CN101405379A - Laundry composition - Google Patents

Abstract

The invention provides a clothes washing agent composition which contains toning dye and pearlescent agent, wherein the toning dye represents toning efficacy of at least 10 and washing removing value in range from 30% to 85%.

Description

Cleaning composition

Technical field

The present invention relates to the liquid composition field, preferred aqueous composition field, described composition comprises pearling agent and fabric dope dye.

Background of invention

The dress of textile article, especially white fabric articles and washing can cause original fabric color decolouring.For example, the white fabrics of repetitive scrubbing demonstrates jaundice in appearance in color, and this makes fabric look of the remote past and shabby.For overcoming the jaundice of worthless white fabrics and similar other light changing color of textile, some laundry detergent product comprises dope dye or blueing dyestuff, described dyestuff during clothes washing and/or the rinse cycle attached to fabric on.

Yet after usefulness comprised the washing composition repetitive scrubbing fabric of blueing dyestuff, described blueing dyestuff was tending towards being deposited on the fabric, makes fabric present blue color.So the repeated washing white fabric articles is tending towards making goods to present blue outward appearance rather than white appearance.For overcoming the accumulation of this blueing dyestuff on fabric, proposed to carry out chlorine and handled.Though chlorine is handled the blueing dyestuff that can remove depalletizing effectively, the chlorine processing is extra and normally inconvenient step in washing process.In addition, chlorine is handled and to be caused the washing cost to increase and make fabric crude, thereby and inadvisable impels the fabric degraded to increase.Therefore, need a kind of improved laundry detergent, it can resist worthless white fabrics jaundice and similar other light changing color of textile.

The applicant finds that though can resist the worthless jaundice of white fabrics effectively, dope dye is tending towards making described composition to present very dark pitch-dark look.Such colourity is not preferred, expectation or attracting for the human consumer.Therefore, except the above, another target of composition production merchant is to improve the aesthetic property of liquid composition, and they are made the more attractive to the human consumer, and reflects the performance of composition better.

Therefore, need a kind of laundry detergent of improvement, described laundry detergent can be given the aesthetic property that desirable color harmony improves to fabric, and not because the worthless accumulation on fabric of the described fabric of clothes washing.

Summary of the invention

According to the present invention, a kind of laundry detergent composition is provided, described composition comprises dope dye and pearling agent, and wherein said dope dye shows at least 10 toning effect and in about 30% washing value of removing to about 85% scope.

According to the present invention, a kind of method of clothes washing textile article also is provided, described method is included in laundering of textile fabrics goods in the washing soln, described washing soln comprises laundry detergent composition, described composition comprises dope dye and pearling agent, and wherein said dope dye shows at least 10 toning effect and in about 30% washing value of removing to about 85% scope.

Detailed Description Of The Invention

Liquid composition of the present invention is suitable for use as clothes washing or hard surface cleaning treatment compositions.So-called term clothes washing treatment compositions is meant and is intended to comprise that the Treatment of Washing that is useful on washs the liquid composition of clothing, comprises cleaning compositions and softening compositio or care composition.Composition of the present invention is a liquid, seals and/or unitized dose but may be packaged in the container or as capsule.A kind of form in back is described in greater detail in hereinafter.Liquid composition can be for aqueous or nonaqueous.When described composition comprises water, they can comprise 2% to 90%, and more preferably 20% to 80%, 25% to 65% water most preferably.Nonaqueous composition comprises less than 12%, preferably less than 10%, most preferably less than 9.5% water.It is non-aqueous that the composition that is used for unitized dose product (it comprises the liquid composition that is coated in the water-soluble film) is described to usually.The composition that is used for this purposes according to the present invention comprises 2% to 15%, and more preferably 2% to 10%, and 4% to 9% water most preferably from about.

At 20s ^-1Under 21 ℃, composition of the present invention preferably has 1cps to 1500cps (1mPa*s to 1500mPa*s), 100cps to 1000cps (100mPa*s to 1000mPa*s) more preferably from about, and the viscosity of 200cps to 500cps (200mPa*s to 500mPa*s) most preferably.Viscosity can be determined with ordinary method.Yet, can use AR 550 rheometers that derive from TA Instruments and use the Plate Steel spindle of the gap size of 40mm diameter and 500 μ m to measure according to viscosity of the present invention.At 20s ^-1Under shear viscosity and 0.05 ^-1Under low-shear viscosity can by under 21 ℃ in 3 fens clock times by 0.1 ^-1To 25 ^-1The logarithm shearing rate scan obtain.Wherein the preferred rheological characteristics of Miao Shuing can be used the inner existing rheology modifier acquisition that has the structure of detergent ingredients or pass through to use the outside.Preferred laundry detergent liquid composition has about 100cps to 1500cps, more preferably the high shear rate viscosity of 100cps to 1000cps.Unitary dose laundry detergent liquid composition has the high shear rate viscosity of 400cps to 1000cps.The clothes washing softening compositio has 10cps to 1000cps, more preferably 10cps to 800cps, most preferably the high shear rate viscosity of 10cps to 500cps.Hand dishwashing composition has 300cps to 4000cps, more preferably the high shear rate viscosity of 300cps to 1000cps.

The composition of interpolation pearling agent is preferably transparent or semitransparent, but also can be opaque.Described composition (before adding described pearling agent) preferably has 5 to 3000NTU absolute turbidity, as measured with turbidity type turbidometer.Turbidity use according to the present invention derives from McVanInstruments, and the Analyte NEP 160 with probe NEP260 of Australia measures.In one embodiment of the invention, has pearlescent gloss even found to have to make above the also available an amount of pearlescent material of the composition of 2800NTU turbidity.Yet the applicant finds that when the turbidity of composition increases, the transmittance that passes composition will reduce.The minimizing of this transmittance causes pearlescent particles emission light still less, and this further causes the reduction of pearl effect.Therefore the applicant finds, and this effect can obtain to a certain degree improvement by adding more high-load pearling agent.Yet, reach threshold value during for 3000NTU at turbidity.After reaching threshold value, add the level that more pearling agent can't improve pearl effect.

As measured when liquid being dissolved to 1% content in softening water, liquid of the present invention preferably has 3 to 10, and more preferably 5 to 9, even more preferably 6 to 9,7.1 to 8.5 pH most preferably.

Pearling agent

According to pearling agent of the present invention is crystalline or vitreous solid, can reflect and the transparent or semitransparent compound of refracted ray with the generation pearl effect.Usually, pearling agent is the crystalline particle, is undissolved in having mixed their composition.Preferably, pearling agent has the shape of thin slice or spheroid.According to the present invention, spheroid is understood that general sphere.Granularity strides across the maximum diameter of spheroid and measures.Platy shaped particle is meant that two sizes of particulate (length and width) are at least 5 times of the 3rd size (degree of depth or thickness).Other crystalline form as cubes or needles or other crystalline form, does not show pearl effect.Many pearling agents such as mica are the natural mineral with monoclinic crystal.As if shape influence the stability of reagent.Sphere, even sheet reagent more preferably are stabilizations the most successfully.

Pearling agent is known in the document, uses but generally be used for shampoo, amendment or personal cleanliness.They are described to is material from the nacre outward appearance to composition that give.At International Journal of Cosmetic Science, describe in the 205th to 214 page by the 19th volume by R.L.Crombie for the mechanism of pearly-lustre.Be not bound by theory, it is believed that pearly-lustre passes through to be produced by the specular reflection of the light shown in figure below.

When they are substantially parallel to each other when placing with different content in composition, the light that is reflected by pearly-lustre small pieces or spheroid produces depth perception and reflecting feel.Some light reflect from pearling agent, and remaining light will pass reagent.The light that passes pearling agent can directly pass or be refracted.Reflection, refractive light produces distinct colors, brightness and gloss.On the other hand, opalizer is understood that to be different from pearling agent.Wherein pearling agent reflection and refracted ray are so that produce this pearl effect, and opalizer then can be not like this.On the contrary, opalizer can transmitted ray, and with light in all direction diffusions.

Described pearling agent preferably has less than the D0.99 of 50 μ m (being sometimes referred to as D99) volume granularity.More preferably, described pearling agent has less than 40 μ m, most preferably less than the D0.99 of 30 μ m.Most preferably, particle has the volume granularity greater than 1 μ m.Most preferably, described pearling agent has 0.1 μ m to 50 μ m, more preferably 0.5 μ m to 25 μ m, and the size-grade distribution of 1 μ m to 20 μ m most preferably.Described D0.99 is granulometric facies for the measuring of size-grade distribution, and is meant that in this case 99% described particle has the volume granularity less than 50 μ m.The Hydro 2000G equipment that use can derive from Malvern Instruments Ltd. comes measurement volumes granularity and size-grade distribution.Granularity has the effect of stablizing described reagent.Granularity and distribution are more little, and they suspend easy more quilt.Yet the granularity that reduces pearling agent also will reduce the effect of reagent.

Be not bound by theory, the applicant believes in the transmission of the light at the interface of pearling agent and its liquid medium that is suspended depends on the physical law that is subjected to the domination of Fresnel formula.The ratio of the light that will be reflected by pearling agent increases along with the increase of the refractive index difference between pearling agent and liquid medium.Remaining light will reflect according to energy conservation, and pass liquid medium transmission and run into another pearling agent surface until it.Therefore, give the visible pearly-lustre, it is believed that the difference aspect refractive index must be enough high, so that the reflection of competent light is proportional with the amount of the light that is refracted in order to make the composition that comprises pearling agent.

The liquid composition that comprises less water and more organic solvent is compared with the composition that comprises more water, will have higher refractive index usually.Therefore the applicant finds to have in the composition of high refractive index at this type of, and the not high enough pearling agent of specific refractory power can not given enough visible pearly-lustres, even be introduced into (surpassing 3% usually) with high-content in described composition.Therefore, the preferred pearly pigment with high refractive index that uses is to remain on quite low level with the pigment content in the described preparation.Therefore, preferably select pearling agent, it is had surpass 1.41, more preferably surpass 1.8, even more preferably surpass 2.0 refractive index.Preferably, at pearling agent with added the composition of pearling agent then or the difference of the refractive index between the medium is at least 0.02.Preferably, the difference of the refractive index between pearling agent and composition is at least 0.2, more preferably at least 0.6.The applicant finds that the refractive index of reagent is high more, and reagent will be effective more aspect the generation pearl effect.Yet this effect also depends on the difference on reagent and the composition refractive index.Difference is big more, and the effect of feeling will be big more.

