CN102257109B - Laundry detergent composition - Google Patents
Laundry detergent composition Download PDFInfo
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- CN102257109B CN102257109B CN2009801510329A CN200980151032A CN102257109B CN 102257109 B CN102257109 B CN 102257109B CN 2009801510329 A CN2009801510329 A CN 2009801510329A CN 200980151032 A CN200980151032 A CN 200980151032A CN 102257109 B CN102257109 B CN 102257109B
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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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/86—Mixtures of anionic, cationic, and non-ionic compounds
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- Oil, Petroleum & Natural Gas (AREA)
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- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
Abstract
The present invention relates to a laundry composition comprising 0.5 to 20 wt% hydroxamate and 5 to 80 wt% of a surfactant system comprising anionic and nonionic surfactant in a ratio of from 1 :1.1 to 19:1. The composition exhibits enhanced detergency, especially in relation to particulate stains.
Description
The present invention relates in the laundry detergent composition (laundry detergent compositions) at the zeolite with lower concentration and phosphate builders use hydroxamic acid and corresponding salt thereof, cause the detersive power that improves and greasiness removal.
The improvement of greasiness removal is one of permanent object of detergent industry,, because this can cause saving the use of chemical in detergent composition, maybe can cause in lower temperature and/or with the washing of shorter time, thus conserve energy.Therefore, still exist improving clean effect, the interest of laundry detergent composition to the clean effect first (primary detergency effect) of textiles spot particularly, described textiles spot are for example particle spots (spot that for example contains dirt or clay) or based on the spot (for example grass) of plant.Especially, in laundry processes, the particle spot is difficult to remove.
Hydroxamic acid is a class chemical compound that wherein azanol is inserted in carboxylic acid.The general structure of hydroxamic acid is as follows:
R wherein
1Organic residue, alkyl or alkenyl (alkylene) group for example.Described hydroxamic acid can exist with its corresponding an alkali metal salt or hydroxamic acid salt form.
Described hydroxamate can be passed through to form with positively charged ion replacing acid hydrogen atom by corresponding hydroxamic acid (hydroxamic acid) easily:
L
+It is for example ammonium of basic metal (for example potassium, sodium) or ammonium or replacement of monovalent cation.
Known hydroxamic acid and hydroxamate can be used as metal chelator.They also are used in detergent composition to improve bleachability, and as builder material.
EP 388 389 A2 disclose the helping of SYNTHETIC OPTICAL WHITNER that do not contain of containing hydroxamic acid and their derivative and have washed not enough (under built) liquid detergent composition, and described hydroxamic acid and their derivative help to remove from fabric the wine spot that can bleach in laundry processes.Hydroxamic acid in formula 1 is disclosed, wherein R
1The optional substituted straight or branched C of representative
5-C
21Alkyl or C
5-C
21Kiki alkenyl group, or substituted phenyl group randomly, and R
2Represent hydrogen, or substituted C randomly
1-C
6Alkyl group, or substituted phenyl group randomly.At hard water (20
oDeutschland hardness, its be approximately 143 milligrams of calcium/liter) in when hydroxamate is used for detergent composition, one of embodiment presents the bleachability of improvement.Described embodiment uses C in the detergent formulations that contains anion surfactant and non-ionic surfactant mixture
12Straight chain, C
12Side chain, C
13Side chain and C
18Hydroxamate.In example I, II and IV, there is the excessive nonionogenic tenside of 1.25:1 at least, and be 100% anion surfactant in EXAMPLE III.Described liquid also contains the ethanol of 6wt% at least, and it helps to dissolve the long-chain hydroxamate.
EP 384 912 A2 disclose hydroxamic acid and their derivative through help wash, mainly be as the purposes of the stablizer of peroxy bleaching compound in granular detergent composition.The full formula detergent powder embodiment that contains the 20wt% zeolite uses C
12, C
13And C
12The side chain hydroxamate.Also used C
18
US 4,874, and 539 disclose and can be used as detergent additives especially as the polymerization carboxyl hydroxamic acid of metal ion chelation agent, and with the detergent powder of metal ion sequestrant not, compare, and what also caused improving removes the tea spot from test cloth.
US 4,863, and 636 disclose the liquid detergent composition that contains one or more cleansing surfactants and one or more N-hydroxyl imides or carboxyl hydroxamic acid detergent additives.These compounds have played the effect of active metallic ion sequestrant, have caused the greasiness removal that improves.
WO97/48786 discloses the multicomponent system that uses together with the washing composition material, and it contains oxide catalyst, suitable oxygenant, at least a amboceptor (it especially is selected from hydroxamic acid and hydroxamic acid derivs), auxiliary amboceptor (co-mediator) and at least a unhindered amina of amboceptor of each a small amount of insertion randomly.This system causes the detergent bleaching that improves function and less dielectric dissipation.
GB 1317445 discloses the detergent composition of an alkali metal salt that contains hydroxamic acid.The effect of this salt is the corrosion that prevents the copper and copper alloy that uses in the structure of washing machine.
We have been surprisingly found that now, can improve clean effect first by add specific hydroxamic acid and/or hydroxamate in specific laundry detergent composition, especially for red clay (red clay) particulate dirt.
Detergent for washing clothes needs to remove daily dirt and the spot of usually finding in wash load (wash load).Debatable two kinds of specific spots while especially washing children's clothing or motion clothing, are clay dirt spot and careless spot.The anti-especially clay of a type of removing separately by tensio-active agent is red clay, for example red clay (red pottery clay) or red Georgia clay (Red Georgia clay).It is the particulate dirt spot.
