CN102317426A - Improvements relating to fabric treatment compositions - Google Patents
Improvements relating to fabric treatment compositions Download PDFInfo
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- CN102317426A CN102317426A CN2009801568122A CN200980156812A CN102317426A CN 102317426 A CN102317426 A CN 102317426A CN 2009801568122 A CN2009801568122 A CN 2009801568122A CN 200980156812 A CN200980156812 A CN 200980156812A CN 102317426 A CN102317426 A CN 102317426A
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/382—Vegetable products, e.g. soya meal, wood flour, sawdust
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—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
- C11D3/227—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin with nitrogen-containing groups
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3707—Polyethers, e.g. polyalkyleneoxides
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3715—Polyesters or polycarbonates
-
- 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
- C11D3/3723—Polyamines or polyalkyleneimines
-
- 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
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
Abstract
A fabric cleaning composition for use in a laundering process which comprises: a) at least one anionic surfactant, b) at least one nonionic surfactant, c) a powder of botanical origin, and d) a polymeric deposition aid at a level of from 0. 01 to 2% by total weight of the composition, wherein the powder of botanical origin has a particle size of from 0. 1 to 100 [mu]m, preferably from 0. 5 to 50 and most preferably from 1 to 45 [mu]m.
Description
Technical field
The present invention relates to comprise the clean fabric compsn of plant origin micro mist.
Background technology
The fabric softness of using clay particle to give from washing or cleaning is known in the art.Similarly, the purposes of the nano particle of silicon-dioxide or titanium oxide and micro-encapsulated fragrance particle fully openly has been used for enhanced perfume compound effect.
US2003/0087788 (Rhodia Inc) but open water discrete particles; The hydrophobicity spices that comprises the drop form, said hydrophobicity spices are finely dispersed in can be for sealing in the water-soluble/dispersible solid organic substrate of the polypeptide in plant or synthetic source (for example soybean or wheat) and by it.
EP0908171 (Gem Energy Industry Ltd) discloses a kind of dry powder herbal medicine cleaning compsns, comprises (a) herbal medicine as soap or washing composition; (b) as the herbal medicine of foaming promotor; (c) as the herbal medicine of pore forming material; (d) as the herbal medicine of painted or color restoration or maintaniing agent; (e) as the herbal medicine of amendment.
WO00/77153 (Unilever plc) discloses a kind of detergent tablet, comprises the particle that (a) contains organic surface active agent and detergent builder compound; But (b) the water-insoluble water-swellable particle of vegetable material, it comprises Mierocrystalline cellulose and xylogen, and Root-bark of Coconut for example can be through obtaining broken the entering in the liquid dispersion of vegetable material on the basis of not separating its fiber.
We have now found that the micronised powder of plant origin can be deposited on the fabric by the washing cleaning products, gives fabric beneficial agent or new fragrant enhancement.The instance of this powder comprises the ginger that is used for spices; Be used for pure and fresh bitter orange, lemon or orange; The petal that is used for perfume compound; Leafing agent, for example oat benevolence powder, rice or bran powder; The pigment that is used for the various natural origins of anti-inflammatory benefit, for example curcuma powder; The seed that is used for perfume compound, for example Elettaria cardamomum (L.) Maton and coriandrum; The various dried herbs that are used for perfume compound and antimicrobial benefit, for example peppermint, wild marjoram, green tea, Folium Lauri nobilis and tea tree.
Summary of the invention
Aspect first, the present invention provides a kind of clean fabric compsn that is used for washing step, comprising:
A) at least a AS,
B) at least a nonionogenic tenside,
C) powder of plant origin and
D) 0.01 of composition total weight to 2% polymer deposition auxiliary agent,
Wherein the powder of plant origin has 0.1 to 100 μ m, preferred 0.5 to 50 μ m and the granularity of 1 to 45 μ m most preferably.
Aspect second of the present invention, a kind of method of handling fabric is provided, comprise and using like each step at the compositions-treated textile article of preceding claim definition.
In yet another aspect, the present invention provides a kind of textile article that comprises the plant microparticle, by the treatment process generation of second aspect of the present invention.
In another aspect of the present invention, a kind of preparation method for compositions is provided, comprise powder efflorescence to 0.1 with plant origin to 100 microns, preferred 0.2 to 90 micron, more preferably 0.5 to 60 micron, more preferably 1 to 45 micron and 2 to 30 microns granularity most preferably.
Detailed Description Of The Invention
The powder of plant origin
The present invention requires the purposes of ultrafine powder.The powder that is suitable for the present composition is the sl. sol. of plant origin, preferred insoluble grainy texture thing.They are fragrance preferably, and to preferably include one or more fragrant sesame oil smart.
Powder of the present invention can have Any shape, and may not be spheric, can have the long-width ratio (ratio of length over diameter) greater than 1.In context of the present invention, micronization, ultra-fine or finely divided expression granularity have 0.1 to 100 micron, and preferred 0.2 to 90 micron, more preferably 0.5 to 60 micron, more preferably 1 to 45 micron and 2 to 30 microns greatest axis most preferably.
The particle of suitable dimension can be through any suitable method, for example efflorescence, acquisition such as mill.Classification for example through screening, can be used to separate required size range.
Powder is a vegetable-derived materials; And can be derived from any part of plant, for example stem tuber, fruit, flower, flower part (calyx, stamen etc.), seed, bean or pea, beanpod, pith, bark, bar, stem, blade, root, rhizome, shell, crust, pericarp and composition thereof.
