CN102076836A - Laundry treatment compositions - Google Patents
Laundry treatment compositions Download PDFInfo
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- CN102076836A CN102076836A CN200980124127.1A CN200980124127A CN102076836A CN 102076836 A CN102076836 A CN 102076836A CN 200980124127 A CN200980124127 A CN 200980124127A CN 102076836 A CN102076836 A CN 102076836A
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- Prior art keywords
- softening
- particle
- silicone
- polysaccharide
- emulsion
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/001—Softening compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents ; Methods for using cleaning compositions
- C11D11/0082—Special methods for preparing compositions containing mixtures of detergents ; Methods for using cleaning compositions one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
- C11D11/0088—Special methods for preparing compositions containing mixtures of detergents ; Methods for using cleaning compositions one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads the liquefied ingredients being sprayed or adsorbed onto solid particles
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/10—Carbonates ; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/22—Carbohydrates or derivatives thereof
- C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
-
- 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
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
-
- 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
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
- C11D3/3742—Nitrogen containing silicones
Abstract
According to the invention there is provided a solid softening granule comprising an inorganic carrier selected from alkali metal and alkaline earth metal salts of carbonate and bicarbonate, or a mixture thereof, and a softening system comprising of a locust bean gum polysaccharide and a softening silicone; a process to make the granule is also provided, as well as a laundry treatment composition comprising the softening granule and use of the laundry composition and a method of treating a textile with said laundry composition.
Description
Technical field
The present invention relates to add the softening particle (solid softening granules) of the solid that washs in the laundry treatment compositions that adds, relate to described fabric-softening particulate preparation method, relate to the home method (domestic method) of handling textiles and relate to described fabric-softening particulate and use.
Background technology
Giving soft feel to the clothing of washing is that the human consumer is desirable.A kind of approach that realizes this effect is to use independent rinse conditioner except washing composition.But using the single product of cleaning and softening demand is provided is more easily, and they are called as " it is softening to be in the suds " product.
WO 04/111169 discloses the polysaccharide of hydrolysis-stable, and it is covalently bound to the softening thing class of the first polymer spun fabric and optional with the softening thing class emulsification of the second polymer spun fabric.
A problem that exists in washing field softening is that this type of remollescent is prepared in the cleaning product.Many useful tenderizer compositions are liquid or emulsion.The whole bag of tricks is used to these liquid or emulsion are joined in the powder formulation.
A kind of encapsulated route has been proposed in WO 2006/117385.Disclosed is the redispersible emulsion of a kind of solid, comprises by laundry and nurses the emulsion oil-in-water that becomes to be grouped into, and it is encapsulated in by in the stable housing of polyvalent metal ion.Case material is preferably polysaccharide, for example alginate.
A kind of granulating route has been proposed, so that softening particle to be provided in WO 2007/009621.Disclosed is wherein with the method for blocking handkerchief (kappa) carrageenin or alginate polymer matrix granule silicone oil emulsion.
Yet problem of this alginate capsule thing and particulate is when in the storage of high temperature and high humidity because the leakage of silicone oil, and they are unsettled.Further problem is in joining laundry product the time, and they stay the visible residue on the clothing of washing.
Summary of the invention
We have found that using soluble inorganic carrier to granulate provides softening particle, it has overcome one or more foregoing problems, and acceptable fabric-softening further is provided.
In one aspect, the invention provides the softening particle of a kind of solid, comprising:
(i) from 1 to 30wt.% softening system (softening system), it comprises Viscogum BE polysaccharide and softening silicone (softening silicone), and weight ratio is from 1: 200 to 1: 5; With,
(ii) from 70 to 99wt.% inorganic carrier, it is selected from the carbonate and the supercarbonate of basic metal and alkaline-earth metal, or their mixture.
A second aspect of the present invention provides a kind of laundry treatment compositions, comprises from the softening particle of the described solid of 0.1 to 25wt.% first aspect the tensio-active agent from 2 to 70wt.% and from 1 to 70wt.% washing assistant.
The application that a third aspect of the present invention provides the described laundry treatment compositions of the second aspect of significant quantity to be in the suds softening (soften) fabric.
A fourth aspect of the present invention provides a kind of home method of handling textiles, may further comprise the steps:
(i) handle textiles with the aqueous solution from 1 to 20g/l of the described laundry treatment compositions of second aspect; With,
(ii) rinsing and dry described textiles.
A fifth aspect of the present invention provides the described solid of first aspect to soften the particulate preparation method, and wherein this method may further comprise the steps:
A) provide the emulsion (emulsion) that comprises water and softening system, described softening system comprises that weight ratio is Viscogum BE polysaccharide and the softening silicone from 1: 200 to 1: 5;
B) with inorganic carrier described emulsion is granulated in high shear mixer, described inorganic carrier is selected from carbonate and the supercarbonate or their mixture of basic metal and alkaline-earth metal; With,
C) particle that obtains of drying.
Embodiment
Except as otherwise noted, otherwise the amount of the component that exists in the laundry treatment compositions of mentioning herein is meant the weight percent that accounts for total composition.
Solid softens particle
The softening particle of described solid is in particle form.Described particle preferably has from 0.1 to 5mm, more preferably from 0.2 to 3mm, most preferably is from 0.25 to 1.5mm size range.Particle size can for example use sizing screen to measure.
Softening system
The softening particle of described solid comprises from 1 to 30wt. preferably from 2.5 to 27.5wt.%, more preferably from 5 to 25wt.% softening system.Should softening system comprise Viscogum BE polysaccharide and softening silicone.
Polysaccharide
Polysaccharide is from 1: 200 to 1: 5 with respect to the weight ratio of softening silicone in softening system, preferably from 1: 50 to 1: 5, and more preferably weight part from 1: 20 to 1: 5.
Described polysaccharide is with 0.005 to 5wt.%, and preferred 0.05 to 3wt.% level is present in the described particle.
Polysaccharide comprises a plurality of sugar rings with pendant hydroxyl group.Described polysaccharide is a Viscogum BE.This is a kind of polysaccharide that Mierocrystalline cellulose is had avidity.
Described polysaccharide can be straight chain or side chain.Many naturally occurring polysaccharide have branching at least to a certain degree, in any case or at least some sugar rings are forms of the side-chain radical on the polysaccharide main chain.