Therefore, the invention provides and comprise following laundry detergent composition:
A) 0.5 to 20 wt%, preferred 0.5 hydroxamic acid or its corresponding hydroxamate to the following structure of 6wt%:
R wherein
1Be
The C of straight or branched
4-C
20Alkyl, or
The C of the replacement of straight or branched
4-C
20Alkyl, or
The C of straight or branched
4-C
20Alkenyl, or
The C of the replacement of straight or branched
4-C
20Alkenyl, or
Alkyl ether groups CH
3(CH
2)
n(EO)
m, wherein n be 2 to 20 and m be 1 to 12, or
The alkyl ether groups CH that replaces
3(CH
2)
n(EO)
m, wherein n be 2 to 20 and m be 1 to 12, and
The type that replaces comprises following one or more :-NH
2,-OH ,-S-,-O-,-COOH and
And R
2Be selected from hydrogen and with side chain R
1Group forms the part of the part of ring texture,
B) concentration is 3 to 80wt% cleansing surfactants system; Described cleansing surfactants system contains
(i) anion surfactant; With
(ii) nonionogenic tenside
Wherein (i) is positioned at the scope of 1:1.1 to 19:1 to the ratio of (ii), and a) to b) weight ratio be positioned at the scope of 1:5 to 1:15
C) randomly, complement to other composition of 100wt%, to be zeolite and phosphate builders exist with ethanol and exist with the concentration that is less than 5wt% to be less than 5wt% condition.
Should be appreciated that, mention that carbonatoms comprises the combination chain long material, condition is within some hydroxamic acid salt materials are positioned at the scope of pointing out, and ratio is determined by any material that eliminating drops on outside the scope of pointing out with amount.
Within soap is not included in the calculating of anion surfactant amount and ratio.
Do not wish to exist ethanol fully, because it is explosion hazard during manufacture and afterwards.Owing to there being the hydroxamate of high density relatively in preparation, so if there is the tensio-active agent of high density, essential searching substitutes the hydrotropic agent system.Our preferred concentration is 6wt% at least, more preferably the hydrotropic agent system that contains propylene glycol and glycerine of 10wt% at least.By use hydroxamate and the tensio-active agent of high density in described composition, can use composition still less in each washing, this storage and transportation for the concentrate formulation that obtains has consequent benefit.This type of concentrate formulation contains 20wt% at least, preferred 30wt% at least and more preferably over the cleansing surfactants system of 40wt%.
Preferred hydroxamate is R wherein
2Hydrogen and R
1C
8To C
14Alkyl, preferred alkyl (normal alkyl), most preferably saturated those.
Described detergent composition is preferred for aqueous cleaning solution, but can contain one or more, is suitable for the solvent of home laundry purpose.Preferably, produce the greasiness removal that improves during the main washing of laundry processes, namely preferably wherein using the laundry detergent composition of described hydroxamate is main cleaning product.Described washings does not preferably contain formate.In addition, it does not preferably contain SYNTHETIC OPTICAL WHITNER, particularly peroxygen bleach.
Described composition can contain 1 to 15wt% soap.Preferred soap is by the saturated fatty acid manufacturing.
Particularly preferred composition contains the antifouling polymeric of 0.5wt% (soil release polymer) at least.This has improved the repeatedly scourability for the detergent system of removing clay.Because the very high dirt of decontamination first removal efficiency means the waste concentration that increases in washings, thereby must prevent that it is deposited on identical or different fabric portions again, it is also useful therefore containing the antiredeposition polymkeric substance of 0.5wt% at least.
Particle red clay dirt for optimum is removed, and the preferred ratio of hydroxamate and cleansing surfactants system is positioned at the scope of 1:7 to 1:13.Even preferred ratio range calculates as 1:9 by weight to 1:11.
Remove for particle red clay dirt, anion surfactant is at least 1:1 to the preferred ratio of nonionogenic tenside, more preferably 3:2 at least.Preferably, it mostly is 9:1 most.Therefore most preferred scope be 1:1 to 9:1, or 3:2 is to 9:1.
Described composition is particularly suitable for the particle spot, for example dirt and clay, especially red clay and also unexpectedly be used for grass.
The present invention also extends to hydroxamic acid or the purposes of its corresponding hydroxamate in laundry detergent composition of 0.5 to 20wt% following structure:
Wherein, R
1C
8Alkyl group, and R
2Be hydrogen atom, be used for improve and to remove the particulate dirt spot from textile substrate, it is 3 to 80wt% the cleansing surfactants system that comprises anion surfactant and nonionogenic tenside that wherein said composition further contains concentration; Randomly complement to other composition of 100wt%.
Can hydroxamate be added in described laundry detergent composition in any suitable mode in those of ordinary skills' ken.
Embodiment
In this manual, when using term " hydroxamic acid " or " hydroxamate ", unless otherwise indicated, otherwise it comprises hydroxamic acid and corresponding hydroxamate (salt of hydroxamic acid).
Unless otherwise indicated, otherwise all percentage ratios of mentioning in literary composition all based on whole composition, calculate by weight.Abbreviation " wt% " is construed as the % by weight of whole composition.
Process contaminated fabric with the laundry detergent composition that contains hydroxamate according to the present invention, and detersive power is the greasiness removal through measure of described laundry composition to spot first.This is different process from so-called use polymkeric substance antifouling, it is the processing (by washing or other this type of processing) of using polymkeric substance to carry out fabric, described fabric is contaminated subsequently, and described antifouling polymeric has the effect of more easily removing described spot.
Be suitable for chemical structure, molecule segment and substituting group to give a definition:
Unless otherwise indicated, otherwise the molecular weight of monomer and polymkeric substance represent with weight-average molecular weight.
Textiles/fabric substrate of using can be any typical textiles/fabric substrate, for example cotton (woven, knitting and denim), polyester (woven, knitting and fento), nylon, silk (silk), polyester-cotton blend (polyester/cotton blend), polyester elastane, cotton spandex fiber, gluing artificial silk (viscose rayon), acrylic acid or the like or wool.Particularly suitable textiles/fabric substrate is cotton, polyester-cotton blend and polyester base.
The particle spot is to comprise for example spot of dust, dirt, clay, mud or coal ash.They are mainly solid in essence and come in contact with fabric in the routine use of fabric.
Hydroxamic acid and derivative
The general structure of the hydroxamic acid in context of the present invention is shown in formula 3, and R
1As defined above.Work as R
1Alkyl ether groups CH
3(CH
2)
n(EO)
m, wherein n be 2 to 20 and m be 1 to 12 o'clock, so described this side group of moieties end-blocking.Preferably, R
1Select free C
4, C
5, C
6, C
7, C
8, C
9, C
10, C
11, C
12Or C
14The group that the alkyl group forms, most preferably R
1C at least
8-14The alkyl group.When using C
8During material, it is called octanohydroxamic acid.Sylvite is useful especially.
