CN104011192B - Isotropic liquid detergent comprising soil release polymer - Google Patents

Isotropic liquid detergent comprising soil release polymer Download PDF

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Publication number
CN104011192B
CN104011192B CN201280063058.XA CN201280063058A CN104011192B CN 104011192 B CN104011192 B CN 104011192B CN 201280063058 A CN201280063058 A CN 201280063058A CN 104011192 B CN104011192 B CN 104011192B
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composition
composition according
acid
liquid
bottle
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CN104011192A (en
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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

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

A kind of isotropic liquid detergent composition, it has scope 6.0 to pH in the bottle less than 7, and the composition is also included in addition to comprising water：A) most 60wt% stain release type surfactant, it includes at least 5wt% anionic sulphonate and/or sulfate surfactant, the anionic sulphonate and/or sulfate surfactant include the surfactant acid neutralized with one or more materials, it is more than the pKa of the conjugate acid of one or more materials 2 units higher than pH in the bottle of detergent liquid composition, b) at least 0.3wt% aliphatic acid neutralized with one or more material parts, it is more than the pKa of the conjugate acid of one or more materials 2 units higher than pH in the bottle of detergent liquid composition, c) at least 1.0wt%, preferably at least 1.8wt% triethanolamine (TEA)；And d) at least 0.5wt% soil release polymer (SRP).

Description

Isotropic liquid detergent comprising soil release polymer
Technical field
The present invention relates to isotropic liquid detergent composition, its comprising water, hydrotropic agent, anionic sulphonate or Sulfate surfactant and polyester base soil release polymer.
Background technology
WO09153184 propose it is a kind of can be by using the mixture replacing selected from polymer and the more effective composition of enzyme Surfactant and the laundry detergent liquid concentrate designed.A kind of preferred composition uses the polyethyleneimine of ethoxylation The combination of amine (EPEI) and polyester soil release polymers (SRP), with the significantly lower washing of delivering more usual than high-performance liquid The excellent greasy dirt of surfactant level acquisition and particulate stain removal.Exemplary composition includes anion surfactant simultaneously And further comprise that, by the soaps in sodium hydroxide with aliphatic acid formation, the anion surfactant includes and uses hydroxide The linear alkylbenzene sulfonate (LAS) that sodium is neutralized.Said composition is alkaline.It has been found that the SRP for embodiment have passed through alkaline water Solution, and the basic hydrolysis using triethanolamine (TEA) by being catalyzed in the composition.
A kind of obvious solution of SRP hydrolytically unstable sex chromosome mosaicism is to separate said composition, and by its It is stored in single room, so that SRP is not contacted with TEA or alkaline matter.It is this to be probably based on sour certain formulations Based on the teaching in EP294893, US2010229313 and US3893929.However, using separated composition be it is undesirable, Because it can increase cost and complexity.Consumer wishes to deliver all cleaning substances from single main cleaning solution.
Main cleaning solution is configured to acidity and there is sizable technology prejudice.Generally believe that they can produce acidic cleaning bar Part, it is reduced due to the performance of surfactant system and some possible enzymes, and cleaning will be caused insufficient.US5290475 (Colgate) it is a document, it in order to improve SRP stability to preparing show technology prejudice in acid condition. Liquid softens and antistatic nonionic detergent composition includes nonionic detergent, the anionic detergent as main component Agent, cationic fabric softener-antistatic additive and polyethylene terephthalate-polyoxyethylene terephthalate type Water-soluble portion decontamination promote polymer.In order to help detergent and Optical Bleaching Agent that may be present in liquid detergent Dissolving, generally include the alkaline matter of small scale or the mixture of such material.Suitable alkaline matter include it is single-, Two-and three-alkanolamine, alkylamine, ammonium hydroxide and alkali metal hydroxide.Wherein, material preferably is alkanolamine, preferably Three alkanolamines, wherein particularly preferred triethanolamine.During the pH of final liquid detergent comprising this alkaline matter generally will be Property or it is slightly alkaline.Satisfactorily pH scopes are 7 to 10, preferably from about 7.5 to 9.5.
The pH that WO9742286 (P＆G) teaches laundry detergent in page 3 and generally had is more than 7.5.Contained according to page 9 There is SRP composition, it discloses when being measured as 10% aqueous solution, the pH with about 7.2 to about 8.9.
US4785060 (Colgate) discloses the PET POET of the HMW prepared using hybrid catalyst system SRP.It is said that these SRP are in the suds in the presence of builder keeps their performance at a high ph.Wrapped according to them are instructed It is contained in both solid and liquid detergent composition.The disclosure of which, which is taught, minimizes included alkanolamine such as TEA With ionizable salt such as Na.It teaches in the row of the 10th column the 13rd to 15, it is preferable that be generally used for improving liquid detergent mixing Nertralizer used in thing pH is sodium hydroxide.In the 17th to 18 row, its continue to instruct " should generally avoid triethanolamine salt and Free triethanolamine ".PH scopes will be 6 to 10, preferably 6.1 to 8.9, generally more preferably 6.5 to 7.5.
US4759876 (Colgate) discloses the decontamination comprising SRP and promotes liquid detergent composition.The composition Further comprise the enzyme stabilizers for stablizing ratio, it also functions as the buffer of liquid detergent composition pH is maintained at into a certain Neutrality or slightly acid range, to stablize SRP and fluorescent whitening agent.It is said that said composition " is kept substantially " its dirt in storage Hydrolyze fluorescent brightening and decontamination promotes characteristic, brighten and handle so that the clothing washed with it is cleaned effectively.However, coming from The US5110506 of same assignee shows that performance is good not as ' 876 are proposed.It is also clear that according to ' 876 disclosure, In storage, pH turns to acid.We determined that this may should be attributed to SRP decomposition because its in storage more than just hydrolyzing January. Do not include any soaps.It is said that enzyme stabilizers/the buffer can keep pH 6.2 or higher.The pH provided after storage Scope is 6.2 to 6.5.However, it is 5.8 to 7 to also give the pH scopes that will not further make the polymer unstable.
In US5110506 (Colgate), except disclosing the detergency ability difference that ' 876 liquid is obtained after storage Outside, it is specific very expensive it also teaches minimize 2EO and 3EO contents by the way that the nonionic is changed over Material can obtain the small improvement of the detergency ability after storage.The liquid with pH in the range of 7.3 to 8.1 is taught to wash Wash agent.This shows that pH still can change due to hydrolysis.It is probably due to being converted to more effective type that the cleaning claimed, which improves, Nonionic surfactant.