Described polysaccharide can be chosen the side-chain radical of the esterification of the hydrolyzable release with connection, for example acetate groups wantonly.But preferably, this polysaccharide is the polysaccharide (NHP) of non-hydrolysable, and it does not contain the side-chain radical of the esterification of hydrolyzable release.
Viscogum BE is an example of polysaccharide, has the polysaccharide main chain that β-1,4 connects, and has the sugar or the polysaccharide side chain branch point of different levels.
Viscogum BE is a kind of galactomannan polysaccharide and the main chain with β-1,4 connection that has the semi-lactosi side chain.
Described Viscogum BE polysaccharide is a kind of uncharged polysaccharide.
In a kind of preferred Viscogum BE polysaccharide, at least some these hydroxyls are replaced by one or more silicone groups independently or substitute.Be meant that for given substituting group type " average substitution degree " each sugar encircles the substituent average number of the type and measures at all sugar rings for all polysaccharide molecules in the sample.
Preferably, the average substitution degree of silicone group on polysaccharide main chain is from 0.00001 to 0.5, preferably from 0.001 to 0.5, more preferably from 0.001 to 0.1.A further preferable range is from 0.01 to 0.05.
Preferably, described polysaccharide has one or more silicone groups that connect that are attached thereto with covalent manner.If one or more silicone groups are connected with polysaccharide, then they be with emulsion in softening silicone irrelevant and be what to separate.The silicone material that is connected with polysaccharide can be and described softening silicone identical materials, but and not require so necessary.
Preferably, the key between described silicone and the polysaccharide is to make material at 40 ℃ with at 10.5 pH rate of decay constant (decay rate the constant) (k of (this material of 0.01wt% and the anion surfactant of 0.1wt%) in the aqueous solution
d) be k
d＜10
-3s
-1
The silicone material that is connected with polysaccharide is polymeric long-chain silicone material preferably, is preferably selected from polydialkysiloxane, its sulfonamide derivatives and their mixture.
In one or more described silicone groups and polysaccharide material covalently bound, one or more oh groups on the polysaccharide and the reaction-ity group reaction that is connected on the silicone chains, or described in WO 04/111169, the one or more oh groups on the polysaccharide of being referred to be converted into another kind can with the group that is connected to the reaction-ity group reaction on the silicone chains.
The preferred linking group that is used for the silicone group is connected to polysaccharide is by amido linkage, ester bond, ehter bond, amino-formate bond, triazine key, carbonic acid ester bond, amine key or ester-alkylene base key.
A functionalized further method of the silicone of polysaccharide is disclosed among the WO 2006/117386.The document has disclosed the use mechanism polysaccharide has been carried out chemical modification, and it relates to using and has at least two operations in the opposite direction and to handle polysaccharide with the milling train of the adjacent roller of friction-motion speed rotation.A kind of chemical modifier that uses can be the polysiloxane of epoxy-functional, and described polysaccharide mixes before mechanical workout and/or in the course of processing with chemical modifier.
Described polysaccharide with one or more covalently bound silicone groups can be called polysaccharide-silicone conjugate (conjugate) easily at this.
Most preferred polysaccharide-silicone conjugate material is called ' LBG-silicone ' herein by the Viscogum BE that one or more polydimethylsiloxane chains replace.
Softening silicone
In described softening system, the weight ratio of described polysaccharide or polysaccharide-silicone conjugate and described softening silicone is to count from 1: 200 to 1: 5 with weight part, preferably from 1: 50 to 1: 5, more preferably from 1: 20 to 1: 5.
The exist level of described softening silicone in particle is from 0.995 to 29.995wt.%, preferably from 0.91 to 27.3wt.%.Described softening silicone most preferred level in particle be the particle gross weight 10 to 25wt.%.
Described softening silicone is selected from polydialkysiloxane, its sulfonamide derivatives and their mixture.Preferably described softening silicone is an amodimethicone, and is independently selected from any silicone that covalent linkage is received described polysaccharide.More preferably, described softening silicone is the hindered amine silicone.The preferred dynamic viscosity of described softening silicone is＞2, and 500mPas is (at about 100s
-1Shearing rate and 20 ℃ temperature).
The softening particle of described solid comprises polysaccharide and softening silicone.These components can preferably be combined in the emulsion together, to be easy to be processed into the softening particle of described solid.
When using emulsion, this emulsion comprises softening silicone and polysaccharide (preferred polysaccharide-silicone conjugate) as previously discussed.
This emulsion further comprises other liquid composition, and preferred polar solvent is as water.Described emulsion generally has 30 to 99.9%, described other liquid composition (for example water) of preferred 40 to 99%.Described emulsion can be for example high water miscible liquid, or low water miscible liquid.Low water miscible liquid can be the water such as 30 to 60%, preferred 40 to 55% water.High water miscible liquid can be the water such as 60 to 99.9%, preferred 80 to 99% water.Middle water miscible liquid can be the water such as 55 to 80%.Described emulsion can be concentrated so that low water miscible liquid to be provided.
Described emulsion can also contain emulsifying agent, is preferred for the emulsifying surfactant of described softening silicone and polysaccharide or polysaccharide-silicone conjugate.In preferable case, described polysaccharide-silicone conjugate itself is an emulsifying agent.
Described emulsifying agent, if exist, preferably one or more tensio-active agents for example, are selected from disclosed any type, subtype or specific surfactant in any context in this article.
Described emulsifying agent most preferably comprises nonionogenic tenside or is made up of nonionogenic tenside.Additionally or alternatively, one or more additional surface promoting agents that are selected from negatively charged ion, positively charged ion, zwitter-ion and amphoterics can be added into or as described emulsifying agent.
By mix described softening silicone, polysaccharide (preferred polysaccharide-silicone conjugate), polar solvent (for example water) and preferably and emulsifying agent in high shear mixer, as tensio-active agent, particularly nonionogenic tenside prepares described emulsion.
Inorganic carrier
Described inorganic carrier is selected from the carbonate and the supercarbonate of basic metal and alkaline-earth metal, or their mixture.
