CN104011192A - Isotropic liquid detergents comprising soil release polymer - Google Patents

Isotropic liquid detergents comprising soil release polymer Download PDF

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Publication number
CN104011192A
CN104011192A CN201280063058.XA CN201280063058A CN104011192A CN 104011192 A CN104011192 A CN 104011192A CN 201280063058 A CN201280063058 A CN 201280063058A CN 104011192 A CN104011192 A CN 104011192A
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composition
acid
aforementioned
bottle
srp
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CN201280063058.XA
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CN104011192B (en
Inventor
S·乔普拉-甘迪希
A·D·格林
A·J·帕里
J·F·韦尔斯
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Unilever IP Holdings BV
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Unilever NV
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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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/37—Mixtures of compounds all of which are anionic
    • 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
    • C11D10/00—Compositions of detergents, not provided for by one single preceding group
    • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • C11D10/042—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap based on anionic surface-active compounds and soap
    • 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
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/30—Amines; Substituted amines ; Quaternized amines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3715—Polyesters or polycarbonates

Abstract

An isotropic liquid detergent composition with an in-bottle pH in the range 6.0 to less than 7, the composition comprising, in addition to water: a) up to 60 wt% detersive surfactant including at least 5 wt% anionic sulphonate and /or sulphate surfactant comprising surfactant acid neutralised with one or more materials the pKa of whose conjugate acid(s) lies more than 2 units higher than the in-bottle pH of the detergent liquid composition b) at least 0.3 wt% fatty acid partially neutralised with one or more materials the pKa of whose conjugate acid(s) lies more than 2 units higher than the in-bottle pH of the detergent liquid composition c) at least 1.0 wt%, preferably at least 1.8 wt%, Triethanolamine (TEA); and d) at least 0.5 wt% soil release polymer (SRP).

Description

The isotropic liquid detergent that comprises soil release polymer
Technical field
The present invention relates to isotropic liquid detergent composition, it comprises water, hydrotropic agent, anionic sulphonate or sulfate surfactant and polyester based soil release polymer.
Background technology
WO09153184 has proposed a kind ofly can be selected from the detergent for washing clothes liquid concentrate that the mixture replacing tensio-active agent of the more effective constituent of polymkeric substance and enzyme designs by use.Preferred composition uses the polymine (EPEI) of ethoxylation and a combination for polyester soil release polymers (SRP), to obtain good greasy dirt and particulate stain removal than tensio-active agent level in the common significantly lower washing of sending of high-performance liquid.Exemplary composition comprises anion surfactant and further comprises that described anion surfactant comprises the linear alkylbenzene sulfonate with sodium hydroxide neutralization by sodium hydroxide and the soap class that forms of lipid acid.Said composition is alkaline.Have been found that for the SRP of embodiment and passed through alkaline hydrolysis, and described alkaline hydrolysis by being used trolamine (TEA) to carry out catalysis in composition.
The apparent solution of one of the hydrolytic instability problem of SRP is that said composition is separated, and is stored in independent chamber, thereby SRP is not contacted with TEA or alkaline matter.This part preparation based on sour may be the instruction based in EP294893, US2010229313 and US3893929.But it is less desirable using composition separately, because it can increase cost and complicacy.Human consumer wishes to send all cleaning substances from single main washings.
Main washings is mixed with to acidity and has sizable technology prejudice.Generally believe that they can produce acidic cleaning condition, its performance due to surfactant system and possible some enzymes reduces, and will cause cleaning insufficient.US5290475 (Colgate) is one section of document, and it is prepared and show technology prejudice under acidic conditions the stability in order to improve SRP.Softening and the antistatic nonionic detergent composition of liquid comprises as the decontamination of the water-soluble portion of nonionic detergent, anionic detergent, cationic fabric softener-static inhibitor and polyethylene terephthalate-polyoxyethylene terephthalate type of main component and promotes polymkeric substance.For the washing composition that helps may exist in liquid washing agent and the dissolving of optical whitening agent, generally include the alkaline matter of small proportion or the mixture of such material.That suitable alkaline matter comprises is single-, two-and three-alkanolamine, alkylamine, ammonium hydroxide and alkali metal hydroxide.Wherein, preferred material is alkanolamine, preferably three alkanolamines, wherein trolamine particularly preferably.The pH of the final liquid washing agent that comprises this alkaline matter conventionally will be for neutral or slightly alkaline.PH scope is 7 to 10 satisfactorily, preferred approximately 7.5 to 9.5.
The pH that WO9742286 (P & G) has instructed detergent for washing clothes conventionally to have at page 3 is greater than 7.5.According to the 9th page of composition that contains SRP, it discloses in the time measuring as 10% aqueous solution, has approximately 7.2 to approximately 8.9 pH.
US4785060 (Colgate) discloses the PET POET SRP that uses high molecular prepared by hybrid catalyst system.These SRP are allegedly in the suds and under high pH, keep their performance under the existence of washing assistant.According to instruction, they are comprised in solid and liquid detergent composition in the two.Its disclosure has been instructed and has been minimized comprised alkanolamine such as TEA and ionizable salt are such as Na.It has been instructed at the 10th hurdle the 13rd to 15 row, and preferably, being generally used for improving the neutralizing agent that liquid scrubbing agent composition pH uses is sodium hydroxide.At the 17th to 18 row, it continues instruction " conventionally should avoid triethanolamine salt and free trolamine ".PH scope will be 6 to 10, preferably 6.1 to 8.9, conventionally more preferably 6.5 to 7.5.
US4759876 (Colgate) discloses the decontamination that comprises SRP and has promoted liquid detergent composition.Described composition further comprises the enzyme stabilizers of stablizing ratio, and its buffer reagent that also serves as liquid detergent composition, pH is remained on to a certain neutrality or acid range slightly, is stablized SRP and white dyes.It is said that said composition " keeps " its dirt hydrolysis fluorescent brightening and decontamination to promote characteristic in when storage substantially, thereby brightened and process by effectively clean with the clothing of its washing.But, from same transferee's US5110506 show performance do not have ' 876 propose so good.And, obviously disclosing of basis ' 876, in the time of storage, pH turns to acidity.We determine this decomposition of SRP due to, because it exceedes just hydrolysis in January in storage.Do not comprise any soap class.Described enzyme stabilizers/buffer reagent allegedly can keep pH 6.2 or higher.The pH scope providing after storage is 6.2 to 6.5.But also having provided and further can not made the unsettled pH scope of this polymkeric substance is 5.8 to 7.
In US5110506 (Colgate), except disclose detergency ability that ' 876 liquid obtains after storage poor, it has also been instructed by described nonionic is changed over 2EO and the minimized specific very expensive material of 3EO content can be obtained in the storage little improvement of detergency ability afterwards.Instruct and there is the liquid washing agent of pH in 7.3 to 8.1 scopes.This shows that pH still can be because hydrolysis changes.The clean improvement of claiming may be owing to being converted to the more nonionogenic tenside of life type.
