CN103168095A - A detergent composition having shading dyes and lipase - Google Patents

Abstract

A detergent composition has shading dyes and lipase. The invention relates to detergent compositions having shading dyes and lipase. It has been determined that combination of lipase with specific shading dyes provides lower redeposition of soil. This is manifested as higher reflectance and lower yellowing, especially over multiple washes on knitted cotton, knitted polyester and polyester fabrics, Disclosed is a detergent composition comprising: (i)a surfactant; (ii)a hydrophobic dye; (iii)a direct dye; (iv)an acid dye; and, (v)lipase.

Description

There is the detergent composition that covers dyestuff and lipase

Invention field

The present invention relates to have the detergent composition that covers (shading) dyestuff and lipase.

background and correlation technique

The discussion that runs through any prior art of this specification sheets should never be considered to admit that such prior art is extensive known or the part of formation this area conventional, well-known general knowledge.

White garments is very welcome.They can be by various fabrics, and for example 100% cotton, polyester-cotton blend (poly-cotton), 100% polyester or nylon are made.Known fabrics, especially white fabrics will tend to show after after a while tinge yellowish.This may be that the incomplete removal due to dirt, the deposition of oily skin residue and the oxidation of sebum cause.The yellowing of white fabrics is not the phenomenon of instantaneous or short-term.White fabrics must be washed and wear repeatedly, just feel tinge yellowish.

This problem can be to a certain extent by being used fluorescent agent to solve.They absorb ultraviolet ray and send visible ray, make the clothes of yellowing seem vivider.This problem also can be covered dyestuff by use and be solved.These dyestuffs have added blue cast to fabric, shelter thus and tinge yellowish and make fabric seem whiter and vivider.Covering dyestuff contributes to keep and reactivation (re-invigorate) whiteness.Known fluorescent agent and cover deposition of dye on fabric.Some cover on the fabric that dyestuff only is deposited on some particular types.This may depend on the chemical interaction between fabric and dyestuff.For example, hydrophobicity is covered deposition of dye on water-repellent fabrics.Substantive dyestuff and matching stain blue and purple show special practicality on cotton.Solvent dye and dispersed dye are given polyester, nylon and elasticity matter fabric benefit.Have been noted that dirt or sebum gathering prevention or at least having reduced the deposition of covering dyestuff on fabric.This may be the incomplete removal because of dirt during washing or sebum.

Detergent composition with the combination of covering dyestuff is known.

Usually use such combination so that composition comprises the dyestuff that can be deposited on various fabrics.

EP1921132 A2 (Unilever, 2008) disclose the laundry treatment compositions with tensio-active agent and dye combinations, these dyestuffs have the visual effect as the homogencous dyes of the peak absorbtivity wavelength that has 540 nm-650 nm on cotton to human eye together.One of described dyestuff is the light stability dyestuff to cotton substantive dyeing.

WO 2010/145887 A1 (Unilever, 2010) discloses the laundry treatment compositions with anionic dyestuff-polymkeric substance, and this anionic dyestuff-polymkeric substance provides improved fabric to cover and promoted the dirt removal.This application instruction has the composition of tensio-active agent and dye-polymer, and described dye-polymer obtains by the polymerization of dye monomer and olefin comonomer.This application does not have description to cover the combination of dyestuff and lipase for the impact that reduces soil redeposition.

Enzyme, particularly lipase have been used for improving clean in detergent composition.Known lipase contributes to grease to remove.The hydrolysis of lipase-catalyzed triglyceride level, triglyceride level forms for example, for example, main ingredient as sebum, animal tallow (lard, butter, butter) and vegetables oil (sweet oil, Trisun Oil R 80, peanut oil) of many fatty dirts that generally run into.

The detergent composition that has lipase and cover dyestuff is also disclosed.

US2007191250 A1 (P& G) disclose the detergent composition that comprises some lipase Variant and cover dyestuff, the described dyestuff that covers is selected from dyestuff and dyestuff-clay conjugates (conjugate).This application disclose due to by the functionalized triglyceride hydrolysis in short-chain fat acyl group unit therefore the effect of lipase cause stench.These triglyceride level discharges the voltaile fatty acid of stench after steatolysis.The combination that this problem has been covered dyestuff and some lipase Variant by use in the past solves, this has been considered to increase the level that grease is removed, and obtains covering dyestuff better for accessibility (accessibility) and so improved deposition of fabric face.

We are definite, and lipase and specific combination of covering dyestuff provide lower soil redeposition.This shows as higher reflectance and lower yellow degree, especially with respect to the repeatedly washing for knitted cotton, knitting polyester and polyester textile.

Summary of the invention

According to first aspect, the invention provides the detergent composition that comprises tensio-active agent, hydrophobic dye, substantive dyestuff, matching stain and lipase.

According to second aspect, the invention provides the method for laundering of textile fabrics, it comprises the step of using according to the compositions-treated fabric of first aspect.

According to the third aspect, the invention provides the method for processing fabric, said method comprising the steps of:

(i) process fabric with the aqueous solution that comprises following component:

(a) tensio-active agent of 0.3 g/l-10 g/l;

(b) hydrophobic dye of 0.1 ppb-500 ppm;

(c) substantive dyestuff of 0.1 ppb-500 ppm;

(d) matching stain of 0.1 ppb-500 ppm; With

(e) lipase of 0.3 ppb-10 ppm;

(ii) rinse fabric; With

(iii) dry fabric.

According to fourth aspect, the composition that the invention provides first aspect reduces the purposes of soil redeposition on fabric.

Term " comprises " and not is intended to limit any key element of describing subsequently, but comprises the key element with main or secondary function importance do not illustrated.In other words, the step of listing, key element or selection do not need exhaustive.No matter when use word " to comprise " or " having ", these terms all are intended to be equivalent to as defined above " comprising ".

Except in the situation that in operational example and Comparative Examples or explicitly pointing out in addition, otherwise mean in this specification sheets that all numerical value of material quantity should be understood to be modified by word " approximately ".

Should be noted that when illustrating any concentration or weight range, any specific upper limit concentration can be associated with any specific least concentration or amount.

