CN1308665A - Builder component - Google Patents
Builder component Download PDFInfo
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- CN1308665A CN1308665A CN 99808400 CN99808400A CN1308665A CN 1308665 A CN1308665 A CN 1308665A CN 99808400 CN99808400 CN 99808400 CN 99808400 A CN99808400 A CN 99808400A CN 1308665 A CN1308665 A CN 1308665A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/32—Alkali metal silicates
-
- 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
- C11D3/1273—Crystalline layered silicates of type NaMeSixO2x+1YH2O
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- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Detergent Compositions (AREA)
Abstract
The invention provides a builder component comprising a ground crystalline layered silicate which comprises at least 95 %, or even 98 % or even 100 % by weight of crystalline layered silicate having a particle size of less than 150 microns or even 102 microns, whilst having a weight average particle size of more than 15.0 microns, preferably from 16.0 to 48.8 microns. The builder component can be used in particular in solid detergent compositions.
Description
Technical field
The present invention relates to have the builder component that improves distribution and the good washing aid performance of dissolved, it is specially adapted to detergent composition.
Background of invention
In the many decades in the past, detergent manufacturers fixes attention on the substitute of the improved washing assistant of exploitation as phosphate builders.On the one hand, developed new washing assistant material, on the other hand, for example improved existing washing assistant or washing assistant mixture by content or the ratio of optimizing the washing assistant material.Generally, most of washing composition also use multi-carboxy acid salt washing agent and silicate-like builder, for example silico-aluminate, amorphous and crystalline sodium disilicate.
Found that it is that product can not always distribute satisfactorily that the Betengent product user one of mainly complains.This cause product for example with the form of gel remain in the distribution chamber, washing machine neutralization also remains on the fabric after the washing.For some component or high density product, under the cold water washing condition or when in washing process, using limited amount water, for example in the starting stage of washing process, the situation when the product in less water contact distribution chamber or the washing machine, the problems referred to above are outstanding especially.
Relating to product agglomerative problem is that product can not be supplied with washing effectively, because not only bonding component can not distribute well, and the product that is captured in the gel can not distribute well, and these components are helpless to cleaning performance thus.In addition, the component of mixing some tendency gelling or caking in washing composition has negative impact to the flowability of product.
Another problem of relevant some detergent component is that they can not always dissolve satisfactorily, for example silico-aluminate, amorphous silicate, thick silicate material.This can cause cleaning performance to reduce or product is deposited on the fabric or in the washing machine.
The inventor now finds to distribute those good components to dissolve unsatisfactorily usually, tends to deposit on the fabric that is in the suds and forms residue thereon.On the other hand, the good component of dissolving with water initial contact the time tendency gelling.
The builder component that the inventor now finds to contain the crystalline layered silicate material of porphyrize dissolves easily and the excellent effect of washing that helps is provided, and the grain graininess of the crystalline layered silicate material of described porphyrize is lower than about 100 microns, and average particle size is greater than about 15 microns.Preferably, also to make its 90% weight particles have granularity be the 17.3-88.2 micron to this builder component.
They find, the detergent composition that comprises this builder component and other silicate material are for example compared than volume particle size, material, silico-aluminate, amorphous material or non-stratified material than small grain size, have flowability, the improvement of improvement distributivity, reduced gelling and in distribution device, less product residue thing arranged in washing machine and on fabric.Believe that laminate structure is necessary for the formation that reduces gel, and granularity is distributed and dissolving for providing to product, it is necessary having good flowability simultaneously.In addition, believe that the material of porphyrize has the surface tissue of improvement, make thus to help and wash and distribution improves.
In addition, discovery with this crystalline layered silicate material with other detergent component tensio-active agent for example that forms residue or gel tendency is arranged, particularly anion surfactant closely mixes and has reduced this component residue or agglomerative and form, and has improved the distribution of component and effective cleaning performance thus.
Summary of the invention
The invention provides a kind of builder component that comprises the crystalline layered silicate of porphyrize, wherein the crystalline layered silicate of porphyrize comprise at least 95% or even 98% or even the granularity of 100% weight be lower than 150 microns or even 102 microns, and average particle size is greater than 15.0 microns, the crystalline layered silicate of preferred 16.0-48.8 micron.
This builder component is specially adapted to solid detergent composition, particularly solid laundry and dishwashing detergent composition.
The builder system that the invention still further relates to the crystalline layered silicate that comprises porphyrize is used to improve the purposes of the distributivity of detergent component in the detergent composition that comprises tensio-active agent and other detergent component, the crystalline layered silicate of described porphyrize comprise at least 95% or even 98% or even the granularity of 100% weight be lower than 150 microns or even 102 microns, and average particle size is greater than 15.0 microns, the crystalline layered silicate of preferred 16.0-48.8 micron.
Detailed Description Of The Invention builder component crystalline layered silicate
The crystalline layered silicate of the porphyrize in the builder component of the present invention comprise at least 95% or even 98% or even the granularity of 100% weight be lower than 150 microns or even 102 microns or even be lower than 88.2 microns or even be lower than 65.6 microns, and average particle size is greater than 15.0 microns, preferred 16.0-48.8 micron or even the crystalline layered silicate of 17.3-42.1 micron, described granularity be with as the MalvernInstruments SB.OC light scattering device mensuration described in the Malvern equipment user specification sheets.
As measuring with Malvern Instruments SB.OC light scattering device, preferably, when average particle size is the 16.0-48.8 micron, the particle of at least 90% weight has granularity 17.3-88.2, with when average particle size is the 17.3-42.1 micron, the particle of at least 90% weight has granularity 23.3-76.0.
The material of this porphyrize can obtain with any polishing, preferably the material that obtains this porphyrize at the ball mill or the air spray grinding machine for grinding crystalline layered silicate material bigger than the present invention material particle size of porcelain system.
The preferred crystalline layered silicate of the present invention has general formula:
NaMSi
xO
2x+1.yH
2O wherein M is sodium or hydrogen, and x is the numerical value of 1.9-4, and y is the numerical value of 0-20.This class crystalline layered sodium silicate is disclosed among the EP-A-0164514, and their preparation method is disclosed among DE-A-3417649 and the DE-A-3742043.For the object of the invention, the x in the above general formula is 2,3 or 4, is preferably 2.M is preferably H, K or Na or its mixture, preferred Na.Most preferred material is α-Na
2Si
2O
5, β-Na
2Si
2O
5Or δ-Na
2Si
2O
5Or its mixture, preferably 75%Na at least
2Si
2O
5, for example be the NaSKS-6 that buys from Clariant.
Crystalline layered silicate material, particularly formula Na
2Si
2O
5Material can randomly comprise other element for example B, P, S, for example obtain by the method for describing among the EP578986-B.
Component of the present invention can comprise other detergent builders or other detergent component as described herein.Generally, this builder component can comprise as many as 85% or preferred 75% or 50% other component.In view of the above, preferred builder component of the present invention comprises the intimate mixture of crystalline layered silicate and other component." closely mixing/blended " or " intimate mixture " are when when this paper uses, and for the object of the invention, the meaning is that grain fraction is uniformly distributed in the particle basically.
This intimate mixture can obtain with any method that comprises blending ingredients, and the blending ingredients step can be spray-drying process, method of tableting, extrusion process and a part that comprises the comminution granulation of agglomeration technique.In view of the above, preferred first step comprises the mixture that makes crystalline layered silicate and preferably include other component of tensio-active agent, and this granulating mixture is become particle.
This tight mixing step is preferably by finishing tensio-active agent and crystalline layered silicate agglomeration.This available any conventional agglomeration technique is finished.Therefore, builder component agglomerate preferably.
Preferable material is organic acid or salt, comprise (many) carboxylic acids and its salt, comprise polymkeric substance for example vinylformic acid and/or toxilic acid polymkeric substance, polymkeric substance, mineral acid or salt comprise carbonate and vitriol, other silicate material, comprise amorphous silicate as described herein, metasilicate, other crystalline layered silicate and silico-aluminate.
Preferred builder component of the present invention comprises at least a tensio-active agent as mentioned below, preferably comprises at least a anion surfactant.
Preferred this particle comprises 10%-60% weight, preferred 20%-50% or even other component of 35%-45% and 35%-90%, preferably 40%-80% or even 45%-65% crystalline layered silicate.
Preferred other component comprises tensio-active agent.Preferably, in this builder component, the weight ratio of crystalline layered silicate and tensio-active agent is 4: 5-7: 3, more preferably 1: 1-2: 1, most preferably 5: 4-3: 2.
Preferred this builder component comprises and is lower than 10% weight, preferably is lower than 5% weight percent free water.Free water content described here is 5 gram builder components to be put in the Petri dish and this Petri dish is put in 50 ℃ the convection oven through 2 hours, measures then because the weight loss that the water evaporation causes and definite.
Preferred intimate mixture comprises the polymeric adhesive material.In view of the above, preferably use the least possible adhesive material.Preferred this intimate mixture comprises and is less than 25%, preferably is less than 10%, more preferably less than 5% weight, and 0% weight ethylene oxide polymer most preferably.
Preferred this builder component is present in the detergent composition.In view of the above, preferred lotion-aid combination is to exist with independent particle form, preferred agglomerate, preferred its has 150 microns-1700 microns of average particle size, and more preferably the particle of 80% weight has granularity and has granularity greater than 1180 microns (on the Tyler of sieve mesh 14 sieves) or even 710 microns (on the Tyler of sieve mesh 24 sieve) greater than 300 microns (on the Tyler of sieve mesh 48 sieve 80% weight being arranged) and the particle that is less than 10% weight.
This detergent composition can be any form, comprises water base and non-water base liquid, but preferred said composition is the solids composition of bar, sheet, extrudate form, and said composition is particle or sheet.
When said composition during by granulometric composition, this particle preferably has 150 microns-2500 microns of granularities, or even 1500 microns, or more preferably the particle of the 80% weight particle that has the granularity (on the Tyler of sieve mesh 48 sieve 80% weight being arranged) greater than 300 microns and be less than 10% weight has granularity greater than 1180 microns or even 710 microns (on the Tyler of sieve mesh 24 sieve).
The density of preferred this detergent composition is 300g/l-1500g/l, or more preferably 400g/l or even 580g/l-1200g/l or even 850g/l.
Above-mentioned detergent composition and lotion-aid combination can comprise other component, and preferred ingredients is described in hereinafter.
Found to comprise builder component of the present invention, preferably it closely mixes with any component described herein, has improved distributivity as builder system or its a part of detergent composition.By the detergent composition that comprises as the crystalline layered silicate of builder system or its a part of porphyrize is provided, wherein at least 90% or the crystalline layered silicate of the porphyrize of preferred at least 95% weight have greater than 20.2 microns granularity and at least 90% or preferably the crystalline layered silicate of the porphyrize of at least 95% weight have and be lower than 100.2 microns granularity, thus, the present invention also provides the method for the distributivity of detergent composition that a kind of improvement comprises builder system or its component.
Thus, this means that the detergent composition that the distribution in washing water from the distribution chamber of washing machine or distribution device of this detergent composition or its component does not comprise builder component of the present invention relatively is improved.When this paper narrates, " improve and distribute " comprises the formation that improves dissolving, reduction gelling and reduce residue.Other component
Builder component of the present invention or composition can contain other detergent component.The definite character of these other components and incorporation thereof will depend on this builder component and comprise this builder component composition physical form with and the definite character of the washing operation that is used for.
Builder component of the present invention and composition preferably comprise one or more other detergent components, are selected from tensio-active agent, SYNTHETIC OPTICAL WHITNER, bleaching catalyst, alkaline system, other washing assistant, organic polymer, enzyme, suds suppressor, calcium soap, dispersion agent, dirt suspension and anti redeposition agent, dirt release agent, spices, whitening agent, optical white and other corrosion inhibitor.Tensio-active agent
Builder component of the present invention or detergent composition preferably contain one or more tensio-active agents.This tensio-active agent can comprise any tensio-active agent well known in the art, is selected from negatively charged ion, nonionic, positively charged ion, both sexes and zwitterionics and its mixture.
Should be appreciated that for the object of the invention this detergent composition can comprise in the intimate mixture that is not present in crystalline layered silicate, but be present in the tensio-active agent in other detergent component.Anion surfactant
Preferably comprise anion surfactant according to composition of the present invention and builder component.Any basically anion surfactant that is used for the decontamination purpose all can be included in this detergent composition.These can comprise anion sulfate, sulfonate, carboxylate salt and sarcosinate surfactant (for example, comprise the ammonium salt of sodium, potassium, ammonium and replacement, as one, two and triethanolamine salt).Preferred anionic vitriol and sulfosalt surfactant.
Highly preferred surfactant system comprises sulfonate as described herein and sulfate surfactant, preferred straight or branched alkylbenzene sulfonate and alkyl ethoxy sulfate, and preferably its combination is as the described cats product of text.
Other anion surfactant comprises isethionate, as fatty acid amide, alkyl succinate and the alkyl sulfo succinate of acyl isethinate, N-acyl taurine salt, methylamino esilate, the monoesters of sulfosuccinate (particularly saturated and unsaturated C
12-C
18Monoesters), the diester of sulfosuccinate (particularly saturated and unsaturated C
6-C
14Diester), N-acyl sarcosinate.Resinous acid and hydrogenated resin acid also suit, as rosin, staybelite, and the resinous acid and the hydrogenated resin acid that are present in butter or obtain by butter.The anion sulfoacid salt surfactant
The present invention it is highly preferred that the anion sulfoacid salt surfactant.Be specially adapted to the C of comprising of the present invention
5-C
20The straight or branched alkylbenzene sulfonate also has alkyl ester sulfonate, C
6-C
22Uncle or secondary alkyl sulfonate, C
6-C
24Alkene sulfonate, sulfonated poly carboxylic acid, alkyl glycerol sulfonate, fatty acyl group glycerol sulfonate, fatty oil base glycerol sulfonate and its any mixture.C most preferably
9-C
14Linear alkylbenzene sulfonate.The anion sulfate acid salt surfactant
Be applicable to that anion sulfate tensio-active agent of the present invention comprises straight chain and side chain primary and secondary alkyl-sulphate, alkyl ethoxy sulfate, fatty oil acylglycerol vitriol, alkyl phenol epoxy ethane ether salt, C
5-C
17Acyl group-N-(C
1-C
4Alkyl) and-N-(C
1-C
2Hydroxyalkyl) vitriol of glucosamine sulfate and alkyl polysaccharide is as the vitriol (compound of nonionic non-sulfuric acid salinization is described hereinafter) of alkyl polyglucoside.
Alkyl sulfate surfactant is preferably selected from straight chain and side chain uncle C
10-C
18Alkyl-sulphate, more preferably C
11-C
15Branched-chain alkyl vitriol and C
12-C
14Straight-chain alkyl sulfate.
Alkyl ethoxy sulfate surfactant is preferably selected from every mole by the C of 0.5-20 moles of ethylene oxide ethoxylation
10-C
18Alkyl-sulphate.More preferably, alkyl ethoxy sulfate surfactant be every mole by 0.5-7, the C of the oxyethane ethoxylation of preferred 1-5 mole
11-C
18, preferred C
11-C
15Alkyl-sulphate.
