-and triethanolamine salt).
The preferred anionic sulfosalt surfactant exists as the part of described anion surfactant or anion surfactant.
Other suitable anion surfactant comprises isethionate such as acyl isethionic salt, N-acyl taurine salt, methylamino esilate, alkyl succinate and the sulfosuccinate of fatty acid amide, monoesters (the especially saturated and unsaturated C of sulfo-succinic acid
12-C
18Monoesters), the diester of sulfo-succinic acid (especially saturated and unsaturated C
6-C
14Diester), N-acyl sarcosinate.Resinous acid and hydrogenated resin acid also are fit to, as rosin, staybelite, and the resinous acid and the hydrogenated resin acid that are present in or come from butter.
Anion surfactant such as carbon chain lengths that the useful performance that produces when anion surfactant also is used for component of the present invention is particularly useful for long carbochain are C
12Or those bigger anion surfactants, especially C
14-15Or even up to C
16-C18Carbon chain lengths.The anion sulfate acid salt surfactant
The anion sulfate tensio-active agent that is applicable to component of the present invention comprises that the primary and secondary alkyl-sulphate (has the straight chain of 9-22 carbon atom and branched-chain alkyl or alkenyl part or more preferably C
12-C
18Alkyl), alkyl ethoxy sulfate, fatty oleoyl glycerine vitriol, alkylphenol ethylene oxide ether sulfate, C
5-C
17Acyl group-N-(C
1-C
4Alkyl) and-N-(C
1-C
2Hydroxyalkyl) vitriol of the vitriol of glucosamine sulfate and alkyl polysaccharide such as alkyl polyglucoside (compound of nonionic non-sulfuric acid salt described herein).
Preferred alkyl ethoxy sulfate tensio-active agent is selected from C
9-C
22Alkyl-sulphate (each molecule carries out ethoxylation with the oxyethane of 0.5-20 mole).More preferably described alkyl ethoxy sulfate surfactant is C
11-C
18, C most preferably
11-C
15Alkyl-sulphate (each molecule 0.5-7, preferred 1-5 moles of ethylene oxide is carried out ethoxylation).
A preferred especially aspect of the present invention adopts preferred alkyl-sulphate and and the mixture of alkyl ethoxy sulfate surfactant.These mixtures have been disclosed among the PCT number of patent application WO93/18124.The anion sulfoacid salt surfactant
The anionic sulphonate tensio-active agent of Shi Yonging comprises C herein
5-C
20, more preferably C
10-C
16, more preferably C
11-C
13(straight chain) alkylbenzene sulfonate, alkyl ester sulfonate, C
6-C
22Uncle or secondary alkyl sulfonate, C
6-C
24Alkene sulfonate, sulfonation polycarboxylic acid, alkyl glycerol sulfonate, fatty acyl group glycerol sulfonate, fatty oleoyl glycerol sulfonate, fatty oil base glycerol sulfonate and composition thereof.
The sulfonated surfactants of preferred described alkyl ester has following formula:
R
1-CH(SO
3M)-(A)
x-C(O)-OR
2
R in the formula
1Be C
6-C
22Alkyl, R
2Be C
1-C
6Alkyl, A are C
6-C
22Alkylidene group, alkenylene, x are 0 or 1, and M is a positively charged ion.Preferred counter ion M is sodium, potassium or ammonium.
The sulfonated surfactants of preferred alkyl ester is the alpha-sulfo alkyl ester with following formula, so x is 0.Preferred R
1For having 10-22, the alkyl of preferred 16 carbon atoms or alkenyl, x is preferably 0.R
2Be preferably ethyl or methyl more preferably.
The preferred R in the ester
1Derived from the unsaturated fatty acids that preferably has 1,2 or 3 two key.The also preferred R in the ester
1Derived from naturally occurring fatty ester (preferred palmitinic acid or stearic acid or its mixture).Dianionic surfactant
Dianionic surfactant also is the anion surfactant that is applicable to component of the present invention.The dianionic surfactant of preferred following formula:
R is the C that has of optional replacement in the formula
1-C
28, preferred C
3-C
24, C most preferably
8-C
20The alkyl of chain length, alkenyl, aryl, alkaryl, ether, ester, amine or amide group or hydrogen; A and B independently are selected from has C
1-C
28, preferred C
1-C
5, C most preferably
1Or C
2The alkylidene group of chain length, alkenylene, (gathering) alcoxyl subunit, hydroxy alkylidene, aryl alkylene or acyl ammonia alkylidene group, or covalent linkage, preferred A and B contain at least 2 atoms altogether; A, B and R contain 4 altogether to about 31 carbon atoms; X and Y are for being selected from carboxylate radical, and the anionic group of preferably sulfuric acid root and sulfonate radical, z are 0 or preferred 1; M is a cationic moiety, is preferably to replace or unsubstituted ammonium ion or basic metal or alkaline-earth metal ions.
Most preferably dianionic surfactant has wherein that R is C
10-C
18The alkyl of chain length, A and B independently are C
1Or C
2, X and Y are sulfate radical, and M is the following formula of potassium, ammonium or sodium ion.
Preferred herein dianionic surfactant comprises:
(a) 3 dithionate compounds, preferred 1,3-C7-C23 (being the total carbon number in the molecule) straight or branched alkyl or alkenyl dithionate more preferably have following formula:
R is that chain is about C in the formula
4-C
20Straight or branched alkyl or alkenyl;
(b) 1,4 dithionate compound, preferred 1,4 C
8-C
22Straight or branched alkyl or alkenyl dithionate more preferably have following formula:
R is that chain length is about C in the formula
4-C
18Straight or branched alkyl or alkenyl; Preferred R is selected from octyl group, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl and combination thereof; With
(c) 1,5 dithionate compound, preferred 1,5 C
9-C
23Straight or branched alkyl or alkenyl dithionate more preferably have following formula:
R is that chain length is about C in the formula
4-C
18Straight or branched alkyl or alkenyl.
Can preferred described dianionic surfactant be oxyalkylated dianionic surfactant.
The dianionic surfactant of preferred alkoxylated has following formula:
R is the C that has of optional replacement in the formula
1-C
28, preferred C
3-C
24, C most preferably
8-C
20The alkyl of chain length, alkenyl, aryl, alkaryl, ether, ester, amine or amide group or hydrogen; A and B independently are selected from (optional replacement) and have C
1-C
28, preferred C
1-C
5, C most preferably
1Or C
2Chain length alkyl and alkenyl or covalent linkage, EO/PO is the alkoxyl group part that is selected from the oxyethyl group/propoxy-of oxyethyl group, propoxy-and combination, wherein n and m are independently between about 0 to 10, but m or n are at least 1 at least; Preferred A and B contain at least 2 atoms altogether; A, B and R contain 4 altogether to about 31 carbon atoms; X and Y are the anionic group that is selected from sulfate radical and sulfonate radical, and condition is that at least one of X or Y is for sulfate radical; M is a cationic moiety, is preferably to replace or unsubstituted ammonium ion or basic metal or alkaline-earth metal ions.
Most preferred alkoxylate dianionic surfactant has wherein, and R is C
10-C
18The alkyl of chain length, A and B independently are C
1Or C
2, n and m are 1, and X and Y are sulfate radical, and M is the following formula of potassium, ammonium or sodium ion.Middle chain component alkyl-sulphate or sulfonate
Middle chain component alkyl-sulphate or sulfonate also are the suitable anion surfactants that is applicable to component of the present invention.Preferred medium chain ramose alkyl-sulphate.
These tensio-active agents have linear primary alkyl sulphates main chain (the longest linear carbochain that promptly comprises the sulphating carbon atom), described main chain preferably contains 12-19 carbon atom, and preferably their branch's primary alkyl part contains at least 14 altogether, preferably is not more than 20 carbon atoms.Surpass in the component of the present invention of these sulfate surfactants containing, average total carbon number of preferred ramose primary alkyl part be greater than 14.5 to about 17.5 scope.Therefore described surfactant system preferably contains at least one ramose primary alkyl sulphates surfactant compounds, the longest linear carbochain of described compound is not less than 12 carbon atoms or is not more than 19 carbon atoms, and the total carbon atom number that comprises side chain is necessary at least 14, furthermore, the scope of the average total carbon atom number of branch's primary alkyl part is greater than 14.5 to about 17.5.
Preferred monomethyl ramose primary alkyl sulphates is selected from: 3-methyl pentadecanol vitriol, 4-methyl pentadecanol vitriol, 5-methyl pentadecanol vitriol, 6-methyl pentadecanol vitriol, 7-methyl pentadecanol vitriol, 8-methyl pentadecanol vitriol, 9-methyl pentadecanol vitriol, 10-methyl pentadecanol vitriol, 11-methyl pentadecanol vitriol, 12-methyl pentadecanol vitriol, 13-methyl pentadecanol vitriol, 3-methyl hexadecanol sulfate, 4-methyl hexadecanol sulfate, 5-methyl hexadecanol sulfate, 6-methyl hexadecanol sulfate, 7-methyl hexadecanol sulfate, 8-methyl hexadecanol sulfate, 9-methyl hexadecanol sulfate, 10-methyl hexadecanol sulfate, 11-methyl hexadecanol sulfate, 12-methyl hexadecanol sulfate, 13-methyl hexadecanol sulfate, 14-methyl hexadecanol sulfate and composition thereof.
Preferred dimethyl ramose primary alkyl sulphates is selected from: 2,3-methyl tetradecyl alcohol vitriol, 2,4-methyl tetradecyl alcohol vitriol, 2,5-methyl tetradecyl alcohol vitriol, 2,6-methyl tetradecyl alcohol vitriol, 2,7-methyl tetradecyl alcohol vitriol, 2,8-methyl tetradecyl alcohol vitriol, 2,9-methyl tetradecyl alcohol vitriol, 2,10-methyl tetradecyl alcohol vitriol, 2,11-methyl tetradecyl alcohol vitriol, 2,12-methyl tetradecyl alcohol vitriol, 2,3-methyl pentadecanol vitriol, 2,4-methyl pentadecanol vitriol, 2,5-methyl pentadecanol vitriol, 2,6-methyl pentadecanol vitriol, 2,7-methyl pentadecanol vitriol, 2,8-methyl pentadecanol vitriol, 2,9-methyl pentadecanol vitriol, 2,10-methyl pentadecanol vitriol, 2,11-methyl pentadecanol vitriol, 2,12-methyl pentadecanol vitriol, 2,13-methyl pentadecanol vitriol and composition thereof.
The following ramose primary alkyl sulphates that contains 16 carbon atoms and have a cladon is the example that is used for the preferred branched surfactant of component of the present invention:
6-methyl pentadecyl vitriol with following formula:
M is preferably sodium in the formula.
The following ramose primary alkyl sulphates that contains 17 carbon atoms and have two cladons is the example of preferred branched surfactant of the present invention:
Have 2 of following formula, 8-dimethyl pentadecyl vitriol:
Wherein preferred M is a sodium.The anionic carboxylic acid salt surfactant
The anionic carboxylate tensio-active agent that is fit to comprises alkyl ethoxy carboxylate, many oxyethyl groups of alkyl multi-carboxylate's tensio-active agent and soap (' alkyl carboxylate (carboxyls) '), the secondary soap of especially described herein some (secondary soap).
The alkyl ethoxy carboxylate that is fit to comprises formula RO (CH
2CH
2O)
xCH
2COO
-M
+Those compounds, R is C in the formula
6-C
18Alkyl, x are 0-10, ethoxylate distribute make x be the amount of 0 material less than 20% (by weight), M is a positively charged ion.The alkyl polyethoxye multi-carboxylate tensio-active agent that is fit to comprises that those have formula RO-(CHR
1-CHR
2-O)-R
3Material, R is C in the formula
6-C
18Alkyl, x are 1-25, R
1And R
2Be selected from hydrogen, methyl acid group, Succinic Acid group, hydroxy-butanedioic acid group and their mixture, R
3Be selected from hydrogen, have the replacement of 1-8 carbon atom or do not replace hydrocarbon and composition thereof.
The soap class tensio-active agent that is fit to comprises and contains the unitary secondary soap surfactant of the carboxyl that links to each other with secondary carbon.The preferred secondary soap surfactant that is used for herein is a water-soluble substances, and it is selected from 2-methyl isophthalic acid-undeeanoic acid, 2-ethyl-1-capric acid, 2-propyl group-1-n-nonanoic acid, 2-butyl-1-is sad and the water-soluble salt of 2-amyl group-1-enanthic acid.
Some soap also can be included in the suds suppressor.The basic metal sarcosinate surfactant
Other anion surfactant that is fit to is formula R-CON (R
1) CH
2The basic metal sarcosinate of COOM, R is C in the formula
5-C
17Straight or branched alkyl or alkenyl, R
1Be C
1-C
4Alkyl, M are alkalimetal ion.Preferred example is the sodium salt of myristyl and oleoyl methyl sarkosine.Nonionic surfactant system
Described detergent component can comprise or also comprise a kind of nonionic surfactant system (containing at least two kinds of oxyalkylated tensio-active agents of nonionic).
Almost any oxyalkylated nonionogenic tenside all is applicable to this.Preferred ethoxylation and propenoxylated nonionogenic tenside.