Term weight percent, per-cent by weight, % by weight, wt% etc. are synonyms, and it refers to as the weight of this material divided by the weight of composition and is multiplied by 100 material concentration.

The statement of the digital scope limited by end points comprises all numerals (for example 1-5 comprises 1,1.5,2,2.75,3,3.80,4 and 5) that are included in this scope.

As used in this specification sheets and appending claims, singulative " a ", " an " and " the " comprise plural object, unless clearly pointed out in addition in context.Therefore, for example be mentioned to the mixture that the composition that contains " compound (a compound) " comprises two or more compounds.As used in this specification sheets and appending claims, the term "or" usually with it comprise " and/or " implication use, unless clearly pointed out in addition in context.

In order to understand the features and advantages of the present invention fully, should be with reference to following detailed description.

detailed Description Of The Invention

As used herein, term " detergent composition " comprises particle or powder composition, liquid, sheet, bar and gel.

tensio-active agent

Detergent composition comprises 2 % by weight-70 % by weight tensio-active agent, most preferably 10-30 % by weight.Preferred composition comprises anionic or nonionic surface active agent.The mixture that preferred composition comprises the two.

Generally speaking, the non-ionic type of surfactant system and aniorfic surfactant can be selected from the tensio-active agent be described in lower: ' the 1st volume (Schwartz and Perry by Interscience company delivered in 1949) of Surface Active Agents', the 2nd volume is (by the Schwartz of Interscience company, Perry and Berch delivered in 1958), by Manufacturing Confectioners Company, delivered ' the current version of McCutcheon's Emulsifiers and Detergents', or ' Tenside Taschenbuch', H. Stache, the 2nd edition, Carl Hauser Verlag, 1981.Preferably, the tensio-active agent of use is saturated.

Operable suitable aniorfic surfactant normally has containing having an appointment 8-approximately water miscible organo-sulfate an alkali metal salt and the sulfonic acid alkali metal salts of the alkyl of 22 carbon atoms, and the term alkyl is for comprising the moieties of senior acyl group.The example of suitable synthetic anionic detergent compound is sodium salt and the sylvite of alkyl sodium sulfate ester, especially by the senior C of sulfuric acid that will for example be made by tallow or cocounut oil ₅-C ₁₅those that the alcohol esterification obtains, alkyl C ₈-C ₂₀phenylsulfonic acid sodium salt and sylvite, particularly linear secondary alkyl C ₁₀-C ₁₅the Phenylsulfonic acid sodium salt; With the sodium sulfovinate of alkyl glycerol base ether, those ethers that described ether especially is obtained from the higher alcohols of tallow and cocounut oil and is obtained from the synthol of oil.Preferred anionic detergent compound is C ₆-C ₁₅sodium alkyl benzene sulfonate and sulfuric acid C ₁₂-C ₁₅alkyl ester sodium.Applicable equally is as be recorded in those tensio-active agents (it shows for the resistance of saltouing) in EP-A-328 177 (Unilever), be recorded in alkyl polyglucoside surfactant and alkyl monoglycosides in EP-A-070 074.

Operable suitable nonionic surface active agent comprises, particularly, compound with hydrophobic group and hydrogen atoms, for example fatty alcohol, acid, acid amides or alkylphenol and epoxy alkane, especially independent oxyethane (EO) or the reaction product together with propylene oxide.Concrete non-ionic detergent compound is C ₆-C ₂₂alkylphenol-ethylene oxide condensate, common 5-25 EO, i.e. 5-25 ethylene oxide unit/per molecule, and aliphatic C ₆-C ₁₈uncle or the alcohol of secondary straight or branched and the condensation product of oxyethane, 5-40 EO usually.

Preferred surfactant system is the mixture of anionic and nonionic surface active agent, the anionic of particularly pointing out in EP-A-346 995 (Unilever) and group and the example of nonionic surface active agent.Especially preferred is sulfuric acid C ₆-C ₂₂an alkali metal salt of primary alconol ester and C ₁₂-C- ₁₈the surfactant system of primary alconol 3-7EO Soxylat A 25-7 mixture together.

Preferred composition can comprise the nonionic surface active agent of 4 % by weight-25 % by weight.

cover dyestuff

As used herein, term " covers dyestuff " and refers to such dyestuff: in the time of in being formulated in detergent composition, when fabric contacts with the washing lotion with detergent composition, it can be deposited on fabric, changes thus the tone of fabric by absorbing visible ray.Cover dyestuff and also be known as toning agent (hueing agent).

During the washing or rinse step of washing process, cover deposition of dye on fabric, offer fabric visible tone.

The covering the preference that can depend on the human consumer of white fabrics and being undertaken by any color.Blue and purple is particularly preferred screening agent, and therefore preferably dyestuff or dye mixture are to give the class that blueness or purple cover on white fabrics.Therefore, preferably covering dyestuff is blueness or purple.Such dyestuff is given the blue color of white fabrics or color purple.Hue-angle (hue angle) is 240 °-345 °, more preferably 260 °-320 ° and most preferably 270 °-300 °.

Cover dyestuff and can be divided into several types and classification in several ways.A kind of mode is to depend on that its structure classifies dyestuff.Example comprises azoic dyestuff and anthraquinone dye.Another kind of mode is according to its application model, they to be classified.Example comprises substantive dyestuff and matching stain, dispersed dye, father-in-law's dyestuff and solvent dye.According to another kind of sorting technique, depend on its avidity to fabric, dyestuff is called to hydrophobicity or wetting ability.Another mode that dyestuff is covered in classification depends at the rear dyestuff of single cleaning whether be deposited on fabric and show its effect, or whether it deposits after repeatedly cleaning.In single cleans, the dyestuff of deposition is called as and once cleans dyestuff.Example comprises acid violet 50 (AV50).

Other are called as and gather (build-up) dyestuff.Some examples comprise direct purple 9 (DV9) and solvent violet 13 (SV13).