As used herein, carbonate and supercarbonate are to be used in reference to basic metal or alkaline earth salt, as for example yellow soda ash, sodium bicarbonate, salt of wormwood, saleratus or other salt of obtaining by neutralizing wholly or in part of carbonic acid.It is the weight percent of negatively charged ion carbonate or bicarbonate radical that the weight percent of carbonate or supercarbonate can be expressed as, or comprises the weight percent of cationic whole salt.
Described inorganic carrier can be soluble or insoluble.Preferably described inorganic carrier is soluble.The example of soluble inorganic carrier is carbonate and supercarbonate, particularly, and yellow soda ash and sodium bicarbonate.
" solvable " that use about solvable inorganic carrier is meant that described inorganic carrier dissolves in water.Thereby when the 1g inorganic carrier is put into the 1L aqueous solution and when 293K shakes 2 hours with 100RPM on the rotation wobbler in room temperature, the weight of the inorganic carrier of removing (by via filter screen of a size suitable or filter paper filtering and drying) be lower than add 95% of inorganic carrier weight." soluble " used about described solid inorganic carrier is meant those carriers of not testing by the above-mentioned solubleness of mentioning.
The exist level of described inorganic carrier in the softening particle of solid is from 70 to 99wt.%, preferably from 72.5 to 97.5wt.%, most preferably from 75 to 95wt.%.
Described carbonate carrier is the basic metal that suits or the carbonate of alkaline earth metal cation.The carbonate that preferably described carbonate is the habit modification (habit modified carbonate, HMC).More preferably carbonate material is the yellow soda ash of habit modification.These materials have high surface area and therefore have high bearing capacity.An advantage of these materials is that the height that can realize described softening silicone loads.How by this way the example of modification yellow soda ash can be found in WO2006/081930.Wherein disclosed is a kind of preparation method of modification sodium carbonate carrier material, and this method may further comprise the steps: (i) preparation yellow soda ash; The crystal growth modifier of significant quantity is selected from the group that comprises polyacrylic ester/salt, polyaspartate/salt and poly aspartic acid, the aqueous solution; Form the yellow soda ash of crystal growth modification thus; (ii) the dry described solution of the drying means by any routine is to form the exsiccant solid carrier material.
Preferred supercarbonate is sodium bicarbonate and saleratus.
Preferred solvable inorganic carrier is a yellow soda ash.Most preferred inorganic carrier is the yellow soda ash of habit modification.
The particulate preparation method
Solid of the present invention is softening a kind of suitable preparation method of particulate may further comprise the steps :-
A) provide the emulsion that comprises water and softening system, described softening system comprises that weight ratio is 1: 200 to 1: 5 Viscogum BE polysaccharide and a softening silicone;
B) with inorganic carrier described emulsion is granulated (granulation) in high shear mixer, described inorganic carrier is selected from carbonate and the supercarbonate or their mixture of basic metal and alkaline-earth metal; With,
C) particle that obtains of drying.
Preferably, by water evaporation and the emulsion of enrichment step in a), so that the emulsion that comprises 30 to 60% water to be provided.The suitable equipment that is used at this enrichment step is Buchi
TMRotary Evaporators.
Drying step c) preferably implements from 20 to 100 ℃ level.Described particle can be in the lower end of this temperature range dry air, and baking oven is used in the described particle of high temperature drying.
Therefore described particle can separate, and randomly obtains the particle of desired size by screen cloth.In the employed high shear mixer of this paper, use any suitable equipment such as ultrasonic disruption machine, microjet clarifixator (microfluidizer) or homogenizer to apply mixing.Suitable homogenizer is Manton Gaulin homogenizer or any other high-shear homogenizer such as Ultra Turrax.Suitable laboratory scale high shear mixer is Braun MR4050HC.
Laundry treatment compositions
The softening particle of described solid is delivered to fabric suitably by adding in the laundry treatment compositions.
Suitable laundry treatment compositions comprises from the softening particle of 0.1 to 25wt.% described solid with from 2 to 70wt.% tensio-active agent.
The exist level of described softening particle in laundry treatment compositions is from 0.1 to 25wt.%, preferably from 0.5 to 10wt.%.
That described laundry treatment compositions can adopt is granular, spraying drying or do powder, sheet, formation solid form or any other the similar detergent for washing clothes form well known by persons skilled in the art of mixing.
The preferred laundry treatment compositions form with the softening particle combination of solid of the present invention of being particularly suitable for is granular, spraying drying or does the powder composition that mixes.
Tensio-active agent
Described laundry treatment compositions comprises 2 to 70wt.% tensio-active agent, and most preferably 10 to 30wt.%.Usually, the nonionic of surfactant system and anion surfactant can be selected from the tensio-active agent that is described in following: " Surface Active Agents " Vol.1, Schwartz ﹠amp; Perry, Interscience 1949, Vol.2, Schwartz, Perry ﹠amp; Berch, Interscience 1958, the current version that Manufacturing Confectioners Company publishes " McCutcheon ' s Emulsifiers and Detergents ", or " Tenside-Taschenbuch ", H.Stache, 2nd Edn., Carl Hauser Verlag, 1981.Preferably, the tensio-active agent of use is saturated.
Operable suitable nonionic detergent compounds comprises particularly, having the compound of hydrophobic grouping and hydrogen atoms, for example, fatty alcohol, acid, acid amides or alkylphenol, with oxirane (particularly separately or with the oxyethane of propylene oxide), reaction product.Specific nonionic detergent compounds is C
6To C
22Alkylphenol-ethylene oxide condensate, normally 5 to 25EO, i.e. 5 to 25 ethylene oxide unit per molecules and aliphatics C
8To C
18The condensation product of uncle or secondary straight or branched alcohol and oxyethane is generally 5 to 40EO.