The tensio-active agent of preferred alkoxylated can be selected from alkylphenol nonionic condenses, nonionic ethoxylated alcohol, nonionic alkoxylated fats acid amides, nonionic ethoxylated/propoxylated fatty alcohol, nonionic ethoxylate/propoxylated glycerine and propylene glycol condenses and with the condensation product of the nonionic ethoxylate of propylene oxide/ethylenediamine adduct.
Preferred at least a nonionogenic tenside is the described alcohol alcoxylates tensio-active agent in back.
Also preferred nonionic alkoxylated fatty acid acid amides, it can provide the more softening performance of fabric or skin (when described washing composition and the skin contact).
Most preferably nonionic surfactant system comprises at least two kinds of nonionic alcohol alcoxylates tensio-active agents, and preferably the average alkoxide degree of its a kind of tensio-active agent is 5 or littler, and a kind of average alkoxide degree of tensio-active agent is greater than 5.Highly preferred system comprises that at least a average alkoxide degree is that 3 or 5 the pure and mild at least a average alkoxide degree of nonionic alkoxylate is 5.5 to 15, preferred 6 or 9 nonionic alcohol alcoxylates.
The alkoxide group of nonionogenic tenside is preferably the propoxide group, more preferably the ethoxylate group.
Preferred aliphatic series alcohol and 1-25 mole alkylene oxide, the especially condensation product of oxyethane and/or propylene oxide in the nonionic surfactant system hereinto.The alkyl chain of fatty alcohol can be straight or branched, uncle or secondary alkyl chain, and contain 6-22 carbon atom usually.Especially preferably the condensation product of alcohol that has the alkyl of 8-20 carbon atom.
Nonionic surfactant system of the present invention can contain a kind of alkoxylated fatty acid acid amides, and it preferably contains a kind of compound of following formula:
R in the formula
1Be C
12-C
18Alkyl or alkenyl, R
2Be C
2-C
4Alkylidene group, R
3Be hydrogen or C
1-C
4Alkyl, R
4Be C
1-C
4Alkyl or hydrogen, n are the number of 3-12.
Preferred alkoxylated fatty acid acid amides has C
12-C
14Or C
16-C
18The R of alkyl
1, propylidene or the more preferably R of ethylidene
2, n is 5-10, R
4Be methyl or hydrogen, R
3Be hydrogen or methyl or ethyl.
Detergent component herein also can contain other the non-alkoxy-based non-ionic surface active agent that comprises polyhydroxy fatty acid amide, is applicable to that this polyhydroxy fatty acid amide has formula R
2CONR
1Z, R in the formula
1Be H, C
1-C
4Alkyl, 2-hydroxyethyl, 2-hydroxypropyl, oxyethyl group, propoxy-or its mixture, preferred C
1-C
4Alkyl, more preferably C
1Or C
2Alkyl, most preferably C
1Alkyl (being methyl); R
2Be C
5-C
31Alkyl, preferred straight chain C
5-C
19Alkyl or alkenyl, more preferably straight chain C
9-C
17Alkyl or alkenyl, most preferably straight chain C
11-C
17Alkyl or alkenyl, or its mixture; Z is the polyhydroxy alkyl with straight-chain alkyl chain of at least 3 hydroxyls that directly linked to each other, or its alkoxy derivative (preferred ethoxylation or propoxylation).Z is preferably derived by reducing sugar in reductive amination process; More preferably Z is glycityl.
Detergent component also can comprise other alkyl polysaccharide herein, as be disclosed in and authorized the United States Patent (USP) 4 give Llenado on January 21st, 1986,565,647 alkyl polysaccharide, described alkyl polysaccharide have the hydrophobic grouping of 6-30 carbon atom and contain the polysaccharide such as the polyglucoside of the hydrophilic radical of 1.3-10 sugar unit.
Preferred alkyl polyglycoside has formula R
2O (C
nH
2nO)
t(glycosyl)
x, R in the formula
2Be selected from alkyl, alkyl phenyl, hydroxyalkyl, hydroxyalkyl phenyl and composition thereof, wherein alkyl contains 10-18 carbon atom; N is 2 or 3; T is 0-10, and x is 1.3-8.Glycosyl is preferably derived from glucose.Amphoterics
The amphoterics of Shi Yonging comprises amine oxide surfactant and alkyl both sexes carboxylic acid herein.
The amine oxide that is fit to comprises having formula R
3(OR
4)
xO (R
5)
2Those compounds, R in the formula
3Be selected from alkyl, hydroxyalkyl, amido propyl group and the alkylbenzene group or its mixture that contain 8-26 carbon atom; R
4Be alkylidene group or the hydroxy alkylidene that contains 2-3 carbon atom, or its mixture; X is 0-5, preferred 0-3; R
5The alkyl or the hydroxyalkyl of respectively doing for oneself and containing 1-3, or contain the polyethylene oxide group of 1-3 ethylene oxide group.Preferred C
10-C
18Alkyl dimethyl amine oxide and C
10-C
18Amidoalkyl dimethyl oxidation amine.
The suitable example of alkyl both sexes carboxylic acid is by Miranol, Inc., Dayton, the Miranol that NJ produces
TMC2M Conc.Zwitterionics
Zwitterionics also can add in the detergent composition of the present invention.These tensio-active agents can generalized description be the derivative of derivative, heterocyclic secondary and tertiary amine of secondary amine and tertiary amine or the derivative of quaternary ammonium, quaternary phosphine or uncle's sulfonium compound.Trimethyl-glycine and sultaine tensio-active agent are the example that is used for zwitterionics herein.
The trimethyl-glycine that is fit to is for having formula R (R ')
2N
+R
2COO
-Compound, R is C in the formula
6-C
18Alkyl, R
1Be generally C separately
1-C
3Alkyl, R
2Be C
1-C
5Alkyl.Preferred trimethyl-glycine is C
12-18Dimethyl Ammonium hexanoate and C
10-18Amido propane (or ethane) dimethyl (or diethyl) trimethyl-glycine.The complexing beet alkali surface activator also is applicable to herein.Positive in the plane surface promoting agent
The cats product of Shi Yonging comprises quaternary ammonium surfactant herein.Preferred quaternary ammonium surfactant is single C
6-C
16, preferred C
6-C
10N-alkyl or alkenyl ammonium surfactant, remaining N position is replaced by methyl, hydroxyethyl or hydroxypropyl in the formula.Also preferred monoalkoxyization and bis-alkoxy amine tensio-active agent.
Can be used for herein detergent composition or the another kind of suitable cats product of its component be the cationic ester tensio-active agent.Described cationic ester tensio-active agent comprises at least one ester (compound of key and at least one positively charged ion charged group promptly-COO-) for what (preferably water dispersive) had a surfactant properties.
The cationic ester tensio-active agent (comprising the cholinesterase tensio-active agent) that is fit to has been disclosed in as U.S. Patent number 4228042,4239660 and 4260529.
One preferred aspect, ester bond and positively charged ion charged group are spaced apart base separately mutually in surfactant molecule, described spacer is by containing at least 3 atoms (i.e. the chain length of three atoms), preferred 3-8 atom, more preferably 3-5 atom, most preferably the chain of 3 atoms is formed.The atom that forms the spacer chain is selected from carbon, nitrogen and Sauerstoffatom and arbitrary combination thereof, and condition is only to link to each other with carbon atom on the chain at any nitrogen on the described chain and Sauerstoffatom.Therefore do not comprise have as-O-O-(being superoxide) ,-N-N-and-spacer of N-O-key, and comprise having as-CH
2-O-CH
2-and-CH
2-NH-CH
2The spacer of-key.One preferred aspect, the spacer chain includes only carbon atom, most preferably described chain is a hydrocarbyl chain.Cation mono-alkoxylated amines tensio-active agent
Highly preferred herein cation mono-alkoxylated amines tensio-active agent preferably has following general formula I,
R in the formula
1For containing 6 to 18 carbon atoms of having an appointment, preferred 6 to about 16 carbon atoms, the most preferably from about alkyl of 6 to 14 carbon atoms or alkenyl part; R
2And R
3Independently of one another for to contain 1 alkyl to about 3 carbon atoms, preferable methyl, most preferably R
2And R
3Be methyl; R
4Be selected from hydrogen (preferably), methyl and ethyl; X
-For thereby negatively charged ion such as chlorine negative ion, bromine negative ion, methylsulfate, sulfate radical etc. provide electric neutrality; A is an alkoxyl group, especially oxyethyl group, propoxy-or butoxy; P is 0 to about 30, preferred 2 to about 15, most preferably 2 to about 8.
ApR among the preferred formula I
4The p=1 of group and be hydroxyalkyl, carbonatoms is no more than 6, thus-nitrogen-atoms that the OH group is no more than 3 carbon atom and quaternary ammonium separates.Especially preferred ApR
4Group is-CH
2CH
2OH ,-CH
2CH
2CH
2OH ,-CH
2CH (CH
3) OH and-CH (CH
3) CH
2OH, especially preferred-CH
2CH
2OH.Preferred R
1Group is a straight chained alkyl.The straight chain R that preferably has 8-14 carbon atom
1Group.
The another kind of highly preferred cation mono-alkoxylated amines tensio-active agent that is used for herein has following formula
R in the formula
1Be C
10-C
18Alkyl and combination thereof, especially C
10-C
14Alkyl, preferred C
10-C
12Alkyl, thus X for arbitrarily easily negatively charged ion provide charge balance, preferred chlorine negative ion or bromine negative ion.
The compound that it should be noted that the front type comprises those wherein oxyethyl group (CH
2CH
2O) unit (EO) is by butoxy, isopropoxy [CH (CH
3) CH
2O] and [CH
2CH (CH
3) O] unit (i-Pr) or positive propoxy unit (Pr), or EO and/or Pr and/or the unitary combination metathetical of i-Pr compound.
The preferred levels of used cation mono-alkoxylated amines tensio-active agent is the 0.5%-30% of described component in detergent component of the present invention, more preferably 1%-25%, most preferably 1%-10% (weight).Positively charged ion is two-the alkoxylated amines tensio-active agent
Preferred cationic bis-alkoxy amine tensio-active agent has general formula I I,
R in the formula
1Have an appointment 8 to about 18 carbon atoms for containing, preferred 10 to about 16 carbon atoms, most preferably from about 10 alkyl or alkenyl parts to about 14 carbon atoms; R
2For containing the alkyl of 1-3 carbon atom, preferable methyl; R
3And R
4Can independent variation and be selected from hydrogen (preferably), methyl and ethyl, X-is negatively charged ion such as chlorine negative ion, bromine negative ion, methylsulfate, sulfate radical etc., is enough to provide electric neutrality.A and A ' can independent variation and are selected from C separately
1-C
4Alkoxyl group, especially oxyethyl group (promptly-CH
2CH
2O-), propoxy-, butoxy and combination thereof; P is 1 to about 30, preferred 1 to about 4, and q is 1 to about 30, preferred 1 to about 4, and most preferably p and q are 1.
The highly preferred positively charged ion bis-alkoxy amine tensio-active agent that is used for herein has following formula,
R in the formula
1Be C
10-C
18Alkyl and combination thereof, preferred C
10, C
12, C
14Alkyl and combination thereof.Thereby X for arbitrarily easily negatively charged ion provide charge balance, preferred chlorine negative ion.With reference to the general structure of above-mentioned positively charged ion bis-alkoxy amine, because in preferred compound, R
1Derived from (cocounut oil) C
12-C
14Moieties lipid acid, so R
2Be methyl, ApR
3And A ' qR
4The monosubstituted ethoxy of respectively doing for oneself.
Other positively charged ion bis-alkoxy amine tensio-active agent that is used for herein comprises the compound with following formula,
R in the formula
1Be C
10-C
18Alkyl, preferred C
10-C
14Alkyl, independently p is 1 to about 3, q is 1 to about 3, R
2Be C
1-C
3Alkyl, preferable methyl, X is a negatively charged ion, especially chlorine negative ion or bromine negative ion.
Other compound of aforementioned type comprises those oxyethyl group (CH wherein
2CH
2O) unit (EO) is by butoxy, isopropoxy [CH (CH
3) CH
2O] and [CH
2CH (CH
3) O] unit (i-Pr) or positive propoxy (Pr), or EO and/or Pr and/or the unitary combination metathetical of i-Pr compound.Other composition of described component and the composition that contains described component
Described component can contain other composition.Preferred these compositions are to be usually used in after this described clothing is used tenderizer with washing composition or clothing component.
Fabric softening component of the present invention may reside in detergent composition or the softening compositio.Preferred these compositions are solid, and its existence form is particle, extrudate, thin slice, bulk or sheet.
Described composition can be used for washing automatically or hand washing.Described composition also can be suitable for pre-treatment or immersion, or is used for rinsing or conditioning fabric after the main washing.
Described composition of the present invention also can contain other detergent component.The precise nature of these other components and interpolation level thereof will depend on the physical form of described composition or component and the precise nature of used washing operation.
The preferred present composition contains one or more other detergent components, and described component is selected from aforesaid other tensio-active agent, SYNTHETIC OPTICAL WHITNER, bleaching catalyst, alkali systems, other washing assistant, other organic polymer, enzyme, suds suppressor, soap, calcium soap, dispersion agent, soil-suspending agent and anti redeposition agent, stain remover, spices, whitening agent, optical white and other inhibiter.