Detergent composition according to the present invention comprises three kinds of dyestuffs:

1. hydrophobic dye

Described composition comprises one or more hydrophobic dyes.Under home washings condition commonly used, have been found that hydrophobic dye is substantive dyeing for trevira.Under low-level, it provides and covers white advantage.Hydrophobic dye is defined in 400-750 nm wavelength region has the maximum optical extinction coefficient that is greater than 1000 L/mol/cm, and under the pH of 7-11 scope in the aqueous solution uncharged organic compound.Hydrophobic dye is not containing polarity solvability group.Especially, hydrophobic dye does not comprise any sulfonic group, carboxylic acid group or quaternary ammonium group.

Such dyestuff can be selected from the chemical with Types Below: benzo two furans, methyne, triphenylmethane, naphthalimide, pyrazoles, phthalocyanine, naphthoquinones, anthraquinone and monoazo or two azoic dyestuffs.

Preferred hydrophobic dye is dispersed dye and solvent dye.Many examples of hydrophobic dye find in the type of solvent dye and dispersed dye.

Preferably, by being dissolved in surfactant slurry or, by using the nonionic surface active agent granulation, hydrophobic dye being introduced in detergent composition.This has been recorded in WO/2006/053598 A1 (Unilever).

dispersed dye

Being preferably dispersed dye is anthraquinone dyes.Preferred anthraquinone dye can be represented by following structure:

Wherein R1, R4, R5 and R8 independently Xuan Zi – H ,-OH ,-NH ₂, NHCOCH ₃with-NO ₂, make and only have at most one-NO ₂group and maximum two-H exist as R1, R4, R5 and R8 substituting group; And be selected from-H of R2, R3, R6 and R7, F, Br, Cl or-NO ₂, and-the O aryl.

Preferred dispersed dye comprise 63 ,DIS,PER,SE ,Vio,let, 63 27 (DV27), 63 ,DIS,PER,SE ,Vio,let, 63 26 (DV26), 63 ,DIS,PER,SE ,Vio,let, 63 28 (DV28), 63 ,DIS,PER,SE ,Vio,let, 63 63 (DV63) and 63 ,DIS,PER,SE ,Vio,let, 63 77 (DV77).63 DISPERSE Violet 63 28 (DV28) is most preferred dispersed dye.

Another kind of preferred anthraquinone dye is solvent violet 13 (SV13).It is the synthetic anthraquinone dye with light blue violet tint.It is water insoluble and dissolve in acetone, toluene and benzene.Its chemical formula is C ₂₁h ₁₅nO ₃, and its structure is 1-hydroxyl-4-(p-methylphenyl amino)-anthraquinone, or 1-hydroxyl-4-[(4-aminomethyl phenyl) amino]-9,10-amerantrone or 1-hydroxyl-4-(4-toluidine) anthraquinone.

Monoazo-dyes is also preferred hydrophobic dye.They can be represented by following structure:

Wherein R3 and R4 are the C that wherein optionally has the optional replacement of ether (O-) or ester bond ₂-C ₁₂alkyl chain, described chain optionally by-Cl ,-Br ,-CN ,-NO ₂with-SO ₂cH ₃replace; Mean aryl or heteroaryl with D.

Aromatic ring can also be further preferably by-Cl ,-Br ,-CN ,-NO ₂,-SO ₂cH ₃he – NHCOR replaces; And be selected from-CH of R ₃,-C ₂h ₅with-CH ₂cl.

The structure of most preferred monoazo-dyes is:

Wherein be selected from-Cl of X and Y ,-Br ,-CN ,-NO ₂,-SO ₂cH ₃he – NHCOR, and be selected from-CH of R ₃,-C ₂h ₅with-CH ₂the Cl base.Preferably, X is NHCOCH ₃or NHCOCH ₂cl.

Particularly preferred hydrophobic dye is SV13 and DV28; And DV28 is most preferred hydrophobic dye.DV28 can be from DyStar.

Preferred composition comprises 0.0001 % by weight-0.008 % by weight, preferably the hydrophobic dye of 0.0003 % by weight-0.006 % by weight.When hydrophobic dye is DV28, preferred scope is 0.001 % by weight-0.006 % by weight.When hydrophobic dye is SV13, preferred scope is 0.0003 % by weight-0.0025 % by weight.Preferably DV28 is included with the form of additive.Additive can be preferably by inorganic carrier such as SODA ASH LIGHT 99.2, sodium sulfate or zeolite are made.Additive also can comprise dispersion agent, for example sulfonated lignin.

2. substantive dyestuff

Preferred substantive dyestuff is the direct purple dye of tetrazo of following formula:

Wherein Z is H or phenyl, and the preferred position being indicated by arrow of A ring is by methyl and methoxy substitution, and the A ring can be also the naphthyl ring, and Y group is the phenyl or naphthyl ring, and it is replaced by sulfate radical and can be by methyl list or two replacements.

The non-limiting example of these dyestuffs is directly purple 5,7,9,11,26,31,35,41 and 51 and DV99.The further non-limiting example of these dyestuffs is also direct blue 34,70,71,72,75,78,82 and 120.Most preferred substantive dyestuff is directly purple 9 (DV9).DV99 is also preferred.Such dyestuff is recorded in WO2005/003274 A1 (Unilever).DV9 can be from BASF.

The direct blue dyestuff of the trisazo-that other preferred substantive dyestuff can be following formulas:

Wherein at least two of A, B and C naphthyl ring are replaced by sulfonate radical, and the C ring can be at 5 by NH ₂or the NHPh base replaces, X is by 2 benzyl ring or naphthyl rings that sulfonate radical replaces at the most, and can by the OH base, be replaced at 2, and also can be by NH ₂or the NHPh base replaces.

Because such dyestuff is substantive dyeing, therefore only need to provide on a small quantity the whiteness effect of enhancing, therefore preferred composition comprises 0.00001 % by weight-0.004 % by weight, preferably the substantive dyestuff of 0.0001 % by weight-0.004 % by weight.When substantive dyestuff is DV9, preferred scope is 0.00001 % by weight-0.004 % by weight.Preferably DV9 is included with the form of additive.Additive can be preferably by inorganic carrier such as SODA ASH LIGHT 99.2, sodium sulfate or zeolite are made.Additive also can comprise tensio-active agent or dispersion agent, for example nonionic surface active agent.

In another embodiment, substantive dyestuff can be covalently bound with optical white, for example in WO2006/024612 A1 (Ciba SC Holding AG), puts down in writing.