Liquid composition of the present invention preferably comprises 100% active pearling agent by the weight 0.01% to 2.0% of described composition.More preferably, liquid composition comprises the weight 0.01% to 0.5% by described composition, more preferably 0.01%0.35%, even more preferably 0.01% to 0.2% 100% active pearling agent.The applicant finds, no matter above-mentioned granularity in the composition and content are how, sends good and the preferred pearl effect of human consumer is possible to liquid composition.

Described pearling agent can be organic or inorganic.

Organic pearling agent:

Suitable pearling agent comprises the monoesters and/or the diester of the alkylene dihydric alcohol with following formula:

R wherein ₁C12-C22 alkyl for straight or branched;

R is the C2-C4 alkylidene group of straight or branched;

P be selected from H, C1-C4 alkyl or-COR ₂, R ₂Be the C4-C22 alkyl, preferred C12-C22 alkyl; And

N=1 to 3.

In one embodiment of the invention, long-chain fat family ester has above-mentioned general structure, wherein R ₁Be the C16-C22 alkyl of straight or branched, R is-CH ₂-CH ₂-, and P is selected from H, or-COR ₂, R wherein ₂Be the C4-C22 alkyl, preferred C12-C22 alkyl.

Typical example is ethylene glycol, propylene glycol, Diethylene Glycol, dipropylene glycol, triethylene glycol or Tetraglycol 99 and comprises about 6 to about 22, preferred about 12 lipid acid to about 18 carbon atoms are as the monoesters and/or the diester of caproic acid, sad, 2 ethyl hexanoic acid, capric acid, lauric acid, different tridecylic acid, tetradecanoic acid, palmitinic acid, Zoomeric acid, stearic acid, Unimac 5680, oleic acid, elaidic acid, petroselinic acid, linolic acid, linolenic acid, eicosanoic acid, gadoleic acid, docosoic acid, erucic acid and their mixture.

In one embodiment, ethylene glycol monostearate (EGMS) and/or Unister E 275 (EGDS) and/or polyglycol monostearate ester (PGMS) and/or polyglycol distearate (PGDS) are the pearling agents that is used for composition.These materials have some commercial source.For example, Can derive from Stepan, Empilan

Can derive from Albright﹠amp; Wilson.

In another embodiment, to comprise weight ratio be about 1: 2 mixture to about 2: 1 ethylene glycol diester/ethylene glycol ester to pearling agent.In another embodiment, find that comprising weight ratio is that about 60: 40 pearling agents to about 50: 50 EGDS/EGMS mixture are especially stable in aqeous suspension.

Cocrystallization reagent:

Randomly, cocrystallization reagent is used for strengthening the crystallization of organic pearling agent, makes pearlescent particles form in products obtained therefrom.Suitable cocrystallization reagent includes but not limited to lipid acid and/or Fatty Alcohol(C12-C14 and C12-C18), it has hydroxyl replacement straight or branched, optional, comprise about 12 to about 22, preferred about 16 to about 22, and the alkyl of 18 to 20 carbon atoms more preferably from about is as palmitinic acid, linolic acid, stearic acid, oleic acid, ricinoleate acid, docosyl acid, 16/stearyl alcohol, hydroxyl stearyl alcohol, behenyl alcohol, inferior oleyl alcohol, linolenyl alcohol and their mixture.

When selecting to have more dystectic cocrystallization reagent than organic pearling agent, discovery is in the molten mixture of these cocrystallization reagent and above-mentioned organic pearling agent, described cocrystallization reagent solidifies usually at first to form equally distributed particle, and described particle is as the nucleus of pearling agent subsequent crystallisation.Crystal size by the ratio may command gained between organic pearling agent of suitable selection and the cocrystallization reagent is to strengthen the pearlescent appearance of products obtained therefrom.Find that if use too many cocrystallization reagent, products obtained therefrom will show less attracting pearlescent appearance and more opaque outward appearance.

Exist therein in the embodiment of cocrystallization reagent, described composition comprises C12-C20 lipid acid, C12-C20 Fatty Alcohol(C12-C14 and C12-C18) or their mixture of 1 weight % to 5 weight %.

In another embodiment, the weight ratio between organic pearling agent and the cocrystallization reagent is at about 3: 1 to about 10: 1, or about 5: 1 to about 20: 1 scope.

A kind of method that is widely used for producing the composition that comprises organic pearling agent is to use and at room temperature is the organic pearlescent material of solid.These materials are heated to above their fusing point and join in the composition of preparation.When cooling, nacreous lustre appears in the composition of gained.Yet this method can have shortcoming.Because production material must be heated to the temperature corresponding with the pearlescent material melt temperature by the gross, and in product, only could obtain uniform pearly-lustre by forming uniform molten mixture and using cooling and the agitation condition suitably controlled.

A kind of alternative and preferable methods that organic pearling agent is incorporated in the composition is to use the organic pearly-lustre dispersion of pre-crystalline.This method is called " cold pearl " by those skilled in the art.In this alternative method, long-chain fat family ester is melted, mix with carrier mixture, and in carrier recrystallize to optimum size.Described carrier mixture comprises tensio-active agent usually, preferred 2% to 50% tensio-active agent, and the water of surplus and optional adjuvants.The pearly-lustre crystallization that limits size can be by suitably option table surface-active agent carrier mixture, mixing and cooling conditions obtain.The method of making cold pearl is described in U.S. Pat 4,620, and 976, US4,654,163 (all transferring Hoechest) and WO2004/028676 (transferring Huntsman International).Many cold pearls are commercially available acquisitions.These comprise trade(brand)name, as Stepan, Pearl-2 and Stepan Pearl 4 (by Stepan CompanyNorthfield, IL produces), Mackpearl 202, Mackpearl 15-DS, MackpearlDR-104, Mackpearl DR-106 are (by McIntyre Group, Chicago, IL produces), Euperlan PK900Benz-W and Euperlan PK 3000AM (producing) by Cognis Corp.

The typical embodiments of the present invention of mixing organic pearling agent is the organic pearling agent that comprises by the weight 0.1% to 5% of described composition, dispersive tensio-active agent by the weight 0.5% to 10% of described composition, the cocrystallization combination of agents thing of the significant quantity in solvent system randomly, described solvent system comprises water and one or more optional organic solvents, and comprise by the detersive surfactant of the weight 5% to 40% of described composition with by the weight at least 0.01% of described composition, one or more clothes washing auxiliary substances of preferred at least 1% are as spices, fabric softener, enzyme, SYNTHETIC OPTICAL WHITNER, bleach-activating agent, coupling agent, or their combination.

" significant quantity " of cocrystallization reagent is meant is enough to produce the expectation crystal size of pearling agent and the content of distribution of sizes under given set technique parameter.In some embodiments, the amount of cocrystallization reagent is in the scope of 5 to 30 parts of the organic pearling agents of per 100 parts by weight.

The scatter table surface-active agent that is suitable for cold pearl comprises alkyl-sulphate, sulfated alkyl ether and their mixture, and wherein said alkyl is the C12-C14 alkyl of straight or branched.Typical example includes but not limited to Sodium Lauryl Sulphate BP/USP and ammonium lauryl sulfate.

In one embodiment of the invention, described composition comprises the water of 20 weight % to 65 weight %; The sodium alkyl sulfate of 5 weight % to 25 weight % or sulfated alkyl ether scatter table surface-active agent; With the weight ratio of 0.5 weight % to 15 weight % be 1: 2 to 2: 1 ethylene glycol monostearate and Unister E 275.

In one embodiment of the invention, described composition comprises the water of 20 weight % to 65 weight %; The sodium alkyl sulfate of 5 weight % to 30 weight % or sulfated alkyl ether scatter table surface-active agent; C12-C22 Fatty Alcohol(C12-C14 and C12-C18) or the lipid acid of the long-chain fat family ester of 5 weight % to 30 weight % and 1 weight % to 5 weight %, wherein long-chain fat family ester to the weight ratio of Fatty Alcohol(C12-C14 and C12-C18) and/or lipid acid at about 5: 1 to about 20: 1, or about 3: 1 to about 10: 1 scope.

In another embodiment of the invention, described composition comprises weight by described composition at least about 0.01%, preferred about 0.01% to about 5% pearling agent, cocrystallization reagent and one or more following compositions of significant quantity: detersive surfactant, be used for anionic dyestuff fixing agent, comprise the solvent system of water and organic solvent.Said composition also can comprise other clothes washing and fabric nursing auxiliary agent.

Be used to mix the production technique of organic pearling agent:

The following generation of cold pearl: the temperature that carrier is heated above the fusing point of organic pearling agent and cocrystallization reagent, described temperature is generally about 60 ℃ to 90 ℃, be preferably about 75 ℃ to 80 ℃, described carrier is made of 2% to 50% tensio-active agent, water and other auxiliary agent of surplus.Add to organic pearling agent and cocrystallization reagent in the mixture and mixed about 10 minutes to about 3 hours.Randomly, then temperature is risen to about 80 ℃ to 90 ℃.Can use the high shear grinding device to produce the dispersion drop size of desired pearling agent.

Mixture is cooled off with about 0.5 ℃/minute to 5 ℃/minute rate of cooling.Alternatively, cooling is carried out with two-step approach, and it comprises that wherein said mixture is with about 0.5 ℃/minute to 5 ℃/minute rate of cooling cooling by mixture is once passed through heat exchanger and the step of the gentle slow cool down of instantaneous refrigerative step.The crystallization of pearling agent such as long-chain fat family ester begins when temperature reaches about 50 ℃; Crystallization is proved by the phenomenal growth of mixture viscosity.Mixture is cooled to about 30 ℃ and stop to stir.

Subsequently, the organic pearly-lustre dispersion of the pre-crystallization of cold pearl of gained under agitation can be incorporated in the liquid composition, and need not any heat that adds.Products obtained therefrom has attracting pearlescent appearance, and can keep stable under typical condition of storage in the several months.In other words, the product of gained keeps its pearlescent appearance in the several months, and cold pearl can not show separation or layering from described composition matrix.

Inorganic pearling agent:

Inorganic pearling agent comprises and being selected from by those of the following group of forming: the glass of the mica of the mica of mica, coating of metal oxides, the mica of silica dioxide coating, pearl white coating, pearl white, tetradecanoic acid tetradecyl ester, glass, coating of metal oxides, guanine, glitter (polyester or metal) and their mixture.