The particularly preferred aspect of the present invention is to adopt the mixture of preferred alkyl-sulphate and/or sulfonate and alkyl ethoxy sulfate surfactant.This mixture is disclosed among the PCT number of patent application WO93/18124.The anionic carboxylic acid salt surfactant
Suitable anionic carboxylate tensio-active agent comprises alkyl ethoxy carboxylate, alkyl polyethoxye multi-carboxylate's tensio-active agent and soap (" alkyl carboxylate " soap), the secondary soap class of particularly as described herein some.
Suitable alkyl ethoxy carboxylate comprises having formula RO (CH
2CH
2O)
xCH
2COO
-M
+Those, wherein, R is C
6-C
18Alkyl, x are 0-10, and ethoxylate distributes and should make, by weight, x be 0 amount of substance less than 20%, M is a positively charged ion.Suitable alkyl polyethoxye multi-carboxylate tensio-active agent comprises having formula RO-(CHR
1-CHR
2-O)-R
3Those, wherein R is C
6-C
18Alkyl, x is 1-25, R
1And R
2Be selected from hydrogen, formyloxy, amber acidic group, hydroxy succinic acid base and its mixture, R
3Be selected from hydrogen, have the replacement or the unsubstituted alkyl of 1-8 carbon atom, or its mixture.
Suitable soap class tensio-active agent comprises secondary soap surfactant, and it comprises the carboxyl unit that links to each other with secondary carbon(atom).Being preferred for secondary soap surfactant of the present invention is to be selected from following water-soluble substances: the water-soluble salt that the water-soluble salt of the water-soluble salt of 2-methyl isophthalic acid-undecanoic acid, 2-ethyl-1-capric acid, the water-soluble salt of 2-propyl group-1-n-nonanoic acid, 2-butyl-1-are sad and the water-soluble salt of 2-amyl group-1-enanthic acid.Some soap class also can be used as suds suppressor and adds.The basic metal sarcosinate surfactant
Other suitable anion surfactant is formula R-CON (R
1) CH
2The basic metal sarcosinate of COOM, wherein R is C
5-C
17-straight or branched alkyl or alkenyl, R
1Be C
1-C
4Alkyl, M are alkalimetal ion.Preferred examples is the myristyl and the oleoyl methyl sarcosinate of sodium-salt form.The anion surfactant of mid-chain branched
The present invention is highly preferred, particularly have improvement surfactant properties be the surfactant compounds of the alkyl chain mid-chain branched of following formula, wherein A
bPart is the branched primary alkyl part with following formula:
Wherein the branched primary alkyl part in this formula (comprises R, R
1And R
2Side chain) total carbon atom number in is 13-19; R, R
1And R
2Be selected from hydrogen and C independently of one another
1-C
3Alkyl (preferable methyl), condition are R, R
1And R
2Not all be hydrogen and when z is 0, R or R at least
1Not hydrogen; W is the integer of 0-13; X is the integer of 0-13; Y is the integer of 0-13; Z is the integer of 0-13; And w+x+y is 7-13.
Usually, for the surfactant compounds of the mid-chain branched of surfactant system, the branching of some point (for example in following formula along R, R
1And/or R
2The chain position of part) more preferred than the branching at other some place of promoting agent skeleton surfacewise.Following formula has illustrated the alkyl A of the monomethyl branching that is suitable for according to the present invention
bThe mid-chain branched scope of part (that is, branching takes place which point), preferred mid-chain branched scope and preferred mid-chain branched scope.
It should be noted that the tensio-active agent that replaces for monomethyl, these scopes do not comprise chain two end carbon atoms and with-carbon atom that the X-B group is right after.
Following formula has illustrated the alkyl A of the dimethyl replacement that is suitable for according to the present invention
bThe mid-chain branched scope of part, preferred mid-chain branched scope and preferred mid-chain branched scope.
The A in the following formula wherein preferably
bPart does not have the surfactant compounds of the carbon atom (promptly 4 carbon atoms directly are connected with a carbon atom) of any tetrasubstituted.
Be used for the most preferred mid-chain branched surfactant compounds of detergent composition of the present invention and be mid-chain branched primary alkyl sulfonate and even more preferably sulfate surfactant.Should be appreciated that for the object of the invention the preferred surfactant system comprises the primary alkyl sulphates of two or more mid-chain branched or the mixture of sulfosalt surfactant.
The primary alkyl sulphates tensio-active agent of preferred mid-chain branched has formula:
These tensio-active agents have linear primary alkyl-sulphate chain backbone (the longest carbon straight chain that promptly comprises Sulfated carbon atom), its primary alkyl part that preferably comprises 12-19 carbon atom and their branching preferably comprises at least 14 carbon atoms altogether, preferably is no more than 20 carbon atoms.In the surfactant system that comprises more than a kind of these sulfate surfactants, the average total carbon atom number of the primary alkyl of branching part is preferably greater than 14.5-about 17.5.Therefore, this surfactant system preferably comprises the primary alkyl sulphates surfactant compounds of at least a branching, it has the longest carbon straight chain that is no less than 12 carbon atoms or no more than 19 carbon atoms, must be at least 14 with the total number of carbon atoms that comprises side chain, in addition, for the branched primary alkyl part, average total carbon atom number is greater than 14.5-about 17.5.
R, R
1And R
2Be selected from hydrogen and C independently of one another
1-C
3Alkyl (preferred hydrogen or C
1-C
2Alkyl, more preferably hydrogen or methyl, and most preferable), condition is R, R
1And R
2Not all be hydrogen.In addition, when z is 1, R or R at least
1Not hydrogen.
M is the salifiable positively charged ion of hydrogen or shape, and this depends on synthetic method.The salifiable cationic example of shape is lithium, sodium, potassium, calcium, magnesium, has the quaternary alkylammonium of following formula:
R wherein
3, R
4, R
5And R
6Be hydrogen, C independently
1-C
22Alkylidene group, C
4-C
22Sub-branched alkyl, C
1-C
6Alkanol, C
1-C
22Alkylene group, C
4-C
22The branching alkylene group, and composition thereof.Preferred cation is ammonium (R
3, R
4, R
5And R
6All be hydrogen), sodium, potassium, one, two and three alkanol ammoniums, and composition thereof.The R of the single alkanol ammonium compound of the present invention
3Be C
1-C
6Alkanol, R
4, R
5And R
6Be hydrogen; The R of dialkanol ammonium compound of the present invention
3And R
4Be C
1-C
6Alkanol, R
5And R
6Be hydrogen; The R of the present invention's three alkanol ammonium compounds
3, R
4And R
5Be C
1-C
6Alkanol, R
6Be hydrogen.The preferred alkanol ammonium salt of the present invention is, two and three-quaternary ammonium compound with following formula:
H
3N
+CH
2CH
2OH,H
2N
+(CH
2CH
2OH)
2,HN
+(CH
2CH
2OH)
3。
Preferred M is a sodium, potassium and above-mentioned C
2The alkanol ammonium salt; Most preferably be sodium.
About following formula, w is the integer of 0-13 in addition; X is the integer of 0-13; Y is the integer of 0-13; Z is at least 1 integer; With w+x+y+z be the integer of 8-14.
The primary alkyl sulphates tensio-active agent of preferred mid-chain branched is the primary alkyl sulphates tensio-active agent of 16 carbon altogether, in its skeleton, have 13 carbon and altogether 1,2 or 3 branching unit of 3 carbon atoms (be R, R
1And/or R
2), (the total number of carbon atoms is at least 16 thus).Preferred branching unit can be a propyl group branching unit or three methyl-branched unit.
The another kind of preferred surfactants system of the present invention has the branched primary alkyl sulphates of one or more following formulas:
Comprising the total carbon atom number of side chain is 15-18 and when existing more than a kind of these vitriol, at the average total carbon atom number of branched primary alkyl part with following formula for greater than 14.5-about 17.5; R
1And R
2Be hydrogen or C independently of one another
1-C
3Alkyl; M is a water-soluble cationic; X is 0-11; Y is 0-11; Z is at least 2; With x+y+z be 9-13; Condition is R
1And R
2Not all be hydrogen.
Preferred this surfactant system comprises and accounts for this system weight at least 20%, and more preferably at least 60%, in addition the more preferably primary alkyl sulphates of at least 90% mid-chain branched, preferred R
1And R
2Be hydrogen or methyl independently, condition is R
1And R
2Not all be hydrogen; X+y equals 8,9 or 10, and z is at least 2, and the average total carbon atom number in these sulfate surfactants is preferably 15-17 thus, more preferably 16-17.
In addition, the preferred surfactants system comprises and accounts for this system weight at least about 20%, and more preferably at least 60%, even more preferably alkyl-sulphate or its mixture of at least 90% one or more mid-chain branched with following formula:
Or
Wherein M represents one or more positively charged ions; A, b, d and e are integers, and a+b is 10-16, and d+e is 8-14, in addition wherein:
When a+b=10, a is the integer of 2-9 and the integer that b is 1-8;
When a+b=11, a is the integer of 2-10 and the integer that b is 1-9;
When a+b=12, a is the integer of 2-11 and the integer that b is 1-10;
When a+b=13, a is the integer of 2-12 and the integer that b is 1-11;
When a+b=14, a is the integer of 2-13 and the integer that b is 1-12;
When a+b=15, a is the integer of 2-14 and the integer that b is 1-13;
When a+b=16, a is the integer of 2-15 and the integer that b is 1-14;
When d+e=8, d is the integer of 2-7 and the integer that e is 1-6;
When d+e=9, d is the integer of 2-8 and the integer that e is 1-7;
When d+e=10, d is the integer of 2-9 and the integer that e is 1-8;
When d+e=11, d is the integer of 2-10 and the integer that e is 1-9;
When d+e=12, d is the integer of 2-11 and the integer that e is 1-10;
When d+e=13, d is the integer of 2-12 and the integer that e is 1-11;
When d+e=14, d is the integer of 2-13 and the integer that e is 1-12.
Thus, when existing more than a kind of these sulfate surfactants in this surfactant system, the average the total number of carbon atoms of branched primary alkyl part with following formula is for greater than 14.5-about 17.5.
The primary alkyl sulphates of preferred monomethyl branching is selected from: 3-methyl pentadecylic alcohol vitriol, 4-methyl pentadecylic alcohol vitriol, 5-methyl pentadecylic alcohol vitriol, 6-methyl pentadecylic alcohol vitriol, 7-methyl pentadecylic alcohol vitriol, 8-methyl pentadecylic alcohol vitriol, 9-methyl pentadecylic alcohol vitriol, 10-methyl pentadecylic alcohol vitriol, 11-methyl pentadecylic alcohol vitriol, 12-methyl pentadecylic alcohol vitriol, 13-methyl pentadecylic alcohol vitriol, 3-methyl cetyl alcohol sulfate, 4-methyl cetyl alcohol sulfate, 5-methyl cetyl alcohol sulfate, 6-methyl cetyl alcohol sulfate, 7-methyl cetyl alcohol sulfate, 8-methyl cetyl alcohol sulfate, 9-methyl cetyl alcohol sulfate, 10-methyl cetyl alcohol sulfate, 11-methyl cetyl alcohol sulfate, 12-methyl cetyl alcohol sulfate, 13-methyl cetyl alcohol sulfate, 14-methyl cetyl alcohol sulfate and its mixture.
Preferred dimethyl-branched primary alkyl sulphates is selected from: 2,3-dimethyl tetradecanol vitriol, 2,4-dimethyl tetradecanol vitriol, 2,5-dimethyl tetradecanol vitriol, 2,6-dimethyl tetradecanol vitriol, 2,7-dimethyl tetradecanol vitriol, 2,8-dimethyl tetradecanol vitriol, 2,9-dimethyl tetradecanol vitriol, 2,10-dimethyl tetradecanol vitriol, 2,11-dimethyl tetradecanol vitriol, 2,12-dimethyl tetradecanol vitriol, 2,3-dimethyl pentadecylic alcohol vitriol, 2,4-dimethyl pentadecylic alcohol vitriol, 2,5-dimethyl pentadecylic alcohol vitriol, 2,6-dimethyl pentadecylic alcohol vitriol, 2,7-dimethyl pentadecylic alcohol vitriol, 2,8-dimethyl pentadecylic alcohol vitriol, 2,9-dimethyl pentadecylic alcohol vitriol, 2,10-dimethyl pentadecylic alcohol vitriol, 2,11-dimethyl pentadecylic alcohol vitriol, 2,12-dimethyl pentadecylic alcohol vitriol, 2,13-dimethyl pentadecylic alcohol vitriol and its mixture.
The branched primary alkyl sulphates that below comprises 16 carbon atoms and have a branching unit is the example that is applicable to the preferred branched tensio-active agent of the present composition:
5-methyl pentadecyl vitriol with following formula:
6-methyl pentadecyl vitriol with following formula:
7-methyl pentadecyl vitriol with following formula:
8-methyl pentadecyl vitriol with following formula:
9-methyl pentadecyl vitriol with following formula:
10-methyl pentadecyl vitriol with following formula:
M sodium preferably wherein.
The branched primary alkyl sulphates that below comprises 17 carbon atoms and have two branching units is the example of the preferred branched surfactants according to the present invention:
Have 2 of following formula, 5-dimethyl pentadecyl vitriol:
Have 2 of following formula, 6-dimethyl pentadecyl vitriol:
Have 2 of following formula, 7-dimethyl pentadecyl vitriol:
Have 2 of following formula, 8-dimethyl pentadecyl vitriol:
Have 2 of following formula, 9-dimethyl pentadecyl vitriol:
Have 2 of following formula, 10-dimethyl pentadecyl vitriol:
M sodium preferably wherein.Alkoxy-based non-ionic surface active agent
Basically any alkoxy-based non-ionic surface active agent all is applicable to the present invention.Preferred ethoxylation and propoxylation nonionogenic tenside.
The preferred alkoxylated tensio-active agent can be selected from the alkylphenol condensation of non-ionic type, the ethoxylated alcohol of non-ionic type, the ethoxylated/propoxylated fatty alcohol of non-ionic type, ethoxylated/propoxylated condenses non-ionic type and propylene glycol, and ethoxylation condensation product non-ionic type and propylene oxide/ethylenediamine adduct.Nonionic alcohol alcoxylates tensio-active agent
Nonionogenic tenside can be present in this detergent composition.Preferably the content of the ethoxylated non-ionic surface active agent in intimate mixture is lower than 10% of this mixture weight, preferred even 5% weight.
The condensation product of Fatty Alcohol(C12-C14 and C12-C18) and 1-25 mole alkylene oxide, particularly oxyethane and/or propylene oxide is applicable to the present invention.The alkyl chain of Fatty Alcohol(C12-C14 and C12-C18) can be straight or branched, and uncle or secondary comprises 6-22 carbon atom usually.Particularly preferably be the every mol of alcohol of alkyl and the condensation product of 2-10 moles of ethylene oxide with 8-20 carbon atom.The nonionic polyhydroxy fatty acid amide surfactant
Be applicable to that polyhydroxy fatty acid amide of the present invention is to have those of following structural formula: R
2CONR
1Z, wherein R
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 the straight-chain alkyl that is connected directly to few 3 hydroxyls, or its alkoxy derivative (preferred ethoxylation or propenoxylated).Z preferably derives from the reducing sugar in the reductive amination process; More preferably Z is a glycosyl.The nonionic fatty acid amide surfactant
Suitable fatty acid amide surfactant comprises those with following formula: R
6CON (R
7)
2, R wherein
6For comprising 7-21, the alkyl of preferred 9-17 carbon atom, each R
7Be selected from hydrogen, C
1-C
4Alkyl, C
1-C
4Hydroxyalkyl and-(C
2H
4O)
xH, wherein x is 1-3.The nonionic alkyl polysaccharide surfactant
Be applicable to that alkyl polysaccharide of the present invention is described among the US4565647 of the Llenado that authorized on January 21st, 1986 the hydrophilic polysaccharide group that they have the hydrophobic grouping that contains 6-30 carbon atom and comprise 1.3-10 sugar unit, for example many glycosides.
