CN101133148A - Detergent compositions - Google Patents

Detergent compositions Download PDF

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Publication number
CN101133148A
CN101133148A CNA2006800068987A CN200680006898A CN101133148A CN 101133148 A CN101133148 A CN 101133148A CN A2006800068987 A CNA2006800068987 A CN A2006800068987A CN 200680006898 A CN200680006898 A CN 200680006898A CN 101133148 A CN101133148 A CN 101133148A
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China
Prior art keywords
detergent composition
weight
preferred
lipase
alkyl
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Chinese (zh)
Inventor
N·兰特
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Procter and Gamble Ltd
Procter and Gamble Co
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Procter and Gamble Ltd
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Publication of CN101133148A publication Critical patent/CN101133148A/en
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38627—Preparations containing enzymes, e.g. protease or amylase containing lipase
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3942—Inorganic per-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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3945—Organic per-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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/12—Soft surfaces, e.g. textile

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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)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

Detergent compositions containing high efficiency lipase enzymes and specific detergent formulations comprising a high reserve alkalinity, greater than 6.5, and a bleaching agent comprising hydrogen peroxide source and peracid or precursor thereof such that the Avox to peracid ratio is 1:1 to 35:1, enables control of diacyl peroxide formation. Preferred formulations comprise surfactants selected from alkyl benzene sulphonates in combination with alky ethoxylated sulfates or MES or non-ionic surfactants.

Description

Detergent composition
Technical field
The present invention relates to detergent composition, especially laundry detergent.Specifically, the present invention relates to comprise the washing composition of lipolytic enzyme or lipase.
Background of invention and prior art
Many detergent composition comprise bleach system and are washed spot on the goods to assist in removing.These bleach systems comprise hydrogen peroxide cource usually, as perborate or percarbonate.Except hydrogen peroxide (or oxygen source), usually also by using preliminary shaping peracid or peracid precursors (being commonly referred to bleach-activating agent) to strengthen the performance of hydrogen peroxide bleaching.In use, described bleach-activating agent and excessive hydroperoxidation formation peracid albic material.Typical detergent compositions uses excessive hydrogen peroxide cource.
Modal bleach-activating agent is TAED (tetra acetyl ethylene diamine).With hydroperoxidation in the active albic material that forms be peracetic acid.Other activator can produce has longer carbochain and hydrophobic active substance.These can suitably produce effective bleaching effect, especially to the bleaching effect of oil-dirt.
A well-known embodiment of above-mentioned hydrophobicity bleach-activating agent is nonanoly acyloxy benzene sulfonate (NOBS).This bleach-activating agent reaction forms active albic material and crosses n-nonanoic acid.Yet find that this albic material will form two-C with the bleach-activating agent id reaction 9Acyl peroxide.Other hydrophobicity bleach-activating agent reacts in an identical manner and forms their corresponding diacyl peroxides.These materials are potent albic materials and can be used in the washing process, but they are undissolved.In the existing washing machine of some type, when washing water were discharged from existing washing machine, these compounds may tend to settle down in the sump of existing washing machine.Thereby, potent SYNTHETIC OPTICAL WHITNER with the people for being enriched in these zones.Also find, in the existing washing machine of some type,, when being used for these zones as materials of polymkeric substance and/or rubber sump and being destroyed, understand in these zones and cause damage having washing machine now by the high-content SYNTHETIC OPTICAL WHITNER along with the past of time.
Problem involved in the present invention is how to alleviate this problem, with when obtaining hydrophobicity SYNTHETIC OPTICAL WHITNER beneficial effect, farthest reduces or prevents washing plant is caused damage.
From the later stage 1980s, lipase just is used in the washing composition, so that remove fatty dirt by fatty dirt is resolved into triglyceride level.
Until not long ago, main commercially available lipase such as Lipolase (trade(brand)name, Novozymes) just can the washing process baking stage than producing especially effective function under the low moisture content.These enzymes only just are tending towards producing significant cleaning effect in second washing step, this is owing to the active sites of enzyme during washing process is occupied by water, therefore significant steatolysis just takes place in the dirt that remains on the laundry at baking stage, and the fat of Fen Xieing is removed in next washing step then.Yet developed lipase more efficiently recently, its washing stage at cleaning course also can work effectively.Therefore the cleaning action in second washing step, owing to lipase can be present in first cycles of washing, so cleaning effect is significantly improved.The embodiment of above-mentioned enzyme is described among WO00/60063 and " Research Disclsoure " IP6553D.Hereinafter above-mentioned enzyme is called the first washing lipase.The embodiment of above-mentioned enzyme comprises some variant of Lipolase (wild-type Humicola lanuginosa), and it should comprise the replacement that the amino acid of one or more positively chargeds is carried out near the N-terminal of three-dimensional structure.Described variant also should comprise peptide bond at the C-end, and/or should make that charged amino acid meets some restriction on 90 to 101 and 210 sites.The inventor finds, by adopting the combination of this first detersive enzyme and particular type detergent formulations, can utilize these hydrophobicity bleach-activating agents to realize good greasiness removal effect, can alleviate above-mentioned any rough sledding simultaneously.
The invention definition
According to the present invention, provide the detergent composition that comprises hydrogen peroxide cource, hydrophobicity peracid or its precursor and lipase.Described hydrophobicity peracid or its precursor have chemical formula R-(C=O)-L structure, wherein R is for having 6 to 14 carbon atoms, the alkyl of preferred 8 to 12 carbon atoms, and L is a leavings group, and described lipase is the polypeptide with aminoacid sequence: (a) have and the identity that derives from the wild-type lipase at least 90% of Humicola lanuginosa strain DSM 4109; (b) compare with described wild-type lipase, be included within three-dimensional structure surface lies E1 or the Q24915 dust electric neutrality or electronegative amino acid and replaced by the amino acid of a positively charged; And c) comprises an additional peptide section at the C-end; And/or (d) comprise an additional peptide section, and/or (e) meet following qualifications: i) contain an electronegative amino acid in the E210 position of described wild-type lipase at the N-end; Ii) containing an electronegative amino acid corresponding to the zone of described wild-type lipase 90-101 position; Iii) containing neutrality or electronegative amino acid corresponding to the N94 position of described wild-type lipase and/or having a negative or neutral net charge in zone corresponding to described wild-type lipase 90-101 position; Described detergent composition has the reserve alkalinity greater than 6.5, and the amount of oxygen source and peracid can provide the mol ratio of 1: 1 to 35: 1 available oxygen (from peroxide source) Yu peracid to described detergent composition.
According to the present invention, also provide the detergent composition that comprises hydrogen peroxide cource, hydrophobicity bleach-activating agent and lipase.Described hydrophobicity bleach-activating agent has chemical formula R-(C=O)-L structure, and wherein R is for having 6 to 14 carbon atoms, the alkyl of preferred 8 to 12 carbon atoms, and L is a leavings group.Use lard hereinafter described is washing test first, the lard of washing first that described lipase represented is removed performance than WT Lipolase (trade(brand)name, available from Novozymes) represented better, and described detergent composition has the reserve alkalinity greater than 6.5.The amount of oxygen source and peracid can provide the mol ratio of 1: 1 to 35: 1 available oxygen (from peroxide source) Yu peracid to described detergent composition.
WT Lipolase available from Novozymes is described in US 5869438 sequence numbers 2.
The inventor finds; when the first washing lipase is used for detergent composition; the mol ratio that described detergent composition of while has high reserve alkalinity and available oxygen (from peroxide source) and peracid is the formation of 1: 1 to 35: 1 o'clock may command diacyl peroxide, to alleviate the shortcoming of this type of hydrophobicity peracid or peracid precursors.
Of the present invention one preferred aspect in, detergent composition of the present invention comprises the washing assistant less than 15% weight.Described washing assistant is selected from silico-aluminate (zeolite) washing assistant and/or phosphate builders.The present invention another preferred aspect in, described composition comprises less than the zeolite of 10% weight and/or phosphate builders, even less than the zeolite and/or the phosphate builders of 5% or 4% weight.
