CN100422299C - Detergent compsns. comprising hydrotropes - Google Patents

Abstract

The present invention relates to detergent compositions, especially liquid, granular and tablet forms of laundry detergent compositions, that comprise improved hydrotropes, wherein the hydrotropes are organic molecules in which two polar groups are separated from each other by at least 5 aliphatic carbon atoms; liquid compositions that contain such hydrotropes have a viscosity, dilution profile and dissolution behavior that render the product effective and convenient for use as a liquid laundry detergent composition.

Description

Comprise hydrotropic detergent composition

Invention field

The present invention relates to detergent composition, relate in particular to the laundry detergent composition of liquid, granular and sheet form, said composition comprises improved hydrotropic agent, and wherein hydrotropic agent is at least 5 mutual isolated organic molecules of aliphatic carbon atom of two polar groups quilts in its molecule; Contain viscosity, dilution form and solubility behavior that this hydrotropic fluid composition has, make this product become liquid laundry detergents composition effective and easy to use.

Background of invention

In recent years, the popularization that is different from the Betengent product of granular/powder-form has increased.These different forms comprise liquid state and tablet form.

The liquid laundry detergents product provides many advantages that surpass exsiccant, powdery or microgranular detergent for washing clothes product.The liquid laundry detergents product measures easily, dissolving fast in wash water, need not sweep, and makes it easily be applied to be washed the position of making dirty on the clothing with concentrated solution or dispersion, and the storage area that takies lacking than granulated product usually.In addition, liquid laundry detergents can be in its prescription the raw material of fusion, the drying operation process mesometamorphism that can in particulate or granular laundry detergent product are made, use.Because it has been generally acknowledged that the use liquid laundry detergents is more convenient more than granular laundry detergent, find that they fully are subjected to human consumer's preference.

No matter the advantage of liquid detergent compositions, the granulous product has also kept plurality of advantages.These advantages comprise performance, prescription capacity, lower-packing cost and high product stability.The advantage of product stability and prescription capacity is mainly derived from the essence of granular adulterant, and each component can be stablized respectively in granular adulterant, and with other particle fusion before be isolated into particle.The raw material of the separation of this physics permission use latent instability in composition such as SYNTHETIC OPTICAL WHITNER, enzyme or the like in final detergent composition.

Understand by the compression granulated detergent composition well, detergent composition can be made tablet form.This tablet washs for the human consumer each time to be provided in advance-measure the facility of detergent doses, and the not convenient and irregularity when not measuring the q.s granular detergent composition.This product return those outside or the human consumer who leaves their residence washing clothes sizable facility (for example in the self-service laundry) is provided she or he washs the required so much detergent for washing clothes just in time of clothes because such human consumer only needs to carry.Detergent composition can be made tablet form by the compressed detergent particulate.

A consistency that shortcoming is each composition of conventional liquid detergent compositions.Can compatible mutually detergent for washing clothes component in granular and/or tablet product, in liquid environment, especially in the waterborne liquid environment, often may interact or react to each other.

Solvency action, dissemination and solubility performance that a shortcoming of conventional granular/powder detergent composition is a relative mistake.

A shortcoming of conventional tablet detergent composition is: make enough firm and durable tablets avoiding splinter in manufacturing, transportation and/or storage process, can cracked rapidly mode with will contact washing water with tablet simultaneously the time make the conflict between the tablet.

As mentioned above, supply/preparation liquid detergent compositions there is continuous demand, these liquid detergent compositions not only have outstanding scourability and composition and physical stability, also have to make its viscosity as liquid laundry detergents composition useful and easy to use, dilution form and solubility behavior; To supply/preparation granular/powder detergent composition has continuous demand, these granular/powder detergent compositions have improved solvency action, dissemination and solubility performance, keep granular/powdered detergent inherent prescription adaptability simultaneously; And supply/preparation tablet detergent composition there is continuous requirement, these tablet detergent composition are robust and durable, can resist the breakage in manufacturing, transportation and/or the storage process, but also can be cracked rapidly when the contact washing water, make the component of this tablet in the carrying out washing treatment process, can provide the washing advantage.

Summary of the invention

The present invention has disclosed at detergent composition of the present invention such as water-based or non--water-based liquid laundry detergents composition, in granular/powdery laundry detergent composition and/or the tablet laundry detergent composition, add some hydrotropic agent, can provide 1) a kind of liquid detergent product, the viscosity that it has, dilution form and solubility behavior, make this product become useful and liquid laundry detergents composition easily, and/or 2) a kind of granular/the powdered detergent product, it has improved dissemination, solvency action and/or solubility performance, with do not contain this hydrotropic granulous/powdered detergent product relatively, it has reduced the demand of tensio-active agent, and/or 3) a kind of tablet Betengent product, wherein hydrotropic agent is as tackiness agent, do not compare with there being the hydrotropic tablet Betengent product of this kind, it has improved intensity and wear properties, and outstanding division and dissolution characteristics.

A. liquid product

Contain hydrotropic liquid detergent product and shown outstanding scourability, outstanding composition and physical stability and good product rheological behaviour.These hydrotropic agents of determining can the most normally be classified as organic molecule, and two polar groups are isolated mutually by at least 5 aliphatic carbon atoms in organic molecule.

The liquid detergent product can be water-based or non--water-based.Of the present invention one preferred aspect, the non-aqueous liquid detergent that provides comprises two polar groups by at least 5 mutual isolated hydrotropic agents of aliphatic carbon atom, and by the non--water-based liquid phase that contains tensio-active agent of composition weight meter about 49%～about 99.95% and by about 1%～about 50% the particulate starting material of composition weight meter, particulate starting material is insoluble to said liquid phase basically, and be selected from peroxygen bleach, bleach activator, the organic detergent washing assistant, inorganic alkali source and their mixture, and wherein composition does not contain any following compounds deutero-quaternary ammonium compound: C _16-18Unsaturated fatty acids, methyldiethanolamine or methyl chloride.

B. granular/powder-like product

Contain these hydrotropic granular/the powdered detergent product shown improved dissemination, solvency action and/or solubility performance, with do not contain this hydrotropic granulous/powdered detergent product relatively, it has reduced the demand of tensio-active agent.These hydrotropic agents can the most normally be classified as organic molecule, and first polar group that this organic molecular species has and second polar group are isolated mutually by at least 5 aliphatic carbon atoms.

C. tablet product

Detergent tablet prepared in accordance with the present invention comprises hydrotropic agent (" tackiness agent "), it is characterized in that tackiness agent can the most normally be classified as an organic molecular species, first polar group that this molecule has and second polar group are isolated mutually by at least 5 aliphatic carbon atoms.With do not contain this hydrotropic tablet Betengent product relatively, this tablet Betengent product demonstrates improved intensity and wear properties and outstanding division and dissolution characteristics.

Unless otherwise indicated, all parts used herein, percentage ratio and ratio are all represented with weight percentage.All incorporated herein by reference at whole literature contents that corresponding section is quoted as proof.

Detailed Description Of The Invention

Definition

" Hydrotropic agentThe common meaning of "-here employed " hydrotropic agent " is meant the compound of solubleness in the solubleness that can increase some slightly soluble organic compound, the preferably water; more preferably " hydrotropic agent " is defined as follows (consulting S.E.Friberg and M.Chiu; J: disperse Science and Technology; 9 volumes (5 and 6 phase); 443～457 pages, (1988-1989)):

1. preparation comprises the solution of 25 these special compounds of weight % and 75 weight % water.

2. thereafter when solution temperature is 20 degrees centigrade, be added in the solution sad, the ratio of adding is 1.6 times of special compound weight in the above-mentioned solution.This solution mixes in having the Sotax beaker of propeller for vessels agitator, and this water screw is positioned at approximately 5mm of beaker bottom top, and the speed setting of mixing tank is 200 rev/mins.

3. if sad dissolving fully, if promptly solution only comprises a phase, this is liquid phase mutually, and then this special compound is a hydrotropic agent.

" Non--water-based " or " anhydrous"-here employed " non--water-based " or " anhydrous " are synonyms, and the two all describes free water content wherein less than about 1% liquid.

" Polar group"-here employed " polar group " refers to have the functional group of permanent electric dipole moment, and permanent electric dipole moment is to be produced by the partial charge on the atom of polar link connection.Polar group itself can be anionic or not charged.

" Solvency action"-here employed " solvency action " refers to be in the suds, and Betengent product mixes with water and the speed of release of active ingredients.

" ParticleThe meaning of the employed noun of "-here " particle " is the overall dimension scope of washing composition the finished product or component, or discrete particulate, agglomerate or particulate overall dimension scope in final Betengent product or the component adulterating agent.It does not relate to the granularity grades (promptly describe be less than 100% whole dimension scope) of any of these type of particle clearly, unless granularity grades is represented in the particle adulterating agent 100% discrete particles.To all kinds of particulate constituents in the adulterating agent, no matter whether this particle contacts with other particles, and the discrete particle of the type overall dimension scope has identical or substantially similar composition.For agglomerant component, the particle that this agglomerate is considered to disperse itself, and each discrete particle can be made up of littler particle and binder composition.

" The geometric mean particle diameterThe meaning of the employed phrase of "-here " geometric mean particle diameter " is the geometric sense mid-diameter of one group of discrete particle, be by any standard the granular size measuring technology based on quality, preferably assign to measure by dry sieve.

" geometric standard deviation " or " span "" geometric standard deviation " of-employed here phrase particle size dispersion or the meaning of " span " are the geometric widths of the optimum logarithm-orthogonal function of above-mentioned granular size data, and the diameter that it can be by the 84.13rd hundredths in the cumulative distribution recently obtains (D divided by the 50th hundredths diameter ₈₄₁₃/ D ₅₀); Consult Gotoh etc.: the powder technology handbook, the 6-11 page or leaf, Meral Dekker publishes, 1997.

Hydrotropic agent

The hydrotropic agent of narrating in this paragraph is the basal component of detergent composition of the present invention.

Added hydrotropic agent among the present invention, two polar groups are isolated mutually by at least 5, preferred 6 aliphatic carbon atoms in the hydrotropic agent.The polar group example that suitable hydrotropic agent comprises comprises hydroxyl and carboxylic ions.Particularly preferred hydrotropic agent is selected from:

1,4 cyclohexane dimethanol:

1, the 6-hexylene glycol:

1,7 heptanediol:

And their mixture.

The mixture of the hydrotropic agent molecule that also has these organic molecules or any amount that is fit to, this type of hydrotropic agent molecule is made up of two polar groups, and at least 5 of two polar group quilts, preferred 6 aliphatic carbon atoms are isolated mutually.1,4 cyclohexane dimethanol can exist with its cis-configuration, transconfiguration or two kinds of configuration form of mixtures.

A. liquid product

The present invention includes the liquid laundry detergents composition, said composition can be water-based or non--water-based, and is suitable for the pre-treatment of preceding stain of automatic washing machine or textiles or fabric washing and dirty class.Liquid laundry detergents composition of the present invention can comprise individually solia particle that the liquid-phase of rich tensio-active agent or the liquid that they can contain rich tensio-active agent-reach mutually is suspended in the liquid phase mutually the two.Preferably, the liquid of rich tensio-active agent-contain mutually hydrotropic agent and organic thinner arbitrarily.

The hydrotropic agent of the present invention that mixes liquid product of the present invention provides and has prevented the liquid detergent compositions gelation told about and/or the key component of multiviscosisty here.

In the liquid detergent product of the hydrotropic agent preparation that does not add the present invention definition, when this product contacts water and dilute with water at first, observed gelification in the past.Be not bound by theory, think that the cause that produces this gel phenomenon is that surfactant system has formed sticking tensio-active agent (phase of sheet, spherical or hexagonal configuration typically) mutually under the concentration of certain tensio-active agent and water.Found the dependency between the amount of the viscosity of the water mixture product of the critical dilution range of observing gelification and the sticking tensio-active agent phase that forms.

In a preferred embodiment, detergent composition right and wrong-water-based, have the non--water-based liquid phase of rich tensio-active agent and have the solia particle phase that is suspended in said liquid phase.In this embodiment, this detergent composition will comprise the non--water-based liquid phase that contains tensio-active agent of about 49%～99.95 weight % usually.More preferably, this liquid phase is that tensio-active agent constitutes, and reaching by its content of composition weight meter will be about 52%～98.9%.Most preferably, will comprise about 55%～70% non--water-based liquid phase here by composition weight meter.The density that this liquid phase that contains tensio-active agent has will be approximately 0.6～1.4g/cc usually, more preferably about 0.9～1.3g/cc.

Not bound by theory, think the formation of the sticking tensio-active agent phase that above-mentioned hydrotropic agent can form when having prevented dilution because hydrotropic agent can be effectively interact, make their fractures with orderly structural sheet surfactant molecule and impel form isotropic low-the viscosity table surface-active agent is mutually.

These hydrotropic agents also provide other function for the rheology of improving liquid detergent compositions.For example, it usually is difficult that the quaternized amine raw material of ethoxylation is mixed the detergent composition that contains anion surfactant, because the quaternized amine raw material of ethoxylation causes that anion surfactant comes out from liquid-phase precipitation, cause liquid detergent compositions thickening significantly.But, be sought after in the liquid detergent product, mixing the deposition agent of these clay dirt removers/anti--again, because they provide important performance benefit.The present invention has disclosed and has contained above-mentioned hydrotropic agent, can avoid the precipitation of common observed anion surfactant and the multiviscosisty of composition, thereby has produced the liquid detergent compositions with required rheological properties.

The quaternized amine raw material of ethoxylation will be described in detail hereinafter.

Liquid-the phase that contains tensio-active agent

Preferably by hydrotropic agent, non-ionic type and aniorfic surfactant, and one or more organic thinners form the liquid phase of the liquid detergent compositions here.

Organic thinner-main ingredient of detergent composition liquid phase comprises the organic thinner of one or more water-baseds or non--water-based here.The organic thinner that uses among the present invention can or surfactivity liquid be tensio-active agent, or be called the non--surfactant liquids of solvent here.Term used herein " solvent " means the nonsurfactant liquid portion of this composition.Though some basic and/or selectable components of this composition in fact dissolve in contain " solvent "-liquid phase, can exist other component to be dispersed in the liquid phase that contains " solvent " as particulate starting material.The meaning of term " solvent " is and does not require that in fact this solvent raw material can dissolve whole components of the detergent composition of adding like this.

Contain the surfactant structure liquid phase and will comprise about 50%～90%, more preferably about liquid diluent component of 50%～80%, most preferably about 55%～75% usually.The liquid phase of the present composition preferably will comprise liquid surfactant and non--tensio-active agent solvent the two.

I) Surfactant liquids-suitable the type of surfactant liquids that can be used for forming the liquid phase of the present composition comprises oxyalkylated alcohol, oxyethane (EO)-propylene oxide (PO) block polymer, polyhydroxy fatty acid amide, alkyl polysaccharide etc.These common liquid surfactants are that to have the HLB scope be those tensio-active agents of 10～16.Most preferred surfactant liquids is the nonionic surface active agent of alcohol alkoxylates.

Alcohol alkoxylate is the raw material that meets following chemical general formula:

R ¹(C _mH _2mO) _nOH

R wherein ¹Be C ₈-C ₁₆Alkyl, m are 2～4, and the scope of n is about 2～12.Preferred R ¹Being alkyl, can be primary alkyl or secondary alkyl, contains about 9～15 carbon atoms, more preferably about 10～14 carbon atoms.Also preferred oxyalkylated Fatty Alcohol(C12-C14 and C12-C18) is made the raw material of ethoxylation, contains about 2～12 ethylene oxide moieties in its each molecule, more preferably contains about 3～10 ethylene oxide moieties in each molecule.

Being useful on hydrophile-lyophile balance (HLB) scope that the alkoxy fatty alcohols raw material of liquid phase usually has is about 3～17.More preferably the HLB scope of this raw material will be about 6～15, most preferably about 8～15.

Present composition example useful or that be used as the fatty alcohol alkoxy compound of liquid phase in liquid phase will comprise those pure and mild compounds that contains about 7 moles of ethylene oxide manufacturing by 12～15 carbon atoms.These raw materials are commercial on sale, produced commodity Neodol25-7 by name and Neodol 23-6.5 by shell chemical company.Other useful Neodols comprise Neodol 1-5, are the ethoxylized fatty alcohols that 11 carbon atoms and about 5 moles of ethylene oxide are on average arranged on its alkyl chain; Neodol23-9 is the ethoxylation C that about 9 moles of ethylene oxide are arranged ₁₂-C ₁₃Primary alconol; And Neodol 91-10, be the ethoxylation C that about 10 moles of ethylene oxide are arranged ₉-C ₁₁Primary alconol.The ethoxylate of this type alcohol also is that shell chemical company is on sale with trade(brand)name Dobanol.Dobanol 91-5 is ethoxylation C ₉-C ₁₁Fatty Alcohol(C12-C14 and C12-C18), per molecule Fatty Alcohol(C12-C14 and C12-C18) have average 5 moles of ethylene oxide; And Dobanol 25-7 is ethoxylation C ₁₂-C ₁₅Fatty Alcohol(C12-C14 and C12-C18), per molecule Fatty Alcohol(C12-C14 and C12-C18) have average 7 moles of ethylene oxide.

The example of the ethoxylated alcohol that other are suitable comprises Tergitol 15-S-7 and Tergitol 15-S-9, and the two all is linear secondary alcohol ethoxyl compound, and is commercial on sale, is produced by Union Carbide Corporation.The former is C ₁₁～C ₁₅The mixed ethoxylated product of linear alkane secondary alcohol and 7 moles of ethylene oxide, the latter is the similar products like of reacting with 9 moles of ethylene oxide.