Operable suitable anionic detergent immunomodulator compounds normally has the organic sulfate of the alkyl that comprises about 8～about 22 carbon atoms and the water-soluble alkali metal salts of sulfonate, and the term alkyl is used to comprise the moieties of senior acyl group.The example of the synthetic anionic detergent compound that is fit to is sodium alkyl sulfate and potassium, especially by the senior C of sulfation
8～C
18Those that alcohol obtains are by for example tallow oil (tallow oil) or Oleum Cocois preparation; Alkyl C
9～C
20Benzene sulfonic acid sodium salt and potassium, particularly linear secondary alkyl C
10～C
15Benzene sulfonic acid sodium salt; With alkyl glycerol base ether sodium sulfate, especially be derived from the higher alcohols and those ethers that are derived from the synthol of oil of tallow oil or Oleum Cocois.The preferred anionic surfactants detergent compound is C
11～C
15Sodium alkyl benzene sulfonate and C
12～C
18Sodium alkyl sulfate.Also operable is following tensio-active agent, those that describe among the EP-A-328 177 (Unilever) for example, and it demonstrates has resistance, alkyl polyglycoside tensio-active agent and the alkyl list glycosides described among the EP-A-070 074 to saltouing.
The preferred surfactants system is the mixture of negatively charged ion and nonionic detergent active material, particularly the negatively charged ion of pointing out among the EP-A-346 995 (Unilever) and the group and the example of nonionogenic tenside.Especially preferred is such surfactant system, and it is C
16～C
18An alkali metal salt of primary alcohol sulfate, and C
12～C
15The mixture of primary alconol 3～7EO ethoxylate.
Described nonionic detergent preferably with surfactant system greater than 10%, for example the amount of 25～90wt% exists.Anion surfactant can be for example exists with the amount of about 5wt%～about 40wt% scope of described surfactant system.
Washing assistant or complexing agent
Described laundry treatment compositions can comprise from 1 to 70wt.% washing assistant.
For granular, spraying drying or do the laundry composition that mixes powder type, the level of washing assistant is preferably 1 to 40wt.%.
The washing assistant material can be selected from 1) the calcium sequestrant material, 2) the precipitation threshold material, 3) calcium ion-exchanged material and 4) their mixture.
Preferably when using insoluble inorganic builders (for example zeolite), size at 0.1～10 micrometer range (by from Malvern
TMThe Mastersizer 2000 particle-size analyzers use determination of laser diffraction).
The example of calcium sequestrant washing assistant material comprises alkali metal polyphosphates, for example tripoly phosphate sodium STPP, and organic sequestering agent, for example ethylenediamine tetraacetic acid (EDTA).
The example of precipitation threshold washing assistant material comprises sodium orthophosphate and yellow soda ash.
The example of calcium ion-exchanged washing assistant material comprises various types of water-insoluble crystal or amorphous aluminosilicate, zeolite is that it is most the representative known to the people, for example zeolite A, zeolite B (being also referred to as zeolite P), zeolite C, X zeolite, zeolite Y and EP-A-0, P type zeolite disclosed in 384,070.
Described composition also can comprise washing assistant or the complexing agent of 0～50wt%, for example ethylenediamine tetraacetic acid (EDTA), diethylene triaminepentaacetic acid(DTPA), alkyl or alkenyl succsinic acid, nitrilotriacetic acid(NTA) or other following washing assistants.A lot of washing assistants are because therefore the ability of their complexation of metal ions also is the bleach-stable agent.
Zeolite and carbonate (comprising supercarbonate and sesquicarbonate) are preferred washing assistants.
Described composition can comprise crystalline aluminosilicate as washing assistant, preferred as alkali aluminosilicate, more preferably sodium aluminium silicate.It typically exists with the content that is less than 15wt%.Aluminosilicate is the material with following general formula:
0.8-1.5 M
2O.Al
2O
3.0.8-6 SiO
2
Wherein M is a monovalent cation, is preferably sodium.These materials contain some combination water, and need have the calcium ion-exchanged capacity of 50mg CaO/g at least.Preferred sodium aluminium silicate comprises 1.5～3.5SiO in following formula
2The unit.They can easily prepare by the reaction between water glass and the sodium aluminate as describing in detail in the document.The ratio of tensio-active agent and aluminosilicate (under situation about existing) was preferably greater than 5: 2, more preferably greater than 3: 1.
Alternately, or except that this aluminosilicate washing assistant, can use phosphate builders.Term " phosphoric acid salt " comprises diphosphate, triphosphate and phosphonate species in the art.Other forms of washing assistant comprise silicate, for example soluble silicate, metasilicate, layered silicate (for example from Hoechst SKS-6).
Preferably, laundry detergent formulations is the laundry detergent formulations of no phosphoric acid salt as washing assistant, promptly comprises the phosphoric acid salt that is less than 1wt%.
Screening agent (shading agent)
Described laundry treatment compositions is preferably included in the blueness or the purple screening agent of 0.0001～0.01wt% scope.Described screening agent has reduced the whiteness of the infringement of a lot of colour clothes being felt and improved white garments.
Described screening agent is preferably selected from the blueness and the purple dye of solvent dispersion alkalescence listed in the Colour Index (Society of Dyers and Colourists and American Association of Textile Chemists and Colorists 2002), direct and acid type.
Preferably, there are direct purple or sun blue dyestuff.Preferred described dyestuff is tetrazo, trisazo dye or three benzos two
Piperazine (triphendioxazine) dyestuff.Carcinogenic p-diaminodiphenyl (benzidene) radical dye is not preferred.
Can use the tetrazo cupriferous dye, for example direct purple 66.
Most preferred disazo dyes has following structure:
Wherein:
Ring D and E independently can for shown in naphthyl or phenyl;
R
1Be selected from: hydrogen and C
1～C
4Alkyl, preferred hydrogen;
R
2Be selected from: hydrogen, C
1～C
4Alkyl, replacement or unsubstituted phenyl and replacement or unsubstituted naphthyl, preferred phenyl;
R
3And R
4Be independently selected from: hydrogen and C
1～C
4Alkyl, preferred hydrogen or methyl;
X and Y are independently selected from: hydrogen, C
1～C
4Alkyl and C
1～C
4Alkoxyl group; Preferred described dyestuff has the X=methyl; With the Y=methoxyl group, and n is 0,1 or 2, preferred 1 or 2.
Preferred disazo dyes is directly purple 7, directly purple 9, directly purple 11, directly purple 26, directly purple 31, directly purple 35, directly purple 40, directly purple 41, directly purple 51 and directly purple 99.