The instance of fragrance powder comprises the vanilla bean powder; The ginger powder; Cortex Cinnamomi powder; Cocoa powder; Ground Cloves; The Elettaria cardamomum (L.) Maton powder; The coriandrum powder; The cumin powder; The Carum carvi powder; The dill powder; Red chilly powder; The cyanine powder; Curcuma powder; Coffee bean powder; Tea leaf powder; The tea tree powder; The blackberry leaf powder; Monarda citriodora leaf powder; Herbal medicine powder (Rosmarinus officinalis for example; Thymus vulgaris; Laurus nobilis; Sage; Tarragon; Peppermint; Sweet basil; Herba Melissae officinalis; Verbena; Red Citrus bergamia; Marjoram; True lavender and wild marjoram); The Phytoconcentrol Chamomile powder; Fennel powder; The sour orange peel powder; The lemon fruit peel powder; The natsudaidai fruit peel powder; The red tangerine fruit peel powder; The tangerine fruit peel powder; The lemon grass meal; The apple ground-slag; Lemon endeavor river pear powder; The red clover grass meal; Licorice powder and composition thereof.
Preferred non-fragrant powder comprises ginseng powder, powdered rice hulls, Testa Tritici powder, Buckwheat shell powder and composition thereof.
Powdered material can be crude form, or can be produced by the method for for example aging, fermentation and roasting, and said method can increase or change the formation aromachemicals.
Through the washing cleaning product this powder delivery is loaded onto to the fabric kimonos and can be given a large amount of benefits that otherwise will be difficult to use conveying by washing.These comprise that persistent fragrance and pure and fresh, anti-microbial activity, deodorant activities, skin anti-aging and comfortable (well-being) are active, change fabric sense of touch (feel), nice and cool benefit and warm benefit.
Plant powder of the present invention can be to introduce in the cleaning composition with mode like other powderised constituent class.
The powder of plant origin is with 0.1 to 10 wt% of whole compsns, preferred 0.3 to 6 wt%, more preferably 0.4 to 4 wt% and most preferably the amount of 0.5 to 3 wt% exist.
The powder that is suitable for the plant origin among the present invention is not to extract or material separate, polymkeric substance for example, and for example xylogen, starch or protein, but be in the plant part of the powderised of its bulk state.This powder does not hope to comprise Mierocrystalline cellulose or derivatived cellulose, for example polymer derivant, for example ether of cellulose.Plant part (being preparatory powderised) and powder do not experience for example chemical purification, with the component (but undoubtedly, can being washed or cleaning) of removing xylogen for example or pigment.
The polymer deposition auxiliary agent
Micropowder is deposited on the base material and can be realized through any suitable way by washing prescription of the present invention.
For example, through filtering, wherein the granularity of powder makes particle be intercepted between the fabric fibre.Filtration mechanism need particle or the group of primary granule have with yarn between the size compared of aperture.
Be suitable for filtering granularity and be generally 1 to 30 micron.It is visible that bigger particle begins naked eyes, and the smaller particles removal of tending to be in the suds.About 5 to 15 microns particle is preferred, and is invisible and show through filtering and deposit on the fabric well because they tend to naked eyes.
Micropowder is realized through the polymkeric substance assistant depositing by washing prescription deposition of the present invention and enhancing surpasses the conveying based on filtration method.The polymer deposition auxiliary agent is with 0.0001 to 2% of composition total weight, and is preferred 0.0002 to 1.0%, more preferably 0.0005 to 0.5% and most preferably 0.0005 to 0.05% level suitably exist.
Be suitable for polymer deposition agent of the present invention and comprise the natural polymer and the synthetic polymer of modification.
The polymkeric substance that is suitable for depositing micropowder is open in WO9709406, particularly high MW polyethylene oxide (PEO), and it is used at main washing sedimentary clay particle; EP0299575B1 and WO9527037 disclose high MW PEO, polyacrylic ester, SEPIGEL 305, Z 150PH and polymine, and it is used at main washing sedimentary clay particle; Use similar polymkeric substance tabulation and guar gum with EP0387426B1.
WO 01/07546 A1 openly is used for the suitable wash phase polymer deposition auxiliary agent of emulsion drop, comprises cation guar gum polymkeric substance, cationic polyacrylamide, cationic potato starch and cationic cellulose derivative.
The natural polymer that is suitable for preferred modification of the present invention can be selected from cationic starch, cation guar gum, cationic cellulose and nonionic Viscogum BE (LBG).Preferred cation starch is cation-modified yam starch.
The suitable example of cationic polymers comprises the cation guar gum polymkeric substance; Jaguar (available from Rhone Poulenc) for example, cationic cellulose derivative, for example Celquats (available from National Starch); Flocaid (available from National Starch); Cationic potato starch, for example SoftGel (available from Aralose) and cationic polyacrylamide, for example PCG (available from Allied Colloids).
Suitable nonionic deposition aid comprises high molecular weight polyethylene glycol, for example PEO WSRN 750 (available from Union Carbide).
As the preferred synthetic polymer of deposition aid can be selected from polyethylene oxide (PEO), polymine (PEI), gather (propenoate), gather (acrylic amide), polyethylene terephthalate-polyoxyethylene terephthalate (PET/POET) polymkeric substance and composition thereof.
Negatively charged ion and nonionogenic tenside
Compsn of the present invention comprises at least a AS and at least a nonionogenic tenside.
Compsn of the present invention comprises at least a AS.
Instance comprises sulfonated alkylbenzene, and for example linear alkylbenzene sulfonate particularly has C
8-C
15The linear alkylbenzene sulfonate of alkyl chain length.Preferably the level of linear alkylbenzene sulfonate is 0 wt% to 30 wt%, and more preferably 1 wt% to 25 wt% most preferably is 2 wt% to 15 wt%.
Compsn of the present invention can be to comprise other AS for the additional amount of above-mentioned per-cent.Suitable AS is well known to a person skilled in the art.Instance comprises primary and secondary alkyl-sulphate, particularly C
8-C
20Primary alkyl sulphates; Sulfated alkyl ether; Ethylenic sulfonate; Alkylxylene sulfonate; Dialkyl sulfosuccinates; And fatty sulfonate.Sodium salt is normally preferred.