Useful other types alcohol ethoxylate is the nonionic compound of higher molecular weight in the present composition, as Neodol 45-11, it is similar condensed products than high fat alcohol and oxyethane, wherein 14-15 carbon atom arranged, and every moles of ethylene oxide group number is about 11 than high fat alcohol.Such product shell chemical company commerce is on sale.

If use the part of alcohol alkoxylates nonionic surface active agent as liquid phase in detergent composition of the present invention, preferably the degree of its existence is approximately 1%～60% of the structural liquid phase of composition.More preferably, structural liquid phase will comprise about 5%～40% alcohol alkoxylate component.Most preferably, the structural liquid phase of detergent composition will comprise about 5%～35% alcohol alkoxylate component.The concentration of using alcohol alkoxylate in liquid phase is about 1%～60 weight % of composition corresponding to the concentration of alcohol alkoxylate in total composition, more preferably about 2%～40 weight %, and most preferably about 5%～25 weight %.

The other types surfactant liquids that can use in the present invention is oxyethane (EO)-propylene oxide (PO) block polymer.Such material is well-known nonionic surface active agent, and they are on sale, and commodity are called Pluronic.These materials are that the end that the fragment with ethylene oxide moiety is added to the polypropylene glycol chain forms, to regulate the surface active properties of the block polymer that is generated.Such EO-PO block polymer nonionic surface active agent is at Davidsohn and Milwidsky work Synthetic detergent the 7th editionIn 34-36 page or leaf and 189-191 page or leaf and the United States Patent (USP) 2,674,619 and 2,677,700 very detailed narration is arranged, Synthetic detergentOne book is published by Longman Science and Technology press (1987).The content of all these publications is incorporated herein by reference.And think that these Pluronic type nonionic surface active agent play effective suspension agent to the particulate starting material that is dispersed in the detergent composition liquid phase of the present invention.

May in this composition, useful surfactant liquids type comprise polyhydroxy fatty acid amide surfactant in addition.This type nonionic surface active agent is and the material that meets following chemical formula:

Wherein R is C _9-17Alkyl or alkenyl, p are 1～6, and Z is reducing sugar deutero-glycosyl or its alkoxy derivative.These raw materials comprise C ₁₂-C ₁₈The N-methyl glucose amide.Example has N-methyl-N-1-deoxidation glycosyl coconut oleoyl amine and N-methyl-N-1-desoxy sugar base oil acid amides.The manufacture method of polyhydrony fatty acid, acid amides is known, can find in the United States Patent (USP) 2,703,798 of the United States Patent (USP) 2,965,576 of for example Wilson and Schwartz, and their content is incorporated herein by reference.These raw materials itself and preparation thereof also have very detailed narration in the United States Patent (USP) 5,174,937 of Honsa, this patent was delivered on December 26th, 1992, and is also incorporated herein by reference.

Detergent composition of the present invention also can contain anionic, cationic and/or amphoteric surfactant.In preferred embodiments, liquid phase right and wrong-water-based wherein, liquid phase be by with the non--water-based organic liquid diluent of the present invention narration and a kind of tensio-active agent in conjunction with preparing, common but nonessential selection adds this surfactant structure in the non--water-based liquid phase of this detergent composition.Body structure surface active agent can be anionic, non-ionic type, cationic and/or amphoteric.So individually for they surface-active attribute or can add the tensio-active agent of description for these attributes and structure properties thereof.

Preferred surfactants is an anion surfactant, as alkyl-sulphate, the poly-alkoxy sulfate of alkyl and linear alkyl benzene sulfonate.Can be used as the another kind of common anion surfactant raw material that is added to arbitrarily in the detergent composition of structure component and comprise the anionic tensio-active agent of carboxyl-type.Carboxyl-type anion surfactant comprises C ₁₀-C ₁₈Alkyl alkoxy carboxylicesters (the especially ethoxy carboxylate ester of 1～5 EO) and C ₁₀-C ₁₈Sarcosinate, especially oleoyl sarcosinates.The another kind of common anion surfactant raw material that can be used as the use of structure component comprises the anion surfactant such as the C of other sulfonic acid salinization ₈-C ₁₈Alkane sulfonate and C ₈-C ₁₈Alkene sulfonate.Press composition weight meter, will comprise about 1%～30% structure anion surfactant here usually.

As showing, a preferred type structure anion surfactant comprises one-level or secondary alkyl sulphate salt anionic surfactant.These tensio-active agents are higher C ₈-C ₂₀Those tensio-active agents that the fatty alcohol sulphuric acid salinization is produced.

The chemical general formula that conventional one-level alkyl sulfate surfactant has is:

ROSO ₃ ^-M ⁺

Wherein R is the C of typical linear ₈-C ₂₀Alkyl, it can be a straight or branched, and M is water-dissolubility positively charged ion.Preferred R is C _10-14Alkyl, and M is a basic metal.Most preferably R is about C ₁₂And M is a sodium.

As mentioned above, also can use the structure anion surfactant of conventional secondary alkyl sulphate salt as this composition liquid phase.

If use, comprise about 1%～30% alkyl-sulphate by composition weight meter usually, more preferably press composition weight meter about 5%～25%.Kong-Chan etc. have very at length narrated the non--water-based liquid detergent compositions that contains alkyl-sulphate, peroxygen bleach and bleach activator in WO96/10073, this patent application announces that on April 4th, 1996 content is incorporated herein by reference.

Another kind of preferred anionic surfactants tensio-active agent raw material comprises that alkyl gathers alkoxy sulfate, it can be used as the structure component at random be added to the present invention non--the water-based cleaning composition in.The poly-alkoxy sulfate of the alkyl of having understood such as alkoxylated alkyl group vitriol or sulfated alkyl ether.Such raw material meets following chemical formula:

R ²-O-(C _mH _2mO) _n-SO ₃M

R wherein ²Be C ₁₀-C ₂₂Alkyl, m are 2～4, and n is about 1～15, and M is a salt-forming cation.Preferred R ²Be C ₁₂-C ₁₈Alkyl, m are 2, and n is about 1～10, and M is sodium, potassium, ammonium, alkylammonium or alkanol ammonium.R most preferably ²Be C ₁₂-C ₁₆, m is 2, n is about 1～6, and M is a sodium.Because with the uncompatibility of peroxygen bleach, avoid ammonium, alkylammonium and alkanol ammonium counterion when preferably in this composition, using.

If use, can comprise usually by the poly-alkoxy sulfate of the alkyl of composition weight meter about 1%～30%, more preferably press composition weight meter about 5%～25%.Boutique etc. have very at length narrated the non--water-based liquid detergent compositions that contains poly-alkoxy sulfate of alkyl and polyhydroxy fatty acid amide in PCT application number PCT/US96/04223, the content of this application is incorporated herein by reference.

The most preferred type anion surfactant that is used as the structure component in this composition comprises linear alkyl benzene sulfonate (LAS) tensio-active agent.Especially, this LAS tensio-active agent can be mixed with the powder that contains anion surfactant of specific type, this powder be particularly useful for mixing the present invention non--the water-based liquid detergent compositions.Such powder comprises distinct two-phase.Have one to be insoluble to the non--water-based organic liquid diluent that uses in this composition mutually in the two-phase; Another dissolves in non--water-based organic liquid mutually.This exactly insoluble phase that contains the powder of preferred anionic surfactants tensio-active agent, it can be dispersed in the non--water-based liquid phase of preferred composition, form and assemble short grained network, this allows, and other additional solia particle raw materials stably are suspended in the composition in the finished product.

Further argumentation to the preparation method of suitable tensio-active agent and this tensio-active agent, can in the total pending application of Jay I.Kahn etc., find, the exercise question of this application is " having the non-aqueous preparation that contains the liquid detergent compositions of particulate of structured surface promoting agent liquid phase ", its P﹠amp; The G case number is 6150, and series number is 09/202,964, proposes on December 23rd, 1998, and it is incorporated herein as a reference in view of the above.

Usually, the liquid phase of the present composition can comprise about 25%～70% liquid surfactant.More preferably, the structure liquid phase will comprise about 30%～65% liquid surfactant.This concentration corresponding to liquid surfactant in the total composition is about 10%～70 weight % of composition, more preferably about 20%～50 weight % of composition.The total amount of liquid surfactant is with above-mentioned in this preferred surfactants structure, non--water-based liquid phase, and will be further determines according to the type of other components of composition and amount and according to the characteristic of needed composition.

Ii) Non--the tensio-active agent organic solvent-this detergent composition liquid phase also can comprise one or more non--tensio-active agent organic solvents.This non--preferred those the low polar of surfactant liquids.Be purposes of the present invention, " low-polarity " liquid is if having then the liquid that only has the tendency of a kind of preferred type particulate starting material of very little dissolving, and this particulate starting material is that this composition uses, i.e. peroxygen bleach Sodium peroxoborate or SPC-D.Therefore preferably do not use the solvent such as the ethanol of relative polarity.Suitable type useful in this liquid detergent compositions is low-and polar solvent comprises alkylene glycol mono lower alkyl ether, low molecular poly, lower molecular weight methyl esters and acid amides etc. really.

The preferred type that is used for this composition is low-and polar solvent comprises C ₄-C ₈Side chain or straight-chain alkyl-sub-glycol.Such raw material comprises hexylene glycol (4-methyl-2,4-pentanediol), 1,3 butylene glycol and 1,4-butyleneglycol.

Another kind of preferred type used herein is low-polar solvent comprise single-, two-, three-or four-C ₂-C ₃Alkylene glycol mono C ₂-C ₆Alkyl oxide.The particular example of these compounds comprises diethylene glycol monobutyl ether, Tetraglycol 99 monobutyl ether, dipropylene glycol list ether and dipropylene glycol monobutyl ether.Especially preferred diethylene glycol monobutyl ether, dipropylene glycol monobutyl ether and butoxy-propoxy--propyl alcohol (BPP).This compounds is commercial on sale, and commodity are called Dowanol, Carbitol and Cellosolve.

Here another useful preferred type is low-and polar organic solvent comprises low molecular poly (PEG).The molecular weight that these raw materials have about at least 150.Most preferably molecular weight ranges is approximately 200～600 PEG.

Another preferred type is non--and polar solvent comprises the lower molecular weight methyl esters.The chemical general formula of this raw material is: R ¹-C (O)-OCH ₃, R wherein ¹Scope be 1～about 18.The suitable example of lower molecular weight methyl esters comprises ritalin, methyl propionate, methyl caprylate and methyl laurate.

Certainly, normally used low-polarity is non--other composition component that the tensio-active agent organic solvent must use with liquid detergent compositions, as SYNTHETIC OPTICAL WHITNER and/or activator is compatible and not-reaction.Preferably use the amount of this solvent composition to be about 1%～70% of liquid phase weight.More preferably structural liquid phase will comprise low-polarity of about 10%～60 weight %, and will be non--tenside/solvent, most preferably be about 20%～50 weight % of the structural liquid phase of composition.Non--tenside/solvent these working concentrations in liquid phase pairing non--concentration of tenside/solvent in total composition is about 1%～50 weight % of composition, more preferably about 5%～40 weight %, and most preferably about 10%～30 weight %.

Iii) The adulterant of tensio-active agent and non--tenside/solvent-using in the two the preferred embodiment of non--aqueous tenside liquid and non--water-based, non--tenside/solvent, contain in the liquid phase of structured surface promoting agent tensio-active agent to the ratio of non--surfactant liquids, for example Chun alcoxylates is to the ratio of low polar solvent, can be used for changing the rheological characteristics of the detergent composition of final formation.Usually, surfactant liquids will be in about 50: 1～1: 50 scope to the weight ratio of non--tensio-active agent organic solvent.More preferably this ratio will be in about 3: 1～1: 3 scope, most preferably about 2: 1～1: 2.

The solia particle raw material

Except the liquid phase that contains tensio-active agent, liquid detergent compositions of the present invention also preferably comprises about 1%～50 weight %, the more preferably additional dispersion of about 29%～44 weight % and be suspended in solid phase particle raw material in the liquid phase.The big young pathbreaker of general this particulate starting material is in about 0.1～1500 micron scope, more preferably about 0.1～900 micron.Most preferably the big young pathbreaker of this raw material is in about 5～200 microns scope.

Additional particulate starting material used herein can comprise the detergent composition component of one or more type particulate form, and these components are not dissolved in the composition liquid phase basically.These raw materials comprise peroxygen bleach, bleach activator, organic detergent washing assistant, inorganic alkali source and their mixture.The type of available particulate starting material will be described in detail hereinafter, but some raw material can be included in the particulate constituent arbitrarily or be included in the liquid phase that contains tensio-active agent.

In a preferred embodiment, particulate starting material comprises dye transfer inhibitor PVNO (consult above and describe in detail), silico-aluminate detergent builders and other less particulate constituents.

(a) The SYNTHETIC OPTICAL WHITNER that has optional bleach activatorMost preferred type particulate starting material useful in-this detergent composition comprises the peroxygen bleach particle.This peroxygen bleach can be organic or inorganic in essence.The inorganic peroxy SYNTHETIC OPTICAL WHITNER usually is used in combination with bleach activator.

Useful organic peroxy SYNTHETIC OPTICAL WHITNER comprises percarboxylic acids SYNTHETIC OPTICAL WHITNER and their salt.The suitable example of this class reagent comprises monoperphthalic acid magnesium hexahydrate, metachloroperbenzoic acid magnesium salts, 4-amino in the ninth of the ten Heavenly Stems-4-oxo Perbutyric Acid and diperoxy dodecanedioic acid.The United States Patent (USP) 4,483,781 of the Hartman that this class SYNTHETIC OPTICAL WHITNER has been delivered on November 20th, 1984; European patent application EP-A 133,354 that people such as Banks announced on February 20th, 1985; And it is open in the United States Patent (USP) 4,412,934 delivered on November nineteen eighty-three 1 of people such as Chung.SYNTHETIC OPTICAL WHITNER very preferably comprises that also 6-amino in the ninth of the ten Heavenly Stems-6-oxo crosses oxy hexanoic acid (NAPAA), in people's such as Burus United States Patent (USP) 4,634,551 explanation is arranged, and this patent was delivered on January 6th, 1987.

The form of all right particulate is used the inorganic peroxy SYNTHETIC OPTICAL WHITNER in this detergent composition.Actual inorganic SYNTHETIC OPTICAL WHITNER is preferred.This inorganic peroxy compounds comprises alkali metal perborate and percarbonate raw material, most preferably percarbonate.For example can use Sodium peroxoborate (for example single-or four-hydrate).Suitable inorganic SYNTHETIC OPTICAL WHITNER also can comprise the peroxyhydrate and " percarbonate " SYNTHETIC OPTICAL WHITNER, trisodium phosphate peroxyhydrate, urea peroxyhydrate and the sodium peroxide of equal value of yellow soda ash or potash salt.Also can use persulphate SYNTHETIC OPTICAL WHITNER (OXONE for example, DuPont company is commercial to make).The inorganic peroxy SYNTHETIC OPTICAL WHITNER often has the coating of silicate, borate, vitriol or water-soluble surfactants.For example, the percarbonate particles that can obtain applying from various commercial source such as FMC, Solvay Interox, Tokai Denka and Degussa.

Preferably with the inorganic peroxy SYNTHETIC OPTICAL WHITNER for example perborate, percarbonate etc. combine with bleach activator, this makes original position in aqueous solution (promptly use this composition carry out in the process of fabric washing/bleaching) produce and the corresponding peracid of bleach activator.In the United States Patent (USP) 4,412,934 that people such as United States Patent (USP) 4,915,854 that people such as Mao deliver on April nineteen ninety 10 and Chung deliver on November nineteen eighty-three 1, the various non--limitative examples of bleach activator is disclosed.Typical bleach activator is nonanoyl oxo benzene sulfonate (NOBS) and tetraacetyl ethylene diamine (TAED).Also can use their mixture.Here typical SYNTHETIC OPTICAL WHITNER of useful other and bleach activator are consulted the United States Patent (USP) of above quoting 4,634,551.

In the United States Patent (USP) 5,891,838 that people such as Angell delivered on April 6th, 1999; Reach at the exercise question of DianeParry and narrated other useful acyl ammonia deutero-bleach activators, the latter's P﹠amp in the total unsettled provisional application of " containing non--water-based liquid detergent compositions of inflating particulate matter "; The G case number is 7173P, and series number is 60/088,170, is to propose on June 5th, 1998, and they the two content is incorporated herein by reference.

If peroxygen bleach is used as all or part of additional particulate starting material, they will contain about 1%～30% usually by composition weight meter.More preferably, will contain about 1%～20% by the composition weight meter peroxygen bleach.Most preferably, peroxygen bleach will exist with about 5%～20% degree of composition weight.If the use bleach activator can contain about 0.5%～20%, more preferably about 3%～10% of composition weight.Usually, the degree of using bleach activator is a SYNTHETIC OPTICAL WHITNER to the mol ratio of bleach activator is about 1: 1～10: 1 scope, more preferably about 1.5: 1～5: 1.

(b) The transition metal bleach catalyzer-another kind of additional the particulate starting material that is suspended in this liquid detergent compositions comprises the transition metal bleach catalyzer, and it impels the catalyzed oxidation of fabric face dirt and stain.This compound exists with catalytically effective amount, preferably approximately is 1ppb～about 99.9% of laundry detergent composition, more typical 0.001ppm～about 49% that is approximately, the 500ppm of preferably approximately 0.05ppm～approximately (wherein part per billion of " ppb " expression weight, and " ppm " expression weight 1,000,000/).Transition-metal bleach catalyst comprises and is selected from Mn (II), Mn (III), Mn (IV), Mn (V), Fe (II), Fe (III), Fe (IV), Co (I), Co (II), Co (III), Ni (I), Ni (II), Ni (III), Cu (I), Cu (II), Cu (III), Cr (II), Cr (III), Cr (IV), Cr (V), Cr (VI), V (III), V (IV), V (V), Mo (IV), Mo (V), Mo (VI), W (IV), W (V), W (VI), Pd (II), Ru (II), Ru (III), and the transition metal of Ru (IV) and the many rings of big ring rigid ligand coordinate mixture, the big ring of preferred intersection-bridging encircles part more, this part has at least 4 part atoms, and wherein at least two is end of the bridge part atom.Title people such as Daryle H.Busch has very in detail accurately been discussed these catalyzer, the P﹠amp of this application in the total unsettled provisional application of " Catalyst And Method of catalyzed oxidation "; The G case number is 6524P, and series number is 60/040,629, and its content is incorporated herein by reference.

