CN86105211A - Liquid detergent composition - Google Patents
Liquid detergent composition Download PDFInfo
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- CN86105211A CN86105211A CN198686105211A CN86105211A CN86105211A CN 86105211 A CN86105211 A CN 86105211A CN 198686105211 A CN198686105211 A CN 198686105211A CN 86105211 A CN86105211 A CN 86105211A CN 86105211 A CN86105211 A CN 86105211A
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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
- C11D3/16—Organic compounds
- C11D3/37—Polymers
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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
- C11D3/3746—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
- C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions
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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
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
Abstract
A kind of transparent or semitransparent liquid detergent composition, it at room temperature is transfusible, has anti-soil redeposition function, improved cleaning performance and regulates the effect of viscosity.It contains at least a tensio-active agent, and content is 1～60%, contains at least a water-soluble multivalent chelating agent synergistic agent, and content can reach 20%, contains a kind of promoting agent that is selected from acrylic acid homopolymer and multipolymer, and content is 0.1～2%.Described composition gross weight 100%, remaining part is water and other additives.
Description
The present invention relates to non-beneficiated or with the transparent or semitransparent liquid washing agent of water-soluble synergistic agent synergic.This class washing composition generally contains 1～60% tensio-active agent; Maximum 5% foam control agent; Maximum 10% water-soluble washing synergistic agent; 0.1～3% the promoting agent that can play effects such as antiredeposition, adjusting viscosity and raising cleaning performance; 100% remaining part is water and other composition.In a most preferred embodiment, promoting agent is a kind of polymkeric substance of water miscible or water dispersible, and it is the undersaturated lightly crosslinked lower alphatic carboxylic acid polymkeric substance of a kind of alpha-beta position olefinic, and the molecular weight under the room temperature is about 50～5,000,000.This class washing composition is effective especially for cotton fabric and cotton/polyester blend fabric.
As mentioned above, the laundry disclosed herein promoting agent that washes the agent composition by liquid the effect that can play anti-soil redeposition, regulate viscosity and improve cleaning performance.This promoting agent has been used for cleaning composition in the past, has determined that in prior art it is neutral, crosslinked polyacrylic ester, modified polyacrylic acid thickening material and sodium polyacrylate.The consumption of the open promoting agent of prior art is about 0.1～2% of a composition gross weight.
English Patent 2,079,305 have introduced the synergy liquid enzyme detergent that mainly contains enzyme, polyvalent alcohol, boric acid and neutral crosslinked polypropylene.It is introduced that polyacrylic ester is the crosslinked water-soluble acrylic polymer of linking agent (consumption is not more than 10%) that contains vinyl with a kind of.The object lesson of the polyacrylic ester of mentioning in this patent comprises Carbopol
934,940 and 941(B.F.Goodrich company product, the said firm is transferee of the present invention).According to open, the content of polyacrylic ester is 0.1～2% of detergent composition gross weight.In the liquid enzymes washing composition, adopt the result of polyvalent alcohol, boric acid and polyacrylic ester to produce stable moisture synergy liquid enzyme detergent, this washing composition not only has good storage stability, and have gratifying enzyme stability, especially all the more so under pH value condition with higher.
Non-synergy washing liquid disclosed herein is not subjected to the restriction of this English Patent, is patentable because this patent both failed call do not advise that polyacrylic ester uses with non-beneficiated liquid enzymes washing composition yet.This is the disclosed contents of 21～26 row according to this patent, and this place addresses in prior art existing people and advises adopting a certain proportion of polyvalent alcohol and boric acid.Though this patent is introduced polyacrylic ester and polyvalent alcohol and boric acid one are not used from synergy liquid body washing composition, the middle portion of this patent on page 2 the 2nd hurdle discloses the synergistic agent that also can adopt any kind of.All be applicable to the disclosed liquid enzymes washing composition of English Patent though any synergistic agent be it seems, have only aqueous solution synergistic agent just to be applicable to the washing liquid of introducing here.Be important a bit below pointing out, promptly the bottom on this patent page 2 second hurdle discloses in the liquid enzymes washing composition and also can contain other conventional material.Many various conventional materials have been listed in the there, comprise soil-suspending agent.People do not know that also polyacrylic ester can be used as soil-suspending agent when proposing this patent application (becoming English Patent later on).Prior art is at that time only recognized United States Patent (USP) 4,092, and the disclosed carboxymethyl cellulose in top, 273 the 10th hurdle and other material can be used as soil-suspending agent.Carboxymethyl cellulose is effectively to cotton fabric, but then invalid to cotton/polyester blend fabric.Be sure of to be that the applicant finds as soil-suspending agent and to be open first with polyacrylic ester and other suitable polymers disclosed herein.Therefore, the material of employing polyacrylic ester and other similarity disclosed herein is made soil-suspending agent and can be eliminated conventional soil-suspending agent.And invention disclosed herein is not the liquid washing agent that obtains to have gratifying storage stability and enzyme stability by the interaction of polyvalent alcohol, boric acid and polyacrylic ester.
United States Patent (USP) 4,147,650 have introduced the paste-like detergent that contains alkali metal hydroxide and/or silicate, condensed phosphate, clorox and sodium polyacrylate.This patent asserts that paste-like detergent is more superior than granulated detergent or liquid washing agent, because the easy conglomeration of granulated detergent, the concentration of liquid washing agent then is subjected to the restriction of the solubleness of its composition.This patent asserts that its disclosed paste-like detergent can adopt more complicated phosphoric acid salt and alkali composition, because soup compound does not require true solution.The paste-like detergent that this patent is introduced is made of more uniformly the semi-fluid composition.Sodium polyacrylate and tripoly phosphate sodium STPP play synergy to form uniform pulpous state suspension, impel all even dispersion fully.As long as the consumption of tripoly phosphate sodium STPP is no more than 30% and be not less than 5%, just can generate gratifying pulpous state suspension.If the consumption of tripoly phosphate sodium STPP surpasses 30%, the viscosity of slurry can become too big or even solidify.The minimum of tripoly phosphate sodium STPP is 5%, and the minimum dosage of polyacrylate is that 1%(all refers to dry weight).Generally, the content of polyacrylic ester can be 1～10%(moisture free weight in the detergent composition).
Liquid detergent composition disclosed herein is not subjected to United States Patent (USP) 4,147,650 restriction is patentable, because each composition is consoluet in the liquid washing agent, so liquid detergent composition is transparent or semitransparent under the situation that does not contain pigment.Can see significantly from above discussion, be not consoluet by its composition that defines the paste-like detergent composition therein, is not transparent or semitransparent therefore.In addition, though liquid washing agent described here also can contain tripoly phosphate sodium STPP, its content is subjected to the restriction of its solubleness (being at most about 10%) in water.Therefore, owing to can not contain tripoly phosphate sodium STPP in the liquid washing agent disclosed herein, also just do not have United States Patent (USP) 4,147,650 tripoly phosphate sodium STPPs that relied on and the synergy between the sodium polyacrylate illustrate that this is a kind of different washing composition.