Preferred alkyl polyglycoside has following formula:
R
2O (C
nH
2nO)
t(glycosyl)
xR wherein
2Be selected from alkyl, alkyl phenyl, hydroxyalkyl, hydroxyalkyl phenyl and its mixture, wherein alkyl contains 10-18 carbon atom; N is 2 or 3; T is 0-10; X is 1.3-8.This glycosyl is preferably obtained by glucose.Amphoterics
Be suitable for amphoterics of the present invention and comprise amine oxide surfactant and alkyl both sexes carboxylic acid.
Suitable amine oxide comprises formula R
3(OR
4)
xN
0(R
5)
2Those compounds, R wherein
3Be selected from the alkyl, hydroxyalkyl, acyl group amido propyl group and the alkyl phenyl that contain 8-26 carbon atom, or its mixture; R
4Be alkylidene group or the hydroxy alkylidene that contains 2-3 carbon atom, or its mixture; X is 0-5, preferred 0-3; Each R
5Be alkyl or the hydroxyalkyl that contains 1-3 carbon atom, perhaps contain the polyethylene oxide group of 1-3 ethylene oxide group.Preferred C
10-C
18Alkyl dimethyl amine oxide and C
10-C
18Acyl group amidoalkyl dimethyl oxidation amine.
The example of suitable alkyl both sexes dicarboxylic acid is Miranol (TM) C2M Conc., by Miranol, and Inc., Dayton, NJ produces.Zwitterionics
Zwitterionics also can add in detergent composition of the present invention or the builder component.These tensio-active agents can be described as the derivative of derivative, heterocyclic secondary and the tertiary amine of secondary amine and tertiary amine widely, or the derivative of quaternary ammonium, quaternary phosphine or uncle's sulfonium compound.Trimethyl-glycine and sultaine tensio-active agent are the examples that is used for zwitterionics of the present invention.
Suitable trimethyl-glycine is those compounds with following formula: R (R ')
2N
+R
2COO
-, wherein R is C
6-C
18Alkyl, each R
1Be generally C
1-C
3Alkyl, R
2Be C
1-C
5Alkyl.Preferred trimethyl-glycine is C
12-C
18Dimethylamino hexanoate and C
10-C
18Acyl group amido propane (or ethane) dimethyl (or diethyl) trimethyl-glycine.The compound betaine tensio-active agent also is applicable to the present invention.Cats product
Be suitable for cats product of the present invention and comprise quaternary ammonium surfactant.The preferably single C of quaternary ammonium surfactant
6-C
16, preferred C
6-C
10N-alkyl or alkenyl ammonium surfactant, wherein all the other positions of N are replaced by methyl, hydroxyethyl or hydroxypropyl.Preferred monoalkoxyization and bis-alkoxy amine tensio-active agent in addition.
The suitable cats product of another group that can be used for detergent composition of the present invention or its component is the cationic ester tensio-active agent.This cationic ester tensio-active agent is water dispersible preferably, is to comprise at least one ester bond (promptly-COO-) and the compound with surfactant properties of at least one positively charged ion charged group.
Suitable cationic ester tensio-active agent comprises the cholinesterase tensio-active agent, for example is disclosed in US 4228042,4239660 and 4260529.
In a kind of preferred situation, ester bond and positively charged ion charged group are spaced apart base and are separated from each other in surfactant molecule, described spacer is made up of a kind of chain, this chain comprises at least three atoms (i.e. three atom chain lengths), preferred 3-8 atom, more preferably 3-5 atom, most preferably 3 atoms.The atom that forms the spacer chain is selected from carbon, nitrogen and Sauerstoffatom and its any mixture, and condition is that any nitrogen-atoms in described chain or Sauerstoffatom only link to each other with carbon atom in the chain.Therefore, got rid of for example have-O-O-(being superoxide) ,-N-N-and-spacer of N-O-key, and comprise for example having-CH
2-O-CH
2-and-CH
2-NH-CH
2The spacer of-key.In preferred situation, the spacer chain only comprises carbon atom, and most preferably described chain is a hydrocarbyl chain.Cation mono alkoxylated amines tensio-active agent
The present invention it is highly preferred that the cation mono alkoxylated amines tensio-active agent with formula I:
R wherein
1Be to contain about 18 carbon atoms of the 6-that has an appointment, preferred about 16 carbon atoms of 6-, the most preferably from about alkyl of about 14 carbon atoms of 6-or alkenyl part; R
2And R
3Each is the alkyl that contains about 3 carbon atoms of 1-independently, preferable methyl, most preferably R
2And R
3It all is methyl; R
4Be selected from hydrogen (preferably), methyl and ethyl, X
-Provide electroneutral negatively charged ion, for example chlorine, bromine, methylsulfate, sulfate radical etc.A is an alkoxyl group, particularly oxyethyl group, propoxy-or butoxy; P is that 0-is about 30, and preferred 2-is about 15, and most preferably 2-about 8.
In the formula I, preferred ApR
4Group has p=1 and is the hydroxyalkyl with no more than 6 carbon atoms, thus-and the OH group separated with quaternary nitrogen atoms by no more than 3 carbon atoms.Particularly preferred ApR
4Group is-CH
2CH
2OH ,-CH
2CH
2CH
2OH ,-CH
2CH (CH
3) OH and-CH (CH
3) CH
2OH ,-CH
2CH
2OH is particularly preferred.Preferred R
1Group is a straight chained alkyl.Straight chain R with 8-14 carbon atom
1Group is preferred.
Be used for the highly preferred cation mono alkoxylated amines of another kind of the present invention tensio-active agent and have following formula:
R wherein
1Be C
10-C
18Alkyl and their mixture, particularly C
10-C
14Alkyl, preferred C
10And C
12Alkyl, X provide any suitable negatively charged ion of charge balance, preferred chlorine or bromine.
As described, the compound of the above-mentioned type comprises wherein oxyethyl group (CH
2CH
2O) unit (EO) is by butoxy, isopropoxy [CH (CH
3) CH
2O] and [CH
2CH (CH
3O] unit (i-Pr) or positive propoxy unit (Pr) or EO and/or Pr and/or the unitary mixture of i-Pr displaced those.
Be used for the content of the cation mono alkoxylated amines tensio-active agent of detergent composition of the present invention, the weight by said composition is preferably 0.1%-20%, more preferably 0.2%-7%, most preferably 0.3%-3.0%.Positively charged ion bis-alkoxy amine tensio-active agent
Positively charged ion bis-alkoxy amine tensio-active agent preferably has the general formula II:
R wherein
1Be to contain about 18 carbon atoms of the 8-that has an appointment, preferred about 16 carbon atoms of 10-, the most preferably from about alkyl of about 14 carbon atoms of 10-or alkenyl part; R
2Be the alkyl that contains 1-3 carbon atom, preferable methyl; R
3And R
4Can change independently, they are selected from hydrogen (preferably), methyl and ethyl; X
-Be to be enough to provide electroneutral negatively charged ion, for example chlorine, bromine, methylsulfate, sulfate radical etc.A and A ' can change independently, respectively are selected from C
1-C
4Alkoxyl group, particularly oxyethyl group (promptly-CH
2CH
2O-), propoxy-, butoxy and their mixture; P is that 1-is about 30, and preferred 1-is about 4, and q is that 1-is about 30, and preferred 1-is about 4, and most preferably p and q are 1.
Be used for the highly preferred positively charged ion bis-alkoxy of the present invention amine tensio-active agent and have following formula:
R wherein
1Be C
10-C
18Alkyl and its mixture, preferred C
10, C
12, C
14Alkyl and its mixture, X provides any negatively charged ion easily of charge balance, preferred chlorine.About above-mentioned positively charged ion bis-alkoxy amine formula, in preferred compound, R
1Be by (cocounut oil) C
12-C
14The lipid acid of moieties obtains, R
2Be methyl, ApR
3And A ' qR
4All are monosubstituted ethoxies.
Be applicable to that other positively charged ion bis-alkoxy amine tensio-active agent of the present invention comprises the compound of following formula:
R wherein
1Be C
10-C
18Alkyl, preferred C
10-C
14Alkyl, p is that 1-is about 3 independently, q is that 1-is about 3, R
2Be C
1-C
3Alkyl, preferable methyl, X is a negatively charged ion, particularly chlorine or bromine.
Other compound of the above-mentioned type comprises wherein oxyethyl group (CH
2CH
2O) unit (EO) is by butoxy (Bu), isopropoxy [CH (CH
3) CH
2O] and [CH
2CH (CH
3O] unit (i-Pr) or positive propoxy unit (Pr) or EO and/or Pr and/or the unitary mixture of i-Pr displaced those.The perhydrate SYNTHETIC OPTICAL WHITNER
Builder component of the present invention, but other preferred ingredient of the preferred present composition is the perhydrate SYNTHETIC OPTICAL WHITNER, for example peroxyboric acid metal-salt, percarbonic acid metal-salt, particularly sodium salt.Perborate can be monohydrate or tetrahydrate.SPC-D has corresponding to 2Na
2CO
33H
2O
2Chemical formula, it can be purchased by crystalline solid forms.
Peroxide Potassium peroxysulfate, its sodium salt are the optional inorganic perhydrate salts of another kind that is used for detergent composition of the present invention.The organic peroxide acid bleach system
The preferred feature of the present composition or agglomerate is the organic peroxide acid bleach system.In a preferred embodiment, bleach system contains hydrogen peroxide cource and organic peroxide acid bleach precursor compound.Situ reaction by precursor and hydrogen peroxide cource can produce organic peroxide acid.The preferred source of hydrogen peroxide comprises inorganic hydrogen peroxide compound SYNTHETIC OPTICAL WHITNER, perborate bleach for example of the presently claimed invention.In another preferred embodiment, the ready-formed organic peroxide acid directly adds in the composition.Also can imagine the composition that contains with the mixture of ready-formed organic peroxide acid blended hydrogen peroxide cource and organic peroxy acid precursor.Peroxyacid bleach precursor
Peroxyacid bleach precursor is the compound that produces peroxy acid in crossing hydrolysis reaction with hydroperoxidation.Usually, peroxyacid bleach precursor is expressed from the next:
Wherein, L is a leavings group, and X is any functionality substantially, so that the peroxy acid structure that produces when crossing hydrolysis is:
In detergent composition weight, the content of peroxyacid bleach precursor compound is preferably 0.5-20%, more preferably 1-15%, most preferably 1.5-10%.
Suitable peroxyacid bleach precursor compound comprises one or more N-or O-carboxyl groups usually, and this precursor can be selected from type widely.Suitable type comprises the acylated derivatives of acid anhydrides, ester, imide, lactan and imidazoles and oxime.The example of the useful matter in these classes is disclosed in GB-A-1586789.Suitable ester is disclosed in GB-A-836988,864798,1147871,2143231 and EP-A-0170386.Leavings group
Leavings group hereinafter referred to as the L group must have enough reactivities to the hydrolysis reaction of crossing that occurs in the Best Times section (for example cycles of washing).But if L is too active, this activator will be difficult to stably be used for bleaching composition.
Preferred L group is selected from following radicals and its mixture:
Wherein, R
1Be alkyl, aryl or the alkaryl that comprises 1-14 carbon atom, R
3For comprising the alkyl chain of 1-8 carbon atom, R
4Be H or R
3, Y is H or solubilization radical.R
1, R
3And R
4In any can be replaced by any functional group basically, comprise for example alkyl, hydroxyl, alkoxyl group, halogen, amine, nitrosyl radical, amido and ammonium or alkyl ammonium group.
Preferred solubilization radical is-SO
3 -M
+,-CO
2 -M
+,-SO
4 -M
+,-N
+(R
3)
4X
-And O＜--N (R
3)
3, most preferably-SO
3 -M
+With-CO
2 -M
+, wherein, R
3For comprising the alkyl of 1-4 carbon atom, M is for providing deliquescent positively charged ion to bleach-activating agent, and X is for providing deliquescent negatively charged ion to bleach-activating agent.Preferred M is the ammonium cation of basic metal, ammonium or replacement, most preferably sodium and potassium, and X is halogen, hydroxide radical, methylsulfate or acetic acid anion.Alkyl percarboxylic acids bleach precursor
Alkyl percarboxylic acids bleach precursor forms percarboxylic acids when crossing hydrolysis.Preferred such precursor provides peracetic acid when crossing hydrolysis.
Preferred imide-type alkyl peroxycarboxylic acid precursors compound comprises N, N, and N ', N '-tetra-acetylatedization Alkylenediamine, wherein, alkylidene group comprises 1-6 carbon atom, and particularly wherein alkylidene group comprises those compounds of 1,2 and 6 carbon atom.Preferred especially tetraacetyl ethylene diamine (TAED).TAED preferably is not present in the agglomerated particle of the present invention, but preferably is present in the detergent composition of the present invention by granulometric composition.
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 applicable to the present invention, and it comprises the compound of following general formula:
Wherein, R
1For having the alkyl of 1-14 carbon atom, R
2For having the alkylidene group of 1-14 carbon atom, R
5For H or comprise the alkyl of 1-10 carbon atom, L can be any leavings group basically.The bleach activating immunomodulator compounds that the acid amides of the type replaces is stated in EP-A-0170386.Peroxybenzoic acid precursors
The peroxybenzoic acid precursors compound provides peroxybenzoic acid when crossing hydrolysis.Suitable O-acylations peroxybenzoic acid precursors compound comprises and replacing and not unsubstituted benzoyloxy benzene sulfonate; and Sorbitol Powder, glucose and all sugar are carried out benzoylated product with benzoylation reagent; these compounds of inferior acid amide type comprise the urea that N-benzoyl succinimide, four benzoyl quadrols and N-benzoyl replace.Suitable imidazole type peroxybenzoic acid precursors comprises N-benzoyl imidazoles and N-benzoyl benzo imidazoles.The peroxybenzoic acid precursors that contains the N-acyl group that other is useful comprises N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl Pyrrolidonecarboxylic acid.The positively charged ion peroxyacid precursor
Positively charged ion peroxyacid precursor compound produces the positively charged ion peroxy acid when crossing hydrolysis.
Usually, the positively charged ion peroxyacid precursor is by with positively charged functional group such as ammonium or alkyl ammonium group, and preferred ethyl or ammonium methyl group replace the peroxy acid part of suitable peroxyacid precursor compound and form.The positively charged ion peroxyacid precursor has suitable negatively charged ion such as halogen ionic salt is present in the solid detergent composition as a kind of usually.