(c) The organic washing-assisting detergent raw material-another kind of additional the particulate starting material that is suspended in this liquid detergent compositions includes machine washing and washs the detergent builders raw material, is used for offsetting the influence of using the calcium that runs in this cleaning compositions/bleaching process or other ions, the water hardness.The example of these raw materials comprises basic metal, Citrate trianion, succinate, malonate, lipid acid, carboxymethyl succinate, carboxylate salt, polycarboxylate and poly-acetyl carboxylate salt.Special example comprises sodium, potassium and the lithium salts of oxidation acid Succinic Acid, mellitic acid, benzene polycarboxylic acid and citric acid.Compound and the alkyl hydroxy phosphonic acid ester of the trade(brand)name Dequest that other examples of Organophosphonate type sequestrant such as Monsanto sell.It is most preferred that Citrate trianion.

Other suitable organic washing-assisting detergents comprise known polymkeric substance and multipolymer with higher molecular weight of washing assistant characteristic.For example this raw material comprises suitable polyacrylic acid, poly-maleic acid and poly propenoic acid acid/maleic acid copolymers and their salt, the compound of the Sokalan trade mark of selling as BASF, and their molecular weight ranges is about 5,000～100,000.

The organic washing-assisting detergent of another suitable type comprises the water-dissolubility salt of more senior lipid acid, i.e. " soap ".Soap comprises sodium, potassium, ammonium and the alkyl alcohol ammonium salt of basic metal soap as more senior lipid acid, and more senior lipid acid contains about 8～about 24 carbon atoms, 12～about 18 carbon atoms of preferably approximately.Soap can by fat and the direct saponification of grease or in prepare with free fatty acids.Useful especially is sodium and sylvite by cocounut oil and tallow derived fatty acid mixture, i.e. sodium tallowate soap or tallow potash soap and coconut soap.

If use as all or part of additional particulate starting material, insoluble here organic detergent washing assistant can comprise the about 2%～20% of composition weight usually, and more preferably this washing assistant raw material can contain about 4%～10% of composition weight.

(d) Inorganic alkali sourceThe additional particulate starting material that is suspended in this liquid detergent compositions of-another possibility type can comprise a kind of normally alkaline in essence material of water-based washing soln that makes that this composition forms.This material also may or the effect of unable to get up detergent builders, and as offsetting the raw material of the water hardness to the disadvantageous effect of de-sludging performance.

The example of suitable alkali source comprises water-molten alkali-metal carbonate, supercarbonate, borate, silicate (silicate) and (partially) silicate (metasilicate).Although because ecology reason, water-molten phosphoric acid salt is not preferred, can be used as alkali source yet.Phosphoric acid salt comprises alkali-metal pyrophosphate salt, orthophosphoric acid salt, poly-phosphate and phosphonate.In all these alkali sources, alkaline carbonate such as yellow soda ash are most preferred.

If but the alkali source of salt hydrate form also can be used as siccative in this liquid detergent compositions.Also the existence for the alkali source of siccative can provide the chemically interests of stable composition component, and these composition component such as peroxygen bleach are subjected to the influence of water easily and lost efficacy.

If use as all or part of additional particulate starting material component, alkali source will contain about 1%～25% of composition weight usually here.About 2%～15% the alkali source that more preferably can contain composition weight.Though these raw materials are water-molten, will be insoluble to usually in the non--aqueous detergent composition of narration here.

As what point out hereinafter, water-based of the present invention and non--water-based liquid detergent compositions form can be SYNTHETIC OPTICAL WHITNER and/or other raw materials with solid particulate suspend and be dispersed in whole contain tensio-active agent, the form in the liquid phase structural, preferably non--water-based preferably.General structural non--the water-based liquid phase will contain the about 49%～99.95%, more preferably about 52%～98.5% of composition weight, and dispersive additional solid raw material contains about 1%～50%, more preferably about 29%～44% of composition weight.

Very a spot of water can be admixed in non--water-based liquid detergent compositions that the present embodiment contains particulate.Yet in these embodiments, in any case here the amount of free-water should be no more than about 1% by composition weight meter.More preferably, the water-content of non-here-aqueous detergent composition will be less than about 1 weight %.

As what disclose here, the present composition also can be used for forming the water-based laundry detergent composition.People such as people's such as Fredj U.S. Patent number 5,783,548 and Smerznak U.S. Patent number 5,648,327 in can find to be used for the suitable annexing ingredient of water-based liquid laundry detergents composition.

Here non--water-based the liquid detergent compositions that contains particulate in the commercial market and use under the condition of these compositions will be relative tack with mutually stable.Usually the range of viscosities of this composition will be approximately 300～8, and 000cps more preferably is approximately 1000～4,000cps.Be purpose of the present invention, viscosity is at shearing rate 20s with Carrimed CSL2 rheometer ^-1Following mensuration.

In people's such as Jay I.Kahn total pending application, discussed the preparation of non--water-based liquid detergent compositions in detail, the exercise question of this application is " having the non-aqueous preparation that contains the liquid detergent compositions of particulate of structural-tensio-active agent liquid phase ", its P﹠amp; The G case number is 6150, and series number is to propose on December 23rd, 09/202,964,1998, and its content is incorporated herein by reference.

This liquid detergent compositions that adds significant quantity in water forms water-based washing/liquid lime chloride, make present in an amount at least sufficient to formation contain about 500～10, the aqueous solution of 000ppm composition.More preferably in water-based washing/liquid lime chloride, provide about 800～8, this detergent composition of 000ppm.

B. granular/powder-like product

The present invention is granular/the powdered detergent product except comprising one or more hydrotropic agents, also preferably comprise following one or more preferred components, and one or more optional conventional detergent additives raw materials.These conventional additives raw materials can be included in one or more solia particle raw materials that the part of liquid product above or conventional hereinafter detergent additives raw material are partly narrated.

Form needed phase and product viscosity though can use hydrotropic agent to provide as everyone knows, but do not deliver gelification and/or the multiviscosisty that to use these organic molecules to prevent the detergent composition told about here as hydrotropic agent in the past, thereby and improved the dissolving and the dispersing property of granulated detergent product.In the Betengent product of the hydrotropic agent preparation that does not add the present invention's definition, when contacting water and dilute with water at first, this product observed gelification in the past.

Be not bound by theory, think that this gel phenomenon is to be produced by the particle that contains tensio-active agent, washing-liquid or wash-water in this particle with certain surfactant concentration contact water the time, or form sticking tensio-active agent phase (sheet, spherical or hexagonal phase typically), perhaps form " micelle-gelinite " of inside-connection.Found the viscosity of the product-water mixture in observing the critical dilution range of gelification, and a kind of dependency between the amount of the sticking tensio-active agent phase that forms in this scope.

Especially significantly problem has appearred in those areas of (as in Japan) automatic washing machine laundering of textile fabrics in cold relatively wash water or under the stirring of gentleness.Under cold relatively washing-water temp, exemplary surfactants water figure has shown the stabilized zone of height-viscosity net phase or gel surface promoting agent phase.And stirrer does not give the formation that enough mechanical energies destroy these height-viscosity phase under the state that gentleness is stirred.

Here the granular detergent composition of telling about can or single particle form, maybe can be each by its peculiar multiple particle form of forming.When washing composition was made up of multiple detergent particles, preferred above-mentioned organic water-soluble growth substance was comprised among the particle of rich tensio-active agent or is applied in these particulate surfaces.

Preferred component

Detergent surfactantUseful anion surfactant is divided into according to the present invention in detergent composition and the isolated alkyl sulfate surfactant of ionogen among-the present invention, and remaining is by the anion surfactant of each particle formulation.For the purposes of the present invention; alkyl-sulphate is defined as alkyl-sulphate, alkyl alkoxy sulfate, alkylsulfonate, alkyl alkoxy carboxylate salt, alkyl alkoxylated suifate, reaches the mixture that all the other anion surfactants are selected from alkylbenzene sulfonate, sulfonated, alkane sulfonate, alkyl ester sulfonate, sarcosinate, taurate, reach them.

If exist, anion surfactant all will typically exist with effective amount in the detergent composition.More preferably, said composition can contain about at least 0.5%, more preferably about at least 5% even more preferably about at least 10% anion surfactant of said composition weight.Composition also will preferably contain about 50% even about 30% the anion surfactant of no more than said composition weight more preferably about 90%, more preferably no more than said composition weight of no more than said composition weight.

Outstanding comprehensive cleaning capacity can be provided alone, and especially when uniting use with polyhydroxy fatty acid amide (consulting hereinafter), under wide temperature range, wash concentration and washing time, has good fats/oils cleaning action, soluble alkyl-sulphate, reaching the alkyl sulfate surfactant that has improved preparation performance in the liquid detergent prescription is that chemical formula is ROSO ₃M can be water-soluble salt or acid, R C10-C24 alkyl preferably wherein preferably has the alkyl or the hydroxyalkyl of C10-C20 alkyl composition, more preferably C12-C18 alkyl or hydroxyalkyl; And M is for example alkali (IA family) metallic cation (as sodium, potassium, lithium) of H or positively charged ion, that replace or unsubstituted ammonium cation such as methyl-, dimethyl-and trimethyl ammonium and quaternary ammonium cation for example tetramethyl--ammonium and lupetidine salt, and by alkanolamine such as thanomin, diethanolamine, trolamine and composition thereof deutero-positively charged ion etc.Typically, to lower wash temperature (for example being lower than about 50 ℃) C _12-16Alkyl chain is preferred and to higher wash temperature (for example being higher than about 50 ℃) C _16-18Alkyl chain is preferred.

Another kind of suitable alkyl sulfate surfactant is secondary (2, a 3) alkyl-sulphate according to the present invention.These tensio-active agents preferably chemical formula are:

X and (y+1) be integers about at least 7, preferred about at least 9 wherein.Preferred these tensio-active agents contain 10～18 carbon atoms.The United States Patent (USP) of delivering in the 8 days February in 1966 of Morris 3,234,258, the United States Patent (USP) of delivering on December 24th, 1991 of Lutz 5,075,041, people's such as Lutz the United States Patent (USP) of delivering on September 20th, 1,994 5,349,101, and the United States Patent (USP) of delivering on February 14 nineteen ninety-five of Prieto 5, disclose the suitable example of these anion surfactants in 389,277, each patent content is incorporated herein by reference.

Another kind of suitable alkyl sulfate surfactant is alkyl alkoxylated vitriol according to the present invention.These tensio-active agents be can be water-soluble salt or acid, typically have chemical formula RO (A) mSO ₃M, wherein R is unsubstituted C10-C24 alkyl or the hydroxyalkyl group with C10-C24 alkyl composition, preferred C12-C20 alkyl or hydroxyalkyl, more preferably C12-C18 alkyl or hydroxyalkyl; A is oxyethyl group or propoxy-unit; M typically is about 0.5～about 6, more preferably about 0.5～about 3 greater than zero; And M is H or positively charged ion, positively charged ion can be for example metallic cation (for example sodium, potassium, lithium etc.), ammonium or replacement-ammonium cation.What it is desirable to is the vitriol and the propenoxylated vitriol of alkyl of alkyl ethoxylated.The specific examples that replaces ammonium cation comprise methyl-, dimethyl-, trimethylammonium-ammonium and quaternary ammonium cation such as tetramethyl--ammonium, lupetidine salt, and by alkanolamine such as monoethanolamine, diethanolamine and trolamine, and composition thereof the deutero-positively charged ion.The tensio-active agent of making example is C12-C18 alkyl polyethoxylated (1.0) vitriol, C12-C18 alkyl polyethoxylated (2.25) vitriol, C12-C18 alkyl polyethoxylated (3.0) vitriol, reaches C12-C18 alkyl polyethoxylated (4.0) vitriol, and wherein M is selected from sodium and potassium easily.Tensio-active agent used herein can be made by natural or synthetic raw polyol.Chain length represents that the average hydrocarbon chain that comprises side chain distributes.The anion surfactant component can comprise alkyl-sulphate and conventional pure source deutero-sulfated alkyl ether, conventional pure source for example natural alcohol and as with trade name NEODOL ^TM, ALFOL ^TM, LIAL ^TM, LUTENSOL ^TMDeng the synthol of selling.Known sulfated alkyl ether is also as alkyl polyethoxylated vitriol.

Another kind of alkyl sulfate surfactant according to the present invention is the tensio-active agent of branching in the middle of one or more (preferably two or more mixture) chains, preferably has the alkyl alkoxy alcohol of the middle branching of chain of following chemical formula:

The middle branched-alkyl vitriol of chain with following chemical formula:

Alkyl alkoxy sulfate with branching in the middle of the chain with following chemical formula:

Wherein the total number of carbon atoms of the branched primary alkyl of these chemical formulas part (contains R, R ¹, and R ²Branch, but do not contain the carbon atom that comprises any EO/PO alkoxyl group part) be 14～20; And in addition to these surfactant mixtures, the average the total number of carbon atoms that wherein has the branched primary alkyl part of above-mentioned chemical formula is to arrive in about 17.5 the scope (preferably about 15～about 17) greater than 14.5; R, R ¹, and R ²Respectively be independently selected from hydrogen, C ₁-C ₃Alkyl and their mixture, as long as preferable methyl is R, R ¹, and R ²All not hydrogen, reach when z is 1, at least R or R ¹Not hydrogen.M is a water-soluble cationic, and can comprise the positively charged ion more than a type, for example mixture of sodium and potassium.Index w is 0～13 integer; X is 0～13 integer; Y is 0～13 integer; Z is at least 1 integer; Condition is that w+x+y+z is 8～14.EO and PO represent ethyleneoxy group unit and propylidene oxygen base unit, and their chemical formula is respectively:

Yet other oxyalkyl units especially trimethylene oxygen base, butoxy and their mixture are the oxyalkyl units that appends to the middle branched-alkyl part of chain that suits.

The tensio-active agent of branching is the mixture that comprises surfactant system in the middle of the preferred chain.Therefore when surfactant system comprised alkoxy-based surface-active agent, exponent m was illustrated in oxyalkylated average degree in the surfactant mixture.Exponent m is about at least 0.01 like this, preferably from about 0.1, more preferably from about 0.5, most preferably from about 1 to about 30, preferably to about 10, more preferably in about 5 scope.When the surfactant system of branching only comprises oxyalkylated tensio-active agent in the middle of considering chain, the distribution of the value representation of exponent m and the corresponding oxyalkylated average degree of m, or it can be the single corresponding specific chains of alkoxylate (for example ethoxylation and/or propoxylation) element number accurately with m that has.

Being suitable for the chemical formula that branched surfactants has in the middle of the preferred chain of the present invention of surfactant system of the present invention is:

Or chemical formula is:

Wherein a, b, d and e are integers, and a+b is 10～16, and d+e be 8～14; M is selected from the ammonium of sodium, potassium, magnesium, ammonium and replacement and their mixture.

In two embodiments, preferably prepared the surfactant system that the present invention comprises branched surfactants in the middle of the chain.In the middle of the chain that first preferred embodiment comprises branched surfactants be by comprise 25% or be less than 25% chain in the middle of the unitary raw material of branched-alkyl form.Therefore, with any other conventional surfactants admixture before, the branched surfactants component will comprise 25% or be less than the surfactant molecule of non--linear surface promoting agent of 25% in the middle of the chain.

Branched surfactants is formed by the unitary raw material of branched-alkyl in the middle of comprising about 25%～about 70% chain in the middle of the chain that second preferred embodiment comprises.Therefore, with any other conventional surfactants admixture before, the branched surfactants component will comprise the surfactant molecule of non--linear surface promoting agent of about 25%～about 70% in the middle of the chain.

At U.S.'s number of patent application 60/061,971 on October 14th, 1997, act on behalf of case 6881P; On October 14th, 1997, U.S.'s number of patent application 60/061,975 was acted on behalf of case 6882P; On October 14th, 1997, U.S.'s number of patent application 60/062,086 was acted on behalf of case 6883P; On October 14th, 1997, U.S.'s number of patent application 60/061,916 was acted on behalf of case 6884P; On October 14th, 1997, U.S.'s number of patent application 60/061,970 was acted on behalf of case 6885P; On October 14th, 1997 U.S.'s number of patent application 60/062,407, act on behalf of and further narrated these tensio-active agents among the case 6886P: branched surfactants can be in U.S. Patent Application Serial 60/032 in the middle of other suitable chains, 035 (case 6401P), 60/031,845 (case 6402P), 60/031,916 (case 6403P), 60/031,917 (case 6404P), 60/031,761 (case 6405P), 60/031, find among 762 (case 6406P) and 60/031,844 (the case 6409P).The mixture of these branched chain surfactants and conventional linear surface promoting agent also is suitable for the present composition.

Among the anion surfactant of the present invention that is not included in according to the present invention in the alkyl-sulphate, a spendable analog anion surfactants comprises alkyl ester sulfonate.These are desirable because they can by renewable non--petroleum source preparation.Can realize the preparation of alkyl sulfonate surfactants component according to disclosed currently known methods in the technical literature.For example according to " association of U.S. oil chemistry man magazine " 52 volume (1975) 323-329 pages or leaves, linear C8-C20 carboxylicesters can be by SO ₃Gas is sulfonated.Suitable starting raw material comprises natural in by deutero-fatty substances such as tallow, plam oil and cocounut oil.