3. matching stain

Described detergent composition also comprises matching stain.

The matching stain of cotton substantive dyeing is given and is comprised cotton fabric benefit.Preferred dyestuff and dye mixture are blueness or purple.Preferred matching stain is azines.Its core texture is as follows:

R wherein _a, R _b, R _cand R _dbe selected from: the C of H, side chain or straight chain ₁-C ₇alkyl chain, benzyl, phenyl and naphthyl; Described dyestuff by least one-SO ₃ ^-huo – COO ^-base replaces; The B ring is without negative charge group or its salt; Can be further substituted the formation naphthyl with the A ring;

Described dyestuff optionally is selected from following group and is replaced: amine, methyl, ethyl, hydroxyl, methoxyl group, oxyethyl group, phenoxy group, Cl, Br, I, F and NO2.

With regard to the azines of described core texture, preferably the A ring is further substituted the formation naphthyl.Described dyestuff is preferably by two-SO ₃ ^-base replaces and there is no other charged substituting groups.It will be appreciated by those skilled in the art that metallic cation with the sodium example can easily change and such variation within the scope of the invention, for example basic metal (alkali earth metal) and alkaline-earth metal, and these are preferred, particularly potassium and sodium.

It will be appreciated by those skilled in the art that except azines by least one SO ₃ ^-huo – COO ^-base replaces and B encircles outside the requirement without negative charge group or its salt, in the situation that do not affect dyestuff, is deposited on demand the effect on cotton, and substituting group changes on a large scale.Radicals R as above _a, R _b, R _cand R _dcan be with other substituting groups.

With regard to the ring of the B without the negative charge group, this B is SO3-or COO-particularly.

Preferred azines has following structure:

R wherein ₁, R ₂, R ₃and R ₄be selected from: H, Me, Et, n-Pr and i-Pr; And described dyestuff is optionally by methoxy substitution.

Further preferred dyestuff has following structure:

。

Preferred azines is: acid blue 98, acid violet 50, and acid blue 59, more preferably acid violet 50 (CAS No. 6837-46-3; C.I. 50325) and acid blue 98.Most preferably, azines is acid violet 50 (AV50).This dyestuff can be from Clariant.

Preferred composition comprises 0.00001 % by weight-0.1 % by weight, preferred 0.0001 % by weight-0.01 % by weight, and the azines of 0.0005 % by weight-0.005 % by weight most preferably.When dyestuff is AV50, preferred scope is 0.0001 % by weight-0.005 % by weight.Preferably the AV50 dyestuff is included with the form of additive.Additive can preferably be made as SODA ASH LIGHT 99.2, sodium sulfate or zeolite by inorganic carrier.Additive also can comprise tensio-active agent or dispersion agent and tackiness agent.

Other preferably non--azine matching stain be acid violet 17, Acid Black 1, CI 45430, azogeramine 7 and acid blue 29.

Dyestuff can be introduced in every way.For example, to the insensitive dyestuff of heat, can be included in by spray-dired slurries.The another kind of mode that dyestuff is introduced particulate detergent product is that it is added to additive granules, by after described particle-be dosed in base materials powder.In this case, in particle, certain density dyestuff may be arranged, the risk that it may exist spot and dyestuff to destroy on fabric.As the dye strength in fruit granule is less than 0.1 % by weight, can avoid this risk.Dyestuff can particle form introduce, described particle by carrier, for example make by Soda ash light, wilkinite, zeolite and sodium sulfate.Such carrier is also very generally for detergent composition.The use of such particle can contribute to reduce spot and spot.For liquid product, dyestuff can add in liquid simply and blend obtains substantially even.

lipase

Detergent composition according to the present invention comprises lipase.Lipase (also being known as esterase) is catalysis edible-fat and oil, and the ester linkage hydrolyzing of triglyceride level becomes free lipid acid, monoglyceride and triglyceride and the enzyme of glycerine.Think that the basic function of lipase is to reduce gathering of sebum.The use of lipase is concerned especially for cold washing, because then oil & fat is solid-state and therefore more is difficult to remove.Also think that the effect of lipase is not during main washing, but repeatedly showing between washing.Think that at first lipase is adsorbed on dirt during main washing, suppress but its effect is subject to tensio-active agent.During rinse stage, lipase keeps being adsorbed and degrading dirt matrix.Lipase also is suitable for comprising relatively large aniorfic surfactant, is generally the detergent composition of 20-40 % by weight.Lipase also is considered to remove stain, such as tomato-oil, pasta sauce, fragrant garlic sauce, machine oil, water white oil such as sweet oil and Semen Maydis oil.Think that lipase continues its effect during drying stage, forms lipid acid, triglyceride and monoglyceride.When clothing is made dirty again, some lipase are Already on clothing.During upper once washing, carry the dirt of the deposition that makes new advances secretly and be entrained with remaining dirt matrix with less degree subsequently.Also think that the absorption of lipase is along with the ionic strength of detergent composition increases and increases.

Preferred lipase comprises those of bacterium or fungic origin.The mutant that comprises chemical modification or protein engineering.The example of useful lipase comprise from humicola lanuginosa( humicola) lipase, more preferably comprise a kind of of polypeptide with aminoacid sequence, described sequence with from dredge the hair humicola lanuginosa( humicola lanuginose) wild-type lipase, most preferably strain DSM 4109 has at least 90% sequence identity.

The example of useful lipase comprise from humicola lanuginosa((synonym: thermophilic hyphomycete( thermomyces)) lipase, for example be recorded in EP258068 and EP305216 from dredge the hair humicola lanuginosa and (dredge the thermophilic hyphomycete of cotton shape( t. lanuginosus)) or be recorded in WO96/13580 from humicola insolens( h. insolens); pseudomonas( pseudomonas) lipase, for example from pseudomonas alcaligenes( p. alcaligenes) or pseudomonas pseudoalcaligenes( p. pseudoalcaligenes) (EP218272), burkholderia( p. cepacia) (EP331376), amurpseudomonas ( p. stutzeri) (GB 1,372,034), pseudomonas fluorescens( p. stutzeri), pseudomonassp. bacterial strain SD 705 (WO95/06720 and WO96/27002), p. wisconsinensis(WO96/12012); genus bacillus( bacillus) lipase, for example from subtilis( b. subtilis) (Dartois etc. (1993), Biochemica et Biophysica Acta, 1131,253-360), bacstearothermophilus( b. stearothermophilus) (JP64/744992) or bacillus pumilus( b. pumilus) (WO 91/16422).