The peroxyacid precursor that this positively charged ion replaces can be the derivative of peroxybenzoic acid or its replacement, precursor compound as the aforementioned.Perhaps, the peroxyacid precursor compound can be the alkyl peroxy acids precursor that alkyl peroxycarboxylic acid precursors compound or acid amides as described below replace.
The positively charged ion peroxyacid precursor is stated in following document: US 4,904, and 406; 4,751,015; 4,988,451; 4,397,757; 5,269,962; 5,127,852; 5,093,022; 5,106,528; U.K.1,382,594; EP 475,512; 458,396 and 284,292; JP87-318,332.
The example of preferred cation peroxyacid precursor is stated in UK number of patent application 9407944.9 and US number of patent application 08/298903,08/298650,08/298904 and 08/298906.
Suitable positively charged ion peroxyacid precursor comprises alkyl that ammonium or alkylammonium replace or in the tetra-acetylated glucose benzoyl peroxide of benzoyloxy benzene sulfonate, N-acetylize hexanolactam and single benzoyl any.Preferred N-acylations hexanolactam cationoid peroxyacid precursor comprises trialkyl ammonium methylene radical benzoyl caprolactam and trialkyl ammonium methylene radical alkyl hexanolactam.Benzoxazine organic peroxy acid precursor
What also be suitable for is benzoxazine type precursor compound, EP-A-332 for example, and 294 and EP-A-482, those described in 807 particularly have the compound of following formula:
Wherein, R
1Be H, alkyl, alkaryl, aryl or aralkyl.The ready-formed organic peroxide acid
Detergent composition of the present invention except that comprising organic peroxyacid bleach precursor compound or as an alternative also can comprise the ready-formed organic peroxide acid, and in the weight of the present composition, its content is generally 1-15%, more preferably 1-10%.
A preferred class organic peroxy acid compound is the compound with acid amides replacement of following general formula:
Wherein, R
1Be alkyl, aryl or the alkaryl with 1-14 carbon atom, R
2Be alkylidene group, arylidene and the alkyl arylene with 1-14 carbon atom, R
5For H or have alkyl, aryl or the alkaryl of 1-10 carbon atom.The organic peroxy acid compound that such acid amides replaces is stated in EP-A-0179386.
Other organic peroxide acid comprises diacyl and four acyl peroxides, particularly diperoxy dodecanedioic acid, diperoxy tetradecane diacid and diperoxy Thapsic acid.Single-as and two to cross nonane diacid, single-and two cross undecane dicarboxylic acid and the amino oxy hexanoic acid of crossing of N-phthaloyl also is suitable for the present invention.Bleaching catalyst
Builder component of the present invention or composition can contain a kind of bleaching catalyst that contains transition metal.
A kind of bleaching catalyst of suitable type is to comprise the active transition-metal cation of the bleach catalyst with regulation such as copper, iron or manganese positively charged ion, have very little or do not have the active assistant metal positively charged ion of bleach catalyst such as zinc or aluminium cations, with the catalyst system of the sequestrant of the stability constant with catalysis and assistant metal positively charged ion defined, described sequestrant is ethylenediamine tetraacetic acid (EDTA), ethylenediamine tetraacetic (methylene phosphonic acid) and its water-soluble salt particularly.This catalyzer is disclosed in US4, in 430,243.
The bleaching catalyst of other type comprises and is disclosed in US 5,246, the manganese basigamy compound in 621 and US5,244,594.The preferred embodiment of these catalyzer comprises: Mn
IV 2(u-O)
3(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane)
2(PF
6)
2, Mn
III 2(u-O)
1(u-OAc)
2(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane)
2(ClO
4)
2, Mn
IV 4(u-O)
6(1,4, the 7-7-triazacyclononane)
4(ClO
4)
2, Mn
IIIMn
IV 4(u-O)
1(u-OAc)
2(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane)
2(ClO
4)
3And their mixture.Other is described in the European patent application publication No. 549272.Other is applicable to that ligand of the present invention 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 its mixture.
All bleaching catalysts useful to the present invention also can be elected to be the bleaching catalyst that the present invention is suitable for.For example, the bleaching catalyst that is fit to is referring to US 4,246, and 612 and 5,227,084.Also referring to US 5,194,416, it has lectured for example Mn (1,4,7-trimethylammonium-1,4,7-7-triazacyclononane)-(OCH of monokaryon manganese (IV) title complex
3)
3(PF
6).
As the another kind of bleaching catalyst that is disclosed among the US 5114606 is manganese (III) and/or (IV) and the water-soluble complexes that has the non-carboxylation polyol ligand of three continuous C-OH groups at least.Preferred ligand comprises Sorbitol Powder, iditol, galactitol, mannitol, Xylitol, arabitol, adonitol, meso-tetrahydroxybutane, meso-inositol, lactose and its mixture.
U.S. Pat 5114611 has been lectured bleaching catalyst, and it comprises the title complex of transition metal and non-(greatly) ring ligand, and described transition metal comprises Mn, Co, Fe or Cu.Described ligand has formula:
R wherein
1, R
2, R
3And R
4Each can be selected from the alkyl and the aryl of H, replacement, makes each R
1-N=C-R
2And R
3-C=N-R
4Formation five or six-ring.Described ring also can be substituted.B is an abutment, is selected from O, S, CR
5R
6, NR
7And C=O, wherein R
5, R
6And R
7Each can be H, alkyl or aryl, comprises replacing or unsubstituted group.Preferred ligand comprises pyridine, pyridazine, pyrimidine, pyrazine, imidazoles, pyrazoles and triazole ring.Randomly, described ring can be substituted base for example alkyl, aryl, alkoxyl group, halogen and nitro replacement.Particularly preferably be ligand 2,2 '-two pyridine amine.Preferred bleaching catalyst comprises Co, Cu, the two pyridine methane of Mn, Fe-and two pyridine amine complex.Highly preferred catalyzer comprises Co (2,2 ' two pyridine amine) Cl
2, two (different sulfo-cyanato-) two pyridine amine cobalts (II), three pairs of pyridine amine cobalts (II) perchlorate, Co (2,2 '-two pyridine amine)
2O
2ClO
4, two (2,2 '-two pyridine amine) copper (II) perchlorate, three (two-2-pyridine amine) iron (II) perchlorate and its mixture.
Other example comprises the double-core Mn title complex that cooperates with four-N-dentate and two-N-dentate ligand, comprises N
4Mn
III(u-O)
2Mn
IVN
4 +[Bipy
2Mn
III(u-O)
2Mn
IVBipy
2]-(ClO
4)
3
Other bleaching catalyst is disclosed in the following document, for example European patent application publication No. 408,131 (cobalt complex catalyzer), European patent application publication No. 384,503 and 306,089 (metal-porphyrin catalyst), US 4,728,455 (manganese/polygamy position polymerization of olefin using catalyst body catalyst), US 4,711, and 748 and European patent application publication No. 224,952 (being adsorbed in the Mn catalyst on the silico-aluminate), US 4,601,845 (being loaded with the silico-aluminate of manganese and zinc or magnesium salts), US4,626,373 (manganese/ligand catalyzer), US 4,119,557 (iron complex catalyzer), German Pat. specification sheets 2,054,019 (cobalt chelates catalyzer), Canadian866,191 (salt that contain transition metal), US 4,430,243 (sequestrant with manganese positively charged ion and on-catalytic metallic cation) and US 4,728,455 (gluconic acid Mn catalysts).
Bleaching catalyst generally is to be used for the present composition and method with catalytically effective amount." catalytically effective amount " meaning be this amount no matter under which type of contrast experiment's condition of use, all be enough to strengthen the spot on bleaching and the removal target substrates or some spots of being paid close attention to.This experiment condition will change according to washing plant type of using and user's custom.Some users select to use very hot water; Other user uses temperature or even cold water in washing operation.Certainly, the catalytic performance of bleaching catalyst will be subjected to the influence of these Considerations, can suitably be adjusted in the amount of the bleaching catalyst that uses in the washing composition of complete formula and the bleaching composition.In practical situation, not limited to, the present composition and method can be conditioned so that provide in wash water solution at least about per active bleaching catalyst of 1/10000000th, preferably provide about 1ppm to about 200ppm catalyzer in washing soln.In order to further specify this point, using under perborate and bleach precursor 40 ℃, the European condition of pH10, about 3 micromole's Mn catalysts are effective.Under U.S.'s condition,, may need concentration to increase 3-5 doubly in order to obtain equifinality.Other washing assistant material water soluble detergency promoter
Builder component of the present invention or preferred composition can comprise the water soluble detergency promoter compound, and by the weight of said composition, generally its content is 1-80%, preferred 10-60%, more preferably 15-40%.
Detergent composition of the present invention can comprise phosphatic washing assistant material, preferably comprise tetrasodium pyrophosphate or even more preferably anhydrous sodium tripolyphosphate, its content is 0.5%-60%, more preferably 5%-50%, more preferably 8%-40%.Preferred said composition does not contain phosphatic washing assistant material.
Suitable water soluble detergency promoter compound comprises water-soluble monomer multi-carboxylate or its sour form, homopolymerization or copolymerization poly carboxylic acid or its salt, wherein poly carboxylic acid comprises and is no more than at least two carboxyls that two carbon atoms separate are opened each other, and described washing-aid compound also comprises the mixture of borate and aforementioned any compound.
Carboxylate salt or multi-carboxy acid salt washing agent can be monomer type or oligomer types, but because Cost And Performance, the multi-carboxylate of preferred monomers type usually.
The suitable carboxylate salt that contains a carboxyl comprises the water-soluble salt and the ether derivant thereof of lactic acid, oxyacetic acid.The multi-carboxylate of containing two carboxyls comprises the water-soluble salt of succsinic acid, propanedioic acid, (ethylidene dioxy base) oxalic acid, toxilic acid, Glyoxylic acid hydrate, tartrate, tartronic acid and fumaric acid and ether carboxylate and sulfinyl carboxylate salt.The multi-carboxylate or its acid that contain three carboxyls comprise particularly water-soluble citrate, aconitate and citraconate, and the succinate derivative, as English Patent 1,379,241 described carboxy methoxy-succinic acid salt, the newborn acyloxy succinate described in the English Patent 1389732, HOII P 7205873 described aminosuccinic acid salt, and English Patent 1,387,447 described oxygen multi-carboxylate material, for example 2-oxa-s-1,1,3-tricarballylic acid salt.The most preferred poly carboxylic acid that contains three carboxyls is a citric acid, and by the weight of composition, preferably its content is 0.1%-15%, more preferably 0.5%-8%.
The multi-carboxylate of containing four carboxyls comprises English Patent 1,261,829 disclosed oxygen disuccinate, and 1,1,2,2-ethane tetracarboxylic acid hydrochlorate, 1,1,3,3-propane tetracarboxylic acid salt and 1,1,2,3-propane tetracarboxylic acid salt.Comprise the substituent multi-carboxylate of sulfo group and comprise English Patent 1,398,421 and 1,398,422 and US3,936,448 disclosed sulfo-succinic acid salt derivatives, and English Patent 1,439,000 described sulfonation pyrolytic Citrate trianion.Preferred multi-carboxylate is contained the hydroxycarboxylate of 3 carboxyls of as many as, Citrate trianion more specifically for per molecule.
The parent acid of monomer or oligomeric multi-carboxylate's sequestrant or also expect as useful builder component with the mixture of its salt, for example, citric acid or Citrate trianion/citric acid mixture.
By the weight of said composition, preferred polymeric or oligomeric multi-carboxylate's content is lower than 5%, preferably is lower than 3% or even be lower than 2% or even 0%.
The borate washing assistant and contain can washing composition store or wash conditions under to produce boratory washing assistant be the useful water soluble detergency promoter of the present invention.Insoluble washing-aid compound
Builder component of the present invention or composition can comprise insoluble washing-aid compound, but by said composition weight, preferably its content only is 0%-25%, most preferably 0%-15%, even 0%-10%.
Basically the example of water-insoluble washing assistant comprises sodium silicoaluminate.
The aluminosilicate zeolite that is suitable for has unit structure cell formula Na
z[(AlO
2)
z(SiO
2)
y] xH
2O, wherein z and y are at least 6, and the mol ratio of z and y is 1.0-0.5, and x is at least 5, preferred 7.5-276, more preferably 10-264.Alumino-silicate materials can be hydrated form, and preferably xln contains 10-28%, preferred 18-22% combination water.
Aluminosilicate zeolite can be natural product, but preferably synthetic obtaining.Synthetic crystallization type aluminosilicate ion exchange material can be by zeolite A, zeolite B, zeolite P, the X zeolite of registration, and zeolite HS and composition thereof buys.Zeolite A has following formula:
Na
12[(AlO
2)
12(SiO
2)
12] xH
2O wherein x is 20-30, particularly 27.X zeolite has formula: Na
86[(AlO
2)
86(SiO
2)
106] 276H
2O.
Zeolite MAP builder is in addition preferred aluminosilicate zeolite.Zeolite MAP is stated in EP384070A (Unilever).It is defined as the zeolite P type alkali metal aluminosilicate, and its ratio with silicon and aluminium is not more than 1.33, is preferably 0.9-1.33, more preferably 0.9-1.2.
Making us interested especially is silicon and the ratio of aluminium is not more than 1.15, is not more than 1.07 zeolite MAP more specifically.
In preferred situation, the granularity of zeolite MAP detergent builders is represented as d
50, its value is 1.0-10.0 μ m, more preferably 2.0-7.0 μ m, most preferably 2.5-5.0 μ m.
d
50Value is meant that 50 weight % particulate diameters are worth less than this.This granularity specifically can be measured or be measured with laser particle size analyzer as the microscope that adopts scanning electron microscope to carry out by the routine analysis technical measurement.Other determines d
50The method of value is open in EP 384070A.
Builder component of the present invention or composition also can comprise other silicate material, comprise that amorphous silicic acid salt material, metasilicate, other granularity are higher than 150 microns coarse crystallization layered silicate material.By the weight of said composition, preferably the content of other silicate material is lower than 20%, preferably is lower than 15% or even be lower than 10%.Heavy metal ion chelating agent
Heavy metal ion chelating agent also is other component that the present invention is suitable for.So-called heavy metal ion chelating agent has been meant the component of chelating heavy metal ion effect at this paper.These components also can have calcium and magnesium sequestering power, but preferably they demonstrate the selectivity in conjunction with heavy metal ion such as iron, manganese and copper.
The content of heavy metal ion chelating agent is generally the 0.005-10% of present composition weight, preferred 0.1%-5%, more preferably 0.25-7.5%, most preferably 0.3-2%.
Be suitable for heavy metal ion chelating agent of the present invention and include organic phosphonates, as amino alkylidenyl many (alkylene phosphonic acids salt), basic metal ethane 1-hydroxyl diphosphonate and WSI 3310 salt.
Preferred diethylenetriamine five (methylene phosphonic acid salt), quadrol three (methylene phosphonic acid salt), hexamethylene-diamine four (methylene phosphonic acid salt) and hydroxyl-ethylidene 1 in the above-mentioned substance, 1-diphosphonate, 1,1-hydroxyl ethane di 2 ethylhexyl phosphonic acid and 1,1-hydroxyl ethane dimethylene phosphonic acids.