United States Patent (USP) 4,215,004 also relates to the slurry detergent composition.Such washing composition is a Strong power synergy washing composition, goes back alkali metal containing oxyhydroxide, washing agent, sodium polyacrylate, modified polyacrylic acid and water-fast aluminosilicate ion exchange material and/or complicated phosphoric acid salt except that containing other conventional additives.
Liquid detergent composition disclosed herein is not subjected to United States Patent (USP) 4,21 yet, and 004 restriction is patentable, and its reason is not subjected to United States Patent (USP) 4,147 with explanation, and the reason of 650 restrictions is identical.The fundamental difference of liquid washing agent of the present invention and paste-like detergent mainly is liquid washing agent institute inherent feature.
United States Patent (USP) 4,092,273 and 4,368,147 all relate to liquid washing agent, and these two pieces of patents come from same parent patent application.The washing composition of these two pieces of patent disclosures, the viscosity under 24 ℃ is 40～120 centipoises, contains nonionogenic tenside, a kind of alkanol, a kind of viscosity modifier and water.In one piece of patent, viscosity modifier is water-soluble dicarboxylate, then is the combination of sodium formiate or potassium formiate and alkanol at another piece patent medium viscosity conditioning agent therein.These two pieces of patents only relate to liquid detergent composition.
Liquid washing agent disclosed herein is transparent or translucent, it is characterized in that containing water-soluble multivalent chelating agent synergistic agent and a kind of activeconstituents that can play antiredeposition, improve effects such as viscosity and raising cleaning performance.Preferably a kind of molecular weight of this activeconstituents is about 500,000～5,000,000 acrylate copolymer, and its consumption is 0.05～5% of a liquid detergent composition weight.
The present invention relates to transparent or semitransparent liquid washing agent.Why this class I liquid I washing composition has transparent or semitransparent character all is water miscible owing to its all the components and is perfect solutionization.In the general scope about 6～12 of its pH value, be preferably 8～10 ℃.Best washing composition is near neutral.The viscosity of this class washing composition under 24 ℃ is 40～200 centipoises, and is easy at room temperature pour into.This class washing composition comprises non-synergy liquid washing agent and contains the synergy liquid washing agent of water-soluble sequestering agent synergistic agent (as Citrate trianion, soap, linear polypropylene acid esters etc.).Yellow soda ash is not the sequestering agent synergistic agent.In this class washing composition, the content of tensio-active agent is 1～60% of liquid detergent composition weight, is preferably 10～40%; The content of water-soluble multivalent chelating agent synergistic agent mostly is 20% most, preferably is no more than 10%; The content that can play the promoting agent of effects such as antiredeposition, improvement viscosity and raising cleaning performance is 0.05～5%, is preferably 0.1～2%; 100% remaining part of liquid detergent composition weight is water and other conventional additives.
Known paste-like detergent is different in the character of liquid washing agent described here and the prior art.Paste-like detergent is the more uniform material that many semi-fluids become branch to form, and is not true solution.Because slurry is not a true solution, so paste-like detergent can adopt more complicated phosphoric acid salt and alkali composition, because these compositions do not need perfect solutionization.When adopting polyacrylate, polyacrylate and tri-polyphosphate play synergy, and other composition that does not have perfect solutionization is suspended in the paste-like detergent.
When the promoting agent of mentioning is used for liquid washing agent, can make the performance of washing composition be better than not containing in the prior art liquid washing agent of this class promoting agent greatly here.When adopting the promoting agent consumption of being advised here in the liquid washing agent, promoting agent just can play anti-soil dirt resedimentation and improve cleaning performance, and this is confirmed on cotton fabric and cotton/polyester blend fabric.Surprisingly, a kind of known anti redeposition agent one carboxymethyl cellulose that is applicable to cotton fabric, though be effectively to cotton fabric, invalid to cotton/polyester blend fabric.This promoting agent adds the viscosity that can regulate washing composition behind the liquid washing agent, this shows no matter how different the consumption of anion surfactant and/or nonionogenic tenside is, it is invariable that the viscosity of liquid washing agent almost keeps, and remains in 40～200 centipoise scopes that are suitable for pouring into.When changing in the consumption of anion surfactant and nonionogenic tenside and 10～35% scopes of relative proportion in the liquid washing agent gross weight, the viscosity of this class I liquid I washing composition can remain in the transfusible scope.When adopting surfactant mixture (as anion surfactant and nonionogenic tenside), both relative proportions can be 10/1～1/10, are preferably 6/1～1/6.
The consumption that is applicable to the water-soluble multivalent chelating agent synergistic agent here can reach 20% of liquid detergent composition gross weight, preferably is no more than 10%.It is condition that the consumption of the synergistic agent of mentioning here will be dissolved in composition fully with it.The water-soluble multivalent chelating agent synergistic agent is that those are by generating soluble title complex and the free ca in the cleaning system, magnesium ion concentration are reduced to the desired level synergistic agent of (being less than 5ppm lime carbonate usually) with calcium, magnesium ion.The example of this class synergistic agent comprises alkali metal citrates, particularly Trisodium Citrate; Lauric acid an alkali metal salt, particularly sodium laurate; The silicate base metal-salt; The linear polypropylene acid esters; Tetrapotassium pyrophosphate etc.Other solubleness does not reach claimed range or is not that the synergistic agent of sequestering agent also can use, but is only limited in its amount ranges that can be dissolved in liquid detergent composition.For example, tripoly phosphate sodium STPP can be dissolved in water about 10%, and tetrapotassium pyrophosphate can be dissolved into about 25% in water.Therefore, according to spirit of the present invention, the consumption of this class synergistic agent can only reach till its solubleness in liquid detergent composition.But in most preferred embodiment, suitable synergistic agent still is selected from the water-soluble multivalent chelating agent synergistic agent of introducing above.
Suitable tensio-active agent system is selected from anionic, non-ionic, cationic, zwitterionic or the amphoteric material.The consumption of tensio-active agent is 5～50 of a liquid detergent composition weight, is preferably 10～40%.Can adopt the mixture of surfactant mixture, particularly anion surfactant and nonionogenic tenside.