Compsn of the present invention also comprises at least a nonionogenic tenside.Operable ionic surfactant pack is drawn together the primary and secondary alcohol ethoxylate, and particularly every mol of alcohol is with the C of average 1 to 20 moles of ethylene oxide ethoxylation
8-C
20Fatty alcohol, and be more especially every mol of alcohol, with the C of average 1 to 10 moles of ethylene oxide ethoxylation
10-C
15The primary and secondary fatty alcohol.The ionic surfactant pack of non-ethoxylatedization is drawn together alkyl poly glucoside, glycerol monoethers, and polyhydroxy amides (glucamide).
Preferably the level of nonionogenic tenside is 0.5 wt% to 30 wt%, and more preferably 1 wt% to 25 wt% most preferably is 2 wt% to 15 wt%.
The clean fabric compsn
Clean fabric compsn of the present invention is suitable in washing methods, using.Said composition is preferably main washing cleaning compsns, or softening compositio in the washing.
Compsn of the present invention can be any physical form, solid for example, for example powder or particle, tablet, solid bar, slurry, gel or liquid, water fluid for example, spraying, rod, dipping base material, foam or mousse.Especially, compsn can be liquid, powder, or unitary dose, for example tablet cleaning composition.
Liquid product of the present invention can have 6 to 12 pH (for softening compositio in the fabric washing).It is stable that this pH scope preferably keeps in the preservation period of product.
Compsn of the present invention can comprise at least a other surface active cpd, is selected from soap, cats product, zwitterionics, amphoterics and composition thereof.The selection of surface active cpd (tensio-active agent) and amount will be depended on the intended purpose of detergent composition.In fabric cleaning composition, as well known to a person skilled in the art, can select the different surface active agents system according to hand washing product and the product that is intended for different washing plant types.
Many suitable tensio-active agents be can get and be documented in the document for example " Surface-Active Agents and Detergents (tensio-active agent and washing composition) ", I and II volume, Schwartz, Perry and Berch.The selection of surface active cpd (tensio-active agent) and amount will be depended on the intended purpose of detergent composition.In fabric cleaning composition, as well known to a person skilled in the art, can select the different surface active agents system according to hand washing product and the product that is intended for different washing plant types.
The total amount that exists of tensio-active agent also will depend on predetermined end-use, and for example at the compsn that is used for hand-washing fabric, can be up to 60 wt%.At the compsn of fabric that is used for machine-washing, the total amount of 5 to 40 wt% is normally suitable.Typically, said composition will comprise at least 2 wt%, for example 2-60 wt%, preferably 15-40 wt%, most preferably all surfaces promoting agent of 25-35 wt%.
The detergent composition that is suitable for the automatic fabric washing equipment of great majority contains non-soap surfactant of negatively charged ion or nonionogenic tenside usually, or both are optional with the combination of soap with any adequate rate.
Can comprise that some can be used for the monoalkyl cationic surfactant of the main cleaning composition of fabric.Operable cats product comprises general formula R
1R
2R
3R
4N
+X
-Quaternary ammonium salt, wherein the R group typically is alkyl, hydroxyalkyl or ethoxylated alkyl for long or short hydrocarbon chain, X is gegenion (R wherein for example
1Be C
8-C
22Alkyl, preferred C
8-C
10Or C
12-C
14Alkyl, R
2Be methyl, R
3And R
4Can be identical or different and be the compound of methyl or hydroxyethyl); And cationic ester (for example cholinesterase).
Operable both sexes and zwitterionics comprise alkyl amine oxide, trimethyl-glycine and sultaine.
Softening in the washing
When compsn when being the property of softening by cleaning composition, it can comprise sugared polyester or softening silicone oil.
The sugar polyester is preferably selected from sucrose polyfatty acid esters, glucose polyester and cellobiose polyester, most preferably sucrose polyfatty acid esters.
The sugar polyester can be liquid, soft solid or solid.
Be used for preferably sucrose polyester of the present invention, each sugar ring has 2 to 4 hydrocarbon chains, and wherein hydrocarbon chain has the length of 12 to 22 carbon atoms.Preferred especially sucrose polyfatty acid esters is sucrose four eruciate.
The Ryoto Sugar Ester ER290 of the instance of preferred sucrose polyfatty acid esters for providing by Mitsubishi Kagaku Foods Corporation; It is sucrose four eruciate; With specification sheets, be mainly four eruciate, five eruciate and six eruciate and have 2 HLB value according to producer.
The sugar polyester can be pure, maybe can comprise impurity.When existing, impurity is preferably selected from free fatty acids, fatty acid methyl ester, soap, inorganic salt and composition thereof.
Most preferred SPE is commercially available, Emanon SCR-PK (available from KAO) for example, and it is palm-kernel deutero-SPE, mainly comprises C
12-C
14, have about 20% C
18Single degree of unsaturation, and SPE-THSBO (available from Clariant), it mainly has C derived from the contact hardening VT 18
16-C
18Chain has about 80% single and two degrees of unsaturation.The average esterification degree of above-mentioned preferred SPE is 4.2 to 4.7.
SCR-PK comprises 20% impurity at the most, and SPE-THSBO is pure.SCR-PK comprises the K soap of 4 to 6 wt%, the free fatty acids of 2.5 wt%, the fatty acid methyl ester of 10 to 15 wt% be lower than 1% KCl.
The sugar polyester is a nonionic oil, needs emulsifying agent, and promptly sugared polyester is necessary for the emulsification form.Emulsifying agent is preferably selected from cats product, AS, nonionogenic tenside and composition thereof.
In addition, ultra-fine grain of the present invention itself can be used as non-ionic softener, the stablizer and the emulsifying agent of for example sugared polyester (SPE).Paid close attention to the research (Binks, B. P. Current Opinions in Colloid Interface Science (the up-to-date viewpoint of colloidal interface science), 2002,7,21) of solid particulate recently once more as emulsifying agent.