Other is applicable to that heavy metal ion chelating agent of the present invention comprises nitrilotriacetic acid(NTA) and polyamino carboxylic acid, as ethylenediamine tetraacetic acid (EDTA), ethylenediamine disuccinic acid, quadrol two pentanedioic acids, 2-hydroxy propylidene diamines disuccinic acid or its any salt.
Other is applicable to that heavy metal ion chelating agent of the present invention is an iminodiacetic acid derivatives, as 2-hydroxyethyl oxalic acid or glyceryl iminodiethanoic acid, and as EP-A-317,542 and EP-A-399, described in 133.The present invention also can adopt as EP-A-5126,102 described iminodiethanoic acid-N-2-hydroxypropyl sulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid sequestrant.The present invention also can adopt EP-A-509,382 described Beta-alanine-N, N '-oxalic acid, aspartic acid-N, single acetate of N '-oxalic acid, aspartic acid-N-and imino-diacetic succsinic acid sequestrant.
EP-A-476,257 have narrated the suitable sequestrant based on amino.EP-A-510,311 have narrated the suitable sequestrant that is obtained by collagen, Keratin sulfate or casein.EP-A-528, a kind of suitable alkyl imino oxalic acid sequestrant of 859 narrations.Pyridine dicarboxylic acid and 2-phosphinylidyne butane-1,2, the 4-tricarboxylic acid also is fit to.Glycine acid amides-N, N '-disuccinic acid (GADS), quadrol-N, N '-two pentanedioic acid (EDDCG) and 2-hydroxyl propylene diamine-N, N '-disuccinic acid (HPDDS) also is fit to.
Particularly preferably be diethylene triaminepentaacetic acid(DTPA), quadrol-N, N '-disuccinic acid (EDDS) and 1, the ammonium salt of 1-hydroxyl ethane di 2 ethylhexyl phosphonic acid or its basic metal, alkaline-earth metal, ammonium or replacement, or its mixture.Enzyme
Can be used for another kind of preferred ingredient of the present invention is one or more additional enzymes.
Preferred additional enzymes material comprises the commercial lipase of purchasing, at, amylase, neutrality and Sumizyme MP, cellulase, restriction endonuclease (endolase), esterase, polygalacturonase, Sumylact L and the peroxidase that is routinely added in the detergent composition.Suitable enzyme is discussed in US3519570 and 3533139 to some extent.
The preferred commercial proteolytic enzyme of purchasing comprises those proteolytic enzyme of being sold with trade(brand)name Alcalase, Savinase, Primase, Durazym and Esperase by Novo Industries A/S (Denmark), by Gist-Brocades those proteolytic enzyme, by those proteolytic enzyme of Genencor International sale and those proteolytic enzyme of selling with trade(brand)name Opticlean and Optimase by Solvay Enzymes with trade(brand)name Maxatase, Maxacal and Maxapem sale.Proteolytic enzyme is pressed the content that composition weight meter can the 0.0001%-4% organized enzyme and is added in the present composition.
Preferably amylase comprises, for example the α-Dian Fenmei that the special bacterial strain by bacillus licheniformis of detailed description obtains among the GB-1269839 (Novo).The preferred commercial amylase of purchasing comprises those amylase of for example being sold those amylase and sold with trade(brand)name Termamyl, Duramyl and BAN by Novo IndustriesA/S with trade(brand)name Rapidase by Gist-Brocades.Highly preferred amylase is to be described among PCT/US 9703635 and WO95/26397 and the WO96/23873 those.
By the weight of composition, amylase adds in the present composition with the content of 0.0001%-2% organized enzyme.
By the weight of composition, lipolytic enzyme can 0.0001%-2%, preferably 0.001%-1%, the most preferably active lipolytic enzyme content existence of 0.001%-0.5%.
Lipase can be obtained by fungi or bacterial origin, for example by the detritus enzyme belong to, the bacterial strain of the generation lipase of Thermomicrobium (Thermomyces) or Rhodopseudomonas obtains, described bacterial strain comprises pseudomonas pseudoalcaligenes or Pseudomonas fluorescens.The lipase that is obtained by the mutation of the chemistry of these bacterial strains or genetic modification also can be used among the present invention.Preferred lipase is obtained by pseudomonas pseudoalcaligenes, and it is stated in the European patent EP-B-0218272 that authorizes.
Another preferred lipase of the present invention is as described in European patent application EP-A-0258068, be the gene that obtains by fetal hair detritus bacterium by the clone and express the lipase that this gene obtains in as the host at aspergillus oryzae, it is from Novo Industri A/S Bagsvaerd, Denmark, Lipolase is purchased with trade(brand)name.This lipase also is described among the US4810414 of the Huge-Jensen of on March 7th, 1989 promulgation etc.Organic polymer
Organic polymer is preferred other component of the present composition or agglomerate, and they play the effect that for example the agglomerate component is bonded together.
So-called organic polymer looks like here and is meant any basically organic polymer that is used as tackiness agent, dispersion agent, anti redeposition agent and soil-suspending agent in detergent composition usually, be included in any high molecular organic polymer that is stated as the clay flocculating agent herein, comprise the quaternised ethoxylation of the present invention (gathering) amine clay class washing agent/anti redeposition agent.
Press composition weight meter, the incorporation of organic polymer in detergent composition of the present invention is generally 0.01-30%, preferred 0.1-15%, more preferably 0.5-10%.
The example of organic polymer comprises water-soluble organic homopolymerization or copolymerization poly carboxylic acid or its salt, and wherein poly carboxylic acid comprises at least two and is no more than the carboxyl that two carbon atoms separate are opened each other.The polymkeric substance of back one type is disclosed in GB-A-1, in 596,756.The example of this salt be molecular weight 1000-5000 polyacrylate and with the multipolymer of maleic anhydride, this multipolymer has molecular weight 2000-100,000, particularly 40,000-80,000.
Polyamino compound can be used for the present invention, comprises those materials that obtained by aspartate-derived, for example those disclosed among EP-A-305282, EP-A-305283 and the EP-A-351629.
Comprising the ter-polymers, particularly molecular-weight average that are selected from toxilic acid, vinylformic acid, poly aspartic acid and vinyl alcohol monomeric unit is 5, and 000-10, those of 000 also are applicable to the present invention.
Other organic polymer that is fit to add in the detergent composition of the present invention comprises derivatived cellulose, as methylcellulose gum, carboxymethyl cellulose, Vltra tears and Natvosol.
Other useful organic polymer is that polyoxyethylene glycol, particularly molecular weight are 1000-10000, more preferably 2000-8000, most preferably from about those polyoxyethylene glycol of 4000.
The highly preferred polymeric component of the present invention is the U.S. Pat 5415807 according to the U.S. Pat 4968451 of Scheibel etc. and Gosselink etc., particularly according to the cotton and the non-cotton dirt release agent polymkeric substance of U.S. Patent application 60/051517.
Be used for another kind of organic compound of the present invention, it is a kind of preferred clay suspending agent/anti redeposition agent, and it can be cationic ethoxy monoamine and the diamines with following formula:
Wherein X is a non-ionic group, is selected from H, C
1-C
4Alkyl or hydroxyalkyl acrylate or ether group and its mixture, a are 0-20, preferred 0-4 (as ethylidene, propylidene, hexa-methylene), and b is 1 or 0; For positively charged ion monoamine (b=0), n is at least 16, and general range is 20-35; For cationic diamine (b=1), n is at least about 12, and general range is about 12-about 42.
Be used for other dispersion agent/anti redeposition agent of the present invention and be described in EP-B-011965, US4659802 and US 4664848.Press down foam system
When detergent composition of the present invention is mixed with the composition of machine washing usefulness, can comprise a kind of foam system that presses down, by the weight of composition, its content is 0.01-15%, preferred 0.02-10%, more preferably 0.05-3%.
Being used for the suitable foam that presses down of the present invention is to comprise any basically known defoamer compound, comprises for example polysiloxane defoamers compound and 2-alkyl alkanol defoamer compound.
Defoamer compound is meant detergent composition solution, the foaming that produces when particularly stirring this solution or for example inhibiting any compound of puff or its mixture.
Being used for the particularly preferred defoamer compound of the present invention is the polysiloxane defoamers compound, and it is defined as any defoamer compound that comprises the polysiloxane component at this paper.This polysiloxane defoamers compound generally also contains silica component.Used herein and also be that the term " polysiloxane " of industrial common employing comprises the various relative high molecular weight polymers that contain siloxane unit and all kinds alkyl.Preferred polysiloxane defoamers compound is a siloxanes, particularly has the unitary polydimethylsiloxane of trimethyl silyl end-blocking.
Other suitable defoamer compound comprises monobasic aliphatic carboxylic acid and its soluble salt.These substance descriptions are in the US 2954347 of the Wayne St.John of mandate on September 27 nineteen sixty.Monobasic aliphatic carboxylic acid and salt thereof as suds suppressor generally have the 10-24 of containing carbon atom, the hydrocarbyl chain of preferred 12-18 carbon atom.The salt that is fit to comprises an alkali metal salt, sodium salt for example, sylvite, and lithium salts and ammonium salt and alkanol ammonium salts.
Other suitable defoamer compound comprises for example high-molecular weight fatty acid ester (as glycerine fatty acid three esters), monohydroxy-alcohol fatty acid ester, aliphatic C
18-C
40Ketone (as stearone), N-alkylation aminotriazine, as three to six alkyl melamines or two to the tetraalkyl diammonium chloride for triazine, it is that cyanuryl chloride and 2 or 3 moles contain the uncle of 1-24 carbon atom or the reaction product of secondary amine, propylene oxide, distearyl acid amides and single stearyl di(2-ethylhexyl)phosphate basic metal (as sodium, potassium, lithium) salt and phosphoric acid ester.
The preferred foam system that presses down comprises:
(a) defoamer compound, preferred polysiloxane defoamers compound most preferably comprises the polysiloxane defoamers compound of following composition:
(ⅰ) polydimethylsiloxane, its content accounts for the 50%-99% of polysiloxane defoamers compound weight, preferred 75%-95%; With
(ⅱ) silicon-dioxide, its content account for the 1%-50% of polysiloxane/silicon-dioxide defoamer compound weight, preferred 5%-25%;
The incorporation of wherein said silicon-dioxide/polysiloxane defoamers compound is 5%-50%, preferred 10%-40% weight;
(b) a kind of compound dispersing agent, most preferably comprise silicone glycol comb copolymer (rake copolymer), its polyoxyethylene content is 72%-78%, and the ratio of oxyethane and propylene oxide is 1: 0.9-1: 1.1, its content is 0.5%-10%, preferred 1%-10% weight; Particularly preferred the type silicone glycol comb copolymer is DC0544, is purchased with trade(brand)name DCO544 from DOWCorning company;
(c) a kind of inertia carrying object compound, most preferably it comprises C
16-C
18Ethoxylated alcohol, its ethoxylation degree are 5-50, preferred 8-15, and its content is 5%-80%, preferred 10%-70% weight.
Particularly preferred granular suds suppressing system is described among the EP-A-0210731, should pressing down foam system, to comprise a kind of polysiloxane defoaming compounds and a kind of fusing point be 50-85 ℃ organic carrier material, wherein the organic carrier material comprises the monoesters of glycerine and a kind of lipid acid, and described lipid acid has the carbochain that contains 12-20 carbon atom.EP-A-0210721 discloses other preferred granular suds suppressing system, and wherein the organic carrier material is lipid acid or the alcohol with the carbochain that contains 12-20 carbon atom, or its mixture, and its fusing point is 45-80 ℃.
Other highly preferred foam system that presses down comprises polydimethylsiloxane or polysiloxane mixture for example polydimethylsiloxane, silico-aluminate and multi-carboxy acid copolymer, for example lactic acid (laic) and acrylic acid multipolymer.The polymeric dye transfer inhibitor
The present composition also can comprise 0.01-10%, the polymeric dye transfer inhibitor of preferred 0.05-0.5% weight.
The polymeric dye transfer inhibitor is preferably selected from multipolymer, polyvinylpyrrolidonepolymers polymers or its mixture of polyamine N-oxide pllymers, N-vinyl pyrrolidone and N-vinyl imidazole, so these polymkeric substance can be cross-linked polymers.White dyes
The present composition also can randomly contain the hydrophilic white dyes of some type of have an appointment 0.005% to 5% (weight).
Can be used for hydrophilic white dyes of the present invention and have the following formula structure:
R wherein
1Be selected from anilino, N-2-pair-hydroxyethyl and NH-2-hydroxyethyl; R
2Be selected from N-2-pair-hydroxyethyl, N-2-hydroxyethyl-N-methylamino-, morpholino, chlorine and amino; With M be salt-forming cation such as sodium or potassium.
In following formula, work as R
1Be anilino, R
2Be N-2-two-when hydroxyethyl and M were positively charged ion such as sodium, whitening agent was 4,4 '-two [(4-anilino-6-(N-2-two-hydroxyethyl)-guanamine-yl) amino]-2,2 '-Stilbene disulfonic acid and disodium salt.Such special whitening agent can be bought from Ciba-Geigy company according to trade(brand)name Tinopal-UNPA-GX commercial.Tinopal-CBS-X and Tinopal-UNPA-GX are the preferred hydrophilic white dyess that can be used in the detergent composition of the present invention.
In following formula, work as R
1Be anilino, R
2Be N-2-hydroxyethyl-N-2-methylamino-and M when being positively charged ion such as sodium, whitening agent is 4,4 '-two [(4-anilino-6-(N-2-hydroxyethyl-N-methylamino-)-guanamine-yl) amino]-2,2 '-Stilbene disulfonic acid disodium salt.Such special whitening agent can be bought from Ciba-Geigy company according to trade(brand)name Tinopal 5BM-GX in commerce.
In following formula, work as R
1Be anilino, R
2Be morpholino and M when being positively charged ion such as sodium, whitening agent is 4,4 '-two [(4-anilino-6-morpholino-guanamine-yl) amino]-2,2 '-Stilbene disulfonic acid sodium salt.Such special whitening agent can be bought from Ciba-Geigy company is commercial according to trade(brand)name Tinopal-DMS-X and Tinopal AMS-GX.The polymerization dirt release agent
Can randomly use the polymerization dirt release agent in the present composition, hereinafter referred is " SRA ".If you are using, SRA ' s generally accounts for 0.01% to 10.0% of composition weight, is typically 0.1% to 5%, and preferred 0.2% to 3.0%.
The hydrophobic part that preferred SRA ' s generally has the hydrophilic segment that makes hydrophobic fiber such as polyester and nylon surface hydrophilic and is deposited on the hydrophobic fiber and keeps being attached thereto in whole washing and rinse cycle, so it is as the fixture of hydrophilic segment.This can be so that spot easier being cleaned in washing process afterwards that produces subsequently of handling with SRA.
Preferred SRA ' s comprises the terephthalate of oligomerisation, and it generally by comprising the method preparation of at least a transesterify/oligomerisation reaction, carries out under metal catalyst such as titanium alkoxide (IV) usually.This ester can use can by one, two, three, four or more position add other monomers preparations of ester structure, certainly, do not form fine and close full crosslinking structure.