GB1466639 (P＆G) discloses the surfactant neutralized with monoethanolamine and SRP detergent liquid.Including Some free TEA are so that washings keep alkalescence.Disclose two distinct types of liquid.In the first type, selection Specific nonionic surfactant assigns composition enough physical stabilities.In second of type, aliphatic acid (soap is included Class) to provide extended storage stability.The embodiment of seemingly second of the type of composition of embodiment 1.It includes 1.5% oil Sour TEA salt and 5% SRP (coming from table 1).It was found that it is alkaline compositions.
US4411831 (Purex) discloses a kind of aqueous detergent composition of stabilization, and it has enhanced decontamination property And be substantially made up of SRP (there is LAS) and nonionic and buffer, the buffer keeps the waterborne compositions enough PH in 5.0 to 9.0, preferably 6.5 to 7.5.Embodiment is being adjusted to 7 main washing group comprising LAS and nonionic and pH Zelcon4780SRP has been used in compound.Hydrotropic agent is used as using SXS.TEA or soap are not used in this embodiment Class.The disclosure of which teaches the comparative example liquid without buffer and produces acid pH in storage.It is said that acid pH is to brightening Agent is harmful to.We have appreciated that acid pH, which is due to SRP, decomposes what is produced.Add buffer to stablize pH to the solution used.Due to PH is more alkaline, and this will cause SRP to decompose increase.Brightening agent can be protected, the true purpose of this seemingly invention.Institute The suitable buffer of teaching includes bicarbonate, orthophosphates, borate and alkanolamine hydrochlorate.
US4713194 (P＆G) discusses the readily degradable of the SRP in alkaline environment, and if proposed in particulate composition Middle use then is protected by coating (enrobing) to SRP, or by product if being used in fluid composition PH is adjusted to 7.0 to 8.5.Embodiment includes the fatty acid distribution of coconut oil of high content.
US6262007 (P＆G) describes acid detergent liquid, and it includes SRP to reduce with viscosity during temperature drop Increase.Some embodiments include TEA, but not including that hydrotropic agent or aliphatic acid.
The concentrated liquid detergent composition for including SRP is needed, it even all provides excellent clear after extension storage Clean property.
Invention summary
According to the present invention there is provided a kind of isotropic liquid detergent composition, it has scope 6.0 to less than 7 (in-bottle) pH in bottle, the composition is also included in addition to comprising water：
A) most 60wt% stain release type surfactant, it includes at least 5wt% anionic sulphonate and/or sulfuric acid Salt surfactant, the anionic sulphonate and/or sulfate surfactant include what is neutralized with one or more materials Surfactant acid, pKa 2 lists higher than pH in the bottle of detergent liquid composition of the conjugate acid of one or more materials It is more than position,
B) at least 0.3wt% aliphatic acid neutralized with one or more material parts, one or more materials It is more than the pKa of conjugate acid 2 units higher than pH in the bottle of detergent liquid composition,
C) at least 1.0wt%, preferably at least 1.8wt% triethanolamine (TEA)；With
D) at least 0.5wt% soil release polymer (SRP).
Preferably, the composition is with pH in 6.3 to 6.7 bottle.Refer to any container of fluid storage wherein in bottle Or packaging.It can be doleiform formula, squeezable or rigid, upright or inversion storage or unit dosage form plastics Packaging, such as soluble pouch (pouch) or wafer (sachet).
Aliphatic acid provides buffer capacity, but inside acidic composition can be caused to be separated at low temperature comprising it.Therefore, It can only be included with relative low content.The aliphatic acid can not be as being preferably hydrogen for neutralize anion surfactant a) The material of sodium oxide molybdena or MEA (MEA) is equally all removed, because the material can not stablize the composition in itself. Preferably, aliphatic acid is saturation.Most preferably, its usage amount is 0.5 to 1.5wt%.
Contribute to the stability of aliphatic acid using TEA, therefore, TEA is included with content high as being allowed by SRP Inside.TEA amount is preferably no more than 3.7wt%, most preferably 2.0 to 3.5wt%.
Advantageously, the pKa of the conjugate acid of one or more materials is higher by 2 than pH in the bottle of detergent liquid composition It is more than individual unit, one or more materials include 0.08 to 0.25wt%, preferably 0.1 to 0.23wt% NaOH and/or MEA (or MEA).The definition of non-buffered component is intended to be in buffering area (moderate acid interested：6.0 to less than 7) all common weak base and highly basic outside.Therefore, for neutralizing anionic surfactant acid to prepare anionic surface More than the pka of the conjugate acid of activating agent a) material 2 units higher than pH in the bottle of detergent liquid composition, the material exists It can not significantly play buffer under pH in the bottle of the composition storage.On the contrary, TEA is in the bottle of moderate acid under pH Really buffer is played.
SRP is that one deposited to from wash solution on polyester birdss of the same feather flock together compound.Its preferably have by terephthalate and The polyester compatibility part that glycol (preferably 1,2 propane diols) condensation is formed, and it further comprises end-capped hydrophily portion Point, the end-capped hydrophilic parts are included with alkyl-blocked ethylene oxide repeating units.Its usage amount can be more than 0.5wt%, and can exist with the content for being up to 15wt%.Different SRP mixture can be used.
The liquid generally includes hydrotropic agent.When deployed, hydrotropic content will be at least 5wt%, excellent Selection of land at least 9wt%, more preferably at least 14wt%.For cost reasons, hydrotropic amount is preferably less than composition 25wt%, more preferably less than 20wt%.It is preferred that hydrotropic agent be 1,2 propane diols (MPG).
Advantageously, in order to improve particulate stain removal, the composition includes at least 3%, preferably at least 5wt% ethoxy Base polyethyleneimine (EPEI).
Detailed description of the invention
In addition to essential characteristic, composition of the invention can include other compositions.Such composition is adjusted including viscosity Save agent, it is blowing promotor, preservative (such as bactericide), pH buffer, polyelectrolyte, anti-shrinking medium, anti wrinkling agent, antioxidant, anti- Shine agent, corrosion inhibitor, drape imparting agents (drape imparting agents), antistatic additive and ironing aids, colouring agent, pearl Photo etching (pearlisers) and/or opacifier and masking dyestuff (shading dye).
The main aspect of composition further described below and optional aspect.
Isotropic liquid
The amount of stain release type surfactant accounts at least 10wt% of total fluid composition, preferably comprises from 12 and arrives 60wt%.Root The active stain release type surfactant total content most preferably having according to the composition of the present invention is at least 15wt%.