The alkyl sulfonate surfactants that preferably is particularly useful for doing washing comprises the alkyl sulfonate surfactants of following structural chemistry formula:

R wherein ³Be the alkyl of C8-C20, preferred alkyl or their mixing; R ⁴Be the C1-C6 alkyl, preferred alkyl or their mixing; And M is the positively charged ion of solubility-salt formation.Suitable salt comprises metal-salt such as sodium, potassium and lithium salts, and replace or unsubstituted ammonium salt such as methyl-, dimethyl-, trimethylammonium-, and quaternary ammonium cation, for example tetramethyl--ammonium and lupetidine salt, and by alkanolamine deutero-positively charged ion for example monoethanolamine-amine, diethanolamine and trolamine.Preferably, R ³Be the alkyl of C10-C16, and R ⁴Be methyl, ethyl or sec.-propyl.Especially preferably R wherein ³Be the methyl ester sulfonate of C14-C16 alkyl.

Another kind of available anion surfactant comprises alkylbenzene sulfonate.It comprises the type of hard (ABS, TPBS), linearity, also is commonly referred to as LAS, and as C ₉-C ₂₀Linear alkyl benzene sulfonate, particularly linear alkyl C ₁₀-C ₁₅Benzene sulfonic acid sodium salt can be by known as various HF or solid HF method DETAL for example (UOP) method prepares, or uses for example AlCl of other lewis acid catalysts ₃Prepare, or use acid silicon dioxide/aluminum oxide to prepare, or prepare by chlorinated hydrocarbon.These tensio-active agents be can be water-soluble salt or acid, typical chemical formula is RASO ₃M, wherein R is side chain or linear C10-C24 alkyl, preferred C10-C20 alkyl, more preferably C10-C18 alkyl; A is an aryl, preferred benzene or toluene, more preferably benzene unit; Reaching M is H or positively charged ion, and positively charged ion can be the ammonium cation as metallic cation (for example sodium, potassium, lithium etc.), ammonium or replacement.

The surfactant system of laundry detergent composition of the present invention also can comprise about 0.001%, the preferably approximately 1% of surfactant system weight, more preferably about 5%, most preferably about 10% to about 100%, preferably approximately 60%, the more preferably alkylaryl sulfonate surfactants of one or more (preferably two or more mixture) modifications of about 30%, or MLAS preferred surfactant, wherein aryl unit is a phenyl ring, and the chemical formula that it has is:

Wherein L is the acyclic hydrocarbon group part that comprises 6～18 carbon atoms; R ¹, R ², and R ³Each is hydrogen or C independently ₁-C ₃Alkyl, condition are R ¹And R ²Be not connected the unitary end of L; M is the water-soluble cationic with electric charge q, wherein a and b together value to satisfy charge balance.

The total unsettled Application No. 60/053 that proposes on July 21st, 1997,319, act on behalf of case 6766P, the Application No. 60/053 that on July 21st, 1997 proposed, 318, act on behalf of case 6767P, the Application No. 60/053 that on July 21st, 1997 proposed, 321, act on behalf of case 6768P, the Application No. 60/053209 that on July 21st, 1997 proposed, act on behalf of case 6769P, the Application No. 60/053 that on July 21st, 1997 proposed, 328, act on behalf of case 6770P, the Application No. 60/053 that on July 21st, 1997 proposed, 186, act on behalf of case 6771P, the Application No. 60/105 that on October 20th, 1998 proposed, 017, act on behalf of case 7303P, the Application No. 60/104,962 that on October 20th, 1998 proposed, act on behalf of case 7304P, and the Application No. 60/144,519 of proposition on July 19th, 1999, act on behalf of and further narrated these and other suitable MLAS tensio-active agent among the case 7663P.These modified surface promoting agents and conventional surfactants and/or as also be suitable for the present composition at the mixture of the branched chain surfactant of this narration.

In " tensio-active agent and washing composition " (volume I and volume II, Schwartz, Perry and Berch work), provided the example of suitable anion surfactant.Multiple such tensio-active agent is also usually disclosed in 58 row～29 hurdles, 23 hurdles, 23 row of the United States Patent (USP) 3,929,678 that people such as Laughlin delivered on December 30th, 1975.

This composition also can comprise other anion surfactants that washing is useful.This can comprise that the soap salt (comprises for example sodium; potassium; the ammonium salt of ammonium and replacement as single-; two-and triethanolamine salt); C8-C22 primary alkyl or secondary alkyl sulfonate; the C8-C24 alkene sulfonate; as in british patent specification 1; the sulfonated polycarboxylate that the sulfonation of passing through alkaline earth metal citrate cracking product of narration prepares in 082,179; alkyl glycerol sulfonate; the fatty acyl glycerol sulfonate; fatty oil base glycerol vitriol; alkylphenol ethyleneoxy group ether sulfate; alkane sulfonate; alkylphosphonic; isethionate such as acyl-hydroxyethyl sulfonate; the N-acyl taurine salt; the methylamino esilate of fatty acid amide; amber alkyl amide salts and sulfosuccinate; sulfosuccinate monoesters (especially saturated with undersaturated C12-C18 monoesters); sulfosuccinic acid diester (especially saturated with undersaturated C6-C14 dibasic acid esters); the N-acyl sarcosinate; alkyl polysaccharide vitriol such as alkyl dextran glycosides vitriol (non-ionic type non-sulfuric acid salt compound will be narrated hereinafter); branched primary alkyl sulphates; has chemical formula RO (CH ₂CH ₂O) _kCH ₂COO ^-M ⁺Alkyl polyethoxye carboxylate salt (wherein R is the C8-C22 alkyl, and k is 0～10 integer, and M be the positively charged ion of water-soluble salt-formations), reach by the hydroxyethylsulfonic acid esterification with sodium hydroxide neutral lipid acid.Resinous acid and hydrogenated resin acid also suit, as exist in rosin, hydrogenated rosins, the tallol or by its deutero-resinous acid and hydrogenated resin acid." tensio-active agent and washing composition " (volume I and volume II, Schwartz, Perry and Berch work) provided further example.Multiple such tensio-active agent is also usually disclosed in 58 row～29 hurdles, 23 hurdles, 23 row of the United States Patent (USP) of delivering in people's such as Laughlin 30 days December in 1975 3,929,678.

Another kind of useful anion surfactant is so-called dianionic surfactant.These tensio-active agents are the tensio-active agents that have two anionic groups in surfactant molecule at least.The total unsettled United States Patent (USP) series number 60/020 that proposes on June 28th, 1,503 (case 6160P), 60/020,772 (case 6161P), 60/020,928 (case 6158P), 60/020,832 (case 6159P) and 60/020, among 773 (the case 6162P), and the United States Patent (USP) 60/023 of proposition on August 8th, 1996,539 (case 6192P), 60/023493 (case 6194P), 60/023,540 (case 6193P) and 60/023, further narrated some suitable dianionic surfactants among 527 (the case 6195P), these contents are incorporated herein by reference.

C. tablet product

Tablet Betengent product of the present invention is except comprising one or more hydrotropic agents (" tackiness agent ", because they have bonding effect in tablet) outside, one or more preferred components hereinafter and one or more optional conventional detergent additives raw materials also preferably contained.These conventional additives raw materials can comprise that preamble is at liquid product part and/or granular/powder-like product part or one or more solia particle raw materials of hereinafter partly narrating at conventional detergent additives raw material.

The detergent tablet agent prescription contains tackiness agent at least in a small amount usually in composition, so that the globality of bonding effect and promotion tablet to be provided.Be purpose of the present invention, the bonding effect of detergent base particulate starting material characterizes to destroy the required power of tablet, and this tablet is to serve as that the basis extrudes under the contractive condition of control with underproof detergent base.The pharmaceutical dosage forms that the people such as H.A.Lieberman that published in 1989 edit: the method (and relating to radially cracking pressure) that has provided the evaluation tablet strength in tablet the 1st volume.

Discovery adds these hydrotropic agent compounds in particulate starting material prepared in accordance with the present invention, have bonding effect when forming tablet by the compressed microparticles raw material, and splitted performance in outstanding washing-water also is provided simultaneously.Contain this hydrotropic detergent tablet and conventional tablet relatively, under fixation pressure, have higher draw tensile strength, or under lower pressure, have equal tensile strength.

These hydrotropic agents contain the effect except providing sticking, also provide to prevent the detergent composition gelation told about and/or the key component of multiviscosisty here.In the Betengent product of the hydrotropic agent preparation that does not add the present invention's definition, when this product contacts water and dilute with water first, observed gelification in the past.Be not bound by theory, think the cause of gel phenomenon be the particle that contains tensio-active agent with the surfactant concentration of determining washing-liquid or wash-water in during contact water, form sticking tensio-active agent phase (being typically sheet, spherical or hexagonal phase).The viscosity and the dependency between the amount of the sticking tensio-active agent phase that this scope forms of this product-water mixture in observing the critical dilution range of gelification have been found.

Be not bound by theory, think that above-mentioned hydrotropic agent prevents the generation of the sticking tensio-active agent phase that can form in when dilution, because hydrotropic agent can be is effectively interacted with orderly structural sheet surfactant molecule, make their fractures, impel form isotropic low-viscosity table surface-active agent phase.

The present invention also has additional effect, promptly contains " operational boundaries (operating window) " that these special hydrotropic agents have developed detergent tablet.When making detergent tablet with technical scale, operational boundaries relates to the scope of the tap density of detergent tablet.Because a plurality of variablees are arranged, the density of detergent tablet and ideal or preferred density some variation a little in the process of industry-scale manufacturing detergent tablet.Operational boundaries is the density range around the preferred density, just in time is not preferred density in the tablet density of this scope, but still is desirable.Below operational boundaries, density is too low, is charging and the insufficient result of cohesive force in the compression step process, and this tablet is very frangible, breaks in processing and storage process probably.More than operational boundaries, it is too tight that tablet is loaded, and tablet may dissolve in washing lotion and disperse insufficient in washing process.

Except above-mentioned these hydrotropic agents, this detergent tablet also can comprise additional non--the gelation tackiness agent.Non--gelation binder not only provides the adherent effect, also helps dissolving.

If use the non-gelling tackiness agent, suitable non--gelation tackiness agent comprises synthetic organic polymer such as polyoxyethylene glycol, polyvinylpyrrolidone, polyacrylic ester and water-molten acrylate copolymer.The handbook of pharmaceutical excipients second edition has following tackiness agent classification: Sudan Gum-arabic, alginic acid, carbopol preparation, Xylo-Mucine, dextrin, ethyl cellulose, gelatin, guar gum, hydrogenant I type vegetables oil, Natvosol, Vltra tears, liquid glucose, aluminum magnesium silicate, maltodextrin, methylcellulose gum, polymethacrylate, polyvinyl pyrrolidone, sodiun alginate, starch and zein.Most preferred adhesive such as cationic polymers also have active cleaning function in clothes washing, the hexanediamine quaternary ammonium compound of cationic polymers such as ethoxylation, two (hexa-methylene) three amines or other polyethylene amines, toxilic acid acrylate copolymer as five amines, ethoxylation.

Non--the preferred spray of gelation binder materials, the melting temperature that is therefore had suitably below 90 ℃, preferably below 70 ℃, and even more preferably below 50 ℃ other activeconstituentss damage or degraded in the matrix so that can not make.Most preferred non--waterborne liquid tackiness agent (promptly not being the aqueous solution) can be with the form spraying of fusing.But they also can be solid adhesive, be admixed in the matrix by the dried mode that adds, but they have bonding characteristic in tablet.

That detergent tablet prepared in accordance with the present invention will comprise will be about 0.05%～about 5%, preferably approximately 0.1%～about 3%, about basic hydrotropic agent of 0.1%～about 1% most preferably, and two polar groups are isolated mutually by at least 5, preferred 6 aliphatic carbon atoms in this hydrotropic agent.If randomly use non--gelation binder materials, they will be in detergent tablet be that about 0.1%～about 7%, preferably approximately 0.5%～about 5%, more preferably about 1%～about 3% of detergent tablet exists with the usage quantity.If randomly use non--gelification tackiness agent, they will the ratio with non--gelation tackiness agent and distinctive hydrotropic agent tackiness agent be about 2: 1～about 60: 1, preferably approximately existence in 3: 1～about 30: 1, more preferably about 3: 1～about 15: 1 in detergent tablet.

Disintegrating agentAlthough-tablet must have good whole before using, they also must be in use with wash-can be cracked rapidly when water contacts.Can comprise that to impel tablet splitted disintegrating agent be known.The disintegrating agent of various kinds also is known, and they comprise by disintegrating agent expansion causing this class disintegrating agent of splitted.Propose various expansion and disintegration agent in the document, preferably directly mainly pointed to starch, Mierocrystalline cellulose and water-soluble organic polymer.For example at EP-A-466, inorganic expansion and disintegration agent such as wilkinite have also been mentioned in 484.

Some raw material can play the effect of tackiness agent and disintegrating agent.Mention also in the document that disintegrating agent can provide the attached synergy that helps, anti--characteristic of deposition or softening fabrics again.Preferred disintegration dosage is 1～5%.EP-A-466,484 propose that tablet can have the heterogeneous structure that comprises a plurality of zone of dispersions, zone of dispersion is each layer, insert or coating for example.

Tablet is made-can be simply by solids component is mixed, and this mixture of compression prepares detergent tablet of the present invention in the conventional tablet press that uses as the pharmaceutical factory.The preferred main component, particularly gelation tensio-active agent of using particulate form.Any liquid component, for example tensio-active agent or suds suppressor can be admixed in the solia particle composition in a usual manner.

Some compositions such as washing assistant and tensio-active agent can be sprayed-drying in a usual manner, then in suitable pressure lower compression.Preferably used according to the invention less than 100000N, be more preferably less than 50000N even be more preferably less than 5000N and most preferably less than the force compresses tablet of 3000N.Really the most preferred embodiment is to use the force compresses tablet less than 2500N.

Can make the particulate starting material that the present invention is used to produce tablet by any micronize or granulation process.An example of these methods is spraying drying (also flowing or Countercurrent Spray Dryer), and it generally provides 600g/l or is lower than the low bulk density of 600g/l.The particulate starting material of higher density can prepare by granulating and compacting in high shearing batch mixer/granulator or by continuous granulating and debulking methods (for example using Lodige (R) CB and/or Lodige (R) KM mixing tank).Other suitable methods comprise fluidized bed method, compaction method (compaction for example rolls), extrusion molding, and by any particulate starting material of any chemical method as preparations such as flocculation, crystallization transmissions.Independent particle can also be any other particle, granule, spheroid or particulate.

The component of particulate starting material can mix by any ordinary method.Suitable batch mixing in for example concrete mixer, Nautamixer, ribbon blender or any other mixing tank.In addition, blending means can be carried out continuously, and each composition weight is metered on the travelling belt, in one or more rotating cylinders or mixing tank they is mixed.Non--gelation tackiness agent can be directed onto on the mixture of some or all components of particulate starting material.Other liquid components can be directed onto no matter separate or the mixture of the component of premix on.For example spices and white dyes slurry can be sprayed.Trickle isolating glidant (separant such as zeolite, carbonate, silica) can be added in the particulate starting material after spraying tackiness agent.Preferably make that mixture is less to be clamminess handling the end.

Can use any compressing method to make tablet, as compressing tablet, briquetting or extrude preferred compressing tablet.Suitable equipment comprises single stamping machine of standard or rotary press (as Courtoy (R), Korch (R), Manesty (R) or Bonals (R)).It is 20mm～60mm that tablet prepared in accordance with the present invention preferably has diameter, preferably at least 35 reach up to 55mm, and weight is 15g～100g.The tablet height to the ratio of diameter (or width) be preferably greater than 1: 3, more preferably greater than 1: 2.The compaction pressure for preparing these tablets uses requires to be no more than 100000kN/m ², preferably be no more than 30000kN/m ², more preferably no more than 5000kN/m ², even more preferably no more than 3000kN/m ², and be most preferably not exceeding 1000kN/m ²In according to a preferred embodiment of the invention, the density that tablet has is at least 0.9g/cc, more preferably 1.0g/cc at least, and preferably less than 2.0g/cc, be more preferably less than 1.5g/cc even be more preferably less than 1.25g/cc and most preferably less than 1.1g/cc.

Many-synusia agent can be by the known technology manufacturing.

Coating-by making the soundness that coating tablets can further improve the tablet according to the present invention, coating covers non--coated tablet according to the present invention, therefore keeping or further improving dissemination simultaneously, has further improved the mechanical characteristics of tablet.

In one embodiment of the invention, can be coated with the shop to tablet then and make tablet nonhygroscopic, or only with the very slow speed moisture absorption.This coating also is firm, thereby can relax the mechanical shock that tablet stands in processing, packing and transportation, produces no more than very low-level breakage or wearing and tearing.Last preferred coatings is crisp, thereby tablet can be broken when standing stronger mechanical shock.If coating material can disperse under alkaline condition or is favourable by tensio-active agent emulsification easily.This helps being avoided in the form of button fly front washing machine in the process wash(ing)cycle problem of visible resistates is arranged, and avoids having on washing articles the deposition of the particle or the micelle of coating material.

The water-soluble ASTM of following E1 148-87 testing scheme is measured, and the title of ASTM E1 148-87 is " standard method of test of measuring water solubility ".

The suitable coating raw material is a dicarboxylic acid.Shi Yi dicarboxylic acid is selected from oxalic acid, propanedioic acid, succsinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, undecane diacid, dodecanedioic acid, undecane dicarboxylic acid and their mixture especially.The fusing point that the preferred coatings raw material has is 40 ℃～200 ℃.