Detailed Description Of The Invention
Peroxide source
Inorganic perhydrate salts is preferred peroxide source.The content of these salt is preferably 0.05% to 40% weight by the weight of described detergent composition, more preferably 1% to 30% weight, or 2% to 20% weight.The embodiment of inorganic perhydrate salts comprises perborate, percarbonate, persulphate, percarbonate and persilicate.Most preferably be generally the perborate of monohydrate or tetrahydrate, or more particularly, most preferably percarbonate.These are an alkali metal salt normally, particular certain cancers.The typical case is incorporated into inorganic perhydrate salts in the detergent composition of the present invention as crystalline solid.Described crystalline solid can be chosen applied package stability for example to be improved wantonly.Suitable coating comprises inorganic salt such as alkalimetal silicate, carbonate or borate or their mixture, perhaps organic substance such as wax, oil or fatty soap.
Hydrophobicity peracid or peracid precursors
Suitable compounds comprises that chemical formula is the compound of R-(C=O) O-O-M or R-(C=O)-L, and wherein R has 6 to 14 carbon atoms for the alkyl of optional branching, more preferably has 8 to 12 carbon atoms; M is counter ion, is preferably sodium, potassium or hydrogen; And L is a leavings group.Preferred leavings group is phenylformic acid and derivative thereof, and Phenylsulfonic acid root especially.
Suitable embodiment comprises caprinoyl aminobenzoic acid or its salt, dodecane acyl-oxygen base Phenylsulfonic acid sodium salt or sylvite, last of the ten Heavenly stems acyloxy benzene sulfonate, 3,5,5-trimethyl acetyl oxygen base benzene sulfonate, perhaps even preferred nonanoly acyloxy benzene sulfonate (NOBS).
Usually, peracid or the peracid precursors content in described composition is counted 0.5% to 10% weight by the weight of described detergent composition, preferred 0.5% to 5% weight, preferred 0.5% to 4% weight.
Randomly, except described hydrophobicity peracid or peracid precursors, also wetting ability peracid or peracid precursors can be incorporated in the detergent composition of the present invention.These comprise the material with chemical formula given in hydrophobicity peracid/precursor above, but the carbon atom that the R group comprises is less than 6, preferably less than 4.Preferred embodiment is TAED.If exist, its content is no more than 7% weight usually, is generally 0.1% to 5% weight.
Can select the amount of hydrogen peroxide cource and peracid or peracid precursors to make that the available oxygen (from peroxide source) and the mol ratio of peracid are 1: 1 to 35: 1.Preferred mol ratio is 2: 1 to 10: 1, or even 3: 1 or even 5: 1 to 8: 1.
Lipase
Be used for of the present invention with reference on the lipase being wild-type lipase derived from Humicola lanuginosa strain DSM 4109.It is described in EP258068 and EP305216, and has the aminoacid sequence of No. 2 shown positions of SEQ ID 1 to 269 of US5869438.(appendix is in this) in this specification sheets, benchmark lipase also is called as Lipolase.
The amino acid whose replacement of positively charged
Near electric neutrality that lipase of the present invention comprises one or more (for example 2 to 4, especially 2) E1 or Q249 or electronegative amino acid is by the amino acid of positively charged, the replacement of preferred R.
Described replacement occurs on the three-dimensional structure surface in E1 or the Q24915  scope, on any one position in 1 to 11,90,95,169,171 to 175,192 to 211,213 to 226,228 to 258,260 to 262.
Described replacement can occur in the scope of E1 or Q24910 , on any one position in 1 to 7,10,175,195,197 to 202,204 to 206,209,215,219 to 224,230 to 239,242 to 254.
Described replacement can occur in the scope of E115 , on any one position in 1 to 11,169,171,192 to 199,217 to 225,228 to 240,243 to 247,249,261 to 262.
Described replacement most preferably occurs in the scope of E110 , on any one position in 1 to 7,10,219 to 224 and 230 to 239.
Therefore, some preferably to replace be S3R, S224R, P229R, T231R, N233R, D234R and T244R.
The additional peptide section of C-terminal
Described lipase can comprise the additional peptide section that is connected to the terminal L269 of C-.Described peptide is added on and has improved scourability for the first time in the multiple washing composition.
Described peptide bond preferably is made up of 1 to 5 amino acid, as being made up of 2,3 or 4 amino acid.Amino acid in the peptide bond can be numbered to 270,271 etc.
Described peptide bond can be made up of electric neutrality (as hydrophobicity) amino acid, as PGL or PG.In an alternative embodiment, the lipase peptide bond is made up of electric neutrality (as hydrophobicity) amino acid and amino acid C, and described lipase comprise C on suitable location to amino acid whose replacement, with peptide bond in C form disulfide linkage.Embodiment is:
270C with G23C or T37C bonding
271C with K24C, T37C, N26C or R81C bonding
272C with D27C, T35C, E56C, T64C or R81C bonding.
Amino acid on 90 to 101 and 210
The preferred used lipase charged amino acid on 90 to 101 and 210 of the present invention meets some restriction.Therefore, amino acid 210 can be negative electricity.But the E210 neutral, or it can have replacement E210D/C/Y, preferred E210D.
Described lipase can comprise electronegative amino acid on any position (especially 94 to 101) of 90 to 101, as on D96 and/or E99 position.
In addition, described lipase can comprise electric neutrality or electronegative amino acid on the N94 position, i.e. N94 position (electric neutrality or electronegative) is as N94N/D/E.
Equally, have negative or neutral net charge in described lipase can be 90 to 101 (especially 94 to the 101) zone, promptly electronegative amino acid no is equal to or greater than the amino acid no of positively charged.Therefore, described zone is not compared with Lipolase and is changed, amino acid (K98) with two electronegative amino acid (D96 and E99) and a positively charged, and on 94 (N94) position, have an electroneutral amino acid, or described zone can be by the modification of one or more replacement institute.
Alternatively, two kinds among three seed amino acid N94, N96 and the E99 can have negative charge or electric charge no change.Therefore, all these three seed amino acids can be constant can the replacement of protected property or electronegative replacement change i.e. N94 (electric neutrality or electronegative), D (electronegative) and E99 (electronegative).Embodiment is N94D/E and D96E.Equally, a kind of being substituted in these three kinds to increase electric charge, i.e. N94 (positively charged), D96 (electric neutrality or positively charged) or E99 (electric neutrality or positively charged).Embodiment is N94K/R, D96I/L/N/S/W or E99N/Q/K/R/H.
Described in WO00/60063, replace the performance that electric neutrality amino acid can improve anionic detergent with electronegative amino acid (N94D/E).Amino acid (N94K/R) replacement electric neutrality amino acid with positively charged can provide good performance to the variant lipase in anionic detergent and the anionic/nonionic washing composition (for example 40% to 70% anionic washing composition is arranged in the whole tensio-active agent).Replace Q249R/K/H and/or may be useful with electric neutrality or electronegative aminoacid replacement R209 (as R209P/S).Described lipase can be chosen wantonly and comprise replacement G91A.
Described lipase can be chosen wantonly and comprise one or more additional amino acid whose replacements.Above-mentioned replacement can be for example to carry out according to principle known in the art, as is described in the replacement of WO92/05249, WO94/25577, WO95/22615, WO97/04079 and WO97/07202.The specific embodiment that replaces suitable combination is provided in the table of the leap the 4th of WO00/60063 and page 5.Be described in WO00/60063 about amino-acid modified name.
Preferred lipase is described among the WO00/60063, Lipex (the registrar name of an article of Novozymes) most preferably, it is the variant of Humicolalanuginosa (thermophilic fungus) lipase (Lipolase, the registrar name of an article of Novozymes) with mutation T 231R and N233R.
The common amount that exists of lipase of mixing in the detergent composition of the present invention is 10LU/g to a 20000LU/g detergent composition, or even 100LU/g to 10000LU/g.About the described LU unit definition of lipase activity in WO99/42566.Lipase dosage typically is 0.01mg/L to 5mg/L active lipase protein in washing soln, more typically is the zymoprotein of 0.1mg/L to 2mg/L.
Described lipase can any form easily be incorporated in the detergent composition, is generally dustless particle, stabilising liq or shielded (for example coating) enzyme granulate form.
Lard is washing test first
According to following test, compare by The performance test results and can determine whether concrete lipase can have and better wash lard first than WTLipolase (, being described in US 5869438 sequence numbers 2) and remove performance available from Novozymes with the The performance test results of WT Lipolase and any concrete lipase.