Latest activity about the surfactivity colloidal solid has concentrated on extremely low long-width ratio (sphere) particle.Only nearest, people such as Alargova, Langmuir, 2006,22,765-774 has proved that the high-aspect-ratio particle can be used for emulsion-stabilizingization.
When as main laundering of textile fabrics cleaning composition, compsn of the present invention also will comprise one or more washing assistants usually.The total amount of washing assistant in compsn will be 0 to 80 wt% usually, be preferably 0 to 60 wt%.
The inorganic builders that can exist comprises yellow soda ash, if desired, combines with the crystallization seed that is used for lime carbonate, and is disclosed like GB 1 437 950 (Unilever); Crystallization and amorphous aluminosilicate; Zeolite for example; As disclosed among the GB 1 473 201 (Henkel), amorphous aluminosilicate is as disclosed among the GB 1 473 202 (Henkel); With blended crystallization/amorphous aluminosilicate, as disclosed among the GB 1 470 250 (Procter & Gamble); And layered silicate, as disclosed among EP 164 514B (Hoechst).Inorganic phosphate builders, for example sodium orthophosphate, trisodium phosphate and tripoly phosphate sodium STPP also are suitable for the present invention.
The aluminosilicate washing assistant of compsn preferred package alkali metal containing of the present invention, preferred sodium.Sodium aluminium silicate usually can be with 5 to 60wt% (anhydrous bases), and preferred 10 to 50 wt%, the particularly amount of 25 to 50 wt% introduce.
Alkali metal aluminosilicate can have general formula: 0.8-1.5 Na for crystallization or unbodied or its mixture
2O.Al
2O
3.0.8-6 SiO
2These materials comprise certain combination water, and need have the calcium ion exchange capacity of at least 50 mg CaO/g.Preferred sodium aluminium silicate (in above structural formula) comprises 1.5-3.5 SiO
2The unit.Amorphous and crystalline material can easily prepare through the reaction between water glass and the sodium aluminate, like what describe in detail in the document.Suitable crystalline aluminium water glass IX washing assistant is for example described in GB 1 429 143 (Procter & Gamble).This type of preferred sodium aluminium silicate is known commercially available zeolite A and X and composition thereof.
Zeolite can be for being widely used in the commercially available zeolite 4A in the cloth-washing detergent powder now.In another embodiment of the invention, the zeolite builders of introducing the present composition is maximum aluminium zeolite P (zeolite MAP), like what describe among EP 384 070A (Unilever) and ask for protection.Zeolite MAP is defined as silicon/aluminum ratio and is no more than 1.33, is preferably the alkali metal aluminosilicate of 0.90 to 1.33 and more preferably 0.90 to 1.20 zeolite P type.
Under the situation of zeolite MAP, silicon is no more than 1.07 to aluminum ratio, and more preferably about 1.00 zeolite MAP is preferred especially.The calcium-binding capacity of zeolite MAP is generally every g anhydrous material at least 150 mg CaO.
Zeolite can be replenished by other inorganic builders, and for example amorphous aluminosilicate or layered silicate are for example available from the SKS-6 of Clariant.
Zeolite can be replenished by organic washing-assisting detergent.The organic washing-assisting detergent that can exist comprises polycarboxylate polymer, for example polyacrylate, vinylformic acid/maleic acid and vinylformic acid phosphinate; The monomer multi-carboxylate, like Citrate trianion, glyconate; Oxygen base disuccinate, the glycerine list-, two-and three SUMATRIPTAN SUCCINATEs, carboxyl methoxy succinate; Carboxyl methyl oxygen propylmalonic acid salt; Two VPP salt (dipicolinates), hydroxyethyliminodia,etates, alkyl-and alkenyl malonate and SUMATRIPTAN SUCCINATE; With the alpha-sulfonated fatty hydrochlorate.This tabulation is not intended exhaustive.
Preferred especially organic washing-assisting detergent is a Citrate trianion, and it is with 1 to 30 wt%, preferred 5 to 30 wt%, and more preferably the amount of 10 to 25 wt% is suitably used; And XPA, being more especially vinylformic acid/maleic acid, it is with 0.5 to 15 wt%, and the amount of preferred 1 to 10 wt% is suitably used.
Inorganic and organic washing-assisting detergent are preferably with an alkali metal salt, and particularly the form of sodium salt exists.
Washing assistant is suitably with 10 to 80 wt%, and more preferably the total amount of 20 to 60 wt% exists.Washing assistant can be inorganic or organic.
The washing assistant that is selected from zeolite, phosphoric acid salt and Citrate trianion (b) that helps cleaning composition can most preferably comprise 10 to 80 wt% of the present invention.
Laundry detergent composition will comprise other detergent ingredients as known in the art usually.These can suitably be selected from bleach additive composition, enzyme, yellow soda ash, water glass, sodium sulfate, Foam Control, profoamer, perfume compound, fabric conditioner, dirt polymer-stripping, dye transfer inhibitor, light stripping agent, fluorescent agent and colored particulate (speckle).Compsn of the present invention also can suitably contain bleach systems.Fabric cleaning composition can comprise the peroxy bleaching agent compound that can in the aqueous solution, produce hydrogen peroxide, for example inorganic persalt or organic peroxide acid ideally.
Suitable peroxy bleaching agent compound comprises organo-peroxide, for example urea peroxide, and inorganic persalt, for example alkali metal perborate, percarbonate, perphosphate, persilicate and persulphate.Preferred inorganic persalt is Sodium peroxoborate monohydrate and tetrahydrate, and SPC-D.
Particularly preferably be the SPC-D of protective coating with the stabilization removal effect that can resist moisture.SPC-D with the protective coating that comprises sodium metaborate and water glass has been disclosed among GB 2 123 044B (Kao).
Peroxy bleaching agent compound is suitably with 0.1 to 35 wt%, and the amount of preferred 0.5 to 25 wt% exists.Peroxy bleaching agent compound can be used in combination with SYNTHETIC OPTICAL WHITNER promoting agent (bleach precursor) to improve the bleaching action under the low wash temperature.Bleach precursor is suitably with 0.1 to 8 wt%, and the amount of preferred 0.5 to 5 wt% exists.