GB1466639 (P & G) discloses has the tensio-active agent of thanomin neutralization and the detergent liquid of SRP.Comprise some free TEA so that washing water keep alkalescence.Two kinds of dissimilar liquid are disclosed.In the first type, select specific nonionogenic tenside to give composition enough physical stabilities.In the second type, comprise lipid acid (soap class) so that extended storage stability to be provided.Embodiment 1 is the embodiment of the second type of composition seemingly.It comprises 1.5% oleic acid TEA salt and 5% SRP (from table 1).Find that it is alkaline compositions.
US4411831 (Purex) discloses a kind of stable aqueous detergent composition, it has the decontamination character of enhancing and is substantially made up of SRP (having LAS) and nonionic and buffer reagent, described buffer reagent enough keeps the pH of this waterborne compositions 5.0 to 9.0, and preferably 6.5 to 7.5.Embodiment is to have used Zelcon4780SRP in 7 main cleaning composition comprising LAS and nonionic and pH regulator.Use SXS as hydrotropic agent.Do not use in this embodiment TEA or soap class.Its disclosure has been instructed and or not the time storing, has not been produced acid pH containing the comparative example liquid of buffer reagent.It is said that acid pH is harmful to whitening agent.We understand acid pH and produce because SRP decomposes.Add buffer reagent to stablize pH to the solution adopting.Because pH is more alkaline, this will cause SRP to decompose increases.Whitening agent can be protected, the true object of this seemingly this invention.The suitable buffer reagent of instructing comprises supercarbonate, orthophosphoric acid salt, borate and alkanolamine salt hydrochlorate.
US4713194 (P & G) has discussed the readily degradable of SRP in alkaline environment; if and propose to use in particulate composition, by coated (enrobing), SRP is protected, if or use in liquid composition, be 7.0 to 8.5 by the pH regulator of product.The fatty acid distribution of coconut oil that embodiment comprises high-content.
US6262007 (P & G) has described acid detergent liquid, and it comprises that viscosity when SRP declines with temperature to reduce increases.Some embodiment comprises TEA, but does not comprise hydrotropic agent or lipid acid.
Need to comprise the concentrated liquid detergent composition of SRP, it even all provides good spatter property after extending storage.
invention summary
According to the present invention, a kind of isotropic liquid detergent composition is provided, its have scope 6.0 to be less than 7 bottle in (in-bottle) pH, described composition, except comprising water, also comprises:
A) the stain release type tensio-active agent of maximum 60wt%, it comprises at least anionic sulphonate and/or the sulfate surfactant of 5wt%, described anionic sulphonate and/or sulfate surfactant comprise the surfactant acid with one or more material neutralizations, the pKa of the conjugate acid of described one or more materials is higher 2 more than unit than pH in the bottle of detergent liquid composition
B) lipid acid of one or more material parts of the use of 0.3wt% neutralization at least, the pKa of the conjugate acid of described one or more materials is higher 2 more than unit than pH in the bottle of detergent liquid composition,
C) 1.0wt% at least, the preferably trolamine of 1.8wt% (TEA) at least; With
D) soil release polymer of 0.5wt% (SRP) at least.
Preferably, described composition has 6.3 to 6.7 the interior pH of bottle.In bottle, refer to fluid storage any container or packaging therein.It can be doleiform formula, squeezable or rigidity, upright or inversion plastic wrapping storage or unit dosage form, such as solubility bag agent (pouch) or wafer (sachet).
Lipid acid provides surge capability, but comprising it causes acidic composition to be separated at low temperatures in interior meeting.Therefore, it can only be included with relative low levels.Described lipid acid can not as for neutralize anionic surfactant a) preferably for whole being removed the material of sodium hydroxide or monoethanolamine (MEA), because described material itself can not be stablized described composition.Preferably, lipid acid is saturated.Most preferably, its usage quantity is 0.5 to 1.5wt%.
Use TEA to contribute to the stability of lipid acid, therefore, TEA is included with the equally high content that can be allowed by SRP.Preferably 3.7wt% at the most of the amount of TEA, most preferably is 2.0 to 3.5wt%.
Advantageously, the pKa of the conjugate acid of described one or more materials is higher 2 more than unit than pH in the bottle of detergent liquid composition, described one or more materials comprise 0.08 to 0.25wt%, preferably 0.1 to 0.23wt% NaOH and/or monoethanolamine (or MEA).The definition of non-buffer components is intended to contain all common weak base and the highly basic outside interested buffer zone (moderate acid: 6.0 to being less than 7).Therefore, higher 2 more than unit than pH in the bottle of detergent liquid composition to prepare the pka of conjugate acid of anion surfactant material a) for neutralize anionic surfactant acid, described material can not play significantly buffer reagent under pH in the bottle of described composition storage.On the contrary, TEA really plays buffer reagent effect in the bottle of moderate acid under pH.
SRP deposits to the base polymer polyester from washing soln.It preferably has by terephthalate and glycol (preferably 1,2 propylene glycol) condensation form polyester affinity part, and it further comprises end-capped hydrophilic parts, described end-capped hydrophilic parts comprises with alkyl-blocked oxyethane repeating unit.Its usage quantity can be for being greater than 0.5wt%, and can exist with the content up to 15wt%.Can use the mixture of different SRP.
Described liquid generally includes hydrotropic agent.In the time using, hydrotropic content will be 5wt% at least, preferably 9wt% at least, more preferably 14wt% at least.For cost reason, hydrotropic amount is preferably less than the 25wt% of composition, is most preferably less than 20wt%.Preferred hydrotropic agent is 1,2 propylene glycol (MPG).
Advantageously, in order to improve particulate stain removal, described composition comprises at least 3%, the ethoxylation polymine (EPEI) of 5wt% at least preferably.
detailed Description Of The Invention
Except essential characteristic, composition of the present invention can comprise other composition.Such composition comprises viscosity modifier, frothing aid, sanitas (for example sterilant), pH buffer reagent, polyelectrolyte, anti-shrinking medium, anti wrinkling agent, oxidation inhibitor, sun-screening agent, inhibitor, drape imparting agent (drape imparting agents), static inhibitor and flatiron auxiliary agent, tinting material, pearling agent (pearlisers) and/or opalizer and covers dyestuff (shading dye).
Further describe as follows the main aspect of composition and optional aspect.
isotropic liquid
The amount of stain release type tensio-active agent accounts at least 10wt% of total liquid composition, preferably accounts for 12 to 60wt%.The active stain release type tensio-active agent total content that composition according to the present invention most preferably has is 15wt% at least.