Suitable mica comprises white mica or fluorine hydroxyl potassium aluminium.Sheet mica is preferably with thin metal oxide layer coating.Preferred metal oxide is selected from the group of being made up of following: rutile, titanium dioxide, ferric oxide, stannic oxide, aluminum oxide and their mixture.The crystalline pearl layer is by forming at the mica of about 732 ℃ of calcinings with coating of metal oxides.Described heat produces the inert pigment that is insoluble to resin, has stable color, and can stand the thermal stresses of following process.

Color in these pearling agents manifests with the interference effect between the light of specular reflection corner reflection by top and the lower surface at metal oxide layer.When the visual angle was transformed into the non-mirror reflection angle, the reagent loss colour intensity also provided pearlescent appearance.

Preferred inorganic pearling agent is selected from the group of being made up of following: mica and pearl white and their mixture.Most preferred inorganic pearling agent is a mica.The suitable inorganic pearling agent of commercially available acquisition derives from Merck with trade(brand)name Iriodin, Biron, Xirona, Timiron, Colorona, Dichrona, Candurin and Ronastar.The inorganic pearling agent of other commercially available acquisition can trade(brand)name Biju, Bi-Lite, Chroma-Lite, Pearl-Glo, Mearlite derive from BASF (Engelhard Mearl) and with trade(brand)name Prestige Soft Silver and PrestigeSilk Silver Star derives from Eckart.

Organic pearling agent as ethylene glycol monostearate and Unister E 275, only the time provides pearly-lustre in motion when described composition.Therefore, only when described composition was toppled over, described composition just showed pearly-lustre.Because dynamic and static pearly-lustre is provided, therefore inorganic pearlescent material is preferred.So-called dynamically pearly-lustre is meant when described composition compositions table when moving and reveals pearl effect.So-called static pearly-lustre is meant that compositions table reveals pearly-lustre when described composition is static state.

Inorganic pearling agent can obtain by powder type, or obtains with the slurries form of powder in suitable suspension agent.Suitable suspension agent comprises oxystearic acid ethylhexyl, hydrogenated castor oil.The slurries of powder or powder can be joined in the composition and need not any additional operation.

Dope dye

Be included in that dope dye in this detergent composition shows at least 10 toning effect and in about 30% washing value of removing to about 85% scope.Find that this type of dyestuff shows good painted effect in clothes washing cycle period, over-drastic is worthless to be gathered and can not show during clothes washing.The toning effect of dyestuff is compared by the fabric sample that washs in fabric sample that will wash in the solution that does not comprise dyestuff and the solution that is comprising dyestuff and is measured, and shows that whether dope dye is effective to provide the tone of expectation, for example whitens.Specifically, use 25cm * 25cm fabric small pieces, can comprise the example (270g/m of 16oz cotton double knitting fabric ², brighten with Uvitex BNB white dyes, derive from Test Fabrics.P.O.Box 26, Weston, PA, 18643).Although preferably use the white cotton material, other fabric sample also can use.At room temperature, sample is comprised AATCC standard heavy-filth liquid (HDL) listed in 1.55g such as the table 1 at one liter and test washing 45 minutes and rinsing in the distilled water of washing composition.Use washing composition (contrast) that does not contain dyestuff and the production of detergents sample separately that uses the tested dyestuff of desire that comprises the 30ppm wash concentration.Behind rinsing and dry each fabric sample, the toning effect DE that is in the suds ^* _EffAssess with following formula:

DE ^* _eff＝((L ^* _c-L ^* _s) ²(a ^* _c-a ^* _s) ²(b ^* _c-b ^* _s) ²) ^1/2

Wherein said subscript c and s are meant the described L that measures for contrast (that is the fabric sample that, washs) respectively in not having the washing composition of dyestuff ^*, a ^*And b ^*Value, and the fabric sample that washs in comprising the washing composition of dyestuff is screened.Use has D65 illumination, and 10 ° of observers and UV filter the Hunter Colorquest reflectivity photometer of getting rid of and carry out described L ^*, a ^*And b ^*The measurement of value.The dope dye that is applicable to this detergent composition shows at least 10 toning effect.In a more particular embodiment, dope dye shows at least 15 toning effect.

The indication that the washing value of removing is gathered on fabric for dope dye opposing, although and so represent that described dope dye is effective to mix colours, behind repeated washing, will can not cause that fabric is worthless to turn blue.Described washing value of removing is following to be determined: according to AATCC Test Method61-2003, Test 2A, to derive from the fabric sample small pieces of 15cm * 5cm size of above-mentioned toning effect test under 49 ℃, in the 150mL table 1 in the listed HDL detergent solution, the last washing of Launderometer 45 minutes.Described detergent concentration is that the AATCC HDL that 1.55g/ rises fills a prescription in distilled water.After rinsing was also air-dry in the dark, residual colo(u)r pick-up was by the DE that is provided by following formula is provided ^* _ResAssessment:

DE ^* _res＝((L ^* _c-L ^* _s) ²(a ^* _c-a ^* _s) ²(b ^* _c-b ^* _s) ²) ^1/2

Wherein said subscript c and s are meant the described L that measures for contrast (that is the fabric sample of initial washing in not having the washing composition of dyestuff) respectively ^*, a ^*And b ^*Value, and the fabric sample of initial washing is screened in comprising the washing composition of dyestuff.Then according to described formula calculating washing value of removing: remove per-cent (%)=100 * (1-DE for dyestuff ^* _Res/ DE ^* _Eff).The dope dye that is applicable to this detergent composition shows in about 30% washing value of removing to about 85% scope.In a specific embodiment, described dope dye shows in about 40% to about 85%, perhaps about 45% washing value of removing to about 85% scope.

Table 1

Composition	Weight %
		The C11.8 linear alkyl benzene sulphonic acid	12.00
Neodol 23-9	8.00
		Citric acid	1.20
C12-14 lipid acid	4.00
		Sodium hydroxide 1	2.65
Thanomin	0.13
		Borax	1.00
DTPA 2	0.30
		1, the 2-propylene glycol	8.00
Whitening agent 15	0.04
		Water	Surplus

¹Preparation pH regulator to 8.5

²Diethylenetriamine five acetic acid, five sodium-salt

The dope dye that comprises capacity in laundry detergent composition provides painted effect with the fabric that washs in the solution that is comprising washing composition.In one embodiment, described detergent composition comprises about by weight 0.0001% to about dope dye of 0.05%, more particularly about 0.001% to about 0.1%.

The exemplary dyes that shows the toning effect and make up according to washing value of removing of the present invention comprises that some is as triarylmethane blueness and basic purple dye listed in the table 2, as methylene blue listed in the table 3 and basic purple dye, as anthraquinone dye listed in the table 4, anthraquinone dye Basic Blue 35 and alkali blue 80, azoic dyestuff alkali blue 16, alkali blue 65, alkali blue 66, alkali blue 67, Blue 71, alkali blue 159, alkaline purple 19, alkaline purple 35, alkaline purple 38, the purple 48 oxazine dye Basic Blue 3s of alkalescence, Blue 75, alkali blue 95, alkali blue 122, alkali blue 124, alkali blue 141, Nile blue A and xanthene dyestuff alkalescence purple 10, and their mixture.

Table 2

Table 3

Table 4

Authorize Milliken Research Corporation and incorporate the United States Patent (USP) 3,157,663,3,927 of this paper with way of reference into, 044,4,113,721,4,400,320,4,601,725,4,871,371,5,766,268,5,770,552,5,770,557,5,773,405 and 6,417,155 have described and have comprised the tinting material that is dissolved in the polyoxyalkylene in the polar solvent.Other suitable dope dye is present in to be authorized Milliken Research Corporation and incorporates into way of reference in the United States Patent (USP) 4,137,243,5,591,833 and 6,458,193 of this paper.U.S.4,137,243 have described oxyalkylated anthraquinone polymeric colorant, and it comprises and has variable substituting group, comprises 3 ring anthraquinone chromophores of polymer chain.

In one embodiment, described dope dye is oxyalkylated tritane polymeric colorant, as is described in United States Patent (USP) 4, in 871,371 those and/or oxyalkylated thienyl polymeric colorant, as be described in United States Patent (USP) 4, in 601,725 those.

When the tinting material of gained shows at least 10 toning effect and during in about 30% washing value of removing to about 85% scope, this type of material can be used for the present invention.

In an embodiment of detergent composition of the present invention, also can use non-dope dye with the dope dye combination.Described non-dope dye can be non-entity in nature.The combination of dope dye and non-dope dye, making can tailor-made product color and fabric color.

What also be applicable to this paper is reactive dyestuffs.Reactive dyestuffs are that a class is at the dyestuff that is suitable for can forming with matrix under the painted condition covalent linkage.On the angle of chemical structure, typical reactive dyestuffs comprise the functional group of chromophoric group and one or more so-called anchoring agent groups, its can with matrix, as Mierocrystalline cellulose, wool, silk and tynex reaction.The typical chromophoric group of reactive dyestuffs is azo, anthraquinone, phthalocyanine, first

With three phenyl dioxazines.The typical anchoring agent group of reactive dyestuffs is trichloropyrimidine base, a chlorotriazine base, vinylsulfonyl, dichloro-quinoxaline base, a Cyanuric trifluoride base, difluoro chloropyrimide base and dichlorotriazine base.Addition and substitution reaction are two kinds of possible reaction mechanisms between reactive dyestuffs and fabric fibre.Yet this type of reaction usually takes place under suitable dyeing condition, is 10 to 12 as having high-load reactive dyestuffs in the dye bath, have the temperature that is higher than 30 ℃ and the pH of described dye bath, and in described dye bath common other component that exists.Because wash conditions is more than described dyeing condition gentleness, it is believed that in fact the reactive dyestuffs in this paper laundry detergent composition can not react with the fabric of clothes washing in its aqueous solution.The reactive dyestuffs that are applicable to this paper comprise Cibacron Brilliant Blue FN-6, Cibacron Red FN-R, Levafix Royal blue E-FR, Drimarene Violet K-2RL, Drimarene Blue K-2RL and their mixture.

Optional composition components

Liquid composition of the present invention can comprise other composition, and described other composition is selected from the catalogue of the optional member that hereinafter proposes.Unless hereinafter specify, " significant quantity " of concrete clothes washing auxiliary agent is preferably 0.01% by the weight of detergent composition, more preferably 0.1%, even more preferably 1% to 20%, more preferably to 15%, even more preferably to 10%, also even more preferably to 7%, most preferably to 5%.