Hot hydroxamic acid K salt
But although not too preferred, other hydroxamic acid also is suitable for the present invention.This type of compound that is fit to includes but not limited to following compound:
Methionin hydroxamate * HCl
Methionine(Met) hydroxamate norvaline hydroxamate
The commercially available acquisition of this type of hydroxamic acid.
Do not wish to be limit by theory, we believe that described hydroxamate is combined and works by the metal ion that exists in the dirt with on fabric.This keying action (it is actually the known chelating ability of described hydroxamate) itself is to removing crude removal without any effect from fabric.Key is that described hydroxamate " afterbody " is described radicals R
1Reduced and passed through radicals R
2Folding any branching of getting back on amate nitrogen.Select described afterbody to have the avidity of Surfactant system.This means that the dirt removal ability of crossing already the surfactant system of optimizing is by using described hydroxamate to be further enhanced, because in fact it say into the difficulty of removing particulate matter (clay) is that described surfactant system by acting on described hydroxamic acid molecules of salt is removed " dirt ", wherein said hydroxamic acid molecules of salt is fixed on described particle by the combination of the metal ion that embeds in they and loam mould particle now.Described cleansing surfactants will adhere to described hydroxamate, cause on the whole more tensio-active agent and described fabric to interact, and cause better decontamination.Thereby described hydroxamic acid plays the effect that connects molecule, thereby promotes particulate dirt remove and be suspended to washings and improve detersive power first from fabric.
When using concentrated liquid detergent composition, compare with traditional laundry processes (pH 9-10.5) of using granular detergent composition, due to pH in laundry processes relatively low (pH 7.5-8), so this raising of the detersive power first of surfactant system is valuable especially.Well help to wash with higher pH in the laundry processes that cushions (adopt conventional through zeolite or phosphoric acid salt, help the powder-product of washing to realize) with traditional warp and compare, therefore, because the surface charge electronegativity of dirt is less, use antifouling that pH lower in the laundry processes of liquid detergent composition may cause reducing.The repellency that this surface charge of described dirt may cause the dirt Surfactant to increase, may cause the dirt that reduces to discharge.Therefore, in a preferred embodiment, described hydroxamate is used to liquid detergent composition, and in cleansing surfactants concentration described in described liquid detergent composition, is more preferably 20 to 80wt%.
Described hydroxamic acid salt pair transition metal such as iron comparison alkaline-earth metal such as calcium and magnesium have higher avidity, therefore described hydroxamic acid mainly plays the dirt that improves on fabric, the particularly effect of the removal of particulate dirt is not other washing assistant as calcium and magnesium.If helping, described laundry composition washes deficiency (underbuilt); Especially when it contained the zeolite that is less than 5wt% or phosphate builders, this was optionally useful especially.
Tensio-active agent
Wherein using the laundry detergent composition of described hydroxamate to contain concentration is 3 to 80wt% cleansing surfactants system.For the cleansing surfactants system, we refer to wherein the textile fabric that the part as laundry processes is processed, and cleaning is provided is the tensio-active agent of decontamination effect improving.Other tensio-active agent (it is not cleansing surfactants) can be as the part of described composition.
Preferably, described cleansing surfactants, more preferably exists with 10 to 50wt% concentration to 60wt% with 5.Even more preferably, described cleansing surfactants system accounts at least 20 or 30 or 40wt% even of described composition.
Usually, any tensio-active agent can be used as cleansing surfactants, comprise negatively charged ion, nonionic, positively charged ion and both sexes or zwitterionics, or these combination, there be negatively charged ion and the nonionogenic tenside of the proportional range of afore mentioned rules in condition.
Cats product can be randomly exists as the part of described cleansing surfactants.
Anion surfactant,, preferably with 1 to 40wt%, more preferably exists with 1.5 to 25wt% concentration to 50wt% with 0.1.Nonionogenic tenside is with 0.1 to 50wt%, and preferred 1 arrives 40wt%, and more preferably 1.5 to 25wt% concentration adds.Anion surfactant to the ratio of nonionogenic tenside be 19:1 to 1:1.1, more preferably 9:1 is to 1:1.
Usually, the nonionic of described surfactant system and anion surfactant can be selected from the tensio-active agent to describe Publication about Document: Schwartz﹠amp; Perry, " Surface Active Agents " Vol. 1, Interscience 1949; Schwartz, Perry ﹠amp; Berch, Interscience 1958, and Vol. 2; The existing version that Manufacturing Confectioners Company publishes " McCutcheon ' s Emulsifiers and Detergents ", or " Tenside-Taschenbuch ", H. Stache, 2
ndEdn., Carl Hauser Verlag, 1981.
Nonionogenic tenside
For purpose of the present disclosure, unless otherwise indicated, " nonionogenic tenside " should be defined as has the amphiphile, amphiphilic molecule that is less than approximately 10,000 molecular weight, and it is substantially free of any functional group that presents net charge at the normal washing pH of 6-11.
, although preferred material further has been discussed hereinafter, can use the nonionogenic tenside of any type.It is highly preferred that fatty acid alkoxylates, particularly ethoxylate, have the C of containing
8-C
35, preferred C
8-C
30, more preferably C
10-C
24, C particularly preferably
10-C
18The alkyl chain of carbon atom, for example serial from the Neodol of Shell (The Hauge, The Netherlands); The ethylene oxide/propylene oxide block polymer, it can have 1,000 to 30,000 molecular weight, for example from the Pluronic (trade mark) of BASF (Ludwigshafen, Germany); And alkylphenol ethoxylate, for example can be from the Triton X-100 of Dow Chemical (Midland, Mich., USA) acquisition.
Should think that other nonionogenic tenside also within the scope of the invention.These comprise the condenses of alkanolamine and lipid acid, for example cocamide DEA, polyol esters of fatty acids for example can be from Uniqema (Gouda, The Netherlands) Span that obtains is serial, the polyol esters of fatty acids of ethoxylation for example can be from Uniqema (Gouda, The Netherlands) Tween that obtains is serial, alkyl poly glucoside for example can be from Cognis (D ü sseldorf, Germany) the APG series that obtains and alkyl pyrrolidone are for example by ISP (wayne, N.J., the Surfadone series product of USA) selling.In addition, also can use and above do not mention especially but meet the nonionogenic tenside of definition.