Described composition can be concentrated composition, and it is designed to be added in the washing of 10 liters with low dose, and this requires them to be diluted in the water of at least 500 times of their own vols, comprises the main washing liq of 0.5g/l tensio-active agent at the most to form.They can also be the concentrate compositions that is designed for the automatic washing machine of hand washing or top-loaded.In hand washing, may use less water, and in the automatic washing machine of top-loaded, conventionally use the water of higher amount.Correspondingly adjust the dosage of detergent liquid, to provide similar washing liq concentration.
tensio-active agent
Tensio-active agent contributes to from the textile material dirt that gets on, and contributes to the dirt of removal to be maintained in the suspension of solution or washing liq.The blend of anion surfactant or negatively charged ion and nonionic surface active agent is preferred feature of the present invention.The amount of anion surfactant is preferably at least 5wt%.
Preferably, anion surfactant has formed the main body of on-soap tensio-active agent (a).
Anion surfactant
Preferred alkylsulfonate is alkylbenzene sulfonate, especially has C 8-C 15the linear alkylbenzene sulfonate of alkyl chain length.The counter ion of anion surfactant are generally basic metal, are generally sodium, but also can use other counter ion, such as MEA, TEA or ammonium.
Preferred linear alkyl sulfonate surfactant is Detal LAS, and it has 8 to 15, more preferably 12 to 14 alkyl chain length.
Also expect the sulphate anion surface active agent that described composition comprises alkyl polyethoxylated, it has formula (I):
RO(C 2H 4O) xSO 3 -M + (I)
Wherein, R is the alkyl chain (saturated or undersaturated) with 10 to 22 carbon atoms, and M is the ammonium cation of the positively charged ion that makes described compound water-soluble, especially basic metal, ammonium or replacement, and x average out to 1 to 15.
Preferably, R is the alkyl chain with 12 to 16 carbon atoms, and M is sodium and x average out to 1 to 3, and preferably x is 3; This is anion surfactant Zetesol NL (SLES).It is the sodium salt of lauryl ether sulfuric acid, is mainly wherein that the alkyl group of C12 lauryl is by average 3 moles of ethylene oxide/mole ethoxylation.
nonionogenic tenside
Nonionic surface active agent comprises primary and secondary alcohol ethoxylate, the C of average 1 to 20 moles of ethylene oxide ethoxylation for especially every mol of alcohol 8-C 20fatty alcohol, and be more specifically the C of every mol of alcohol with the ethoxylation of average 1-10 moles of ethylene oxide 10-C 15primary and secondary fatty alcohol.The ionic surfactant pack of non-ethoxylated is drawn together alkyglycosides, glycerol monoethers and polyhydroxy amides (glucamide).Can use the mixture of nonionogenic tenside.In the time being included in wherein; composition contains 0.2wt% to 40wt%; be preferably 1wt% to 20wt%; more preferably 5 to 15wt% nonionogenic tenside, such as the N-acyl group N-alkyl derivative (" glucamide ") of alcohol ethoxylate, nonyl phenol ethoxylate, alkyglycosides, alkyl dimethyl amine oxide, ethoxylated fatty acid single ethanol amide, fatty monoethanol amide, polyhydroxy alkyl fatty amide or glucosamine.
Operable ionic surfactant pack is drawn together primary and secondary alcohol ethoxylate, especially uses the C of the oxyethane ethoxylation of average 1 to 35 mole of every mol of alcohol 8-C 20fatty alcohol, and more particularly by the C of the oxyethane ethoxylation of average 1 to 10 mole of every mol of alcohol 10-C 15primary and secondary fatty alcohol.
amine oxide
Described composition can comprise the amine oxide of 10wt% at the most, and it has formula:
R 1N(O)(CH 2R 2) 2
Wherein R 1long-chain part, each CH 2r 2it is short chain part.R 2preferably be selected from hydrogen, methyl and-CH 2oH.Generally speaking, R 1be the hydrocarbyl portion of uncle's hydrocarbyl portion or side chain, it can be saturated or undersaturated, preferably, and R 1it is primary alkyl part.R 1it is the hydrocarbyl portion with approximately 8 to approximately 18 carbon chain lengths.
The R of preferred amine oxide 1for C 8-C 18alkyl, and R 2for H.These amine oxides are exemplified as C 12-14alkyl dimethyl amine oxide, cetyl dimethyl amine oxide, octadecyl amine oxide.
Preferred amine oxide material is lauryl dimethyl amine oxide, is also called dimethyl dodecyl amine oxide or DDAO.This amine oxide material can be with trade(brand)name oB is purchased from Hunstman.
Being applicable to amine oxide herein also can be available from Akzo Chemie and Ethyl Corp.Other amine oxide manufacturerss compile originally and the survey article of Kirk-Othmer referring to McCutcheon's.
Although R in certain preferred aspects 2for H, but R 2can be more bigger than H.Particularly, R 2can be CH 2oH, such as: two (2-hydroxyethyl) amine oxides of hexadecyl, two (2-hydroxyethyl) amine oxides of tallow, two (2-hydroxyethyl) amine oxides of stearyl and two (2-hydroxyethyl) amine oxides of oleyl.
Preferred amine oxide has following formula:
O --N +(Me) 2R 1 (3)
Wherein, R 1c 12-16alkyl, is preferably C 12-14alkyl; Me is methyl group.
zwitterionics
Can use have 95%wt at the most LAS not containing non-ionic system, precondition is to have some zwitterionics, such as carboxybetaine (carbobetaine).Preferred zwitter-ion material is carboxybetaine, and it can be with the name of an article bB is available from Huntsman.Trimethyl-glycine has improved the granular dirt soil release performance in composition of the present invention.
Preferred composition comprises at least amine oxide or carboxybetaine or its mixture of 1wt%.
other tensio-active agent
Can in the mixture of detersive surfactant, add other tensio-active agent except preferred LAS, SLES, nonionogenic tenside and zwitterionics (trimethyl-glycine).But, preferably substantially there is not cats product.
Although more not preferred, can use the C of some alkyl sulfate surfactant (PAS), especially non-ethoxylated 12-15primary and secondary alkyl-sulphate.The commercially available particularly preferred material available from Cognis is Sulphopon1214G.
other polymkeric substance
EPEI
The particularly preferred polymer classes using in conjunction with soil release polymer (SRP) is the polymine (EPEI) of ethoxylation.Polymine is by ethyleneimine unit-CH 2cH 2the material of NH-composition, and the in the situation that of collateralization, the hydrogen on nitrogen is substituted by another chain of ethyleneimine unit.These polymines can pass through, and for example in the situation that catalyzer exists prepared by polymerising ethylene imines, and described catalyzer is such as carbonic acid gas, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid etc.Be disclosed in the people's such as disclosed Ulrich on the 5th in December nineteen thirty-nine U.S. Patent No. 2,182,306 for the preparation of the concrete grammar of these polyamine main chains; In May, 1962 people such as disclosed Mayle on the 8th U.S. Patent No. 3,033,746; In July, 1940 people such as disclosed Esselmann on the 16th U.S. Patent No. 2,208,095; September nineteen fifty-seven disclosed Crowther on the 17th U.S. Patent No. 2,806,839; And May nineteen fifty-one disclosed Wilson on the 21st U.S. Patent No. 2,553,696 in.