Tensio-active agent or detersive surfactant

Composition of the present invention can comprise about by weight tensio-active agent of 1% to 80%.Preferably, this based composition preferably includes about by weight tensio-active agent of 5% to 50%.Tensio-active agent of the present invention can use in two ways.The first, they can be used as dispersion agent and be used for the organic pearling agent of aforesaid cold pearl.The second, they can be used as detersive surfactant and be used for dirt suspension purpose.

Used detersive surfactant can be anionic type, nonionic type, zwitter-ion type, amphoteric type or cation type, perhaps can comprise the compatible blend of these types.Preferred tensio-active agent is selected from the group of being made up of following: anion surfactant, nonionogenic tenside, cats product and their mixture.Preferably, composition is substantially free of beet alkali surface activator.Can be used for the United States Patent (USP) 3 that detergent surfactant of the present invention is described in the Norris that announced on May 23rd, 1972,664,961, the people's such as Laughlin that announced on December 30th, 1975 United States Patent (USP) 3,919,678, the United States Patent (USP) 4 of the Murphy of the United States Patent (USP) announcement on December 16th, 4,222,905 and 1980 of the Cockrell that announced on September 16th, 1980, in 239,659.Negatively charged ion and nonionogenic tenside are preferred.

Useful anion surfactant itself can be several different types.For example, the water-soluble salt of higher fatty acid, promptly " soap " is useful anion surfactant in the composition of this paper.This comprises alkali metal soap, as comprises about 8 to about 24 carbon atoms, preferred about 12 sodium salt, sylvite, ammonium salt and alkanol ammonium salts to the higher fatty acid of about 18 carbon atoms.Soap can make by the direct saponification of fat and oil, also can make by the neutralization of free fatty acids.What be particularly useful is sodium salt and sylvite derived from the mixture of the lipid acid of Oleum Cocois and butter, that is, and and butter sodium or potassium and cocounut oil sodium or potash soap.

The other no soap anionic surfactant that is applicable to this paper comprises water-soluble salt, and the basic metal of preferred organic reaction of Salmon-Saxl product and ammonium salt, described product have in its molecular structure and comprise about 10 alkyl and sulfonic group or sulfate groups to about 20 carbon atoms.(be included in being the moieties of acyl group in the term " alkyl ").The example of this class synthetic surfactant is sodium salt, sylvite and the ammonium salt of a) alkylsurfuric acid, especially by sulfation higher alcohols (C ₈-C ₁₈Individual carbon atom) resulting those, for example by in reduction butter or the Oleum Cocois glyceryl ester produced those; B) sodium sulfate salt of alkyl polyethoxylated, sylvite and ammonium salt, especially wherein alkyl comprises 10 to 22, preferred 12 to 18 carbon atoms, and wherein the polyethoxylated chain comprises 1 to 15, those of preferred 1 to 6 ethoxylation part; And c) sodium salt of alkyl benzene sulphonate (ABS) and sylvite, wherein alkyl comprises about 9 to about 15 carbon atoms, is the straight or branched configuration, for example is described in United States Patent (USP) 2,220, those types in 099 and 2,477,383.Especially valuable is linear alkylbenzene sulfonate, and wherein the average carbon atom number in the alkyl is about 11 to 13, is abbreviated as C ₁₁-C ₁₃LAS.

Preferred nonionic is chemical formula R ¹(OC ₂H ₄) _nThose of OH, wherein R ¹Be C ₁₀-C ₁₆Alkyl or C ₈-C ₁₂Alkyl phenyl, and n is 3 to about 80.Especially preferred is C ₁₂-C ₁₅Pure and about 5 condensation products to about 20 moles every mol of alcohol of oxyethane are as C ₁₂-C ₁₃The every mol of alcohol condensation of pure and about 6.5 moles oxyethane.

Fabric care benefit agents

Composition preferred embodiment according to this paper comprises fabric care benefit agents.As used herein; " fabric care benefit agents " is meant any following material: pledge clothes/when having this an amount of material on the fabric; it can be to clothes and fabric; especially cotton clothing thing and contain cotton high clothes and fabric the fabric care benefit effect is provided, for example fabric-softening, color protection, reduce balling-up/fluff, resistance to wear, anti-fold or the like.The limiting examples of fabric care benefit agents comprises cats product, siloxanes, polyolefin-wax, latex, oily sugar derivatives, cationic polysaccharide, urethane, lipid acid and their mixture.In certain embodiments, in the time of in being present in composition, the suitable content of fabric care benefit agents mostly is 30% most by the weight of described composition, is more typically about 1% to about 20%, is preferably about 2% to about 10%.

For purpose of the present invention, silicone derivative is any following silicone material, and it can be sent the fabric care benefit effect and can be used as emulsion, latex, dispersion, suspension etc. and be incorporated in the liquid treatment composition.In laundry product, they are the most common mixes with suitable tensio-active agent.The present invention has also comprised directly emulsification or has been distributed to any pure siloxane in the cleaning product, this is because cleaning product comprises many different tensio-active agents usually, described tensio-active agent can have the character of emulsifying agent, dispersion agent, suspension agent etc., therefore helps emulsification, dispersion and/or the suspension of water-insoluble silicone derivative.By being deposited on the fabric, these silicone derivatives can provide one or more fabric care benefit effects to fabric, comprise the protection of anti-fold, color, reduce balling-up/fluff, resistance to wear, fabric-softening or the like.Can be used for " the Silicones-Fields ofApplication and Technology Trends " of the case description of siloxanes of the present invention in Yoshiaki Ono, Shin-Etsu Silicones Ltd, " Principles of Polymer Science and Technology inCosmetics and Personal Care " (1999) of Japan and M.D.Berthiaume.

Suitable siloxanes comprises siloxanes liquid, as poly-(two) alkylsiloxane, especially polydimethylsiloxane and cyclic siloxanes.Poly-(two) alkylsiloxane can be for side chain, partial cross-linked or straight chain, and has following structure:

Each R wherein ₁Be independently selected from H, straight chain, side chain and have the cyclic alkyl of 1 to 20 carbon atom, straight chain, side chain and have a closed chain thiazolinyl of 2 to 20 carbon atoms, alkylaryl and aryl alkenyl with 7 to 20 carbon atoms, alkoxyl group with 1 to 20 carbon atom, hydroxyl, and their combination, w is selected from 3 to 10, and k is selected from 2 to 10,000.

Polydimethylsiloxanederivative derivative of the present invention includes but not limited to the siloxanes of organo-functional group.

An embodiment of siloxanes that contains functional group is for being described in US 6,903,061B2, US6,833,344 and WO-02/018528 in ABn type siloxanes.The example of the commercially available acquisition of these siloxanes is Waro and Silsoft 843, by GE Silicones, and Wilton, CT. sells.

Another embodiment of functionalized siloxanes is the siloxane groups with following general formula

Wherein:

(a) each R " be independently selected from R and-X-Q; Wherein:

(i) R is selected from following group: C ₁-C ₈Alkyl or aryl, hydrogen, C ₁-C ₃Alkoxyl group or their combination;

(b) X is selected from following linking group: alkylidene group-(CH ₂) _p-; Or

-CH ₂-CH (OH)-CH ₂-; Wherein:

(i) p is 2 to 6,

(c) Q is-(O-CHR ₂-CH ₂) _q-Z; Wherein the q average out to about 2 to about 20; And further wherein:

(i) R ₂For being selected from following group: H, C ₁-C ₃Alkyl; With

(ii) Z is selected from following group :-OR ₃,-OC (O) R ₃,-CO-R ₄-COOH ,-SO ₃,-PO (OH) ₂,

Wherein:

R ₃For being selected from following group: H, C ₁-C ₂₆The alkyl of alkyl or replacement, C ₆-C ₂₆The aryl of aryl or replacement, C ₇-C ₂₆The alkylaryl of alkylaryl or replacement; In some embodiments, R ₃For being selected from following group: H, methyl, ethyl propyl or benzyl;

R ₄For being selected from following group :-CH ₂-; Or-CH ₂CH ₂-;

R ₅For being independently selected from following group: H, C ₁-C ₃Alkyl;

-(CH ₂) _p-NH ₂With-X (O-CHR ₂-CH ₂) _q-Z;

(d) k average out to about 1 is to about 25,000, or about 3 to about 12,000; With

(e) m average out to 4 is to about 50,000, or about 10 to about 20,000.

The example that comprises functionalized siloxanes in the present invention is polyether silicon, alkylsiloxane, phenyl siloxane, aminosiloxane, silicone resin, siloxanes mercaptan, cationic silicone etc.

Functionalized siloxanes or with one or more dissimilar functional groups, as the multipolymer of amino, alkoxyl group, alkyl, phenyl, polyethers, acrylate, silicon hydride, mercapto propyl group, carboxylic acid, quaternised nitrogen.The limiting examples of the siloxanes of commercially available acquisition comprises SM2125, Silwet 7622, can be commercially available from GE Silicones, and DC8822 and PP-5495, and DC-5562, all can be commercially available from Dow Corning.Other example comprises KF-888, KF-889, all derives from Shin Etsu Silicones, Akron, OH;

SW-12,

DW-18,

DW-AV,

Q-Plus,

Ca-1, CA-2,

SA-1 and

PE-100 all derives from NoveonInc., Cleveland, OH.Additional limiting examples comprises the Phoenix Chemical Inc.'s that derives from Somerville

CA-20,

SM-40,

PAN-150.

Aspect siloxane emulsion, granularity can be about 1nm to 100 micron, and is preferably about 10nm to about 10 microns, comprises microemulsion (less than 150nm), standard emulsion (about 200nm is to about 500nm) and big emulsion (about 1 micron to about 20 microns).

Be applicable to that the oily sugar derivatives among the present invention proposes in WO 98/16538.Under situation of the present invention, initial CPE or RSE represent cyclic polyol derivative or reductive carbohydrate derivative respectively, its hydroxyl or reductive carbohydrate by 35% to 100% cyclic polyol produces, esterified and/or the etherificate of described carbohydrate, and wherein two or more esters or ether are connected on C8 to C22 alkyl or the alkenyl chain independently at least.Usually CPE and RSE have 3 or more a plurality of ester or ether or their mixture.Preferably two or more esters of CPE and RSE or ether are connected on C8 to C22 alkyl or the alkenyl chain independently.C8 to C22 alkyl or alkenyl chain can be for straight or brancheds.In one embodiment, 40% to 100% hydroxyl be esterification or etherificate.In another embodiment, 50% to 100% hydroxyl be esterification or etherificate.