Coating can make in many ways and implement.Two kinds preferably are coated with laying method and are: a) be coated with the shop with raw material melted; And b) solution with raw material is coated with the shop.

In a), coating material is used in its temperature more than fusing point, and solidifies on tablet.At b) in, use the solution coat coating, solvent seasoning stays adherent coating.Largely insoluble raw material can be administered on the tablet by for example spraying or dipping.Normally, when raw material melted is sprayed onto on the tablet, it will solidify rapidly and form adherent coating.Leave then when tablet floods in raw material melted, cooling causes the rapid solidification of coating material once more fast.Clearly, fusing point at room temperature can not fully solidify at the largely insoluble raw material below 40 ℃, also finds in fact to use fusing point at about raw material more than 200 ℃.Preferred feedstock fused scope is 60 ℃～160 ℃, more preferably 70 ℃～120 ℃.

" fusing point " is meant that raw material becomes the temperature of clear liquid when slowly heating in as kapillary.

Can use the coating of any desired thickness according to the present invention.For more number, form coating with 1%～10%, preferred 1.5%～5% of tablet weight.

The preferred tablet coating is stone, and provides additional strength to tablet.

In a preferred embodiment of the invention, in coating, add disintegrating agent to improve the fragmentation that coating is in the suds.In case contact water, this disintegrating agent will expand and make coating to be broken into small pieces.This will improve the dispersion of coating in washing soln.Disintegrating agent with up to 30%, amount preferred 5%～20%, most preferably 5～10 weight % is suspended in the coating melts.In handbook of pharmaceutical excipients (1986), told about possible disintegrating agent.The suitable example of disintegrating agent comprises starch: starch, the starch Sunmorl N 60S of natural, modification or pre-gelledization; Glue: agaropectin, guar gum, carob bean gum, kuteera gum, pectin, tragacanth gum; Croscarmylose sodium; Polyvinylpolypyrrolidone; Mierocrystalline cellulose; Carboxymethyl cellulose; Alginic acid and salt thereof comprise sodiun alginate; Titanium dioxide silica alkane; Clay; Polyvinylpyrrolidone; Soybean polysaccharide; Ion exchange resin and their mixture.

Tensile strength-according to the shape of the composition and the tablet of starting raw material, can regulate employed pressure, make it not influence tensile strength and the splitting time in washing machine.This method can be used for preparing the even or stratified tablet of any size or shape.

The tensile strength of cylinder shape tablet is corresponding to cracking pressure (DFS) radially, and it is a kind of mode of expressing tablet strength, and is determined by following equation:

$=\frac{2F}{\mathrm{\πDt}}$

Wherein F is the maximum, force (newton) that causes fail in tension (fragmentation), is measured by the VK200 tablet hardness tester that Van Kell Industrial Co., Ltd produces.D is that tablet diameters and t are tablet thickness.

(method of pharmaceutical dosage forms: 213～217 pages of tablet the 2nd volumes) preferably radially cracking pressure is at least 25kPa.

This method can be applied to non-cylinder shape tablet similarly, since with the high vertical cross section of sheet be not circular, along vertical with the high direction of sheet and determine tensile strength with the orthogonal direction applied force in tablet side, wherein tablet side and non-circular cross section are vertical thus.

Optional conventional detergent additives composition

Except the component of the invention described above composition, the agent of this cleaning compositions can preferably contain various other annexing ingredients.

(a) Inorganic detergent builders-detergent composition of the present invention also can randomly contain one or more and exceed the above inorganic detergent builders of listed type, and they also play alkali source.These optional inorganic builders can comprise for example silico-aluminate such as zeolite.People such as Corkill have discussed aluminosilicate zeolite and they application as detergent builders more fully in the United States Patent (USP) of delivering on August 12nd, 1,986 4,605,509, incorporated herein by reference in it.Be suitable in this detergent composition also just like those crystalline layered silicates of discussing in this ' 509 United States Patent (USP).If use, can comprise about 2%～15% optional inorganic detergent builders by composition weight meter here.

(b) Enzyme-for the purpose of various fabric washing widely, comprise the removal of albumen-Ji, carbohydrate-Ji or triglyceride level-Ji stain; Prevent to flow out the migration of dyestuff; Restore with fabric, can comprise enzyme in the prescription here.Think and add the performance that above-mentioned distinctive hydrotropic agent will improve enzyme in the detergent composition.This is because hydrotropic agent increases the dissolution rate of detergent composition, and enzyme contact water and the speed that is activated also will increase, and the corresponding washing advantage that the enzyme that is activated provides also will increase.In water-based and non--aqueous detergent composition, all can see this behavior.

The enzyme that adds comprises proteolytic enzyme, amylase, lipase, mannase, cellulase and peroxidase and their mixture.The enzyme that also can comprise other types.They can be from any suitable origin, as originates from plant, animal, bacterium, fungi and yeast.Yet several factors such as pH-activity and/or optimum stabilization are depended in their selection, and thermostability is with respect to stability of activated detergent, washing assistant etc.At this one side enzyme preferred bacterium or fungi, as bacterial amylase and proteolytic enzyme, and fungal cellulase.

Usually the amount that adds enzyme is that every gram composition is enough to provide weight up to about 5mg, the about organized enzyme of 3mg of 0.01mg～approximately more typically.In other words, this composition will typically comprise the commercial enzyme preparation of about 0.001%～about 5%, preferred 0.01%～1.0 weight %.Proteolytic enzyme exists with this commercial formulation usually, and the amount of existence is enough to provide the activity of 0.005～0.1 Anson unit (AU) for every gram composition.

The suitable example of proteolytic enzyme is a subtilysin, and it derives from special bacterial strain Bacillus subtilus and Bacillus licheniformis.The suitable proteolytic enzyme that another kind derives from bacillus strain has maximum activity at the entire area of pH8-12, and it is by Novo Industries A/S exploitation and sale, and registered trademark is called ESPERASE

Narrated the preparation of this kind of enzyme and similar enzyme in the british patent specification 1,243,784 of Novo Industries A/S.The proteolytic ferment that protein-Ji stain is removed in commercial on sale being suitable for comprises the commodity ALCALASE by name that Novo Industries A/S (Denmark) sells

And SAVINASE

(Denmark), and the commodity MAXATASE by name that sells of International Bio-Synthetics company (Holland) Proteolytic ferment.Other proteolytic enzyme comprise that protease A (consults the european patent application of announcing on January 9th, 1,985 130,756) and proteolytic enzyme B (consulting the european patent application 130,756 that people such as the european patent application series number 87303761.8 that proposed on April 28th, 1987 and Bott announced on January 9th, 1985).

Amylase comprises the amylase of for example middle narration of british patent specification 1,296,839 (Novo Industries A/S), the RAPDASE of International Bio-Syrithetics company

, and the TERMAMYL of NovoIndustries A/S

Mannase comprises following three kinds of mannosans-degrading enzymes: EC 3.2.1.25: beta-Mannosidase, EC 3.2.1.78: the inscribe-1 that ranges " mannase ", the 4-beta-Mannosidase, and EC3.2.1.100:1,4-β-mannobiose glycosides enzyme (IUPAC classification-enzyme nomenclature, 1992 ISBN 0-12-227165-3, Academic Press publishes).

More preferably, detergent composition of the present invention comprises the β-1 that is called mannase, 4-mannosidase (EC 3.2.1.78).Term " mannase " or " polygalactomannan enzyme " expression is called mannosans inscribe-1.4-beta-Mannosidase and has other name according to the formal name of document and is called 'beta '-mannase and inscribe-1, the mannase of 4-mannase definition, its catalytic reaction be any hydrolysis mannosans, gala-mannosans, grape-mannosans, and gala-grape-mannosans in 1,4-β-D-seminose glycosidic bond.Particularly mannase (EC 3.2.1.78) constitutes one group of polysaccharidase, this group enzyme liberating mannosans, its representative can be ruptured and be contained the enzyme of the unitary polysaccharide chain of seminose, the glycosidic link in mannosans, grape-mannosans, gala-mannosans and the gala-grape-mannosans that promptly can rupture.Mannosans be main chain by β-1, the polysaccharide that the seminose that 4-connects is formed; Grape-mannosans is to have more or less the seminose of alternative β-1,4 connection regularly and the polysaccharide of glucose main chain; Gala-mannosans and gala-grape-mannosans is mannosans and the grape-mannosans that has the galactose side of α-1,6 connection.These compounds can be acetylation.

Use the cellulase enzyme in the quick-dissolving detergent composition, the preferred amount that adds is for being enough to provide weight up to about 5mg, the more preferably about organized enzyme of 3mg of 0.01mg～approximately in every gram composition.In other words, this composition preferably comprises the commercial enzyme preparation of about 0.001%～about 5%, preferred 0.01%-1.0 weight %.The spendable cellulase of the present invention comprise bacterium or fungal cellulase the two.The preferred optimal ph that they have is 5～9.5.The United States Patent (USP) 4 that people such as Barbesgoard delivered on March 6th, 1984,435, suitable cellulase is disclosed in 307, it has disclosed the fungal cellulase of being produced by insolens humicola lanuginosa and humicola lanuginosa strain DSM 1800, or by the fungal cellulase that belongs to the Aeromonas microorganisms producing of production of cellulose enzyme 212, and the cellulase that extracts in the hepatopancreas by a nautical mile mollusk (Dolabella Auricula Solander).In GB-A-2.075.028, GB-A-2.095.275 and DE-OS-2.247.832, also disclosed suitable cellulase.In addition, especially being fit to cellulase used herein is at WO 92-13057 (Procter ﹠amp; Gamble company) disclosed cellulase in.Most preferably, the cellulase that is used for the rapidly dissolving washing detergent composition is commercial available from NOVO Industries A/S, and this name of product is CAREZYME

And CELLUZYME

The lipase enzyme that suitable washing composition uses comprises those as English Patent 1,372, the enzyme that Pseudomonadeae microorganism that discloses in 034 such as Pseudomonas stutzeri ATCC 19.154 produce.Also consult the lipase in the Japanese patent application 53,20487 that on February 24th, 1978, the open public examined.This lipase can obtain from Japan Nagoya Amano Pharmaceutical company limited, and trade(brand)name is lipase P AMANO

, hereinafter be called " Amano-P ".Other commercial lipase comprise AMANO-CES

, be to be derived from for example lipase of the sticking look bacillus NRRLB 3673 of var.lipolyticum of sticking look bacillus, commercial Toyo Jozo company from Japanese Tagata obtains; Comprise the sticking look bacillus lipase of U.S. U.S.Biochemical company and Dutch Disoynth company in addition and be derived from the lipase of gladiolus pseudomonas.Preferred lipase used herein be commercial from Novo Industries A/S obtain by fine hair humicola lanuginosa deutero-LIPOLASE

Enzyme (also consulting EPO 341,947).

Peroxidase enzyme and oxygen source such as percarbonate, perborate, persulphate, hydrogen peroxide etc. are used in combination.They are used for " solution bleaching ", prevent that promptly the dyestuff that shifts out from substrate or colorant from moving to the washing operation process on other substrates in the washing soln.The peroxidase enzyme is known in the art, for example comprises horseradish peroxidase, ligninase and halo peroxidase such as chloro-and bromoperoxidase.The detergent composition that contains peroxidase is open in the PCT of for example O.Kirk International Application No. WO 89/099813, and the announcement on October 19th, 1989 of this patent has also transferred Novo Industries A/S.

In the United States Patent (USP) 3,553,139 that people such as McCarty delivered on January 5th, 1971, also disclose large-scale enzyme material and they have been mixed the method for synthetic detergent composition.These enzymes are further disclosed in the United States Patent (USP) 4,507,219 that United States Patent (USP) 4,101,457 that people such as Place delivered on July 18th, 1978 and Hughes1985 delivered at March 26.The method that these prescriptions are mixed in the useful enzyme material of liquid detergent prescription and they is disclosed in the United States Patent (USP) 4,261,868 that people such as Hora delivered on April 14th, 1981.Can use various technology to stablize the enzyme that is used for washing composition.Open and the enzyme stabilization technique of having demonstrated in the european patent application publication number of announcing in United States Patent (USP) 3,600,319 that people such as Gedge delivered on August 17th, 1971 and the 29 days October in 1986 of Venegas 0 199 405, the application number 86200586.5.For example also narrating the enzyme stabilising system in the United States Patent (USP) 3,519,570.Here especially preferably use form with conventional granulates shape enzyme to be added to enzyme in the composition here.These particulate sizes are usually about 100～1,000 micrometer range, more preferably about 200～800 microns, and will be suspended in the liquid phase of whole composition.The enzyme granulate of discovery in the present composition compares according to enzymic activity confining force and other enzyme forms in time, demonstrates welcome especially enzyme stability.Like this, use the composition of enzyme granulate needn't contain conventional enzyme stabilizers, and when enzyme mixes the water-based liquid detergent, must often use stablizer.

(c) Sequestrant-this detergent composition also can be chosen wantonly and contain sequestrant, and sequestrant is used for chelated metal ions for example iron and/or manganese in this detergent composition.This like this sequestrant be fit to composition in metallic impurity form mixture, otherwise impurity tends to reduce the activity of composition component such as peroxygen bleach.Useful chelating agents can comprise aminocarboxylic acid ester, phosphonic acid ester, amido phosphonate, the multifunctional-aromatic chelator of replacement and their mixture.

The aminocarboxylate that contains agent as optional chela comprises ethylene dinitrilotetra-acetic acid salt, N-hydroxyethyl-quadrol triacetate, triglycollamic acid salt, ethylenediamine tetrapropionic acid(EDTP) salt, Triethylenetetramine (TETA) six acetate, diethylenetriamine five acetate, ethylenediamine disuccinate and ethanol Diglycocol.An alkali metal salt of preferred these raw materials.

If allow to contain low-level at least total phosphorus in the detergent composition, amido phosphonate also suits to be used as sequestrant in the present composition, it comprises that ethylenediamine tetraacetic (methylene radical-phosphonium salt) does not contain alkyl or kiki alkenyl group more than about 6 carbon atoms as preferred these amino phosphonates do of DEQUEST..

Preferred sequestrant comprises hydroxyl-ethyl di 2 ethylhexyl phosphonic acid (HEDP), diethylenetriamine five acetic acid (DTPA), ethylenediamine disuccinic acid (EDDS) and pyridine dicarboxylic acid (DPA) and their salt.Certainly, in using this cleaning compositions/bleached woven fabric process, sequestrant also can play the effect of detergent builders.If use, can contain about 0.1%～4% sequestrant by this composition weight meter.More preferably sequestrant will contain about 0.2%～2% of this detergent composition weight.

(d) Suds suppressor-because the concentration height of detergent composition, foam inhibition effect has special importance in the present invention.United States Patent (USP) 4,489 has very at length been narrated the use of suds suppressor in " high density cleaning course " in 455 and 4,489,574.

The various widely raw materials that have as suds suppressor.Those skilled in the art understand suds suppressor well.Consult for example 430～447 pages of (JohnWiley ﹠amp of the complete works of third edition the 7th volume of Kirk Othmer chemical industry; Sons company publishes, 1979).One class suds suppressor of particularly important comprises mono carboxylic lipid acid and soluble salt thereof.Consult the United States Patent (USP) 2,954,347 of the Wayne St.John that delivers September 27 nineteen sixty.Be used as the hydrocarbyl chain that suds suppressor mono carboxylic lipid acid and salt thereof typically have 10～about 24 carbon atoms, preferred 12～18 carbon atoms.Suitable salt comprises an alkali metal salt such as sodium, potassium and lithium salts and ammonium and alkanol ammonium salts.

This detergent composition also can contain non--tensio-active agent suds suppressor, for example comprise: the mixture of high-molecular weight hydrocarbon, N-alkylation aminotriazine, single-stearic acyl phosphoric acid salt, silicone suds suppressor, secondary alcohol (for example, 2-alkyl chain triacontanol) and these alcohol and silicone oil.In the United States Patent (USP) of delivering on May 5th, 1981 as people such as Gandolfo 4,265,779, narrated the hydro carbons suds suppressor.This area has been understood silicone suds suppressor well, has delivered people's such as Gandolfo United States Patent (USP) 4,265,779 and the Starch that announces February 7 nineteen ninety in for example on May 5th, 1981, and is open in the european patent application 89307851.9 of M.S.The mixture of pure and mild silicone oil is at United States Patent (USP) 4,798,679,4,075,118 and EP 150,872 in state.

The additional example of above-mentioned suds suppressor can find in the temporary patent application of Pramod K.Reddy, and this application proposed on November 6th, 1998, and title is " hydrophilic index that contains the water-based liquid laundry detergents composition of LAS ", files in patent cooperation, P﹠amp; G case 7332P, series number 60/107,477, its content is incorporated herein by reference.

Preferred particulate foam control agent used herein contains siloxanes defoaming compounds, organic raw material and solid support material, and wherein siloxanes defoaming compounds and organic raw material are deposited on the solid support material.Preferred local products starch of solid support material or zeolite.The siloxanes defoaming compounds is selected from poly-diorganosiloxane, solid silica and their mixture.Preferred organic raw material is selected from:

(a) at least a have the lipid acid that contains 12～20 carbon atom carbochains, and the melting range of said organic raw material is 45 ℃～80 ℃ and water insoluble:

(b) at least a have a Fatty Alcohol(C12-C14 and C12-C18) that contains 12～20 carbon atom carbochains, and the melting range of said organic raw material is 45 ℃～80 ℃ and water insoluble;

(c) mixture of at least a lipid acid and a kind of Fatty Alcohol(C12-C14 and C12-C18) respectively has the carbochain that contains 12～20 carbon atoms, and the melting range of said organic raw material is 45 ℃～80 ℃ and water insoluble;

(d) melting range is 50 ℃～85 ℃ the organic raw material that contains glycerol fatty acid monoester, and this lipid acid has the carbochain that contains 12～20 carbon atoms; And

(e) dispersed polymeres; And their mixture.