Preferably, to comprise weight-average molecular weight be approximately 300 to approximately 10000 polymine main chain to described EPEI; Wherein be intended to make described polymkeric substance not contain to the modification of described polymine main chain quaternized and non-ionic.This class nonionic EPEI can be expressed as PEI (X) YEO, and wherein X is the molecular weight of unmodified PEI, and Y is the average mol of the ethoxylation of every nitrogen-atoms in polymine main chain.Described ethoxylation can be 9 to 40 oxyethyl group part/modifications, is preferably 16 to 26, most preferably is 18 to 22.
In the time using, the content of the EPEI polymkeric substance existing in described composition is preferably 25wt% at the most, and preferably content is 3wt% at least, and more preferably 4 to 15wt%, most preferably 5wt% at least.The ratio of on-soap tensio-active agent and EPEI is 2:1 to 7:1, preferably 3:1 to 6:1, or 5:1 even.
other polymer type
Except polyester soil release polymers, also can use dye transfer inhibiting polymers, antiredeposition polymkeric substance and cotton material soil release polymer, especially those polymkeric substance of the cellulosic material based on modification.
hydrotropic agent
In content of the present invention, hydrotropic agent is neither the water solvent of unconventional tensio-active agent again, and the solubilising that it has assisted the tensio-active agent in waterborne liquid and other component, makes its isotropy.In suitable hydrotropic agent, below these can be used as preferably and mention: MPG (MPG), glycerine, isopropyl benzene sodium sulfonate, ethanol, other glycols (for example dipropylene glycol), diether and urea.
Cause owing to the hydrolysis of SRP except us storage time turn to more acidic composition, we also observe in the time that it comprises the SRP to alkaline hydrolysis sensitivity, the physical stability of composition seems also to improve; Especially we find that the SRP being sold with trade(brand)name Texcare SRN170 by Clariant when be stored in alkaline detergent composition is unstable, and this polymkeric substance are covered to contain wonderful composition viscosity reduction is provided in alkaline detergent composition.Use freshly prepd polymkeric substance, we also observe this effect.We believe that SRP plays hydrotropic effect in isotropic detergent liquid.
enzyme
Preferably, in described composition, can there is at least one or plurality of enzymes.Preferably, at least two kinds, more preferably at least three kinds of dissimilar enzymes can be used in combination.
lipase
Lipase is particularly preferred enzyme.Described composition preferably comprises approximately 5 lipase to about 20000LU/g.Preferably 800LU/g at least.Preferred lipase comprises those of bacterium or originated from fungus.Comprise chemically modified or protein engineering mutant.The example of useful lipase comprises the lipase from Humicola (Humicola), more preferably comprise the polypeptide with aminoacid sequence, described aminoacid sequence be derived from pubescence humicola lanuginosa (Humicola lanuginosa), most preferably the wild-type lipase of DSM4109 bacterial strain has the lipase of at least 90% sequence identity.Amount in described composition is higher than the amount being conventionally present in liquid washing agent.Especially, this can represent by the ratio of on-soap tensio-active agent and lipase.Particularly preferably being can be with trade mark Lipoclean tMavailable from the lipase of Novozymes.
As noted above, suitable lipase comprises the lipase of bacterium or originated from fungus.Comprise chemically modified or protein engineering mutant.The example of useful lipase comprises the lipase from Humicola (Humicola) (Thermomyces synonym), for example, described in EP258068 and EP305216 from pubescence humicola lanuginosa (H.lanuginosa) (T.lanuginosus), or described in WO96/13580 from Humicola insolens (H.insolens); False silk zygosaccharomyces lipase, for example, from Pseudomonas alcaligenes (P.alcaligenes) or pseudomonas pseudoalcaligenes (P.pseudoalcaligenes) (EP218272), pseudomonas cepacia (P.cepacia) (EP331376), pseudomonas stanieri (GB1372034), Pseudomonas fluorescens (P.fluorescens), pseudomonas strain SD705 (WO95/06720 and WO96/27002), Wisconsin pseudomonas (P.wisconsinensis) (WO96/12012); Bacillus lipase, for example, from subtilis (B.subtilis) (Dartois etc. (1993), Biochemica et Biophysica Acta, 1131,253-360), bacillus acidocldarius (B.stearothermophilus) (JP64/74992) or bacillus pumilus (B.pumilus) (WO91/16422).As noted above, preferred lipase has homology highly with the lipase of the agriotype that is derived from pubescence humicola lanuginosa.
Other examples have lipase Variant, such as those described in WO92/05249, WO94/01541, EP407 225, EP260 105, WO95/35381, WO96/00292, WO95/30744, WO94/25578, WO95/14783, WO95/22615, WO97/04079 and WO97/07202.
Preferred commercially available lipase comprises Lipolase tMwith Lipolase Ultra tM, Lipex tMand Lipoclean tM(Novozymes A/S).
Except lipase or as the surrogate of lipase, can there is one or more other enzymes.
Advantageously, in composition of the present invention, exist the calcium of relative high-content to there is beneficial effect for the turnover ratio of certain enzyme, especially lipase and preferably from the lipase of Humicola of described enzyme.
Preferred lipase comprises the first washing lipase, is derived from Lipex tMtrade mark derives from the pubescence humicola lanuginosa DSM4109 bacterial strain of Novozymes.From Novozymes but the similar enzyme being considered to outside above-mentioned restriction can title Lipoclean tMderive from Novozymes, and this is also preferred.
phospholipid hydrolase:
Method of the present invention can be carried out under the phosphine lipase that classifies as EC3.1.1.4 and/or EC3.1.1.32 exists.Term Phospholipid hydrolase is a kind of enzyme as used herein, and it has activity to phosphatide.Phosphatide, such as Yelkin TTS or phosphatidylcholine, it is by also forming at the glycerine of the 3rd position esterification with phosphoric acid in the position esterification of outside (sn-1) and middle (sn-2) with two lipid acid; Phosphoric acid and then can esterifiedly be amino alcohol.Phospholipid hydrolase is the enzyme that participates in phosphatide hydrolysis.Can distinguish the phospholipase activity of several types, comprise phospholipase A1 and A2, its fatty acyl group of hydrolysis (respectively in sn-1 and sn-2 position) is to form lysophospholipid; With the lysophospholipase (or phospholipase B) that can be hydrolyzed remaining fatty acyl group in lysophospholipid.Phospholipase C and Phospholipase D (phosphodiesterase) discharge respectively DG and phosphatidic acid.
