CN1035067C - Detergent compositions - Google Patents

Abstract

Granular detergent compositions comprising ethylenediamine-N,N'-disuccinic acid or salts thereof and a crystalline layered sodium silicate of formula LMSixO2xH.yH2O wherein L is an alkali metal, and M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 are provided. The compositions also preferably comprise surfactant and additional non-phosphate detergent builder compounds.

Description

Detergent composition

What the present invention relates to is to contain layered crystal silicate and quadrol-N, the detergent composition of N '-disuccinic acid or its salt.

The detergent composition that contains lamina sodium silicate is known technology, and is open as this having been done in DE-A-3742043 and EP-A-0337219.These open source literatures point out that stratiform crystalline form water glass has stronger hardness of minerals sequestering power than corresponding amorphous silicate, are favourable as the detergent builder material therefore.

Contain ni1-phosphorus, sequestrant, quadrol-N, the laundry detergent composition of N '-disuccinic acid (EDDS) also is a known technology, as disclosed in EP-A-0267653.The document points out that adding EDDS helps to remove food, beverage and some other the organic spot on the fabric in laundry processes in laundry composition.The document points out also that simultaneously EDDS can be used as all or part of substituent of phosphoric acid salt sequestrant of popular use in many existing laundry articles for use.

A known problem relevant with laundry processes is in washing process, can deposit and form insoluble inorganic salt hard scale on fabric face.These hard scales after washing finishes still in large quantities former state stay on the fabric face.Through after wash(ing)cycle repeatedly, the further long-pending knot of insoluble inorganic salt.Can make fabric face dirty dark thus, variable color.Above-mentioned inorganic salt mainly are meant calcium or magnesium salts, or the salt of heavy metal ion such as zinc, iron, manganese and copper.

The applicant is verified, and the deposition of insoluble heavy metal ion salt is to make fabric face send out the major cause of dirty and variable color.The applicant confirms that also when usefulness contained the detergent composition laundering of textile fabrics of peroxygen bleach, this heavy metal ion salt hard scale on the fabric face can make fabric local damage occur.The reason of this effect is and since the effect catalyzing activation of heavy metal ion salt the peroxygen bleach on the fabric face, make the fabric breakage therefrom.

Now, the applicant has found that, uses the laundry detergent composition that contains layered crystal water glass and EDDS simultaneously, after wash(ing)cycle repeatedly, can alleviate aforementioned insoluble inorganic salt, particularly the problem of heavy metal ion salt fouling on fabric.What make us feeling surprised is that the effect that EDDS and layered crystal silicate use simultaneously is better than significantly and only contains wherein a kind of composition of component.

Therefore, one of purpose of the present invention provides the detergent composition that contains layered crystal silicate and EDDS, and said composition can reduce the amount of scale buildup of inorganic salt on fabric face in the laundry processes, especially can reduce the repeatedly hard scale of the long-pending knot in washing back.

Another object of the present invention provides following detergent composition, be that said composition can reduce the long-pending knot amount of inorganic salt hard scale on fabric face that contains heavy metal ion in laundry processes, make the white of white fabrics lasting thus, and the color and luster loss of DYED FABRICS in said washing process reduced.

Subtract so, the problem that contains the inorganic salt generation surface scale of heavy metal ion in washing process is very serious problem to laundry processes, but in fact, the salt crust problem all can run in any washing or cleaning process basically.Therefore, can expect that detergent composition of the present invention can also be used for alleviating as the automatic tableware washing process and comprise the salt crust that any process of cleaning hard surfaces occurs.

According to the present invention, the detergent composition that is provided comprises: (a) 1%-80% (wt) general formula is LMSi _x0 _2x+1YH ₂The layered crystal silicate-like builder material of O, L is a basic metal in the formula, and M is sodium or hydrogen, and x is the number among the 1.9-4, and y is the number among the 0-20; (b) quadrol-N of 0.05%-10% (wt), the salt of N '-disuccinic acid or its basic metal, alkaline-earth metal, ammonium or replacement ammonium, or their mixture; (c) 0%-30% (wt) be selected from a kind of detergent use tensio-active agent in anion surfactant, nonionogenic tenside, zwitterionics, amphoterics, cats product and their mixture: (d) other nonphosphate builders compound of 0%-50% (wt).

Detergent composition of the present invention comprises two kinds of basal component, i.e. layered crystal silicate and quadrol-N, N '-disuccinic acid or its salt.

In fact detergent composition of the present invention can have any profile.Embodiment preferred comprises granular composition, especially concentrated granular shape laundry composition, and heavy duty detergent liquid composition.

The general formula of layered crystal silicate material is:

LMSi _xO _2x+1YH ₂L is a basic metal in the O formula, preferred Na, and M is sodium or hydrogen, and x is the number among the 1.9-4, and y is the number among the 0-20.Such layered crystal water glass is disclosed among the EP-A-0164514, and their preparation method is disclosed among DE-A-3417649 and the DE-A-3742043.With regard to the object of the invention, the x in the above-mentioned general formula is a numerical value 2,3 or 4, preferred 2.Preferred especially M is a sodium, and y is 0, the preferred embodiment of this formula comprise α-, β-, γ-and δ-shape Na ₂Si ₂O ₅These materials can be obtained by Hoechst AG FRG, are respectively NaSKS-5, NaSKS-7, NaSKS-11 and NaSKS-6.Most preferred material is δ-Na ₂Si ₂O ₅, i.e. NaSKS-6.The processed granularity of these materials is 150-1000 μ m, and tap density is at least 800g/L, preferably the free-flowing solid of about 900g/L.Yet, add man-hour, because crystal is crisp, therefore be easy to the cracked granularity that makes less than 100 μ m.