Highly preferred other composition is a soil release polymer, especially polyester or polysaccharide or derivatives thereof, cellulose-based polymer (Mierocrystalline cellulose that comprises carboxymethyl cellulose, ether of cellulose or ester or amine or acid amides modification), the spices of sealing, effervesce source (being preferably based on carbonate and acid compound, especially citric acid, oxysuccinic acid or toxilic acid), phosphonate washing assistant, dye transfer inhibitor and processing aid such as hydrotropic agent.Herein will be for a more detailed description to these compositions.
Can highly comprise preferably carboxymethyl cellulose compound (its level be described composition weight at least 0.5% or even 0.75% or even 1%), comprise perhaps or also comprise that level is at least 0.5% or even 0.75% or even 1% polysaccharide of a described composition weight.
Can contain cationic softening agent by preferred described composition.Highly preferred water-insoluble quaternary ammonium compound has two C
12-C
24Alkyl or alkenyl chain, optional by various functional groups as-OH ,-O-,-CONH-,-replacements such as COO-.
Well-known water-fast substantially quaternary ammonium compound has formula R
1R
2R
3R
4NX, R in the formula
1And R
2Representative has the alkyl of about 12-24 carbon atom; R
3And R
4Representative contains 1 alkyl to about 4 carbon atoms; X is a negatively charged ion, is preferably selected from halogenide, methylsulfate and ethyl sulphate.These, representative example of tenderizer comprised ditallow dimethyl ammonium chloride, methylsulfuric acid ditallow Dimethyl Ammonium, two hexadecyl alkyl dimethyl ammonium chloride, two (hydrogenated tallow alkyl) alkyl dimethyl ammonium chloride, two octadecyl dimethyl ammonium chloride, two eicosyl alkyl dimethyl ammonium chloride, two docosyl alkyl dimethyl ammonium chloride, methylsulfuric acid two (h-tallow base) Dimethyl Ammonium, double hexadecyl diethyl ammonium chloride, two (cocounut oil alkyl) alkyl dimethyl ammonium chloride in season.Preferred ditallow dimethyl ammonium chloride, two (hydrogenated tallow alkyl) alkyl dimethyl ammonium chloride, methylsulfuric acid two (cocounut oil alkyl) Dimethyl Ammonium.
Also suitable herein have U.S. Patent number 4127489 an imidazoles fabric softener of (incorporating this paper into the reference form).Term " fabric " tenderizer used herein " to be not included in pH be the cationic detersive active materials of about 6 times solvabilities in 20 ℃ water greater than 10 grams per liters.
Especially preferred have a ditallow methylamine.Its commodity have ArmeenM2HT from AKZONV, from the Genamin SH301 of FARBWERKEHOECHST and from the NoramM2SH of CECACOMPANY.The perhydrate SYNTHETIC OPTICAL WHITNER
A kind of preferred other component of described component or composition is perhydrate SYNTHETIC OPTICAL WHITNER such as metal perborate, metal percarbonate (especially sodium salt).Perborate can be single hydration or four hydrations.SPC-D corresponding 2Na
2CO
3.3H
2O
2And its commodity are crystalline solid forms.
Peroxide Potassium peroxysulfate, sodium are to be used for the optional inorganic perhydrate salts of another kind of detergent component herein.The organic peroxide acid bleach systems
A kind of preferred feature of described composition or component is the organic peroxide acid bleach systems.In a preferred example, described bleach systems comprises hydrogen peroxide cource and organic peroxide acid bleach precursor compound.Reaction in by described precursor and hydrogen peroxide cource is produced organic peroxide acid.Preferred hydrogen peroxide cource comprises the perborate bleach in inorganic hydrogen peroxide compound SYNTHETIC OPTICAL WHITNER such as the claimed invention.In another preferred example, preformed organic peroxide acid is directly added in the described composition.Another kind of scheme is to contain and the pre-composition that forms the mixture of organic peroxide acid bonded hydrogen peroxide cource and organic peroxy acid precursor.Peroxyacid bleach precursor
Peroxyacid bleach precursor is the compound that generates peroxy acid in crossing hydrolysis (perhydrolysis) reaction with hydroperoxidation.Usually peroxyacid bleach precursor can be expressed as
L is a leavings group in the formula, and X can be any functional group basically, and the structure of the peroxy acid that generates in crossing hydrolysis is like this
The 0.5-20% (weight) that the preferred adding level of peroxyacid bleach precursor compound is described detergent composition, more preferably 1-15% (weight), most preferably 1.5-10% (weight).
The peroxyacid bleach precursor compound that is fit to contains one or more N-or O-carboxyl groups usually, can extensively select its precursor-type.The type that is fit to comprises acid anhydrides, ester, imide, lactan and the acylated derivatives of imidazoles and oxime.The example that belongs to the useful materials of these types is disclosed among the GB-A-1586789.The ester that is fit to be disclosed in GB-A-836988,864798,1147871,2143231 and EP-A-0170386 in.Leavings group
Leavings group (after this representing with the L group) must have enough activity to the hydrolysis reaction of crossing that carries out in optimal time section (as cycles of washing).But if the L activity is too strong, this activator will be difficult to stably be used for bleaching composition.
Preferred L group is selected from:
With
With
And composition thereof, R in the formula
1Be alkyl, aryl or the alkaryl that contains 1-14 carbon atom, R
3For containing the alkyl chain of 1-8 carbon atom, R
4Be H or R
3Y is H or solubilizing group.R
1, R
3And R
4Any can be replaced by following any functional group basically, these functional groups comprise as alkyl, hydroxyl, alkoxyl group, halogen, amine, nitrosyl radical, acid amides and ammonium or alkyl ammonium group.
Preferred solubilization group is-SO
3 -M
+,-CO
2 -M
+,-SO
4 -M
+,-N
+(R
3)
4X
-And O ← N (R
3)
3And most preferably-SO
3 -M
+With-CO
2 -M
+, R in the formula
3For containing the alkyl chain of 1-4 carbon atom, M is for providing bleach-activating agent deliquescent positively charged ion, and X is for providing bleach-activating agent deliquescent negatively charged ion.Preferred M is basic metal, ammonium or replaces ammonium cation, most preferably sodium and potassium, and X is halogen anion, hydroxide radical, methylsulfate or acetic acid anion.Alkyl percarboxylic acids bleach precursor
Alkyl percarboxylic acids bleach precursor forms percarboxylic acids in crossing hydrolysis.Preferred this class precursor provides peracetic acid in crossing hydrolysis reaction.
The alkyl peroxycarboxylic acid precursors compound of preferred imide type comprises N, N, N
1, N
1Tetra-acetylated Alkylenediamine, wherein alkylidene group contains those compounds that 1-6 carbon atom, particularly alkylidene group contain 1,2 and 6 carbon atom.Especially preferred tetra acetyl ethylene diamine (TAED).Preferred TAED is not present in the agglomerated particle of the present invention, comprises in the described particulate detergent composition but preferably be present in.
Other preferred alkyl peroxycarboxylic acid precursors comprises 3,5,5-trimethyl acetyl oxygen base benzene sulfonic acid sodium salt (different-NOBS), acyloxy benzene sulfonic acid sodium salt in the ninth of the ten Heavenly Stems (NOBS), acetoxyl group benzene sulfonic acid sodium salt (ABS) and penta-acetyl glucose.The alkyl peroxy acids precursor that acid amides replaces
The alkyl peroxy acids precursor compound that acid amides replaces is suitable for herein, and it comprises those compounds with following general formula:
Or
R in the formula
1For having about 1 alkyl, R to about 14 carbon atoms
2For containing the alkylidene group of 1 to 14 carbon atom of having an appointment, R
5For H or contain the alkyl of 1-10 carbon atom, L can be any leavings group basically.The bleach activating immunomodulator compounds that such acid amides replaces is described in EP-A-0170386.Peroxybenzoic acid precursors
The peroxybenzoic acid precursors compound provides peroxybenzoic acid in crossing hydrolysis.The O-acidylate peroxybenzoic acid precursors compound that is fit to comprises and replacing and unsubstituted benzoyloxy benzene sulfonate; the benzoylation product of sorbyl alcohol, glucose and all sugar and benzoylation reagent; and those compounds of imide type, comprise the urea that N-benzoyl succinimide, four benzoyl quadrols and N-benzoyl replace.The imidazole type peroxybenzoic acid precursors that is fit to comprises N-benzoyl imidazoles and N-benzoyl benzoglyoxaline.The peroxybenzoic acid precursors that contains the N-acyl group that other is useful comprises N-benzoyl pyrrole alkane ketone, dibenzoyl taurine and benzoyl Pyrrolidonecarboxylic acid.Preformed organic peroxide acid
Described organic peroxide acid bleach systems can contain (except organic peroxide acid bleach precursor compound or as its substitute) organic peroxide acid bleach precursor compound (preformed hydrophobic organic peroxide acid), usually its level is 0.05-20% (weight), more preferably 1-10% (weight).
The preferred hydrophobic organic peroxy acid compound of one class is the compound that acid amides replaces, and it has following general formula,
Or
R in the formula
1Be aryl or the alkaryl with 1-14 carbon atom, R
2Be alkylidene group, arylidene and the alkyl arylene that contains 1-14 carbon atom, R
5For H or contain alkyl, aryl or the alkaryl of 1-10 carbon atom.Preferred R
1Contain 6 to 12 carbon atoms of having an appointment.Preferred R
2Contain 4 to 8 carbon atoms of having an appointment.R
1Can or contain branching, replacement or both alkaryls for the aryl of straight or branched alkyl, replacement, it can come from synthetic source or natural source (comprising as butter).R
2Similar structural changes can be arranged.R
2Can comprise alkyl, aryl, wherein said R
2Also can contain halogen, nitrogen, sulphur or other typical substituting group or organic compound.Preferred R
5Be H or methyl.R
1And R
5Should not contain and surpass 18 total carbon atom number.The bleach activator compound that this class acid amides replaces is described in EP-A-0170386.The suitable example of this class reagent comprises magnesium salts, 4-nonyl amino-4-oxo Perbutyric Acid and the diperoxy dodecanedioic acid of (6-octyl group amino)-6-oxo-caproic acid, (6-nonyl amino)-6-oxo-caproic acid, (6-decyl amino)-6-oxo-caproic acid, monoperphthalic acid magnesium hexahydrate, metachloroperbenzoic acid.These SYNTHETIC OPTICAL WHITNER are disclosed in US.4, and 483,781, U.S.4,634,551, EP 0,133,354, U.S.4,412,934 and EP0,170,386.For the object of the invention, preferred hydrophobic pre-formation peroxy acid bleach immunomodulator compounds is single nonyl acyl ammonia peroxycarboxylic acid.
Other suitable organic peroxide acid comprises having the diperoxy docosandioic acid that is no more than 7 carbon atoms, as diperoxy dodecandioic acid, diperoxy tetradecane diacid and diperoxy Thapsic acid.
Other suitable organic peroxide acid comprises the diamino peroxy acid that is disclosed among the WO95/032175, and it has following general formula:
R is selected from C in the formula
1-C
12Alkylidene group, C
5-C
12Cycloalkylidene, C
6-C
12Arylidene and combination thereof;
R
1And R
2Independently be selected from H, C
1-C
16Alkyl and C
6-C
12Aryl and can with R
3Form C together with two nitrogen
3-C
12The group of ring; R
3Be selected from C
1-C
12Alkylidene group, C
5-C
12Cycloalkylidene and C
6-C
12Arylidene; Selecting n and n ' respectively is an integer, makes it and is 1; Selecting m and m ' respectively is an integer, makes it and is 1;
M is selected from H, basic metal, alkaline-earth metal, ammonium, alkanol ammonium cation and free radical and combination thereof.
Other suitable organic peroxide acid comprises the amido peroxy acid that is disclosed in WO95/16673, and it has following general formula:
X-Ar-CO-NY-R(Z)-CO-OOH
X represents the substituting group of hydrogen or compatibility in the formula, and Ar is an aryl, and R represents (CH
2)
n, n=2 or 3 in the formula, Y and Z be the independent representative aryl that is selected from hydrogen or alkyl or aryl or alkaryl or replaced by the substituting group of compatibility respectively, and condition is that at least one of Y and Z is not hydrogen if during n=3.Substituent X on the preferred benzene nucleus is hydrogen or a position or para-orienting group, and described substituting group is selected from halogen (being generally the chlorine atom) or some non-release non-interference groups such as alkyl (can easily up to C6 such as methyl, ethyl or propyl group).Perhaps, X can represent the secondary acyl ammonia percarboxylic acids substituting group with following formula:
-CO-NY-R(Z)-CO-OOH
R, Y, Z and n definition are as above in the formula.
MOOC-R
1CO-NR
2-R
3-NR
4-CO-R
5COOOM
R in the formula
1Be selected from C
1-C
12Alkylidene group, C
5-C
12Cycloalkylidene, C
6-C
12Arylidene and combination thereof;
Highly preferred herein phthalyl amido peroxyacid (PAP).Bleaching catalyst
Described composition or component can comprise and contain the transition metal bleach catalyzer.