Preferred bleach precursor is a peroxycarboxylic acid precursors, is more particularly peracetic acid precursors and crosses the n-nonanoic acid precursor.Being suitable for preferred especially bleach precursor of the present invention is N, N, N', N' ,-tetra acetyl ethylene diamine (TAED) and acyloxy Supragil GN in the ninth of the ten Heavenly Stems (SNOBS).Disclosed novel quaternary ammonium and phosphorus
bleach precursor among focus attentions equally on US 4 751 015 and US 4 818 426 (Lever Brothers Company) and EP 402 971 A (Unilever), and disclosed cationic bleach agent precursor among EP 284 292A and EP 303 520A (Kao).
Bleach systems can replenish or substitute with peroxy acid, and the instance of this peracid can find in US 4 686 063 and US 5 397 501 (Unilever).Preferred examples is the imidopercarboxylic acids of the peracid of description among EP A 325 288, EP A 349 940, DE 382 3172 and the EP 325 289.Special preferred examples is that phthaloyl imino is crossed oxy hexanoic acid (PAP).This peracid is suitably with 0.1 to 12%, and preferred 0.5 to 10% exists.
Bleach-stable agent (polyvalent transition metal sequestrant) also can exist.Suitable bleach-stable agent comprises ethylenediamine tetraacetic-acetate (EDTA), diethylentriamine pentacetate (DTPA); Polyphosphonate; For example Dequest (trade mark), ethylenediamine tetramethylene phosphonic acid salt (EDTMP) and diethylenetriamine pentamethylene phosphate (DETPMP) and nonphosphate stablizer, for example EDDS (quadrol two succinates).These bleach-stable agent can be used for decontamination equally, when comprising low-level SYNTHETIC OPTICAL WHITNER material or not having in the product of SYNTHETIC OPTICAL WHITNER material.
Preferred especially bleach systems comprises peroxy bleaching agent compound (preferred SPC-D; Optional with the SYNTHETIC OPTICAL WHITNER promoting agent); With transition metal bleach agent catalyzer, like what describe among EP 458 397A, EP 458 398A and EP 509 787A (Unilever) and ask for protection.
Also can comprise one or more enzymes according to compsn of the present invention.Suitable enzyme comprises proteolytic enzyme, glycase, cellulase, oxydase, mistake oxygenase and the lypase that can be used for being incorporated in the detergent composition.Preferred proteolytic enzymes (proteolytic enzyme) is the catalytic activity protein material, in the time of in the textile stains in being present in hydrolysis reaction, and the albumen type of its degraded or change spot.They can belong to any suitable source, for example plant, animal, bacterium or yeast source.
Can obtain various character and source and in 4 to 12 various pH scopes, have active proteolytic ferment or proteolytic enzyme and be used for the present invention.The instance of suitable proteolytic ferment is served as reasons
B.
Subtilis B.licheniformisThe subtilyne that obtains of special strain system, for example commercially available subtilysin Maxatase (trade mark) is as being provided by Delft ,Holland Gist Brocades N.V., and Alcalase (trade mark), as being provided by Copenhagen, Denmark Novo Industri A/S.
Specially suitable proteolytic enzyme for obtaining from the strain system that in 8 to 12 pH scope, has very big active Bacillaceae, for example with registrar name of an article Esperase (trade mark) and Savinase (trade mark) available from Novo Industri A/S.These and being prepared among the GB 1 243 785 of similar enzyme are described.Other commercial protease is that (trade mark is available from West Germany Miles Kali-Chemie, Hannover) and Superase (trade mark is available from U.S. Pfizer) for Kazusase (trade mark is available from Japanese Showa-Denko), Optimase.
Detersive enzyme uses with about 0.1 to about 3.0 wt% amount with particle form usually.But can use any nonlimiting examples of suitable physical of enzyme.
Compsn of the present invention can comprise alkaline carbonate, and preferred yellow soda ash is handled so that strengthen washing and be easy to.Yellow soda ash can be suitably with 1 to 60 wt%, and the amount of preferred 2 to 40 wt% exists.But, contain hardly or not carbonated sodium compsn equally within the scope of the present invention.
Can be through introducing small quantities of powder structural agent (structurant), for example lipid acid (or fatty acid soaps), sugar, propenoate or propenoate/maleate copolymer or water glass improve flow of powder.Preferred pulvered structure agent is a fatty acid soaps, and suitably the amount with 1 to 5 wt% exists.The amount of water glass can suitably be 0.1 to 5 wt%.
Other material that may reside in the detergent composition of the present invention comprises water glass; Anti redeposition agent, for example cellulose polymer compound; The dirt polymer-stripping; Inorganic salt, for example sodium sulfate; Foam Control (lather control agent) or profoamer depend on the circumstances; Proteolyze and lipolytic enzyme; Dyestuff; Colored particulate; Perfume compound; Foam Control (foam controllers); Fluorescent agent and decoupling polymkeric substance.This tabulation is not intended exhaustive.
When in washing lotion, diluting (during typical wash(ing)cycle), detergent composition will produce 7 to 10.5 washing lotion pH usually for main washing washing composition.
Through the compatible slip to the insensitive composition of heat of spraying drying, spraying is gone up or reinforced those in back are inappropriate for the composition of handling through slip then, comes suitably to prepare granular detergent composition.To have no problem aspect the composition that experienced detergent formulation teacher should comprise and should not comprise in confirming slip.
Granular detergent composition of the present invention preferably has at least 400 g/ liters, more preferably the bulk density of at least 500 g/ liter.Special preferred compositions has at least 650 g/ liters, more preferably the bulk density of at least 700 g/ liter.