The example of the negatively charged ion synthetic surfactant that is suitable for has C
8～C
20Alkylbenzene sulfonate, C
8～C
22Primary alkyl or secondary alkyl sulfonate, C
8～C
24Ethylenic sulfonate carries out sulfonation and the sulfonation poly carboxylic acid that makes by the pyrolysis product of alkali earth salt, C
8～C
22Alkylsulfonate contains the nearly C of 10 moles of ethylene oxide
8～C
24Alkyl polyoxyethylene glycol sulfonate etc.Here said suitable salt is meant the ammonium salt (as monoethanolamine, diethanolamine, trolamine) of sodium salt, sylvite, ammonium salt and replacement especially.Other examples of anionic surfactants that is suitable for is seen Schwatz, " tensio-active agent and washing composition " the volume I of Perry and Berch and volume II [" Surface Active Agents and Detergents " (Vol. I and II)].
The example of nonionic synthetic detergent has oxyethane, propylene oxide and/or butylene oxide ring and C
8～C
18Alkylphenol, C
8～C
18Primary-or secondary fatty alcohol or C
8～C
18The condensation product of fatty acid amide.The example of other nonionogenic tenside comprises having a C
8～C
18Alkyl chain and two C
1-3The tertiary amine oxide of alkyl chain.Top bibliography has also been introduced many nonionogenic tensides.
The average mol of contained oxyethane and/or propylene oxide is 1～30 in the above-mentioned nonionogenic tenside; Also can adopt the mixture of various nonionogenic tensides, comprise the mixture of low and higher nonionogenic tenside of extent of alkoxylation.
The example of cationic detergent has quaternary ammonium compound, as alkyl dimethyl hydrogen fontanel ammonium, but does not wish to adopt this cationoid tensio-active agent in the enzyme detergent composition, because it can cause uncompatibility.
The example of both sexes washing agent or zwitter-ion washing agent has the N-alkyl amino acid, sultaine, and the condensation product of lipid acid and protein hydrolystate, but because cost is higher, use with teepol or nonionic washing agent usually.
Also can adopt the mixture of various active washing agents, preferably the mixture of negatively charged ion and nonionogenic tenside.Also available soap, as the ammonium salt of sodium salt, sylvite and the replacement of available polymerized fatty acid, preferably anionic and/or nonionic synthetic detergent uses with one.
Deposition capability and cleaning performance are effective especially again to the anti-soil dirt that improves cotton fabric and cotton/polyester blend fabric for above-mentioned active ingredient.In addition, activeconstituents also is effective viscosity modifier, and the viscosity of liquid detergent composition is remained unchanged basically, is in the scope of transfusible 40～200 centipoises (measuring down for 24 ℃).For the transparent liquid detergent that only adopts nonionogenic tenside, 0.1% activeconstituents can not only improve cleaning performance, and can regulate viscosity and antiredeposition.But for the liquid washing agent that only adopts anion surfactant, then need 0.5% activeconstituents not only to improve cleaning performance but also control viscosity and antiredeposition.
Here the promoting agent system that is suitable for is selected from compound agent, and the compound agent that adopt comprises commercially available polymkeric substance, as the Carbopol of BFGoodrich company supply
And other polymkeric substance with following trade name, as Acrisint
Junlon
, Rheogic
, Acrysol
, Alcoprint
, EMA
, Gaftex
And Polycarbophil
Deng polymeric material.The compound agent that wherein is specially adapted to here comprises the Carbopol615 that BFGoodrich company supplies, 676,940,941 and 1342 resins; The Acrisint 310 of Sigma chemical company supply; The Junlon PW-150 of Japan Showa Tsusho company supply and all the other products of this series; The Rheogic series product of Japan Showa Tsusho company supply; The Hiviswako 103 of Japan Wako pure chemistry industrial supply and all the other products of this series; Rohm﹠amp; The Acrysol ICS-1 and the relevant compound agent of the supply of Haas company; The Alcoprint PTF and the relevant compound agent of the supply of Britain Allied Colloids company; The EMA-91 and the relevant compound agent of the supply of Monsanto company; The Gaftex PT of GAF company supply and similar compound agent.
Compound agent is chosen from carboxylic polymkeric substance and polymeric amide usually.Preferably be selected from the homopolymer of acrylic acid homopolymer, alkyl acrylate and vinylformic acid or acrylate and the suitable multipolymer that comonomer generated or the multipolymer of vinylformic acid and acrylate.This class compound agent can be non-crosslinked or lightly crosslinked, and can distinguish that it is water miscible or water-swellable according to its functional group.The lightly crosslinked material here is can reach 10%(weight by consumption) about, to be no more than 5% for well, it is crosslinked to be preferably 0.01～2% suitable crosslinking agent.Noncrosslinking compound agent is water-soluble usually, and lightly crosslinked compound agent is swelling in water then usually, though exception is all arranged.For example, be non-crosslinked though a kind of this class compound agent is arranged, can only be in water swelling.Sometimes be difficult to distinguish water miscible and water-swellable, because some is water-soluble and water dispersible.
More particularly, be applicable to that a main class compound agent here is a polyacrylic acid, it can be that carbonatoms is the homopolymer of 3～5 alpha-beta position olefinic unsaturated monocarboxylic acid and the multipolymer of this olefinic unsaturated monocarboxylic acid and one or more suitable comonomers.It is single unsaturated monocarboxylic acid of 3～5 and be no more than 20%(and preferably be no more than 10% that the acrylic acid copolymer system is selected from one or more carbonatomss) multipolymer that one or more other copolymerisable monomers generated of weight.Be used for vinylformic acid of the present invention and preferably have following general formula:
R is selected from hydrogen, fontanel element, cyano group (C=N), univalent alkyl, monovalence aryl, monovalence aralkyl, monovalence alkaryl and monovalence alicyclic radical in the formula.The most suitable with vinylformic acid and methacrylic acid in this class compound agent, because their price is generally lower, is easy to obtain and can generates good polymkeric substance.
Suitable comonomer is selected from the alkyl acrylate of representing with following general formula,
R ' is hydrogen, methyl or ethyl in the formula; R is that carbonatoms is 10～30 alkyl, is preferably 10～20; It is 1～9 alkyl, alkoxyl group, fontanel substituted alkyl, Qing Wanji etc. that R also can be selected from carbonatoms.Typical acrylate comprises methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate, methyl methacrylate, ethylacrylic acid methyl esters, Octyl acrylate, Octyl methacrylate, the own ester of vinylformic acid (2-ethyl), methacrylic acid (just-and hexyl) ester, isodecyl methacrylate, vinylformic acid 12 (alkane) ester, vinylformic acid 18 (alkane) ester, vinylformic acid 22 (alkane) ester, vinylformic acid 30 (alkane) ester and corresponding methacrylic ester.The mixture of two kinds, three kinds or more kinds of acrylate can be successfully and a kind of carboxylic acid monomer's copolymerization.The useful multipolymer of one class is the methacrylic ester that those its alkyl contain 10～20 carbon atoms.Typical multipolymer is by 15%(weight) about isodecyl methacrylate, 10%(weight) about methacrylic acid 12 (alkane) ester and 7%(weight) about methacrylic acid 18 (alkane) ester and acrylic acid copolymer and getting.