Other examples comprise lipase Variant, for example are recorded in those in WO92/05249, WO94/01541, EP407225, EP260105, WO95/35381, WO96/00292, WO95/30744, WO94/25578, WO95/14783, WO95/22615, WO97/04079 and WO97/07202, WO00/60063, WO09/107091 and WO09/111258.

Preferred lipase can trade mark LIPOCLEAN , LIPOLASE , LIPOLASE ultra and LIPEX obtain.LIPEX particularly preferably , and further LIPEX 100 TB particularly preferably.The activity of business lipase is typically expressed as lipase unit (Lipase Unit) or LU.Different lipase preparations can have different activity.For fungal lipase, these can be 2,000-2, the scope of 000,000 LU/g.Activity also can be expressed as FIP unit/g or FCC III LU/g.Such new fats unit of enzyme is equivalent to the LU in 10 Geju City, or 1,000 FIP unit/g=10,000 LU/g.

Preferred composition comprises the lipase with 5-20000 LU/g.

In order to prevent unscheduled event and to alleviate safety problem, business lipase applies with inert material usually.Therefore, the particle form that is the additive material that comprises very small amount of active lipase and surplus for the business lipase of detergent powder, bar and sheet.

Described particle comprises lipase enriched material, inorganic salt, tackiness agent and coating.Their free flows (free-flowing), make not caking, and grain dissolution is faster.

On the other hand, the lipase that is suitable for liquid washing agent can liquid form obtains.Example is LIPEX 100 L.

The lipase that preferred composition has 0.0001 % by weight-0.1 % by weight.The lipase that further preferred composition has 0.0009 % by weight-0.00186 % by weight.

Except tensio-active agent, cover dyestuff and lipase, described detergent composition can also comprise other known compositions.These compositions comprise:

hydrotrote

Term " hydrotrote " generally refers to have the solvability that increases some slightly soluble organic compound, the compound of preferred water miscible ability.Example comprises sodium xylene sulfonate.

solvent

In the situation of liquid or gelatinous composition, described composition can comprise for example for example Virahol or glycol ethers of water or organic solvent of solvent.

metal chelator

Described composition can comprise metal chelator, for example carbonate, supercarbonate and sesquicarbonate.Metal chelator can be bleaching stibilizer (being the heavy metal sequestering agent).Suitable metal chelator comprises edetate (EDTA), diethylentriamine pentacetate (DTPA), ethylenediamine disuccinate (EDDS), and polyphosphonic acid salt DEQUESTS for example , ethylenediamine tetramethylene phosphonic acid salt (EDTMP) and diethylenetriamine pentamethylene phosphate (DETPMP).

washing assistant or complexing agent

Washing assistant can be selected from calcium sequestering agent material, deposited material, calcium ion-exchanged material and composition thereof.

The example of calcium sequestering agent washing assistant comprises alkali metal polyphosphates, for example tripoly phosphate sodium STPP and organic sequestering agent, for example ethylenediamine tetraacetic acid (EDTA).The example of precipitation washing assistant comprises sodium orthophosphate and sodium carbonate.The example of calcium ion-exchanged washing assistant material comprises various types of water-insoluble crystal or amorphous aluminum silicate, its mesolite is the most known representative, for example Wessalith CS, zeolite B (also being known as zeolite P), zeolite C, X zeolite, zeolite Y and as be recorded in the zeolite P-type in EP 0384070.Low-cost formula optimization comprises carbonate (comprising supercarbonate and sesquicarbonate) and/or Citrate trianion as washing assistant.

In the situation that there is washing assistant, described composition can comprise aptly and be less than 20 % by weight, preferably is less than 10 % by weight, and most preferably is less than the washing assistant of 10 % by weight.

other cover dyestuff

Except hydrophobic dye, substantive dyestuff and matching stain; Preferred composition can also comprise other dyestuffs.Such dyestuff can be selected from:

basic dyestuff

Basic dyestuff is the organic dye with clean positive electricity.They are deposited on cotton.They are practical especially for the use in the composition mainly comprising cationic surfactant.Dyestuff can be selected from alkalescence purple and the alkali blue dyestuff of listing in international color index (Colour Index International).Preferred example comprises triarylmethane basic dyestuff, methane basic dyestuff, anthraquinone basic dyestuff, alkali blue 16, Blue 71, alkali blue 159, alkali blue 19, Basic Blue 35, alkaline purple 38, alkalescence purple 48; Alkaline purple 3, alkaline purple 75, alkalescence purple 95, alkaline purple 1 22, alkaline purple 1 24, basic violet 14 1.Also can use thiazole dye.Example comprises alkali blue 41,54,65,66,67,162 and 164.

reactive dyestuffs

Reactive dyestuffs be contain can with the dyestuff of fibrin reaction and organic group dyestuff is connected with Mierocrystalline cellulose with covalent linkage.They are deposited on cotton.Preferably, active group be with organism class polymer reaction for example, hydrolysising group or the active group of the dyestuff that makes dyestuff be connected with this organism class.Dyestuff can be selected from reactive violet and the reactive blue dye of listing in the international color index.

Preferred example comprises Reactive Blue 19 100, Reactive blue 163, Reactive blue 182 and Reactive blue 96.

dye conjugate

The power of dye conjugate by physically come in conjunction with directly, acidity or basic dyestuff and polymkeric substance or particle form.

Depend on the selection of polymkeric substance or particle, they can be deposited on cotton or synthetics.These materials are recorded in WO2006/055787 A1 (P& G) in.

optical white

Preferred composition can comprise the optical white of 0.00001 % by weight-1 % by weight, preferably phthalocyanine.

other enzymes

Except lipase, one or more other enzyme also may reside in preferred composition.Such enzyme comprises proteolytic enzyme, α-amylase, cellulase, peroxidase/oxide compound enzyme, pectate lyase and mannase (mannanases).