proteolytic enzyme:
Applicable proteolytic enzyme comprises animal, plant or microbe-derived those.Microbe-derived is preferred.Comprise chemically modified or protein engineering mutant.Proteolytic enzyme can be serine protease or metalloprotease, preferred alkaline microbial protease or tryptase.Preferred commercially available proteolytic enzyme comprises Alcalase tM, Savinase tM, Primase tM, Duralase tM, Dyrazym tM, Esperase tM, Everlase tM, Polarzyme tM, and Kannase tM, (NovozymesA/S), Maxatase tM, Maxacal tM, Maxapem tM, Properase tM, Purafect tM, Purafect OxP tM, FN2 tMand FN3 tM(Genencor International Inc.).
at:
Method of the present invention can be carried out under the existence that is categorized as the in EC3.1.1.74.At used according to the invention can be any source.Preferred at is microbe-derived, and particularly bacterium, fungi or yeast are originated.
amylase:
Applicable amylase (α and/or β) comprises those of bacterium or originated from fungus.Comprise chemically modified or protein engineering mutant.Amylase comprises, for example, derive from the α-amylase of bacillus (Bacillus), as be described in more detail in GB1, the specific bacterial strain of Bacillus licheniformis (B.licheniformis) in 296,839 or bacillus (Bacillus sp.) bacterial strain of describing in WO95/026397 or WO00/060060.Commercially available amylase is Duramyl tM, Termamyl tM, TermamylUltra tM, Natalase tM, Stainzyme tM, Fungamyl tMand BAN tM(Novozymes A/S), Rapidase tMand Purastar tM(from Genencor International Inc.).
cellulase:
Applicable cellulase comprises those of bacterium or originated from fungus.Comprise mutant chemically modified or protein engineering.Applicable cellulase comprises from bacillus (Bacillus), Rhodopseudomonas (Pseudomonas), humicola lanuginosa (Humicola) belongs to, fusarium (Fusarium), Thielavia (Thielavia), the cellulase of Acremonium (Acremonium), for example, by Humicola insolens (Humicola insolens), Thielavia terrestris (Thielavia terrestris), thermophilic fungus destroyed wire (Myceliophthora thermophila), and the fungal cellulase that produces of Fusarium oxysporum (Fusarium oxysporum), it is disclosed in US4, 435, 307, US5, 648, 263, US5, 691, 178, US5, 776, 757, WO89/09259, WO96/029397, in WO98/012307.Commercially available cellulase comprises Celluzyme tM, Carezyme tM, Endolase tM, Renozyme tM(Novozymes A/S), Clazinase tMwith Puradax HA tM(Genencor International Inc.) and KAC-500 (B) tM(Kao Corporation).
peroxidase/oxydase:
Suitable peroxidase/oxydase comprises those of plant, bacterium or originated from fungus.Comprise mutant chemically modified or protein engineering.Useful peroxidase comprises the peroxidase from Coprinus (Coprinus), for example, from grey lecher's umbrella (C.cinereus) and variant thereof, as those described in WO93/24618, WO95/10602 and WO98/15257.Commercially available peroxidase comprises Guardzyme tMand Novozym tM51004 (Novozymes A/S).
pectate lyase:
Pectate lyase (also referred to as polygalacturonic acid lyase): the example of pectate lyase comprises clones such as erwinia (Erwinia), Rhodopseudomonas (Pseudomonas), Klebsiella (Klebsiella) and xanthomonas (Xanthomonas) and from subtilis (Bacillus subtilis) (Nasser et al. (1993) FEBS Letts.335:319-326) and genus bacillus (Bacillus sp.) YA-14 (Kim et al. (1994) Biosci.Biotech.Biochem.58:947-949) pectate lyase obtaining from different Pseudomonas.Also described by bacillus pumilus (Bacillus pumilus) (Dave and Vaughn (1971) J.Bacteriol.108:166-174), bacillus polymyxa (B.polymyxa) (Nagel and Vaughn (1961) Arch.Biochem.Biophys.93:344-352), bacstearothermophilus (B.stearothermophilus) (Karbassi and Vaughn (1980) Can.J.Microbiol.26:377-384), what bacillus (Bacillus sp.) (Hasegawa and Nagel (1966) J.Food Sci.31:838-845) and genus bacillus (Bacillus sp.) RK9 (Kelly and Fogarty (1978) Can.J.Microbiol.24:1164-1172) produced is the purifying that 8-10 has the pectate lyase of maximum activity at pH.
Can rely on above-mentioned any and divalent cation and/or heat-staple pectate lyase is implemented the present invention.In preferred embodiments, pectate lyase is included in Heffron etc., (1995) Mol.Plant-Microbe Interact.8:331-334 and Henrissat etc., disclosed pectate lyase in (1995) Plant Physiol.107:963-976.The pectate lyase of concrete expection is disclosed in WO99/27083 and WO99/27084.The pectate lyase (deriving from Bacillus licheniformis (B.licheniformis)) of other concrete expection is disclosed in U.S. Patent number 6,284, in 524 (this file is incorporated herein by reference at this).The Pectate lyase variants of concrete expection is disclosed in WO02/006442, especially disclosed variant (this file is incorporated herein by reference at this) in the embodiment of WO02/006442.
The example of commercially available alkaline pectate lyase comprises from NovozymesA/S, the BIOPREP of Denmark tMand SCOURZYME tM.
mannase:
Mannase: the example of mannase (EC3.2.1.78) comprises the mannase of bacterium and originated from fungus.In specific embodiment, mannase can derive from the bacterial strain of the filamentous fungus of Eurotium (Aspergillus), is preferably black-koji mould (Aspergillus niger) or microorganism Aspergillus aculeatus (Aspergillus aculeatus) (WO94/25576).WO93/24622 discloses and has separated the mannase from Trichodermareesei (Trichoderma reseei).From several bacteriums, separate mannase, comprised those of bacillus biology.For example, Talbot etc., Appl.Environ.Microbiol., the 56th volume, o. 11th, 3505-3510 page (1990) has been described the 'beta '-mannase available from bacstearothermophilus (Bacillus stearothermophilus).Mendoza etc., World J.Microbiol.Biotech., the 10th volume, the 5th phase, 551-555 page (1994) has been described the 'beta '-mannase available from subtilis (Bacillus subtilis).JP-A-03047076 discloses the 'beta '-mannase available from bacillus (Bacillus sp.).JP-A-63056289 has described production alkalescence, heat-staple 'beta '-mannase.JP-A-63036775 relates to bacillus (Bacillus) microorganism FERM P-8856, and it produces 'beta '-mannase and beta-Mannosidase.JP-A-08051975 discloses the alkaline ' beta '-mannase that belongs to (Bacillus sp.) AM-001 from Alkaliphilic bacillus.Purifying mannase from bacillus amyloliquefaciens (Bacillus amyloliquefaciens) is disclosed in WO97/11164.WO91/18974 has described a kind of hemicellulase, such as dextranase, zytase or mannase actives.Be contemplated that alkaline family 5 and 26 mannases that are derived from disclosed sticky agar bacillus (Bacillus agaradhaerens), Bacillus licheniformis (Bacillus licheniformis), Alkaliphilic bacillus (Bacillus halodurans), Bacillus clausii (Bacillus clausii), bacillus (Bacillus sp.) and Humicola insolens (Humicola insolens) in WO99/64619.Especially be contemplated that the mannase of the bacillus (Bacillus sp.) using in the embodiment of WO99/64619.