Preferred nonionogenic tenside is that average degree of ethoxylation is 7 fatty acid ethoxylate, the alcoxylates with a propylene oxide and a plurality of ethylene oxide units, Ecosurf SA7 or SA9, APGs and the branched-chain alcoho Guerbet nonionogenic tenside that for example can obtain from Dow Chemical based on the tensio-active agent of seed oil.
Anion surfactant
" anion surfactant " here is defined as and contains one or more amphiphile, amphiphilic molecules that present the functional group of clean anionic charge when 6 to 11 normal washing pH is in the aqueous solution.
Preferred anion surfactant is an alkali metal salt of organosulfur reaction product, and described organosulfur reaction product has the alkyl group that contains 6 to 24 carbon atoms of having an appointment and selects free sulphonate and the group of the group that sulfate group forms in its molecular structure.
Although can use any anion surfactant described below, for example sulfated alkyl ether, soap, fatty sulfonate, alkylbenzene sulfonate, sulfosuccinate, primary alkyl sulphates, alkene sulfonate, alkane sulfonate and organophosphate; But preferred anion surfactant is following alkali and alkaline earth metal ions salt: fatty acid carboxylate salt, and aliphatic alcohol sulfate, preferred primary alkyl sulphates, more preferably they are by ethoxylation, for example sulfated alkyl ether; Alkylbenzene sulfonate, alkyl ester fatty acid sulfonate, particularly methyl ester fatty acid sulfonate and their mixture.
Positively charged ion, amphoterics and/or zwitterionics
Therein described hydroxamate is used as according to also having positively charged ion, amphoterics and/or zwitterionics in the laundry detergent composition of cosurfactant of the present invention (cosurfactant).
Preferred cats product is general formula R
1R
2R
3R
4N
+X
-Quaternary ammonium salt, R wherein for example
1C
12-C
14Alkyl group, R
2And R
3Methyl group, R
4The 2-hydroxyethyl groups, and X
-Chlorion.This material can be commercially available with the form of the 40wt% aqueous solution from Clariant GmbH with Praepagen (trade mark) HY.
In a preferred embodiment, wherein use the laundry detergent composition of described hydroxamate further to comprise both sexes or zwitterionics according to the present invention.Amphoterics is the molecule that contains acid and basic group and at the normal pH of washing of 6-11, will exist as zwitter-ion.Preferably, both sexes or zwitterionics,, more preferably with 0.25 to 15wt%, even more preferably exist with 0.5 to 10wt% concentration to 20wt% with 0.1.
The zwitterionics that is fit to is illustrated as those of the derivative that can broadly be described as aliphatic quaternary ammonium, sulfonium and phosphonium compounds, has one and contains have an appointment 8 long chain alkyl group to about 18 carbon atoms and at least one and select the water soluble group of the group of free sulfate radical, sulfonate radical, carboxylate radical, phosphate radical or phosphonate radical composition.The general formula of these compounds is:
R
1(R
2)
xY
+R
3Z
-
R wherein
1Comprise alkyl, alkenyl or hydroxyalkyl group with 8 to 18 carbon atoms, 0 to 10 ethylidene-oxygen groups or 0 to 2 glyceryl unit; Y is nitrogen, sulphur or phosphorus atom; R
2Alkyl or the hydroxyalkyl group with 1 to 3 carbon atom; X is 1 when Y is sulphur atom, and x is 2 when Y is nitrogen or phosphorus atom; R
3That to have the alkyl of 1 to 5 carbon atom or hydroxyalkyl group and Z be the group that selects the group that free sulfate radical, sulfonate radical, carboxylate radical, phosphate radical or phosphonate radical form.
Preferred amphoterics is amine oxide, for example cocoyl dimethyl amine oxide compound (coco dimethyl amine oxide).
Preferred zwitterionics is betaines, particularly the amido betaine class.Preferred trimethyl-glycine is C
8To C
18Alkylamidoalkyl alkyl betaine, for example cocamidopropyl trimethyl-glycine (coco amido betaine).Can comprise these as cosurfactant, the weight that is preferably based on whole composition is with 0 to 10wt%, more preferably with 1 to 5wt% amount, exists.Operable other trimethyl-glycine is sulphur trimethyl-glycine (sulfatobetaines), for example 3-(dodecyl dimethyl ammonium)-1-propane vitriol; And 2-(cocoyl Dimethyl Ammonium)-1-ethane vitriol.Sultaine, for example: 3-(dodecyl dimethyl-ammonium)-2-hydroxyl-1-propane sulfonate; 3-(tetradecyl-Dimethyl Ammonium)-1-propane sulfonate; 3-(C
12-C
14Alkyl-amidopropyl Dimethyl Ammonium)-2-hydroxyl-1-propane sulfonate; And 3-(cocoyl Dimethyl Ammonium)-1-propane sulfonate.Carboxybetaine, for example (dodecyl dimethyl ammonium) acetate (also referred to as lauryl betaine); (tetradecyl Dimethyl Ammonium) acetate (also referred to as the tetradecyl trimethyl-glycine); (cocoyl Dimethyl Ammonium) acetate (also referred to as coco betaine (coconut betaine)); (oil base Dimethyl Ammonium) acetate (also referred to as oil-based betaine); (dodecyloxy methyl dimethoxy base ammonium) acetate; (cocamidopropyl-propyl-dimethyl ammonium) acetate (also referred to as cocamidopropyl-CAB or CAPB).
Sulfonium trimethyl-glycine (sulfoniumbetaines), for example: (dodecyl dimethyl sulfonium) acetate; And 3-(cocoyl dimethyl-sulfonium)-1-propane sulfonate.
Phosphonium trimethyl-glycine (phosphoniumbetaines), for example 4-(San Jia Ji Phosphonium)-1-n-Hexadecane sulfonate; 3-(Shi Er Wan base Er Jia Ji Phosphonium)-1-propane sulfonate; With
2-(Shi Er Wan base Er Jia Ji Phosphonium)-1-ethane vitriol.