The bleaching catalyst that one class is suitable is to contain transition-metal cation such as copper, iron or the manganese positively charged ion with definition bleaching activity, has sequestrant faint or that do not have the active assistant metal positively charged ion of bleach catalyst such as zinc or aluminium cations and catalysis and assistant metal positively charged ion are had the definition stability constant, especially ethylenediamine tetraacetic acid (EDTA), ethylenediamine tetraacetic (methylene phosphonic acid) and water-soluble salt thereof.These catalyzer are disclosed in United States Patent (USP) 4,430,243.
The bleaching catalyst of other type comprises and is disclosed in United States Patent (USP) 5,246,621 and United States Patent (USP) 5,244,594 in the manganese base complex.The preferred example of these catalyzer comprises Mn
IV 2(u-O)
3(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane)
2-(PF
6)
2Mn
III 2(u-O)
1(u-OAc)
2(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane)
2-(C1O
4)
2Mn
IV 4(u-O)
6(1,4, the 7-7-triazacyclononane)
4-(C1O
4)
2Mn
IIIMn
IV 4(u-O)
1(u-OAc)
2(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane)
2-(C1O
4)
3And composition thereof.Other bleaching catalyst is disclosed in European patent application published numbers 549,272.Other part that is applicable to this comprises 1,5,9-trimethylammonium-1,5,9-triazododecane, 2-methyl isophthalic acid, 4,7-7-triazacyclononane, 2-methyl isophthalic acid, 4,7-7-triazacyclononane, 1,2,4,7-tetramethyl--1,4,7-7-triazacyclononane and composition thereof.
The bleaching catalyst of Shi Yonging also can be selected to the present invention herein.The example of suitable bleaching catalyst is referring to United States Patent (USP) 4,246, and 612 and United States Patent (USP) 5,227,084.Also referring to United States Patent (USP) 5,194,416, it mentions monokaryon manganese (IV) complex compound such as Mn (1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) (OCH
3)
3(PF
6).
Be disclosed in United States Patent (USP) 5,114,606 another kind of suitable bleaching catalyst is manganese (III) and/or the water soluble complex (IV) with a part, and described part is the polyol with non-carboxylate salt of at least three continuous C-OH functional groups.Preferred part comprises sorbyl alcohol, iditol, galactitol, mannitol, Xylitol (xylithol), arabitol, adonit, meso-tetrahydroxybutane, meso-inositol, lactose and composition thereof.
United States Patent (USP) 5,114,611 mention a kind of complex compound that comprises the transition metal (comprising manganese, cobalt, iron or copper) of the part with one non-(greatly) ring.Described part has following formula:
R in the formula
1, R
2, R
3And R
4Can be selected from H, substituted alkyl and aryl respectively, make each R
1-N=C-R
2And R
3-C=N-R
4Form five yuan or six-ring.Can further replace described ring.B is for being selected from O, S, CR
5R
6, NR
7With the abutment of C=O, wherein R
5, R
6And R
7Can be respectively H, alkyl or aryl (comprise replace or not substituted radical).Preferred part comprises pyridine, pyridazine, pyrimidine, pyrazine, imidazoles, pyrazoles and triazole ring.Optional described ring can be replaced by various substituting groups such as alkyl, aryl, alkoxyl group, halogenide and nitro.Especially preferred part 2,2 '-two pyridine amine.Preferred bleaching catalyst comprise cobalt, copper, manganese, iron ,-two pyridyl methane and-two pyridine amine complexes.Highly preferred catalyzer comprises Co (2,2 '-two pyridine amine) Cl
2, the two pyridine amine-cobalts of two (isothiocyanatos) (II), three (two pyridine amine)-cobaltous perchlorate (II), Co (2, the two pyridine amine of 2-)
2O
2ClO
4, two-(2,2 '-two pyridine amine) cupric perchlorates (II), three (two-2-pyridine amine) Iron triperchlorate (II) and composition thereof.
The double-core manganese that other example comprises with four-N-coordination thing and two-N-coordination thing part carries out complexing, it comprises N
4Mn
III(u-O)
2Mn
IVN
4)
+[Bipy
2Mn
III(u-O)
2Mn
IVBipy
2]-(ClO
4)
3
Other bleaching catalyst is described in as European patent application published numbers 408,131 (cobalt complex catalysts), European patent application published numbers 384,503 and 306,089 (catalysis of metalloporphyrin agent), U.S.4,728,455 (manganese/polygamy position thing ligand catalyst), U.S.4,711,748 and European patent application published number 224,952 (manganese that on aluminosilicate catalyst, absorb), U.S.4,601,845 (having carried the aluminosilicate carrier of manganese salt and zinc salt or magnesium salts), U.S.4,626,373 (manganese/ligand catalysts), U.S.4,119,557 (iron complex catalyzer), German patent specification 2,054,019 (cobalt chelates catalyzer), Canadian Patent 866,191 (salt that contains transition metal), U.S.4,430,243 (sequestrant) and U.S.4 with manganese positively charged ion and non-catalytic metallic cation, 728,455 (gluconic acid Mn catalysts).
Usually with catalytically effective amount described bleaching catalyst is used for compositions herein and method." catalytically effective amount " is meant no matter the amount that all is enough to improve bleaching and removes spot and color spot from target substrate under which kind of compare test condition.Custom according to used wash type and user changes described test condition.In laundry operations, some users select to use hot water, and other use warm water or even cold water.Certainly, the catalytic performance of bleaching catalyst will be subjected to the influence of this factor, and can suitably regulate the level that is used for the used bleaching catalyst of full formula washing composition and bleaching composition.In fact (unrestricted) is provided in the aqueous cleaning solution at least ten million/a active bleaching catalyst material approximately thereby can regulate compositions herein and method, and preferably is provided in the washings the extremely catalyst substance of about 200ppm of about 1ppm.In order to further specify this point, be 10 at 40 ℃ with pH, under the European condition that adopts perborate and bleach precursor, about 3 micromolar Mn catalysts are effective.Under U.S.'s condition, doubly obtain identical result thereby may need to increase concentration 3-5.Heavy metal ion chelating agent
The present composition or component preferably contain the heavy metal ion chelating agent as optional components.Heavy metal ion chelating agent is meant the component of serving as heavy metal ion chelating agent herein.These components also can have the sequestering power of calcium and magnesium, but preferably they to having selectivity in conjunction with heavy metal ion such as iron, manganese and copper.
The common amount of heavy metal ion chelating agent is the 0.005-10% of described composition or composition weight, preferred 0.1-5%, more preferably 0.25-7.5%, most preferably 0.3-2%.
The heavy metal ion chelating agent of Shi Yonging includes organic phosphonates such as amino alkylidenyl poly-(alkylene phosphonic acids salt), basic metal ethane 1-hydroxyl diphosphonate and nitrilo propylidene phosphonate herein.
In the above in the compound, preferred heavy metal ion chelating agent is diethylenetriamine five (methylene phosphonic acid salt), quadrol three (methylene phosphonic acid salt), hexanediamine four (methylene phosphonic acid salt) and hydroxyl-ethylidene 1,1-diphosphonate, 1,1-hydroxyl hexane di 2 ethylhexyl phosphonic acid and 1,1-hydroxyl ethane dimethylene phosphonic acids.
The suitable heavy metal ion chelating agent of other of Shi Yonging comprises nitrilotriacetic acid(NTA) and polyamino carboxylic acid such as second diamino tetraacethyl, quadrol two Succinic Acid, quadrol two pentanedioic acids, 2-hydroxyl propylene diamine two Succinic Acid or its any salt herein.
The heavy metal ion chelating agent that is fit to of other of Shi Yonging is iminodiacetic acid derivatives such as 2-hydroxyethyl oxalic acid or glyceryl iminodiethanoic acid (being described in EP-A-317,542 and EP-A-399,133) herein.Be described in EP-A-516,102 iminodiethanoic acid-N-2-hydroxypropyl sulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid sequestrant also are applicable to this.Be described in EP-A-509, Beta-alanine-N of 382, N '-oxalic acid, aspartic acid-N, single acetate of N '-oxalic acid, aspartic acid-N-and imino-diacetic Succinic Acid sequestrant also are fit to.
EP-A-476,257 have described the sequestrant based on amino that is fit to.EP-A-510,331 have described by collagen protein, Keratin sulfate or the casein derived and next sequestrant that is fit to.EP-A-528,859 have described the alkyl imino oxalic acid sequestrant that is fit to.Pyridine dicarboxylic acid and 2-phosphinylidyne butane-1,2, the 4-tricarboxylic acid also is fit to.G-NH2-N, N '-two Succinic Acid (GADS), quadrol-N-N '-two pentanedioic acid (EDDG) and 2-hydroxyl propylene diamine-N-N '-two Succinic Acid (HPDDS) also are fit to.
Especially preferred diethylene triaminepentaacetic acid(DTPA), quadrol-N, N '-two Succinic Acid (EDDS) and 1,1-hydroxyl ethane di 2 ethylhexyl phosphonic acid or its an alkali metal salt, alkaline earth salt, ammonium salt or substituted ammonium salt, or its mixture.Enzyme
The another kind of preferred composition that is used for component herein or composition is the enzyme of one or more interpolations.
The preferred enzyme material that adds comprises lipase, keratanase, amylase, neutrality and Sumizyme MP, cellulase, endolase, esterase, polygalacturonase, Sumylact L and the peroxidase that is routinely added to the commercial offers in the detergent composition.The enzyme that is fit to is at United States Patent (USP) 3,519, discusses in 570 and 3,533,139.
The proteolytic enzyme that preferred commercially available protein enzyme comprises the proteolytic enzyme sold with the trade(brand)name of Alcalase, Savinase, Primase, Durazym and Esperase by Novo IndustriesA/S (Denmark), sold with the trade(brand)name of Maxatase, Maxacal and Maxapem by Gist-Brocades, by Genencor International sell proteolytic enzyme and those proteolytic enzyme of selling with the trade(brand)name of Opticlean and Optimase by Solvay Enzymes.The proteolytic enzyme that can add the present composition can join in the composition of the present invention with the level of the organized enzyme of the 0.0001-4% of described composition weight.
Preferred amylase comprises the α-Dian Fenmei that obtains as the specific bacterial strain by Bacillus licheniformis (B licheniformis), its more detailed content be described in GB-1,269,839 (Novo).Preferred commodity starch enzyme comprise as sell with the trade(brand)name of Rapidase by Gist-Brocades those, by NovoIndustriesA/S with Termamyl, those amylase that the trade(brand)name of Duramyl and BAN is sold.Highly preferred amylase can be for being described in those amylase of PCT/US9703635 and WO95/26397 and WO96/23873.
Amylase can add in the composition of the present invention with the organized enzyme level of 0.0001-2% (weight).
Lipolytic enzyme can be with 0.0001-2% (weight), preferred 0.001-1% (weight), and most preferably the level of the active lipolytic enzyme of 0.001-0.5% (weight) exists.
Lipase can be to come from fungi or bacterium, by as by Humicola sp., Thermomyces sp. or the production of Pseudomonas sp. bacterial strain obtain.Also be applicable to this from the chemistry of these bacterial strains or the lipase of gene modification mutant.Preferred lipase is derived from pseudomonas pseudoalcaligenes (Pseudomonas pseudoalcaligenes), and it is described in the European patent EP-B-0218272 of mandate.
Another kind of herein preferred lipase is by cloning from the gene of Humicola lanuginosa and express acquisition (being described in European patent application EP-A-0258 068) in Aspergillus oryza (host), it is by Novo Industri A/S, Bagsvaerd, Denmark obtains commercial offers with the trade(brand)name of Lipolase.This lipase also is described in and authorized the United States Patent (USP) 4,810,414 give Huge-Jensen etc. on March 7th, 1989.The organic polymer that adds
Organic polymer is the preferred interpolation component of composition or component herein, and preferably exists with the form of the component of any grain fraction, and wherein said polymkeric substance can be used for grain fraction is bonded together mutually.Organic polymer herein is meant any basically polymerizable organic compound of the dispersion agent, anti redeposition agent or the stain remover that are used as detergent composition usually.
Usually the level that adds the organic polymer of detergent composition of the present invention is the 0.01-30% of described composition or composition weight, preferred 0.1-15%, most preferably 0.5-10%.
The example of organic polymer comprises water-soluble organic homopolymerization or copolymerization polycarboxylic acid or their salt, and wherein said polycarboxylic acid comprises and is no more than two separated at least two carboxyls of carbon atom.The polymkeric substance of latter type is disclosed in GB-A-1, and 596,756.The example of these salt is the multipolymer of the polyacrylic ester of weight-average molecular weight (MWt) with 1000-5000 and they and maleic anhydride, and the molecular weight of these multipolymers is 2000-100,000, especially 40, and 000-80,000.
Polyamino compounds is applicable to this, they comprise as be disclosed in EP-A-305282, EP-A-305283 and EP-A-351629 by aspartate-derived and those materials that come.
Contain and be selected from the monomeric terpolymer of toxilic acid, vinylformic acid, poly aspartic acid and vinyl alcohol, especially molecular-weight average is 5,000-10, and those multipolymers of 000 also are applicable to this.
Being suitable for adding herein, other organic polymer of detergent composition comprises derivatived cellulose such as methylcellulose gum, carboxymethyl cellulose, Vltra tears and Natvosol.