Suitable proteolytic enzyme comprises animal, plant or microbe-derived those.The preferred microorganism source.The mutant that comprises chemical modification or protein engineering.Proteolytic enzyme can be serine protease or metalloprotease, the proteolytic enzyme of preferred alkaline microbial protease or trypsinase shape.The proteolytic enzyme that preferred business obtains comprises ALCALASE , SAVINASE , PRIMASE , DURALASE , DYRAZYM , ESPERASE , EVERLASE , POLARZYME , KANNASE , MAXATASE , MAXACAL , MAXAPEM , PROPERASE , PURAFECT and PURAFECT oxP.

Suitable amylase (α and/or β) comprises those of bacterium or originated from fungus.The mutant that comprises chemical modification or protein engineering.Amylase comprises, the α-amylase for example obtained by bacillus, for example bacillus licheniformis( b. lichenformis) special bacterial strain.But the amylase that business obtains is DURAMYL , TERMAMYL , TERMAMYL ultra, NATALASE , STAINZYME , FUNGAMYL bAN , RAPIDASE and PURASTAR .

Suitable cellulase comprises those of bacterium or originated from fungus.Also can use the mutant of chemical modification or protein engineering.Suitable cellulase comprises from the cellulase with the subordinate: genus bacillus, pseudomonas, humicola lanuginosa, sickle-like bacteria( fusarium), thielavia, acremonium, for example by humicola insolens, thielavia terrestris( thielavia terrestris), thermophilicly ruin a bacterium( myceliophthora thermophila) and point born of the same parents sickle-like bacteria( fusarium oxysporum) fungal cellulase that produces.But the cellulase that business obtains comprises CELLUZYME , CAREZYME , ENDOLASE , RENOZYME , CLAZINASE and PURADAX hA.Suitable peroxidase/oxide compound enzyme comprises those of plant, bacterium or originated from fungus.Also can use the mutant of chemical modification or protein engineering.The example of available peroxidase comprise from the ghost agaric( coprinus), for example from c. cinereusperoxidase, and its variant, as be recorded in those in WO 93/24618, WO 95/10602 and WO 98/15257.But the peroxidase that business obtains comprises GUARDZYME and NOVOZYM 51004.

enzyme stabilizers

Any enzyme existed in described composition can be used conventional stablizer stable; described stablizer is polyvalent alcohol for example; as propylene glycol or glycerine, sugar or sugar alcohol, lactic acid; boric acid or boric acid derivatives; aromatic borate for example; or phenyl-boron dihydroxide derivative boric acid 4-formyl radical phenylester for example, and described composition can be according to the preparation of putting down in writing in for example WO 92/19709 and WO 92/19708.In the situation that the alkyl sufficiently long to be to form side chain or closed chain, described alkyl comprises the alkyl chain of side chain, ring-type and straight chain.Described alkyl is preferably straight or branched, most preferably is straight chain.

perfume compound

Preferred composition can also comprise perfume compound.This perfume compound can be natural origin or synthetic.They comprise single compound and mixture.The specific examples of such component can be at Perfume and Flavor Chemicals, S. Arctander 1969, and Montclair, find in N.J. (USA).

In this article, perfume compound not only refers to the product spices all be mixed with, but also can refer to the selected component of that spices, those that particularly are easy to lose, and for example so-called head is fragrant.Described perfume compound can pure oil or packing forms use.

fluorescent agent

In order further to improve whiteness, preferred composition can comprise fluorescent agent (also referred to as white dyes).But fluorescent agent is such fluorescent agent business that know and many to be obtained.

Usually, these fluorescent agents are with its an alkali metal salt, for example form supply and the use of sodium salt.The total amount that can be used for one or more fluorescent agents in preferred composition is generally 0.005 % by weight-2 % by weight, more preferably 0.01 % by weight-0.1 % by weight.Preferred fluorescent agent type comprises two-styrylbiphenyl compounds, for example TINOPAL cBS-X, diamines Stilbene disulfonic acid compound, for example TINOPAL the pure Xtra of DMS and BLANKOPHOR hRH, and pyrazoline compounds, for example BLANKOPHOR sN.Preferred fluorescent agent is: 2-(4-styryl-3-sulfo group phenyl)-2H-naphthols [1,2-d] tetrazolium sodium, 4,4'-is two, and { [(4-anilino-6-(N-methyl-N-2-hydroxyethyl) amino 1,3,5-triazine-2-yl)] amino } two { [(4-anilino-6-morpholino-l of Stilbene-2-2 '-disulfonic acid disodium, 4,4 ' –, 3,5-triazine-2-yl)] amino } Stilbene-2-2 '-disulfonic acid disodium, and 4,4 '-bis-(2-sulphophenyl vinyl) biphenyl disodium.

polymkeric substance

Described composition can comprise one or more polymkeric substance.Example is carboxymethyl cellulose, PVP, PEG, poly-(vinyl alcohol), poly-(vinyl pyridine-N-oxide compound), poly-(vinyl imidazole), polycarboxylate for example polyacrylic ester, toxilic acid/acrylic copolymer and lauryl methacrylate/acrylic copolymer.

Instantly detergent composition is used polymkeric substance as the descriptiona dye delivery inhibitor usually.These polymkeric substance stop the migration of dyestuff, especially in long soak time process.Any suitable descriptiona dye delivery inhibitor all can be used in preferred composition.Generally speaking, such descriptiona dye delivery inhibitor comprises multipolymer, manganese phthalocyanine, the peroxidase of polyvinyl pyrrolidone polymers, polyamine N-oxide pllymers, NVP and N-vinyl imidazole, and composition thereof.

The DTI polymkeric substance of preferred nitrogenous combination dye.In these polymkeric substance, preferred for example polymkeric substance and the multipolymer of vinyl pyrrolidone and/or vinyl imidazole of cyclic amine.Also preferably the multipolymer of NVP and N-vinyl imidazole polymkeric substance (as a class, is called (" PVPVI ").These multipolymers can be straight or brancheds.Suitable PVPVI polymkeric substance comprises SOKALAN hP56, it can obtain from BASF business.