The example of commercially available mannase comprises can derive from NovozymesA/S, the Man naway of Denmark tM.
Any aromas/fragrances of described enzyme and existence or perfume compound precursor can show some and interact, and should be selected, so that this interaction is not negative effect.Can isolate to avoid some negative interaction by one or another kind of in encapsulated enzyme and perfume compound precursor and/or other in product.
enzyme stabilizers:
Any enzyme existing in described composition all can be stablized with conventional stablizer, for example, polyvalent alcohol (such as propylene glycol or glycerine), sugar or for example boric acid aromatic ester of sugar alcohol, lactic acid, boric acid or boric acid derivatives or phenyl-boron dihydroxide derivative (such as 4-formylphenyl boric acid), and described composition can be prepared described in for example WO92/19709 and WO92/19708.
lignin compound:
In the time comprising lipase, lignin compound can be with the optimized amount of repetition test for described composition.Xylogen is the component of all vascular plants, is mainly present between cellularstructure and between cell and cell walls.
Preferably, lignin compound comprises lignin polymers, and more preferably it is modified lignin resin polymkeric substance.Modified lignin resin polymkeric substance is thereby that after chemical reaction is by the covalently bound chemical part xylogen to xylogen as used herein.The chemical part of described connection is preferably by random replacement.
Preferred modified lignin resin polymkeric substance is by the xylogen of negatively charged ion, positively charged ion or alkoxy base or the replacement of its mixture.Preferably, this replacement occurs on the aliphatic portion of xylogen, and is random.Preferably, modified lignin resin polymkeric substance is replaced by anionic group, and preferably anionic group is sulfonate radical.A kind of preferred cation group is quaternary amine.Preferred alkoxyl group is for having the polyoxyalkylene chain of 5 to 30 alkoxyl group parts (most preferably oxyethyl group) repeating unit.Preferably, modified lignin mahogany sulfonate is replaced by negatively charged ion or alkoxy base.The lignin polymers of modification is for discussing in WO/2010/033743.Most preferably, the lignin polymers of modification is sulfonated lignin (lignosulfonate/naphtalene sulfonate classes).Sulfonated lignin can obtain by Howard method.
Exemplary sulfonated lignin can be available from various sources, comprise hardwood, cork and recirculation or arrange thing outward.Can use sulfonated lignin with undressed or pure form, for example, with " former state " or whole soln state (whole liquor condition) or with the lignosulfonic acid salt form of purifying, wherein carbohydrate and other sugared composition have been removed or have destroyed, or wherein inorganic components is partly or entirely eliminated.Sulfonated lignin can use with salt form, comprise calcium lignin sulphonate, sodium lignosulfonate, ammonium lignosulphonate, lignosulfonic acid potassium, magnesium lignosulfonate, and composition thereof or blend.
Sulfonated lignin preferably have 2000 to 100000 weight-average molecular weight.Its basic structural unit is phenylpropyl alcohol alkane.Sulfonation degree is preferably 0.3 to 1.0 of each phenylpropyl alcohol alkane unit sulfate group.
Sulfonated lignin can obtain from many suppliers, comprise Borregaard LignoTech, Georgia-Pacific Corporation, Lenzing AG and Tembec Inc.
At Lauten, R.A., Myrvold, B.O.and Gundersen, S.A. (2010) New Developments in the Commercial Utilization of Lignosulfonates, in Surfactants from Renewable Resources (eds M.Kjellin and I.Johansson), John Wiley & Sons, Ltd, Chichester, has discussed sulfonated lignin in UK.
fluorescent agent:
Described composition comprises that fluorescent agent may be favourable.Conventionally, these fluorescent agents for example, with form supply and the use of its an alkali metal salt (sodium salt).The total amount of the fluorescent agent using in described composition is generally 0.005 to 2wt%, and more preferably 0.01 to 0.5wt%.
Preferred fluorescent agent type is: distyryl biphenyl based compound (for example Tinopal (trade mark) CBS-X), diamines stilbene disulfonic acid compound (for example Tinopal DMS pure Xtra and Blankophor (trade mark) HRH) and pyrazoline compounds (for example, Blankophor SN).
Preferred fluorescent agent is: 2 (4-styryl-3-sulfophenyl)-2H-naphthols [1,2-d] 1-Sodium-1,2,4-Triazole, 4,4'-bis-{ [4-anilino-6-(N-methyl-N-2-hydroxyethyl) amino 1,3,5-triazine-2-yl)] amino } stilbene-2-2' disulfonic acid disodium, 4,4'-bis-{ [4-anilino-6-morpholinyl-1,3,5-triazine-2-yl)] amino } stilbene-2-2' disulfonic acid disodium, and 4,4'-bis-(2-sulphophenyl vinyl) biphenyl disodium.
bleaching catalyst:
Can comprise the effective bleach systems of content according to detergent composition of the present invention.This class system is not used conventional percarbonate and bleach activator mode conventionally.
Also can use the present invention for the preparation of bleaching via air or bleaching catalyst system.Technician can obtain suitable complex compound and be used to form organic molecule (part) precursor of complex compound, for example, available from WO98/39098; WO98/39406, WO97/48787, WO00/29537; WO00/52124 and WO00/60045, be incorporated herein by reference.The example of preferred catalyzer is the transition metal complex of MeN4Py part (N, two (pyridine-2-base-methyl)-1 of N-, two (pyridine-2-yl)-1-ethylamines of 1-).Suitable bispidon catalyst substance and effect thereof are described in WO02/48301.
Also can use optical white.In content of the present invention, " optical white " is any chemical substance that forms reactive albic material under daylight being exposed to, and preferably in described reaction, not permanently consumes.Preferred optical white comprises singlet oxygen optical white and radical photoinitiator SYNTHETIC OPTICAL WHITNER.Suitable singlet oxygen optical white can be selected from Water Soluble Phthalocyanines, especially metallized phthalocyanine compound, and wherein said metal is Zn or Al-Z1, wherein Z1 is halogen ion, sulfate radical, nitrate radical, carboxylate radical, alkane acid group or hydroxyl ion.Preferably, described phthalocyanine has 1-4 SO of covalent bonding with it 3x group, wherein X is basic metal or ammonium ion.This compounds is described among WO2005/014769 (Ciba).