This powder can be through back tower (post-tower) densification of spray-dired powder, or through there not being the tower method fully, for example dry blend granulation prepares; Under two kinds of situation, can advantageously use high-speed mixer/tablets press.Use the method for high-speed mixer/tablets press for example open in EP 340 013A, EP 367 339A, EP 390 251 A and EP 420 317A (Unilever).
Micropowder of the present invention is very suitable for introducing in the detergent powder especially.
Can form the compsn of the component that comprises necessary concentration through mixing its necessity and optional ingredients, prepare liquid detergent composition with any desired sequence.Also can be in fine and close form according to liquid compsn of the present invention, this means with the liquid washing agent of routine and compare that it will comprise lower level water.
Fabric treatment composition of the present invention also can comprise the auxiliary agent of standard in makeup, medicine and/or the dermatological field, for example wetting ability or oleophilicity gelifying agent, wetting ability or oleophilicity promoting agent, sanitas, oxidation inhibitor, solvent, spices, filler, screening agent, sterilant, odour absorbents, light stripping agent (singlet oxygen or radical type) and dyestuff.The amount of these various auxiliary agents be in the field under consideration normally used those, and for example be 0.01 to 20% of composition total weight.The instance that is used for suitable sterilant of the present invention comprises Proxel, and (1,2-phenyl isothiazoline-3-ketone (1,2-benzisothiazolin-3-one)) can be available from for example Univar, Avecia and Uniqema; With Kathon CG (methylchloroisothiazandnone and methylisothiazolinone), available from Rhom and Haas.
Base material
When being used to wash, base material can be any base material, hopes the deposition vegetable particle above that and experiences the for example processing of washing method.
Especially, base material can be fabric, preferably includes cotton, polyester and gathers cotton.
Handle
Can be accomplished by any method with compositions-treated base material of the present invention, said method for example is washing, soak or clean base material, also can for example spray through directly applying, friction, drop, smear to wait and accomplish.
Processing can comprise makes base material contact with the aqueous medium that comprises material of the present invention.
Can with the isolating processing of home washings step of routine in, to fabric processing is provided for example to be used for the spray composition form that family expenses (or industry) use.Suitable spraying distribution device discloses in WO 96/15310 (Procter & Gamble) and is hereby incorporated by.
Compsn of the present invention can be used to during washing step for example to reduce stench for fabric provides fragrance and/or smell benefit.
Embodiment
Embodiment
Now according to following non-limiting example explanation embodiment of the present invention.Except as otherwise noted, all proportions provides with the wt% of whole compsns.
Embodiment 1: be used for the preparation of the present invention's powder
(a) centrifugal milling
Use is with the plant powder of Retsch ZM1000 ultra centrifugal mill prepared sizes in the scope of asking for protection of 10,000 rpm speed running.This runner milling is equipped with 24 tooth rotors and 0.12 mm screen cloth.
For avoiding at the heats material of milling, they before being admitted to runner milling with the dry ice blend.
(b) size classification
Use Endecotts Ltd (Britain) test screen cloth to be divided into different granularity grades then from centrifugal fine powder of milling.
The screen cloth of different orifice size is laminated to each other, and 10 g powder are placed on the top mesh, and the screen cloth lamination is placed on the Retsch AS200 sieve shaker, makes powder be divided into different granularity grades.Retsch control is set to the amplitude with 1.5 mm, shakes 5 minutes, has 10 seconds vibration interval.Take off the screen cloth lamination at interval, manual work is beaten several times.
Some scented plants powder serious coalescence that becomes during the technology of milling.This point makes that to carry out size classification unrealistic through shaking.But powder can easily be brushed screen cloth, to allow to be divided into different size ranges.
Table 1 provides two instances that are retained in the granularity grades on each screen cloth from 10 g initial powders.
Table 1: shake (ginger) and brush and smear after (Elettaria cardamomum (L.) Maton) 30 minutes the weight fraction on the screen cloth that is retained in from 10 g initial powders.
Below all, in the particle deposition experiment, use the granularity grades of＜45 μ m.
Embodiment 2: according to the detergent composition 1 to 4 that comprises herbal medicine and spices of the present invention
Table 2 shows liquid detergent formula of the present invention.All concentration are based on 100% composition.
* Aztec Spice=cacao shell 60%, Chinese cassia tree 5%, vanilla bean 20%, cloves 5%, ginger 10%.
Fruiteria=apple residue 20%, lemongrass 5%, orange peel 20%, lemon peel 20%, blackberry leaf 15%, ginger 10%, tangerine peel 10%.
Harmony=Monarda citriodora leaf 30%, Phytoconcentrol Chamomile 30%, salviae officinalis folium 20%, bitter orange 10%, lemon endeavor river pear 5%, red clover 5%.
Citrus orchid=orange peel 40%, lemon peel 20%, tangerine peel 15%, limepeel 15%, true lavender 10%.
Embodiment 3: from powder sedimentary evaluation on fabric of compsn 1 to 4
For estimating particulate deposition from washing, use Linitester, it is by the rolling of 100 ml small scales simulation automatic washing device.
Can contact front and back with fabric through measuring solution, the turbidity of washing soln or light transmission quantize the deposition level from the aromatic particulate of washing soln.Be the condition of simulation wash environment, implement following steps :-
Preparation comprises the surfactant soln of the mixture (the Synperonic A7 of 5 g in 1 premium on currency and 5.5 g in and LAS (90% activity)) of negatively charged ion and nonionogenic tenside.
Also prepare the buffer agent solution (CaHCO of 2.42 g in 1 premium on currency
3Ca with 7.55 g
2CO
3).
The complete detergent composition that is different from table 2, above-mentioned tensio-active agent/buffer agent solution keeps transparent under the dilution of simulation washing experiment, can only derive from the mensuration of the turbidity of plant powder thus.
At last, prepare three kinds of different deposited polymers, i.e. the aqueous solution of Softgel BDA, Viscogum BE (LBG) and Ucare JR-30M.These polymers solns are respectively with 0.1% and 2% preparation, and the metering proper level gets among the Linitester from these solution.