In constant temperature Terg-O-Tometer (TOM), carry out the circulation cleaning test, then hang and do, the scourability of test lipolytic enzyme.Test conditions is as follows:
Washing liq: every beaker 1000mL
Sample: have 7 in every beaker without this (9 * 9cm) (providing) spot: dye red lard (0.75mg Sudan red/every gram lard) of the cotton sample preparation that compresses with Sudan red dyestuff (Sigma) by Warwick-Equest.50 μ L are heated to the central authorities that lard/Sudan red of 70 ℃ is administered to each sample.After using spot, sample was heated 25 minutes in baking box in 75 ℃ down, at room temperature preserve then and spend the night.
The water that is used for preparing washing liquid: 3.2mM Ca 2+/ Mg 2+(ratio is 5: 1)
Washing composition: 5g/L detergent composition A.
Detergent composition A:
0.300g/L alkyl-sulphate (AS; C 14-16)
0.650g/L alcohol ethoxylate (AEO; C 12-14, 6EO)
1.750g/L zeolite P
0.145g/L Na 2CO 3
0.020g/L Sokalan CP5(BASF)
0.050g/L CMC (carboxymethyl cellulose)
The detergent composition A of 5g/L is blended into hardness increase (3.2mMCa 2+/ Mg 2+(5: 1)) deionized water in, and by adding NaOH, manually with pH regulator to pH 10.2.Add lipase.
The concentration of lipolytic enzyme: 0 and 12500LU/L
Washing time: 20 minutes
Wash temperature: 30 ℃
Rinsing: under the mobile tap water, washed 15 minutes
Dry: (about 20 ℃, 30% to 40%RH) spend the night under the envrionment conditions.
Evaluation: under 460nm, measure reflectivity.
Determine that the per-cent of removing lard is:
δ reflectivity (dR) is defined as:
(R (sample of in the washing composition of fatty enzyme, being washed)-R (sample of in the washing composition of fatty enzyme not, being washed))
In Elrepho 2000 equipment, measure reflectivity (it also is called as the renvoi rate) available from Datacolor.Described equipment uses 2 xenon flash lamps irradiation samples also to measure catoptrical amount, so that the response of complete white is 100% reflectivity and is 0% reflectivity to the response of complete black.Relatively the lard removal effect that obtains owing to the existence of enzyme then can be given and be compared WTLipolase TMMore the lipase of best performance is applicable in the composition of the present invention.
Reserve alkalinity
Term used herein " reserve alkalinity " is measure (the g/NaOH/100g detergent composition) of detergent composition surge capability.It is by measuring the detergent composition solution titration of 1% (w/v) to pH 7.5 with hydrochloric acid, promptly in order to calculate reserve alkalinity as herein defined:
Titre during T=to pH7.5 (mL)
The M=HCl volumetric molar concentration is 0.2
The molecular weight of 40=NaOH
Vol=cumulative volume (being 1000mL)
W=product weight (10g)
Aliquot＝(100mL)
Obtain the full formula detergent composition sample of the accurate weighing of 10g to 2 significant digits.Should in the dedusting cupboard, use the Pascall sampling thief to obtain sample.In plastic beaker, add the 10g sample, and add the not carbonated deionized water of 200mL.On mixing platform, use magneton, with the speed stirring of 15.7rad/s (150rpm),, and stirred at least 15 minutes until dissolving fully.Content in the beaker is transferred in 1 liter of volumetric flask, and complements to 1 liter with deionized water.Mix, exist side by side and promptly use the 100mL pipette, get the aliquots containig of 100mL ± 1mL.Use can be read the pH meter to ± 0.01pH unit, and measure and the pH and the temperature of record sample, and stir, be 21 ℃+/-2 ℃ to guarantee temperature.Stir simultaneously with 0.2M hydrochloric acid is titrating, measure just in time 7.5 until pH.What milliliter hydrochloric acid that record uses.Get the average titer of three identical revision tests.Carry out described calculating, the RA when calculating to pH 7.5.
The RA of detergent composition of the present invention will be preferably greater than 8 greater than 7.5.Described RA can be greater than 9 even greater than 9.5 or 6.5 or higher.Described RA can mostly be 20 or higher most.
Can provide suitable reserve alkalinity by for example one or more alkalimetal silicates (except the crystalline layered silicate), alkaline carbonate.Described alkalimetal silicate is typically amorphous silicate, is generally the sodium salt of 1.2 to 2.2 ratios.Described alkaline carbonate is typically yellow soda ash, sodium bicarbonate and/or concentrated crystal soda.STPP and persalt such as perborate and percarbonate also have contribution to basicity.Need shock absorption, during washing process, keeping alkaline pH, in and the acidity of dirt, especially by lipid acid that lipase discharged.
Described detergent composition preferably comprises the silicate of 0% weight to 50% weight, more generally comprises the silicate of 5% to 30% weight, or the silicate of 7% to 20% weight.Described silicate is generally water glass.
For suitable reserve alkalinity is provided, detergent composition of the present invention can comprise carbonate, and the typical case comprises 1% weight to 70% weight, or 5% weight to 50% weight, or the carbonate of 10% weight to 30% weight.Preferred carbonate is yellow soda ash and/or sodium bicarbonate and/or concentrated crystal soda.Carbonate can all be incorporated in the detergent composition or via mixing salt and partly be incorporated in the detergent composition as Burkeite.Highly preferred carbonate is yellow soda ash.Preferably, described composition can comprise the yellow soda ash of 5% weight to 50% weight, or 10% to 40% weight, or even the yellow soda ash of 15% to 35% weight.Also suitable 1% weight to 20% weight that comprises of described composition, or even 2% to 10% or the sodium bicarbonate of 8% weight.
If contain zeolite, then the weight ratio of yellow soda ash and/or water glass and zeolite builders can be suitably at least 5: 1, preferably at least 10: 1, or at least 15: 1, or at least 20: 1, or even at least 25: 1.
Carbonate or be typically particle form to small part carbonate, the weight average particle diameter that the typical case has is in 200 to 500 microns scope.Yet, preferred carbonate or to small part carbonate be the micronized particle shape, the average particle size that the typical case has is in 4 to 40 microns scope.When carbonate or when small part carbonate is the common granular mixture form that forms with detersive surfactant such as alkoxylate anionic detersive surfactant, this is especially preferred.
For required reserve alkalinity is provided, the content that is typically the carbonate of yellow soda ash and water glass and/or silicate is preferably 10% to 70% weight by the gross weight of described composition, or 10% or even 15% to 50% weight.
Washing assistant
According to the present invention, the amount that is selected from the powerful washing assistant of phosphoric acid salt and/or zeolite builders is lower than 15% weight by the gross weight of described detergent composition, preferably is lower than 10% weight, or even is lower than 8% or 5% or 4% or 3% or 2% weight.
Of the present invention another preferred aspect in, the total content that is selected from the weak washing assistant of layered silicate (SKS-6), citric acid, Citrate trianion and nitrilotriacetic acid(NTA) or its salt is lower than 15% weight by the gross weight of described detergent composition, more preferably less than 8% weight, more preferably less than 4% weight, or even be lower than 3% or 2% weight.Typically, the content separately of layered silicate, citric acid, Citrate trianion and nitrilotriacetic acid(NTA) or its salt is lower than 10% weight by the gross weight of described composition, or even is lower than 5% weight or % weight.
Tensio-active agent
The preferred adjuvant component of present composition camber is a tensio-active agent.This detergent composition preferably includes one or more tensio-active agents.Typically, detergent composition comprises (by the weight of described composition) 0% to 50%, and is preferred 5%, more preferably 10% or even 15% weight to 40%, or to 30%, or to one or more tensio-active agents of 20%.Preferred surfactants is anion surfactant, nonionogenic tenside, cats product, zwitterionics, amphoterics, cats product and their mixture.