Preferred dispersed polymeres is selected from multipolymer, polyacrylic ester and their mixture of vinylformic acid and toxilic acid.

Spendable silicone suds suppressor known in the art is the people's such as Gandolfo that for example deliver on May 5th, 1981 United States Patent (USP) 4,265,779 and the Starch that announces February 7 nineteen ninety, disclosed suds suppressor in the european patent application 89307851.9 of M.S.Silicone antifoam agent and foam control agent in the granular detergent composition disclosed in people's such as Bartolotta United States Patent (USP) 3,933,672 and the people's such as Baginski that delivered on March 24th, 1987 United States Patent (USP) 4,652,392.Siloxanes suds suppressor example used herein be the particulate foam control agent press down the bubble degree, basic composition is of particulate foam control agent:

(a) be about 20cs～about 1 at 25 ℃ of fluid viscosities, the polydimethylsiloxane fluid of 500cs;

(b) per 100 weight part (CH ₃) ₃SiO _1/2In the silicone resin (i) that the unit is formed about 5～about 50 parts of SiO are arranged ₂The unit, SiO ₂Unit and (CH ₃) ₃SiO _1/2Ratio be 0.6: 1～about 1.2: 1; And

(c) about 1～about 20 parts of solid silica gels are arranged in (i) of per 100 weight parts.

In the United States Patent (USP) of delivering people's such as Brown 9 days June in 1998 5,762,647, very at length narrated and be suitable for other suds suppressor of the present invention.

(e) Dye transfer inhibitor and other fabric care compositions-the present composition also can comprise one or more raw materials, and these raw materials can effectively suppress the migration of dyestuff from a fabric to another in cleaning process.In containing the liquid phase of non-aqueous tensio-active agent or in the solia particle raw material, all can comprise these reagent.

General this dye transfer inhibitor comprises multipolymer, manganese phthalocyanine, peroxidase and their mixture of polyvinyl pyrrolidone polymers, N-oxidation polyamines polymkeric substance, N-vinyl pyrrolidone and N-vinyl imidazole.That the amount that comprises these reagent by composition weight meter typically is is about 0.01%～about 10%, preferably approximately 0.01%～about 5%, and more preferably about 0.05%～about 2%.

More specifically, here use preferred N-oxidation polyamines polymkeric substance to contain following structural chemistry formula unit: R-Ax-P, wherein P is a polymerizable unit, can be attached on the two unit with a part or the N-O group that N-O group or N-O group can form polymerizable unit on this unit; A be down a kind of in the array structure :-NC (O)-,-C (O) O-,-S-,-O-,-N=; X is 0 or 1; And R is aliphatics, ethoxylated fat family, aromatic series, heterocycle or alicyclic group or any their combination, can be the part of these groups with the nitrogen or the N-O group of N-O group on this group.Preferred N-oxidation polyamines is that wherein R is the compound of heterocyclic group, as pyridine, pyrroles, imidazoles, tetramethyleneimine, piperidines and their derivative.

The N-O group can be represented with following general structure:

R wherein ₁, R ₂, R ₃Be aliphatics, aromatic series, heterocycle or alicyclic group or their combination; X, y and z are 0 or 1; And the nitrogen of N-O group can be attached on the above-mentioned group or forms the part of above-mentioned group.PKa＜10 that the amine oxide unit of N-oxidation polyamines has, preferred pKa＜7, more preferably pKa＜6.

Any main polymer chain all can use, as long as formed amine oxide polymers is water miscible and has the dye migration rejection characteristic.The example of suitable polymer blend main chain has polyethylene, polyalkylene, polyester, polyethers, polymeric amide, polyimide, polyacrylic ester and their mixture.These polymkeric substance comprise random or segmented copolymer, and wherein a kind of monomer type is the N-amine oxide, and other monomer types are a kind of N-oxide compounds.It is 10: 1～1: 1 to the ratio of N-amine oxide that the N-amine oxide polymers typically has amine, 000,000.Yet the quantity that the amine oxide group exists in oxidation polyamines polymkeric substance can change by the N-oxidation of suitable copolymerization or suitable degree.Can obtain the almost oxidation polyamines of any polymerization degree.Molecular-weight average is typically 500～1,000,000 scope, more preferably 1,000～500,000, most preferably 5,000～100,000.

The useful most preferred N-oxidation polyamines of this detergent composition is poly-(4-vinyl-N-pyridine oxide), and its molecular-weight average is about 50,000, and the ratio of amine and N-amine oxide is about 1: 4.The preferred raw material of this class is known as " PVNO ".

Can further find suitable dye transfer inhibitor in the people's such as Panandiker that deliver in November 14 nineteen ninety-five the United States Patent (USP) 5,466,802, its content is incorporated herein by reference.

Except dye transfer inhibitor, the present invention further comprises the additive reagent that the fabric nursing function is provided.As mentioned above, additional these reagent may be necessary, because the high density of washing composition may be damaged clothing and the fabric that contacts with the water-based washing soln in the water-based washing soln that the present invention uses.

The present invention also can comprise some raw materials like this, and these raw materials are added in the scouring agent product, make they itself with combine with the fabric of this product washing and the fiber of textiles, thereby make the tendency reduction that the outward appearance of the fabric/textile that is washed goes bad or minimize.Certainly, the additional raw material of any this Betengent product should be able to be of value to the outward appearance and the globality of fabric, can exceedingly not hinder the ability of its expectation function of scouring agent Product Fulfillment.The benefit of this appearance of fabrics comprise as improvement be washed fabric whole outward appearances, reduce bead and wearability etc. is not faded, improved to nappy formation, protection color.

A kind of such fabric care agent is 30 polymines, PEI 600 E20, it especially play a part to prevent dyestuff from the clothing surface transport to the water-based washing soln, but also provide other fabric nursing effects, the chemical general formula that it has is:

Wherein B is that the polymine main chain prolongs by ramose.E is the ethyleneoxy group unit with following chemical formula:

-(CH ₂CH ₂O) _mH

Wherein the mean value of m is about 20.Here mean value 20 refers to enough oxyethane or other suitable reactants and the reaction of polymine starting raw material, makes the degree of the complete ethoxylation to 20 in each a N-H unit oxyethyl group.Yet those skilled in the art recognizes that the unitary hydrogen atom of some N-H will be replaced less than 20 ethoxy unit and some will be replaced by the ethoxy unit more than 20, so the mean number of ethoxylation is 20.

The unit that constitutes poly-alkylene imines main chain is primary amine, secondary amine and tertiary amine unit.The primary amine unit has following chemical formula:

H ₂N-CH ₂CH ₂]-and-NH ₂

It is the end group that stops main chain and any side chain; The secondary amine unit has following chemical formula:

Its hydrogen atom is replaced by average 20 ethyleneoxy group unit after modification; And the tertiary amine unit has following chemical formula:

It is the tapping point of main chain and time chain, and B represents that chain structure prolongs by ramose.The tertiary amine unit does not have can substituted hydrogen atom, and therefore can not be replaced and modification by the ethyleneoxy group unit.In polyamine main chain forming process, cyclic action can occur, therefore in original poly-alkylene imines main chain mixture, may have a certain amount of cyclic polyamine.With the linear and poly-same mode of alkylene imines of side chain, each primary amine of ring-type alkylene imines and secondary amine unit carry out modification by adding alkylidene group oxygen base unit.

The numerical value that index w, x and y have makes that the molecular-weight average before the polymine backbone modification is about 600 dalton.In addition, those skilled in the art generally acknowledge must stop each side chain with the primary amine unit, and therefore the value of index w is y+1 when not having the cyclic amine main chain to exist.Each ethylidene main chain-NCH ₂CH ₂-unitary molecular-weight average is about 43 dalton.

Polyamine of the present invention for example can prepare by the polymerization of ethylene imine in the presence of catalyzer such as carbonic acid gas, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid etc.The United States Patent (USP) of delivering in people's such as Ulrich December 5 nineteen thirty-nine 2,182,306, the United States Patent (USP) of delivering 8 days Mays in 1962 of people such as Mayle 3,033,746, the United States Patent (USP) 2 delivered on July 16th, 1940 of people such as Esselmann, 208,095, the United States Patent (USP) of delivering September 17 nineteen fifty-seven of Crowther 2,806,839 and the United States Patent (USP) 2 delivered on May 21 nineteen fifty-one of Wilson, disclose the effect method for preparing these polyamine main chains in 553,696, full content is incorporated herein by reference.

Other suitable fabric care agents that are used for this detergent composition comprise dye maintenance polymers.An example of this polymkeric substance is imidazoles-epichlorohydrin adducts:

(idealized structure)

The imidazoles that it has: the ratio of Epicholorohydrin is 1.36: 1.Exercise question people such as Rajan K.Panandiker is in the total unsettled provisional application of " laundry detergent composition of band cationic charge dye maintenance polymers ", further dye maintenance polymers and dye maintenance parameter testing have been narrated, this application proposed on March 25th, 1999, had P﹠amp; G case 7488P and series number 60/126,074, its content is incorporated herein by reference.As mentioned above, these dye maintenance polymers also provide whole fabric nursing functions except that the color care protection.

(f) Thickening material, viscosity control agent and/or dispersion agent-this detergent composition also can randomly contain polymer raw material, keeps the ability of its solia particle ingredients suspension in order to improve composition.This like this raw material can play the effect of thickening material, viscosity control agent and/or dispersion agent.This raw material often is the polymeric polycarboxylate, but can comprise other polymer raw materials such as polyvinylpyrrolidone (PVP) or polyamide resin.

Polymeric polycarboxylate raw material can prepare unsaturated monomer optimization acid form monomer by the polymerization or the copolymerization of suitable unsaturated monomer.The unsaturated monomer carboxylic acid that polymerizable forms suitable polymeric polycarboxylate comprises vinylformic acid, toxilic acid (or maleic anhydride), fumaric acid, methylene-succinic acid, equisetic acid, methylfumaric acid, twists health acid and methylene radical propanedioic acid.Have not carboxylic monomer fragment such as vinyl methyl ether, vinylbenzene in these polymeric polycarboxylates, ethene etc. suit, and need only about 40% of the no more than polymer weight of these segmental content.

Shi Yi polymeric polycarboxylate can be derived by vinylformic acid and obtains especially.Here useful this vinylformic acid-based polyalcohol is water-molten polyacrylic salt.The molecular-weight average of this acid-based polymer is preferably in about scope of 2,000～100,000, and is more preferably about 2,000～10,000, even more preferably about 4,000～7,000, and most preferably about 4,000～5,000.This acrylate copolymer water-molten salt can comprise as an alkali metal salt.Such soluble polymer raw material is known.For example, this type of use polyacrylic ester in detergent composition is disclosed in the United States Patent (USP) 3,308,067 that deliver the 7 days March in 1967 of Diehl.This raw material also can be finished the function of washing assistant.

Other suitable suitable polymer blend raw materials as thickening material, viscosity control agent and/or dispersion agent comprise: the polymkeric substance of castor oil derivative, urethane derivative and polyoxyethylene glycol.

If use, the degree that optional thickening material, viscosity control agent and/or dispersion agent exist in this composition is about 0.1%～4 weight %.More preferably this raw material can contain about 0.1%～2% of this detergent composition weight.

(g) The deposition agent of clay dirt remover/anti--again-the present composition also can randomly contain and has that the clay dirt is removed and anti--amine of the water of deposition characteristics-dissolubility ethoxylation again.If use, can contain about 0.01%～about 5% by composition weight meter decontamination material here.

Most preferred dirt removes and anti--and deposition agent is the tetren of ethoxylation again.Further narrated the example of the amine of ethoxylation in the United States Patent (USP) 4,597,898 of the VanderMeer that delivers on July 1st, 1986.Another organizes preferred clay dirt remover-anti redeposition agent is the cation compound that discloses in the european patent application 111,965 of the Oh that announces on June 27th, 1984 and Gosselink.The deposition agent of other spendable clay dirt removers/anti--again is included in the amine polymer of disclosed ethoxylation in the european patent application 111,984 of the Gosselink that announced on June 27th, 1984; Disclosed amphoteric ion polymer in the european patent application 112,592 of the Gosselink that announces on July 4th, 1984; With disclosed amine oxide in the United States Patent (USP) 4,548,744 of the Connor that delivered on October 22nd, 1985.The preferred compound of removing the clay dirt comprises the quaternised amine of ethoxylation.The preferred quaternised amine raw material of ethoxylation is selected from the compound with following chemical general formula:

Wherein each x independently less than about 16, preferably approximately 6～about 13, more preferably about 6～about 8, or wherein each x independently greater than about 35.Being suitable for those raw materials as defined above of the present invention can be available from German BASF AG and Witco chemical company.

Determined that degree of ethoxylation is important to the viscosity of the final detergent composition of narration here.Especially for following general structural formula:

When x less than about 13 the time, the raw material that the quaternized amine of this ethoxylation is removed the clay dirt can be used as liquid and is added in the liquid heavy-duty laundry detergent composition of the present invention, and does not cause unwelcome multiviscosisty under low temperature.Equally, when the identical and degree of ethoxylation of structure greater than about 35 the time, promptly when x greater than about 35 the time, the raw material of these higher degree of ethoxylation can be used as that infusible stable solid adds prescription under high temperature, and does not cause the multiviscosisty of product under the low temperature.

Will of course be appreciated that and in this composition, can randomly use other conventional fluorescent brightening formulation compounds that so that fabrics in general " brightness " effect to be provided, but not real dye migration suppresses effect.This application is that conventional reaching understood by fine to detergent formulation.

Also can in this composition, use the deposition agent of other clay dirt removers known in the art and/or anti--again.It is another kind of that preferred resisting-deposition agent comprises carboxymethyl cellulose (CMC) material again.Fine these materials of understanding in this area.

(h) The liquid bleach activatorIt is the bleach activator of liquid that-detergent composition of the present invention also can randomly contain in room temperature, and it is added in the liquid phase of this detergent composition with liquid form.One of this liquid bleach activator is a Vanay, and it is used as solvent in the composition stores process, but is exercised the function of bleach activator by peroxidation in being discharged into wash water solution the time.Other examples of bleach activator comprise Triethyl citrate acetate (ATC) and nonanoyl Valerolactim.The liquid bleach activator dissolves in this composition liquid phase.

(i) Brightener, dyestuff and/or spices-detergent composition of the present invention also can randomly contain conventional brightener, bleaching catalyst, dyestuff and/or spices.Certainly these brighteners, silicone oil, bleaching catalyst, dyestuff and spices must be in water-based or non--waterborne liquid environment and right and wrong compatible-reactive with other composition component.If exist, brightener, dyestuff and/or spices will typically contain about 0.0001%～2% by composition weight meter here.

(j) Structural elasticity reagentThat-liquid detergent compositions of the present invention also can contain is about 0.1%～5%, the solia particle raw material of the fine dispersion of preferably approximately 0.1%～2 weight %, can comprise for example mixture of carbon, SD-3 bentonite, clay or these raw materials of pyrogenic silica, titanium dioxide, insoluble carbonate, fine dispersion of silicon-dioxide.Clay is that those skilled in the art understand very much, can commercial utilization such as the product of Rheox company.The trickle particulate starting material of this class plays structural elasticity reagent in product of the present invention.The mean particle size scope that these raw materials have is about 7～40 nanometers, more preferably about 7～15 nanometers.The specific surface area scope that these raw materials have is about 40～400m ²/ g.

Here the elasticity reagent raw material of fine dispersion does not increase the transportation stability that product viscosity is improved the liquid detergent product by the elasticity that increases tensio-active agent-structure liquid phase.This high frequency that makes product to resist and may run in the transportation is vibrated, and makes it can not stand the unwelcome settled structure deteriorate of product that causes.

When using titanium dioxide, this raw material also makes the suspended particulates raw material in this detergent composition present pure white look, and this effect has been improved whole outward appearances of product.

(k) Microsphere-the present invention can use microsphere.Suitable microsphere can be made with one or more water-insoluble raw material, and raw material is selected from: polymkeric substance, silicon-containing material, stupalith and their mixture.For microsphere further is discussed, consult Kirk-Othmer chemical industry complete works, the third edition, the 16th volume, 628-651 page or leaf " microencapsulation " (John Wiley ﹠amp; Sons publishes, 1979), this content is incorporated herein by reference.

Polymeric microspheres of the present invention is preferably made by water-insoluble raw material, and water-insoluble raw material is selected from thermoplastics, vinyl cyanide, methacrylonitrile, polyacrylonitrile, polymethacrylonitrile and their mixture.The present invention contains silica microsphere and is preferably made by the silicon-containing material that one or more are selected from glass.Preferred especially borosilicate glass.

Commercial available microsphere is that employing Sweden Akzo-Nobel company logo is EXPANCEL Pq Corp.'s commodity are called PM6545, PM6550, PM7220, PM7228, EXTENDOSPHERES

, LUXSIL

, Q-CEL , SPHERICEL

With the Malinckrodt company logo be ALBUMEX

Product.

Suitable microsphere example can find in people's such as Broeckx total unsettled temporary patent application with the further content of liquid detergent that contains microsphere, the title of this application is " the stable non--water-based liquid laundry detergents that comprises low-density particles ", has P ﹠amp; G case 7417P, interim series number proposed on February 10th, 60/119,555,1999, and its content is incorporated herein by reference.

Except the above-mentioned type microsphere, be used for the microsphere that the present invention suits also can wash by being dissolved in-biomaterial (as starch and protein) of water makes, this content is very at length open in people's such as Sadlowski total unsettled temporary patent application, the title of this application is the low-density filler particles of water " non-aqueous liquid detergent and dissolving in washes-", P﹠amp; G case 7707P, on August 10th, 1999 submitted to, and its content is incorporated herein by reference.