Under situation of the present invention, term cyclic polyol comprises the carbohydrate of form of ownership.Especially preferred is CPE and the RSE that derives from monose and disaccharides.The example of monose comprises wood sugar, pectinose, semi-lactosi, fructose and glucose.The example of recuding sugars is a sorbitan.The example of disaccharides is sucrose, lactose, maltose and cellobiose.Sucrose is especially preferred.

Preferably CPE or RSE have 4 or more a plurality of ester or ether.If cyclic CPE is a disaccharides, then preferably disaccharides has three or more esters or ether.Especially preferred is the sucrose ester that contains 4 or more a plurality of ester groups.These can trade(brand)name Olean from Procter﹠amp; Gamble Company, Cincinnati OH is commercially available.

If the cyclic polyol is a reducing sugar, the ring of then favourable thing CPE contains an ether, preferably in the C1 position.The alkyl esterification of last hydroxyl.

But all provide the water-insoluble fabric care benefit agents of the dispersible polyolefin of fabric care benefit effect in all can being used as according to the present invention.This polyolefine can be the form of wax, emulsion, dispersion or suspension.Its limiting examples is discussed hereinafter.

Preferably, polyolefine can be polyethylene, polypropylene or their mixture.Polyolefine can be at least by modification partly to comprise various functional groups, for example carboxyl, alkylamide, sulfonic acid or amide group.More preferably, employed polyolefine can be at least partly by carboxy-modified among the present invention, and is perhaps in other words, oxidized.Specifically, oxidized or be preferred in composition of the present invention by carboxy-modified polyethylene.

In order to be easy to preparation, dispersible polyolefin is preferably by using emulsifying agent to be introduced into as the suspension or the emulsion of dispersible polyolefin.This polyolefine suspension or emulsion preferably comprise about by weight 1% to about 60%, and more preferably from about 10% to about 55%, most preferably from about 20% to about 50% polyolefine.This polyolefine preferably has about 20 ℃ to 170 ℃, and more preferably from about 50 ℃ to 140 ℃ cured dropping point is (referring to ASTM D3954-94, the 15.04th volume---" Standard Test Method for Dropping Point of Waxes ", described method is incorporated herein with way of reference).Suitable polyethylene wax can be discussed to derive from and include but not limited to following supplier: Honeywell (A-C polyethylene), Clariant (Velustrol emulsion) and BASF (LUWAX).

When using emulsion, described emulsifying agent can be any suitable emulsifying agent, comprises negatively charged ion, positively charged ion or nonionogenic tenside or their mixture.Almost any suitable tensio-active agent all can be used as emulsifying agent of the present invention.Disperse described dispersible polyolefin by using with 1: 100 emulsifying agent or suspension agent to about 1: 2 ratio.Preferably, described ratio is in about 1: 50 to 1: 5 scope.

Usually by emulsion polymerisation process preparation, it comprises one or more monomers, one or more emulsifying agents, initiator to polymer latex, and other component of being familiar with of this area those skilled in the art.All provide the polymer latex of fabric care benefit effect all to can be used as water-insoluble fabric care benefit agents of the present invention.The limiting examples of suitable polymers latex comprise be disclosed among the WO 02/018451 announce with title Rhodia Chimie those.Other limiting examples comprises the monomer that is used to produce polymer latex, for example:

1) 100% or the pure acrylic acid butyl ester;

2) contain at least 20% (weight monomer ratio) butyl acrylate of butyl acrylate and the mixture of divinyl;

3) butyl acrylate and less than other monomer except divinyl of 20% (weight monomer ratio);

4) having alkyl carbon chain is C6 or greater than the alkyl acrylate of C6;

5) having alkyl carbon chain is C6 or greater than C6's with less than other monomeric alkyl acrylate of 50% (weight monomer ratio);

6) the 3rd monomer (less than 20% weight monomer ratio) is added into 1) to 5) monomer system in.

The polymer latex of the suitable fabric care benefit agents among the present invention comprises having-120 ℃ to about 120 ℃ approximately, and preferred-80 ℃ of those of about 60 ℃ of second-order transition temperatures extremely approximately.Suitable emulsifying agent comprises anion surfactant, cats product, nonionogenic tenside and amphoterics.Suitable initiator comprises the initiator that all are applicable to the letex polymerization effect of polymer latex.The granularity of polymer latex can for about 1nm to about 10 μ m, and be preferably extremely about 1 μ m of about 10nm.

Cats product is the another kind of care actives of the present invention that can be used for.The example of cats product has following formula

Be disclosed among the US2005/0164905, wherein R ₁And R ₂Be independently selected from the group of forming by following: C ₁-C ₄Alkyl, C ₁-C ₄Hydroxyalkyl, benzyl and--(C _nH _2nO) _xH, wherein x has 2 to 5 value; And n has 1 to 4 value; X is a negatively charged ion;

R ₃And R ₄Respectively be C ₈-C ₂₂Alkyl or (2) R ₃Be C ₈-C ₂₂Alkyl, and R ₄Be selected from the group of forming by following: C ₁-C ₁₀Alkyl, C ₁-C ₁₀Hydroxyalkyl, benzyl,--(C _nH _2nO) _xH, wherein x has 2 to 5 value; And n has 1 to 4 value.

Another kind of preferred fabric care benefit agents is a lipid acid.In the time of on depositing to fabric, lipid acid or its soap will provide fabric nursing (flexibility, shape keep) to laundering of textile fabrics.Useful lipid acid (or soap=alkali metal soap, as sodium, potassium, ammonium and the alkylammonium salt of lipid acid) be higher fatty acid, it comprises about 8 to about 24 carbon atoms, and more preferably from about 12 to about 18 carbon atoms.Soap can make by the direct saponification of fat and oil, also can make by the neutralization of free fatty acids.What be particularly useful is sodium salt and sylvite derived from the mixture of the lipid acid of Oleum Cocois and butter, that is, and and butter sodium or potassium and cocounut oil sodium or potash soap.Lipid acid can derive from natural or synthetic source, is saturated with undersaturated, has the chain of straight or branched.

Detergency enzymes

The suitable detergency enzymes that can be used for this paper comprises proteolytic enzyme, amylase, lipase, cellulase, carbohydrase (comprising mannase and endo-dextranase) and their mixture.Can use enzyme according to their amount that the field proposed, for example according to supplier such as amount that Novo and Genencor recommended.Typical content in described composition is about 0.0001% to about 5%.In certain embodiments of the invention, when enzyme existed, they can low-down content (for example about 0.001% or lower content) uses; Or they are used for heavy dirty laundry detergent formulations according to the present invention with higher content (for example about 0.1% or higher content).According to the preference of some human consumer, the present invention includes and contain the enzyme and the embodiment of synthase not " abiotic " washing composition.

Deposition aid

As used herein, " deposition aid " be meant any in washing process significantly the reinforced fabric care benefit agents on fabric sedimentary cationic polymers or the combination of cationic polymers.Preferably, effectively deposition aid can be by physical force such as Van der Waals for, or non-covalent chemical bond such as hydrogen bond and/or ionic linkage and the water-insoluble fabric care benefit agents is had very strong binding ability.Preferably, it is for natural textile fiber, and especially cotton fibre has very strong avidity.

Preferably, deposition aid is cationic polymers or amphiphilic polymers.Amphiphilic polymers of the present invention also will have clean cationic charge, that is, the positively charged ion total charge on these polymkeric substance will be above the negatively charged ion total charge.The cationic charge density of polymkeric substance at about 0.05 milliequivalent/gram to the scope of about 6 milliequivalent/grams.Electric density is by calculating with the molecular weight of every repeating unit net charge number divided by repeating unit.In one embodiment, described electric density changes to the scope of about 3 milliequivalent/grams at about 0.1 milliequivalent/gram.Described positive charge can be on the side chain of the main chain of polymkeric substance or polymkeric substance.

The limiting examples of deposition aid is cationic polysaccharide, chitosan and derivative thereof and cation synthesising copolymer.More particularly, preferred deposition aid is selected from the group of being made up of following: cationic hydroxyethyl cellulose, cationic starch, cationic guar gum derivative and their mixture.

The ether of cellulose of the commercially available acquisition of structural formula I type comprises JR 30M, JR 400, JR125, LR 400 and LK 400 polymkeric substance, and by Amerchol Corporation, Edgewater NJ sells; And Celquat H200 and Celquat L-200, can derive from National Starch and Chemical Company or Bridgewater, NJ.Cationic starch is can trade(brand)name Cato commercially available from National Starch and Chemical Company.The example of cationic guar gum is Jaguar C13 and Jaguar Excel, can derive from the Rhodia of Cranburry NJ, Inc..

Comprise according to the limiting examples of preferred polymers of the present invention and to comprise following monomeric multipolymer

A) cationic monomer, described cationic monomer is selected from the group of being made up of following: N, N-methylacrylic acid dialkyl aminoalkyl ester, N, N-propenoic acid dialkyl aminoalkyl ester, N, N-dialkyl aminoalkyl acrylamide, N, N-dialkyl aminoalkyl Methacrylamide, their quaternised derivatives, vinyl-amine and derivative, allylamine and derivative thereof, vinyl imidazole, quaternised vinyl imidazole and poly (dially dialkyl) ammonium chloride; With

B) second monomer, described second monomer is selected from the group of being made up of following: acrylamide (AM), N, N-dialkyl group acrylamide, MAAm, N, N-dialkyl group MAAm, C1-C12 alkyl acrylate, C1-C12 acrylic acid hydroxy alkyl ester, C1-C12 vinylformic acid hydroxyethyl alkyl ester, C1-C12 alkyl methacrylate, C1-C12 hydroxyalkyl methacrylate, vinyl-acetic ester, vinyl alcohol, vinyl formamide, vinyl acetamide, vinyl alkyl ethers, vinyl butyrate and their derivative and mixture.