Other organic polymer that is suitable for is a polyoxyethylene glycol, and especially molecular weight is 1000-10000, more preferably 2000-8000, most preferably from about those polyoxyethylene glycol of 4000.
Polyethylene oxide is the preferred component of adding, and especially is present in the particle as wetting Agent for Printing Inks with herein clay, preferably also combines with wax or oil phase.
Highly preferred herein polymeric component is the United States Patent (USP) 5,415,807 according to people such as people's such as Scheibel United States Patent (USP) 4,968,451 and Gosselink, especially according to the cotton goods and the non-cotton goods soil release polymer of Application No. 60/051517.
The another kind of organic compound of the preferably clay dispersion agent/anti redeposition agent that herein uses can be the ethoxylation positively charged ion monoamine and the diamines of following formula,
X is a non-ionic group in the formula, is selected from H, C
1-C
4Alkyl or hydroxy alkyl ester or ether and combination thereof, a is 0-20, preferred 0-4 (as ethylidene, propylidene, hexa-methylene), b is 1 or 0; For positively charged ion monoamine (b=0), n is at least 16, and scope is 20-35 usually; For cationic diamine (b=1), it is about 12 that n is at least, and scope is about 12 to 42 usually.
Other dispersion agent used herein/deposition agent is described in EP-B-011965 and United States Patent (USP) 4,659,802 and United States Patent (USP) 4,664,848 again.Press down foam system
When the preparation machine cleaning composition, component and detergent composition can contain and press down foam system herein, and there is level in it is the 0.01-15% of described composition or composition weight, preferred 0.02-10%, most preferably 0.05-3%.
The foam that presses down that is applicable to this is to consist essentially of any known defoaming compounds, comprises as silicone defoamer and 2-alkyl alcanol defoaming compounds.
Defoaming compounds herein is meant that any can be used in as suppressing produces the foamy compound of (especially under the situation of stirred solution) or the mixture of these compounds by detergent composition solution.
The especially preferred defoaming compounds that is used for herein is the silicone defoaming compounds that comprises the silicone component that herein is defined as to any defoaming compounds.These silicone defoaming compounds also contain silica component usually.General term " silicone " used herein and industrial comprises the various higher molecular weight polymer that contain siloxane unit and dissimilar alkyl.Preferred silicone defoaming compounds is a siloxanes, especially has the unitary polydimethylsiloxane of trimethylsilyl end-block.
Other defoaming compounds that is fit to comprises mono carboxylic lipid acid and soluble salt thereof.These materials are described in and authorize the United States Patent (USP) 2,954,347 that gives Wayne St.John September 27 nineteen sixty.Usually have 10-24 carbon atom as the mono carboxylic lipid acid of suds suppressor and the hydrocarbon chain of salt thereof, preferred 12-18 carbon atom.The salt that is fit to comprises an alkali metal salt such as sodium, potassium and lithium salts and ammonium salt and alkanol ammonium salts.
Other defoaming compounds that is fit to comprises as the fatty acid ester of high-molecular weight fatty ester (as fatty acid glyceryl ester), monovalent alcohol, aliphatic C
18-C
40To tetraalkyl diamines chlorination triazine, they are cyanuryl chlorides and the product, propylene oxide, two stearic amide and single stearyl two basic metal (as sodium, potassium, lithium) phosphoric acid salt and the phosphoric acid ester that contain two moles of 1-24 carbon atom or three moles of uncles or secondary amine formation to ketone (as stearone) N-alkylation aminotriazine as three to six alkyl melamines or two.
The preferred foam system that presses down comprises:
(a) defoaming compounds, preferred silicone defoaming compounds, silicone defoaming compounds most preferably, it comprises following combination:
(i) polydimethylsiloxane, its level are the 50-99% of silicone defoaming compounds weight, preferred 75-95%; With
(ii) silicon-dioxide, its level is the 1-50% of silicone/silicon-dioxide defoaming compounds weight, preferred 5-25%;
The adding level of wherein said silica/silicon ketone defoaming compounds is 5-50%, preferred 10-40% (weight);
(b) compound dispersing agent most preferably comprises rake shape (rake) multipolymer of silicone dibasic alcohol, and the amount of polyoxyalkylene is 72-78%, and oxyethane is 1: 0.9 to 1: 1.1 with the ratio of propylene oxide, and its level is 0.5-10%, preferred 1-10% (weight); Especially preferred this class silicone dibasic alcohol rake shape multipolymer is DCO544, available from the commodity of the DCO544 by name of DOW Corning;
(c) inert support fluid compound, most preferably containing degree of ethoxylation is 5-50, the C of preferred 8-15
16-C
18Ethoxylated alcohol, its level are 5-80%, preferred 10-70% (weight);
Highly preferred granular suds suppressing system is described in EP-A-0210731 and comprises the silicone defoaming compounds and melting range is 50-85 ℃ a organic support material, wherein said organic support material comprises monoglyceride and has the lipid acid of 12-20 carbon atom, EP-A-0210721 discloses other preferred granular suds suppressing system, wherein organic support material is lipid acid or the alcohol that 45 ℃-80 ℃ of fusing points and its carbochain contain 12-20 carbon atom, or its mixture.
Other highly preferred foam system that presses down comprises polydimethylsiloxane or silicone mixture, as polydimethylsiloxane, silico-aluminate and polycarboxylic acid polymkeric substance such as laic and acrylic acid multipolymer.
Also highly preferably there is soap.The polymeric dye migration inhibitor
Component herein or composition also can comprise 0.01-10%, the polymeric dye migration inhibitor of preferred 0.05-0.5% (weight).
The polymeric dye migration inhibitor is preferably selected from polyamine N-oxide pllymers, the multipolymer of N-vinyl pyrrolidone and N-vinyl imidazole, polyvinylpyrrolidonepolymers polymers or its combination, and these polymkeric substance can be cross-linked polymers thus.White dyes
Component herein and composition all preferably contain about 0.05-5% of promising described composition weight, more preferably 0.07-3% or even 0.1-2.5% or, be about 0.05-5% of described composition weight, more preferably 0.1-3% or even the hydrophilic white dyes of some type of 0.12-2.5%.
The hydrophilic white dyes of Shi Yonging comprises that those have the compound of following structural formula herein.
R in the formula
1Be selected from anilino, N-2-two-hydroxyethyl and NH-2-hydroxyethyl; R
2Be selected from N-2-pair-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morpholinyl, chlorine and amino; M is salt-forming cation such as sodium or potassium.
In following formula, work as R
1Be anilino, R
2Be N-2-pair-hydroxyethyl, when M was positively charged ion such as sodium, described whitening agent was 4,4 '-two [(4-anilino-6-(N-2-couple-hydroxyethyl)-s-triazine-2-yl) amino]-2,2 '-Stilbene disulfonic acid and disodium salt.This concrete whitening agent is sold with the trade(brand)name of Tinopal-UNPA-GX by Ciba-GeigyCorporation.Tinopal-CBS-X and Tinopal-UNPA-GX are the preferred hydrophilic white dyess that are suitable for of detergent composition herein.
In following formula, work as R
1Be anilino, R
2When being positively charged ion such as sodium for N-2-hydroxyethyl-N-2-methylamino-and M, described whitening agent is 4,4 '-two [(4-anilino-6-(N-2-two-hydroxyethyl-N-methylamino)-s-triazine-2-yl)-amino] 2, and 2 '-Stilbene disulfonic acid disodium salt.This concrete whitening agent is sold with the trade(brand)name of Tinopal-5BM-GX by Ciba-Geigy Corporation.
In following formula, work as R
1Be anilino, R
2When being positively charged ion such as sodium for morpholinyl and M, described whitening agent is 4,4 '-two [(4-anilino-6-morpholinyl-s-triazine-2-yl) amino] 2,2 '-Stilbene disulfonic acid sodium salt.This concrete whitening agent is sold with the trade(brand)name of Tinopal-DMS-X and Tinopal AMS-GX by Ciba-Geigy Corporation.The polymerization stain remover
Polymerization stain remover (after this being called " SRA ") can be chosen wantonly and be used for component of the present invention or composition.If use, generally include 0.01-10.0%, be generally 0.1-5%, the SRA of preferred 0.2-3.0% (weight).
Preferred SRA has hydrophilic segment and hydrophobic part usually, hydrophilic segment makes the surface hydrophilic of hydrophobic fiber such as polyester and nylon, hydrophobic part is deposited on above the hydrophobic fiber and keeps adhering on it in finishing washing and rinse cycle, serves as the anchor of hydrophilic segment thus.This makes the dirt of handling with SRA be easier to be eliminated in the subsequent wash program.
Preferred SRA comprises low polyterephthalate, generally by adopting at least a transesterification reaction/oligomerization of metal catalyst such as pure titanium (IV) to prepare usually.These esters can adopt the preparation of other monomer, these monomers can one, two, three, four or more a plurality of position add ester structure, not have to form tight crosslinked overall texture certainly.
The SRA that is fit to comprises that sulfonated products that contains the terephthaloyl and the basic linear ester oligopolymer of the oligomer ester main chain of oxyalkylene oxygen repeating unit and the allyl deriv sulfonation end-blocking that links to each other with the main chain covalency partly (as are described in the United States Patent (USP) 4 that J.J.Scheibel and E.P.Gosselink are given in mandate on November 6 nineteen ninety; 968,451).These ester oligomers can be prepared by following method: (a) ethoxylated allyl; (b) in secondary transesterification reaction/oligomerization program, make (a) product and dimethyl terephthalate (DMT) (" DMT ") and 1,2-propylene glycol (" PG ") reaction; (c) in water, make the reaction of (b) product and sodium metabisulfite.Other SRA comprises and authorized the U.S.4 give people such as Gosselink on December 8th, 1987,711, nonionic in 730 end capped 1,2-propylidene/polyoxyethylene terephthalate polyester, for example those materials of producing by transesterify/oligomerization of poly-(ethylene glycol) methyl ether, DMT, PG and poly-(ethylene glycol) (" PEG ").Other example of SRA comprises: on January 26th, 1988 was authorized the end capped oligomer ester of part or all of negatively charged ion of the United States Patent (USP) 4,721,580 that gives people such as Gosselink, as ethylene glycol (" EG "), PG, DMT and 3, and 6-two oxa-s-8-hydroxyl perfluorooctane sulfonate; Authorized the U.S.4 that gives Gosselink on October 27th, 1987,702, the end capped block polyester oligopolymer of nonionic in 857, as by DMT, methyl (Me)-end capped PEG and EG and/or PG, or the combination of DMT, EG and/or PG, the block oligomers that the PEG of methyl blocking and dimethyl-5-sulfoisophthalic acid sodium is produced; And on October 31st, 1989 authorize and to give Maldonado; people's such as Gosselink U.S.4; 877; negatively charged ion in 896; especially the end capped terephthalate of sulfo group aroyl; the latter is used to do washing and the typical SRA of fabric-conditioning product, and an example is by a sulfosalicylic acid list sodium salt, PG and DMT, and is optional but preferably further comprise the ester composition of PEG (as the PEG 3400) preparation of adding.
SRA also comprises: the simple segmented copolymer of ethylene glycol terephthalate or propylene glycol ester terephthalate and polyethylene oxide or poly(propylene oxide) terephthalate, can be referring to authorizing the U.S.3 that gives Hays on May 25th, 1976,959, authorized the U.S.3 that gives Basadur on July 8th, 230 and 1975,893,929; Derivatived cellulose is as the hydroxy ethers cellulose polymer compound that provides with METHOCEL from Dow; C
1-C
4Alkylcellulose and C
4Hydroxy alkyl cellulose is referring to authorizing the U.S.4 that gives people such as Nicol, 000,093 on December 28th, 1976; And methyl cellulose ether, wherein the unitary average substitution degree of each dextrose anhydrous (methyl) is about 1.6 to 2.3, the soltion viscosity of 2% aqueous solution that records under 20 ℃ is about 80 to 120 centipoises.These materials obtain supply with METOLOSESM100 and METOLOSESM200, and they are the trade(brand)names by the methyl cellulose ether of Shin-etsu Kagaku Kogyo KK production.Also height preferred polysaccharide polymkeric substance.
The SRA of other type comprises: (I) adopt the vulcabond coupling agent to connect the nonionic terephthalate of polyester structure, and referring to people's such as Violland U.S.4,201,824 and people's such as Lagasse U.S.4,240,918; (II) have the SRA of carboxylicesters end group, by with 1,2, thereby the 4-benzenetricarboxylic anhydride adds among the known SRA and end capped hydroxyl is converted into 1,2, the preparation of 4-benzenetricarboxylic acid ester.With regard to suitable selecting catalyst, 1,2, the 4-benzenetricarboxylic anhydride is by 1,2, the ester of the isolated carboxylic acid of 4-benzenetricarboxylic anhydride, rather than form bonding with polymer ends by opening anhydride bond.Nonionic or anionic SRA can be used as raw material, condition be they have can esterification hydroxyl end groups.Referring to people's such as Tung U.S.4,525,524.Other type comprises: (III) the negatively charged ion terephthalic acid ester group SRA variant of carbamate connection, and referring to people's such as Violland U.S.4201,824.Other optional components
Be suitable for being included in the filling salt that other optional member in the present composition or the component comprises spices, colorant and replacement vitriol filling salt (filer salt).