The microsphere that uses of the present invention can be used as and encloses central core by detergent component basically and formed the particulate center in addition.The catalogue of these components-does not exclusively comprise organic and inorganic builders raw material, alkali source raw material and other coating ingredients.Describe the microsphere of band coating in people's such as Aouad total unsettled temporary patent application in detail, the title of this application is " have to dissolve in and wash-the non-aqueous liquid detergent of low density filler particulate of water ", P﹠amp; G case 7708P, on August 10th, 1999 submitted to, and its content is incorporated herein by reference.In the people's such as Sadlowski that above introduce total unsettled provisional application, also discussed the microsphere of band coating, this application P﹠amp; The G case number is 7707.

(i) Effervescent-tablet also comprises effervescent in another preferred embodiment of the present invention.

Here effervescive definition is meant that the chemical reaction between solvable acid source and the alkaline carbonate generates carbon dioxide, causes bubble to be emitted by liquid, that is:

C ₆H ₈O ₇+3NaHCO ₃→Na ₃C ₆H ₅O ₇+3CO ₂+3H ₂O

The further example of acid plus carbonate source and other effervescent systems can be at (pharmaceutical dosage forms: find 287～291 pages of tablet the 1st volumes).

Can add effervescent except detergent ingredients in the tablet mixture.In detergent tablet, add the splitting time that effervescent has been improved tablet.The amount of preferred effervescent is 5～20% of a tablet weight, and most preferably 10～20%.Preferred effervescent adds as the agglomerate or the constrictor of variable grain, and does not add as spacer particles.

Because the gas that the tablet effervesce causes, tablet can have higher D.F.S. and still have the splitting time identical with there not being the effervescive tablet.When effervescent tablet keeps when not having the identical D.F.S of effervescive tablet, the splitting time of effervescent tablet will be faster.

By using compound such as sodium-acetate or urea that further dispersion aids can be provided.Also can be at the pharmaceutical dosage forms that people such as H.A.Lieberman edit: the catalogue of finding suitable dispersion aids among the tablet first roll second edition ISBN 0-8247-8044-2.

The effervescent system can comprise bronsted lowry acids and bases bronsted lowry, as citric acid and sodium bicarbonate; And/or the effervescent system can comprise enzyme, as catalase and/or peroxidase and peroxide source such as hydrogen peroxide.

(m) Tackiness agent-non-gelling tackiness agent can be incorporated in the particle that forms tablet, so that further help dissemination.

As using the non-gelling tackiness agent, suitable non--gelation tackiness agent comprises the synthetic organic polymer, as polyoxyethylene glycol, polyvinylpyrrolidone, polyacrylic ester and water-molten acrylate copolymer.Following tackiness agent classification is arranged: Sudan Gum-arabic, alginic acid, carbopol preparation, Xylo-Mucine, dextrin, ethyl cellulose, gelatin, guar gum, I type hydrogenant vegetables oil, Natvosol, Vltra tears, Liquid Glucose, aluminum magnesium silicate, maltodextrin, methylcellulose gum, polymethacrylate, polyvinyl pyrrolidone, sodiun alginate, starch and zein in the handbook of pharmaceutical excipients second edition.Most preferred tackiness agent also has active cleaning function in clothes washing, be the hexanediamine quaternary ammonium compound of ethoxylation, two (hexa-methylene) triamine or other polyethylene amines as five amine, ethoxylation, toxilic acid acrylate copolymer as cationic polymers.

Non--the preferred spray of gelation binder materials, the melting temperature that is therefore had suitably below 90 ℃, preferably below 70 ℃, and even more preferably below 50 ℃ other activeconstituentss damage or degraded in the matrix so that can not make.Most preferred non--waterborne liquid tackiness agent (promptly not being the aqueous solution) can be with the form spraying of fusing.But they also can be solid adhesive, be admixed in the matrix by the dried mode that adds, but they have bonding characteristic in tablet.

Preferably using the amount of non--gelation binder materials to be 0.1～15% of composition, more preferably below 5%, is the active raw material of not doing washing if reach tackiness agent, especially is below the 2 weight % of tablet.

Preferably avoid using the gelation tackiness agent of liquid or fusing form, as nonionic surface active agent.Nonionic surface active agent and other gelation tackiness agents are not excluded outside composition, but preferably are worked in the detergent tablet as the particulate starting material component rather than with liquid.

(n) Clay-be used for instant compositions to provide the clay mineral of softening properties can be described to the distensible clay of three-layer, promptly aluminium-silicate and britesorb have the loading capacity that is at least the 50meq/100g clay.The term " distensible " that is used to illustrate clay relates to enlargement or expansible ability behind the layered clay structure contact water.Used herein three-expansible clay of layer is those raw materials of the terre verte that classifies as on the geology.

Terre verte-type clay that two kinds of completely different classifications are arranged: have aluminum oxide in the silicate crystal lattice of first kind of terre verte; There is magnesium oxide in the silicate crystal lattice of the second class terre verte.Chemical general formula to aluminum oxide and magnesium oxide type smectic clays is respectively Al ₂(Si ₂O ₅) ₂(OH) ₂And Mg ₃(Si ₂O ₅) (OH) ₂Will be appreciated that the treatment process that the scope of water of hydration in the above-mentioned chemical formula can be subjected to according to clay and change.This use to smectic clays among the present invention is inessential, and the expandable characteristics of hydrated clay is by the lattice silicate structures shape.In terre verte crystalline lattice, can occur atom in addition and be replaced, simultaneously coexistence metallic cation such as Na in water of hydration by iron and magnesium ⁺, Ca ⁺⁺And H ⁺, so that charge balance to be provided.Unless hereinafter indicate, this here positively charged ion replaces substantial for the use right and wrong of clay, because therefore the physical property of needed clay does not change basically.

Here the useful further feature of the distensible aluminium-silicate of three-layer is the dioctahedral type crystal lattices, and distensible three-layer Magnesium Silicate q-agent has the trioctahedron crystal lattices.

As mentioned above, the clay that the present composition uses contains the cation balance ion, as hydrogen, sodium ion, potassium ion, calcium ion, magnesium ion etc.Custom is that clay is distinguished on the basis with a kind of positively charged ion main or unique absorption, and for example the sodium clay is that the positively charged ion that wherein absorbs mainly is a kind of clay of sodium.The positively charged ion of this absorption can participate in aqueous solution in the cationic permutoid reaction that exists.The permutoid reaction that typically relates to terre verte-type clay is represented by following equation:

Smectic clays (Na)+NH ₄OH → smectic clays (NH ₄)+NaOH.

Because monovalent ammonium ion replacement-equivalent sodium in above-mentioned balanced reaction, therefore (meq./100g) measures cation exchange capacity (being called " base-exchange capacity " sometimes) to custom with the milligramequivalent number of every 100g clay exchange.Available several different methods is measured the cation exchange capacity of clay, comprise electrodialysis and ammonium ion exchange, follow titration or adopt methylene blue method, the 264-265 page or leaf has been stated whole these methods fully in the Grimshaw work " clay chemistry and physics " of Interscience publication (1971).The factor that the cation exchange capacity of clay mineral relates to such as the expandable characteristics of clay, to small part by the clay electric charge of crystalline network decision etc.The loading capacity of clay changes in big scope, is about 2meq/100g to being about 150meq/100g or bigger to some montmorillonitic clay from kaolin.The loading capacity that illite clay has is in certain lower scope, i.e. the about 26meq/100g of illite clay average out to.

Illite and kaolinite clay because their loading capacity is low relatively, are not the clays that instant compositions is preferably used.As mentioned above, illite and kaolinite clay are the main ingredient that constitutes the clay dirt really, rely on this composition to remove from fabric face.Yet find terre verte as having the nontronite that loading capacity is about 70meq/100g, and loading capacity is that instant compositions is useful greater than the polynite of 70meq/100g, they are deposited on desired ramollescence are provided on the fabric.Therefore, the feature of useful here clay mineral is to have the distensible three-layer terre verte-type clay of loading capacity for about at least 50meq/100g.

Though tend to do not retrained,, as if can obtain favourable softening (the reaching potential dye scavenging effect etc.) function of instant compositions owing to the physical property and the ion exchange property of use clay by theory.This illustrative experiment has shown, and non--distensible clay has kaolin and the illite clay of loading capacity below 50meq/100g as two classes, and the favorable characteristics of clay that instant compositions is used can not be provided.

The smectic clays that this composition uses is all can utilize commodity.These clays comprise for example montmorillonite, rich volchonskoite, nontronite, hectorite, saponite, sauconite and vermiculite.Here clay can utilize various commodity, and Tathagata is from the trade(brand)name Thixogel#1 and the Gelwhite GP of the Georgia of New Jersey Elizabeth Kaolin company; Volclay BC and Volclay#325 from the AmericanColloid company of this state, Illinois Skokie; Black Hills wilkinite BH450 from International Minerals ﹠ Chemical Corp. (US) P.O. Box 207. 1401 South Third Stre; Reach Veegum Pro and Veegum F from R.T.Vanderbilt company.Should admit that the terre verte-type mineral that obtain can comprise the loose mixture of various mineral entity under above-mentioned trade(brand)name.The mixture of this smectite minerals is suitable to be used here.

When using any useful cation exchange capacity at least approximately during the terre verte of 50meq/100g-type clay here, the preferred clay of some kind.For example Gelwhite GP is the smectic clays of very white form, and therefore it is preferred when preparing the detergent composition of white particulate.Contain at least 3% iron (with Fe in the crystal lattices of terre verte-type clay mineral Volclay BC ₂O ₃Expression), having very high loading capacity, is one of effective and the most most realistic clay that is used for laundry composition, and it is preferred from the position of product performance.

Be fit to clay mineral used herein and can show accurate 14 by terre verte

The general knowledge advantage of X-ray diffraction pattern select.The combination that exchange capacity that this feature mode and aforesaid way carry out is measured is for the application of special terre verte-type mineral in the granular detergent composition disclosed herein provides the basis of selecting.

Clay is preferably mainly with the particulate form, and at least 50% (preferably at least 75% or at least 90%) was particle form, and granular size is at least 100mm and up to 1800mm, preferably up to 1180mm, preferred 150～850mm.Preferred particulates medium clay soil amount is at least 50%, usually at least 70% or 90% of a particle weight.

(o) Flocculation agentThe polymkeric substance of-most flocculation clays is the polymkeric substance and the multipolymer of suitable long-chain, derived from monomer such as oxyethane, acrylamide, vinylformic acid, dimethylaminoethyl methacrylate, vinyl alcohol, vinyl pyrrolidone and ethylene imine.Glue also suits as guar gum.

Optimization ethylene oxide, acrylamide or polymerizing acrylic acid thing.If the molecular weight of these polymkeric substance in 100000～1,000 ten thousand scope, then improves the deposition of the clay of softening fabrics significantly.The weight-average molecular weight that preferred these polymkeric substance have is 150000～500 ten thousand.

Most preferred polymkeric substance is poly-(oxyethane).With reference to the standard poly-(oxyethane) of narrow molecular weight distributions, use gel permeation chromatography to be easy to determine molecular weight distribution.

The amount of preferred flocculation agent is 0.5～10% of a tablet weight, most preferably about 2～6%.

Preferred flocculation agent is mainly with the particulate form, at least 50 weight % (preferably at least 75% and most preferably at least 90%) are particle form, the granular size that has for 100mm at least to up to 1800mm, preferably up to 1180mm and 150～850mm most preferably, the amount of flocculation agent is at least 50%, usually at least 70% or 90% of a particle weight in the preferred particulates.

Other components that generally are used for detergent composition and can mix detergent tablet of the present invention comprise sequestrant, dirt releasing agent, anti-soil thing deposition agent, dispersion agent, brightener, suds suppressor, fabric softener, dye transfer inhibitor and spices again.

Should illustrate if raw clay mixes before tablet or the cleaning combination its compression, can reach and improve division or dispersive purpose.For example, contain the tablet that mixes compressed clay before the tablet, mix before the tablet not the tablet of compressed identical raw clay relatively with containing, cracked rapidlyer.In particular for division or the dispersive clay particle of getting help, the size of the employed pressure of compression clay is important.

In addition, compression is used for the remollescent clay and mixes cleaning combination or tablet then, and division that not only is improved or dispersiveness have also been softened fabric well.Preferably clay component compression raw clay obtains.

Preferable methods comprises raw clay with 10MPa at least or even 20MPa or even the step of the pressure compression of 40MPa at least.Finishing of this step is for example to pass through with raw clay with randomly with one or more other composition compressing tablets or roll-type extrusion, form clay tablet or thin slice, preferably then make the clay platelet of compression or the dimension reduction of tablet, form the compression clay particle as milling.This particle can mix tablet or cleaning combination then.

Tabletting method and roll-type extrusion method are known in the art.For example, can be on Lloyd 50K tabletting machine or utilize the Chilsonator roll-type extrusion equipment of Fitzpatrick company to finish the compression of clay.

In order to make the present invention easier to understand, arrange the following example as a reference.Embodiment only is illustrative rather than limits its scope.

Proposing the following example only is illustrative purposes, in any case can not be construed as the restriction to the appended claim scope.

Be used for the abbreviation of embodiment

In detergent composition, the component sign of abbreviation has following meanings:

LAS: linear C11-13 sodium alkyl benzene sulfonate

TAS: tallow alkyl sodium sulfate

C45AS: C14-C15 sodium alkyl sulfate

C45E3S: with the C14-C15 alkylsurfuric acid sodium salt of 3 moles of ethylene oxide condensations

QAS: R2.N+ (CH3) 2 (C2H4OH) is R2=C12-C14 wherein

Soap: by the mixture deutero-linear alkyl carboxylic acid of tallow and coconut fatty acid 80/20

Sodium

Zeolite A: chemical formula is Na ₁₂(AlO ₂SiO ₂) ₁₂27H ₂The hydrated sodium aluminosilicate salt of O

The main granular size scope that has is 0.1～10 micron

(weight is represented with dry weight)

NaSKS-6: chemical formula is d-Na ₂Si ₂O ₅Crystallization stratotype silicate

Citric acid: Citric Acid, usp, Anhydrous Powder

Carbonate: anhydrous sodium carbonate, granular size are 200 μ m～900 μ m

Supercarbonate: anhydrous sodium bicarbonate, particle size dispersion are 400 μ m～1200 μ m

Silicate: amorphous sodium silicate (SiO ₂: Na ₂O=2.0: 1)

Vitriol: anhydrous sodium sulphate

Sal epsom: anhydrous magnesium sulfate

Citrate trianion: trisodium citrate monocalcium salt compound, activity 86.4%, particle size dispersion is

425μm～850μm

MA/AA: 1: 4 multipolymer of toxilic acid/vinylformic acid, molecular-weight average about 70,000

AA: polyacrylic acid sodium polymer, molecular-weight average 4,500

CMC: sodium carboxymethyl-cellulose

Proteolytic enzyme: proteolytic ferment has 4 weight % organized enzymes, as institute among the WO 95/10591

State, sell by Genencor Int.Inc.

Cellulase: cellulolytic enzyme, have 0.23 weight % organized enzyme,

NOVO Industries A/S sells, trade(brand)name Carezyme

Amylase: amylolytic enzyme, have 1.6 weight % organized enzymes,

NOVO Industries A/S sells, trade(brand)name Termamyl 120T

Lipase: lipolytic enzyme, have 2.0 weight % organized enzymes,

NOVO Industries A/S sells, trade(brand)name Lipolase

Perborate: Sodium peroxoborate

Percarbonate: SPC-D

NOBS: nonanoly acyloxy benzene sulfonate, sodium-salt form

NAC-OBS: (the amino hexanoyl of 6-nonanoyl) oxygen base benzene sulfonate

TAED: tetraacetyl ethylene diamine

DTPA: diethylenetriamine five acetic acid

EDDS: the quadrol-N of sodium-salt form, N '-disuccinic acid, (S, S) isomer

Photosensitizers: sulfonation zinc phthalocyanine phthalocyanine is encapsulated in bleaching (I) the dextrin soluble polymer

CHDM: 1,4 cyclohexane dimethanol

Brightener: 4,4 '-two (4-anilino-6-morpholino-1.3.5-triazine-2-yl) amino) Stilbene-2:2 '-

Disulfonic acid disodium salt

HEDP 1,1-hydroxyl ethane di 2 ethylhexyl phosphonic acid

PEGx: polyoxyethylene glycol, molecular weight are x (typically being 4,000)

QEA: two ((C ₂H ₅O) (C ₂H ₄O) _n) (CH ₃)-N ⁺-C ₆H ₁₂-N ⁺-(CH ₃) two ((C ₂H ₅O)-

(C ₂H ₄O)) _n, n=20～30 wherein

SRP: the short block polymer of diethoxyization poly-(1,2-propylene glycol terephthalate)

Siloxanes: the polydimethylsiloxane foam control agent of band siloxanes-alkylidene oxide

Defoamer: make the multipolymer of dispersion agent, said foam control agent to the ratio of said dispersion agent is

10∶1～100∶1

All component concentration provides by composition weight % in the following example.

Liquid product preparation embodiment

Example I

Being prepared as follows of non-aqueous liquid detergent compositions that comprises rich tensio-active agent liquid phase and solid phase:

Weight %

Composition A composition B

The surfactivity 21.27 20.14 of non-ionic type

BPP solvent 18.30 17.33

LAS tensio-active agent 15.83 14.99

The quaternised amine 1.29 1.22 of ethoxylation

Raw clay

Hydrotropic agent 4.80 0.00

Trisodium citrate dihydrate 6.73 6.37

Yellow soda ash 9.89 9.37

Bleach activator 5.94 5.62

Sodium peroxoborate 11.87 11.24

EDDS 1.17 1.11

Duramyl enzyme 0.79 0.87

Carezyme enzyme 0.03 0.03

Proteinase-10 .79 0.75

Defoamer 0.61 0.85

Plastic microspheres 0.51 0.49

Titanium dioxide 0.50 0.47

Brightener 0.20 0.19

PEG 8000 0.40 0.38

Spices 1.72 1.63

Other are 2.16 2.15 years old

Liquid detergent compositions A is prepared in accordance with the present invention, so it contains preferred hydrotropic agent 1,4 cyclohexane dimethanol.Can consult above, liquid detergent compositions B is not except containing water-soluble growth substance and other components thereof balance external a little again, and composition B almost is identical with composition A.