Preferred solvent and dispersed dye are selected from monoazo or anthraquinone dye, most preferred solvent purple 13,63 ,DIS,PER,SE ,Vio,let, 63 27,63 ,DIS,PER,SE ,Vio,let, 63 26,63 ,DIS,PER,SE ,Vio,let, 63 28,63 ,DIS,PER,SE ,Vio,let, 63 63 and 63 ,DIS,PER,SE ,Vio,let, 63 77.
A kind of preferred pigment is pigment Violet 23.
Enzyme
Described laundry treatment compositions preferably includes one or more enzymes, and it provides clean-up performance and/or fabric nursing benefit.The example of the enzyme that is fit to is including, but not limited to hemicellulase, peroxidase, proteolytic enzyme, cellulase, zytase, lipase, Phospholipid hydrolase, esterase, at, polygalacturonase, mannase, pectin lyase, M-Zyme, reductase enzyme, oxydase, phenol oxidase, lipoxygenase, ligninase, Starch debranching enzyme, tannase, pentosanase, malanases, arabinofuranosidase/xylosidase, Unidasa, chondroitinase, laccase and amylase or their mixture.Typical combination is for example can comprise proteolytic enzyme and lipase and in conjunction with diastatic enzyme mixture.In the time of in being present in cleaning compositions, aforesaid extra enzyme can be with about 0.00001wt%～about 2wt% of said composition weight, about 0.0001wt%～about 1wt% or even the content of about 0.001wt%～about 0.5wt% zymoprotein exist.
Preferred enzyme is a cellulase.
Fluorescent agent
Described laundry treatment compositions preferably includes fluorescent agent (white dyes).Fluorescent agent is that known and a lot of this fluorescent agents are commercially available getting.Usually, these fluorescent agents are that form with its an alkali metal salt (for example sodium salt) provides and uses.The total amount of described one or more fluorescent agents that use in composition is generally 0.005～2wt%, more preferably 0.01～0.1wt%.Preferred white dyes kind is: two-styrylbiphenyl compounds, for example Tinopal (trade mark) CBS-X; Diamines Stilbene disulfonic acid compound, for example Tinopal DMS pure Xtra and Blankophor (trade mark) HRH; And pyrazoline compounds, for example Blankophor SN.Preferred white dyes is: 2-(4-styryl-3-sulfo group phenyl)-2H-naphtho-[1,2-d] triazole sodium, 4,4 '-it is two that { [(4-anilino-6-(N-methyl-N-2-hydroxyethyl) amino 1,3,5-triazine-2-yl)] amino } Stilbene-2-2 ' disulfonic acid disodium, 4,4 '-two { [(4-anilinos-6-morpholino-1,3,5-triazine-2-yl)] amino } Stilbene-2-2 ' disulfonic acid disodium and 4,4 '-two (2-sulfo group styryl (sulfoslyryl)) biphenyl disodium.
Spices
Preferably, described laundry treatment compositions comprises spices.Described spices is preferably at 0.001～3wt% scope, most preferably 0.1～1wt%.The example of a lot of spices that are fit to is provided in the OPD 1993 Chemicals Buyers Directory 80th Annual Edition that CTFA (Cosmetic, Toiletry and Fragrance Association) the 1992 International Buyers Guide and the Schnell Publishing Co of CFTA Publications publication publish.
It is common having multiple perfume composition in prescription.In composition of the present invention, expection will have four kinds or more kinds of, and preferred five kinds or more kinds of, more preferably six kinds or more kinds of, or even seven kinds or more kinds of different perfume composition.
In spice mixt, preferred 15～25wt% is preceding flavor (top notes).Before flavor by Poucher (Journal of the Society of Cosmetic Chemists 6 (2): 80[1955]) definition.Flavor is selected from citrus oil, phantol, phanteine, lavandula angustifolia, dihydromyrcenol, rose oxide and cis-3-hexenol before preferred.
Spices and preceding flavor can be used to point out whiteness benefit of the present invention.
Polymkeric substance
Described laundry treatment compositions can comprise one or more polymkeric substance.Example is carboxymethyl cellulose, polyoxyethylene glycol, polyvinyl alcohol, polycarboxylate/salt for example polyacrylic ester/salt, toxilic acid/acrylic copolymer and lauryl methacrylate(LMA)/acrylic copolymer.
SYNTHETIC OPTICAL WHITNER
Described laundry treatment compositions also can contain bleach systems aptly.If there is SYNTHETIC OPTICAL WHITNER, then preferably, composition of the present invention contains the peroxy bleaching agent compound that can obtain hydrogen peroxide in the aqueous solution, for example inorganic or organic peroxide acid, and inorganic persalt such as alkali metal perborate, percarbonate, superphosphate, persilicate and persulphate.Bleach additive composition is generally as adding behind the powder.
If present, peroxy bleaching agent compound, for example SPC-D is suitable to 5-35wt%, the existence of the amount of preferred 10-25wt%.Peroxy bleaching agent compound, for example SPC-D can be united use with activator of bleaching agent (bleach precursor), to improve the bleaching action under low wash temperature.This bleach precursor is suitable to 1-8wt%, and the amount of preferred 2-5wt% exists.
Preferred bleach precursor is a peroxycarboxylic acid precursors, more especially peracetic acid precursors and peroxybenzoic acid precursors; And peroxycarbonic acid precursors.The especially preferred a kind of bleach precursor that is suitable among the present invention is N, N, N ', N '-tetra acetyl ethylene diamine (TAED).
Bleach-stable agent (heavy metal chelant) also can exist.Suitable bleach-stable agent comprises edetate (EDTA), quadrol two succinates (EDDS) and aminopolyphosphonic acid salt such as ethylenediamine tetramethylene phosphonic acid salt (EDTMP) and diethylenetriamine pentamethylenophosphonic acid(DTPP) salt (DETPMP).
Experiment
The preparation of embodiment 1-carbonate/LBG-silicone particles
Embodiment 1a
Viscogum BE polydimethylsiloxane conjugate (LBG-silicone conjugate) preparation example
LBG-silicone conjugate can be by the method preparation that discloses among the WO 04/111169.A preparation example is as follows.