Most preferred polymkeric substance is acrylamide-diallyldimethylammonium chloride multipolymer, acrylamide-methacryloyl amido oxypropyl trimethyl ammonium chloride copolymer, acrylamide-N, N-dimethylamino methyl ethyl acrylate copolymer, acrylamide-N, N-dimethylamino methyl ethyl acrylate copolymer, Hydroxyethyl acrylate-dimethylamino methyl ethyl acrylate copolymer, Hydroxyethyl acrylate-dimethylamino methyl ethyl acrylate copolymer, Hydroxyethyl acrylate-methacryloyl amido oxypropyl trimethyl ammonium chloride copolymer.

Rheology modifier

In a preferred embodiment of the invention, described composition comprises rheology modifier.Described rheology modifier is selected from the group of being made up of following: non-polymeric crystalline, hydroxyl-functional materials, polymerization rheology modifier, described polymerization rheology modifier is given the shear-thinning characteristic to the liquid, aqueous matrix of described composition.This type of rheology modifier is preferably at 20s ^-1And give the shear viscosity of aqueous liquid composition 1 to 1500cps and at (0.05s under 21 ℃ ^-1And 21 ℃) under greater than those of the low-shear viscosity of 5000cps.Use derives from AR 550 rheometers of TA Instruments and measures according to viscosity of the present invention, and described rheometer uses the Plate Steel spindle of 40mm diameter and the gap size of 500 μ m.At 20s ^-1Under shear viscosity and 0.5 ^-1Under low-shear viscosity can under 21 ℃ in 3 fens clock times 0.1 ^-1To 25 ^-1The logarithm shearing rate scan obtain.Crystalline, hydroxyl-functional materials are on the spot during crystallization, to form the rheology modifier of class filamentary texture system in whole composition matrix in matrix.The polymeric rheology modifier preferably is selected from the combination of polyacrylic ester, polymerization natural gum, other non-gummy polysaccharide and these polymeric materials.

In general, the content of rheology modifier counts 0.01% to 1% by the weight of the composition of this paper, and is preferred 0.05% to 0.75%, and more preferably 0.1% to 0.5%.

The rheology modifier of composition of the present invention is used to provide the matrix of " shear-thinning ".The shear-thinning fluid is the sort of for viscosity degradation when using shearing for described fluid.Therefore, when static, promptly in the storage or transportation of detergent product, the fluid matrix of composition should have higher viscosity.Yet when composition use was sheared, for example in the process that composition is poured out or extruded from its container, the viscosity of matrix should be lowered to can be easily and realize the degree that fluid product distributes like a cork.

It is normally known in this area to form shear-thinning fluidic material with water or other liquid, aqueous combination the time.Can select these materials to be used for the composition of this paper, precondition is that they can be used for forming the liquid, aqueous matrix with rheological properties proposed above.

Especially a kind of structurizing reagent that can be used for composition of the present invention comprises non-polymeric (except the alkoxylate of routine) crystalline hydroxy functional substance.When this material in matrix on the spot during crystallization, it can form the thread structurizing system of class in whole liquid matrix.This type of material can be described as crystalline hydroxyl lipid acid, aliphatic ester or aliphatics wax usually.

Preferred crystalline, the specific examples that comprises the rheology modifier of hydroxyl comprise Viscotrol C and derivative thereof.Especially preferred is the hydrogenated castor oil derivative, for example hydrogenated castor oil and hydrogenated castor wax.Commercially available acquisition, castor oil-base crystalline, the rheology modifier that comprises hydroxyl comprise and derive from Rheox, Inc.'s (now being Elementis)

The alternative commercially available material that be suitable for use as crystalline, comprises the rheology modifier of hydroxyl is those of formula III above.The example of this class rheology modifier is R, R and S, 1 of S type, the mixture of 4-two-O-benzyl-D-threitol and any optically active or non-optically active.

These preferred crystalline, comprise the rheology modifier of hydroxyl and they and be attached in the moisture shear-thinning matrix and be described in greater detail in United States Patent (USP) 6,080,708 and PCT announce WO 02/40627.

Suitable polymerization rheology modifier comprises those of polyacrylic ester, polysaccharide or polysaccharide derivates class.Usually the polysaccharide derivates as rheology modifier comprises the polymerization gum substance.This type of natural gum comprises pectin, alginate, Arabic semi-lactosi (Sudan Gum-arabic), carrageenin, gelling gum, xanthan gum and guar gum.

Another kind of alternative and suitable rheology modifier is solvent and polycarboxylic acid ester polymer's combination.More particularly, described solvent is preferably aklylene glycol.More preferably, described solvent is a dipropylene glycol.Preferably, described polycarboxylic acid ester polymer is polyacrylic ester, polymethacrylate or their mixture.The content of described solvent is preferably 0.5% to 15% of composition, and preferred 2% to 9%.Described polycarboxylic acid ester polymer's content is preferably 0.1% to 10% of composition, and more preferably 2% to 5%.Solvent composition preferably comprises dipropylene glycol and 1, the mixture of 2-propylene glycol.Dipropylene glycol and 1, the ratio of 2-propylene glycol is preferably 3: 1 to 1: 3, more preferably 1: 1.Polyacrylic ester is preferably the multipolymer of undersaturated one or two carbonic acid and (methyl) acrylic acid 1 to 30C alkyl ester.In another preferred embodiment, rheology modifier is undersaturated one or the polyacrylic ester of two carbonic acid and (methyl) acrylic acid 1 to 30C alkyl ester.This analog copolymer can derive from NoveonInc by trade(brand)name Carbopol Aqua 30.

Washing assistant

Composition of the present invention can randomly comprise washing assistant.Suitable washing assistant is discussed hereinafter:

Suitable polycarboxylate washing assistant comprises the cyclic compound, especially alicyclic compound, as be described in United States Patent (USP) 3,923, those in 679,3,835,163,4,158,635,4,120,874 and 4,102,903.

Other useful washing assistant comprises the multipolymer, 1 of described ether hydroxyl polycarboxylic acid salt, maleic anhydride and vinyl ether or vinyl methyl, 3,5-trihydroxybenzene-2,4,6-trisulfonic acid and carboxymethyl hydroxy-butanedioic acid, multiple basic metal, ammonium and the substituted ammonium salt of polynary acetate such as ethylenediamine tetraacetic acid (EDTA) and nitrilotriacetic acid(NTA), and polycarboxylate such as mellitic acid, succsinic acid, oxygen di-succsinic acid, More Malay acid, benzene 1,3,5-tricarboxylic acid, carboxymethyl hydroxy-butanedioic acid and their resolvability salt.

Because their operability that comes from renewable resources and biological degradability, the Citrate trianion washing assistant is citric acid and their resolvability salt (especially sodium salt) for example, is the polycarboxylate washing assistant that is even more important that is used for heavy dirty type liquid detergent preparation.The hydroxy-butanedioic acid hydrogen salt also is particularly useful in these compositions and combination.

Being equally applicable in the liquid composition of the present invention is 3,3-dicarboxyl-4-oxa--1, and the 6-adipate, and relevant compound is published in the United States Patent (USP) 4,566,984 of the Bush that announced on January 28th, 1986.Useful succsinic acid washing assistant comprises C5-C20 alkyl and alkenyl succinic and salt thereof.A kind of especially preferred this compounds is the dodecylene Succinic Acid.The concrete example of succinate washing assistant comprises: lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecylene succinate (preferably), 2-15 carbene succinates or the like.The lauryl succinate is a preferred washing assistant in this group, and is described among the EP-A-0200263 that announced on November 5th, 1986.

The specific examples of nitrogenous not phosphorated aminocarboxylate comprises ethylenediamine disuccinic acid and salt (quadrol disuccinate thereof, EDDS), ethylenediamine tetraacetic acid (EDTA) and salt (edetate thereof, EDTA) and diethylene triaminepentaacetic acid(DTPA) and salt thereof (diethylentriamine pentacetate, DTPA).

Other suitable polycarboxylate be disclosed in the people's such as Crutchfield that announced on March 13rd, 1979 United States Patent (USP) 4,144,226 and the United States Patent (USP) 3,308,067 of the Diehl that announced on March 7th, 1967 in.Also can be referring to the United States Patent (USP) 3,723,322 of Diehl.These materials comprise aliphatic carboxylic acid, as the water-soluble salt of toxilic acid, methylene-succinic acid, methylfumaric acid, fumaric acid, equisetic acid, citraconic acid and homopolymerization of methylene radical propanedioic acid and multipolymer.

Bleach systems

The bleach systems that is applicable to this paper comprises one or more SYNTHETIC OPTICAL WHITNER.The limiting examples of suitable SYNTHETIC OPTICAL WHITNER is selected from the group of being made up of following: catalytic metal complexes, active peroxygen source, bleach-activating agent, bleach enhancers, optical white, SYNTHETIC OPTICAL WHITNER enzyme, radical initiator and inferior halite SYNTHETIC OPTICAL WHITNER.

Suitable active peroxygen source include but not limited to preformed peracid, with the hydrogen peroxide cource of bleach-activating agent combination or their mixture.Suitable preformed peracid includes but not limited to be selected from the compound by the following group of forming: percarboxylic acids and salt thereof, percarbonic acid and salt thereof, mistake imido acid and salt, permonosulphuric acid and salt thereof and their mixture.Suitable hydrogen peroxide cource includes but not limited to be selected from the compound by the following group of forming: perborate compound, percarbonate compound, superphosphate compound and their mixture.Type and content that active peroxygen source is fit to are present in United States Patent (USP) 5,576, in 282,6,306,812 and 6,326,348.

Spices

Spices preferably is incorporated in the detergent composition of the present invention.But the described fragrance component of premix adds in the detergent composition of the present invention then to form fragrant-inner agent.As used herein, term " spices " comprises independent fragrance component and fragrant-inner agent.More preferably, composition of the present invention comprises perfume microcapsule.Perfume microcapsule comprises capsule and is encapsulated in by the perfume base that is selected from the capsule of being made by the following group of forming: urea and formaldehyde, trimeric cyanamide and formaldehyde, phenol and formaldehyde, gelatin, urethane, polymeric amide, ether of cellulose, cellulose ester, polymethacrylate and their mixture.The capsule wrapper technology can be referring to (marcel Dekker Inc 1996) " Microencapsulation " that edited by Benita and Simon: methods andindustrial applications.

The content of fragrant-inner agent in detergent composition is generally about 0.0001% to about 2% or higher by the weight of described detergent composition, for example to about 10%; Preferred about 0.0002% to about 0.8%, and more preferably from about 0.003% to about 0.6%, and most preferably from about 0.005% to about 0.5%.