The composition can be the composition of concentration, and it is designed to add into 10 liters of washing with low dose, this It is required that they are diluted at least 500 times of water of their own volume, to be formed comprising at most 0.5g/l surfactants Main wash liquid.They can also be the concentrate composition of the automatic washing machine designed for hand washing or top-loaded.In hand washing It is middle to use less water, and in the automatic washing machine of top-loaded usually using higher amount water.Correspondingly adjustment is washed The dosage of agent liquid is washed, to provide similar wash liquid concentration.
Surfactant
Surfactant contributes to from textile material dirt up, and additionally aid the dirt of removal is maintained at it is molten In the suspension of liquid or wash liquid.The blend of anion surfactant or anion and nonionic surface active agent is The preferred feature of the present invention.The amount of anion surfactant is preferably at least 5wt%.
Preferably, anion surfactant forms the main body of nonsoap surfactant (a).
Anion surfactant
It is preferred that alkylsulfonate be alkylbenzenesulfonate, especially with C8-C15Long alkyl chains straight chained alkyl Benzene sulfonate.
It is preferred that linear alkyl sulfonate surfactant be Detal LAS, its have 8 to 15, more preferably 12 to 14 long alkyl chains.
It is also expected to the composition includes the sulphate anion surface active agent of alkyl polyethoxylate, it has formula (I)：
RO(C2H4O)xSO3 -M+ (I)
Wherein, R is the alkyl chain (saturation is undersaturated) with 10 to 22 carbon atoms, and M is so that the compound It is dissolved in the cation of water, especially alkali metal, ammonium or substituted ammonium cation, 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, preferably x are 3；This For anion surfactant sodium laureth sulfate (SLES).It is the sodium salt of laureth sulfate, wherein mainly C12 The alkyl group of lauryl has been averaged 3 moles of ethylene oxide/moles ethoxylated.
Nonionic surfactant
Nonionic surface active agent includes primary and secondary alcohol ethoxylate, is especially rubbed per mol of alcohol with average 1 to 20 The C of your oxirane ethoxylation8-C20Aliphatic alcohol, and be more specifically with average 1-10 moles of ethylene oxide per mol of alcohol The C of ethoxylation10-C15Primary and secondary aliphatic alcohol.Unethoxylated nonionic surfactant includes alkyglycosides, sweet Oily monoether and polyhydroxy amides (glucamide).The mixture of nonionic surfactant can be used.When being included therein, Then composition contains 0.2wt% to 40wt%, preferably 1wt% to 20wt%, more preferably 5 to 15wt% non-ionic surface Activating agent, such as alcohol ethoxylate, nonyl phenol ethoxylate, alkyglycosides, alkyl dimethyl amine oxide, ethoxy Base fatty monoethanol amide, fatty monoethanol amide, the N- acyl groups N- of polyhydroxy alkyl fatty acid amides or gucosamine Alkyl derivative (" glucamide ").
The nonionic surfactant that can be used includes primary and secondary alcohol ethoxylate, is especially averaged with per mol of alcohol The C of 1 to 35 mole of oxirane ethoxylation8-C20Aliphatic alcohol, and it is more particularly average 1 to 10 mole by every mol of alcohol Oxirane ethoxylation C10-C15Primary and secondary aliphatic alcohol.
Amine oxide
The composition may comprise up to 10wt% amine oxide, and it has formula：
R1N(O)(CH2R2)2
Wherein R1It is long-chain moiety, each CH2R2It is short chain moieties.R2It is preferably chosen from hydrogen, methyl and-CH2OH.It is general and Speech, R1It is the hydrocarbyl portion of primary hydrocarbyl portion or side chain, it can be saturation or undersaturated, it is preferable that R1It is primary alkyl portion Point.R1It is the hydrocarbyl portion of the carbon chain lengths with about 8 to about 18.
It is preferred that amine oxide R1For C8-C18Alkyl, and R2For H.These amine oxide examples are C12-14Alkyl dimethyl Amine oxide, cetyl dimethyl amine oxide, octadecyl amine oxide.
It is preferred that amine oxide material be lauryl dimethyl amine oxide, also known as DDAO or DDAO.This amine oxide material can be with trade nameOB is commercially available from Hunstman.
Suitable for this paper amine oxide also available from Akzo Chemie and Ethyl Corp.Other amine oxide manufacturers are joined See the survey article of McCutcheon's compilings originally with Kirk-Othmer.
Although R in certain preferred aspects2For H, but R2Can be more bigger than H.Specifically, R2Can be CH2OH, Such as：Double (2- ethoxys) amine oxides of cetyl, double (2- ethoxys) amine oxides of tallow, stearyl double (2- ethoxys) oxidation Amine and double (2- ethoxys) amine oxides of oleyl.
It is preferred that amine oxide there is following formula：
O--N+(Me)2R1 (3)
Wherein, R1It is C12-16Alkyl, preferably C12-14Alkyl；Me is methyl group.
Zwitterionic surfactant
Can be used with most 95%wt LAS be free of non-ionic system, precondition be exist some both sexes from Sub- surfactant, such as carboxybetaine (carbobetaine).It is preferred that amphion material be carboxybetaine, it can With with the name of an articleBB is obtained from Huntsman.Glycine betaine improves the particulate soil decontamination in the composition of the present invention Property.
It is preferred that composition include at least 1wt% amine oxide or carboxybetaine or its mixture.
Other surfactants
It can be added into the mixture of detersive surfactant and remove preferred LAS, SLES, nonionic surfactant and two Other surfactants outside property ionic surface active agent (glycine betaine).It is preferable, however, that being substantially not present cationic surface work Property agent.
It is especially unethoxylated although some alkyl sulfate surfactants (PAS) less preferably, can be used C12-15Primary and secondary alkyl sulfate.The commercially available particularly preferred species obtained from Cognis is Sulphopon1214G.
Other polymer
EPEI
It is the polyethyleneimine of ethoxylation with reference to the particularly preferred polymer classes that soil release polymer (SRP) is used (EPEI).Polyethyleneimine is by ethylene imine units-CH2CH2The material of NH- compositions, and in the case of collateralization, nitrogen On hydrogen substituted by another chain of ethylene imine units.These polyethyleneimines can exist by, for example, in catalyst In the case of polymerising ethylene imines prepare, the catalyst such as carbon dioxide, sodium hydrogensulfite, sulfuric acid, hydrogen peroxide, salt Acid, acetic acid etc..Ulrich et al. disclosed in 5 days December nineteen thirty-nine is disclosed in for preparing the specific method of these polyamine main chains United States Patent (USP) No.2,182,306；The United States Patent (USP) No.3,033,746 of Mayle et al. disclosed in 8 days Mays in 1962；1940 The United States Patent (USP) No.2,208,095 of Esselmann et al. disclosed in July 16；Crowther disclosed in nineteen fifty-seven September 17 days United States Patent (USP) No.2,806,839；And in the United States Patent (USP) No.2,553,696 of Wilson disclosed in 21 days Mays nineteen fifty-one.