Adopt heating (150 ℃) and stirring under nitrogen, (27g) is dissolved in anhydrous dimethyl sulphoxide (300cm with lithium chloride
3) in.In case the lithium chloride dissolving is cooled to 120 ℃ with solution, under vigorous stirring, slowly added Viscogum BE (3.5g) in the clock time then at 20 minutes.
The viscous soln that will so obtain further is cooled to 70 ℃ then, and (54mg 0.5mmol), and continues to stir and heated two hours to add carbonyl dimidazoles.Add the end capped polydimethylsiloxane of diamino propyl group then, 3,000MWt, (1g, 0.33mmol), solution stirred 18 hours under heating condition.
Described solution is cooled to room temperature, then it is added drop-wise in the acetone (3 liters) of vigorous stirring with precipitation polymers.Solution is carried out centrifugal with separated product, described product is used acetone (2 * 200cm then
3) washing, vacuum-drying then (40 ℃) is spent the night to obtain pale solid (3.1g).
From the product of hydrolysis (at 20%DCl/D
2Among the O 70 ℃ of heating 1 hour) 1H NMR, find that the PDMS group is 53 * 10 to the substitution value of sugar unit
-4
Embodiment 1b
Formation comprises Duo Tang ﹠amp; The method example of the emulsion of softening silicone
The softening system (being emulsion in this case) that comprises polysaccharide (being LBG-silicone conjugate) and softening silicone can be by the method preparation that discloses among the WO 04/111169.A preparation example is as follows.
LBG-silicone conjugate is weighed in the bottle with the water of the emulsifying agent of choosing wantonly (using Synperonic A7) with aequum.Use ultrasonic probe (Soniprobe
TM) stir this mixture with half power, until can't see undissolved polysaccharide (2-3 minute).To soften silicone (Q2-8220) then joins in the bottle.Use is equipped with the cutting head of 25mm diameter and the Silverson of square hole high-shear screen cloth
TMThe L4R high shear mixer is being set 5 sheared mixts 4 minutes.
Synperonic A7
TMBe dodecane six ethoxylate nonionic surfactant.Q2-8220
TMBe amodimethicone oil from Dow Corning.Adopt the cone-plate method to use " Bohlin CV 120 high resolving power " viscometer at 22 ℃ and 100s
-1Its viscosimetric analysis of shearing rate is 160mPas.
Embodiment 1c
Use the method for granulating example of the softening system of emulsion
The softening system of emulsion is by disclosed method preparation among the WO 04/111169.The modification of the softening silicone emulsion of the activity that is available commercially by adding LBG-silicone conjugate.This is the softening system of emulsion that is used for following method of granulating.
20% activity substance content level of the emulsion of using and gained particulate % activity substance content are represented total silicone active substance, are the combination of LBG-silicone conjugate and softening silicone in this case.
For each emulsion, the weight ratio of LBG-silicone conjugate and softening silicone is 1: 9.Therefore 20% activity substance content level of emulsion is made up of the softening silicone of 2%LBG-silicone conjugate+18%.
Particle A
In laboratory scale high shear mixer (Braun MR4050HC), the softening system of the emulsion of 14.7g is granulated with the yellow soda ash of 20g habit modification.The particle that produces is then in about 25 ℃ of dry airs.The exsiccant product sieves between 180 and 1400 microns.These particulate " active substance " content is 8.5%.
Particle B
In laboratory scale high shear mixer (Braun MR4050HC), the softening system of the emulsion of 14.7g is granulated with the yellow soda ash of 20g habit modification.The particle that produces is then in about 45 ℃ of dry airs.The exsiccant product sieves between 180 and 1400 microns.These particulate " active substance " content is 11.2%.
Particle C
The softening system of the emulsion of 100g is passed through at Buchi
TMRemove moisture in the Rotary Evaporators and be concentrated into final weight 56.2g (enriched material has 35.6% activity substance content now).
In laboratory scale high shear mixer (Braun MR4050HC), this spissated emulsion of 20.75g is granulated with the yellow soda ash of 30g habit modification.The particle that produces is then at 45 ℃ of oven dryings.The exsiccant product sieves between 180 and 1400 microns.These particulate " active substance " content is 17.4%.
Particle D
The softening system of the emulsion of 100g is passed through at Buchi
TMRemove moisture in the Rotary Evaporators and be concentrated into final weight 56.2g (enriched material has 35.6% activity substance content now).
In laboratory scale high shear mixer (Braun MR4050HC), this concentrated emulsion of 20.75g is granulated with the yellow soda ash of 30g habit modification.The particle that produces is then at 85 ℃ of oven dryings.The exsiccant product sieves between 180 and 1400 microns.These particulate " active substance " content is 19.8%.
Particle E
The softening system of the emulsion of 100g is passed through at Buchi
TMRemove moisture in the Rotary Evaporators and be concentrated into final weight 56.2g (enriched material has 35.6% activity substance content now).
In laboratory scale high shear mixer (Braun MR4050HC), this concentrated emulsion of 13.3g is granulated with the yellow soda ash (light soda ash (light ash) is from Brunner Mond) of 25g class of trade.The particle that produces is then at 85 ℃ of oven dryings.The exsiccant product sieves between 180 and 1400 microns.These particulate " active substance " content is 15.9%.
Table 1
| Particle | The emulsion enrichment step? | Inorganic carrier | Drying temperature ℃ | The active substance level |
| A | Not | The NaCO of habit modification 3 | 25 | 8.5 |
| B | Not | The NaCO of habit modification 3 | 45 | 11.2％ |
| C | Be | The NaCO of habit modification 3 | 45 | 17.4％ |
| D | Be | The NaCO of habit modification 3 | 85 | 19.8％ |
| E | Be | NaCO 3 | 85 | 15.9％ |
Embodiment 2-pliability benefit
Produce contrast alginate particle according to WO 2006/117385.
Silicone dosage is based on the theoretical silicone level in the particle.These are calculated with the equal silicone dosage that provides every gram fabric 2mg silicone for every kind of grain type on the fabric monitor (supposing that 100% silicone absorbs (pick-up)).Be on close level in the Persil powder 4.3% silicone of this silicone.
Used fabric in softening test (white cotton towel cloth (terry towelling)) and residue test (the cotton double rib Chinese cloth (black jersey cotton interlock) of black), pre-wash before using.Use standard destarch rules for this pre-wash, normally 60 ℃ with Europe with reference to detergent washing 2 times.