Described laundry detergent composition preferably contains carboxybetaine or sultaine, or their mixture is as both sexes or zwitterionics.Particularly preferably be lauryl betaine.When using together, described trimethyl-glycine and hydroxamate can provide the particulate dirt that even further improves to remove in composition according to the present invention.
Detergent builder compound
Wherein used the laundry detergent composition of described hydroxamate preferably to contain the detergent builder compound of lower concentration, based on the gross weight of whole composition.Inorganic builders zeolite and phosphatic amount are less than 5wt%.It is harmful to environment when a large amount of the use that these washing assistants are considered to.In addition, they need to use to have obvious wash-aid effect with high density, and this contradicts with new-type concentrated high weight efficiency detergent for washing clothes preparation.
Preferred described washing assistant is selected from alkali and alkaline earth metal ions carbonate (for example sodium carbonate), silicate (for example layered silicate) and organic washing-assisting detergent for example Citrate trianion (for example Trisodium Citrate), succinate, sulfamate and malonate and these any combination.Preferred described organic washing-assisting detergent.They can be with 1wt% or higher, and the concentration of the highest for example 50wt% is used.
The organic washing-assisting detergent that can exist comprises polycarboxylate polymkeric substance for example polyacrylate and vinylformic acid/maleic acid; Polyaspartic acid salts; The monomer multi-carboxylate for example Citrate trianion, gluconate, oxygen base two succinates, glycerine list-, two-and three succinates, carboxymethyl oxygen base succinate, carboxyl-methyl oxygen propylmalonic acid salt, two picoline hydrochlorates (dipicolinates), hydroxyethyliminodia,etates, alkyl-and alkenyl malonate and succinate; Soap with sulfonation.
Can use on a small quantity organic washing-assisting detergent.Particularly preferred organic washing-assisting detergent is Citrate trianion,, suitably with 1 to 30wt%, preferably with 1.5 to 10wt% amount, uses; And acrylic polymers, more particularly vinylformic acid/maleic acid,, suitably with 0.5 to 15wt%, preferably use with 1 to 10wt% amount.
No matter washing assistant, be inorganic or organically, all preferably with an alkali metal salt, particularly the form of sodium salt exists.
The composition that other is optional
The necessary component of describing in detail in claim, preparation can comprise that one or more optional compositions are to strengthen the property and characteristic.Although in order to implement these compositions of the present invention, needn't exist, using of materials helps to make described preparation to use and accepted by the human consumer usually very much.
the example of optional components comprises, but be not limited to: hydrotropic agent, white dyes, optical white, fiber lubricant, reductive agent, enzyme, enzyme stabilizers (for example borate/ester and polyvalent alcohol), powder finishing composition (powder finishing agent), defoamer, SYNTHETIC OPTICAL WHITNER, bleaching catalyst, stain control agent is especially for cotton or polyester or both antifouling polymerics, anti redeposition agent is the antiredeposition polymkeric substance particularly, dye transfer inhibitor, buffer reagent, tinting material, spices, fragrance precursor, rheology modifier, anti-grey polymkeric substance (anti-ashing polymer), sanitas, wormer, drive dirty agent, water-resisting agent, suspension agent, attractive in appearance dose (aesthetic agent), structural agent, sterilizing agent, solvent (comprising water-based and non-aqueous solvent), fabric finishing agent, laking agent, winkle removing agent (wrinkle-reducing agent), fabric conditioner and reodorant.
these optional compositions can include but not limited to following any or multiple: soap, peracid and persalt SYNTHETIC OPTICAL WHITNER, bleach-activating agent, sequestrant, ether of cellulose and ester, other anti redeposition agent, sodium sulfate, water glass, sodium-chlor, calcium chloride, sodium bicarbonate, other inorganic salt, fluorescent agent, optical white, Polyvinylpyrolidone (PVP), other dye transfer inhibiting polymers, Foam Control, profoamer, acrylic polymers and vinylformic acid/toxilic acid polymkeric substance, proteolytic enzyme, lipase, cellulase, amylase, other detergent enzymes, citric acid, antifouling polymeric, the fabric-conditioning compound, coloured speckles and perfume compound.
Described laundry detergent composition can suitably contain the bleach system based on peroxy bleaching compound, and described peroxy bleaching compound is inorganic persalt or organic peracid for example, can produce hydrogen peroxide in the aqueous solution.Suitable peroxy bleaching compound comprises for example urea peroxide of organo-peroxide, and inorganic persalt for example alkali metal perborate, percarbonate, superphosphate, persilicate and persulphate.Preferred inorganic persalt is Sodium peroxoborate monohydrate and tetrahydrate, and SPC-D.Particularly preferably be and have the SPC-D of resisting the unsettled protective coating that is caused by moisture.SPC-D with the protective coating that contains sodium metaborate and water glass is open in GB 2 123 044B (Kao).
Described peroxy bleaching compound suitably with 5 to 35wt%, preferably with 10 to 25wt% amount, exist.
Described peroxy bleaching compound can be combined with bleach-activating agent (bleach precursor) to improve the bleaching action in low wash temperature.Described bleach precursor suitably with 1 to 8wt%, preferably with 2 to 5wt% amount, exist.
Preferred bleach precursor is peroxycarboxylic acid precursors, more particularly peracetic acid precursors and peroxybenzoic acid precursors; And peroxycarbonic acid precursors.The particularly preferred bleach precursor that is fit to use in the present invention is N, N, N ', N '-tetra acetyl ethylene diamine (TAED).Allowing equally the people interested is peroxybenzoic acid precursors, N particularly, N, N-trimethyl ammonium toluene acyloxy benzene sulfonate.
Can also there is bleach-stable agent (heavy metal chelant).The bleach-stable agent that is fit to comprises for example Dequest (trade mark) of edetate (EDTA) and polyphosphonic acid salt, EDTMP.
But although top such description does not preferably contain SYNTHETIC OPTICAL WHITNER for described composition, and dependence is by the clay greasiness removal of the improvement of described novel hydroxamate and tensio-active agent combination acquisition.Especially true for liquid composition.
Described detergent composition can also contain one or more enzymes.The enzyme that is fit to comprises proteolytic enzyme, amylase, cellulase, oxydase, peroxidase and the lipase that can be used for adding in detergent composition.