Also can be preferably and neutralizing agent, buffer reagent, phase modifier (phase regulants), hydrotropic agent, enzyme stabilizers, polyacid, foaming regulator, opalizer, antioxidant, sterilant, optical white, spot decorations agent and the dyestuff of carbonate, a small amount of (as being less than about 20% (weight)) (as authorizing the United States Patent (USP) 4 that gives people such as Barrat in 1981,285, those materials described in 841 add this paper with for referencial use at this) exist together.The form of composition
Composition of the present invention can be produced by the whole bag of tricks, and these methods comprise that doing of all cpds that is included in the described detergent component mixed, the combination of agglomeration, compacting or spraying drying or these technology.
Composition can adopt the various physical form that comprise liquid herein, but preferred solid form such as sheet, thin slice, lozenge and bulk, the preferred particulates form.
The present composition also can be used for bleaching interpolation composition (for example comprising chlorine bleach) or add composition with bleaching being used in combination.
Detergent composition herein, especially clothing is 280 grams per liters-200 grams per liters with the tap density of washing composition, perhaps preferred 300 grams per liters or even 350 grams per liters or 420 grams per liter to 2000 grams per liters or preferred 1500 grams per liters or 100 grams per liters or even to 700 grams per liters.The chloro SYNTHETIC OPTICAL WHITNER
Described detergent composition can contain the chloro SYNTHETIC OPTICAL WHITNER as other component.But because preferred detergent composition of the present invention is solid, most liquid chloro SYNTHETIC OPTICAL WHITNER will be not suitable for these detergent composition and have only particle or powder chloro SYNTHETIC OPTICAL WHITNER is fit to.
Perhaps, described detergent composition can be mixed with the chloro bleach-compatible, guarantee that thus the chloro SYNTHETIC OPTICAL WHITNER can be added in the detergent composition by the user in the beginning of washing process or process.
The chloro SYNTHETIC OPTICAL WHITNER can form hypochlorite in the aqueous solution.The chemical expression of hypochlorite ion is OCl
-
These SYNTHETIC OPTICAL WHITNER that generate hypochlorite in the aqueous solution comprise adduct, chloramines, chlorimide, chloral-formamide and the chlorimides of basic metal and alkaline-earth metal hypochlorite, hypochlorite.The object lesson of this compounds comprises clorox, potassium hypochlorite, single alkali formula Losantin, two basic magnesium hypochlorites, Efficacious Disinfeitant dodecahydrate, potassium dichloroisocyanurate, Surchlor GR 60, Surchlor GR 60 dihydrate, trichlorocyanuric acid, 1,3-two chloro-5,5-T10, N-Clofenamide, chloramine-T, dichloramine-T, chloramine B and dichloramine B.The preferred SYNTHETIC OPTICAL WHITNER that is used for composition of the present invention is clorox, potassium hypochlorite or its mixture.Preferred chloro SYNTHETIC OPTICAL WHITNER can be Triclosan (trade(brand)name).
The SYNTHETIC OPTICAL WHITNER of most of above-mentioned generation hypochlorites can solid or conc forms obtain supply and when preparation composition of the present invention, be dissolved in water.Some of above-mentioned materials obtain supply with the form of the aqueous solution.The clothes washing method
Machine laundry method herein is usually included in the washing machine with wherein dissolving and disperseing the machine-wash wash water solution processing of detergent composition of the present invention of significant quantity to stain clothing.The detergent composition of significant quantity is meant 10 grams is dissolved in or is scattered in 5 to 65 liters of washing solns to 300 gram products that this significant quantity is typical product dosage and the washing soln volume that is generally used for conventional machine washing method laundry.
Compositions herein can be used for conventional washing machine and low water is filled washing machine (low-waterfill machines).
A preferred use aspect is the hand washing composition.Another preferred aspect described detergent composition be pre-treatment or soak composition, be used for the fabric that pre-treatment or immersion are stained and stain.
The abbreviation of Shi Yonging in an embodiment
In detergent composition, the abbreviation component of mark has following implication.The LAS straight chain C
11-13Sodium alkyl benzene sulfonate TAS tallow alkyl sodium sulfate C
XyS C
1x-C
1ySodium alkyl sulfate C
46SAS C
14-C
16Secondary (2,3) sodium alkyl sulfate C
XyE
zThe C of S and the condensation of z moles of ethylene oxide
1x-C
1ySodium alkyl sulfate C
XyE
zC with the condensation of average z moles of ethylene oxide
1x-C
1yPrimary of basic straight chain
Alcohol QAS R
2.N
+(CH
3)
2(C
2H
4OH), R
2=C
12-C
14QAS1 R
2.N
+(CH
3)
2(C
2H
4OH), R
2=C
8-C
11SADS formula 2-(R) .C
4H
7-1,4-(SO
4-)
2C
14-C
22Alkyl two sodium sulfate
Salt, R=C in the formula
10-C
18SADE2S formula 2-(R) .C
4H
7-1,4-(SO
4-)
2C
14-C
22Alkyl two sodium sulfate with
The condenses of z moles of ethylene oxide, R=C in the formula
10-C
18MES C
18The x-sulfo methyl ester APA C of lipid acid
8-C
10Amido propyl group dimethylamine soap is derived from the straight chain alkane of 80/20 mixture of butter and fatty acid distribution of coconut oil
Yl carboxylic acid sodium STS toluenesulfonic acid sodium salt CFAA C
12-C
14(cocounut oil) alkyl N-methyl glucose amide TFAA C
16-C
18Alkyl N-methyl glucose amide TPKFA C
16-C
18The full cut lipid acid of topping STPP anhydrous sodium tripolyphosphate TSPP tetrasodium pyrophosphate ZeoliteA formula Na
12(AlO
2SiO
2)
12.27H
2The hydrated sodium aluminosilicate of O, particle diameter
Be 0.1-10 micron (expressing weight) NaSKS-6 formula δ-Na based on anhydride
2Si
2O
5Crystal layered silicate anhydrous citric acid citric acid borate Sodium Tetraborate carbonate particle diameter to be distributed as 200 microns to 900 microns anhydrous sodium carbonate supercarbonate size distribution be 400 microns to 1200 microns anhydrous sodium bicarbonate silicate amorphous sodium silicate (SiO
2: Na
2O=2.0: 1) vitriol anhydrous sodium sulphate sal epsom anhydrous magnesium sulfate Citrate trianion two hydration trisodium citrates, activity is 86.4%, size distribution is 425
Toxilic acid/acrylic copolymer of 1: 4 of-850 microns MA/AA of micron, molecular-weight average is about 70,000MA/AA (1) toxilic acid/acrylic copolymer of 4: 6, molecular-weight average is about 10, the 000AA molecular-weight average is 4, the plain ether polymerization degree of 500 polyacrylic acid sodium polymer CMC sodium carboxyme-thylcellulose fibre is 650 methyl cellulose ether, available from Shin Etsu
Chemicals protease protein lytic enzyme, the organized enzyme with 3.3% (weight) is by NOVO
IndustriesA/S sells proteolytic enzyme I proteolytic ferment with the trade(brand)name of Savinase, and the organized enzyme with 4% (weight) is described in WO
95/10591, sell the Alcalase proteolytic ferment by Genencor Int.Inc., the organized enzyme with 5.3% (weight) is by NOVO
IndustriesA/S sells the cellulase cellulolytic enzyme, the organized enzyme with 0.23% (weight), by
NOVOIndustriesA/S sells the amylase amylolytic enzyme with the trade(brand)name of Carezyme, and the organized enzyme with 1.6% (weight) is by NOVO
IndustriesA/S sells the amylolytic enzyme lipase fat hydrolase that amylase II is disclosed in PCT/US9703635 with the trade(brand)name of Termamy 120T, and the organized enzyme with 2.0% (weight) is by NOVO
Industries A/S sells lipase II fat hydrolase with the trade(brand)name of Lipolase, and the organized enzyme with 2.0% (weight) is by NOVO
Industries A/S sells the Endolase endoglucanase with the trade(brand)name of Lipolase Ultra, and the organized enzyme with 1.5% (weight) is by NOVO
IndustriedA/S sells PB4 mark formula NaBO
23H
2O.H
2O
2Sodium perborate tetrahydrate PB1 mark formula NaBO
2.H
2O
2Anhydrous sodium perborate SYNTHETIC OPTICAL WHITNER percarbonate mark formula 2Na
2CO
3.3H
2O
2SODIUM PERCARBONATE DOBS sodium-salt form the last of the ten Heavenly stems acyloxy benzene sulfonate DPDA diperoxy dodecanedioic acid NOBS sodium-salt form acyloxy benzene sulfonate DOBA caprinoyl p-methoxybenzoic acid TAED tetra acetyl ethylene diamine DTPA diethylene-triamine pentaacetic acid DTPMP diethylenetriamines five (the methylene phosphonic acid salt) in the last of the ten Heavenly stems of 12 carbon acyloxy benzene sulfonate DOBS sodium-salt forms of nonanoly acyloxy benzene sulfonate NACA-OBS (6-nonanoyl amido caproyl) oxygen base benzene sulfonate LOBS sodium-salt form, by Monsanto with
The trade(brand)name of Dequest 2060 is sold EDDS quadrol-N, N '-two Succinic Acid, (the S of sodium-salt form, S) the isomer light activating agent is encapsulated in sulfonation phthalocyanine phthalocyanine zinc light activating agent in SYNTHETIC OPTICAL WHITNER (1) the dextrin soluble polymer and is encapsulated in aluminum phthalocyanine whitening agent 14 in SYNTHETIC OPTICAL WHITNER (2) the dextrin soluble polymer, 4 '-two (2-sulfo group styryl) biphenyl disodium whitening agent 24,4 '-two (4-anilino-6-morpholine also-1.3.5-triazine-2-yl) amino) Stilbene-
2: 2 '-disulfonic acid disodium HEDP 1,1-hydroxyl ethane di 2 ethylhexyl phosphonic acid PEG
xPolyoxyethylene glycol, molecular weight is that x (is generally 4,000) PEO polyethylene oxide, molecular-weight average is 50,000TEPAE tetren ethoxylate PVI polyvinyl imidazol, and molecular-weight average is 20, the 000PVP polyvinylpyrrolidonepolymers polymers, molecular-weight average is 60,000PVNO polyvinylpyridine N-oxide polymer, and molecular-weight average is
50, the multipolymer of 000PVPVI Polyvinylpyrolidone (PVP) and vinyl imidazole, average mark
The son amount is 20, the two ((C of 000QEA
2H
5O) (C
2H
4O)
n) (CH
3)-N
+-C
6H
12-N
+-(CH
3)
Two ((C
2H
5O) (C
2H
4O))
n, wherein n is the 20-30PEI polymine, and molecular-weight average is 1800, and average ethoxyquin degree is
7 ethylene oxy residues of each nitrogen clay I POLARGEL NF II smectite-type clay flocculation agent I molecular weight is 200,000 to 400,000 polyethylene oxide flocculation agent II molecular weight is 400,000 to 1,000,000 polyethylene oxide flocculation agent III molecular weight is 200,000 to 400,000 acrylamide and/or propylene
The short block of the end capped polyester SRP2 of the end capped polyester soil release polymers SRPII of acid polymer SRPI negatively charged ion polysaccharide soil release polymer SRP1 nonionic diethoxyization poly-(terephthalic acid 1,2 propylene glycol ester) is poly-
Compound silicone defoamer siloxanes-oxyalkylene copolymers is as the polydimethylsiloxane of dispersion agent
Foam Control, described Foam Control with the ratio of described dispersion agent is
10: 1-100: the water base single styrene latex mixture of 1 opalizer, by BASF
Aktiengesellschaft sells the carbonate or the organic carboxyl acid/salt of alabaster wax spot decorations agent band look with the trade(brand)name of Lytron 621
Be component of the present invention (weight percentage of described component) below.