Other vinylidene comonomer also can adopt, particularly use with acrylate, this comprises vinyl cyanide, is of great use in the interpolymer of this olefinically unsaturated nitriles in the present invention, preferably carbonatoms is 3～10 monoene unsaturated nitrile, as vinyl cyanide, methacrylonitrile etc.Best is vinyl cyanide and methacrylonitrile.For example concerning some polymkeric substance, the consumption of these comonomers is about 5～30%(weight of comonomer gross weight).
Acrylic amide comprises the monoene unsaturated amides that can join in the interpolymer of the present invention, has a hydrogen atom on the nitrogen-atoms of its acid amides at least, and two key is on the alpha-beta position of carbonyl.Preferably acrylamide and Methacrylamide, its consumption for example can be about 1～30% of comonomer gross weight.Other acrylamide also has α, and the N-alcohol amide of β ethylenically unsaturated carboxylic acids comprises that those carbonatomss are 4～10.N-alcohol amide type monomer should be used α, and β-monoene belongs to the N-alcohol amide of unsaturated monocarboxylic acid, preferably N hydroxymethyl acrylamide and N-methylol methacrylamide, its consumption for example can be 1～20%(weight) about.Also available N-alkoxymethyl acrylamide.Preferably those its alkyl contain the alkoxymethyl acrylamide of 2～5 carbon atoms, and N-butoxymethyl acrylamide is useful.
Other vinylidene comonomer generally also comprises at least a other ethylenically unsaturated monomer except top those that introduce, preferably at least a other vinylidene monomer (is to contain one in each molecule at least
The monomer of end group), consumption can reach the monomer gross weight about 30% or more than 30%.Suitable monomers comprises the alpha-olefin that contains 2-12 carbon atom, as ethene and propylene, contains the diene of 4～10 carbon atoms, divinyl for example, and vinyl ester and allyl ester are as vinyl-acetic ester; Vinyl-arene is as vinylbenzene; Vinyl and allyl ethers and ketone are as vinyl methyl ether and methyl vinyl ketone; Vinylformic acid Qing Wanji ester, as vinylformic acid (α-Qing Wanji) ester, acrylic acid α-or β-cyanogen propyl diester, vinyl fontanelle compound and vinylchlorid, vinylidene chloride etc.; Maleic acid ester and fumarate etc.
Here the polyacrylic acid of Jie Shaoing can be with containing at least two
The suitable multiple functional radical vinylidene monomer of end group (for example divinyl, isoprene, Vinylstyrene, divinyl naphthalene, allyl acrylate etc.) is crosslinked.Useful especially cross-linking monomer is the polyene-based polyether that per molecule contains an above alkene ether during preparation multipolymer.The most useful cross-linking monomer have two keys be connected alkenyl on the terminal methylene radical (
).They are got by the polyvalent alcohol etherificate that contains 4 carbon atoms and 3 hydroxyls at least at least.Product is the complex mixture with polyether of different number ethers.Analytical results is pointed out the mean number of ether on each molecule.The efficient of polyether linking agent increases along with the number of possibility polymeric base on the molecule.Wish to adopt the polyether that on average contains 2 or 2 above alkene ethers in the per molecule.Other cross-linking monomers comprise the diallyl ester, diformazan is for allyl ethers, acrylic acid allyl ester or first be for allyl ester and acrylamide, tetra allylic tin, tetrem thiazolinyl silane, polyene-based methane, diacrylate, and dimethacrylate, divinyl compound such as Vinylstyrene, phosphoric acid polyenoid propyl diester, diene propoxylation compound and phosphorous acid ester etc.Typical linking agent is the allyl group tetramethylolmethane, allyl sucrose, trimethyol propane triacrylate, diacrylate (1, the 6-hexylene glycol) ester, trimethylolpropane allyl ether, pentaerythritol triacrylate, dimethacrylate four methylene esters, diacrylate four methylene esters, glycol diacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate etc.Allyl group tetramethylolmethane, the consumption of allyl sucrose and trimethylolpropane allyl ether be below 5% of monomer gross weight, below 3%, particularly 0.1～2.0% left and right sides Shi Neng obtains fabulous polymkeric substance.
Illustrate a bit, in general, lightly crosslinked synthetic thickening agent described here can be in water swelling, the thickening material of non-crosslinked is then water-soluble.But this two classes thickening material all is applicable to the present invention.
Be suitable for polyacrylic acid homopolymer of the present invention and useful multipolymer be included in preparation in the organic solvent (particularly benzene), molecular weight is about 100,000～10,000,000 crosslinked or noncrosslinking polymkeric substance.What especially be fit to is that molecular weight is about 200,000～5,000,000 lightly crosslinked polyacrylic acid homopolymer.The polyacrylic acid homopolymer is acid, in and salify to be used for the present invention.
Other polycarboxylic acid resins are to be the resinous polymer of lightly crosslinked, the swellable of main ingredient with the carboxylic acid.These materials are to carry out polymeric in the aqueous solution of a soluble non-oxide reduction divalence mineral ion (as sal epsom).The common consumption of this salt is about 1/2nd moles.Main ingredient can be carried out homopolymerization or be carried out copolymerization with a suitable comonomer.Suitable carboxylic acid comprises that carbonatoms is 3～5 single unsaturated monocarboxylic acid or di-carboxylic acid and salt and acid anhydride.Concrete example comprises vinylformic acid and salt thereof, methacrylic acid and salt thereof, fumaric acid, toxilic acid and acid anhydride thereof, methylene-succinic acid etc.Vinylformic acid preferably.But the linking agent of how unsaturated copolymerization that constitutes the small portion of these resin Compositions contain two or more can with monomer crosslinked two keys, it can be aromatics or aliphatic series.United States Patent (USP) 2,810,716 example 1 discloses this resinoid preparation method: the mixture of the 100 gram vinylformic acid of preparation earlier, 1.2 gram Vinylstyrenes and 1.0 gram benzoyl peroxides, then this mixture is joined in the sal epsom saturated aqueous solution, and be heated to 95 ℃, obtain 100.5 gram height swollen resins after 16 minutes.This resinoid is known technically.