Method
RotaWash
TMLoad (Front Loading Automatic, FLA) condition in the washing machine automatically before being used to simulate typical full-scale Europe.This RotaWash
TMBe a kind of small washing machine, have 12 independently washings ' basin ((pots)) ', each basin has the volume of 250ml.In these experiments, each washtub comprises single piece of fabric.
Utilize RotaWash, the condition of using is below simulated those conditions of 40 ℃ of cotton washings of standard in the European FLA washing machine as far as possible.Four repeated washing basins of every kind of grain type operation.This shears measurement (instrumental shear measurements) for equipment and has provided enough repetitions.
40 ℃ of temperature
Water hardness Wirral water (12-14 ° of French hardness (French Hardness))
Liquid: cloth ratio 8: 1 (liquid=132ml)
Cloth type white towel fabric, 1 every basin (21cm
2)～16.5g
25 in the every basin of ball (ballbearings)
Powder Persil
TMBio does not add spices (predissolve before in joining basin)
Powder dose 5.8g/l (liquid storage of the 11.6g/l of 66ml adds 66ml Wirral water)
Washing time 45 minutes
Rinsing rinsing in 2 * 10 minutes (following stirring), 250ml is used in each rinsing
Wirral water
Drying is dried
Following chart (table 2) shows from Persil
TMBio powder (2006UK, the commercially available detergent for washing clothes product that gets), send by the pliability of shearing sluggish (Shear Hysteresis) (equipment is sheared and measured) measurement, interpolation is according to the various LBG-silicone particles of embodiment 1 preparation, and with the softening particle contrast of alginate.
Table 2
| Composition | Shear sluggish 2HG5 |
| Contrast (Persil TMThe Bio powder) | 6.20 |
| The alginate particle, 80% silicone | 3.61 |
| Particle D LBG-silicone/carbonate particle, 17.4% silicone | 4.10 |
| Particle C LBG-silicone/carbonate particle, 19.8% silicone | 4.22 |
When with the contrast contrast, for the alginate particle and for two kinds of LBG-silicone/carbonate particles, particle D﹠amp; C, shear hysteresis reduce show the low friction valve of fabric and therefore demonstrate pliability benefit the fabric of washing.
The subjective assessment of adopting the fabric of silicone washing be with do not have tenderizer compare for hand obviously more soft show from carbonate particle and from the alginate particle delivery the acceptable ramollescence of human consumer.
The storage physicals that embodiment 3-improves
Compare with the alginate particle, at 28 ℃/70%RH (8 week) storage, carbonate particle demonstrates the physicals (reducing oil leakage and viscosity) of improvement.After during this period of time, it is free-pouring that carbonate particle remains, and the coherent viscosity agglomerate of the silicone that the alginate particle is leaked, it is unacceptable using in preparation.
The minimizing of embodiment 4-visible residue
The condition of using is below simulated those conditions of 30 ℃ of residue tests of standard in the full-scale FLA washing machine as far as possible, uses the washing of black knitted cotton to add loading, low agitator treating (woolen knitwear wash(ing)cycle).Equally, use RotaWash
TM, two repeated washing basins of every kind of grain type operation.
30 ℃ of temperature
Water hardness Wirral water (12-14 ° of French hardness)
Liquid: cloth ratio 8: 1 (liquid=132ml)
Cloth type black double rib Chinese cloth, 1 every basin, 1 every basin (21cm
2)～16.5g
Ball does not contain, and stirs to reduce
Powder Persil
TMBio does not add spices (predissolve before joining basin)
Powder dose 5.8g/l (the 11.6g/l liquid storage of 66ml adds 66ml Wirral water)
Washing time 24 minutes
Rinsing rinsing in 2 * 10 minutes (following stirring), 250ml is used in each rinsing
Wirral water
Drying is dried
Use Persil
TMBio powder+LBG-silicone/carbonate particle (respectively with the particle ' C ' that comes from table 1 and ' D ' test) and Persil
TMThe visual evaluation of the black fabric of Bio powder+alginate particle washing shows, carbonate particle (' C ' and ' D ' both) is compared with the alginate particle has remarkable lower visual level of residue.This is based on 3 people to the visual evaluation of wash with exsiccant black monitoring fabric.Be different from the alginate particle, do not see the particle residue thing for carbonate particle.For observing same result from the fabric of two repeated washings.
Claims (15)
1. solid softens particle, comprising:
(i) 1 to 30wt.% softening system, it comprises that weight ratio is 1: 200 to 1: 5 Viscogum BE polysaccharide and a softening silicone; With,
(ii) 70 to 99wt.% inorganic carrier, it is selected from the carbonate and the supercarbonate of basic metal and alkaline-earth metal, or their mixture.
2. solid as claimed in claim 1 softens particle, and wherein said softening system is present in the described softening particle with 5 to 25wt.% level.
3. as claim 1 or the softening particle of the described solid of claim 2, wherein said inorganic carrier is present in the described softening particle with 75 to 95wt.% level.
4. as the softening particle of above-mentioned any described solid of claim, wherein said softening silicone is present in the described softening particle with 10 to 25wt.% level.
5. it is covalently bound that as the softening particle of above-mentioned any described solid of claim, wherein said Viscogum BE polysaccharide and one or more are selected from the silicone material of polydialkysiloxane, its sulfonamide derivatives and their mixture.
6. as the softening particle of above-mentioned any described solid of claim, wherein said inorganic carrier is soluble.
7. solid as claimed in claim 6 softens particle, and wherein said solvable inorganic carrier is a yellow soda ash, the yellow soda ash of preferred habit modification.
8. as the softening particle of above-mentioned any described solid of claim, the softening silicone that wherein is present in the emulsion comprises amodimethicone.
9. as the softening particle of above-mentioned any described solid of claim, wherein said Viscogum BE polysaccharide has one or more covalently bound silicone chains, and described softening silicone comprises that amodimethicone and described inorganic carrier are the yellow soda ash of habit modification.
10. laundry treatment compositions comprises:
(i) 0.1 to the claim 1 to 9 of 25wt.% the softening particle of each described solid,
(ii) 2 to 70wt.% tensio-active agent; With,
(iii) 1 to 70wt.% washing assistant.