In granular detergent composition, generally approximately 0.1 to the about amount of 3.0wt%, with particle form, to use detergency enzymes.But, also can use with any effective amount the enzyme of any suitable physical form.
Can also there is anti redeposition agent, for example cellulose ester and ether, for example Xylo-Mucine.
Described composition can also contain antifouling polymeric, and for example sulfonation and PET/POET polymkeric substance unsulfonated (end-blocking and not end-blocking), and polyoxyethylene glycol/polyvinyl alcohol graft copolymerized multipolymer is Sokolan (trade mark) HP22 for example.Particularly preferred antifouling polymeric is to describe in WO 95 32997A (Rhodia Chimie) and the not end capped polyesters of claimed sulfonation.
Product form and preparation
Can take any suitable form according to product of the present invention, solid, liquid or paste (paste) composition for example, for example as particle (powder, particle), sheet or bar.Preferably, described product is to have the concentrated liquid of the surfactant concentration of 30wt% at least.Such composition needs hydrotropic existence to dissolve described composition.Preferably avoid ethanol.Preferred hydrotropic agent is propylene glycol and glycerine.Based on this instruction, the technician does not need creativeness just can select other hydrotropic agent and avoids using high volatile volatile solvent such as ethanol.
According to the second embodiment of the present invention, described detergent composition is particulate forms.In described cleansing surfactants system, the ratio of anion surfactant and nonionogenic tenside preferably is at least 3:2 so, preferably 7:2 at least.
Starch (slurry) by spraying drying, and randomly mix afterwards (being dry mixed) further composition can prepare low powder to medium tap density.The approach that can be used for the powder manufacturing comprises for example scraped film evaporator of spraying drying, drum drying, fluidised bed drying and scraped film type drying plant.A kind of preferred form of scraped film type equipment is scraped film evaporator.A kind of this suitable scraped film evaporator is based on " the Dryex system " of the scraped film evaporator that can obtain from Ballestra S.p.A..Alternative equipment will be Chemithon " Turbo Tube " dryer system, and wherein high active surfactant is stuck with paste and is heated and is metered in Multi-tube steam cover drying receptacle.
By mixing and prilling process, for example use high-speed mixer/granulator or other without tower method (non-tower process), can prepare " concentrated " or " compression " powder.
, by pressed powder, particularly " concentrate " powder and can prepare tablet.
Further describe the present invention referring now to following indefiniteness embodiment.
Embodiment
The measurement of antifouling index (SRI)
SRI is measuring that on textiles, how many spots are removed during washing process.The intensity of any spot can provide Δ E* to each spot and measure with regard to the difference between spot and cleaning cloth by means of reflexometer.It is defined as Δ E* and is calculated as follows:
L*, a* and b* be CIE 1976 (
L*, a*, b*) coordinate of the color space, the Application standard reflexometer is measured.Can and measure afterwards Δ E* before the washing spot, so that Δ E* to be provided
bw(before washing) and Δ E*
aw(after washing).SRI is defined as so:
SRI 100 means that spot is completely removed.
Δ E after washing is the L ab color space difference between spot after cleaning (not washing) fabric and washing.Therefore the Δ E after the washing 0 means that spot is completely removed.Therefore, SRI
awBe 100 to be the spots of removing fully.Described cleaning (or untapped) fabric is without washing " absolute standard ".For each experiment, it refers to the pieces of fabric that is equal to the pieces of fabric that applies spot.Therefore, its point in the L a b color space remains unchanged.
Embodiment 1: the preparation of octanohydroxamic acid salt (sylvite)
(p.319-330) disclosed method prepares the sylvite of octanohydroxamic acid salt for Journal of Colloid and Interface Science, 1975, Vol.50 by Raghavan and Fuerstenau.
Embodiment 2: remove the red clay spot on knitting polyester (2:1)
The preparation washings, as shown in table 1 with shown in concentration, contain primary alkyl sulphates (PAS, anion surfactant, from Kao Emal PH10) and alcohol ethoxylate (nonionogenic tenside C as tensio-active agent
12-7EO, Neodol 25-7 is from Shell).In addition, described washings contains the NaCl that concentration is 5mM.The water hardness be 6 ℉ H (soft water, approximately 24 milligrams of calcium/liter), and water temperature is 30 ℃., owing to using soft water not need washing assistant or sequestrant, therefore to composition, do not add these compositions.
The concentration of tensio-active agent and hydroxamate in table 1 washings
Following result is to use the Tergotometer washing machine to measure and obtain following standard schedule (being called soft water Tergotometer washing rules) for remove the red clay spot from knitting polyester cloth.The red clay that uses is the potter's clay form.
Soft water Tergotometer washs rules:
1. measure the color of spot on the textiles cloth
2. set Tergotometer to 25 ℃.
3. add water and preparation liquid storage (stock solutions) in each tank, stirred 1 minute.
4. the cloth and the ballast (ballast) that add pollution, start Tergotometer.
5. made it to wash 12 minutes
6. 6
oIn French hard water, the rinsing cloth is 1 minute, repeats rinsing.
7. dry cloth spends the night.
8. measure the color of spot on described textiles cloth
The greasiness removal index (SRI) of red clay spot on the knitting polyester of table 2
This tests demonstration, and the preparation that contains octanohydroxamic acid salt causes in soft water from the significantly better red clay greasiness removal of knitting polyester., because this is experiment in soft water,, so the mechanism that described hydroxamic acid is had an effect is not as washing assistant, therefore got rid of the washing assistant effect as the mechanism of action of improving clean effect.
Embodiment 3: from knitting polyester, remove Georgia clay spot and slave brocade except the burring spot
Prepare two kinds of liquid washing agents.Concentration by appointment as shown in table 3, the tensio-active agent that uses is sodium alkyl benzene sulfonate (Na LAS, anion surfactant), alcohol ethoxylate (nonionogenic tenside C
12-7EO, Neodol 25-7 is from Shell) and the saturated soap (fatty acid distribution of coconut oil (Prifac 5908 is from Uniqema)) through neutralizing.What also use is n-compound (washing assistant (Trisodium Citrate), hydrotropic agent (5% glycerine and 9% propylene glycol), buffer reagent and sequestrant (Dequest 2066 phosphonates), the enzyme (Savinase Ultra 16L proteolytic enzyme) of laundry liquid washing agent., as listed in table 3, use respectively preparation 3 and two kinds of washingss of 4 preparations, so that the tensio-active agent shown in table 4 and hydroxamic acid salt concn to be provided.In described washings the water hardness be 26 ℉ H (medium water, approximately 104 milligrams of calcium/liter), water temperature is 40 ℃.PH is buffered to 7 to 8.