Also can contain other conventional materials in the liquid detergent composition of the present invention, as hydrotropic agent, inhibiter, dyestuff, spices, silicate, white dyes, foaming aids, suds suppressor (as silicone), sterilant, anti-tarnishing agent, tranquillizer, fabric softener, oxygen release SYNTHETIC OPTICAL WHITNER (as hydrogen peroxide, sodium perborate, SPC-D), band SYNTHETIC OPTICAL WHITNER parent or do not cross with two of SYNTHETIC OPTICAL WHITNER parent between benzene diformazan acid anhydride, reducing bleach (as S-WAT), buffer reagent etc.
Washing liquid is known at present.The label of the main washing liquid in the U.S. and West Europe shows that all this washing liquid is non-beneficiated or with water-soluble weak de-sludging synergistic agent (as Trisodium Citrate, sodium laurate etc.) synergic.These washing liquids also are transparent or semitransparent, and its pH value is near neutral, and transfusible viscosity is 40～200 centipoises.Usually its prescription is as follows:
Tensio-active agent 15～40%
Foam control agent 0～5%
Soluble de-sludging synergistic agent 0～10%
Viscosity modifier 2～10%
Water, spices, colorant etc. fill up 100%(weight)
Above-mentioned prescription comprises synergic and non-beneficiated washing composition, because the consumption of synergistic agent is 0～10%.Non-beneficiated washing composition does not contain the de-sludging synergistic agent certainly, and the synergy washing composition then contains water-soluble de-sludging synergistic agent, and the content of synergistic agent can reach 10%(weight).
There is not promoting agent described here in the above-mentioned prescription.When preparing liquid washing agent by invention disclosed herein, the consumption of viscosity modifier can be 0.05～5%(weight) about, be preferably 0.1～2%.Clearly, by the not only used viscosity modifier difference of washing liquid of method that the present invention introduced preparation, its consumption reduces half, and the purposes of washing liquid is wider, and usefulness is better, and is not only effective to cotton fabric, and also is effective to cotton/polyester blend fabric.Here said usefulness and deposition properties again, it is relevant to improve performances such as cleaning performance and adjusting viscosity.
Following example proves that washing liquid of the present invention has the usefulness of regulating viscosity, antiredeposition and raising cleaning performance.
The advantage that has adopted different promoting agents to speak of previously in the example below with proof.Testing used promoting agent is the Carbopol that BF Goodrich company is supplied
941 and 1342 materials.The molecular weight of these promoting agents and aqueous solution regulation are as follows:
C-941 C-1342
Molecular weight 1,250,000 1,000,000
Viscosity (centipoise)
The 0.5%(minimum) 4,000-
The 0.5%(maximum) 10,000-
The 1.0%(minimum)-10,000
The 1.0%(maximum)-30,000
Embodiment 1
The effect of bright some promoting agent of this illustration in anion surfactant and nonionogenic tenside.Test with two kinds of typical anion surfactants and three kinds of typical nonionogenic tensides.
Testing used anion surfactant is:
(a) linear alkyl benzene sulphonate adopts commercially available Conoco C-550, is Conoco chemical company (part of Conoco company) product; With
(b) alpha-olefin sodium sulfonate adopts commercially available Conco AOS-40, is the product of Continental chemical company.
Testing used nonionogenic tenside is:
(1) ethoxylated linear alcohols of modification, the HLB value is 100, adopts commercially available Plurafac RA-20, is the product of BASF Wyandotte company;
(2) the line style C of oxyethyl group
12-15Primary alconol, the HLB value is 12.0, adopts commercially available Neodol 25-7, is the product of Shell chemical company; With
(3) Nonylphenoxy multi-ethoxyl alcohol, the HLB value is 12.2, adopts commercially available Surfonic N-95, is the product of Jefferson chemical company.
Though nonionogenic tenside Plurafac RA-20 structurally is similar with Neodol 25-7, both viscosity performances have very big difference, and this may be because alkyl chain distributes and/or the ethylene oxide unit number is slightly different.
The preparation method of the liquid washing agent sample of test is as follows: the first step: prepare 1.0% Carbopol resinogen slip, and its pH value is adjusted to 8.0; Second step: the former slip of proper amt is mixed to generate desired product composition with specific tensio-active agent (pH value is adjusted to 8.0); The 3rd step: readjust to 8.0+0.5 with the pH value of 10% sodium hydroxide, with the apparent viscosity of Brabender Rheotron Bob and Cup rotational viscometer these samples of mensuration under the shearing rate of 30 ℃ and 144/ second with the gained detergent product.Promoting agent with neutralization in advance before tensio-active agent mixes, make its pH value reach 8.0.Tensio-active agent also is neutralized to pH value 8.0 in advance.The viscosity of five kinds of tensio-active agents and two kinds of promoting agents is shown in following table I:
The table I
The % anion surfactant does not have 0.5% 0.5%
C-550 Carbopol C-941 C-1342
10 2.18 59.07 159.10
15 5.12 17.32 102.10
20 22.9 62.8 80.24
25 201.71 240.72 71.94
30 664.05 597.65 96.29
35 1660.13 664.05 207.52
The % anion surfactant does not have 0.5% 0.5%
AOS-40 Carbopol C-941 C-1342
10 1.45 61.91 116.21
15 2.00 22.51 66.68
20 2.88 14.12 43.72
25 4.40 12.52 32.93
30 6.75 13.29 33.76
35 13.06 - -
The % nonionogenic tenside does not have 0.05% 0.1% 0.1%
RA-20 Carbopol C-941 C-941 C-1342
10 1.70 44.82 178.46 212.50
15 2.56 36.80 152.18 185.10
20 5.11 35.97 163.25 149.96
25 10.35 49.80 160.20 171.55
30 21.68 72.49 190.91 224.12
35 43.09 116.21 259.81 282.22
The % nonionogenic tenside does not have 0.1% 0.1%
Neodal 25-7 Carbopol C-941 C-1342
10 18.54 332.86 423.33
15 79.69 641.92 639.15
20 294.67 1037.58 1109.52
25 705.55 1541.15 1657.36
30 1245.1 - -
The % nonionogenic tenside does not have 0.05% 0.1% 0.1%
Surfonic N-95 Carbopol C-941 C-941 C-1342
10 9.28 162.69 381.00 473.14
15 30.14 234.08 558.91 581.04
20 85.77 348.63 816.23 788.56
25 215.82 558.91 965.64 1162.09
30 456.53 913.07 1577.12 1535.62
35 733.22 - - -
Above digital proof several important factors.The promoting agent consumption is the viscosity of washing composition is almost remained unchanged at 0.1～0.5% o'clock in the liquid washing agent of test, and be in the transfusible range of viscosities, even the consumption of tensio-active agent is still like this when changing in 10～35% so bigger scopes, this explanation promoting agent has the effect of tangible adjusting viscosity.The digital proof of nonionogenic tenside Plurafac RA-20, anion surfactant Conoco C-550 and anion surfactant Conoco AOS-40 this point.