Component | ?I | ??II | ??III | ??IV | V | ??VI | ?VII | ?VIII | ???IX | ?X | ??XI | ??XII |
Clay I and/or II | ?10 .0 | ??15. ??0 | ??8.0 | ??7.0 | 5.0 | ??10. ??0 | ??20. ??0 | ?25.0 | ???8.0 | ?10. ?0 | ??10 ??0 | ??15. ??0 |
Flocculation agent I or II | ?0. ?1 | ??0.5 | ??1.0 | ??2.0 | 2.5 | ??1.0 | ??3.0 | ?0.2 | ???0.1 | ?1.0 | ??0. ??5 | ??2.0 |
???LAS | ?10 .0 | ??8.0 | ??18. ??0 | ??20. ??0 | - | ???- | ??- | ??- | ???30. ???0 | ??35. ??0 | ???- | ??18. ??0 |
???TAS | ?2 | ??- | ??- | ??- | 3.0 | ?6.0 | ???- | ??- | ???- | ??- | ???- | ??- |
?0 | ||||||||||||
??C24AS | ?2 ?0 | ?- | ??4.0 | ?- | ??10. ??0 | ??20 | ???- | ??- | ??- | ???- | ??- | ??- |
??MBAS | ?- | ?- | ??- | ?- | ??5.0 | ??- | ???- | ??- | ??- | ???- | ??12 ??.0 | ??- |
C24E7 or E9 | ?- | ?- | ??- | ?- | ??2.0 | ??- | ???6.0 | ??- | ??- | ???2.0 | ??- | ??- |
C24E3 or E4 | ?- | ?- | ??- | ?- | ??2.0 | ??- | ???- | ??6.0 | ???- | ???- | ??- | ??2.0 |
????QAS | ?1. ?0 | ?- | ??- | ?- | ??- | ??- | ???- | ??2.0 | ???- | ???4.0 | ??- | ??- |
Oxysuccinic acid | ?- | ?2.0 | ??- | ?- | ??2.0 | ??- | ???- | ??2.0 | ???- | ???5.0 | ??- | ??- |
Citric acid | ?- | ?- | ??4.0 | ?- | ??- | ??- | ???- | ??- | ??5.0 | ???- | ??- | ??- |
Carbonate | ?10 ?.0 | ?15 ?0 | ??10. ??0 | ?12. ?0 | ??4.0 | ??- | ???20. ???0 | ??10.0 | ??5.0 | ???5.0 | ??5. ??0 | ??- |
Supercarbonate | ?- | ?- | ??- | ?- | ??6.0 | ??- | ???- | ??- | ??- | ???- | ??- | ??- |
Zeolite A or MAP | ?15 ?.0 | ?- | ??- | ?- | ??20. ??0 | ??- | ???- | ??- | ??- | ???20. ???0 | ??15 ??.0 | ??5.0 |
??STPP | ?- | ?10. ?0 | ??15. ??0 | ?30 | ??- | ??18. ??0 | ???15. ???0 | ??20.0 | ??30. ??0 | ???- | ??- | ??5.0 |
Silicate | ?5. ?0 | ?10 | ??5.0 | ??7.0 | ??- | ???- | ??4.0 | ??2.0 | ???- | ??5. ??0 | ??- | |
??SKS-6 | ?2. ?0 | ?- | ??- | ?- | ??- | ??- | ???5.0 | ??- | ??- | ??5.0 | ??- | ??- |
??MA/AA | ?1. ?0 | ?- | ??- | ?- | ??- | ??- | ???- | ??- | ??- | ??1.0 | ??1. ??0 | ??- |
Vitriol | ?- | ?- | ??- | ?- | ??- | ??5.0 | ???- | ??- | ??- | ??- | ??5. ??0 | ??- |
Whitening agent | ?0 ?1 | ?0.1 | ??0.0 ??5 | ?0.2 | ??0.5 | ??0.3 | ???- | ??0.1 | ??- | ??0.8 | ??1. ??0 | ??- |
??SRP | ?- | ?- | ??- | ?- | ??- | ??1.5 | ???- | ??- | ??- | ??0.8 | ??- | ??- |
??TAED | ?- | ?- | ??5.0 | ?- | ??- | ??- | ???- | ??- | ??- | ???- | ??- | ??- |
Siccative # | ?- | ?- | ??2.0 | ?- | ??2.0 | ??- | ???- | ??- | ??- | ???- | ??- | ??- |
??HEDP/ ??EDDS | ?- | ?- | ??- | ?- | ??0.5 | ??- | ???- | ??2.0 | ??1.0 | ???- | ??- | ??0.8 |
??STS | ?0. | ?0.7 | ??- | ?- | ??- | ??1.0 | ???2.0 | ???- | ???- | ???- | ??2. | ??- |
??5 | ??0 | |||||||||||
????CMC | ??- | ??- | ??- | ??- | ??- | ??1.2 | ??- | ??- | ??- | ???- | ??1 ??0 | ??0.5 |
Percarbonate | ??- | ??- | ??7.0 | ??- | ??- | ??3.0 | ??- | ??- | ??- | ???- | ??10 ??.0 | |
Suds suppressor/soap | ??0. ??5 | ??0.5 | ??- | ??- | ??0.5 | ??1.0 | ??0.8 | ??0.5 | ??- | ???- | ??2. ??0 | ??- |
Enzyme | ??1. ??0 | ??- | ??- | ??- | ??- | ??- | ??- | ??1.0 | ??2.0 | ???- | ??- | ??- |
Moisture | ||||||||||||
Spices | ?- | ??- | ??1.0 | ??2.0 | ??0.5 | ??- | ??- | ??- | ??0.8 | ???2.0 | ??- | ??- |
??PEG4000 | ?- | ??1.0 | ??- | ??- | ??- | ??1.0 | ??- | ??- | ??- | ???- | ??- | ??- |
# (overdrying or anhydrous salt/zeolite or overdrying zeolite or silicon-dioxide)
All levels of following embodiment are all in described composition weight percentage ratio.
Embodiment 1
Be the detergent formulation of sheet of the present invention, bulk or granular recipe below.
A | ?B | ?C | ?D | |
Component I-XII | Surplus | Surplus | Surplus | Surplus |
Above being sprayed on | ||||
Whitening agent | 0.02 | ?- | ?- | ?0.02 |
?C 45E 7Or E 9 | ?- | ?- | ?2.0 | ?1.0 |
?C 45E 3Or E 4 | ?- | ?- | ?2.0 | ?4.0 |
Spices | 0.5 | ?- | ?0.5 | ?0.2 |
Silicone defoamer | 0.3 | ?- | ?- | ?- |
Do and add | ||||
QEA | - | ?- | ?- | ?1.0 |
?HEDP/EDDS | 0.3 | ?- | ?0.5 | ?0.5 |
Vitriol | 2.0 | ?- | ?0.5 | ?1.0 |
Carbonate | 2.0 | ?10. | 15.0 | ?12.0 |
Citric acid | 2.5 | ?- | ?- | ?2.0 |
?QAS | ?- | - | ?0.5 | ?0.5 |
?SKS-6 | ?3.5 | - | ?- | ?5.0 |
Percarbonate | ?- | - | ?15.0 | ?9.0 |
?PB4 | ?- | - | ?- | ?3.0 |
?TAED/NOBS | ?- | - | ?- | ?5.0 |
?PAP | ?- | - | ?2.0 | ?- |
Proteolytic enzyme | ?1.0 | 1.0 | ?1.0 | ?1.0 |
Lipase | ?- | 0.4 | ?- | ?0.2 |
Amylase | ?0.2 | 0.2 | ?0.2 | ?0.4 |
Whitening agent | ?0.05 | - | ?- | ?0.05 |
Spices | ?1.0 | 0.2 | ?0.5 | ?0.3 |
The agent of spot decorations | ?1.2 | 0.5 | ?2.0 | ?- |
Trace/a small amount of component to 100% |
Embodiment 2
Be the detergent formulation of sheet of the present invention, bulk or granular recipe below.
E | ?F | ?G | ?H | ?I | ?J | |
Component I-XII | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus |
Above being sprayed on | ||||||
?C 45E 7 | ?- | ?2.0 | ?- | ?- | ?2.0 | ?2.0 |
?C 25E 9 | ?3.0 | ?- | ?- | ?- | ?- | ?- |
?C 23E 9 | ?- | ?- | ?1.5 | ?2.0 | ?- | ?2.0 |
Spices | ?0.3 | ?0.3 | ?0.3 | ?2.0 | ?0.3 | ?0.3 |
Agglomerate | ||||||
C 45AS | ?5.0 | ?5.0 | ?- | ?2.0 | ?5.0 | ?- |
?LAS | ?2.0 | ?2.0 | ?7.0 | ??- | ?- | ?8.0 |
?STPP/Zeolite ?A | ?7.5 | ?7.5 | ?7.5 | ?8.0 | ?7.5 | ?7.5 |
Carbonate | 4.0 | ?4.0 | ?4.0 | ?5.0 | ?4.0 | ?4.0 |
PEG4000 | 0.5 | ?0.5 | ?0.5 | ?- | ?0.5 | ?0.5 |
Trace ingredients (water etc.) | 2.0 | ?2.0 | ?2.0 | ?2.0 | ?2.0 | ?2.0 |
Do and add | - | ?- | ?- | ?- | ?- | ??- |
Citric acid | - | ?- | ?- | ?- | ?2.0 | ??- |
?PB4 | - | ?3.0 | ?- | ?- | ?- | ??- |
?PB1 | - | ?- | ?4.0 | ?1.0 | ?- | ??- |
Percarbonate | 12.0 | ?- | ?- | ?1.0 | ?- | ?2.0 |
Carbonate | - | 5.3 | ?20.0 | ?5.0 | ?14.0 | ?24.0 |
?NOBS | 0.5 | ?- | ?0.4 | ?0.3 | ?- | ?0.6 |
?PAP | - | ?0.9 | ?- | ?- | ?0.3 | ??- |
?TAED | 0.6 | ?0.4 | ?0.6 | ?0.3 | ?0.9 | ?0.5 |
Methylcellulose gum | 0.2 | ?- | ?- | ?- | ?- | ?0.5 |
?DTPA | 0.7 | ?0.5 | ?1.0 | ?0.5 | ?0.5 | ?1.2 |
The agent of spot decorations | 0.3 | ?0.2 | ?2.0 | ?- | ?0.7 | ?0.5 |
?SKS-6 | 8.0 | ?- | ?- | ?- | ?- | ??- |
?STS | - | ?- | ?2.0 | ?- | ?1.0 | ??- |
Cumene sulfonic acid | - | 1.0 | ?- | ?- | ?- | ?2.0 |
Lipase | 0.2 | ?- | ?0.2 | ?- | ?0.2 | ?0.4 |
Cellulase | 0.2 | ?0.2 | ?0.2 | ?0.3 | ?0.2 | ?0.2 |
Amylase II | 0.2 | ?- | ?0.1 | ?- | ?0.2 | ??- |
Proteolytic enzyme | 0.5 | ?0.5 | ?0.5 | ?0.3 | ?0.5 | ?0.5 |
?PVPVI | - | ?- | ?- | ?- | ?0.5 | ?0.1 |
?PVP | - | ?- | ?- | ?- | ?0.5 | ??- |
?PVNO | - | ?- | ?0.5 | ?0.3 | ?- | ??- |
?QEA | - | ?- | ?- | ?- | ?1.0 | ??- |
SRP I, II or III | 0.2 | ?0.5 | ?0.3 | ?- | ?0.2 | ??- |
Silicone defoamer | 0.2 | ?0.4 | ?0.2 | ?- | ?0.1 | ??- |
Sal epsom | - | - | 0.2 | - | ?0.2 | ?- |
Trace/minor constituent to 100% |
Embodiment 3
Be the detergent formulation of sheet of the present invention, bulk or granular recipe below.
K | ?L | ?M | ?N | |
Component I-XII | Surplus | Surplus | Surplus | Surplus |
Above being sprayed on | ||||
C 25E 3Or E 4 | ?- | ?- | ?- | ?2.0 |
C 45E 5Or E 7 | ?- | ?- | ?- | ?2.0 |
Whitening agent/optical white | ?- | ?- | ?0.5 | ?0.5 |
Spices | ?0.2 | ?0.3 | ?0.3 | ?- |
Do and add | ||||
Carbonate | ?5.0 | ?10.0 | ?13.0 | ?5.0 |
PVPVI/PVNO | ?0.5 | ?- | ?0.3 | ?- |
Proteolytic enzyme | ?1.0 | ?1.0 | ?1.0 | ?0.5 |
Lipase | ?0.4 | ?- | ?- | ?0.4 |
Amylase | ?0.1 | ?- | ?- | ?0.1 |
Cellulase | ?0.1 | ?- | ?- | ?0.1 |
DTPA | ?0.5 | ?0.3 | ?0.5 | ?1.0 |
PB1 | ?5 | ?3.0 | ?10 | ?4.0 |
PAP/DOBA | ?1.0 | ?- | ?0.4 | ?- |
TAED | ?0.5 | ?0.3 | ?0.5 | ?0.6 |
Vitriol | ?4.0 | ?5.0 | ?- | ?5.0 |
SRPI, II or III | ?0.2 | ?0.4 | ?1.0 | ?0.5 |
Defoamer | ?- | ?0.5 | ?- | ?- |
The agent of spot decorations | ?1.8 | ?0.8 | ?0.7 | ?- |
Flocculation agent | - | - | 0.1 | ?0.2 |
Spices (starch) | - | 0.2 | ?0.3 | ?0.5 |
Trace/minor constituent to 100% |
Embodiment 6
Be the detergent formulation of sheet of the present invention, bulk or granular recipe below.