Preferably, the EPEI includes the polyethyleneimine backbone that weight average molecular weight is about 300 to about 10000；It is wherein right The modification of the polyethyleneimine backbone is intended to not contain the polymer quaternized and non-ionic.This kind of nonionic EPEI It is unmodified PEI molecular weight that PEI (X) YEO, wherein X, which can be expressed as, and Y is every nitrogen original in polyethyleneimine backbone The average mol of the ethoxylation of son.The ethoxylation can be 9 to 40 epoxy groups/modifications, be preferably 16 To 26, most preferably 18 to 22.
When deployed, the content of EPEI polymer present in the composition is preferably at most 25wt%, preferably Content is at least 3wt%, most preferably at least more preferably 4 to 15wt%, 5wt%.Nonsoap surfactant and EPEI's Ratio is 2:1 to 7:1, preferably 3:1 to 6:1, or even 5:1.
Other polymer types
In addition to polyester soil release polymers, dye transfer inhibiting polymers, antiredeposition polymer and cotton it is also possible to use Material soil release polymer, is based especially on those polymer of modified cellulosic material.
Hydrotropic agent
In present disclosure, hydrotropic agent is not only non-aqueous but also the solvent of unconventional surfactant, and it is facilitated The solubilising of surfactant and other components in waterborne liquid, makes its isotropism.In suitable hydrotropic agent, below this It can be referred to a bit as preferred：MPG (MPG), glycerine, sodium cumene sulfonate, ethanol, other glycols (such as dipropyl Glycol), diether and urea.
Except turning to more acidic composition when we, which are attributed to, is stored caused by SRP hydrolysis, we have also observed that when it During comprising the SRP sensitive to basic hydrolysis, the physical stability of composition seems also to be improved；Especially we have found that when storage There is the SRP sold when in alkaline detergent composition with trade name Texcare SRN170 by Clariant unstable, and By the polymer cover containing in alkaline detergent composition provide wonderful composition viscosity reduce.I.e. using new The polymer of preparation, we also observe the effect.It is believed that SRP plays hydrotropic in isotropic detergent liquid The effect of agent.
Enzyme
Preferably, there may be at least one or more of enzyme in the composition.Preferably, at least two, more preferably At least three kinds different types of enzymes can be applied in combination.
Lipase
Lipase is particularly preferred enzyme.The composition preferably includes about 5 to about 20000LU/g lipase.It is excellent Selection of land at least 800LU/g.It is preferred that lipase include those of bacterium or originated from fungus.Including chemical modification or protein engineering Mutant.The example of useful lipase includes the lipase from Humicola (Humicola), more preferably including with ammonia The polypeptide of base acid sequence, the amino acid sequence is with being derived from Humicola lanuginosa (Humicola lanuginosa), most preferably The wild type lipase of DSM4109 bacterial strains has the lipase of at least 90% sequence identity.Amount in the composition Higher than the amount being typically found in liquid detergent.Especially, this can be by the ratio of nonsoap surfactant and lipase To represent.Particularly preferably can be with trade mark LipocleanTMLipase obtained from Novozymes.
As noted above, suitable lipase includes the lipase of bacterium or originated from fungus.Including chemical modification or albumen Matter engineered mutants.The example of useful lipase is included from Humicola (Humicola) (Thermomyces is synonymous) Humicola lanuginosa (H.lanuginosa) is come from described in lipase, such as EP258068 and EP305216 (T.lanuginosus) Humicola insolens (H.insolens) are come from, or as described in WO96/13580；False silk zygosaccharomyces Lipase, for example, from Pseudomonas alcaligenes (P.alcaligenes) or pseudomonas pseudoalcaligenes (P.pseudoalcaligenes) (EP218272), Pseudomonas cepacia (P.cepacia) (EP331376), the false unit cells of Si Shi Bacterium (GB1372034), Pseudomonas fluorescens (P.fluorescens), pseudomonas strain SD705 (WO95/06720 and WO96/27002), Wisconsin pseudomonad (P.wisconsinensis) (WO96/12012)；Bacillus lipase, For example, from bacillus subtilis (B.subtilis) (Dartois etc. (1993), Biochemica et Biophysica Acta, 1131,253-360), bacillus alcalophilus (B.stearothermophilus) (JP64/74992) or short and small gemma bar Bacterium (B.pumilus) (WO91/16422).As noted above, lipase preferably and the agriotype from Humicola lanuginosa Lipase there is the homology of height.
Other examples have a lipase Variant, such as WO92/05249, WO94/01541, EP407 225, EP260 105, WO95/35381、WO96/00292、WO95/30744、WO94/25578、WO95/14783、WO95/22615、WO97/04079 With those described in WO97/07202.
It is preferred that commercially available lipase include LipolaseTMWith Lipolase UltraTM、LipexTMAnd LipocleanTM (Novozymes A/S)。
In addition to lipase or as the substitute of lipase, one or more other enzymes may be present.
Advantageously, exist in the present compositions the calcium of high relative contents have for the conversion ratio of certain enzyme it is beneficial Effect, the preferably enzyme especially lipase and the lipase from Humicola.
It is preferred that lipase include first washing lipase, from LipexTMThe pubescence that trade mark derives from Novozymes is rotten The mould DSM4109 bacterial strains of matter.From Novozymes but be considered as the similar enzyme outside above-mentioned limitation can be with title LipocleanTMDerived from Novozymes, and this is also preferred.
Phosphatidase:
The method of the present invention can be carried out in the presence of EC3.1.1.4 and/or EC 3.1.1.32 phosphine lipase is classified as.Such as Terms used herein phosphatidase is a kind of enzyme, and it is active to phosphatide.Phosphatide, such as lecithin or phosphatidyl choline, its By being esterified and using the glycerine that phosphoric acid is esterified in the 3rd position in outside (sn-1) and middle (sn-2) position with two aliphatic acid Composition；Phosphoric acid and then it can be esterified as amino alcohol.Phosphatidase is the enzyme for participating in phospholipid hydrolysis.The phosphatide of several types can be distinguished Enzymatic activity, including phospholipase A1 and A2, it hydrolyzes a fatty acyl group (respectively at sn-1 and sn-2) to form lysophosphatide； With can hydrolyze the lysophospholipase (or phospholipase B) of remaining fatty acyl group in lysophosphatide.Phospholipase C and phospholipase D (phosphorus Acid diesters enzyme) diacylglycerol and phosphatidic acid are discharged respectively.