In the time existing, described bleaching catalyst is incorporated to the content of about 10wt% with approximately 0.0001 conventionally, and preferably approximately 0.001 to about 5wt%.
In order to reduce or to prevent and other liquid component, can be for example by sealing guard catalyst.
spices
Consider that composition of the present invention is designed to the very product dosage of low levels and uses, it is favourable guaranteeing to effectively utilize spices.
Guarantee that effectively utilizing the particularly preferred mode of spices is to use the spices of sealing.The use of encapsulated perfume has reduced the amount of the spices steam that described composition produces before being diluted.When improving described concentration of perfume, so that the amount of flavorants of each washing while remaining on rational high-content, this is important.
Even more preferably, described spices is not only sealed, and the spices of sealing also has deposition aid, to improve the efficiency of spices deposition and the stop on fabric.Described deposition aid is preferably by covalent linkage, entanglement or adsorb by force and attach in encapsulation object, preferably by covalent linkage or entanglement.
cover dyestuff
Cover dyestuff and can be used for improving the performance of the composition using in method of the present invention.When it is in composition of the present invention and when the method according to this invention uses, cover the deposition of dyestuff on fabric and improve.Preferred dyestuff is purple or blueness.These that it is believed that low levels cover the deposition of dyestuff on fabric and have hidden the yellowing of fabric.The further advantage of covering dyestuff is, they can be used for hiding any yellow-buff colouration of described composition self.
Suitable and preferred dye type is as described in WO09/153184.
Covering dyestuff can use not existing under white dyes, but especially preferably uses the combination of covering dyestuff and white dyes, for example, in order to reduce the yellowing causing due to adsorbed white dyes chemical transformation.
synergistic agent and sequestering agent
Described detergent composition also optionally comprises organic washing synergistic agent or the sequestering agent material of relative low levels.Example comprises basic metal, Citrate trianion, succinate, malonate, carboxymethyl succinate, carboxylate salt, polycarboxylate and poly-ethanoyl carboxylate salt.Concrete example comprises sodium salt, sylvite and the lithium salts of oxygen di-succsinic acid, mellitic acid, benzene polycarboxylic acid and citric acid.Other example is DEQUEST tM, the organic phosphonate type sequestering agent that it is sold for Thermphos, and alkane hydroxyethylidene diphosphonic acid salt.Especially preferred sequestering agent be by Thermphos with 2010 HEDP that sell, also referred to as HEDP.Also suitable, but not preferably 2066 (diethylenetriamine pentamethylenophosphonic acid(DTPP) or Heptasodium DTPMP).
Other suitable organic synergistic agent comprises known high-molecular weight polymer and the multipolymer with synergistic agent performance.For example, this class material comprises suitable polyacrylic acid, polymaleic acid and poly propenoic acid maleic acid and its esters, for example by BASF with title SOKALAN tMthe material of selling.
If used, described organic synergistic agent material can account for described composition approximately 0.5% to 20wt%, preferably 1wt% to 10wt%.Preferably synergistic agent content is lower than the 10wt% of described composition, and preferably lower than 5wt%.
external structure agent
Described composition can be by using its rheological characteristics of one or more substance changes that forms structured network in said composition.Suitable structurising agent comprises hydrogenated castor oil, microfibrous cellulose and natural based structures agent, such as pulp citrus fiber.Pulp citrus fiber is particularly preferred, particularly in the situation that described composition comprises lipase.
visual cues thing
Described composition can comprise and preferably comprise the solid visual cues thing that is insoluble to described composition.Preferably, they are combined with external structure agent, to guarantee that they keep suspending.Preferred visual cues thing is by the film formed lamellar prompting of polymer thin thing, and may comprise functional component, this composition potentially unstable in the time being exposed to alkaline liquid.Enzyme and bleaching catalyst are the examples of this composition.Also has spices, particularly micro-spices of sealing.
packaging and dosage
Described liquid can be used as unitary dose and is packaged in polymeric film, and can adjust described polymeric film and make it was insoluble before adding in washing water.More preferably liquid is supplied in the multipurpose plastic bag with top or bottom closure member.Measuring apparatus can be supplied together with described packaging, its as lid part or integrate in its system.
using method
According to what instruct in WO2009/153184, liquid according to the present invention is intended to can be delivered to common front loading automatic washing machine with the dosage level of 20ml through preparation.Low surfactant content during washing is compensated by the existence of enzyme, stable soil release polymer and optional additional high-efficiency cleaning composition (such as EPEI).But the present invention is also applicable to the more conventional dosage level of about 35ml.For obtaining the suitable liquid of this type, only need in the liquid of described 20ml type, add the spices in other water and possibility situation.In the composition that described soil release polymer more dilutes at these, be also stable.
The present invention is existing to be described further in connection with non-limiting example.
Embodiment
In the following embodiments, important material abbreviation is as follows:
MPG is MPG.
TEA is trolamine.
NI 7EO is C 12-15alcohol ethoxylate 7EO nonionic 25-7 (from Shell Chemicals).
LAS acid is C 12-14linear alkyl benzene sulphonic acid.
5908 is saturated lauryl lipid acid, from Croda.
SLES 3EO is the Zetesol NL with 3 moles of EO.
bB is alkyl betaine, from Huntsman (cocoyl dimethyl carboxybetaine).
EPEI is the Clean-polymkeric substance of polymine of Sokalan HP20-ethoxylation: PEI (600), has 20 EO, from BASF.
Spices is without oil flavors.
SRP is soil release polymer.
5908 is saturated lauryl lipid acid, from Croda.
MEA is monoethanolamine.
NaOH is 47% sodium hydroxide solution.
2066 is diethylenetriamine pentamethylenophosphonic acid(DTPP) (or DTPMP seven sodium).
2010 is HEDP (1-hydroxy ethylene-1,1 ,-di 2 ethylhexyl phosphonic acid).
for Lipex100L, from Novozymes.
for cellulase, from Novozymes.
Stainzyme 12L is the amylase for liquid dosage, from Novozymes.
Mannaway is mannase, from Novozymes.
All experiments below all have 2 pre-wash and once main washing.After prewashing for the second time, application DMO spot.Knitting polyester/braiding the cotton of 50:50 in washings and fabric that load is is 25:1 at ratio.Use 100 RPM to carry out washing in 30 minutes.E～5-10 has removed DMO spot goodly; E～37 are equivalent to not exist the performance under SRP; E～50 are equivalent to the spot before washing.