Can easily see the hydrotropic effect of discussing here by the experiment test of measuring liquid detergent compositions dissolution rate in water.

The test of liquid detergent product dissolution rate in water

1. glass beaker is at the about 25 ℃ 3 liters of deionized waters of packing into.

2. in water, put into 5cm magnetic stirrer and conductance electrode.At first at the speed mixing water of 400rpm, and it is constant to keep speed in whole experiment.

3. the sieve cup of a 85ml capacity is placed on the surface of water in the middle of the beaker, and the sieve cup has 60 eye mesh screens, and the mode of placement is to make just in time face on the water of sieve cup top, makes water only not enter the sieve cup by screen cloth from the top.

4. add 1ml liquid detergent product (passing through syringe) very lentamente to sieve cup central authorities.This is T ₀, measure at T ₀The time specific conductivity.

5. with the specific conductivity of regular interval replicate measurement Betengent product-water mixture, as 0.5,1,2,4,6 and 10 minutes.

In due course between after (for example 10 minutes), immerse a mixture and make a liquid detergent product of staying in the sieve cup be added in this product-water mixture and increase stirring velocity by sieving cup.

7. when all prods dissolving and specific conductivity reach steady-state value, said value record is got off.

With above be described in detail " The test of liquid detergent product dissolution rate in water" test this two compositions.With water-immersed electrode tested-when detergent composition solution begins and be transformed into % when dissolving and measure specific conductivity, obtain following result:

Force detergent composition all dissolving and mensuration specific conductivity with stirring at a high speed after 11 minutes:

All dissolvings

100

100

146

100

Dissolving numerical value is by the specific conductivity of measuring during divided by whole dissolvings in the specific conductivity of each independent timing and multiply by 100 and obtain.

Example II

According to being prepared as follows of water-based liquid detergent compositions of the present invention:

Composition C

Component Weight %

C _12-15Alkyl oxide (2.5) vitriol 18.0

C _12-13Alkylethoxylate (9.0) 2.00

C _12-14Glucose amide 3.50

Citric acid 3.00

C _12-14Lipid acid 2.00

CHDM 5.00

MEA is to pH 8

Ethanol 3.0

Propylene glycol 6.0

Dyestuff, spices, brightener, enzyme, sanitas,

Suds suppressor, other small components, water Remaining sum

100％

EXAMPLE III

Being prepared as follows of non-aqueous liquid detergent compositions that comprises the liquid phase of rich tensio-active agent and solid phase:

Weight %

Combination of compositions compositions combination of compositions thing

A B C D E

NaLAS 14.6 14.9 13.9 13.0 14.9

HLAS 0.0 0.0 1.0 1.9 0.0

Nonionic surface active agent 20.6 20.7 20.7 20.7 20.7

Trisodium citrate dihydrate 3.3 3.3 3.3 3.3 3.3

Vinylformic acid maleic acid 2.9 2.9 2.9 2.9 2.9

EDDS 1.2 1.2 1.2 1.2 1.2

Ethoxylation quaternised 1.3 1.3 1.2 1.3 1.3

The amine raw clay

Sodium peroxoborate 11.5 11.5 11.5 11.5 11.5

Bleach activator 2.9 5.8 2.9 2.9 2.9

Triactin 12.5 0.0 12.5 12.5 8.7

Yellow soda ash 9.6 9.6 9.6 9.6 9.6

BPP solvent 9.1 17.8 9.1 9.1 12.0

Hydrotropic agent 3.8 4.8 3.8 3.8 4.8

Acetic acid 0.2 0.0 0.1 0.0 0.0

Proteinase-10 .8 0.8 0.8 0.8 0.8

Duramyl enzyme 0.8 0.4 0.4 0.4 0.4

Mannase 0.2 0.2 0.2 0.2 0.2

Carezyme enzyme 0.1 0.0 0.0 0.0 0.0

Brightener 0.2 0.2 0.2 0.2 0.2

Titanium dioxide 0.5 0.5 0.5 0.5 0.5

PEG 8000 0.5 0.5 0.5 0.5 0.5

Spices 1.7 1.7 1.7 1.7 1.7

Siloxanes 0.7 0.7 0.7 0.7 0.7

Silicone surfactant 0.3 0.3 0.3 0.3 0.3

DC3225

Hydrogenation C16-18 fatty acid sodium salt 0.5 0.5 0.5 0.5 0.5

Other remaining sum remaining sum remaining sum remaining sum remaining sums

Granulous/powder-like product preparation embodiment

Example I

Following is according to composition of the present invention.

	A	B	C	D	E	F	G	H	I
										Spray-dried granules
LAS	10.0	10.0	15.0	5.0	5.0	10.0	-	-	-
										QAS			1.0	1.0			-	-	-
DTPA, HEDP and/or EDDS	0.3	0.3	0.5	0.3			-	-	-
										MgSO 4	0.5	0.5	0.1	-			-	-	-
Trisodium Citrate	-	-	-	3.0	5.0		-	-	-
										Yellow soda ash	10.0	10	15	10	7	10	-	-	-
Sodium sulfate	5.0	5.0	-	-	5.0	3.0	-	-	-
										Water glass 1.6R	-	-	-	-	2.0		-	-	-
Zeolite A	16.0	18.0	20.0	20.0	-	-	-	-	-
										SKS-6	-	-	-	3.0	5.0	-	-	-	-
MA/AA or AA	1.0	2.0	11.0	-	-	2.0	-	-	-
										CHDM	0.5	2.0	2.5	1.5	4.0	1.0	-	-	-
QEA	1.0	-	-	-	1.0	-	-	-	-
										Brightener	0.05	0.05	0.05	-	0.05	-	-	-	-
Silicone oil	0.01	0.01	0.01	-	-	0.01	-	-	-
Agglomerate
										LAS			-	-	-	-	0.2	0.2	0.01
C 45AS			-	-	-	-	2.0	-	1.0
										AE 3			-	-	-	-	-	1.0	0.5
Carbonate			-	-	4.0	1.0	1.0	1.0	-
										Trisodium Citrate			-	-	-	-	-	-	5.0
CFAA					-	-	-	-	-

Citric acid			-	-	-	4.0	-	1.0	1.0
										QEA			-	-	-	2.0	2.0	1.0	-
SRP			-	-	-	1.0	1.0	0.2	-
										Zeolite A			-	-	-	15.0	26.0	15. 0	16.0
Water glass			-	-	-	-	-	-	-
										CHDM	-	-	-	-	-	-	3.0	-	-
										Builder agglomerates
SKS-6	6.0	-	-	-	6.0	3.0	-	7.0	10.0
										LAS	4.0	5.0	-	-	5.0	3.0	-	1.0	12.0
										The dried particulate constituent that adds
Oxysuccinic acid/carbonate (40: 20: 40)	8.0	-	10.0	4.0	-	8.0	-	-	4.0
										QEA	-	-	-	0.2	0.5	-	-	-	-
NACAOBS	3.0	-	-	1.5	-	-	-	2.5	-
										NOBS	-	3.0	3.0	-	-	-	-	-	5.0
TAED	2.5	-	-	1.5	2.5	6.5	-	1.5	-
										LAS (thin slice)	10.0	10.0	-	-	-	-	-	8.0	-
										Spray
Brightener	0.2	0.2	0.3	0.1	0.2	0.1	-	0.6	-
										Dyestuff	-	-	-	0.3	0.05	0.1	-	-	-
AE7	-	-	-	-	-	0.5	-	0.7	-
										Spices	-	-	-	0.8	-	0.5	-	0.5	-
										Dried adding

Citrate trianion	-	-	20.0	4.0	-	5.0	15.0	-	5.0
										Percarbonate	15.0	3.0	6.0	10.0	-	-	-	18. 0	5.0
Perborate	-	-	-	-	6.0	18.0	-	-	-
										Photobleaching	0.02	0.02	0.02	0.1	0.05	-	0.3	-	0.03
Enzyme (cellulase, amylase, proteolytic enzyme, lipase)	1.3	0.3	0.5	0.5	0.8	2.0	0.5	0.1 6	0.2
										Carbonate	0.0	10.0	-	-	-	5.0	8.0	10. 0	5.0
Spices (inclosure capsule)	0.6	0.5	0.5	-	0.3	0.5	0.2	0.1	0.6
										Suds suppressor	1.0	0.6	0.3	-	0.10	0.5	1.0	0.3	1.2
Soap	0.5	0.2	0.3	3.0	0.5	-	-	0.3	-
										Citric acid	-	-	-	6.0	6.0	-	-	-	5.0
Painted carbonate (blue, green)	0.5	0.5	1.0	2.0	-	0.5	0.5	0.5	1.0
										SKS-6	-	-	-	4.0	-	-	-	6.0	-
Filler adds to 100%

The geometric mean particle diameter that the particle of the composition at least 90 weight % of the foregoing description has is that about 850 microns and geometric standard deviation are about 1.2.These compositions have improved aesthetic conceptions, flowability and solubleness unexpectedly.

Tablet product preparation embodiment

Embodiment 1a

I) being prepared as follows of detergent base powder composition A (consulting table 1): whole particulate starting materials of binder composition A are mixed in mixing rotating cylinder, form uniform particle mixture.

Ii) 1 part of polyoxyethylene glycol is sprayed onto among 99 parts of base-material powder composition A, mixes simultaneously.

Iii) make tablet with following manner: the 54g mixture is conveyed in the circular die that diameter is 5.5cm, and with the pressure lower compression of Instron 4464 press at 2.0kN.This tablet tensile strength that obtains under this pressure (or radially cracking pressure) is 19.2kPa.The pharmaceutical dosage forms that 1989 people such as H.A.Lieberman that publish edit: the tablet first roll has provided the method for evaluation tablet strength (being also referred to as radially cracking pressure).

Embodiment 1b

I) prepare same composition A according to method identical among the embodiment 1a.

Ii) 0.9 part of polyoxyethylene glycol and 0.1 part of 1,4 cyclohexane dimethanol are mixed and are sprayed onto among 99 parts of base-material powder composition A, mix simultaneously.

Iii) make tablet according to identical mode described in the embodiment 1a.This tablet tensile strength that obtains under the pressure of 2.0kN (or radially cracking pressure) is 23.6kPa.

According to following detailed composite formula, prepare embodiment 2a～3b in the mode of similar aforesaid method:

Table 1

	Composition A	Composition B	Composition C
					(％)	(％)	(％)
The anionic agglomerate 1	34	34	34
				The non-ionic type agglomerate 2	9.57	9.57	9.57
Stratotype silicate 3	2.7	1.5	1.5
				SPC-D	12.43	12.43	12.43
The bleach activator agglomerate 4	6.48	6.48	6.48
				Yellow soda ash	19.01	18.96	18.46
The EEDS/ sulphate particle 5	0.50	0.50	0.50
				Hydroxyl ethane di 2 ethylhexyl phosphonic acid tetra-na salt	0.8	0.8	0.8
White dyes	0.11	0.11	0.11
				Zinc phthalocyanine sulfonate capsule 6	0.027	0.027	0.027
Soap powder	1.49	0.74	0.74
				Suds suppressor 7	1.8	1.8	1.8
Citric acid	7.51	7.51	7.51
				Proteolytic enzyme	0.8	0.8	0.8
Cellulase	0.16	0.16	0.16
				Amylase	0.61	0.61	0.61
Polyoxyethylene glycol, molecular weight 4000, thin slice	-	1.5	1.5
				LINER ALKYL BENZENE SULPHONIC ACID SOFT 96 sodium salt/di-isopropyl benzene sulfonate 8	1	1	1.5

1: the anionic agglomerate comprises 37% aniorfic surfactant, 2% cationic surfactant, 22% stratotype silicate, 10% acetate, 6% carbonate and 23% zeolite.

2: the non-ionic type agglomerate comprises 24% nonionic surface active agent, 6% ethoxylation hexanediamine quaternary ammonium salt, 40% acetate/zeolite mixture, 20% carbonate and 10% zeolite.

3: stratotype silicate comprises 95%SKS 6 and 5% silicate.

4: the bleach activator agglomerate comprises 81%TAED, 17% vinylformic acid/maleic acid (acid type) and 2% water.

5: quadrol-N, N-disuccinic acid sodium salt/sulphate particle comprises 58% quadrol-N, N-disuccinic acid sodium salt, 23% vitriol and 19% water.

The active zinc phthalocyanine of 6:10% sulfonate capsule.

7: suds suppressor comprises 11.5% silicone oil (available from Dow Coming), 59% zeolite and 29.5% water.

8: LINER ALKYL BENZENE SULPHONIC ACID SOFT 96 sodium salt/di-isopropyl benzene sulfonate comprises 67% linear alkyl benzene sulfonate and 33% di-isopropyl benzene sulfonate.

To be sprayed onto in the above-mentioned detergent base powder according to the tablet binder composition of following combination:

Table 2

	Embodiment 1a	Embodiment 1b	Embodiment 2a	Embodiment 2b	Embodiment 3a	Embodiment 3b
							Powders A	99％	99％
Powder B			98.5％	98.5％
							Powder C					98.5％	98.5％
Polyoxyethylene glycol	1％	0.9％	1.50％	1.35％	1.5％	1.3％
							1,4 cyclohexane dimethanol		0.1％		0.15％		0.2％

Ii) reach the intensity of the described test tablet of other parts of the present invention then according to step I above.

Table 3

	Embodiment 1a	Embodiment 1b	Embodiment 2a	Embodiment 2b	Embodiment 3a	Embodiment 3b
							Tablet tensile strength (kPa)	19.2	23.6	12.4	14.7	16	19

The tensile strength of tablet samples that contains CHDM is greater than in fact same composition but do not contain the CHDM tablet samples of CHDM.

Equally operational boundaries is evaluated:

Table 4

	Embodiment 3a	Embodiment 3b
			Density during tablet hardness 5.5kP	1035	1010
The density of tablet during 15% dosage	1052	1035

((operational boundaries of the tablet samples of width=17g/l) is not roomy than not containing CHDM for the operational boundaries of the tablet samples of width=25g/l) to contain CHDM.

The detergent tablet agent dose of above listing in the table 4 can be tested to determine that the Betengent product amount of distributing in the automatic carrying out washing treatment process is measured in this experiment in the following manner by experiment:

1. nominally each 50 two tablets of tablet that restrain is weighed, is put into Baucknecht then

In the material feeder of WA9850 washing machine, the temperature of supplying with the water of washing machine is set at 20 ℃, and hardness is per gallon 21 grains, and the material feeder water inlet flows-and speed setting is 8l/min.

2. connect washing and will be set in washing procedure 4 (white/coloured, short period) wash(ing)cycle, check the tablet residue weight of staying in the material feeder.

3. dosage percentage ratio resistates amount is determined as follows:

The initial tablet weight in % dosage=residue weight * 100/

Repetitive routine determines that the resistates amount reaches with ten independent basic calculation average residual excess amounts that are measured as for 10 times.

Understand the present invention so in detail, those skilled in the art will know can carry out the various variations that do not deviate from the scope of the invention, and thinks that the content that the present invention is not illustrated the book narration limits.

Claims (9)

1. non-aqueous liquid laundry detergents composition, it comprises:

A) press composition weight meter, 49%～99.95% non--water-based liquid phase that contains tensio-active agent; And

B) press composition weight meter, 1%～50% the particulate starting material that is insoluble to said liquid phase basically, particulate starting material are selected from peroxygen bleach, bleach activator, organic detergent washing assistant, inorganic alkali source, enzyme, brightener, polymkeric substance and their mixture;

C) hydrotropic agent, wherein hydrotropic agent is selected from:

(a) 1,4 cyclohexane dimethanol:

(b) 1, the 6-hexylene glycol:

(c) 1, the 7-heptanediol:

With

(d) their mixture,

And

Wherein composition does not contain any following compounds deutero-quaternary ammonium compound: C _16-18Unsaturated fatty acids, methyldiethanolamine or methyl chloride.

2. according to the non-aqueous liquid laundry detergents composition of claim 1, wherein the further feature of detergent composition is that its composition is selected from: nonionic surface active agent; Be selected from the organic additive of Vanay, Triethyl citrate acetate or their mixture; Enzyme; Quaternized amine raw material of ethoxylation and their mixture.

3. according to the non-aqueous liquid detergent compositions of claim 1, wherein detergent composition contains 0.01%～10% fabric care agent.

4. according to the non-aqueous liquid detergent compositions of claim 1, non--the density that the water-based liquid phase has that wherein contains tensio-active agent is 0.6～1.4 gram/cubic centimetre.

5. according to the non-aqueous liquid detergent compositions of claim 4, wherein the granular size that has of particulate starting material is 0.1～1500 micron.

6. according to the non-aqueous liquid detergent compositions of claim 1, it further comprises median particle size is 10 microns～150 microns microsphere.

7. according to the non-aqueous liquid detergent compositions of claim 6, it comprises the microsphere that mean density is 0.1 grams per milliliter～1.8 grams per milliliters.

8. the method for a contamination with wash fabric, it comprises the step that said fabric is contacted with non-aqueous liquid detergent compositions according to claim 1 in the water-based washing soln.

9. the method for a contamination with wash fabric, it comprises the step that said fabric is contacted with laundry detergent composition according to claim 3 in the water-based washing soln.