This viscosity adjustment interaction energy of promoting agent makes the cost reduction of prescription be convenient to the liquid detergent composition of goods of jointization neatly.
Adopt the promoting agent that uses at present, can reduce equably along with the increase of surfactant concentration, can not obtain the effect of the such adjusting viscosity of promoting agent described here as viscosity such as ethanol, propyl alcohol, sodium formiate, potassium formiate, hexanodioic acid sodium.The effect of other viscosity modifier that uses is then opposite at present, and promptly the increase viscosity along with surfactant concentration improves equably, has played common thickening material.The example of this class viscosity modifier comprises glycerine, propylene glycol or any polyvalent alcohol.Therefore, all do not accomplish this point for these two kinds: although promptly surfactant concentrations changes viscosity and almost remains unchanged in very wide scope.
For some commercially available promoting agent, do not have the effect of regulating viscosity.This is applicable to nonionogenic tenside Neodol 25-7 and Surfonic N-95.The effect of promoting agent in these tensio-active agents is viscosity modifier, not equal to be conventional thickening material.In these examples, add 0.1% promoting agent viscosity is improved equably along with each increase of surfactant concentration.
This test card is understood another characteristics of the present invention, and promptly the consumption of Chang Gui viscosity modifier is 2～10%, and the consumption of promoting agent disclosed in this invention only is about 0.1%.Even only consider weight, its difference also is very significant.And promoting agent disclosed herein can also produce the performance of antiredeposition and improve cleaning performance, and conventional viscosity modifier then can not.
Example 2
This example proves raising cleaning or de-sludging performance and the sedimentary again effect of anti-soil dirt that some promoting agent is played in liquid detergent composition.De-sludging test is undertaken by ASTMD 3050-75 method, the standard method of this dirt amount that to be a kind of mensuration remove from the fabric of making dirty artificially.Anti-soil dirt deposition test is again undertaken by ASTMD 4008-81 method, and this is a kind of anti-soil dirt standard method of deposition properties again of measuring scouring agent.Adopt the cotton fabric and the cotton/polyester blend fabric of standard during test.Although the test method regulation adopts 0.15% detergent composition, in each test, all used 0.3% detergent composition.But in other respects, as test conditions and material all by the regulation of method.With different compositions on specific fabric the gained result shown in following table II:
The table II
First group:
Nonionic table % keeps in cotton fabric % whiteness
Detergent power cotton fabric cotton/polyester textile on the surface-active agent
Neodol does not have 0.1% and does not have 0.1% nothing 0.1%
25-7
% Carbopol C-941 Carbopol C-941 Carbopol C-941 in water
20 46.3 49.1 91.5 92.3 81.3 81.3
25 47.4 51.0 91.4 92.5 79.6 82.3
20 46.3 47.1 91.5 92.2 81.3 81.7
Second group:
Commodity
" Wisk " washing composition % joins the C-941 in " Wisk "
0 0.5% 1.0% 2.0%
Whiteness on cotton fabric keeps 96.1 96.6 98.2 98.7
The 3rd group:
Anion form % is in the degree maintenance of cotton fabric %
Detergent power cotton fabric cotton/polyester textile on the surface-active agent
Conoco does not have 0.5% 0.5% and does not have 0.5% 0.5% and do not have 0.5% 0.5%
C-550
C-941 C-1342 C-941 C-1342 C-941 C-1342 in water
%
20 3.0 3.3 3.5 92.9 92.2 92.0 75.1 79.8 80.6
The 4th group:
Anion form % is in the degree maintenance of cotton fabric %
Detergent power cotton fabric cotton/polyester textile on the surface-active agent
Conco does not have 0.5% 0.5% and does not have 0.5% 0.5% and do not have 0.5% 0.5% A
OS-40
C-941 C-1342 C-941 C-1342 C-941 C-1342 in water
%
20 25.6 26.1 25.0 93.9 92.8 93.8 85.5 86.1 86.1
Carrying out the de-sludging test is in order to measure the cleaning performance of different liqs washing composition.The whiteness of these tests and measurements soil redeposition effects keeps test quite similar.Although in the de-sludging test, adopt 1 clean cycle, keep then adopting 10 clean cycle in the test in whiteness.
Can draw from the discussion of test-results: effective deviation of de-sludging test is ± 0.5%, and it then is ± 0.2% that whiteness keeps effective deviation of test.
First group of sample of table II comprises the different concns of nonionogenic tenside Neodol 25-7 in water.When the concentration of tensio-active agent in water is 20%, the detergent power 46.3% during not with promoting agent on cotton fabric, add 0.1% Carbopol, 941 promoting agents after detergent power bring up to 49.1%.Be familiar with this professional people and can see that all difference is 2.8%, this be one very big and be serious difference.If the concentration of tensio-active agent in water is 25%, so this difference is just bigger, is 3.6%.Another test is carried out with 20% tensio-active agent, and the result is similar.
Whiteness keeps test to obtain good result.When 20% Action of Surfactant was on cotton fabric, whiteness remained 91.5% during not with promoting agent, added that whiteness keeps bringing up to 92.3% after 0.1% Carbopol, 941 promoting agents.This difference of 0.8% is crucial, and means great improvement.Whiteness maintenance at this specific examples middle cotton/polyester blend fabric also is identical.
When adopting 25% tensio-active agent, also remarkable when whiteness keeps than 20% surfactant concentration.Concerning cotton fabric, improved 1.1%, concerning cotton/polyester blend fabric, then improved 2.7%.These results are incredible, the consumption of especially considering promoting agent only be 0.1% o'clock especially like this.
Carbopol 941 promoting agents with the difference amount in second group of sample add in the washing composition " Wisk ", and measure the whiteness maintenance of cotton fabric.When the add-on of promoting agent was 0.5%, whiteness kept improving significantly, and has improved 0.5%.If the add-on of promoting agent is more, improve to such an extent that also want many.
In the 3rd group and the 4th group of sample, test on cotton fabric and cotton/polyester blend fabric with the anion active agent of two species, the result is very favourable when adding promoting agent described here.
Claims (20)
1, a kind of liquid detergent composition, it is characterized in that it is transparent or semitransparent, can at room temperature pour into, and have anti-soil redeposition function and an improved cleaning performance, said composition contains a kind of tensio-active agent at least, its content is 1～60% of composition gross weight, contain at least a water-soluble multivalent chelating agent synergistic agent, its content can reach 20% of composition gross weight, and containing the promoting agent of q.s so that said composition has anti-soil redeposition function and improved cleaning performance, it is single unsaturated monocarboxylic acid of 3～5 or di-carboxylic acid and the homopolymer of their salt that described promoting agent is selected from carbonatoms, above-mentioned single unsaturated monocarboxylic acid or di-carboxylic acid and their salt and one or more copolymerisable monomers (consumption can reach 20% (the weight)) multipolymer that is generated and the mixture of this class homopolymer and multipolymer.