SRA ' the s that is fit to comprises the sulfonated products of the ester oligomer that is straight chain basically; it contains oligomer ester skeleton and the oxyalkylene oxygen repeating unit and the allyl group deutero-sulfonation terminal portions covalently bound with skeleton of terephthaloyl, for example described in the U.S. Pat 4968451 of J.J.Scheibel that authorizes in November 6 nineteen ninety and E.P.Gosselink.This ester oligomer can prepare through the following steps: (a) ethoxylation allyl alcohol; (b) product and terephthalic acid dimethyl ester (" DMT ") and 1 that will (a) in two step transesterify/oligomerizations, 2-propylene glycol (" PG ") reacts; (C) in water with the product of (b) and sodium metabisulfite reaction.Other SRA ' s comprises the nonionic end capped 1 in the people's such as Gosselink that authorized on December 8th, 1987 the U.S. Pat 4711730,2-propylidene/polyoxyethylene terephthalic acid polyester, for example by poly-(ethylene glycol) methyl ether, DMT, the product of transesterify/oligomerisation preparation of PG and poly-(ethylene glycol) (" PEG ").Other SRA ' s example comprises part and the whole end capped oligomer esters of negatively charged ion in the U.S. Pat 4721580 of the Gosselink that authorized on January 26th, 1988, as derive from ethylene glycol (" EG "), PG, DMT and 3, the oligopolymer of 6-two oxa-s-8-hydroxyl perfluorooctane sulfonate; Nonionic end-blocking block polyester oligopolymer in the U.S. Pat 4702857 of the Gosselink that on October 27th, 1987 authorized, for example by DMT, methyl (Me)-end capped PEG and EG and/or PG preparation, perhaps by DMT, EG and/or PG, the product of the mixture preparation of end capped PEG of Me-and dimethyl-5-sulfoisophthalic acid sodium; With the Maldonado that authorized on October 31st, 1989; negatively charged ion in people's such as Gosselink the U.S. Pat 4877896; especially the end capped terephthalate of sulfo group aroyl; the latter is typical useful SRA ' s in laundry and fabric-conditioning product; one example be by-sulfosalicylic acid list sodium salt, the ester composition of PG and DMT preparation, but randomly preferably also contain the PEG of adding; for example, PEG3400.
SRA ' s also comprises: the simple copolymerization block thing of ethylene terephthalate or terephthalic acid propylene glycol ester and polyoxyethylene or polyoxypropylene terephthalate, referring to the U.S. Pat 3959230 of the Hays on May 25th, 1976 and the U.S. Pat 3893929 of the Basadur on July 8th, 1975; Derivatived cellulose such as the hydroxy ethers cellulose polymer compound bought from Dow by METHOCEL; C
1-C
4Alkylcellulose and C
4Hydroxy alkyl cellulose is referring to the people's such as Nicol on December 28th, 1976 U.S. Pat 4000093; And methyl cellulose ether, it is about 1.6-2.3 that its each anhydroglucose unit has average substitution degree (methyl), the aqueous solution by 2% is about 80-120 centipoise at 20 ℃ of soltion viscosities of measuring down.This material can be buied by METOLOSE SM100 and METOLOSE SM200, and they are the trade(brand)names by the methyl cellulose ether of Shin-etsu Kagaku Kogyo KK production.
Another kind of SRA ' s comprises: (I) uses vulcabond coupler and polyester construction banded nonionic terephthalate, referring to people's such as people's such as Violland U.S. Pat 4201824 and Lagasse U.S. Pat 4240918; (II) has the SRA ' s of carboxylicesters end group, and the conversion terminal hydroxy group becomes the trimellitate preparation among known SRA ' s by trimellitic acid 1,2-anhydride is added for it.By suitable selecting catalyst, trimellitic acid 1,2-anhydride forms the end group banded key with polymkeric substance, and this is to carry out by the isolated carboxylicesters of trimellitic acid 1,2-anhydride rather than by opening the acid anhydride key.Nonionic or negatively charged ion SRA ' s can be used as starting raw material, as long as have can esterified hydroxyl end groups for they, referring to people's such as Tung U.S. Pat 4525524.Other type comprises: (III) links the SRA ' s based on the negatively charged ion terephthalate of urethanes, referring to people's such as Violland U.S. Pat 4201824.Other optional ingredient
Other optional ingredient that is fit to be included in the present composition comprises spices, spot jewelry, pigment or dyestuff, filling salt, and sodium sulfate is preferred filling salt.
In addition, can contain a small amount of (for example being lower than about 20% weight) neutralizing agent, buffer reagent, phase modifier, hydrotropic agent, enzyme stabilizers, polyacid, foaming regulator, opalizer, antioxidant, sterilant and dyestuff, for example those (they quote for referencial use at this paper) of describing in the U.S. Pat 4285841 of the Barrat that authorizes on August 25th, 1981 etc.The form of composition
The present composition can pass through prepared in various methods, comprise all cpds that will comprise in the detergent component do mix, agglomeration, die mould or spraying drying, or the mixing of these technology.
Composition of the present invention can be taked various physical form, comprises liquid, but preferred solid form for example sheet, thin slice, lozenge and bar, preferred particulates or sheet.
The present composition also can be used for or is used in combination with compositions of additives that the bleaching compositions of additives for example comprises chlorine bleach.
Detergent composition of the present invention, particularly detergent for washing clothes preferably have bulk density 280g/l-200g/l, or preferred 300g/l or even 350g/l or 420g/l to 2000g/l, or more preferably to 1500g/l, or 100g/l or even to 700g/l.Clothes washing method
The present invention's clothes washing method of machine-washing generally comprises and is used in containing dissolving or disperseed the present invention of significant quantity to machine-wash and handled soiled clothes with the wash water solution of laundry detergent composition in the washing machine.The detergent composition of significant quantity is meant at 5-65 and rises in the washing soln of volume dissolving or disperse the 10g-300g product that this is typical products consumption and the washing soln volume that is generally used in the conventional machine washing method.
Said composition also is mixed with and is applicable to hard surface cleaning or hand washing or pre-treatment or soaks dirty and soiled fabric.
That uses among the embodiment writes a Chinese character in simplified form
In the washing agent composition, the component symbol of writing a Chinese character in simplified form has following implication: LAS: straight chain C11-13Sodium alkyl benzene sulfonate MES: the C of α-sulfonation18Fatty acid methyl ester TAS: butter sodium alkyl sulfate CxyAS ：C
1X-C
1YSodium alkyl sulfate C46SAS: C14-C
16Secondary (2,3) sodium alkyl sulfate CxyE
zS: with the C of Z mole of ethylene oxide condensation1X-C
1YSodium alkyl sulfate CxyE
z: with average Z mole ethylene oxide condensation be mainly the C of straight chain1X-C
1YPrimary alconol QAS: R2N
+(CH
3)
2(C
2H
4OH),R
2=C
12-C
14
QAS1 ：R
2N
+(CH
3)
2(C
2H
4OH),R
2=C
8-C
11SADS: formula 2-(R) C4H
7-1,4-(SO
4-)
2C14-C
22Alkyl two sodium sulphate, wherein R=C10-C
18SADE2S: formula 2-(R) C4H
7-1,4-(SO
4-)
2C14-C
22Alkyl two sodium sulphate, wherein R=C10-C
18, condensation z mole of oxirane APA: C8-C
10Acylamino-propyl-dimethyl amine soap: straight-chain alkyl carboxylic acid's sodium obtains STS by 80/20 mixture of butter and coconut fatty acid: toluenesulfonic acid sodium salt CFAA: C12-C
14(cocounut oil) alkyl N-methyl glucose amide TFAA: C16-C
18Alkyl N-methyl glucose amide TPKFA: C16-C
18The full cut aliphatic acid of topping STPP: anhydrous sodium phosphate trimer TSPP: tetrasodium pyrophosphate Wessalith CS: formula Na12(AlO
2SiO
2)
12.27H
2The hydrated sodium aluminosilicate of O, primary particle size are 0.1-10 micron (weight that represents by moisture-free basis) NaSKS-6 (I): formula δ-NaSi2O
5Crystalline layered silicate, its weight average granularity is 18 microns, the granularity of at least 90% weight is lower than 65.6 microns NaSKS-6 (II): formula δ-NaSi2O
5Crystalline layered silicate, its weight average granularity is 18 microns, and the granularity of at least 90% weight is lower than 42.1 microns citric acids: anhydrous citric acid borate: Boratex carbonate: granularity is 200-900 micron natrium carbonicum calcinatum bicarbonate: granularity is distributed in the anhydrous sodium bicarbonate silicate of 400-1200 micron: amorphous silicic acid sodium (SiO2∶Na
2O ratio=2.0: 1) sulfate: anhydrous sodium sulfate magnesium sulfate: anhydrous magnesium sulfate citrate: citrate trisodium dihydrate, active 86.4%, granularity is distributed in 425-850 micron MA/AA: 1: 4 maleic acid/acrylic copolymer, mean molecule quantity is 70000 MA/AA (1) approximately: 4: 6 maleic acid/acrylic copolymers, mean molecule quantity is 10000 AA approximately: the polyacrylic acid sodium polymer CMC of mean molecule quantity 4500: sodium carboxymethyl cellulose fibre element ether: the degree of polymerization is 650 methylcellulose ether, buy protease by Shin Etsu Chemicals: by the proteolytic enzyme of Novo Industries A/S with trade name Savinase sale, has 3.3% weight organized enzyme protease I: the proteolytic enzyme of describing in WO95/10591, has 4% weight organized enzyme, sell Alcalase by Genencor Int.Inc.: by the proteolytic enzyme of Novo Industries A/S sale, has 5.3% weight organized enzyme cellulase: by the cellulase of Novo Industries A/S with trade name Carezyme sale, has 0.23% weight organized enzyme amylase: by the amylase of Novo Industries A/S with trade name Termamyl 120T sale, has 1.6% weight organized enzyme ANYLASEⅡ: disclosed amylase lipase in PCT/US9703635: by the lipolytic enzyme of Novo Industries A/S with trade name Lipolase sale, has 2.0% weight organized enzyme lipase (1): by the lipolytic enzyme of Novo Industries A/S with trade name Lipolase Ultra sale, has 2.0% weight organized enzyme Endolase: the Endoglunase enzyme, sold by Novo Industries A/S, has 1.5% weight organized enzyme PB4: normal formula NaBO2.3H
2O.H
2O
2Sodium perborate tetrahydrate PB1: normal formula NaBO2.H
2O
2Anhydrous sodium perborate bleaching agent percarbonate: normal formula 2Na2CO
3·3H
2O
2SODIUM PERCARBONATE DOBS: the last of the ten Heavenly stems acyloxy benzene sulfonate, sodium-salt form DPDA: diperoxy dodecanedioic acid NOBS: nonanoly acyloxy benzene sulfonate, sodium-salt form NACA-OBS: (6-pelargonyl group caproyl) oxygen benzene sulfonate LOBS: 12 carbon acyloxy benzene sulfonate DOBS of sodium-salt form: the acyloxy benzene sulfonate DOBA in the last of the ten Heavenly stems of sodium-salt form: caprinoyl p-methoxybenzoic acid TAED: tetrem acyl ethylenediamine DTPA: diethylene-triamine pentaacetic acid DTPMP: diethylene triamine penta(methylene phosphonic acid), all with trade name Dequest 2060, sell EDDS: ethylenediamine-N by Meng Shan, N '-disuccinic acid, (S, S) isomers, sodium-salt form is photoactivated to be floated: photoactivated the floating of sulfonated phthalocyanine zinc white agent (1) of sealing with the dextrin soluble polymer: the white agent of aluminum phthalocyanine (2) brightening agent of sealing with the dextrin soluble polymer 1: 4, 4 '-two (2-sulphophenyl vinyl) biphenyl disodium brightening agent 2: 4, 4 '-two (4-phenylamino-6-morpholino-1, 3, 5-triazine-2-yl) amino) Stilbene-2: 2 '-disulfonic acid disodium HEDP: hydroxyl ethane 1, 1-di 2 ethylhexyl phosphonic acid PEGx: polyethylene glycol, molecular weight is x (general 4000) PEO: PEO, mean molecule quantity 50000 TEPAE: ethoxylation tetren PVI: polyvinyl imidazoles, mean molecule quantity 20000 PVP: PVP polymer, mean molecule quantity 60000 PVNO: polyvinylpyridine N-oxide polymer, mean molecule quantity 50000 PVPVI: the copolymer of PVP and vinyl imidazole, mean molecule quantity 20000 QEA: two ((C2H
5O)-(C
2H
4O)
n)(CH
3)-N
+-C
6H
12-N
+-(CH
3) two ((C2H
5O)-(C
2H
4O))