The purposes of softening fabrics 11. the described laundry treatment compositions of the claim 10 of significant quantity is in the suds.
12. handle the home method of textiles, may further comprise the steps:
(i) handle textiles with the aqueous solution of the laundry treatment compositions of 1 to 20g/l claim 10; With,
(ii) rinsing and dry described textiles.
13. the softening particulate method of each described solid in the preparation claim 1 to 10, wherein said method may further comprise the steps:
A) provide the emulsion that comprises water and softening system, described softening system comprises that weight ratio is 1: 200 to 1: 5 Viscogum BE polysaccharide and a softening silicone;
B) with inorganic carrier described emulsion is granulated in high shear mixer, described inorganic carrier is selected from carbonate and the supercarbonate or their mixture of basic metal and alkaline-earth metal; With,
C) particle that obtains of drying.
14. method as claimed in claim 13, wherein the emulsion in the step a) concentrates by the water evaporation, so that the emulsion that comprises 30 to 60% water to be provided.
15. as claim 13 or the described method of claim 14, wherein drying step c) implement 20 to 100 ℃ levels.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP08158939 | 2008-06-25 | ||
| EP08158939.2 | 2008-06-25 | ||
| PCT/EP2009/056119 WO2009156233A1 (en) | 2008-06-25 | 2009-05-20 | Laundry treatment compositions |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102076836A true CN102076836A (en) | 2011-05-25 |
| CN102076836B CN102076836B (en) | 2013-05-22 |
Family
ID=39971096
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200980124127.1A Expired - Fee Related CN102076836B (en) | 2008-06-25 | 2009-05-20 | Laundry treatment compositions |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP2294169B1 (en) |
| CN (1) | CN102076836B (en) |
| BR (1) | BRPI0914753A2 (en) |
| ES (1) | ES2398425T3 (en) |
| WO (1) | WO2009156233A1 (en) |
| ZA (1) | ZA201008966B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109563443A (en) * | 2016-08-10 | 2019-04-02 | 荷兰联合利华有限公司 | Laundry composition |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9321873B2 (en) | 2005-07-21 | 2016-04-26 | Akzo Nobel N.V. | Hybrid copolymer compositions for personal care applications |
| NO20073834L (en) | 2006-07-21 | 2008-01-22 | Akzo Nobel Chemicals Int Bv | Sulfonated graft copolymers |
| US8636918B2 (en) | 2011-08-05 | 2014-01-28 | Ecolab Usa Inc. | Cleaning composition containing a polysaccharide hybrid polymer composition and methods of controlling hard water scale |
| US8679366B2 (en) | 2011-08-05 | 2014-03-25 | Ecolab Usa Inc. | Cleaning composition containing a polysaccharide graft polymer composition and methods of controlling hard water scale |
| US8841246B2 (en) | 2011-08-05 | 2014-09-23 | Ecolab Usa Inc. | Cleaning composition containing a polysaccharide hybrid polymer composition and methods of improving drainage |
| US8853144B2 (en) | 2011-08-05 | 2014-10-07 | Ecolab Usa Inc. | Cleaning composition containing a polysaccharide graft polymer composition and methods of improving drainage |
| JP2014532791A (en) | 2011-11-04 | 2014-12-08 | アクゾ ノーベル ケミカルズ インターナショナル ベスローテン フエンノートシャップＡｋｚｏ Ｎｏｂｅｌ Ｃｈｅｍｉｃａｌｓ Ｉｎｔｅｒｎａｔｉｏｎａｌ Ｂ．Ｖ． | Hybrid dendritic copolymer, composition thereof and method for producing the same |
| WO2013064648A1 (en) | 2011-11-04 | 2013-05-10 | Akzo Nobel Chemicals International B.V. | Graft dendrite copolymers, and methods for producing the same |
| US8945314B2 (en) | 2012-07-30 | 2015-02-03 | Ecolab Usa Inc. | Biodegradable stability binding agent for a solid detergent |
| US9365805B2 (en) | 2014-05-15 | 2016-06-14 | Ecolab Usa Inc. | Bio-based pot and pan pre-soak |
| EP3241889B1 (en) * | 2016-05-03 | 2019-03-20 | The Procter and Gamble Company | Cleaning composition |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB0313900D0 (en) * | 2003-06-16 | 2003-07-23 | Unilever Plc | Laundry treatment compositions |
| ATE454439T1 (en) * | 2004-02-03 | 2010-01-15 | Procter & Gamble | LAUNDRY CLEANING OR TREATMENT COMPOSITION AND A PROCESS FOR PRODUCING THE COMPOSITION |
| DE102005020551A1 (en) * | 2005-05-03 | 2006-11-09 | Degussa Ag | Solid, redispersible emulsion |
| GB0514716D0 (en) * | 2005-07-19 | 2005-08-24 | Unilever Plc | Process to form fabric softening particle,particle obtained and its use |
-
2009
- 2009-05-20 BR BRPI0914753A patent/BRPI0914753A2/en not_active IP Right Cessation
- 2009-05-20 EP EP09769082A patent/EP2294169B1/en not_active Not-in-force
- 2009-05-20 WO PCT/EP2009/056119 patent/WO2009156233A1/en active Application Filing
- 2009-05-20 CN CN200980124127.1A patent/CN102076836B/en not_active Expired - Fee Related
- 2009-05-20 ES ES09769082T patent/ES2398425T3/en active Active
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109563443A (en) * | 2016-08-10 | 2019-04-02 | 荷兰联合利华有限公司 | Laundry composition |
| CN109563443B (en) * | 2016-08-10 | 2021-01-26 | 荷兰联合利华有限公司 | Laundry compositions |
Also Published As
| Publication number | Publication date |
|---|---|
| ZA201008966B (en) | 2012-02-29 |
| WO2009156233A1 (en) | 2009-12-30 |
| EP2294169B1 (en) | 2012-10-31 |
| EP2294169A1 (en) | 2011-03-16 |
| BRPI0914753A2 (en) | 2015-10-20 |
| CN102076836B (en) | 2013-05-22 |
| ES2398425T3 (en) | 2013-03-19 |
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