Protease:
Suitable protease includes animal, plant or those microbe-derived.Microbe-derived is preferred.Including Chemical modification or protein engineering mutant.Protease can be serine protease or metalloproteinases, preferably alkaline micro- Bio protease or trypsinlike enzyme.It is preferred that commercially available protease include AlcalaseTM、SavinaseTM、PrimaseTM、 DuralaseTM、DyrazymTM、EsperaseTM、EverlaseTM、PolarzymeTMAnd KannaseTM、(NovozymesA/ S)、MaxataseTM、MaxacalTM、MaxapemTM、ProperaseTM、PurafectTM、Purafect OxPTM、FN2TMWith FN3TM(Genencor International Inc.)。
Cutinase:
The method of the present invention can be carried out in the presence of the cutinase being categorized as in EC3.1.1.74.It is used according to the invention Cutinase can be any source.It is preferred that cutinase be microbe-derived, particularly bacterium, fungi or yeast sources 's.
Amylase:
Suitable amylase (α and/or β) includes those of bacterium or originated from fungus.Including chemical modification or protein Engineered mutants.Amylase includes, for example, the alpha-amylase derived from bacillus (Bacillus), is such as described in more detail in The specific bacterial strain of bacillus licheniformis (B.licheniformis) in GB1,296,839 or in WO95/026397 or WO00/ Bacillus (Bacillus sp.) bacterial strain described in 060060.Commercially available amylase is DuramylTM、 TermamylTM、TermamylUltraTM、NatalaseTM、StainzymeTM、FungamylTMAnd BANTM(Novozymes A/ S)、RapidaseTM and PurastarTM(from Genencor International Inc.).
Cellulase:
Being adapted to cellulase includes those of bacterium or originated from fungus.Including chemical modification or protein engineering mutation Body.Suitable cellulase includes coming from bacillus (Bacillus), pseudomonas (Pseudomonas), humicola lanuginosa (Humicola) category, fusarium (Fusarium), Thielavia (Thielavia), the fibre of Acremonium (Acremonium) The plain enzyme of dimension, such as by Humicola insolens (Humicola insolens), Thielavia terrestris (Thielavia Terrestris), thermophilic fungus destroyed wire (Myceliophthora thermophila) and Fusarium oxysporum (Fusarium Oxysporum the fungal cellulase produced by), it is disclosed in US4,435,307, US5,648,263, US5,691,178, In US5,776,757, WO89/09259, WO96/029397 and WO98/012307.Commercially available cellulase includes CelluzymeTM、CarezymeTM、EndolaseTM、RenozymeTM(Novozymes A/S)、ClazinaseTMAnd Puradax HATM(Genencor International Inc.) and KAC-500 (B)TM(Kao Corporation)。
Peroxidase/oxidizing ferment:
Suitable peroxidase/oxidizing ferment includes those of plant, bacterium or originated from fungus.It is including chemical modification or Protein engineered mutant.Useful peroxidase includes the peroxidase from Coprinus (Coprinus), example Such as from the terrible umbrella (C.cinereus) of grey and its variant, as retouched in WO93/24618, WO95/10602 and WO98/15257 Those stated.Commercially available peroxidase includes GuardzymeTMAnd NovozymTM51004(Novozymes A/S)。
Transelminase：
Transelminase (also referred to as galacturonan lyase)：The example of transelminase is included from difference Pseudomonas such as Erwinia (Erwinia), pseudomonas (Pseudomonas), Klebsiella And xanthomonas (Xanthomonas) and from bacillus subtilis (Bacillus subtilis) (Klebsiella) (Nasser et al.(1993)FEBS Letts.335:319-326) with bacillus (Bacillus sp.) YA-14 (Kim et al.(1994)Biosci.Biotech.Biochem.58:947-949) clone obtained transelminase.Also retouched State 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), bacillus stearothermophilus (B.stearothermophilus) (Karbassi and Vaughn (1980) Can.J.Microbiol.26:377-384), bacillus (Bacillus sp.) (Hasegawa and Nagel (1966) J.Food Sci.31:838-845) with bacillus (Bacillus sp.) RK9 (Kelly and Fogarty (1978) Can.J.Microbiol.24:1164-1172) production is the pure of the transelminase that 8-10 has maximum activity in pH Change.
Transelminase that above-mentioned any one and bivalent cation rely on and/or heat-staple can be used to come real Apply the present invention.In preferred embodiments, transelminase is included in Heffron etc., (1995) Mol.Plant- Microbe Interact.8:331-334 and Henrissat etc., (1995) Plant Physiol.107:Disclosed in 963-976 Transelminase.Specific expected transelminase is disclosed in WO99/27083 and WO99/27084.Others tool Transelminase expected from body (deriving from bacillus licheniformis (B.licheniformis)) is disclosed in U.S. Patent number 6, In 284,524.Specific expected Pectate lyase variants are disclosed in WO02/006442, especially WO02/006442 reality Apply the variant disclosed in example.
The example of commercially available alkaline pectate lyase includes coming from NovozymesA/S, the BIOPREP of DenmarkTMWith SCOURZYMETM。
Mannase：
Mannase: the example of mannase (EC3.2.1.78) includes the mannosan of bacterium and originated from fungus Enzyme.In certain embodiments, mannase can derive from the bacterium of the filamentous fungi of Eurotium (Aspergillus) Strain, preferably black-koji mould (Aspergillus niger) or microorganism Aspergillus aculeatus (Aspergillus aculeatus) (WO94/ 25576).WO93/24622 discloses the mannase for being isolated from trichoderma reesei (Trichoderma reseei).From Mannase has been separated in several bacteriums, has included those of bacillus biology.For example, Talbot etc., Appl.Environ.Microbiol., volume 56, o. 11th, the 3505-3510 pages (1990) are described obtained from stearothermophilus bud The 'beta '-mannase of spore bacillus (Bacillus stearothermophilus).Mendoza etc., World J.Microbiol.Biotech., volume 10, the 5th phase, the 551-555 pages (1994) are described obtained from bacillus subtilis The 'beta '-mannase of (Bacillus subtilis).JP-A-03047076 is disclosed obtained from bacillus (Bacillus Sp. 'beta '-mannase).JP-A-63056289 describes alkalescence, heat-staple 'beta '-mannase production.JP-A- 63036775 are related to bacillus (Bacillus) microorganism FERM P-8856, and it produces 'beta '-mannase and β-sweet dew Glycosidase.JP-A-08051975 discloses the alkaline β-sweet dew for belonging to (Bacillus sp.) AM-001 from Alkaliphilic bacillus Dextranase.Purified mannanase from bacillus amyloliquefaciens (Bacillus amyloliquefaciens) is disclosed in In WO97/11164.WO91/18974 describes a kind of hemicellulase, such as dextranase, zytase or mannase Active matter.It is contemplated that from the viscous agar bacillus (Bacillus disclosed in WO99/64619 Agaradhaerens), bacillus licheniformis (Bacillus licheniformis), Alkaliphilic bacillus (Bacillus Halodurans), Bacillus clausii (Bacillus clausii), bacillus (Bacillus sp.) and special corruption The mannase of alkaline family 5 and 26 of matter mould (Humicola insolens).It is specifically contemplated that be reality in WO99/64619 Apply the mannase of the bacillus (Bacillus sp.) used in example.