Anion surfactant
Suitable anion surfactant typical case comprises one or more parts.Described part is selected from the group of being made up of following groups: carbonate, phosphate radical, phosphonate radical, sulfate radical, sulfonate radical, carboxylate radical and their mixture.Described anion surfactant can be a kind of or more than a kind of C 8-18Alkyl-sulphate and C 8-18The mixture of alkylsulfonate.Suitable anion surfactant independent or that be incorporated in the present composition with form of mixtures can also be C 8-18Alkyl-sulphate and/or C 8-18Alkylsulfonate, randomly, every mole of C 8-18Alkyl-sulphate and/or C 8-18Alkylsulfonate and 1 to 9 mole of C 1-4The alkylene oxide condensation.C 8-18Alkyl-sulphate and/or C 8-18The alkyl chain of alkylsulfonate can be straight or branched, and preferred branched alkyl chain comprises one or more C 1-6A chain portion of alkyl.More particularly, Shi Yi anion surfactant comprises C 10-C 20Side chain, straight chain and random chain primary alkyl sulphates (AS), the typical case has following chemical formula:
CH 3(CH 2) xCH 2-OSO 3 -M +
Wherein, M is for hydrogen or electroneutral positively charged ion is provided, and preferred cation is sodium and ammonium cation, and wherein x is at least 7, preferably is at least 9 integer; The typical case has the C of following formula 10-C 18Secondary (2,3) alkyl-sulphate:
Figure A20068000689800141
Or
Wherein, M is for hydrogen or electroneutral positively charged ion is provided, and preferred cation comprises sodium and ammonium cation, and wherein x is at least 7, preferably is at least 9 integer, and y is at least 8, preferably is at least 9 integer; C 10-C 18The alkyl alkoxy carboxylate salt; As US 6,020, in 303 and US6,060,443 the alkyl-sulphate of mid-chain branched in greater detail; As institute's modified alkylbenzene sulfonates (MLAS) in greater detail among WO99/05243, WO99/05242, WO99/05244, WO99/05082, WO99/05084, WO99/05241, WO99/07656, WO00/23549, the WO00/23548; And their mixture.
The preferred anionic surfactants tensio-active agent is C 8-18Alkyl sulfate and/or C 8-18Alkylbenzene sulfonate.C 8-18Alkyl sulfate and/or C 8-18The alkyl chain of alkylbenzene sulfonate can be straight or branched, and preferred branched alkyl chain comprises one or more C 1-6A chain portion of alkyl.
Other preferred anionic surfactants tensio-active agent is selected from: C 8-18Alkenyl sulfate, C 8-18Olefin sulfonate, C 8-18Alkenyl, C 8-18Alkenyl benzene sulfonate, C 8-18Alkyl dimethyl phenylsulfate, C 8-18Alkyl dimethyl benzene sulfonate, fatty sulfonate, dialkyl sulfosuccinates and their combination.Other available anion surfactant of this paper is included in the typical α-sulfonated fatty acid ester that comprises 6 to 20 carbon atoms and comprise 1 to 10 carbon atom in ester group in the fatty acid group; Typical 2-acyloxy alkane-1-sulfonic acid and the salt thereof that comprises about 2 to 9 carbon atoms and in paraffin section, comprise about 9 to 23 carbon atoms in acyl group; The typical case comprises the sulfonated (AOS) of about 12 to 24 carbon atoms; With the typical β-oxyalkyl chain alkyl sulfonate that comprises about 1 to 3 carbon atom and in paraffin section, comprise about 8 to 20 carbon atoms in alkyl.Also available is to comprise the fatty acid ester sulfonated products that the typical case has 10 to 20 carbon atom alkyls.Preferred C 1-4Alkane sulfonated ester, most preferably methyl ester sulfonate.Preferred C 16-18Methyl ester sulfonate (MES).
Described anion surfactant can salt form exist.For example, anion surfactant can be an alkali metal salt of above-mentioned any material.Preferred basic metal is sodium, potassium and their mixture.
The preferred anionic surfactants detersive surfactant is selected from: straight or branched, replacement or unsubstituted C 12-18Alkyl-sulphate; Straight or branched, replacement or unsubstituted C 10-13Alkylbenzene sulfonate, preferred straight chain C 10-13Alkylbenzene sulfonate; And their mixture.It is highly preferred that straight chain C 10-13Alkylbenzene sulfonate.It is highly preferred that straight chain C obtainable, that preferably can obtain by commercially available linear alkylbenzene (LAB) sulfonation 10-13The alkyl-alkyl benzene sulfonate; Suitable LAB comprises rudimentary 2-phenyl LAB, as by Sasol with trade(brand)name Isochem Those that provide or by Petresa with trade(brand)name Petrelab Those that provide, other suitable LAB comprises senior 2-phenyl LAB, as by Sasol with trade(brand)name Hyblene Those that provide.
Can preferably carry out described anionic detersive surfactant structurally-modified so that the more anti-calcium of this anionic detersive surfactant and more impossiblely from the washing liq that has free calcium ions, be precipitated out.This is structurally-modified can be to introduce methyl or ethyl part near the end group of anionic detersive surfactant, because this can be because of end group sterically hindered obtains anionic detersive surfactant more calcium-insensitive, this can reduce described anionic detersive surfactant complexing free ca positively charged ion so that its avidity that is precipitated out from solution.Other is structurally-modified to be included in the alkyl chain of anionic detersive surfactant and to introduce functional part such as amine moiety.This can obtain anionic detersive surfactant more calcium-insensitive, because in the alkyl chain of anionic detersive surfactant, exist functional group can make the worthless physicochemical property minimum of anionic detersive surfactant, when having free calcium ions in the washing liq, form slick crystalline structure.This can reduce the trend that anionic detersive surfactant is precipitated out from solution.
The alkoxylate anion surfactant
Described composition can comprise the alkoxylate anion surfactant.When existing, the content of above-mentioned tensio-active agent is generally 0.1% weight to 40% weight by the gross weight of described detergent composition, by being 0.1% to 10% weight.Described composition preferably comprises the alkoxylate anionic detersive surfactant of 3% weight to 5% weight, or described composition preferably comprises the alkoxylate anionic detersive surfactant of 1% weight to 3% weight.
Preferably, described oxyalkylated anionic detersive surfactant is a straight or branched, replaces or unsubstituted C 12-18Alkyl alkoxylated vitriol, it has 1 to 30, preferred 1 to 10 average degree of alkoxylation.Preferably, described oxyalkylated anionic detersive surfactant is a straight or branched, replaces or unsubstituted C 12-18Alkyl ethoxylate sulfate, it has 1 to 10 average degree of ethoxylation.Most preferably, described oxyalkylated anionic detersive surfactant is the unsubstituted C of straight chain 12-18Alkyl ethoxylate sulfate, it has 3 to 7 average degree of ethoxylation.
The alkoxylate anionic detersive surfactant also can increase the activity of non-alkoxylate anionic detersive surfactant by reduce possibility that non-alkoxylate anionic detersive surfactant is precipitated out from contain the cationic solution of free ca.Preferably, the weight ratio of non-oxyalkylated anionic detersive surfactant and oxyalkylated anionic detersive surfactant is less than 5: 1, or less than 3: 1, or less than 1.7: 1, even less than 1.5: 1.This ratio provides best pure white maintenance performance, with good hardness tolerance performance and good lathering property.Yet the weight ratio of preferred oxyalkylated anionic detersive surfactant of right and wrong and oxyalkylated anionic detersive surfactant is greater than 5: 1, or greater than 6: 1, or greater than 7: 1, even greater than 10: 1.Above-mentioned ratio provides best greasy dirt clean-up performance, with good hardness tolerance performance and good lathering property.
Suitable alkoxylate anionic detersive surfactant is: available from the Texapan LESTT of Cognis TMCosmacol AES available from Sasol TMBES 151 available from Stephan TMEmpicol ESC70/U TMAnd their mixture.
Non-ionic detersive surfactant
Composition of the present invention can comprise nonionogenic tenside.When existing, its content is generally 0.5% weight to 20% by the gross weight of described composition, more is typically 0.5% to 10% weight.Described composition can comprise 1% weight to 7% weight, or the non-ionic detersive surfactant of 2% weight to 4% weight.In described composition, comprise non-ionic detersive surfactant, help to provide the good whole clean-up performance, especially at high temperature when washing under 60 ℃ or the higher temperature.