To explain in more detail the present invention by the non-limiting examples of preferred composition now.

embodiment:

embodiment 1: the effect of the preferred composition with contrasting to soil redeposition

NTR (Non-Tower Route) the matrix detergent composition of preparation contrast.Prepare another kind of reference composition (C-1).It contains three kinds and covers dyestuff: DV9, DV28 and AV50, but not fatty enzyme.Covering dyestuff is rear quantitative feeding.Prepare other two kinds of reference composition (C-2 and C-3).These compositions comprise the lipase that changes content, but do not cover dyestuff.Preferred composition by preparing the further rear quantitative feeding of lipase in reference composition C-1.Formula is recorded in table-1.

table-1

Composition	Matrix	C-1	C-2	C-3	Ex-1
						Linear alkylbenzene sulphonic acid salt	15	15	15	15	15
Tripoly phosphate sodium STPP	4	4	4	4	4
						Soda ash light	24	24	24	24	24
Sodium-chlor	38	38	38	38	38
						Rhombspar	2	2	2	2	2
Xylo-Mucine	0.3	0.3	0.3	0.3	0.3
						The calcite of precipitation	10	10	10	10	10
TINOPAL CBSX	0.1	0.1	0.1	0.1	0.1
						Perfume compound	0.3	0.3	0.3	0.3	0.3
LIPEX 100 TB	-	-	0.1**	0.05***	0.05
						Soda spot (Soda speckles)	0.5	0.5	0.5	0.5	0.5
DV9 # (DV9 addition of C 1141, derive from BASF)	-	0.5	-	-	0.5
						DV28 @Additive	-	0.5	-	-	0.5
AV50 &Additive	-	1.5	-	-	1.5
						Moisture	3	3	3	3	3
NDOM* and other micro substances are extremely	100	100	100	100	100

NDOM* refers to: nondetergent organic matter

* 0.1 g LIPEX 100 TB comprise approximately 0.00186 g lipase

* * 0.05 g LIPEX 100 TB comprise approximately 0.00093 g lipase

DV9 ^#-it is the 0.5 g SODA ASH LIGHT 99.2 additive that comprises 0.00375 g DV9 dyestuff

DV28 ^@-it is the 0.5 g SODA ASH LIGHT 99.2 additive that comprises 0.006 g DV28 dyestuff

AV50 ^&-it is the 1.5 g sodium sulfate additives that comprise 0.0045 g AV50 dyestuff.

soil redeposition and study-hand washing of fabric yellowing scheme (1,3 and 5 washing)

This experiment is monitored thing for the business clothing test of three types: knitted cotton, knitting polyester and poly-cotton carry out.Before washing clothes test monitoring thing, by GRETAG MACBETH coloreye UV spectrophotometer (UV-gets rid of pattern) is measured its color that is expressed as CIE L*a*b* value, and with R ₄₆₀its reflectance value that value is measured.CIE L*a*b* (CIELAB) is the most complete color space by International Commission on Illumination (Commission Internationale d'Eclairage) appointment.It has been put down in writing all human eye visible colors and has been made as equipment (device) stand-alone mode with for referencial use.These value records are b* (not washing) and R ₄₆₀(not washing).

4 gram detergent powders are dissolved in to 1 liter of 24 °F of .H. (French hardness) water to obtain solution.The dirt bar obtained to the business that adds standard in this solution.The dirt bar that adds three types: by Warwick Equest, Stanley, County Durham, the STANLEY of UK supply earth bar (0.2 g/l), polyhybrid dirt bar (4 g/l) with mixture of sweet oil, lipstick, culinary art oil, tea liquid, jam, curry powder, careless stain, chocolate and earth, and by the dirt that WFK Testgewebe GmbH sells fabric (the Soil Ballast Fabric) SBL2004 that minces bar (6 g/l).The detergent solution that will comprise the dirt bar with glass stick stirs 1 minute, so that dirt is released in solution.Subsequently, each clothes test monitoring thing (size of every-10 cm X 10 cm) in 10 is added with the liquid of 10:1/clothing ratio.To adding cotton in solution: polyester (50:50) mince to keep liquid/clothing ratio.Clothing test monitoring thing is immersed in containing in the detergent solution of dirt 30 minutes.After every 10 minutes, hand mixing solution 1 minute.

Subsequently, with 24 °F of .H. water, all clothing tests are monitored to twice of thing rinsing.For some test monitoring things, this process is only carried out once and the clothing of rinsing test monitoring thing is covered to drying.Subsequently, again measure as previously mentioned b* and R ₄₆₀value.These value annotations are b* (washing) and R ₄₆₀(washing).For some clothing test monitoring things, this process repeats (amounting to 3 washings) again twice, will test afterwards monitoring thing rinsing and drying.For some clothing test monitoring things, before rinsing and dry monitoring thing, this process repeats (amounting to 5 washings) again four times.Subsequently, again measure as previously mentioned b* and R ₄₆₀value.These value annotations are b* (washing) and R ₄₆₀(washing).

Soil redeposition is as when 1 washing, 3 washings and 5 washings finish, and the difference between the R460 value is measured.

Difference (Δ R ₄₆₀) following calculating:

Δ R ₄₆₀=R ₄₆₀(not washing)-R ₄₆₀(washing)

Higher Δ R*460 value shows the higher difference of the whiteness of unwashed clothing and washed clothing.Therefore, higher difference shows that clothing is more not white after washing.In other words, it shows higher soil redeposition level.Therefore, it is preferred providing the composition of lower Δ R*460 value.

The dirt fabric deposited thereon suspended during washing seems dimness, grey or yellow usually.On the occasion of b* mean yellow degree, it is because higher soil redeposition occurs; And negative value means blue cast.Higher b* value representation yellowing.Washed and the b* value of unwashed clothing between following calculating of difference (being expressed as Δ b*):

Δ b*=b* (washed) – b* (not washing)

The higher higher yellowing of Δ b* value representation, i.e. higher soil redeposition level.Therefore, it is preferred providing the composition of lower Δ b* value.