The example of commercially available mannase includes being available from NovozymesA/S, the Man naway of DenmarkTM。
The enzyme and any aromas/fragrances or aromatic precursor of presence can show some interactions, should add To select, so that this interaction not negative effect.Can be by the one or another kind in encapsulated enzyme and aromatic precursor And/or other isolation in product avoid some negative interactions.
Enzyme stabilizers：
Conventional stabilizer can be used to stablize for any enzyme present in the composition, for example, polyalcohol (such as third Glycol or glycerine), sugar or sugar alcohol, lactic acid, boric acid or boronic acid derivatives such as boric acid aromatic ester or phenyl boronic acid derivative (ratio Such as 4- formylphenyl boronic acids), and the composition can enter according to described in such as WO92/19709 and WO92/19708 Row is prepared.
Lignin compound:
When including lipase, the amount that lignin compound can be optimized with repetition test is used in the composition. Lignin is the component of all vascular plants, is primarily present between eucaryotic cell structure and between cell and cell membrane.
Preferably, lignin compound includes lignin polymers, and more preferably it is modified lignin polymer.Such as this The modified lignin polymer that text is used is to pass through chemical reaction chemical part is covalently attached on lignin Lignin.The chemical part of the connection is preferably what is randomly replaced.
It is preferred that modified lignin polymer to be taken by anion, cation or alkoxy base or its mixture The lignin in generation.Preferably, the substitution occurs on the aliphatic portion of lignin, and is random.Preferably, innovation wood Quality polymer is replaced by anionic group, and preferably anionic group is sulfonate radical.A kind of preferred cation group is season Amine.It is preferred that alkoxy be the polyoxyalkylene chain with 5 to 30 alkoxy portions (most preferably ethyoxyl) repeat unit.It is preferred that Ground, modified lignin mahogany sulfonate is replaced by anion or alkoxy base.Modified lignin polymers are WO/2010/ Discussed in 033743.Most preferably, modified lignin polymers are lignosulfonates (lignosulfonate salt).It is wooden Plain sulfonate can be obtained by Howard methods.
Exemplary lignosulfonates can be obtained from various sources, including hardwood, cork and recycling or arrange thing outside.Can To use lignosulfonates in undressed or pure form, for example, with " former state " or whole soln state (whole liquor Condition) or with the lignin sulfonic acid salt form of purifying, wherein carbohydrate and other sugared compositions has been removed or destroyed, or Person's wherein inorganic constituents is partly or entirely eliminated.Lignosulfonates can be used in the form of salts, including sulfomethylated lignin Sour calcium, sodium lignin sulfonate, ammonium lignosulphonate, lignin sulfonic acid potassium, magnesium lignosulfonate and its mixture or blend.
Lignosulfonates preferably have 2000 to 100000 weight average molecular weight.Its basic structural unit is phenylpropyl alcohol Alkane.Sulfonation degree is preferably each 0.3 to 1.0 sulfate group of benzene oxide unit.
Lignosulfonates can be obtained from many suppliers, including Borregaard LignoTech, Georgia- Pacific Corporation, Lenzing AG and Tembec Inc.
In Lauten, R.A., Myrvold, B.O.and Gundersen, S.A. (2010) New Developments in the Commercial Utilization of Lignosulfonates,in Surfactants from Renewable Discussed in Resources (eds M.Kjellin and I.Johansson), John Wiley＆Sons, Ltd, Chichester, UK Lignosulfonates.
Fluorescer:
It is probably favourable that the composition, which includes fluorescer,.Generally, these fluorescers are with its alkali metal salt (such as sodium Salt) form supply and use.The total amount of the fluorescer used in the composition is generally 0.005 to 2wt%, more preferably 0.01 to 0.5wt%.
It is preferred that fluorescer type be：Distyryl biphenyl based compound (such as Tinopal (trade mark) CBS-X), two Amine stilbene disulfonic acid compound (such as Tinopal DMS pure Xtra and Blankophor (trade mark) HRH) and pyrrole Isoxazoline compound (for example, Blankophor SN).
It is preferred that fluorescer be：2 (4- styryl -3- sulfophenyls) -2H- naphthols [1,2-d] 1-Sodium-1,2,4-Triazoles, 4,4'- bis- [4- anilino-s -6- (N- methyl-N-2- ethoxys) amino 1,3,5-triazines -2- bases)] amino } stilbene -2-2' disulfonates, 4,4'- bis- [4- anilino-s -6- morpholinyls -1,3,5-triazines -2- bases)] amino } stilbene -2-2' disulfonates, and 4,4'- bis- (2- sulfostyryls) biphenyl disodium.
Bleaching catalyst:
The effective bleach systems of content may include according to the detergent composition of the present invention.This kind of system is often used without Conventional percarbonate and bleach activator mode.
The present invention can be also used in the preparation for being bleached via air or bleaching catalyst system.Technical staff Suitable complex compound and organic molecule (part) precursor for forming complex compound can be obtained, for example obtained from：WO98/39098； WO98/39406、WO97/48787、WO00/29537；WO00/52124 and WO00/60045, is incorporated herein by reference.It is preferred that The example of catalyst is MeN4Py parts (double (pyridine -2- the bases) -1- aminoethanes of double (pyridine -2- bases-the methyl) -1,1- of N, N-) Transition metal complex.Suitable bispidon catalyst materials and its effect are described in WO02/48301.
Optical white can also be used.In present disclosure, " optical white " is that reaction is being formed under daylight Any chemical substance of property albic material, and preferably permanently consumed in the reaction.It is preferred that photobleaching Agent includes singlet oxygen optical white and free radical optical white.Suitable singlet oxygen optical white may be selected from water soluble metal phthalocyanine Compound, the phthalocyanine compound especially metallized, wherein the metal is Zn or Al-Z1, wherein Z1 is halogen ion, sulfuric acid Root, nitrate anion, carboxylate radical, alkane acid group or hydroxyl ion.Preferably, the phthalocyanine has the 1-4 of covalent bonding therewith individual SO3X group, wherein X are alkali metal or ammonium ion.This kind of compound is described among WO2005/014769 (Ciba).