The content of fragrance component in described fragrant-inner agent is generally about 0.0001% (more preferably 0.01%) to about 99% by the weight of described fragrant-inner agent, preferred about 0.01% to about 50%, more preferably from about 0.2% to about 30%, even more preferably from about 1% to about 20%, and most preferably from about 2% to about 10%.Exemplary fragrance component and fragrant-inner agent are described in United States Patent (USP) 5,445, and 747, in United States Patent (USP) 5,500,138, United States Patent (USP) 5,531,910, United States Patent (USP) 6,491,840 and the United States Patent (USP) 6,903,061.

Solvent system

Solvent system in the composition of the present invention can be to comprise water separately or comprise organic solvent and the solvent system of the mixture of water.Preferred organic comprises 1,2-propylene glycol, ethanol, glycerine, dipropylene glycol, methylpropane glycol and their mixture.Also can use other lower alcohol, C ₁-C ₄Alkanolamine is as monoethanolamine and trolamine.Solvent system can be do not contained, solvent system can be do not contained in the anhydrous solid embodiment for example of the present invention.The content of this solvent system is more typically about 0.1% to about 98%, preferably at least about 10% to about 95%, more typical about 25% to about 75%.

The fabric substantive dyestuff

Composition of the present invention also can comprise the fabric substantive dyestuff.Dyestuff is defined as matching stain, basic dyestuff, reactive dyestuffs, dispersed dye, substantive dyestuff, vat dyes, sulphur dyestuff or solvent dye etc. routinely.For purpose of the present invention, substantive dyestuff, matching stain and reactive dyestuffs are preferred, and substantive dyestuff is most preferred.Substantive dyestuff is that a class is general owing to selective adsorption and by fiber direct water-soluble dye that absorbs from comprise the electrolytical aqueous solution.In described color index system, substantive dyestuff is meant various planar, the height conjugated molecular structures that one or more anion sulfoacid foundation are rolled into a ball that comprise.Matching stain is the anionic dyestuffs that a class is used from acidic solution.Reactive dyestuffs are the dyestuff that a class comprises active group, and described active group can form covalent linkage with some part of natural or synthon molecule.From the viewpoint of chemical structure, the suitable fabric substantive dyestuff that can be used for this paper can be azo-compound, toluylene, oxazine and phthalocyanine.

The suitable fabric substantive dyestuff that can be used for this paper is included in those that are listed in direct purple dye, sun blue dyestuff, acid violet dyestuff and acid blue dye in the described color index.

In a preferred embodiment, described fabric substantive dyestuff is a directly purple 99 of azo, is also referred to as the DV99 dyestuff with following formula:

The composition that capsule is sealed

Composition of the present invention can be encapsulated in water-soluble film.Described water-soluble film can be made by starch, sugar, PEG, wax or their combination of polyvinyl alcohol or other suitable modification, carboxymethyl cellulose, derivatived cellulose, starch, modification.

In another embodiment, water-soluble other auxiliary agent that comprises is as the multipolymer of ethene alcohol and carboxylic acid.United States Patent (USP) 7,022,656B2 (Monosol) has described this type of film composite and advantage thereof.Because with the better consistency of washing composition, an improvement that beneficial effect is the shelf life of packed washing composition of these multipolymers.Another advantage of this type of film is their cold water preferably (being lower than 10 ℃) solubleness.Wherein if present, the content of multipolymer in thin-film material counts at least 60% by the weight of described film.Described polymkeric substance can have any weight-average molecular weight, preferred 1000 dalton to 1,000,000 dalton, more preferably 10,000 dalton to 300,000 dalton, even more preferably 15,000 dalton to 200,000 dalton, 20,000 dalton to 150 most preferably, 000 dalton.Preferably, be present in 60% to 98% of multipolymer in the film and be hydrolyzed, more preferably 80% to 95% be hydrolyzed to improve the solubleness of material.In a highly preferred enforcement, multipolymer comprises 0.1mol% to 30mol%, the described carboxylic acid of preferred 1mol% to 6mol%.

Water-soluble film of the present invention also can comprise additional comonomer.Suitable additional comonomers comprises sulfonate and ethoxylate.The example of preferred sulfonic acid is 2-acrylamide-2-methyl isophthalic acid-propane sulfonic acid (AMPS).Being used for the suitable water-soluble film of the context of the invention can trade(brand)name M8630 ^TMFrom Mono-Sol, Indiana, US is commercially available.The water-soluble film of this paper also can comprise the composition that is different from polymkeric substance or polymeric material.For example, can advantageously add softening agent, for example glycerine, ethylene glycol, Diethylene Glycol, propylene glycol, 2-methyl isophthalic acid, ammediol, sorbyl alcohol and their mixture, divide enzymolysis auxiliary agent, weighting agent, defoamer, emulsification/dispersion agent and/or antiblocking agent at additional water.Described pouch of useful thing or water-soluble film self comprise detergent additives to be delivered in the described washing water, for example, and organic polymer stain remover, dispersion agent, dye transfer inhibitor.Randomly, the film surface of described pouch can smear fine powder to reduce frictional coefficient.Sodium silicoaluminate, silicon-dioxide, talcum and amylose starch are the examples of suitable fine powder.

The pouch that capsule of the present invention is sealed can use any known conventional art manufacturing.More preferably, described pouch usage level form is filled the manufacturing of thermoforming technology.

Other auxiliary agent

The example of the cleaning additive material that other is suitable includes but not limited to oxyalkylated phenylformic acid or its salt, as trimethoxybenzoic acid or its salt (TMBA); The enzyme stabilising system; Sequestrant comprises aminocarboxylate, amino phosphonates do, unazotized phosphonic acid ester and not phosphorated and the not sequestrant of carboxylate-containing; Inorganic builders comprises inorganic builders and water-soluble organic washing-assisting detergent such as zeolite, as polyacrylic ester, acrylate/maleate copolymer etc.; Scavenging agent comprises the fixing agent that is used for anionic dyestuff, the complexing agent that is used for anion surfactant and their mixture; Comprise hydrogen peroxide and catalatic effervescent system; Optional optical whitening agent or white dyes; Soil release polymer; Dispersion agent; Suds suppressor; Dyestuff; Staining agent; Weighting agent salt such as sodium sulfate; Hydrotropic agent such as tosylate, cumene sulfonate and naphthalenesulfonate; Light activating agent; Hydrolyzable tensio-active agent; Sanitas; Oxidation inhibitor; Nonshrink aqua; Anti wrinkling agent; Sterilant; Mycocide; Color spot; Coloured globule, ball or extrudate; Sun-screening agent; Fluorine cpd; Clay; Luminous agent or chemoluminescence agent; Anticorrosive agent and/or utensil protective material; Basicity source or other pH regulator agent; Solubilizing agent; Processing aid; Pigment; Free-radical scavengers and their mixture.Suitable material comprises and is described in United States Patent (USP) 5,705, those in 464,5,710,115,5,698,504,5,695,679,5,686,014 and 5,646,101.The mixture of agent mixture-said components can any ratio manufacturing.

Preparation of compositions

The composition of this paper can prepare by composition being mixed and adding pearling agent usually.Yet, if use rheology modifier, preferably at first form pre-composition, in this pre-composition, rheology modifier is distributed to a part of water that finally is used for constituting described composition.Form this pre-composition, make it comprise structuring liquid.

When stirring described pre-composition, can subsequently tensio-active agent and basic washing auxiliary substance be added in this structurized pre-composition together with water and any optionally washing agent composition auxiliary agent that will use.Can add these materials (or thus, adding these composition component simultaneously) to pre-composition by any easy order.The gained of structurized pre-composition and remaining composition component is combined to form liquid, aqueous matrix, and pearling agent will be added in this matrix.

Used therein in the especially preferred embodiment of crystalline hydroxyl structural agent, can use following steps to activate structural agent:

1) by crystalline hydroxyl stablizer (preferably in the amount by the weight of described pre-composition about 0.1% to about 5%) and water (its content counts at least 20% by the weight of described pre-composition) and one or more tensio-active agent and optional low all salt that are included in the detergent composition that will be used in the composition are made up, forms pre-composition.

2) pre-composition that forms in the step 1) is heated to more than the fusing point of crystalline hydroxyl structural agent.

3) when stirring this mixture, with step 2) in the pre-composition of the heating that forms be cooled to envrionment temperature, make in this mixture, to form the thread structurizing system of class.

4) remainder with the detergent composition component mixes respectively with the water of any order together with surplus, thereby forms isolating mixture.

5) the structurizing pre-composition that will derive from step 3 then under agitation mixes to form structurized liquid, aqueous matrix with the independently mixture that derives from step 4, and obviously visible beads will be sneaked in this matrix.

Embodiment

Following non-limiting example describes the present invention.Except as otherwise noted, all per-cents all by weight.

Embodiment	A	B	C	D
					The many ethoxylates of C14-C15 alkyl (8)	4.00	4.00	4.00	4.00
The many ethoxylates of C12-C14 alkyl (3) sodium sulfate salt	6.78	6.78	6.78	6.78
					The alkyl benzene sulphonate (ABS) of straight chain	1.19	1.19	1.19	1.19
Citric acid	2.40	2.40	2.40	2.40
					C12-18 lipid acid	4.48	4.48	4.48	4.48
Enzyme		1.0	1.0	1.0
					Boric acid	1.25	1.25	1.25	1.25
The hexanediamine quaternary ammonium salt of trans Sulfated ethoxylation	0.71	0.71	0.71	0.71
					Diethylenetriamine pentamethylene phosphonic acids	0.11	0.11	0.11	0.11
White dyes		0.06		0.06
					Mirapol 550 15		0.3	0.3
Polyquaternium 10	0.175
					Hydrogenated castor oil	0.300	0.300	0.300	0.300
Ethanol	1.00	1.00	1.00	1.00
					1, the 2-propylene glycol	0.04	0.04	0.04	0.04
Sodium hydroxide	3.01	3.01	3.01	3.01
					Siloxane emulsion	0.0030	0.0030	0.0030	0.0030
Dope dye DV99	0.049	0.025	0.049	0.020
					Dyestuff	ppm	ppm	ppm	ppm
Mica/TiO 2-Prestige Silk Silver Star-Eckart		0.15		0.15
					BiOCl-Biron Silver CO-Merck	0.15
EGDS pre-composition-Tego Pearl N100-Degussa Goldschmidt			2.0
					Spices	0.65	0.65	0.65	0.65
Water	To 100	To 100	To 100	To 100

15 by Rhodia Chemie, the France supply

^*The composition of unitized dose comprises the liquid composition that is coated in the water-soluble film.