Generally speaking, preferred composition is a class of the Δ R*460 value that provides lower on all fabrics and lower Δ b* value.

table-2

Data show in all compositions, and preferred composition Ex-1 shows lower yellowing (showing as lower Δ b* value) on all types fabric, and the decline of less reflectance (shows as lower Δ R ₄₆₀value).More remarkable at 3 and 5 effect after wash & pressing, especially on knitted cotton and knitting polyester textile.

embodiment 2: adopt to have that lipase covers dyestuff with two kinds and three kinds of machine-washings that cover the composition of dyestuff are studied

During in machine-washing research, the composition of the various formulas of test is included in table 3.

table 3

Composition	C-2	Ex-2	Ex-3	Ex-4	Ex-5
						Linear alkylbenzene sulphonic acid salt	15	15	15	15	15
Tripoly phosphate sodium STPP	4	4	4	4	4
						Soda ash light	24	24	24	24	24
Sodium-chlor	38	38	38	38	38
						Rhombspar	2	2	2	2	2
Xylo-Mucine	0.3	0.3	0.3	0.3	0.3
						The calcite of precipitation	10	10	10	10	10
TINOPAL CBSX	0.1	0.1	0.1	0.1	0.1
						Perfume compound	0.3	0.3	0.3	0.3	0.3
LIPEX 100 TB	0.1**	0.1**	0.1**	0.1**	0.1**
						The soda spot	0.5	0.5	0.5	0.5	0.5
AV50 &Additive	-	0.5	0.5	-	0.5
						DV9 # (DV9 addition of C 1141, derive from BASF)	-	0.5	-	0.5	0.5
DV28 @Additive	-	-	1.5	1.5	1.5
						Moisture	3	3	3	3	3
NDOM* and other micro substances are extremely	100	100	100	100	100

NDOM* refers to: nondetergent organic matter

* 0.1 g LIPEX 100 TB comprise approximately 0.00186 g lipase

AV50 ^&-it is the 1. 5 g sodium sulfate additives that comprise 0.0045 g AV50 dyestuff

DV9 ^#-it is the 0.5 g SODA ASH LIGHT 99.2 additive that comprises 0.00375 g DV9 dyestuff

DV28 ^@-it is the 0.5 g SODA ASH LIGHT 99.2 additive that comprises 0.003 g DV28 dyestuff.

fabric yellowing research-machine-washing scheme (1,3 and 5 washing)

This experiment is for the business clothing test monitoring thing of three types: knitted cotton, nylon elastic matter and woven cotton carry out.Before washing clothes test monitoring thing, measure as previously mentioned its color that is expressed as CIE L*a*b* value.These value records are b* (not washing).

Dosing level by detergent powder with 1.5 grams per liters adds in the portioning machine of washing machine.The dirt bar of the three types that uses in Ex-1 is added to machine.At ambient temperature clothing test monitoring thing is immersed in 24 °F of .H. (French hardness) water to 20 minutes.Cycles of washing is set to 20 minutes.In washing machine, clothing/liquid fraction is 1:20.Subsequently, with 24 °F of .H. water by twice of all clothing test monitoring things rinsing.For some test monitoring things, this process is carried out once and the clothing test monitoring thing of rinsing is covered to drying.Subsequently, again measure as previously mentioned the b* value.These value annotations are b* (washing).For some clothing test monitoring things, this process repeats (amounting to 3 washings) again twice, afterwards by the rinsing of test monitoring thing and drying.For some clothing test monitoring things, before rinsing and dry monitoring thing, this process repeats (amounting to 5 washings) again four times.Subsequently, again measure as previously mentioned the b* value.These value annotations are b* (washing).

Measure as previously mentioned the difference between the b* value.Data are present in table 4.

table 4

Data show in all compositions to have three kinds of preferred composition Ex-5 that cover dyestuff and lipase and show lower yellowing (showing as lower Δ b* value).More remarkable at 3 and 5 effect after wash & pressing, especially on knitted cotton and woven cotton fabric.

The exemplified embodiment of understanding is provided and had lipase and the specific detergent composition that covers the combination of dyestuff, it provides soil redeposition lower on fabric, this shows as higher reflectance and lower yellowing, especially with respect to the repeatedly washing to knitted cotton, knitting polyester and polyester textile.

In this article, the specific form of the present invention that is construed as institute's example and description only is intended to representational, because can make therein some change, only otherwise departing from clearly instruction of the present disclosure gets final product.

Although with reference to specific embodiments, described the present invention, those skilled in the art will be interpreted as that the present invention can be presented as many other forms.

Claims (12)

1. detergent composition, it comprises:

(i) tensio-active agent;

(ii) hydrophobic dye;

(iii) substantive dyestuff;

(iv) matching stain, and

(v) lipase.

2. detergent composition as required for protection as claim 1, the hydrophobic dye that it comprises 0.0001 % by weight-0.008 % by weight.

3. detergent composition as required for protection as claim 1 or 2, wherein said hydrophobic dye is dispersed dye.

4. detergent composition as required for protection as claim 1 or 2, wherein said dispersed dye are anthraquinone dyes.

5. as aforementioned claim any one detergent composition required for protection, the substantive dyestuff that it comprises 0.00001 % by weight-0.004 % by weight.

6. as aforementioned claim any one detergent composition required for protection, wherein said substantive dyestuff is disazo dyes.

7. as aforementioned claim any one detergent composition required for protection, wherein said matching stain is azines.

8. as aforementioned claim any one detergent composition required for protection, the azines that it comprises 0.00001 % by weight-0.1 % by weight.

9. as aforementioned claim any one detergent composition required for protection, the lipase that it comprises 0.0001 % by weight-0.1 % by weight.

10. the method for laundering of textile fabrics, it comprises the step adopted according to the compositions-treated fabric of claim 1.

11. process the method for fabric, it comprises the following steps:

(i) adopt the aqueous solution that comprises following material to process fabric:

(a) tensio-active agent of 0.3 g/l-10 g/l;

(b) hydrophobic dye of 0.1 ppb-500 ppm;

(c) substantive dyestuff of 0.1 ppb-500 ppm;

(d) matching stain of 0.1 ppb-500 ppm; With

(e) lipase of 0.3 ppb-10 ppm, and

The (ii) described fabric of rinsing; With

(iii) dry described fabric.

12. reduce the purposes of soil redeposition according to the composition of claim 1 on fabric.