When it is present, the bleaching catalyst is generally incorporated to about 0.0001 to about 10wt% content, and preferably from about 0.001 To about 5wt%.
In order to reduce or prevent with other liquid components, can be for example by encapsulating guard catalyst.
Spices
It is designed to use with very low loadings of product dosage in view of the composition of the present invention, then ensures to effectively utilize Spices is favourable.
Ensure that effectively using the particularly preferred mode of spices be the spices using encapsulating.The use of encapsulated perfume is reduced The amount of spices steam of the composition produced by before being diluted.When the raising concentration of perfume is so that the perfume (or spice) washed every time When doses is maintained at rational high content, this is important.
Even further preferably, the spices is not only encapsulated, and the spices of encapsulating also has deposition aid, to improve spices The efficiency of deposition and the stop on fabric.The deposition aid is preferably attached to by covalent bond, entanglement or strong absorption In encapsulation object, preferably pass through covalent bond or entanglement.
Cover dyestuff
Masking dyestuff can be used for improving the performance of the composition used in method of the invention.When it is in the group of the present invention In compound and the method according to the invention is in use, deposition of the masking dyestuff on fabric is improved.It is preferred that dyestuff be Purple or blueness.It is believed that these depositions of masking dyestuff on fabric of low content have covered the yellowing of fabric.Cover dyestuff Further advantage is that, they can be used for any yellow-buff colouration for covering the composition itself.
Suitable and preferred dye type is as described in WO09/153184.
Masking dyestuff can be used under in the absence of fluorescent whitening agent, but especially preferably using masking dyestuff and fluorescence The combination of brightening agent, such as in order to reduce by yellowing caused by adsorbed fluorescent whitening agent chemical change.
Synergist and sequestering agent
The detergent composition also optionally includes relatively low content of organic detergent synergist or sequestering agent Material.Example includes alkali metal, citrate, succinate, malonate, carboxymethyl succinates, carboxylate, polycarboxylate With poly- acetyl group carboxylate.Specific sodium salt of the example including oxygen di- butanedioic acid, mellitic acid, benzene polycarboxylic acid and citric acid, Sylvite and lithium salts.Other examples are DEQUESTTM, it is the organic phospho acid salt form sequestering agent that Thermphos is sold, and Alkane hydroxyethylidene diphosphonic acid salt.Especially preferred sequestering agent be by Thermphos withThe HEDP of 2010 sale, Also referred to as 1- hydroxy ethylenes -1,1- di 2 ethylhexyl phosphonic acids.Also it is suitable, but it is not preferred that2066 (diethylidenes three Amine pentamethylene phosphonic acids or Heptasodium DTPMP).
Other suitable organic synergistic agent include known heavy polymer and copolymer with synergist performance.Example Such as, this kind of material includes appropriate polyacrylic acid, poly and poly propenoic acid maleic acid and its esters, for example By BASF with title SOKALANTMThe material of sale.
If used, the organic synergistic agent material can account for about the 0.5% to 20wt% of the composition, preferably 1wt% to 10wt%.It is preferred that synergy agent content is less than the 10wt% of the composition, and preferably shorter than 5wt%.
External structurant
The composition can by using in the composition formed structured network one or more substance changes its Rheological behavior.Suitable structural agent includes rilanit special, microfibrous cellulose and natural based structures agent, such as pulp Citrus fiber.Pulp citrus fiber is particularly preferred, in the case of particularly including lipase in the composition.
Visual cues thing
The composition can include and preferably comprise the solid visual cues thing insoluble in the composition.It is preferred that Ground, they are used in combination with external structurant, to ensure that they keep suspending.It is preferred that visual cues thing be by polymer thin The lamellar reminders of film formation, and functional component may be included, the composition may be unstable when exposed to akaline liquid It is fixed.Enzyme and bleaching catalyst are the examples of this composition.Also spices, the spices of particularly micro- encapsulating.
Packaging and dosage
The liquid can be packaged in polymer film as unit dose, the polymer film can be adjusted and make its It is insoluble before adding in washings.More preferably liquid is supplied in the multipurpose plastic bag with top or bottom closure member Should.Metering device can with it is described packaging together with supply, its as lid a part or integrate in its system.
Application method
According to taught in WO2009/153184, according to the present invention liquid be intended to it is formulated and can be with 20ml Dosage level be delivered to common front loading automatic washing machine.Low surfactant content during washing is by enzyme, steady The presence of fixed soil release polymer and additional high-efficiency cleaning composition (such as EPEI) optionally is compensated.However, the present invention is also Suitable for about 35ml more conventional dosage level., only need to be to the 20ml types to obtain the suitable liquid of this type Spices in the case of other water is added in liquid and be possible.The soil release polymer is also in these compositions more diluted Stable.
The present invention is now described further with reference to non-limiting example.
Embodiment
In the following embodiments, important material abbreviations are as follows：
MPG is MPG.
TEA is triethanolamine.
NI 7EO are C12-15Alcohol ethoxylate 7EO nonionics25-7 (coming from Shell Chemicals)
LAS acid is C12-14Linear alkyl benzene sulfonic acid.
5908 be saturation lauryl aliphatic acid, from Croda.
SLES 3EO are the sodium laureth sulfate with 3 moles of EO.
BB is alkyl betaine, from Huntsman (cocoyl dimethyl carboxybetaine).
EPEI is the Clean- polymer of polyethyleneimine of Sokalan HP20- ethoxylations：PEI (600), with 20 EO, from BASF.
Spices is without oil flavors.
SRP is soil release polymer.
5908 be saturation lauryl aliphatic acid, from Croda.
MEA is MEA.
NaOH is 47% sodium hydroxide solution.
2066 be diethylenetriamine pentamethylenophosphonic acid (or the sodium of DTPMP seven).
2010 be HEDP (1- hydroxy ethylene -1,1,-di 2 ethylhexyl phosphonic acid).
For Lipex100L, from Novozymes.
For cellulase, from Novozymes.
Stainzyme 12L are the amylase for liquid dosage, from Novozymes.
Mannaway is mannase, from Novozymes.
Experiment below all, which all has 2 times, to be pre-washed and once main washing.It is dirty using DMO after second of prewashing Stain.It in ratio is 25 that load, which is,:50 in 1 cleaning solution and fabric:50 knitting polyester/braiding cotton.Use 100 RPM Wash within 30 minutes.Δ E~5-10 is to eliminate DMO spots excellently；Δ E~37 are equivalent in the absence of the property under SRP Energy；Δ E~50 are equivalent to the spot before washing.