2, the composition of claim 1, the content of wherein said promoting agent are 0.05～5%, and this promoting agent is water miscible.
3, the composition of claim 2, the content of wherein said tensio-active agent are 10～40%, and the content of described synergistic agent is 0～10%, and described composition can at room temperature pour into.
4, the composition of claim 3, wherein said synergistic agent are to be selected from the sequestering agent synergistic agent.
5, the composition of claim 3, wherein said synergistic agent are to be selected from Citrate trianion, soap, linear polypropylene acid esters and composition thereof.
6, the composition of claim 3, wherein said synergistic agent are to be selected from sodium laurate, Trisodium Citrate, sodium nitrilo triacetate, tetrapotassium pyrophosphate, tripoly phosphate sodium STPP and composition thereof.
7, the composition of claim 3, wherein said promoting agent system is selected from homopolymer, this acid or its salt and one or more comonomers (consumption can reach 10%(weight) of the following vinylformic acid of structure and its salt) multipolymer; With the mixture of above-mentioned homopolymer and multipolymer,
R system is selected from hydrogen, fontanel element, cyano group, alkyl, aryl, aralkyl, alkaryl and alicyclic radical in the formula.
8, the composition of claim 3, wherein said promoting agent are homopolymer, vinylformic acid or its salt and one or more the suitable comonomers (consumption can reach 10%(weight) that is selected from vinylformic acid itself or its salt) multipolymer that is generated and the mixture of above-mentioned homopolymer and multipolymer; Wherein said tensio-active agent is to be selected from anion surfactant, nonionogenic tenside and both mixtures.
9, the composition of claim 8, wherein said comonomer is selected from the acrylate of following general formula:
R ' is selected from hydrogen, methyl and ethyl in the formula; It is 10～30 alkyl and to be selected from carbonatoms be 1～9 alkyl, alkoxyl group, fontanel substituted alkyl and Qing Wanji that R is selected from carbonatoms.
10, the composition of claim 4, wherein said acid is to be selected from vinylformic acid, methacrylic acid and both mixtures; The consumption of described comonomer can reach 10%, and is to be selected from alkyl acrylate and the alkyl methacrylate that its alkyl contains 1～20 carbon atom; Described homopolymer and multipolymer can be the forms of acid or salt, and its molecular weight is 100,000～10,000,000.
11, the composition of claim 4, wherein said promoting agent are the polymkeric substance that is selected from the mixture of vinylformic acid, methacrylic acid or these two kinds of acid; Described comonomer is selected from alkyl acrylate and the alkyl methacrylate that its alkyl contains 1～20 carbon atom, and consumption can reach 10%(weight); Described homopolymer and multipolymer can be the forms of acid or salt, and its molecular weight is about 200,000～5,000,000.
12, the composition of claim 4, the content of wherein said promoting agent are 0.1～2%, and wherein said tensio-active agent is to be selected from anion surfactant, nonionogenic tenside and both mixtures.
13, the composition of claim 12, the remaining part of said composition gross weight 100% are water and other additives.
14, the composition of claim 13, wherein said promoting agent is crosslinked with little amount of crosslinking agent.
15, the composition of claim 13, wherein said promoting agent are that to be selected from the linking agent of allyl sucrose, allyl group tetramethylolmethane, trimethylolpropane allyl ether and composition thereof with 0.01～2% crosslinked.
16, the composition of claim 14, it is that 24 ℃ of following viscosity are the transfusible composition of 40～200 centipoises, wherein said synergistic agent is to be selected from sodium laurate, Trisodium Citrate, sodium nitrilo triacetate, tetrapotassium pyrophosphate, tripoly phosphate sodium STPP and composition thereof.
17, a kind of liquid detergent composition, it is transparent or semitransparent, at room temperature be transfusible, and has an anti-soil dirt deposition properties again, improved cleaning performance and viscosity adjustment performance, said composition contains at least a tensio-active agent, its content is composition gross weight 1～60%, contain at least a water-soluble multivalent chelating agent synergistic agent, its content can reach 20% of composition gross weight, and containing the promoting agent of q.s so that said composition has anti-soil redeposition function and improved cleaning performance, described promoting agent system is selected from the homopolymer that carbonatoms is 3～5 single unsaturated monocarboxylic acid or di-carboxylic acid and their salt, above-mentioned single unsaturated monocarboxylic acid or di-carboxylic acid and their salt and one or more copolymerisable monomers (consumption can reach 20%(weight)) multipolymer and the mixture of this class homopolymer and multipolymer.
18, the composition of claim 17, the content of wherein said promoting agent are 0.05～5%; The content of described tensio-active agent is 10～40%; The content of described synergistic agent is 0～10%, and described synergistic agent is to be selected from the sequestering agent synergistic agent, and molecular weight is 100,000～10,000,000.
19, the composition of claim 18, wherein said acid is to be selected from vinylformic acid, methacrylic acid and composition thereof; Described comonomer is to be selected from alkyl acrylate and the alkyl methacrylate that its alkyl contains 1～20 carbon atom; Described homopolymer and multipolymer can be the forms of acid or salt, and its molecular weight is 200,000～5,000,000.