Described non-ionic detersive surfactant can be selected from: C 12-C 18Alkylethoxylate is as the NEODOL available from Shell Nonionogenic tenside; C 6-C 12Alkyl phenolic alkoxy thing, wherein said alkoxylate unit are vinyloxy group unit, propenyloxy group unit or their mixture; C 12-C 18Pure and mild C 6-C 12The polycondensate of alkylphenol and ethylene oxide/propylene oxide block polymer is as the Pluronic available from BASF As US6, the C in greater detail of institute in 150,322 14-C 22The alcohol of mid-chain branched, BA; As US6, the C in greater detail of institute in 153,577, US6,020,303 and US6,093,856 14-C 22The alkyl alkoxylates of mid-chain branched, BAE x, x=1 to 30 wherein; As US4, institute's alkyl polysaccharide in greater detail in 565,647, particularly as US4, in 483,780 and US4,483,779 alkyl polyglycoside in greater detail; As US5,332,528, institute's polyhydroxy fatty acid amide in greater detail among WO92/06162, WO93/19146, WO93/19038 and the WO94/09099; As US6,482,994 and WO01/42408 in ether capped in greater detail poly-(alkoxylate) pure tensio-active agent; And their mixture.
Described non-ionic detersive surfactant can be alkyl polyglucoside and/or alkyl alkoxylates alcohol.Preferred non-ionic detersive surfactant is a straight or branched, replaces or unsubstituted C 8-18The alcohol of alkyl ethoxylated, it has average 1 to 50 ethoxylation degree, and more preferably 3 to 40.Nonionogenic tenside has also being particularly useful of 3 to 9 ethoxylation degrees.The HLB value is 13 to 25 nonionogenic tenside, is 15 to 50 as average degree of ethoxylation, or even is 20 to 50 C 8-18Alkyl ethoxylated alcohol also is preferred nonionic in the present composition.The embodiment of these nonionogenic tensides described later is Lutensol AO30 and is described in similar material among the WO04/041982.Because they have good lime soap dispersing agent performance, be useful therefore.
Described non-ionic detersive surfactant not only provides additional soil cleaning performance, but also has increased the activity of anionic detersive surfactant by the possibility that the reduction anionic detersive surfactant is precipitated out from have the cationic solution of free ca.Preferably, the weight ratio of non-alkoxylate anionic detersive surfactant and non-ionic detersive surfactant is less than 8: 1, or less than 7: 1, or less than 6: 1, or less than 5: 1, preferred 1: 1 to 5: 1, or 2: 1 to 5: 1, or even 3: 1 to 4: 1 scope in.
Cationic detersive surfactants
In one aspect of the invention, described detergent composition cation tensio-active agent not.Yet described composition can randomly comprise the cationic detersive surfactants of 0.1% weight to 10% or 5% weight.Yet when existing, described composition preferably comprises 0.5% weight to 3% weight, or 1% to 3% weight, or even the cationic detersive surfactants of 1% weight to 2% weight.This is the optimum content that cationic detersive surfactants provides good clean-up performance.Suitable cationic detersive surfactants is alkyl pyridine compound, alkyl quaternary ammonium compound, Wan base Ji An phosphonium compounds and alkyl ternary sulphur compound.Described cationic detersive surfactants can be selected from: as US6, and alcoxylates quaternary ammonium (AQA) tensio-active agent in greater detail in 136,769; As US6, dimethyl hydroxyl ethyl quaternary ammonium surfactant in greater detail in 004,922; As polyamine cats product in greater detail among WO98/35002, WO98/35003, WO98/35004, WO98/35005 and the WO98/35006; As US4, cationic ester tensio-active agent in greater detail in 228,042, US4,239,660, US4,260,529 and US6,022,844; As US6,221,825 and WO00/47708 in amino surface promoting agent in greater detail, be the amido propyl-dimethyl amine specifically; And their mixture.The preferred cation detersive surfactant is the quaternary ammonium compound with following general formula:
(R)(R 1)(R 2)(R 3)N +X -
Wherein, R is straight or branched, replacement or unsubstituted C 6-18Alkyl or alkenyl part, R 1And R 2Be independently selected from methyl or ethyl part, R 3Be hydroxyl, methylol or hydroxyethyl part, X is for providing electroneutral negatively charged ion, and preferred anionic surfactants comprises halogenide (as muriate), sulfate radical and sulfonate radical.The preferred cation detersive surfactant is a C 6-18Alkyl one hydroxyethyl dimethyl aliquat.Highly preferred cationic detersive surfactants is a C 8-10Alkyl one hydroxyethyl dimethyl aliquat, a C 10-12Alkyl one a hydroxyethyl dimethyl aliquat and a C 10Alkyl one hydroxyethyl dimethyl aliquat.(trade(brand)name Clariant) can be useful and can be used as short infusion for cats product such as Praepagen HY.
Described cationic detersive surfactants provides additional grease soil cleaning performance.Yet cationic detersive surfactants can increase the trend that any non-alkoxylate anionic detersive surfactant is precipitated out from solution.Preferably, in detergent composition of the present invention, described cationic detersive surfactants and any non-alkoxylate anionic detersive surfactant separate.For example, if there is cats product, then cats product and any anion surfactant especially are non-alkoxylate anion surfactants, will preferably be present in the described composition with independent particle.This has farthest reduced any cationic detersive surfactants and has caused the inadvisable sedimentary any influence of anionic detersive surfactant, and guarantees that the gained washing liq is not muddy when contacting with water.If there is cats product, the weight ratio of then non-alkoxylate anionic detersive surfactant and cationic detersive surfactants is at 5: 1 to 25: 1, more preferably 5: 1 to 20: 1, or 6: 1 to 15: 1, or 7: 1 to 10: 1, or even 8: 1 to 9: 1 scope in.
Typically, described detergent composition comprises 1% to 50% weight, the anion surfactant of more typical 2% to 40% weight.Alkylbenzene sulfonate is the preferred anionic surfactants tensio-active agent.
Preferred compositions of the present invention comprises by at least two kinds of formed combinations of different tensio-active agents.Described combination comprises at least a tensio-active agent and at least a tensio-active agent that is selected from second class that is selected from the first kind.Described first kind tensio-active agent comprises alkylbenzene sulfonate and MES tensio-active agent.The described second class tensio-active agent comprises alkoxylate anion surfactant, MES and alkoxy-based non-ionic surface active agent and sulfonated (AOS).Especially preferred combination comprises the combination of alkylbenzene sulfonate (preferred LAS) and MES.In addition, especially preferred combination comprises alkylbenzene sulfonate, preferred LAS and oxyalkylated anion surfactant, the C that preferably has 1 to 10 average degree of alkoxylation 8-18The combination of alkyl alkoxylated vitriol.The 3rd especially preferred combination comprises alkylbenzene sulfonate, and preferred LAS and oxyalkylated nonionogenic tenside preferably have 15 to 50, the C of preferred 20 to 40 degree of alkoxylation 8-18The combination of the alcohol of alkyl ethoxylated.
Typically be 1: 5 to 100: 1 from the weight ratio of described first kind tensio-active agent and weight ratio, preferred 1: 2 to 100: 1 or 1: 1 to 50: 1 even reach 20: 1 or 10: 1 from the described second class tensio-active agent.The content of tensio-active agent as above described in the concrete kind of tensio-active agent.It is preferred having AE3S and/or MES in system, and this is because the hardness tolerance of their excellences and with the ability of the dispersion calcium soap that forms during the lipase washing.
In another embodiment, the tensio-active agent in the detergent composition of the present invention comprises at least three kinds of tensio-active agents, respectively selects at least a from first and second classifications defined above.In addition, the third tensio-active agent is also preferably selected from first and second classifications defined above.
Remove function owing to send dirt by lipase, therefore detergent composition of the present invention can comprise the tensio-active agent of lower aq astoundingly, simultaneously still can represent good cleaning effect, so that the total content of tensio-active agent is lower than 12% weight by the gross weight of described composition, or 10% weight or 8% weight.
In an embodiment preferred of the present invention, described detergent composition also comprises short infusion, and its content is typically 0.01% to 10% weight by the gross weight of described composition, preferred 0.02% to 5% weight.Suitable short infusion comprises fatty acid amide, Marlamid, trimethyl-glycine, sultaine and amine oxide.Especially preferred material is AMONYL 380LC, cocoyl single ethanol amide and amine oxide.Suitable amine oxide is the Admox 12 that is provided by Albemarle.