Softgel BDA (Avebe) is low for having, the cationic potato starch of 0.05% substitution value (cationic charge).Ucare polymkeric substance JR-30M (Amerchol) is for having the cationic hydroxyethyl cellulose of 1.5-2.2% substitution value.LBG (Sigma) is the Viscogum BE polysaccharide, does not have electric charge still can carry out Mierocrystalline cellulose identification (recognition).
Carry out following steps :-
1. surfactant soln (10 ml) and buffer agent solution (10 ml) are joined in the Linitester still.Then water (60 ml) is added with polymers soln and vegetable particle (0.015 g).At last, further add to add water to and amount to 100 g complete solns.
2. the Linitester temperature is set to 40 ℃.
3. (promptly before the deposition) after 5 minutes, the 5 ml samples of taking a sample are used for light transmission and measure.
4. with 20 * 20 cm
2Fabric detects thing and joins in the still.
5. make Linitester operation 20 minutes then.
6. during end of run, take out fabric, rotate and dry.
7. discharge second 5 ml sample (promptly after the deposition) and be used for the light transmission measurement.
On spectrophotometer analytical sample at the percent transmittancy of 560 nm.
Note: comprise the blank assay of surfactant soln, detection thing and polymers soln, as the blank sample of transparence measurement.In this way, can obtain more accurate deposition estimated value.
Following table 3 is summarised in Softgel BDA and exists down, from detergent washing solution＜the mint particles deposition of 45 μ m.Deposition is recently represented with the percentage of the particle total amount in the compsn.
For transmission % being converted into deposition %, according to the function acquisition calibration curve of transmission % as micro mist concentration.
Table 3: in the presence of Softgel BDA, Viscogum BE and polymkeric substance JR, mint particles cotton, gather the deposition on cotton and the polyester.
The contrast of three kinds of fabric type (zero polymkeric substance level in the washing soln) shows the deposition level that is obtained by filtration mechanism.
The result shows that plant origin particulate high level deposition can use the deposition aid polymkeric substance to be transported on the fabric by washing.
Surprisingly compare with the polymkeric substance JR that for example has about 2% electric density, it is so good that the Softgel BDA that is merely 0.05% low cationic charge density works in the anionic detergent agent solution.
Claims (15)
1. clean fabric compsn that is used for washing step, it comprises:
A) at least a AS,
B) at least a nonionogenic tenside,
C) powder of plant origin and
D) 0.0001 of composition total weight to 2% polymer deposition auxiliary agent,
Wherein the powder of plant origin has 0.1 to 100 μ m, preferred 0.5 to 50 μ m and the granularity of 1 to 45 μ m most preferably.
2. according to the compsn of claim 1, wherein the powder of plant origin is selected from stem tuber, fruit, flower, flower part (calyx, stamen etc.), seed, bean or pea, beanpod, pith, bark, bar, stem, blade, root, rhizome, shell, crust, pericarp and composition thereof.
3. according to the compsn of claim 2, wherein powder is selected from vanilla bean powder, ginger powder, Cortex Cinnamomi powder, cocoa powder, Ground Cloves, Elettaria cardamomum (L.) Maton powder, coriandrum powder, cumin powder, Carum carvi powder, dill powder, red chilly powder, cyanine powder, curcuma powder, coffee bean powder, tea leaf powder, tea tree powder, blackberry leaf powder, Monarda citriodora leaf powder, herbal medicine powder, Phytoconcentrol Chamomile powder, fennel powder, sour orange peel powder, lemon fruit peel powder, natsudaidai fruit peel powder, red tangerine fruit peel powder, tangerine fruit peel powder, lemon grass meal, apple ground-slag, lemon endeavor river pear powder, red clover grass meal, licorice powder and composition thereof.
4. according to the compsn of claim 3, its herbal medicine be selected from Rosmarinus officinalis, Thymus vulgaris, Laurus nobilis, Sage, tarragon, peppermint, sweet basil, Herba Melissae officinalis, verbena, red Citrus bergamia, marjoram, true lavender and wild marjoram.
5. according to the compsn of claim 1 or claim 2, wherein powder is selected from ginseng powder, powdered rice hulls, Testa Tritici powder, Buckwheat shell powder and composition thereof.
6. according to each compsn in preceding claim, wherein the powder of plant origin is with 0.1 to 10 wt% of whole compsns, preferred 0.3 to 5 wt%, and most preferably the amount of 0.5 to 3 wt% exists.
7. according to each compsn in preceding claim, wherein plant powder is native state, aged, slaking, fermentation or roasting.
8. according to each compsn in preceding claim, wherein the polymer deposition agent is the natural polymer or the synthetic polymer of modification.
9. according to Claim 8 compsn, wherein the natural polymer of modification is selected from cationic starch, cation guar gum, cationic cellulose and nonionic Viscogum BE (LBG).
10. according to the compsn of claim 9, wherein cationic starch is cation-modified yam starch.
11. compsn according to Claim 8, wherein synthetic polymer be selected from polyethylene oxide (PEO), polymine (PEI), gather (propenoate), gather (acrylic amide), polyethylene terephthalate-polyoxyethylene terephthalate (PET/POET) polymkeric substance and composition thereof.
12. handle the method for fabric, comprise and using like each step at the compositions-treated textile article of preceding claim definition.
13. one kind comprises the particulate textile article, by the treatment process generation of claim 12.
14. preparation comprises that like the method for compositions of each definition of claim 1 to 11 the powder efflorescence with plant origin is 0.1 to 100 μ m, preferred 0.5 to the 50 μ m and the step of the granularity of 1 to 45 μ m most preferably.