20, the composition of claim 19, the remaining part of its 100% weight are water and other additives; Described promoting agent is crosslinked with 0.01～2% the linking agent that is selected from allyl sucrose, allyl group tetramethylolmethane, trimethylolpropane allyl ether and composition thereof.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US76633085A | 1985-08-16 | 1985-08-16 | |
| US766,330 | 1985-08-16 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN86105211A true CN86105211A (en) | 1987-04-01 |
Family
ID=25076129
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN198686105211A Pending CN86105211A (en) | 1985-08-16 | 1986-08-16 | Liquid detergent composition |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0213500A3 (en) |
| JP (1) | JPS6241296A (en) |
| KR (1) | KR870002246A (en) |
| CN (1) | CN86105211A (en) |
| CA (1) | CA1293669C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103827280A (en) * | 2011-09-20 | 2014-05-28 | 宝洁公司 | Detergent compositions comprising specific blend ratios of isoprenoid-based surfactants |
| CN104178362A (en) * | 2013-05-22 | 2014-12-03 | 江苏天恒纳米科技有限公司 | Fading-prevention liquid laundry detergent |
| 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 (33)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6460695A (en) * | 1987-08-28 | 1989-03-07 | Nippon Oils & Fats Co Ltd | Clarifier for transparent soap |
| US5368766A (en) * | 1989-05-18 | 1994-11-29 | Colgate Palmolive Co. | Linear viscoelastic aqueous liquid automatic dishwasher detergent composition |
| GB2232420A (en) * | 1989-05-30 | 1990-12-12 | Unilever Plc | Liquid detergent compositions |
| JP2796535B2 (en) * | 1990-06-01 | 1998-09-10 | ライオン株式会社 | Zeolite-containing liquid detergent composition |
| US5585340A (en) * | 1990-12-14 | 1996-12-17 | Henkel Corporation | Substantially phosphate free acidic cleaner for plastics |
| AU653570B2 (en) * | 1990-12-14 | 1994-10-06 | Henkel Corporation | Substantially phosphate free mildly acidic cleaner for plastics |
| US5409629A (en) * | 1991-07-19 | 1995-04-25 | Rohm And Haas Company | Use of acrylic acid/ethyl acrylate copolymers for enhanced clay soil removal in liquid laundry detergents |
| US5254268A (en) * | 1991-11-19 | 1993-10-19 | Rohm And Haas Company | Anti-static rinse added fabric softener |
| EP0817877A1 (en) * | 1995-03-30 | 1998-01-14 | The Procter & Gamble Company | Dry cleaning article |
| US5591236A (en) * | 1995-03-30 | 1997-01-07 | The Procter & Gamble Company | Polyacrylate emulsified water/solvent fabric cleaning compositions and methods of using same |
| US5547476A (en) * | 1995-03-30 | 1996-08-20 | The Procter & Gamble Company | Dry cleaning process |
| US5632780A (en) * | 1995-03-30 | 1997-05-27 | The Procter & Gamble Company | Dry cleaning and spot removal proces |
| US5630847A (en) * | 1995-03-30 | 1997-05-20 | The Procter & Gamble Company | Perfumable dry cleaning and spot removal process |
| US5942484A (en) * | 1995-03-30 | 1999-08-24 | The Procter & Gamble Company | Phase-stable liquid fabric refreshment composition |
| US5630848A (en) * | 1995-05-25 | 1997-05-20 | The Procter & Gamble Company | Dry cleaning process with hydroentangled carrier substrate |
| US6086634A (en) | 1995-06-05 | 2000-07-11 | Custom Cleaner, Inc. | Dry-cleaning compositions containing polysulfonic acid |
| US5658651A (en) | 1995-09-29 | 1997-08-19 | Creative Products Resource, Inc. | Fabric treatment and softener system for in-dryer use |
| AU5950696A (en) | 1995-06-05 | 1996-12-24 | Creative Products Resource, Inc. | Dry-cleaning kit for in-dryer use |
| US6036727A (en) | 1995-06-05 | 2000-03-14 | Creative Products Resource, Inc. | Anhydrous dry-cleaning compositions containing polysulfonic acid, and dry-cleaning kits for delicate fabrics |
| US5687591A (en) * | 1995-06-20 | 1997-11-18 | The Procter & Gamble Company | Spherical or polyhedral dry cleaning articles |
| US5912408A (en) * | 1995-06-20 | 1999-06-15 | The Procter & Gamble Company | Dry cleaning with enzymes |
| US5681355A (en) * | 1995-08-11 | 1997-10-28 | The Procter & Gamble Company | Heat resistant dry cleaning bag |
| US5789368A (en) * | 1996-01-26 | 1998-08-04 | The Procter & Gamble Company | Fabric care bag |
| US6233771B1 (en) | 1996-01-26 | 2001-05-22 | The Procter & Gamble Company | Stain removal device |
| US5840675A (en) * | 1996-02-28 | 1998-11-24 | The Procter And Gamble Company | Controlled released fabric care article |
| US5891197A (en) * | 1996-08-02 | 1999-04-06 | The Proctor & Gamble Company | Stain receiver for dry cleaning process |
| US5872090A (en) * | 1996-10-25 | 1999-02-16 | The Procter & Gamble Company | Stain removal with bleach |
| US5849039A (en) * | 1997-01-17 | 1998-12-15 | The Procter & Gamble Company | Spot removal process |
| US5762648A (en) * | 1997-01-17 | 1998-06-09 | The Procter & Gamble Company | Fabric treatment in venting bag |
| JP4724895B2 (en) * | 2000-02-28 | 2011-07-13 | 鈴木油脂工業株式会社 | Hand washing cleaner for paint and oil stains |
| EP2088186B1 (en) * | 2003-12-13 | 2013-07-31 | Henkel AG & Co. KGaA | Multi-component thin-to-thick system |
| DE102005026544A1 (en) | 2005-06-08 | 2006-12-14 | Henkel Kgaa | Reinforcement of cleaning performance of detergents by polymer |
| US9279097B1 (en) | 2014-08-14 | 2016-03-08 | Ecolab USA, Inc. | Polymers for industrial laundry detergents |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE615170A (en) * | 1961-03-16 | |||
| BE626321A (en) * | 1961-12-20 | |||
| US3284364A (en) * | 1963-01-25 | 1966-11-08 | American Cyanamid Co | Soil anti-redeposition agents |
| GB2006811B (en) * | 1977-10-26 | 1982-04-28 | Unilever Ltd | Soil-release compositions |
| JPS58222197A (en) * | 1982-06-16 | 1983-12-23 | 花王株式会社 | Detergent composition |
| GB8308263D0 (en) * | 1983-03-25 | 1983-05-05 | Unilever Plc | Aqueous liquid detergent composition |
-
1986
- 1986-08-14 EP EP86111241A patent/EP0213500A3/en not_active Withdrawn
- 1986-08-14 CA CA000515983A patent/CA1293669C/en not_active Expired - Fee Related
- 1986-08-15 JP JP61190687A patent/JPS6241296A/en active Pending
- 1986-08-16 KR KR1019860006746A patent/KR870002246A/en not_active Application Discontinuation
- 1986-08-16 CN CN198686105211A patent/CN86105211A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103827280A (en) * | 2011-09-20 | 2014-05-28 | 宝洁公司 | Detergent compositions comprising specific blend ratios of isoprenoid-based surfactants |
| 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 |
| CN104178362A (en) * | 2013-05-22 | 2014-12-03 | 江苏天恒纳米科技有限公司 | Fading-prevention liquid laundry detergent |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0213500A2 (en) | 1987-03-11 |
| CA1293669C (en) | 1991-12-31 |
| KR870002246A (en) | 1987-03-30 |
| JPS6241296A (en) | 1987-02-23 |
| EP0213500A3 (en) | 1989-02-01 |
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