n, n=20-30 SRP1 wherein: the polyester SRP2 of anion end-blocking: diethoxyization is gathered (phthalic acid 1, 2 inferior propyl ester) short block copolymer PEI: poly-ethylenimine, mean molecule quantity 1800, the average ethoxylation degree of each nitrogen-atoms is that 7 ethyleneoxy residue polysiloxanes disappear: dimethyl silicone polymer foam control agent and mixture as the polysiloxanes of dispersant-oxygen infusion alkene copolymer, the ratio of described foam control agent and described dispersant is 10: 1-100: 1 opacifier: water base single styrene latex mixture, sell wax: paraffin embodiment 1 by BASF Aktiengesellschaft with trade name Lytron 621
Below be according to detergent formulation of the present invention:
Embodiment 2
| ????A | ????B | ????C | ????D | |
| Original washing powder | ||||
| ????????????????STPP | ?????- | ????10.0 | ?????- | |
| Zeolite A | ????16.0 | ?????- | ?????- | ????16.0 |
| ???????????????C45AS | ????4.0 | ?????- | ????4.0 | ????5.0 |
| ????????????????QASI | ?????- | ????1.0 | ?????- | ?????- |
| ??????????MBAS17,2.1 | ????2.0 | ????4.0 | ?????- | ?????- |
| ?????????????C 25AE 3S | ?????- | ????1.0 | ?????- | ????1.0 |
| ???????????????MA/AA | ????2.0 | ????1.0 | ????2.0 | ????1.0 |
| ?????????????????LAS | ????4.0 | ????2.0 | ????3.0 | ????1.6 |
| ?????????????????TAS | ?????- | ????4.0 | ?????- | ?????- |
| Silicate | ?????- | ????3.0 | ?????- | ????3.0 |
| ?????????????????CMC | ????1.0 | ????1.0 | ????0.5 | ????1.0 |
| Whitening agent 2 | ????0.2 | ????0.2 | ?????- | ?????- |
| Soap | ????1.0 | ?????- | ?????- | ????1.0 |
| ???????????????DTPMP | ????0.4 | ????0.4 | ????0.2 | ????0.4 |
| Spray | ||||
| ???????????????C45E7 | ?????- | ????2.5 | ?????- | ?????- |
| ???????????????C25E3 | ????2.5 | ?????- | ?????- | ?????- |
| Polysiloxane defoamers | ????0.3 | ????0.3 | ????0.3 | ????0.3 |
| Spices | ????0.3 | ????0.3 | ????0.3 | ????0.3 |
| Agglomerate | ||||
| ?????????NaSKS-6(Ⅱ) | ????9.0 | ????16.0 | ????10.0 | ????6.8 |
| ?????????????????LAS | ????8.0 | ????9.0 | ????4.0 | ????5.0 |
| Dried additive | ||||
| ???????????????????QEA | ?????- | ????0.5 | ????1.0 | ?????- |
| Carbonate | ????6.0 | ????13.0 | ????15.0 | ????13.0 |
| ???????????????????PB4 | ????18.0 | ????18.0 | ????10.0 | ?????- |
| ???????????????????PB1 | ????4.0 | ????4.0 | ?????- | ?????- |
| ??????????????????NOBS | ????3.0 | ????4.2 | ????1.0 | ?????- |
| The photosensitization SYNTHETIC OPTICAL WHITNER | ????0.02 | ????0.02 | ????0.02 | ????0.02 |
| Mn catalyst | ?????- | ?????- | ????0.5 | ?????- |
| Proteolytic enzyme | ????1.0 | ????1.0 | ????1.0 | ????1.0 |
| Lipase | ????0.4 | ????0.4 | ????0.4 | ????0.4 |
| Amylase | ????0.25 | ????0.30 | ????0.15 | ????0.3 |
| Do the sodium sulfate that mixes | ????3.0 | ????3.0 | ????5.0 | ????3.0 |
| Equipoise (water and other) | ????100.0 | ????100.0 | ????100.0 | ????100.0 |
| Density (g/ liter) | ????630 | ????670 | ????670 | ????670 |
Below be according to detergent formulation of the present invention:
Embodiment 3
| ????E | ????F | ????G | ????H | |
| Basic product: | ||||
| ?TAS | ?????- | ????1.0 | ????4.0 | ?????- |
| ?LAS | ????5.0 | ?????- | ???11.0 | ????8.0 |
| ?C45AS | ????4.0 | ????4.0 | ????6.0 | ????6.0 |
| ?MES | ????3.0 | ?????- | ?????- | ?????- |
| ?QASⅡ | ????0.4 | ?????- | ????1.0 | ?????- |
| ?TFAA | ?????- | ????1.0 | ?????- | ?????- |
| ?C25E5/C45E7/C 2? 5E 3 | ?????- | ????2.0 | ?????- | ????1.0 |
| ?????- | ????18.0 | ?????- | ?????- | |
| Zeolite | ????9.0 | ????5.0 | ?????- | ????8.0 |
| Carbonate | ????13.0 | ????7.5 | ?????- | ????5.0 |
| Supercarbonate | ?????- | ????7.5 | ?????- | ?????- |
| DTPMP | ????0.7 | ????1.0 | ?????- | ?????- |
| SRP1 | ????0.3 | ????0.2 | ?????- | ????0.1 |
| MA/AA | ????2.0 | ????1.5 | ????2.0 | ????1.0 |
| CMC | ????0.8 | ????0.4 | ????0.4 | ????0.2 |
| Proteolytic enzyme | ????0.8 | ????1.0 | ????0.5 | ????0.5 |
| Amylase | ????0.8 | ????0.4 | ?????- | ????0.25 |
| Lipase | ????0.2 | ????0.1 | ????0.2 | ????0.1 |
| Cellulase | ????0.15 | ????0.05 | ?????- | ?????- |
| Photoactivated SYNTHETIC OPTICAL WHITNER (ppm) | ????70ppm | ????45ppm | ?????- | ????10ppm |
| Whitening agent 1 | ????0.2 | ????0.2 | ????0.08 | ????0.2 |
| PB1 | ????6.0 | ????2.0 | ?????- | ?????- |
| NACA | ?????- | ?????- | ?????- | ????3.0 |
| NAC?OBS | ????2.0 | ????1.0 | ????0.9 | ????3.1 |
| Agglomerate: | ||||
| ????NaSKS-6(Ⅰ) | ????6.6 | ????6.0 | ????20.0 | ????10.0 |
| ???????????LAS | ????3.0 | ?????- | ????15.0 | ????7.0 |
| ?????????C45AS | ????3.0 | ????6.0 | ?????- | ?????- |
| Equipoise (moisture content and other) | ????100 | ????100 | ????100 | ????100 |
Below be according to detergent formulation of the present invention:
Embodiment 4
| ????I | ????J | ????K | |
| Original washing powder | |||
| ?????????MBAS?17.5,1.8 | ?????- | ?????- | ????2.0 |
| Zeolite A | ?????- | ????22.0 | ????6.0 |
| Sodium sulfate | ????1.0 | ????5.0 | ?????- |
| ?????????????????MA/AA | ????3.0 | ????3.0 | ????3.0 |
| ???????????????????MES | ?????- | ????5.0 | ?????- |
| ???????????????????LAS | ?????- | ?????- | ????3.5 |
| ?????????????????C45AS | ????3.0 | ????4.0 | ????7.0 |
| Silicate | ?????- | ????1.0 | ????5.0 |
| Soap | ?????- | ?????- | ????2.0 |
| Whitening agent 1 | ????0.2 | ????0.2 | ????0.2 |
| Carbonate | ????8.0 | ????16.0 | ????5.0 |
| Citric acid | ????3.0 | ????2.0 | ????1.5 |
| Spray | |||
| ?????????????????C45E5 | ????1.0 | ????1.0 | ?????- |
| Agglomerate | |||
| NaSKS-6 (I) or (II) | ????17.0 | ????6.0 | ????7.0 |
| ???????????????LAS/MES | ????10.0 | ????6.0 | ????5.0 |
| Moisture | ????0.5 | ????0.1 | ????0.5 |
| The atomizing zeolite | ?????- | ????0.8 | ????0.5 |
| Dried additive | |||
| ????????????PVPVI/PVNO | ????0.5 | ????0.5 | ????0.5 |
| Proteolytic enzyme | ????1.0 | ????1.0 | ????1.0 |
| Lipase | ????0.4 | ????0.4 | ????0.4 |
| Amylase | ????0.1 | ????0.1 | ????0.1 |
| Cellulase | ????0.1 | ????0.1 | ????0.1 |
| ??????????????NOBS | ?????- | ????6.1 | ?????- |
| ????????????NACOBS | ?????- | ?????- | ????4.5 |
| Sodium sulfate | ?????- | ????6.0 | ?????- |
| Equipoise (moisture content and other) | ????100 | ????100 | ????100 |
Below be according to high-density of the present invention and the detergent formulation that contains SYNTHETIC OPTICAL WHITNER:
Embodiment 5
| ????L | ????M | ????N | |
| The powder of blowing | |||
| Zeolite A | ?????- | ?????- | ????15.0 |
| Sodium sulfate | ????0.0 | ????5.0 | ????0.0 |
| ???????????????????LAS | ????3.0 | ?????- | ????3.0 |
| ?????????????????C45AS | ????3.0 | ????2.0 | ????4.0 |
| ???????????????????QAS | ?????- | ?????- | ????1.5 |
| ?????????????????DTPMP | ????0.4 | ????0.4 | ????0.4 |
| ???????????????????CMC | ????0.4 | ????0.4 | ????0.4 |
| ?????????????????MA/AA | ????4.0 | ????2.0 | ????2.0 |
| Agglomerate | |||
| ???????????????????QAS | ????1.0 | ?????- | ?????- |
| ???????????????????LAS | ?????- | ????11.0 | ????7.0 |
| ???????????????????TAS | ????2.0 | ????2.0 | ????1.0 |
| Silicate | ????3.0 | ?????- | ????4.0 |
| Zeolite A | ????8.0 | ????8.0 | ????8.0 |
| Carbonate | ????8.0 | ????8.0 | ????4.0 |
| Agglomerate | |||
| NaSKS-6 (I) or (II) | ????15.0 | ????12.0 | ????5.0 |
| ???????????????????LAS | ????8.0 | ????7.0 | ????4.0 |
| ????????????????????AS | ????5.0 | ?????- | ?????- |
| Spray | |||
| The spices of sealing | ????0.3 | ????0.3 | ????0.3 |
| ???????????????????????????C25E3 | ????2.0 | ?????- | ????2.0 |
| Dried additive | |||
| ?????????????????????????????QEA | ????1.0 | ????0.5 | ????0.5 |
| Citric acid/citrate | ????5.0 | ?????- | ????2.0 |
| Supercarbonate | ?????- | ????3.0 | ?????- |
| Carbonate | ????8.0 | ????15.0 | ????10.0 |
| ?????????????????????????NAC?OBS | ????6.0 | ?????- | ????5.0 |
| Mn catalyst | ?????- | ?????- | ????0.3 |
| ????????????????????????????NOBS | ?????- | ????2.0 | ?????- |
| ?????????????????????????????PB1 | ????14.0 | ????7.0 | ????10.0 |
| Molecular weight 5,000,000 polyoxyethylene | ?????- | ?????- | ????0.2 |
| Wilkinite | ?????- | ?????- | ????10.0 |
| Citric acid | ?????- | ?????- | ????0.5 |
| Proteolytic enzyme | ????1.0 | ????1.0 | ????1.0 |
| Lipase | ????0.4 | ????0.4 | ????0.4 |
| Amylase | ????0.6 | ????0.6 | ????0.6 |
| Cellulase | ????0.6 | ????0.6 | ????0.6 |
| Polysiloxane defoamers | ????5.0 | ????5.0 | ????5.0 |
| Dried additive | |||
| Sodium sulfate | ????0.0 | ????3.0 | ????0.0 |
| Equipoise (moisture and other) | ????100.0 | ????100.0 | ????100.0 |
| Density (g/ liter) | ????850 | ????850 | ????850 |
Below be according to high density detergent agent prescription of the present invention:
Embodiment 6
| ????O | ????P | ????Q | ????R | |
| Agglomerate | ||||
| ?????????????????QAS | ????2.0 | ?????- | ????2.0 | ?????- |
| ?????????????????MES | ?????- | ????2.0 | ?????- | ?????- |
| ?????????????????LAS | ????6.0 | ?????- | ?????- | ?????- |
| ?????????????????TAS | ?????- | ????2.0 | ?????- | ?????- |
| ???????????????C45AS | ????6.0 | ????4.0 | ????2.0 | ?????- |
| ????????MBAS16.5,1.9 | ????4.0 | ?????- | ?????- | ?????- |
| Zeolite A | ????15.0 | ????6.0 | ?????- | ?????- |
| Carbonate | ????4.0 | ????8.0 | ????4.0 | ????8.0 |
| ???????????????MA/AA | ????4.0 | ????2.0 | ?????- | ????2.0 |
| ?????????????????CMC | ????0.5 | ????0.5 | ?????- | ????0.5 |
| ???????????????DTPMP | ????0.4 | ????0.4 | ?????- | ????0.5 |
| Spray | ||||
| ???????????????C25E3 | ????1.0 | ????1.0 | ?????- | ?????- |
| Spices | ????0.5 | ????0.5 | ????0.5 | ????0.5 |
| Agglomerate | ||||
| ???????????????SKS-6 | ????7.0 | ????15.0 | ????20.0 | ????10.0 |
| ?????????????????LAS | ????5.8 | ????9.0 | ????15.0 | ????10.0 |
| Zeolite | ?????- | ????0.9 | ?????- | ?????- |
| ??????????????C45?AS | ?????- | ????3.0 | ?????- | ?????- |
| Water | ????0.08 | ????0.1 | ?????- | ????0.2 |
| Dried additive |
| ???????????EDDS/HEDP | ????0.5 | ????0.3 | ????0.5 | ????0.8 |
| ?????????NaSKS?6(Ⅰ) | ????5.0 | ????6.0 | ????4.0 | ????11.0 |
| Citrate trianion | ?????- | ????1.0 | ?????- | ?????- |
| Citric acid | ????2.0 | ?????- | ????2.0 | ????4.0 |
| ?????????????NAC?OBS | ????4.1 | ?????- | ????5.0 | ????4.0 |
| ????????????????TAED | ????0.8 | ????2.0 | ?????- | ????2.0 |
| Percarbonate | ????20.0 | ????20.0 | ????15.0 | ????17.0 |
| ????????????????SRP1 | ????0.3 | ????0.3 | ?????- | ????0.3 |
| Proteolytic enzyme | ????1.4 | ????1.4 | ????1.0 | ????0.5 |
| Lipase | ????0.4 | ????0.4 | ????0.3 | ?????- |
| Cellulase | ????0.6 | ????0.6 | ????0.5 | ????0.5 |
| Amylase | ????0.6 | ????0.6 | ?????- | ????0.3 |
| ?????????????????QEA | ????1.0 | ?????- | ????1.0 | ????1.0 |
| Polysiloxane defoamers | ????1.0 | ????0.5 | ????0.5 | ????1.5 |
| Whitening agent 1 | ????0.2 | ????0.2 | ?????- | ????6.2 |
| Whitening agent 2 | ????0.2 | ?????- | ????0.2 | ?????- |
| Density (g/ liter) | ????850 | ????850 | ????800 | ????775 |
| ????S | ????T | ????U | ????V | ????W | ????X | |
| ?C45AS | ?11.0 | ??5.0 | ????4.6 | ??6.5 | ??4.1 | ??9.0 |
| ?C25AES | ?1.3 | ??1.0 | ?????- | ??1.3 | ??1.0 | ???- |
| ?LAS | ??- | ??3.0 | ????2.7 | ???- | ??2.0 | ???- |
| ?C25E3/C25E5 | ?1.5 | ??4.7 | ????3.3 | ???- | ??4.7 | ??3.3 |
| ?MBAS?16.5,1.7 | ?15.0 | ??12.0 | ????10.0 | ??10.2 | ??7.0 | ??14.1 |
| ?QAS | ??- | ??1.15 | ????0.6 | ???- | ??1.7 | ???- |
| Zeolite A | ?5.0 | ??16.7 | ?????- | ??7.0 | ??16.7 | ??11.2 |
| SKS-6/LAS agglomerate 5: 4 | ?20.0 | ???- | ????17.5 | ??20.0 | ??9.0 | ??17.5 |
| Citric acid | ??- | ??1.5 | ????2.5 | ???- | ??1.5 | ???- |
| ?MA/AA | ??- | ??0.6 | ?????- | ???- | ??0.6 | ???- |
| ?MA/AA?3 | ??- | ???- | ????7.03 | ???- | ???- | ??7.03 |
| ?AA | ?2.3 | ???- | ?????- | ??2.8 | ???- | ???- |
| ?EDDS | ??- | ??0.3 | ?????- | ???- | ??0.3 | ???- |
| ?HEDP | ??- | ??0.5 | ?????- | ???- | ??0.5 | ???- |
| Carbonate | ?6.0 | ??12.5 | ????14.5 | ??6.0 | ??12.5 | ??14.0 |
| Silicate | ?0.58 | ??0.8 | ????12 | ??0.58 | ??0.8 | ??12 |
| ?PB1 | ?11.0 | ???- | ????14.0 | ???- | ???- | ??4.0 |
| ?NACA-OBS | ??- | ??4.7 | ?????- | ???- | ??2.7 | ???- |
| ?PC | ??- | ??17.3 | ?????- | ??20.0 | ??17.3 | ???- |
| ?NOBS | ??- | ???- | ????4.0 | ???- | ???- | ??4.0 |
| ?TAED | ??- | ??2.5 | ?????- | ???- | ??3.5 | ??2.0 |
| Proteolytic enzyme | ?0.25 | ??0.36 | ????0.2 | ??0.26 | ??0.36 | ??0.2 |
| Lipase | ??- | ???- | ?????- | ???- | ???- | ???- |