15. the purposes of fragrance and/or smell benefit is provided for fabric during washing step at the compsn of preceding claim definition like each.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP08171734.0 | 2008-12-16 | ||
| EP08171734 | 2008-12-16 | ||
| PCT/EP2009/065887 WO2010069732A1 (en) | 2008-12-16 | 2009-11-26 | Improvements relating to fabric treatment compositions |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102317426A true CN102317426A (en) | 2012-01-11 |
| CN102317426B CN102317426B (en) | 2013-11-20 |
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ID=40791408
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009801568122A Expired - Fee Related CN102317426B (en) | 2008-12-16 | 2009-11-26 | Improvements relating to fabric treatment compositions |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP2366012B1 (en) |
| CN (1) | CN102317426B (en) |
| AR (1) | AR074748A1 (en) |
| BR (1) | BRPI0922238A2 (en) |
| ES (1) | ES2415762T3 (en) |
| PL (1) | PL2366012T3 (en) |
| WO (1) | WO2010069732A1 (en) |
| ZA (1) | ZA201103930B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103266026A (en) * | 2013-05-28 | 2013-08-28 | 上海艳紫化工科技有限公司 | Lemon balm oil washing-up liquid |
| CN103451927A (en) * | 2013-08-02 | 2013-12-18 | 吴江市七都镇庙港雅迪针织制衣厂 | Anti-shrinkage antibacterial woolen sweater treatment liquid containing capric triglyceride |
| CN104178379A (en) * | 2014-08-08 | 2014-12-03 | 福州喜自然生物科技有限公司 | Natural washing product with strong oil and dirt removal capacity and preparation method of natural washing product with strong oil and dirt removal capacity |
| CN104804890A (en) * | 2014-01-25 | 2015-07-29 | 无锡市拓普科技开发中心 | Decontaminating and deoiling agent for fabric dyeing |
| CN106046916A (en) * | 2016-08-09 | 2016-10-26 | 丁玉琴 | Preparation method of gel pen ink cleanser |
| CN104245910B (en) * | 2012-04-23 | 2017-02-15 | 荷兰联合利华有限公司 | Externally structured aqueous isotropic liquid detergent compositions |
| CN104271724B (en) * | 2012-04-23 | 2017-02-15 | 荷兰联合利华有限公司 | Externally structured aqueous isotropic liquid detergent compositions |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2641479A1 (en) * | 2012-03-20 | 2013-09-25 | Rudolf Wild GmbH & Co. KG | Composition comprising an extract from sweet blackberry leaves |
| CN111778113B (en) * | 2020-07-10 | 2021-07-16 | 纳爱斯浙江科技有限公司 | Antimicrobial detergent composition |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5898026A (en) * | 1989-09-22 | 1999-04-27 | Colgate Palmolive Company | Liquid crystal compositions |
| US5840669A (en) * | 1997-06-20 | 1998-11-24 | Gem Energy Industry Limited | Herbal dry cleaning powder composition |
| EP1343866B8 (en) * | 2000-12-21 | 2009-04-08 | Unilever N.V. | Cleaning compositions |
| GB0228354D0 (en) * | 2002-12-05 | 2003-01-08 | Unilever Plc | Detergent compositions |
| MX2008014851A (en) * | 2006-06-19 | 2008-12-01 | Unilever Nv | Laundry composition. |
-
2009
- 2009-11-26 ES ES09759950T patent/ES2415762T3/en active Active
- 2009-11-26 CN CN2009801568122A patent/CN102317426B/en not_active Expired - Fee Related
- 2009-11-26 BR BRPI0922238A patent/BRPI0922238A2/en active Search and Examination
- 2009-11-26 WO PCT/EP2009/065887 patent/WO2010069732A1/en active Application Filing
- 2009-11-26 EP EP09759950A patent/EP2366012B1/en active Active
- 2009-11-26 PL PL09759950T patent/PL2366012T3/en unknown
- 2009-12-15 AR ARP090104866A patent/AR074748A1/en not_active Application Discontinuation
-
2011
- 2011-05-27 ZA ZA2011/03930A patent/ZA201103930B/en unknown
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104245910B (en) * | 2012-04-23 | 2017-02-15 | 荷兰联合利华有限公司 | Externally structured aqueous isotropic liquid detergent compositions |
| CN104271724B (en) * | 2012-04-23 | 2017-02-15 | 荷兰联合利华有限公司 | Externally structured aqueous isotropic liquid detergent compositions |
| CN103266026A (en) * | 2013-05-28 | 2013-08-28 | 上海艳紫化工科技有限公司 | Lemon balm oil washing-up liquid |
| CN103451927A (en) * | 2013-08-02 | 2013-12-18 | 吴江市七都镇庙港雅迪针织制衣厂 | Anti-shrinkage antibacterial woolen sweater treatment liquid containing capric triglyceride |
| CN104804890A (en) * | 2014-01-25 | 2015-07-29 | 无锡市拓普科技开发中心 | Decontaminating and deoiling agent for fabric dyeing |
| CN104178379A (en) * | 2014-08-08 | 2014-12-03 | 福州喜自然生物科技有限公司 | Natural washing product with strong oil and dirt removal capacity and preparation method of natural washing product with strong oil and dirt removal capacity |
| CN104178379B (en) * | 2014-08-08 | 2017-09-26 | 福州喜自然生物科技有限公司 | A kind of natural washing product of potent decontamination of deoiling and preparation method thereof |
| CN106046916A (en) * | 2016-08-09 | 2016-10-26 | 丁玉琴 | Preparation method of gel pen ink cleanser |
Also Published As
| Publication number | Publication date |
|---|---|
| BRPI0922238A2 (en) | 2016-08-09 |
| PL2366012T3 (en) | 2013-08-30 |
| ES2415762T3 (en) | 2013-07-26 |
| ZA201103930B (en) | 2012-08-29 |
| WO2010069732A1 (en) | 2010-06-24 |
| EP2366012B1 (en) | 2013-03-20 |
| AR074748A1 (en) | 2011-02-09 |
| CN102317426B (en) | 2013-11-20 |
| EP2366012A1 (en) | 2011-09-21 |
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