O | ?P | ?Q | ?R | ?S | |
Component I-XII | Surplus | Surplus | Surplus | Surplus | Surplus |
Agglomerate | |||||
Clay | 9.0 | - | - | ||
Wax | 0.5 | - | - | ||
Glycerine | 0.5 | - | - | ||
Agglomerate | |||||
LAS | 15.0 | 5.0 | 5.0 | ||
TAS | 1.0 | ||||
Silicate | 3.0 | 3.0 | 4.0 | ||
ZeoliteA | 8.0 | 8.0 | 8.0 | ||
Carbonate | 8.0 | 8.0 | 4.0 | ||
Above being sprayed on | |||||
Spices | 0.3 | - | - | ?0.3 | ?0.3 |
C 45E 7Or E 9 | - | - | ?2.0 | ?2.0 | |
C 25E 3Or E 4 | 2.0 | - | - | ?- | ?2.0 |
Do and add | |||||
Citrate trianion or citric acid | 2.5 | - | 2.0 | ?2.5 | ?2.5 |
Clay I or II | - | 3.0 | 3.0 | ?- | ?- |
Flocculation agent I or II | - | - | - | - | - |
Supercarbonate | - | 3.0 | - | - | - |
Carbonate | 15.0 | - | - | 5.0 | 11.0 |
?TAED | 1.0 | 2.0 | 5.0 | 1.0 | - |
Sodium peroxoborate or SPC-D | 6.0 | 7.0 | 10.0 | 6.0 | - |
SRP I, II or III | 0.2 | 0.1 | 0.2 | 0.5 | 0.3 |
CMC or nonionic cellulose ether | 1.0 | 1.5 | 0.5 | ?- | - |
Proteolytic enzyme | 0.3 | 1.0 | 1.0 | 0.3 | 0.3 |
Lipase | - | 0.4 | 0.4 | - | - |
Amylase | 0.2 | 0.6 | 0.6 | 0.2 | 0.2 |
Cellulase | 0.2 | 0.6 | 0.6 | 0.2 | 0.2 |
Silicone defoamer | - | 5.0 | 5.0 | - | - |
Spices (starch) | 0.2 | 0.3 | - | - | - |
The agent of spot decorations | 0.5 | 0.5 | 0.1 | - | 1.0 |
SKS-6 (silicate 2R) | 3.5 | - | - | - | 3.5 |
Optical white | 0.1 | - | - | 0.1 | 0.1 |
Soap | 0.5 | 2.5 | - | 0.5 | 0.5 |
Sodium sulfate | - | 3.0 | - | - | - |
Trace/minor constituent to 100% | 100.0 | 100.0 | 100.0 | 100.0 | 100.0 |
Density (g/l) | 850 | ?850 | 850 | 850 | 850 |
Claims (19)
1. solid fabric softening component, it comprises:
A) a kind of clay;
B) at least 5% surfactant system;
C) solid carrier material of at least 15% weight;
D) a kind of flocculation agent.
2. according to the component of claim 1, wherein said clay and flocculation agent are intimate mixture each other.
3. according to the component of claim 1 or 2, wherein said clay, flocculation agent, surfactant system and solid support material are intimate mixture each other.
4. according to each component in the aforementioned claim, wherein said solid support material comprises silico-aluminate washing assistant and/or phosphate builders, and preferably there is level in it is the 15-60% of described composition weight.
5. according to each component in the aforementioned claim, wherein said solid support material comprises inorganic carbonate, and preferably there is level in it is the 10-60% of described composition weight.
6. according to each component in the aforementioned claim, the level that exists of wherein said surfactant system is 10-70% (weight), and comprises at least a anion sulfoacid salt surfactant or anion sulfate acid salt surfactant.
7. according to each component in the aforementioned claim, wherein said nonionic surfactant system comprises, preferably includes at least a alcohol alcoxylates tensio-active agent, preferably at least two kinds of alcohol alcoxylates tensio-active agents.
8. according to each composition in the aforementioned claim, wherein said flocculation agent comprises that molecular-weight average is 150,000 to 3,000,000 polyethylene oxide.
9. according to each composition in the aforementioned claim, the level that exists of wherein said clay is 5-60% (weight), preferably includes a kind of smectite-type clay.
10. according to each component in the aforementioned claim, comprise the whitening agent of at least 0.1% weight.
11. according to each component in the aforementioned claim, its existence form is spray-dried granules, agglomerate or extrudate.
12. according to each component in the aforementioned claim, it comprises the water of at least 5% (weight).
13., comprise a kind of fabric care agent that is selected from soil release polymer, cellulose polymer compound, dye transfer inhibitor, cationic softening agent or its mixture according to each component in the aforementioned claim.
14., comprise a kind of carbonate and water swellable decomposition agent or can form the acidic cpd that effervescive is preferably carboxylic acid, or its mixture with carbonate reaction according to each component in the aforementioned claim.
15., comprise a kind of clay mixture according to each component in the aforementioned claim.
16. according to each component in the aforementioned claim, wherein said clay, flocculation agent, surfactant system and solid support material are intimate mixture each other.
17. prepare the method for each component in the aforementioned claim, comprise at first mixed clay and flocculation agent formation intimate mixture, the step of mixing described intimate mixture and surfactant system and solid support material then.
18. the method for each component among the preparation claim 3-16, comprise that at first mixed flocculation agent, surfactant system or its part and/or solid support material or its part form intimate mixture, mix intimate mixture and clay and the remainder of the surfactant system of choosing wantonly and/or the remainder of solid support material subsequently.
19. a detergent composition, it comprises among the claim 1-16 each component, and preferred form is a sheet or block or be particulate composition.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB9907593A GB2348435A (en) | 1999-04-01 | 1999-04-01 | Softening compositions |
GB9907593.9 | 1999-04-01 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN1352677A true CN1352677A (en) | 2002-06-05 |
Family
ID=10850857
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN00808082.8A Pending CN1352677A (en) | 1999-04-01 | 2000-03-30 | Fabric softening component |
Country Status (12)
Country | Link |
---|---|
EP (1) | EP1165732B1 (en) |
JP (1) | JP4744696B2 (en) |
CN (1) | CN1352677A (en) |
AR (1) | AR023244A1 (en) |
AT (1) | ATE386097T1 (en) |
AU (1) | AU4053300A (en) |
BR (1) | BR0009502A (en) |
CA (1) | CA2365964A1 (en) |
DE (1) | DE60038009D1 (en) |
GB (1) | GB2348435A (en) |
MX (1) | MXPA01009878A (en) |
WO (1) | WO2000060039A1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1912084B (en) * | 2005-08-08 | 2010-09-08 | 花王株式会社 | Detergent composition for clothing |
CN113039279A (en) * | 2018-09-21 | 2021-06-25 | 都柏林大学 | Method for producing bio-based surfactants |
CN115916937A (en) * | 2020-05-27 | 2023-04-04 | 联合利华知识产权控股有限公司 | Fabric softening composition |
Families Citing this family (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1048721A1 (en) * | 1999-04-30 | 2000-11-02 | The Procter & Gamble Company | Detergent compositions |
US6627598B1 (en) | 1999-07-22 | 2003-09-30 | The Procter & Gamble Company | Solid detergent compositions comprising an organophilic smectite clay |
GB2352245A (en) * | 1999-07-22 | 2001-01-24 | Procter & Gamble | Detergent compositions |
GB0207483D0 (en) | 2002-03-28 | 2002-05-08 | Unilever Plc | Fabric conditioning compositions |
GB0207484D0 (en) | 2002-03-28 | 2002-05-08 | Unilever Plc | Solid fabric conditioning compositions |
DE60302402T2 (en) * | 2002-09-16 | 2006-06-14 | Unilever Nv | Cleaning or detergent compositions |
WO2005012629A1 (en) * | 2003-07-21 | 2005-02-10 | Amcol International Corporation | Fabric treatment composition |
TWI350309B (en) | 2003-12-26 | 2011-10-11 | Kao Corp | Softening detergent composition |
DE102004005000A1 (en) * | 2004-01-30 | 2005-08-18 | Basf Ag | Method of treating fibrous material |
WO2005078058A1 (en) * | 2004-02-13 | 2005-08-25 | Kao Corporation | Detergent composition |
ATE543896T1 (en) | 2004-04-09 | 2012-02-15 | Unilever Nv | GRANULES AS AN ADDITION TO CLEANING AGENT AND METHOD FOR THE PRODUCTION THEREOF |
JP2008512528A (en) * | 2004-09-08 | 2008-04-24 | クラリアント・プロドゥクテ・(ドイチュラント)・ゲゼルシャフト・ミト・ベシュレンクテル・ハフツング | Bleach mixture |
JP4823224B2 (en) | 2005-08-01 | 2011-11-24 | 花王株式会社 | Soft detergent composition |
DE602005006796D1 (en) * | 2005-08-05 | 2008-06-26 | Procter & Gamble | Particulate fabric treatment composition containing silicones, layered silicates and anionic surfactants |
CN101331220B (en) | 2005-12-28 | 2012-06-13 | 花王株式会社 | Softening detergent composition |
WO2007114484A1 (en) | 2006-03-31 | 2007-10-11 | Kao Corporation | Softening detergent composition |
WO2014090573A1 (en) | 2012-12-12 | 2014-06-19 | Unilever N.V. | Cleaning composition |
GB201419691D0 (en) * | 2014-11-05 | 2014-12-17 | Armstrong John S | Apparatus method and substance for washing glassware and/or dishware |
WO2021115705A1 (en) * | 2019-12-11 | 2021-06-17 | Unilever Ip Holdings B.V. | Detergent composition |
Family Cites Families (14)
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AU549000B2 (en) * | 1981-02-26 | 1986-01-09 | Colgate-Palmolive Pty. Ltd. | Base beads for detergent compositions |
GB8331823D0 (en) * | 1983-11-29 | 1984-01-04 | Procter & Gamble | Laundry compositions |
US4609473A (en) * | 1984-11-26 | 1986-09-02 | Colgate Palmolive Company | Bentonite-sulfate fabric softening particulate agglomerate, processes for manufacture and use thereof, and detergent compositions containing it |
GB2172910B (en) * | 1985-03-28 | 1989-06-21 | Procter & Gamble | Detergent containing a fabric conditioner |
EP0297673B1 (en) * | 1987-06-30 | 1993-11-24 | The Procter & Gamble Company | Detergent/softening compositions containing hectorite clays |
DE3887020T2 (en) * | 1987-07-14 | 1994-06-09 | Procter & Gamble | Detergent compositions. |
EP0313146B2 (en) * | 1987-10-19 | 2001-09-05 | The Procter & Gamble Company | Detergent compositions |
US4844821A (en) * | 1988-02-10 | 1989-07-04 | The Procter & Gamble Company | Stable liquid laundry detergent/fabric conditioning composition |
EP0483411B1 (en) * | 1990-10-29 | 1995-06-07 | The Procter & Gamble Company | Fabric treatment composition |
CN1145095A (en) * | 1994-03-30 | 1997-03-12 | 普罗格特-甘布尔公司 | Laundry detergent bars containing fabric softening clay |
GB2297977A (en) * | 1995-02-07 | 1996-08-21 | Procter & Gamble | Detergent composition containing Zeolite MAP |
DK0865480T3 (en) * | 1995-09-01 | 2002-09-02 | Procter & Gamble | Detergent composition comprising a polymer clay flocculant having a particle size less than 250 Am |
MA24525A1 (en) * | 1997-04-14 | 1998-12-31 | Procter & Gamble | DETERGENT PARTICLE |
GB2327949A (en) * | 1997-08-02 | 1999-02-10 | Procter & Gamble | Detergent tablet |
-
1999
- 1999-04-01 GB GB9907593A patent/GB2348435A/en not_active Withdrawn
-
2000
- 2000-03-30 CA CA002365964A patent/CA2365964A1/en not_active Abandoned
- 2000-03-30 EP EP00919923A patent/EP1165732B1/en not_active Expired - Lifetime
- 2000-03-30 DE DE60038009T patent/DE60038009D1/en not_active Expired - Lifetime
- 2000-03-30 CN CN00808082.8A patent/CN1352677A/en active Pending
- 2000-03-30 AT AT00919923T patent/ATE386097T1/en not_active IP Right Cessation
- 2000-03-30 BR BR0009502-8A patent/BR0009502A/en not_active Application Discontinuation
- 2000-03-30 MX MXPA01009878A patent/MXPA01009878A/en active IP Right Grant
- 2000-03-30 JP JP2000609531A patent/JP4744696B2/en not_active Expired - Fee Related
- 2000-03-30 AU AU40533/00A patent/AU4053300A/en not_active Abandoned
- 2000-03-30 WO PCT/US2000/008517 patent/WO2000060039A1/en active IP Right Grant
- 2000-03-31 AR ARP000101483A patent/AR023244A1/en active IP Right Grant
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1912084B (en) * | 2005-08-08 | 2010-09-08 | 花王株式会社 | Detergent composition for clothing |
CN113039279A (en) * | 2018-09-21 | 2021-06-25 | 都柏林大学 | Method for producing bio-based surfactants |
CN115916937A (en) * | 2020-05-27 | 2023-04-04 | 联合利华知识产权控股有限公司 | Fabric softening composition |
Also Published As
Publication number | Publication date |
---|---|
BR0009502A (en) | 2002-03-26 |
MXPA01009878A (en) | 2002-04-24 |
JP4744696B2 (en) | 2011-08-10 |
GB2348435A (en) | 2000-10-04 |
GB9907593D0 (en) | 1999-05-26 |
WO2000060039A1 (en) | 2000-10-12 |
AU4053300A (en) | 2000-10-23 |
DE60038009D1 (en) | 2008-03-27 |
EP1165732B1 (en) | 2008-02-13 |
ATE386097T1 (en) | 2008-03-15 |
CA2365964A1 (en) | 2000-10-12 |
JP2002541342A (en) | 2002-12-03 |
AR023244A1 (en) | 2002-09-04 |
EP1165732A1 (en) | 2002-01-02 |
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