| Cellulase | ?0.3 | ??0.26 | ?????- | ??0.3 | ??0.26 | ???- |
| Amylase | ??- | ??0.36 | ?????- | ???- | ??0.36 | ???- |
| Whitening agent | ?0.17 | ??0.06 | ????0.30 | ??0.17 | ??0.06 | ??0.30 |
| SRP1 | ?0.4 | ????0.2 | ??0.5 | ????0.4 | ??0.2 | ????0.5 |
| PEG | ?1.6 | ?????- | ??0.19 | ????1.6 | ???- | ????0.19 |
| Vitriol | ?5.5 | ????6.4 | ??3.5 | ????5.5 | ??6.4 | ????3.5 |
| CMC | ??- | ????0.5 | ???- | ?????- | ??0.5 | ?????- |
| MgSO4 | ??- | ????0.13 | ???- | ?????- | ??0.13 | ?????- |
| Optical white | ??- | ????0.0026 | ???- | ?????- | ??0.0026 | ?????- |
| Polysiloxane defoamers | ?0.02 | ????0.21 | ??0.17 | ????0.02 | ??0.21 | ????0.17 |
| Spices | ?0.42 | ????0.55 | ??0.25 | ????0.42 | ??0.55 | ????0.25 |
Following laundry detergent composition Y-AB produced according to the present invention:
Embodiment 8
| ????Y | ????Z | ????AA | ????AB | |
| MBAS?16.5,1.7 | ?????- | ????- | ?????- | ????5.5 |
| C45AS | ????9.0 | ????8.0 | ????4.1 | ????4 |
| C45E1S | ????1.0 | ?????- | ?????- | ?????- |
| LAS | ?????- | ?????- | ????3.7 | ?????- |
| C16?SAS | ?????- | ????2.0 | ?????- | ?????- |
| MES | ?????- | ?????- | ?????- | ????4 |
| C23E6.5 | ?????- | ????1.5 | ?????- | ????1.5 |
| SKS-6/LAS agglomerate 5: 4 | ???18.0 | ????10.0 | ???35.0 | ????12.0 |
| Zeolite A | ????7.8 | ????17.0 | ?????- | ????20.0 |
| AA | ????2.3 | ????2.3 | ????2.3 | ????2.3 |
| Carbonate | ????7.0 | ????7.0 | ???12.5 | ????2.5 |
| Silicate | ????0.6 | ????0.6 | ????0.6 | ?????- |
| Perborate/PC | ???11.0 | ????2.0 | ?????- | ?????- |
| Proteolytic enzyme | ????0.3 | ????0.3 | ????0.3 | ????0.3 |
| Cellulase | ????0.3 | ????0.3 | ????0.3 | ????0.3 |
| SRP1 | ????0.4 | ????0.4 | ????0.4 | ????0.4 |
| Whitening agent | ????0.2 | ????0.2 | ????0.2 | ????0.2 |
| PEG | ????1.6 | ????1.6 | ????1.6 | ????1.6 |
| Vitriol | ????5.5 | ????5.5 | ????5.5 | ????5.5 |
| Polysiloxane defoamers | ???0.42 | ???0.42 | ???0.42 | ????0.42 |
| Moisture and accessory constituent | --equal amount--- | |||
| Density (g/ liter) | ????663 | ????663 | ????663 | ????663 |
Following laundry detergent composition AC-AG produced according to the present invention:
Embodiment 9
| ????AC | ?????AD | ????AE | ????AF | ?????AG | |
| ?MBAS?16.5,1.7 | ????14.8 | ????16.4 | ????12.3 | ????8.2 | ????4.1 |
| ?C45?AS | ????6.0 | ????8.0 | ????4.3 | ????4.0 | ????5.0 |
| ?C45E1S | ????2.0 | ?????- | ?????- | ????1.0 | ?????- |
| ?LAS | ?????- | ?????- | ?????- | ????3.0 | ????5.0 |
| ?C16?SAS | ?????- | ????1.0 | ?????- | ?????- | ?????- |
| ?MES | ?????- | ????5.0 | ?????- | ?????- | ?????- |
| ?TFAA | ????1.6 | ?????0 | ?????0 | ?????0 | ?????0 |
| ?C24E3 | ????4.9 | ????4.9 | ????4.9 | ????4.9 | ????4.9 |
| Zeolite A | ????5.0 | ?????15 | ?????- | ?????- | |
| NaSKS-6/LAS 3: the spray-dired particle of 2- | ?????21 | ??????7 | ????22 | ????17 | ????20 |
| Citrate trianion/citric acid | ????1.0 | ??????3 | ?????3 | ????2.0 | ?????- |
| ?MA/AA | ????4.8 | ????4.8 | ????4.8 | ????4.8 | ????4.8 |
| ?HEDP | ????0.5 | ????0.5 | ????0.5 | ????0.5 | ????0.5 |
| Carbonate | ????8.5 | ????8.5 | ????8.5 | ????8.5 | ????8.5 |
| Percarbonate | ???20.7 | ???20.7 | ???20.7 | ???20.7 | ???20.7 |
| ?TAED | ????4.8 | ????4.8 | ????- | ????- | ????4.8 |
| ?NACA-OBS | ?????- | ?????- | ????5.0 | ????6.0 | ????2.0 |
| Proteolytic enzyme | ????0.9 | ????0.9 | ????0.9 | ????0.9 | ????0.9 |
| Lipase | ???0.15 | ???0.15 | ???0.15 | ???0.15 | ???0.15 |
| Cellulase | ???0.26 | ???0.26 | ???0.26 | ???0.26 | ???0.26 |
| Amylase | ???0.36 | ???0.36 | ???0.36 | ???0.36 | ???0.36 |
| ?SRP1 | ????0.2 | ????0.2 | ????0.2 | ????0.2 | ????0.2 |
| Whitening agent | ????0.2 | ????0.2 | ????0.2 | ????0.2 | ????0.2 |
| Vitriol | ????2.3 | ????2.3 | ????2.3 | ????2.3 | ????2.3 |
| ?QEA | ????1.0 | ????1.0 | ?????- | ?????- | ?????- |
| ?QAS | ????1.0 | ?????- | ?????- | ?????- | ????1.0 |
| Polysiloxane defoamers | ????0.4 | ????0.4 | ????0.4 | ????0.4 | ????0.4 |
| Moisture and accessory constituent | --equal amount--- | ||||
| Density (g/ liter) | ????850 | ????850 | ????850 | ????850 | |
Below prescription is according to composition example of the present invention, and it can be particle or sheet.
| ????AH | ????AI | ????AJ | ????AK | ????AL | |
| Basic product | |||||
| ??????????????????C45?AS/TAS | ????8.0 | ????5.0 | ????3.0 | ????3.0 | ????3.0 |
| ?????????????????????????LAS | ????8.0 | ?????- | ????8.0 | ?????- | ????7.0 |
| ?????????????????????C25AE3S | ????0.5 | ????2.0 | ????1.0 | ?????- | ?????- |
| LAS/NaSKS-6 (I) or (II) agglomerate were with ratio 3: 2 | ????5.0 | ????17.0 | ????9.0 | ????20.0 | ????15.0 |
| ??????????????????C25AE5/AE3 | ????2.0 | ?????- | ????5.0 | ????2.0 | ????2.0 |
| ?????????????????????????QAS | ?????- | ?????- | ?????- | ????1.0 | ????1.0 |
| Zeolite A | ???20.0 | ???10.0 | ???10.0 | ?????- | ????10.0 |
| SKS-6 (I) (dried additive) | ?????- | ?????- | ????2.0 | ?????- | ??????- |
| ???????????????????????MA/AA | ????2.0 | ????2.0 | ????2.0 | ?????- | ??????- |
| ??????????????????????????AA | ?????- | ?????- | ?????- | ?????- | ????4.0 |
| Citrate trianion | ?????- | ????2.0 | ?????- | ?????- | ??????- |
| Citric acid | ????2.0 | ?????- | ????1.5 | ????2.0 | ??????- |
| ????????????????????????DTPA | ????0.2 | ????0.2 | ?????- | ?????- | ??????- |
| ????????????????????????EDDS | ?????- | ?????- | ????0.5 | ????0.1 | ??????- |
| ????????????????????????HEDP | ?????- | ?????- | ????0.2 | ????0.1 | ??????- |
| ?????????????????????????PB1 | ????3.0 | ????5.0 | ????10.0 | ?????- | ????4.0 |
| ??????????????????????????PC | ?????- | ?????- | ?????- | ????18.0 | ??????- |
| ????????????????????????NOBS | ????3.0 | ????4.0 | ?????- | ?????- | ????4.0 |
| ????????????????????NACA?OBS | ?????- | ?????- | ????2.0 | ?????- | ??????- |
| ????????????????????????TAED | ?????- | ?????- | ????2.0 | ????5.0 | ??????- |
| Carbonate | ????15.0 | ????18.0 | ????8.0 | ????15.0 | ????15.0 |
| Vitriol | ????5.0 | ??12.0 | ?2.0 | ???17.0 | ????3.0 |
| Silicate | ?????- | ???1.0 | ???- | ????- | ????8.0 |
| Enzyme | ????0.3 | ???0.3 | ?1.0 | ????1.0 | ????0.2 |
| Other (whitening agent/SRP1/ CMC/ optical white/MgSO4/ PVPVI/ suds suppressor/PEG) | ????0.5 | ???0.5 | ?0.5 | ????0.5 | ????0.5 |
| Spices | ????0.2 | ???0.3 | ?0.5 | ?????0.2 | ????0.1 |
Claims (10)
1. builder component that comprises the crystalline layered silicate of porphyrize, wherein at least 95% or even 98% or even the granularity of the described crystalline layered silicate of 100% weight be lower than 150 microns or even 102 microns, and average particle size is greater than 15.0 microns, preferred 16.0-48.8 micron
2. according to the builder component of claim 1, it comprises formula NaMSi
2O
5YH
2The crystalline layered silicate of the porphyrize of O, wherein M is H, K, or preferred Na or its mixture, y is 0-20, preferred 20.
3. according to the builder component of claim 1 or 2, wherein the crystalline layered silicate of at least 90% weight has granularity 17.3-88.2.
4. according to the builder component of any aforesaid right requirement, it is granular, comprises 40%-80% weight crystal layered silicate, and this silicate is to preferably include at least a anion surfactant with 20%-50% weight tensio-active agent closely to mix.
5. according to the builder component of claim 4, wherein tensio-active agent is the anion sulfoacid salt surfactant, the alkyl-sulphate of preferred alkyl benzene sulfonate or mid-chain branched or sulfosalt surfactant.
6. according to the builder component of any aforesaid right requirement, it is an agglomerate, and preferred average particle size is 300 microns-1100 microns.
7. the builder component that requires according to any aforesaid right, it comprises and is lower than 10% weight, preferably is lower than 5% weight percent free water.
8. one kind comprises the basis detergent composition of the builder component of aforesaid right requirement arbitrarily, and by the weight of said composition, the content of described builder component is preferably 1%-60%, or even 5%-45%.
9. a method for preparing according to the builder component of claim 4 makes crystalline layered silicate and surfactant mixtures, and this mixture pelleting is become particle, preferably forms agglomerate by agglomeration.
10. the builder system of a crystalline layered silicate that comprises porphyrize is used to improve the distributivity of detergent component in the detergent composition that comprises tensio-active agent and other detergent component, the crystalline layered silicate of described porphyrize comprise at least 95% or even 98% or even the granularity of 100% weight be lower than 150 microns or even 102 microns, and average particle size is greater than 15.0 microns, the crystalline layered silicate of preferred 16.0-48.8 micron.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9814667A GB2339194A (en) | 1998-07-08 | 1998-07-08 | Layered crystalline silicate as detergent builder component |
| GB9814667.3 | 1998-07-08 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1308665A true CN1308665A (en) | 2001-08-15 |
Family
ID=10835056
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 99808400 Pending CN1308665A (en) | 1998-07-08 | 1999-07-08 | Builder component |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP1095124A1 (en) |
| CN (1) | CN1308665A (en) |
| CA (1) | CA2336256A1 (en) |
| GB (1) | GB2339194A (en) |
| WO (1) | WO2000002988A1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1752527A3 (en) * | 1998-09-25 | 2010-05-05 | The Procter & Gamble Company | Solid detergent compositions |
| BR9816030B1 (en) * | 1998-09-25 | 2008-11-18 | solid detergent composition and its use. | |
| DE50210858D1 (en) * | 2002-11-02 | 2007-10-18 | Dalli Werke Gmbh & Co Kg | Water-soluble builder of specific particle size in detergents and cleaners |
| EP1416039B1 (en) * | 2002-11-02 | 2008-03-26 | Dalli-Werke GmbH & Co. KG | Use of water soluble builders with a specific particle size in bleach free laundry detergents |
| CN104342327B (en) * | 2013-08-08 | 2018-01-12 | 厦门泰益新洁净科技有限公司 | A kind of grease dirt cleaning agent and its preparation and application |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5236682A (en) * | 1989-10-25 | 1993-08-17 | Hoechst Aktiengesellschaft | Process for producing crystalline sodium silicates having a layered structure |
| DE4000705A1 (en) * | 1990-01-12 | 1991-07-18 | Hoechst Ag | METHOD FOR PRODUCING CRYSTALLINE SODIUM SILICATES |
| US5108646A (en) * | 1990-10-26 | 1992-04-28 | The Procter & Gamble Company | Process for agglomerating aluminosilicate or layered silicate detergent builders |
| GB9108639D0 (en) * | 1991-04-23 | 1991-06-12 | Procter & Gamble | Particulate detergent compositions |
| DE4329064A1 (en) * | 1993-08-28 | 1995-03-02 | Henkel Kgaa | Builders component for detergents or cleaning agents |
| DE4329392A1 (en) * | 1993-09-01 | 1995-03-02 | Henkel Kgaa | Builders component for detergents or cleaning agents |
| US5567404A (en) * | 1994-05-31 | 1996-10-22 | Korea Research Institute Of Chemical Technology | Process for preparation of layered sodium silicate from anhydrous sodium silicate |
| KR0139976B1 (en) * | 1994-05-31 | 1998-06-01 | 강박광 | Process for preparing crystalline sodium silicates having a laminated structure |
| CN1109738C (en) * | 1995-11-22 | 2003-05-28 | 花王株式会社 | Powder detergent composition for clothes washing |
| TW370561B (en) * | 1996-03-15 | 1999-09-21 | Kao Corp | High-density granular detergent composition for clothes washing |
-
1998
- 1998-07-08 GB GB9814667A patent/GB2339194A/en not_active Withdrawn
-
1999
- 1999-07-08 CN CN 99808400 patent/CN1308665A/en active Pending
- 1999-07-08 WO PCT/US1999/015311 patent/WO2000002988A1/en not_active Application Discontinuation
- 1999-07-08 CA CA002336256A patent/CA2336256A1/en not_active Abandoned
- 1999-07-08 EP EP99933733A patent/EP1095124A1/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| GB2339194A (en) | 2000-01-19 |
| WO2000002988A1 (en) | 2000-01-20 |
| EP1095124A1 (en) | 2001-05-02 |
| GB9814667D0 (en) | 1998-09-02 |
| CA2336256A1 (en) | 2000-01-20 |
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