Lime soap dispersing agent
Because these lipase are discharged into dirt in the washing water, therefore especially preferred detergent composition of the present invention comprises the antiredeposition polymkeric substance in addition, as following polymer poly carboxylicesters.In addition, or alternatively, ether of cellulose also is useful as carboxymethyl cellulose (CMC).Suitable CMC is the Tylose CR1500G2 that is sold by Clariant.Suitable polymer blend also is sold by Andercol with trade(brand)name Textilan, Colombia.
Especially preferably comprise additive, as described above MES, AES, the nonionogenic tenside of height ethoxylation or polymkeric substance such as the Acusol 460N (Rohm that demonstration has excellent calcium soap dispersiveness with calcium soap divergent function; Haas).The tabulation of suitable lime soap dispersing agent is shown in the following reference and file that is incorporated herein.
WO9407974 (P﹠amp; G), WO9407984 (P﹠amp; G), WO9407985 (P﹠amp; G), WO9504806 (P﹠amp; G), WO9703379 (P﹠amp; G), US6770610 (Clariant), EP0324568 (Rohm ﹠amp; Haas), EP0768370 (Rohm ﹠amp; Haas), the 71st page to 73 pages of " Cosmetics and Toiletries " the 104th phases in 1989 of M.K.Nagarajan and W.F.Masler, the 159th page to 161 pages of " Tenside Surf. Det " the 27th phases nineteen ninety of W.M.Linfield, the 63rd page to 69 pages of people's such as RG.Bistline " J.Am.Oil Chem.Soc " the 49th phases in 1972.
Find that the existence of soil release polymer is especially useful to improved greasiness removal of further enhancing and cleaning beneficial effect, and is especially true to synthon.Preferred modified cellulose ethers, as methyl hydroxyethylcellulose (MHEC), Tylose MH50G4 and the Tylose MH300G4 that sells by Clariant for example.Soil release polymer based on polyester is especially preferred, because they also can be effective as lime soap dispersing agent.The embodiment of suitable material is Repel-o-Tex PF (being provided by Rhodia), Texcare SRA100 (being provided by Clariant) and SokalanSR100 (BASF).
Except the first washing lipase, described preparation also can comprise one or more other enzymes, for example proteolytic enzyme, amylase, cellulase (especially endo-dextranase), pectin lyase and/or mannase.
Detergent composition of the present invention can be any form easily, for example solid such as Powdered or particulate state or chip solid, stick or moisture or or water-soluble liquid, gel or liquid gel.Any of these form all can be sealed by capsule partially or completely.Yet, the invention particularly relates to solid detergent composition, especially granular composition.When detergent composition of the present invention is solid, usually with tensio-active agent together with the solid matter that is generally washing assistant, be incorporated in agglomerate, extrudate or the spray-dried granules, and these can be mixed, to make according to full formula detergent composition of the present invention.When existing with particle form, detergent composition of the present invention preferably has 350g/L to 1200g/L, more preferably 450g/L to 1000g/L, or even those of the whole bulk density of 500g/L to 900g/L.Preferably, the detergent particles in the particle form detergent composition has 200 μ m to 2000 μ m, the mean particle size of preferred 350 μ m to 600 μ m.
Usually, detergent composition of the present invention will comprise the mixture of detergent particles.Described mixture comprises agglomerate, spray-dried powders and/or the dried combination that adds material such as SYNTHETIC OPTICAL WHITNER, enzyme etc.
In one aspect of the invention, detergent composition of the present invention comprises the anion surfactant that is selected from the table, it is non-alkoxylate anionic detersive surfactant, and preferably it is incorporated in the detergent composition with particle form, as via agglomerate, spray-dried powders, extrudate, globule, ribbon, spicule or thin slice.The preferably spray drying particle.If via agglomerate, then described agglomerate comprises the weight at least 20% by described agglomerate, more preferably the non-alkoxylate anionic detersive surfactant of 25% weight to 65% weight.Preferably, the non-alkoxylate anionic detersive surfactant of part is spray-dried powders form (as the expansible powder), and the non-alkoxylate anionic detersive surfactant of part is that non-spray-dried powders form is (as agglomerate, or extrudate, or flap such as linear alkylbenzene sulfonate flap; Suitable linear alkylbenzene sulfonate flap is with trade(brand)name F90 Supply from Pilot Chemical, or with trade(brand)name Nacconol 90G Supply from Stepan).This is especially preferred when needs mix high-load non-alkoxylate anionic detersive surfactant in composition.
Can be via the spray-dried granules of non-spray-dried powders such as extrudate, agglomerate, preferred agglomerate is incorporated into any alkoxylate anionic detersive surfactant in the detergent composition of the present invention.When needs mix high-load alkoxylate anionic detersive surfactant in described composition, preferred non-spray-dried granules.
Any non-ionic detersive surfactant or be incorporated in the described composition to the form that the small part non-ionic detersive surfactant can liquid spray, wherein said non-ionic detersive surfactant or be sprayed on the remaining set compound with liquid form (as with heat fusing thing form) to the small part non-ionic detersive surfactant.Described non-ionic detersive surfactant or can be included in the middle of the particle that is used for incorporation in the detergent composition of the present invention, and described non-ionic detersive surfactant or can be added on the remaining set compound by dried to the small part non-ionic detersive surfactant to the small part non-ionic detersive surfactant.Described nonionogenic tenside or can be common granular mixture form with solid carrier material such as carbonate, vitriol, burkeite, silicon-dioxide or their any mixture to the small part nonionogenic tenside.
Any non-ionic detersive surfactant or can be the common granular mixture form that forms with alkoxylate anionic detersive surfactant, non-alkoxylate anionic detersive surfactant or cationic detersive surfactants to the small part non-ionic detersive surfactant.Non-ionic detersive surfactant or to the small part non-ionic detersive surfactant can be with alkoxylate anionic detersive surfactant, non-alkoxylate anionic detersive surfactant or cationic detersive surfactants by agglomeration or extrusion.
If there is cationic detersive surfactants, by mixing with particle form, as spray-dried powders, agglomerate, extrudate, thin slice, ribbon, spicule or their any combination, cationic detersive surfactants can be incorporated in the described composition.Preferably, described cationic detersive surfactants or at least the partial cation detersive surfactant be spray-dried powders or agglomerate shape.
Optional decontamination auxiliary agent
Randomly, described detergent ingredients can comprise one or more other decontamination auxiliary agents, or other is used for material auxiliary or that strengthen clean-up performance, handle substrate to be cleaned or improve the aesthetic property of described detergent composition.The common decontamination auxiliary agent of detergent composition comprises people's such as Baskerville United States Patent (USP) 3,936,537.And be published on September 24th, 1997, the composition that is proposed in people's such as Trinh the UK Patent Application 9705617.0.Above-mentioned auxiliary agent is contained in the detergent composition with their fixed consumptions in conventional field, 0% weight that is generally detergent ingredients is to about 80% weight, preferred about 0.5% weight is about 20% weight extremely, and can include the color spot grain, short infusion, suds suppressor, anti-dark and gloomy dose and/or anticorrosive agent, soil-suspending agent, stain remover, dyestuff, weighting agent, white dyes, sterilant, the basicity source, hydrotropic agent, antioxidant, enzyme, enzyme stabilizers, solvent, solubilizing agent, sequestrant, clay removes/anti-redeposition agent, polymeric dispersant, processing aid, fabric softening component, the Electrostatic Control agent, SYNTHETIC OPTICAL WHITNER, bleach-activating agent, bleaching stibilizer, the dye transfer inhibitor, flocculation agent, fabric softener, suds suppressor, fabric integrity agent, spices, whitening agent, optical white, alkali metal sulfates, thionamic acid, sodium sulfate and thionamic acid title complex etc. and their combination.The precise nature of these annexing ingredients and mix physical form that content will depend on composition or component with and the precise nature of the washing operation used.
Preferred zwitterionics comprises one or more quaternised nitrogen-atoms and is selected from the one or more parts of following ionic: one or more parts of carbonate, phosphate radical, sulfate radical, sulfonate radical and their combination.Preferred zwitterionics is an alkyl betaine.Other preferred zwitterionics is an alkyl amine oxide.Also can comprise the negative ions tensio-active agent, it is the title complex that comprises cats product and anion surfactant.Typically, the mol ratio of cats product and anion surfactant was greater than 1: 1 in title complex, so title complex has clean positive charge.