The preparation that table 3 uses
Table 4 is based on the concentration of tensio-active agent and hydroxamate in the washings of the preparation in table 3
Following result is to use Linitest
TMWashing machine is removed Georgia spot and slave brocade except the burring spot from knitting polyester cloth, by standard schedule, (is called Linitest
TMThe washing rules) measure and obtain.
Linitest
TMThe washing rules
1. read before washing spot.
2. open Linitester
TMAnd make it to be heated to 40 ℃.
3. product is dropped in tank, add water in tank.
4. put into spot, ballast and 50 balls in tank.
5. start Linitester
TMAnd made it to wash 30 minutes.
6. rinsing ballast and dress material are 5 minutes.
7. repetition rinsing.
8. dry spot is spent the night.
9. reading after washing spot.
The greasiness removal index (SRI) of grass on Georgia clay spot and knitting polyester on the knitting polyester of table 5 and woven cotton
The use that this experiment illustrates described hydroxamic acid causes the removal of the Georgia clay slave brocade of the better removal of Georgia clay on knitting polyester and grass and improvement.
Although there is Savinase (it has improved careless greasiness removal) in described detergent composition, the interpolation by described hydroxamate has further improved careless greasiness removal.
The representative instance of embodiment 4. detergent composition
Provided in table 6 according to typical detergent composition more of the present invention.
Table 6 is according to typical detergent composition of the present invention
Embodiment 5 has the hydroxamate of different alkyl chain length
Following result is to use the Tergotometer washing machine to remove Georgia clay spot from knitting cotton to measure and obtain by following standard schedule (being called Tergotometer hard water washing rules).Use different hydroxamates according to table 7.
Tergotometer hard water washing rules:
Measure the color of spot on the textiles cloth
Tergotometer is set to 30 ℃.
Add water and preparation liquid storage in each tank, stirred 1 minute.
The cloth and the ballast that add pollution, start Tergotometer.
Made it to wash 12 minutes
26
oIn French hard water, the rinsing cloth is 1 minute, repeats rinsing.
Dry cloth spends the night.
The color of the spot of measurement on described textiles cloth.
Table 7
Table 8
Table 9
Table 8 and 9 has been summed up the result on different clothes.
Embodiment 6: the impact of anion surfactant nonionogenic tenside ratio
Table 10 preparation A is to F (contrast-not containing octanohydroxamic acid salt)
Table 11 contains the preparation of octanohydroxamic acid salt
This embodiment shown with above-mentioned Tergotometer hard water washing rules and measured, change anion surfactant on the ratio of nonionogenic tenside on remove the impact of Georgia clay spot from knitting polyester.Preparation provides with the Comparative formulation that does not contain described hydroxamate and provides in table 10 in table 11.
Result is summarised in table 12.Preparation A_OH, E_OH and F_OH are contrasts.
Table 12
The ratio (slave brocade remove Georgia clay) of the anion surfactant of embodiment 7-higher to nonionogenic tenside
Prepared multiple anionic/nonionic preparation, wherein anion surfactant is at least 4:1 to the ratio of nonionogenic tenside.At first prepared one group of Comparative formulation that does not contain hydroxamate according to table 13.Then prepared one group of corresponding preparations of the octanohydroxamic acid salt that contains 5wt% according to table 14.
Table 13 (Comparative formulation)
The soap that uses is Prifac 5908.Described hydrotropic agent is glycerine and propylene glycol.
Table 14
Following result be use above-mentioned standard hard water Tergotometer washing rules measure and for every kind of preparation in table 13 and 14 with formulation concentrations in the washing of 2.6g/L, the slave brocade is removed Georgia clay spot and is obtained.Result provides in table 15.Embodiment J_OH is comparative.
Table 15
Embodiment 8: selectable anion surfactant: primary alkyl sulphates
Table 16 (Comparative formulation)
Table 17 (preparation that contains hydroxamate)
Following result in table 18 is in the suds and uses the 2.6g/L preparation to use the measurement of hard water Tergotometer washing rules to remove the acquisition of Georgia clay spot from knitting polyester.Provided in table 16 and do not contained the Comparative formulation of hydroxamate and provided the preparation that contains hydroxamate in table 17.Usually, described hydrotropic agent system contains 5wt% glycerine and 9wt% propylene glycol.Due to anion surfactant to the ratio of nonionogenic tenside outside scope required for protection, so composition N_OH and P_OH are comparative.
Table 18
Claims (24)
1. laundry detergent composition, it contains
A) hydroxamic acid of the following structure of 0.5 to 20 wt% or its corresponding hydroxamate:
R wherein
1To select free C
4, C
5, C
6, C
7, C
8, C
9, C
10, C
11, C
12Or C
14The group that alkyl forms;
And R
2For hydrogen,
B) 3 to 80wt% cleansing surfactants system, it contains
(i) anion surfactant; With
(ii) nonionogenic tenside
Wherein (i) is positioned at the scope of 1:1.1 to 19:1 to the ratio of (ii), and a) to b) weight ratio be positioned at the scope of 1:5 to 1:15
C) randomly, complement to other composition of 100wt%, condition is that zeolite and phosphate builders exist with ethanol and exist with the concentration that is less than 5wt% to be less than 5wt% respectively.
2. according to claim 1 composition, wherein hydroxamic acid or its corresponding hydroxamate are 6wt%.
3. according to claim 1 composition, wherein R
1C
8, C
9, C
10, C
11, C
12Or C
14Alkyl.
4. it is 1 to 50wt% detergent builder compound that according to claim 1 composition, wherein said composition contain concentration.
5. according to claim 1 composition, it contains the described cleansing surfactants system of 20wt% at least.
6. according to claim 1 composition, it contains the described cleansing surfactants system of 30wt% at least.
7. according to claim 1 composition, it contains the described cleansing surfactants system over 40wt%.