The pH change records that the SRP stability to hydrolysis (based on the clean-up performance of DMO marker spot on polyester) of the composition 1 providing in table 1 causes along with sodium hydroxide dosage is in table 2.E value is less, and detersive power is better.Before washing, composition is stored at 37 DEG C to 8 weeks, provide the tolerance indication of SRP to standing storage in bottle.
the variation of table 1-composition 1-pH
Raw material % (as 100%)
Deionized water To 100%
MPG 20
NaOH 0
TEA 2
NI7EO 12.74
LAS acid 8.49
Prifac5908 1.5
SLES3EO 4.24
Empigen BB 1.5
EPEI 5.5
SRP 3.75
Spices 2.43
PH adjusting agent 10
table 2 is stored pH to clean impact
PH6.5 and 6.75 times, use the TEA of 2wt% and 3.5wt% to observe functional, show acceptable SRP stability.Therefore the pH that, target is 6.5 and to be less than 7.0 the pH upper limit be preferred with the TEA of 3.5wt% at the most for composition as shown in table 1.For the analogous composition that is diluted with water to 1.5 times of volumes, identical pH scope is that stability is required, and can obtain with the TEA of the 2wt% of corresponding lower aq (in proportion).
dash-control
Detergent liquid should be that pH is stable adding deduct under 5wt% composition, to allow to prepare variable product.In order to obtain this stability, in liquid, must comprise buffer reagent.The buffer reagent using is TEA (pKa7.8) and Prifac5908 lipid acid (because it is mixture, pKa the unknown)..
In WO09153184, use 3% Prifac5908.Under this content, lipid acid has a direct impact for low temperature unstable tool, therefore, reduces the content of lipid acid to improve low-temperature stability (being reduced to 1.71% in 20ml liquid, is correspondingly 0.85% for 35ml composition).Check the impact on froth breaking, discovery is acceptable.Also reduce the impact of Prifac5908 on buffering and pH control with the 20ml composition inspection providing in table 3, discovery is acceptable (table 4).
table 3
Raw material % (as 100%)
Deionized water To 100%
MPG 20
NaOH To target pH
TEA 0-3.5
NI7EO 12.74
LAS acid 8.49
Prifac5908 1.5
SLES3EO 4.24
Empigen BB 1.5
EPEI 5.5
SRP 3.75
Spices 1.39
the pH stability of table 4-look-up table 3 liquid is with the variation of TEA content
The liquid of table 3 is Prifac5908 or TEA if there is no, does not have pH to control.Can with 1.5%Prifac5908 and at least 1%TEA obtain acceptable pH and control.Adopt 0%TEA, compare Gao pH district is controlled, but compare Di pH district drops to and is markedly inferior to pH6.0, and it causes unacceptable low-temperature stability performance.
low-temperature stability
Two kinds of low temperature standards product (recover at ambient temperature) stable 12 weeks at the most at 5 DEG C, and stablize 1 week under freezing/thawing (recovering at ambient temperature).
The content of lipid acid using is the instable critical aspects of low temperature, this under lower pH (along with the ratio rising of lipid acid and soap class) worse and worse.If added with requirement, add TEA and MPG can overcome this unstable.
Stability to hydrolysis based on SRP and pH control, the target pH that the starting point of 20ml liquid composition is 6.5 and minimum 1%TEA and 1.5%Prifac5908.Actual TEA demand is to specify in table 5, and MPG demand is to specify in table 6.
For as the liquid of regulation in table 1, preferred TEA % by weight is 3.5%, and preferred MPG % by weight is 20%.
The starting point of rarer 35ml composition is that identical pH requires and 2%TEA.Content for the required MPG of low-temperature stability is presented in table 7.For the liquid of 35ml, required MPG % by weight is 15%.
the composition 1 liquid low-temperature stability that table 5-contains different TEA content
F/T=freeze thawing
table 6
Raw material % (as 100%)
Deionized water To 100%
MPG 10-25
NaOH To target pH
TEA 3.5
NI7EO 12.74
LAS acid 8.49
Prifac5908 1.5
SLES3EO 4.24
Empigen BB 1.5
EPEI 5.5
SRP 3.75
Spices 1.39
the low-temperature stability of table 7-table 6 liquid is with the changing conditions of pH and MPG content
the isotropic liquid of table 8-35ml
PH scope 6,6.5,7,7.5,8
the stability data of the composition of table 9-table 8
P=is qualified
F=is defective
R=is defective at 5 DEG C, but in the time being warmed to room temperature, becomes isotropic.

Claims (10)

1. an isotropic liquid detergent composition, its have scope 6.0 to be less than 7 bottle in pH, described composition, except comprising water, also comprises:
A) the stain release type tensio-active agent of maximum 60wt%, it comprises at least anionic sulphonate and/or the sulfate surfactant of 5wt%, described anionic sulphonate and/or sulfate surfactant comprise the surfactant acid with one or more material neutralizations, the pKa of the conjugate acid of described one or more materials is higher 2 more than unit than pH in the bottle of detergent liquid composition
B) lipid acid of one or more material parts of the use of 0.3wt% neutralization at least, the pKa of the conjugate acid of described one or more materials is higher 2 more than unit than pH in the bottle of detergent liquid composition,
C) 1.0wt% at least, the preferably trolamine of 1.8wt% (TEA) at least; With
D) soil release polymer of 0.5wt% (SRP) at least.
2. according to the composition of claim 1, it has 6.3 to 6.7 the interior pH of bottle.
3. according to the composition of the aforementioned claim of any one, wherein said lipid acid is saturated.
4. according to the composition of the aforementioned claim of any one, the usage quantity of wherein said lipid acid is 0.5 to 1.5wt%.
5. according to the composition of the aforementioned claim of any one, it comprises maximum 3.7wt%, preferably 2.0 to 3.5wt% trolamine (TEA).
6. according to the composition of the aforementioned claim of any one, the pKa of the conjugate acid of wherein said one or more materials is higher 2 more than unit than pH in the bottle of detergent liquid composition, described one or more materials comprise 0.08 to 0.25wt%, preferably 0.1 to 0.23wt% NaOH and/or monoethanolamine (MEA).
7. according to the composition of the aforementioned claim of any one, wherein said SRP has by terephthalate and glycol, preferably 1, the fabric affinity part that 2 propylene glycol condensations form, and further comprise end-capped hydrophilic parts, described end-capped hydrophilic parts comprises with alkyl-blocked oxyethane repeating unit.
8. according to the composition of the aforementioned claim of any one, it is at least 5wt%, preferably at least 9wt% and the more preferably hydrotropic agent of 14wt% at least that wherein said liquid comprises content, and 1,2 propylene glycol (MPG) most preferably.
9. according to the composition of the aforementioned claim of any one, its polymine that comprises at least ethoxylation of 5wt% (EPEI).
10. according to the composition of the aforementioned claim of any one, wherein said anion surfactant a) comprises at least linear alkylbenzene sulfonate of 5wt% (LAS).
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