Composition of the present invention can comprise bleach enhancers.Preferred bleach boosters is selected from the group of being made up of following material: zwitter-ion imines, negatively charged ion imines polyion, season peroxide inferior amine salt and their combination.Highly preferred bleach boosters is selected from the group of being made up of following material: aromatic imine zwitter-ion, aromatic imine polyion and their combination.The bleach boosters that is fit to is described among US360568, US5360569 and the US5370826.
Preferred adjuvant component is anti-redeposition agent.Preferably, this detergent composition comprises one or more anti-redeposition agent.Preferred anti-redeposition agent is cellulosic polymeric constituent, most preferably carboxymethyl cellulose.
Preferred adjuvant component is a sequestrant.Preferably, this detergent composition comprises one or more sequestrants.Preferably, described detergent composition comprises (by the weight of described composition) 0.01% to 10%, or 0.01% to 5% weight, or the sequestrant of 4% weight or 2% weight.Preferred sequestrant is selected from the group of being made up of following material: hydroxyl ethane-dimethylene-phosphonic acids, ethylenediamine tetraacetic (methylene radical phosphine) acid, diethylentriamine pentacetate, 1,2-edetate, diethylenetriamine five (methyl phosphorus) acid, 1 disuccinic acid and their combination.
Preferred adjuvant component is a dye transfer inhibitor.Preferably, this detergent composition comprises one or more dye transfer inhibitors.Typically, dye transfer inhibitor is a polymeric constituent, and this component is caught dye molecule and maintained described dye molecule in the washing liq by it is suspended in.Preferred dye transfer inhibitor is selected from the group of being made up of following material: polyvinylpyrrolidone, polyvinyl pyridine N-oxide, polyvinylpyrrolidone-polyvinylimidazole copolymers and their combination.
Preferred adjuvant component comprises other enzyme.Preferably, detergent composition comprises one or more additional enzymes.Preferred enzyme is selected from the group of being made up of following material: amylase, arabinase, carbohydrase, cellulase, chondroitinase, at, dextranase, esterase, beta-glucanase, glucoamylase, Unidasa, keratanase, laccase, ligninase, lipoxygenase, malanases, mannase, oxydase, polygalacturonase, pentosanase, peroxidase, phenol oxidase, Phospholipid hydrolase, proteolytic enzyme, Starch debranching enzyme, reductase enzyme, tannase, transferring enzyme, zytase, xyloglucanase enzymes, and their combination.Preferred additional enzymes is selected from the group of being made up of following material: amylase, carbohydrase, cellulase, proteolytic enzyme and their combination.
A kind of preferred adjuvant component is a fabric integrity agent.Preferably, this detergent composition comprises one or more fabric integrity agent.Typically, fabric integrity agent is a polymeric constituent.This component is deposited on fabric face and prevents that fabric from damaging in laundry processes.Preferred fabric integrity agent is the hydrophobically modified Mierocrystalline cellulose.These hydrophobically modified Mierocrystalline celluloses can reduce fabric abrasion, improve the interaction of fiber and fiber, and reduce the dyestuff loss of fabric.The Mierocrystalline cellulose of preferred hydrophobically modified is described among the WO99/14245.Other preferred fabric integrity agent is polymeric constituent and/or oligomeric component, and it can derive from, and preferably the technology of the step by comprising imidazoles and epoxy chloropropane condensation obtains.
A kind of preferred adjuvant component is a salt.Preferably, this detergent composition comprises one or more salt.Described salt is also as alkaline agent, buffer reagent, washing assistant, auxiliary lotion, scale inhibitor, weighting agent, pH regulator agent, stablizer and their combination.Typically, this detergent composition comprises the salt of (by described composition weight meter) 5% to 60%.Preferred salt is alkali-metal aluminate, carbonate, muriate, supercarbonate, nitrate, phosphoric acid salt, silicate, vitriol and their combination.The aluminate that other preferred salt is alkaline-earth metal, carbonate, muriate, supercarbonate, nitrate, phosphoric acid salt, silicate, vitriol and their combination.Particularly preferred salt is sodium sulfate, yellow soda ash, sodium bicarbonate, water glass, sodium sulfate and their combination.Can be randomly, described an alkali metal salt and/or alkaline earth salt can be anhydrous.
Preferred adjuvant component is a stain remover.Preferably, this detergent composition comprises one or more stain removers.Typically, stain remover is a polymkeric substance, and it is modified fabric face and prevents that soil redeposition is on described fabric.Preferred stain remover is a multipolymer, preferably includes the segmented copolymer of one or more terephthalate unit.Preferred stain remover is by dimethyl terephthalate, 1,2-propylene glycol and methyl blocking polyoxyethylene glycol synthetic multipolymer.Other preferred stain remover is the negatively charged ion end capped polyesters.
Composition of the present invention can comprise at least 0.1% weight aptly, or at least 0.5% weight, or at least 2% or 3% weight, or even at least 5% weight, the polymer poly carboxylicesters of maximum 30% weight or 20% weight or 10% weight.Preferred polymer poly carboxylicesters comprises polyacrylic ester and toxilic acid and acrylic acid multipolymer.Suitable polycarboxylate is Sokalan CP, PA and HP classification (BASF), as Sokalan CP5, PA40 and HP22, and the Alcosperse classification (Alco) of polymkeric substance, as Alcosperse 725,747,408,412 and 420.
Described composition also can preferably comprise the dirt dispersant that for example has following chemical formula: two ((C 2H 5O) (C 2H 4O) (CH n) 3)-N +-C xH 2x-N +-(CH 3)-two ((C 2H 5O) (C 2H 4O) n)
Wherein, n=20 to 30, and x=3 to 8.Other suitable dirt dispersant is sulfonation or the sulfation dirt dispersant with following chemical formula:
Sulfonation or Sulfated two ((C 2H 5O) (C 2H 4O) (CH n) 3)-N +-C xH 2x-N +-(CH 3)-two ((C 2H 5O) (C 2H 4O) n)
Wherein, n=20 to 30, and x=3 to 8.Preferably, described composition comprises at least 1% weight, or at least 2% weight, or the dirt dispersant of at least 3% weight.
Softening system
Detergent composition of the present invention can comprise be used for by the washing remollescent tenderizer (as clay), also can randomly have flocculation agent and enzyme.
Further describing more specifically of suitable detergent component is found among the WO97/11151.
Washing methods
The present invention also comprises the method for washing textiles.Described method comprises makes textiles contact with the aqueous solution that comprises detergent composition of the present invention.The present invention in low water temperature as being especially useful below 30 ℃ or below 25 ℃ or 20 ℃.Aqueous cleaning liquid comprises 100ppm at least with the typical case, or the described detergent composition of 500ppm at least.
Embodiment
Below be embodiments of the invention.