Following composition prepares with the continuous liq method with bench scale and pilot scale.Package the product in then in the water-soluble film pouch of 45mL.Described water-soluble film derives from Monosol, and model is M8630.The unitized dose product of gained is monitored for some time of 4 months to physical stability and outward appearance under 35 ℃.Product shows advantages of excellent stability, and meaning does not have as seen separating or precipitating of pearly-lustre material and composition.

Be prepared as follows spissated liquid washing agent:

	1	2	3	4	5	6
							Composition (supposing 100% activity)	Weight %	Weight %	Weight %	Weight %	Weight %	Weight %
AES 1	21.0	12.6	21.0	12.6	21.0	5.7
							LAS 2	--	1.7	--	1.7	--	4.8
The alkyl-sulphate of side chain	--	4.1	--	4.1	--	1.3
							NI 23-9 3	0.4	0.5	0.4	0.5	0.4	0.2
The C12 trimethyl ammonium chloride 4	3.0	--	3.0	--	3.0	--
							Citric acid	2.5	2.4	2.5	2.4	2.5	--
C 12-18Lipid acid	3.4	1.3	3.4	1.3	3.4	0.3
							Proteolytic enzyme B	0.4	0.4	0.4	0.4	0.4	0.1
Carezyme 5	0.1	0.1	0.1	0.1	0.1	--
							Tinopal AMS-X 6	0.1	0.1	0.1	--	0.1	0.3
TinopalCBS-X 6	--	--	--		0.1	--
							Ethoxylation (EO 15) four polyethylene, five imines 7	0.3	0.4	0.3	0.4	0.3	0.4
PEI 600EO 20 8	0.6	0.8	0.6	0.8	0.6	0.3
							The quaternised Sulfated hexanediamine of zwitter-ion ethoxylation 9	0.8	--	0.8	--	0.8	--
PP-5495 10	3.4	3.0	3.4	3.0	3.4	2.7
							KF-889 11	-	--	--	--	3.4	--
Acrylamide/methacryloyl amido oxypropyl trimethyl ammonium chloride 12	0.2	0.2	0.2	0.2	--	0.3
							Diethylentriamine pentacetate, MW=393	0.2	0.3	0.2	0.2	0.2	--
Mica/TiO2 13	0.2	0.1	--	--	--	0.1
							Unister E 275 14	--	--	1.0	1.0		--
Dope dye DV99	0.04	0.04	0.04	0.04	0.04	0.04
							Hydrogenated castor oil	0.1	0.1		0.1	0.1	0.1
Water, spices, dyestuff and other optional reagent/component	Surplus to 100%	Surplus to 100%	Surplus to 100%	Surplus to 100%	Surplus to 100%	Surplus to 100%

	7	8	9
				Composition (supposing 100% activity)	Weight %	Weight %	Weight %
AES 1	21.0	12.6	21.0
				LAS 2	--	1.7	--
The alkyl-sulphate of side chain	--	4.1	--
				NI 23-9 3	0.4	0.5	0.4
The C12 trimethyl ammonium chloride	3.0	--	3.0
				Citric acid	2.5	2.4	2.5
C 12-18Lipid acid	3.4	1.3	3.4
				Proteolytic enzyme B	0.4	0.4	0.4
Carezyme 7	0.1	0.1	0.1
				Tinopal AMS-X 8	0.1	0.1	0.1
TinopalCBS-X 8	--	--	--
				Ethoxylation (EO 15) four polyethylene, five imines 4	0.3	0.4	0.3
PEI 600EO 20 5	0.6	0.8	0.6
				The quaternised Sulfated hexanediamine of zwitter-ion ethoxylation 6	0.8	--	0.8
PP-5495 9	3.4	3.0	3.4
				Mirapol 550 15	0.2	0.2	0.2
Diethylentriamine pentacetate, molecular weight=393	0.2	0.3	0.2
				Mica/TiO2 11	0.2	--	0.1
Unister E 275 12Cold pearl		1.0	--
				Hydrogenated castor oil	0.1	0.1	0.1
Dope dye DV99	0.04	0.04	0.04
				Water, spices, dyestuff and other optional reagent/component	Surplus to 100%	Surplus to 100%	Surplus to 100%

¹C ₁₀-C ₁₈Alkyl ethoxy sulfate

²C ₉-C ₁₅The alkylbenzene sulfonate of straight chain

³C ₁₂-C ₁₃(the EO of ethoxylation ₉) alcohol

⁴By Akzo Chemicals, Chicago, IL supply

⁵By Novozymes, the NC supply

⁶By Ciba Specialty Chemicals, high Point, NC supply

⁷As US 4,597, described in 898

⁸As US 5,565, described in 145

⁹With trade(brand)name

Derive from BASF, and described in WO 01/05874 those

¹⁰By Dow Corning Corporation, Midland, MI supply

¹¹By Shin-Etsu Silicones, Akron, OH supply

¹²By Naperville, the Nalco Chemcials of IL supply

¹³By Ekhard America, Louisville, KY supply

¹⁴By Degussa Corporation, Hopewell, VA supply

¹⁵By Rhodia Chemie, the France supply

¹⁶By Aldrich Chemicals, Greenbay, WI supply

¹⁷By Dow Chemicals, Edgewater, NJ supply

¹⁸Supply by Shell Chemicals

Claims (21)

1. laundry detergent composition, described composition comprises dope dye and pearling agent, and wherein said dope dye shows at least 10 toning effect and in about 30% washing value of removing to about 85% scope.

2. the described laundry detergent composition of claim as described above, wherein said dope dye show at least 15 toning effect and in about 40% washing value of removing to about 85% scope.

3. the described laundry detergent composition of each claim as described above, described composition comprise by weight the tensio-active agent of (a) about 5% to about 90% and (b) about 0.0001% to about 0.1% dope dye.

4. the described laundry detergent composition of each claim as described above, wherein said dope dye is a triarylmethane alkali blue dyestuff; The triarylmethane basic purple dye; Methyne alkali blue dyestuff; The methane basic purple dye; Anthraquinone alkali blue dyestuff; The anthraquinone basic purple dye; Azoic dyestuff alkali blue 16, alkali blue 65, alkali blue 66, alkali blue 67, Blue 71, alkali blue 159, alkaline purple 19, alkaline purple 35, alkaline purple 38 or alkalescence purple 48; Oxazine dye Basic Blue 3, Blue 75, alkali blue 95, alkali blue 122, alkali blue 124, alkali blue 141 or Buddhist nun rowland A; Xanthene dyestuff alkalescence purple 10; Oxyalkylated anthraquinone polymeric colorant; Or their mixture.

5. the described laundry detergent composition of each claim as described above, wherein said dope dye is methyne alkali blue dyestuff or methyne basic purple dye.

6. the described laundry detergent composition of each claim as described above, wherein said dope dye is oxyalkylated anthraquinone polymeric colorant.

7. the described laundry detergent composition of each claim as described above, wherein said dope dye is oxyalkylated tritane polymeric colorant.

8. the described laundry detergent composition of each claim as described above, wherein said dope dye is oxyalkylated thiophene polymeric colorant.

9. the described laundry detergent composition of each claim as described above, wherein said pearling agent is selected from the group of being made up of the organic or inorganic pearling agent.

10. the described laundry detergent composition of each claim as described above, wherein said pearling agent is organic pearling agent, described organic pearling agent is selected from the group with following formula:

R wherein ₁C12-C22 alkyl chain for straight or branched;

R is the C2-C4 alkylidene group of straight or branched;

P be selected from H, C1-C4 alkyl or-COR ₂, R ₂Be the C4-C22 alkyl; And

N=1 to 3.

11. the described laundry detergent composition of each claim as described above, wherein said pearling agent is inorganic pearling agent, and described inorganic pearling agent is selected from the group of being made up of following: the glass of the mica of the mica of mica, coating of metal oxides, pearl white coating, pearl white, glass, coating of metal oxides and their mixture.

12. the described laundry detergent composition of each claim as described above, wherein said inorganic pearling agent is selected from the mica of mica, titania coating, mica, pearl white and their mixture of iron oxide coatings.

13. the described laundry detergent composition of each claim as described above, wherein said composition is a liquid form.

14. the described laundry detergent composition of each claim as described above, wherein said composition is the liquid form that is packaged in the water-soluble film.

15 described laundry detergent compositions of each claim as described above, described laundry detergent composition also comprises the fabric substantive dyestuff.

16. the described laundry detergent composition of each claim as described above, wherein said tensio-active agent comprises anion surfactant and nonionogenic tenside.

17. the described laundry detergent composition of each claim as described above, described laundry detergent composition also comprises one or more annexing ingredients, and described annexing ingredient is selected from the group of being made up of following: decontamination lotion promoter, enzyme, enzyme stabilizers, suds suppressor, soil-suspending agent, stain remover, pH regulator agent, sequestrant, smectic clays, solvent, hydrotropic agent, phase stabilizer, structurizing reagent, dye transfer inhibitor, white dyes, fabric substantive dyestuff and spices.

18. the described laundry detergent composition of each claim as described above, described laundry detergent composition also comprises enzyme, and described enzyme is selected from proteolytic enzyme, amylase, lipase and their mixture.

19. the described laundry detergent composition of each claim as described above, described laundry detergent composition comprises the viscosity modifier that is selected from conditioning agent, and described conditioning agent is given aqueous liquid composition shear-thinning characteristic, and described composition is at 20s ^-1With 21 ℃ under have 1 to 1500cps shear viscosity and at 0.05s ^-1With 21 ℃ under have low-shear viscosity greater than 5000cps.

20. laundry detergent composition as claimed in claim 19, wherein said viscosity modifier is selected from the group of being made up of following material: the combination of polyacrylic ester, polymerization natural gum, other non-gummy polysaccharide and these polymeric materials.

21. the method for laundering of textile fabrics goods, described method are included in the described textile article of washing in the washing soln, described washing soln comprises the described laundry detergent composition of each claim as described above.

22. method for preparing liquid laundry detergent composition as claimed in claim 21, described method comprises makes described dope dye and liquid ingredient combination to form the dope dye pre-composition, and described dope dye pre-composition joined in the composite preparation, described composite preparation comprises the major part of described laundry detergent composition component surplus.