8. according to claim 1 composition, it contains 1 to 15wt% soap.
9. according to claim 8 composition, wherein said soap is prepared by saturated fatty acid.
10. according to claim 1 composition, it contains the antifouling polymeric of 0.5wt% at least.
11. composition according to claim 1, it contains the antiredeposition polymkeric substance of 0.5wt% at least.
12. composition according to claim 1, wherein the ratio of hydroxamic acid salt pair cleansing surfactants system is positioned at the scope of 1:7 to the 1:13 weight part.
13. composition according to claim 1, wherein the ratio of hydroxamic acid salt pair cleansing surfactants system is positioned at the scope of 1:9 to the 1:11 weight part.
14. composition according to claim 1, wherein anion surfactant is at least 1:1 to the ratio of nonionogenic tenside.
15. composition according to claim 1, wherein anion surfactant is at least 3:2 to the ratio of nonionogenic tenside.
16. composition according to claim 14, wherein anion surfactant is that 1:1 is to 9:1 to the ratio of nonionogenic tenside.
17. composition according to claim 14, wherein anion surfactant is that 3:2 is to 9:1 to the ratio of nonionogenic tenside.
18. composition according to claim 1, wherein said composition is liquid composition.
19. composition according to claim 18, it comprises with the concentration of 6wt% at least the hydrotropic agent system that contains propylene glycol and glycerine.
20. composition according to claim 18, it is liquid composition, and containing concentration is the cleansing surfactants that 20 of total composition arrives 80wt%.
21. be used for removing from polyester and cotton fabric the purposes of particulate dirt according to the composition of the claims 1-20 any one.
22. purposes according to claim 21, wherein said particulate dirt is red clay.
23. purposes according to claim 21, wherein said particulate dirt are the Georgia clays.
24.0.5 hydroxamic acid or the purposes of its corresponding hydroxamate in laundry detergent composition to the following structure of 20wt%:
R wherein
1For C
8Alkyl group, and R
2For hydrogen atom, be used for improving and remove the particulate dirt spot from textile substrate, it is 3 to 80wt% cleansing surfactants system and other composition that randomly complements to 100wt% that wherein said composition further contains concentration, and this cleansing surfactants system contains anion surfactant and nonionogenic tenside.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP08171904.9 | 2008-12-17 | ||
| EP08171904 | 2008-12-17 | ||
| PCT/EP2009/067193 WO2010069957A1 (en) | 2008-12-17 | 2009-12-15 | Laundry detergent composition |
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|---|---|
| CN102257109A CN102257109A (en) | 2011-11-23 |
| CN102257109B true CN102257109B (en) | 2013-11-20 |
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| CN2009801510329A Active CN102257109B (en) | 2008-12-17 | 2009-12-15 | Laundry detergent composition |
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| EP (1) | EP2358852B1 (en) |
| CN (1) | CN102257109B (en) |
| AU (1) | AU2009327141B2 (en) |
| BR (1) | BRPI0922587B1 (en) |
| CA (1) | CA2745559A1 (en) |
| ES (1) | ES2731593T3 (en) |
| PL (1) | PL2358852T3 (en) |
| TR (1) | TR201906017T4 (en) |
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| US11560534B2 (en) | 2020-12-15 | 2023-01-24 | Henkel Ag & Co. Kgaa | Surfactant compositions for improved transparency of DADMAC-acrylamide co-polymers |
| WO2022171780A2 (en) | 2021-02-12 | 2022-08-18 | Novozymes A/S | Alpha-amylase variants |
| EP4359518A1 (en) | 2021-06-23 | 2024-05-01 | Novozymes A/S | Alpha-amylase polypeptides |
| WO2023128951A1 (en) * | 2021-12-27 | 2023-07-06 | Eczacibasi Tuketim Urunleri Sanayi Ve Ticaret Anonim Sirketi | Laundry detergent composition with softening property and laundry detergent comprising said composition |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4863636A (en) * | 1988-02-12 | 1989-09-05 | American Cyanamid Company | Substituted N-hydroxyphthalimides and their use as detergent additives |
| EP0388389A2 (en) * | 1989-03-16 | 1990-09-19 | Monsanto Europe S.A./N.V. | Improved detergent compositions |
-
2009
- 2009-12-15 PL PL09768105T patent/PL2358852T3/en unknown
- 2009-12-15 ES ES09768105T patent/ES2731593T3/en active Active
- 2009-12-15 AU AU2009327141A patent/AU2009327141B2/en active Active
- 2009-12-15 CA CA2745559A patent/CA2745559A1/en not_active Abandoned
- 2009-12-15 TR TR2019/06017T patent/TR201906017T4/en unknown
- 2009-12-15 CN CN2009801510329A patent/CN102257109B/en active Active
- 2009-12-15 BR BRPI0922587-0A patent/BRPI0922587B1/en active IP Right Grant
- 2009-12-15 WO PCT/EP2009/067193 patent/WO2010069957A1/en active Application Filing
- 2009-12-15 EP EP09768105.0A patent/EP2358852B1/en active Active
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2011
- 2011-05-20 ZA ZA2011/03716A patent/ZA201103716B/en unknown
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4863636A (en) * | 1988-02-12 | 1989-09-05 | American Cyanamid Company | Substituted N-hydroxyphthalimides and their use as detergent additives |
| EP0388389A2 (en) * | 1989-03-16 | 1990-09-19 | Monsanto Europe S.A./N.V. | Improved detergent compositions |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2010069957A1 (en) | 2010-06-24 |
| BRPI0922587B1 (en) | 2019-04-09 |
| ES2731593T3 (en) | 2019-11-18 |
| AU2009327141B2 (en) | 2014-03-20 |
| CA2745559A1 (en) | 2010-06-24 |
| BRPI0922587A2 (en) | 2016-07-26 |
| AU2009327141A1 (en) | 2010-06-24 |
| CN102257109A (en) | 2011-11-23 |
| TR201906017T4 (en) | 2019-05-21 |
| PL2358852T3 (en) | 2019-09-30 |
| ZA201103716B (en) | 2012-07-25 |
| EP2358852A1 (en) | 2011-08-24 |
| EP2358852B1 (en) | 2019-03-27 |
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