The SRP hydrolytic stabilities (clean-up performance based on DMO labels spot on polyester) of the composition 1 provided in table 1 As pH changes record caused by sodium hydroxide dosage is in table 2.Δ E values are smaller, then detergency is better., will before washing Composition is stored at 37 DEG C 8 weeks, provides tolerance indications of the SRP to long term storage in bottle.
Table 1- compositions 1-pH change
Raw material % (is used as 100%)
Deionized water To 100%
MPG 20
NaOH 0
TEA 2
NI7EO 12.74
LAS acid 8.49
Prifac5908 1.5
SLES 3EO 4.24
Empigen BB 1.5
EPEI 5.5
SRP 3.75
Spices 2.43
PH adjusting agent 10
Table 2 stores influences of the pH to cleaning
Table 2 stores influences of the pH to cleaning
Under pH6.5 and 6.75, observed using 2wt% and 3.5wt% TEA functional, show acceptable SRP Stability.Therefore, the pH that target is 6.5 and the pH upper limits less than 7.0 are with most 3.5wt% TEA for combining as shown in table 1 Thing is preferred.Analogous composition for being diluted with water to 1.5 times of volumes, needed for identical pH scopes are stability, and And can be obtained with the 2wt% of corresponding lower content TEA (i.e. in proportion).
Cushioning control
Detergent liquid should be pH stable under the 5wt% compositions that add deduct, to allow to prepare variable product.In order to obtain Buffer must be included by obtaining in the stability, liquid.The buffer used is TEA (pKa7.8) and Prifac5908 aliphatic acid (because it is mixture, pKa is unknown)..
In WO09153184,3% Prifac5908 is used.Under the content, aliphatic acid is for low temperature unstability With directly affecting, therefore, reduce aliphatic acid content with improve low-temperature stability (reduced in 20ml liquid to 1.71%, Correspondingly for 35ml compositions for 0.85%).The influence to froth breaking is checked, is the discovery that acceptable.Also provided with table 3 The inspection of 20ml compositions reduce Prifac5908 to buffering and pH control influence, be the discovery that acceptable (table 4).
Table 3
Raw material % (is used 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
Table 4- checks the pH stability of the liquid of table 3 with the change of TEA contents
The liquid of table 3 is then controlled if there is no Prifac5908 or TEA without pH.1.5%Prifac5908 can be used At least 1%TEA obtains acceptable pH controls.Using 0%TEA, then compare Gao pH areas are controlled, but relatively low pH areas decline To pH6.0 is markedly inferior to, it causes unacceptable low-temperature stability performance.
Low-temperature stability
Two kinds of low temperature standards product (recover) stable at most 12 weeks at ambient temperature at 5 DEG C, and in freezing/thawing Stablize 1 week under (recovering at ambient temperature).
The content of the aliphatic acid used is the instable critical aspects of low temperature, and this is in relatively low pH (with aliphatic acid and soap Class ratio rise) under worse and worse.If added with requirement, the unstability can be overcome by adding TEA and MPG.
Hydrolytic stability based on SRP and pH controls, the starting points of 20ml fluid compositions for 6.5 target pH and most Few 1%TEA and 1.5%Prifac5908.Actual TEA demands are that specified in table 5, MPG demands are specified in table 6.
For the liquid as specified in table 1, TEA weight % preferably is 3.5%, and MPG weight % preferably is 20%.
The starting point of diluter 35ml compositions is identical pH requirements and 2%TEA.For needed for low-temperature stability MPG content is shown in table 7.For 35ml liquid, required MPG weight % is 15%.
Table 5- contains the liquid cryogen stability of composition 1 of different TEA contents
F/T=freeze thawing
Table 6
Raw material % (is used 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 the liquid of table 7- tables 6 with pH and MPG contents situation of change
The isotropic liquid of table 8-35ml
The stability data of the composition of table 9- tables 8
P=is qualified
F=is unqualified
R=is unqualified at 5 DEG C, but becomes isotropic when warming to room temperature.

Claims (15)

1. a kind of isotropic liquid detergent composition, it has scope 6.0 to pH in the bottle less than 7, the composition In addition to comprising water, also include：
A) most 60wt% stain release type surfactant, it includes at least 5wt% anionic sulphonate and/or sulfate table Face activating agent, the anionic sulphonate and/or sulfate surfactant include the surface neutralized with one or more materials Activating agent acid, pKa 2 units higher than pH in the bottle of detergent liquid composition of the conjugate acid of one or more materials with On,
B) at least 0.3wt% aliphatic acid neutralized with one or more material parts, the conjugation of one or more materials It is more than pKa 2 units higher than pH in the bottle of detergent liquid composition of acid,
C) at least 1.8wt% to most 3.7wt% triethanolamine (TEA)；With
D) at least 0.5wt% polyester soil release polymers (SRP).
2. composition according to claim 1, it is with pH in 6.3 to 6.7 bottle.
3. according to the composition of any one preceding claims, wherein the aliphatic acid is saturation.
4. composition according to claim 1, wherein the usage amount of the aliphatic acid is 0.5 to 1.5wt%.
5. composition according to claim 1, it includes 2.0 to 3.5wt% triethanolamine (TEA).
6. composition according to claim 1, wherein the pKa of the conjugate acid of one or more materials is than detergent liquid group In the bottle of compound more than high 2 units of pH, one or more materials include 0.08 to 0.25wt% NaOH and/or single second Hydramine (MEA).
7. composition according to claim 6, wherein, one or more materials include 0.1 to 0.23wt% NaOH And/or MEA (MEA).
8. composition according to claim 1, wherein the SRP has is condensed the fabric formed by terephthalate and glycol Compatibility part, and end-capped hydrophilic parts are further included, the end-capped hydrophilic parts include and use alkyl The ethylene oxide repeating units of end-blocking.
9. composition according to claim 8, wherein the glycol is 1,2- propane diols.
10. composition according to claim 1, wherein the liquid is at least 5wt% hydrotropic agent comprising content.
11. composition according to claim 10, wherein the liquid is at least 9wt% hydrotropic agent comprising content.
12. composition according to claim 10, wherein the liquid is at least 14wt% hydrotropic agent comprising content.
13. composition according to claim 10, wherein the hydrotropic agent is 1,2- propane diols (MPG).
14. composition according to claim 1, it includes the polyethyleneimine (EPEI) of at least 5wt% ethoxylation.
15. composition according to claim 1, wherein the anion surfactant a) includes at least 5wt% straight chain alkane Base benzene sulfonate (LAS).
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