Composition A B C D
Straight chain C 11-13Sodium alkyl benzene sulfonate 19 14.5 5 6
R 2N +(CH 3) 2(C 2H 4OH), while R 2＝ C 12-14Alkyl Do not exist 0.5 Do not exist Do not exist
R 2N +(CH 3) 2(C 2H 4OH), while R 2＝ C 8-10Alkyl 0.55 Do not exist 0.6 0.9
C with average 3 moles of ethylene oxide 12- C 15The alcohol ether sodium sulfate 1.0 1.0 3.6 Do not exist
C 16-18Methyl esters sodium sulfonate (MES) Do not exist 3.0 Do not exist 3.0
C with every mole of alkyl alcohol condensation of average 3 to 9 moles of EO/ 12-18Straight-chain alcohol ethoxylate Do not exist Do not exist Do not exist 9.2
C with every mole of alkyl alcohol condensation of average 30 moles of EO/ 13-15Alcohol ethoxylate (available from the Lutensol AO30 of BASF) Do not exist Do not exist Do not exist Do not exist
Citric acid Do not exist Do not exist 3.2 2.6
STPP (anhydrous) 9.0 3.0 Do not exist Do not exist
Zeolite A Do not exist 3.4 0.5 Do not exist
Xylo-Mucine 0.6 0.5 0.2 0.7
Weight-average molecular weight is 3000 to 5000 polyacrylic acid sodium polymer 1.0 1.0 Do not exist Do not exist
Toxilic acid/acrylic copolymer, the weight-average molecular weight that has are 50,000 to 90,000, toxilic acid: acrylic acid ratio is 1: 3 to 1: 4 (Sokalan CP5 is available from BASF) Do not exist Do not exist 10.9 12.0
Lime soap dispersing agent (Acusol 460N is available from Rohm ﹠ Haas) Do not exist Do not exist Do not exist Do not exist
DTPA 0.3 0.3 Do not exist Do not exist
EDDS Do not exist Do not exist 0.3 0.2
Proteolytic enzyme-enzymic activity is 15 to 70mg/g 0.2 0.2 0.3 0.3
Amylase-enzymic activity is 25 to 50mg/g 0.1 0.1 0.2 0.4
Lipex available from Novozymes -enzymic activity is 5 to 25mg/g 0.15 0.10 0.2 0.12
The anhydrous sodium perborate monohydrate 4.4 Do not exist Do not exist Do not exist
SPC-D Do not exist 4.4 15 15
Sal epsom 0.5 0.5 0.3 0.4
The nonanoyl phenolsulfonate 1.0 1.9 4 3
Tetra acetyl ethylene diamine 0.28 0.6 1.2 1.0
Whitening agent 0.16 0.30 0.3 0.5
Yellow soda ash 20.0 17.0 17.0 20.0
Water glass (2.0R) 12.0 12.0 15.0 12.0
Optical white 0.0035 0.0035 0.0014 0.0012
The spices of spraying 0.2 0.2 0.34 0.37
The spices that the starch capsule is sealed 0.2 0.2 0.1 0.2
The suds suppressor particle 0.3 0.2 0.3 0.4
Soap Do not exist Do not exist Do not exist 1.0
Na 2SO 4, other composition and moisture To 100 To 100 To 100 To 100
<110>The Procter & Gamble Company
＜120〉detergent composition
<130>CM2956M
<140>06110531.8
<141>2006-02-28
<150>05251269.6
<151>2005-03-03
<160>1
<170>PatentIn 3.3
<210>1
<211>291
<212>PRT
<213>Humicola lanuginosa
<400>1
Met Arg Ser Ser Leu Val Leu Phe Phe Val Ser Ala Trp Thr Ala Leu
1 5 10 15
Ala Ser Pro Ile Arg Arg Glu Val Ser Gln Asp Leu Phe Asn Gln Phe
20 25 30
Asn Leu Phe Ala Gln Tyr Ser Ala Ala Ala Tyr Cys Gly Lys Asn Asn
35 40 45
Asp Ala Pro Ala Gly Thr Asn Ile Thr Cys Thr Gly Asn Ala Cys Pro
50 55 60
Glu Val Glu Lys Ala Asp Ala Thr Phe Leu Tyr Ser Phe Glu Asp Ser
65 70 75 80
Gly Val Gly Asp Val Thr Gly Phe Leu Ala Leu Asp Asn Thr Asn Lys
85 90 95
Leu Ile Val Leu Ser Phe Arg Gly Ser Arg Ser Ile Glu Asn Trp Ile
100 105 110
Gly Asn Leu Asn Phe Asp Leu Lys Glu Ile Asn Asp Ile Cys Ser Gly
115 120 125
Cys Arg Gly His Asp Gly Phe Thr Ser Ser Trp Arg Ser Val Ala Asp
130 135 140
Thr Leu Arg Gln Lys Val Glu Asp Ala Val Arg Glu His Pro Asp Tyr
145 150 155 160
Arg Val Val Phe Thr Gly His Ser Leu Gly Gly Ala Leu Ala Thr Val
165 170 175
Ala Gly Ala Asp Leu Arg Gly Asn Gly Tyr Asp Ile Asp Val Phe Ser
180 185 190
Tyr Gly Ala Pro Arg Val Gly Asn Arg Ala Phe Ala Glu Phe Leu Thr
195 200 205
Val Gln Thr Gly Gly Thr Leu Tyr Arg Ile Thr His Thr Asn Asp Ile
210 215 220
Val Pro Arg Leu Pro Pro Arg Glu Phe Gly Tyr Ser His Ser Ser Pro
225 230 235 240
Glu Tyr Trp Ile Lys Ser Gly Thr Leu Val Pro Val Thr Arg Asn Asp
245 250 255
Ile Val Lys Ile Glu Gly Ile Asp Ala Thr Gly Gly Asn Asn Gln Pro
260 265 270
Asn Ile Pro Asp Ile Pro Ala His Leu Trp Tyr Phe Gly Leu Ile Gly
275 280 285
Thr Cys Leu
290

Claims (10)

1. detergent composition, described detergent composition comprises hydrogen peroxide cource, hydrophobicity peracid and/or its precursor and lipase, described hydrophobicity peracid and/or its precursor have chemical formula R-(C=O)-L structure, wherein R is for having 6 to 14 carbon atoms, the alkyl of preferred 8 to 12 carbon atoms, and L is a leavings group, and described lipase is the polypeptide with aminoacid sequence: (a) have and the identity that derives from the wild-type lipase at least 90% of Humicola lanuginosa strain DSM 4109; (b) compare with described wild-type lipase, be included within three-dimensional structure surface lies E1 or the Q24915 dust electric neutrality or electronegative amino acid and replaced by the amino acid of a positively charged; And c) comprises an additional peptide section at the C-end; And/or (d) comprise an additional peptide section, and/or (e) meet following qualifications: i) contain an electronegative amino acid in the E210 position of described wild-type lipase at the N-end; Ii) containing an electronegative amino acid corresponding to the zone of described wild-type lipase 90-101 position; Iii) containing neutrality or electronegative amino acid corresponding to the N94 position of described wild-type lipase and/or having a negative or neutral net charge in zone corresponding to described wild-type lipase 90-101 position; Described detergent composition has the reserve alkalinity greater than 6.5, and the amount of available oxygen (from described peroxide source) and peracid and/or its precursor can provide the mol ratio of 1: 1 to 35: 1 available oxygen (from described peroxide source) Yu peracid to described detergent composition.
2. detergent composition as claimed in claim 1, described detergent composition have greater than 8 or greater than 9 reserve alkalinity.
3. as claim 1 or the described detergent composition of claim 2, described detergent composition has 2: 1 to 8: 1 the available oxygen and the ratio of peracid.
4. the described detergent composition of each claim as described above, wherein said hydrophobicity bleach-activating agent comprises nonanoly acyloxy benzene sulfonate.
5. the described detergent composition of each claim as described above, described detergent composition comprises the alkoxylated alkyl sulphate tensio-active agent of 0.1% to 40% weight and/or the C of 0.1% to 40% weight 1-4Alkyl ester sulfonate, preferable methyl sulfonated ester (MES), preferably the alkyl benzene sulfonate surfactant with 5% to 40% weight combines.
6. the described detergent composition of each claim as described above, described detergent composition comprises the short infusion of 0.05% to 2% weight, and described short infusion is preferably selected from fatty acid amide, Marlamid, trimethyl-glycine, sultaine and amine oxide or their mixture.
7. the described detergent composition of each claim as described above, described detergent composition comprises 0.05% to 5% weight, the tetra acetyl ethylene diamine of preferred 0.1% to 1% weight (TAED).
8. the described detergent composition of each claim as described above, described detergent composition is a solid detergent composition, is preferably granular detergent composition.
9. washing methods, described washing methods are included in and comprise as described above the aqueous wash medium of the described detergent composition of each claim and wash textiles.
10. washing methods as claimed in claim 9, the temperature of the wherein said aqueous solution are lower than 30 ℃.
CNA2006800068987A 2005-03-03 2006-03-02 Detergent compositions Pending CN101133148A (en)

Applications Claiming Priority (2)

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EP05251269A EP1698689A1 (en) 2005-03-03 2005-03-03 Detergent compositions
EP05251269.6 2005-03-03

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KR (1) KR20070103764A (en)
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AU (1) AU2006218400A1 (en)
BR (1) BRPI0607406A2 (en)
CA (1) CA2597226A1 (en)
EG (1) EG24955A (en)
MX (1) MX2007010725A (en)
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EG24955A (en) 2011-02-21
JP2008531758A (en) 2008-08-14
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AU2006218400A1 (en) 2006-09-08
BRPI0607406A2 (en) 2009-09-01

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