In detergent composition of the present invention, layered crystal silicate-like builder material accounts for the 1%-80% of composition weight, preferred 5%-40%, more preferably 7%-20%.

Layered crystal water glass material is that the form of water-soluble ionizable material intimate mixture is present in the granular detergent composition of the present invention with particulate state and a kind of solid preferably.Said solid is that water-soluble ionizable material is selected from organic acid, organic and the salt of mineral acid and their mixture.To the primary requirement of this material is should contain at least one pKa value less than 9 acidic functionality, makes it to have the ability of the hydroxide ion that discharged by layered crystal silicate of partly neutralizing at least.Find that unexpectedly the ionizable material need not the solution of pH＜7, perhaps need not providing the hydrionic consumption of stoichiometry parity to exist for the hydroxide ion that produces by the crystalline silicate dissolving.In fact,, reduce, can not eliminate it though the neutralizing effect of ionizable material can make fabric damage at the particulate matter duration of storage.

The mean particle size of ionizable material also should be not more than 300 μ m, preferably is not more than 100 μ m.Can impel the uniform distribution of ionizable material and crystalline silicate like this, and it is believed that and when particulate matter is dissolved in the washings, can impel the reduction of local pH value.

The organic acid that is suitable for comprises xitix, citric acid, pentanedioic acid, glyconic acid, oxyacetic acid, oxysuccinic acid, toxilic acid, propanedioic acid, oxalic acid, succsinic acid and tartrate, 1-hydroxyl ethane-1,1-bisphosphate (EHDP), amino polymethylene phosphoric acid such as NTMP, EDTMP﹠amp; DETPMP, and above-mentioned any mixture.The acid salt that is suitable for comprises sodium bicarbonate, sodium bioxalate, sodium pyrosulfate, sodium acid pyrophosphate, acid sodium orthophosphate, sodium hydrotartrate or above-mentioned any mixture.

The pH of the granular mixture of layered crystal silicate and solid, water soluble ionizable material should be at least 10 (measuring by 1%20 ℃ of distilled water solutions), is generally at least 11, is generally at least 11.5.

Contain aspect these particulate detergent composition stable in the processing granular process and in raising, it is useful especially adding some other compositions in layered crystal silicate and ionizable water-soluble cpds.Particularly, the agglomerate of some type can require to add one or more tackiness agents and be beneficial to silicate and ionizable water miscible bonding, make the particle of producing have acceptable physical property, adhesive consumption can account for the 0%-20% of particulate matter weight.Tackiness agent preferably exists with the intimate mixture form with silicate and ionizable water-soluble material.The preferred adhesive fusing point is between 30 ℃-70 ℃.Adhesive consumption preferably accounts for the 1-10% of particulate matter weight, more preferably 2-5%.

Preferred adhesive comprises that every mol of alcohol contains the C of 5-100 moles of ethylene oxide ₁₀-C ₂₀Fatty alcohol ethoxylate, more preferably every mole of C that contains the 20-100 moles of ethylene oxide ₁₅-C ₂₀Primary alcohol ethoxylate.

Some other preferred adhesive comprises some polymeric material.The example of these polymeric materials is that molecular-weight average is 12, and 000-700,000 polyvinylpyrrolidone and molecular-weight average are 600-10,000 polyoxyethylene glycol.Other polymeric material examples that can be used as tackiness agent are multipolymers of maleic anhydride and ethene, vinyltoluene base ether or methylacrylic acid, and wherein maleic anhydride accounts for 20% (mole) of polymkeric substance at least.These polymeric materials can use separately, also can with solvent such as water, propylene glycol and the above-mentioned C that contains 5-100 moles of ethylene oxide/mole ₁₀-C ₂₀Fatty alcohol ethoxylate is used in combination.Other example of tackiness agent also has C ₁₀-C ₂₀List and Glycerol dimer ether and C ₁₀-C ₂₀Lipid acid.Some inorganic salt solution that comprises water glass also can be used for this purpose.

Derivatived cellulose such as methylcellulose gum, carboxymethyl cellulose and Natvosol and homopolymerization or co-poly carboxylic acid or their salt are again some examples of adhesives that are suitable for.

Can also comprise composition commonly used in some other detergent composition in the particulate matter, need only these composition self-consistents, and get final product the synergism of layered crystal silicate is noiseless.Therefore, particulate matter can contain up to negatively charged ion, nonionic, both sexes or the zwitterionics of 50% (with the particulate matter restatement) or any mixture of these tensio-active agents, and some preferred particulate matter embodiments contain tensio-active agent.The example of these tensio-active agents will be for a more detailed description hereinafter.In any case, importantly, join any surfactant material in the particulate matter and would not introduce even can make layered crystal silicate be partly dissolved so free (non-binding) water content.For this purpose, tensio-active agent should be a solid, and it is about 5% that its contained free (non-binding) moisture content should be no more than, and preferably is no more than 2%, is more preferably less than 1%.

Can also add other composition, but total amount is no more than 50% of particulate matter weight, desired condition is identical with above-mentioned tensio-active agent.Therefore, it is solid-state that these inessential compositions are preferably under the normal temperature (room temperature), and contained free (non-binding) moisture content should be no more than 5%, preferably less than 1%.

Can add some anhydrous liq compositions by the amount that is no more than particulate matter weight 20%, in these components, tangible solvability can not be arranged but condition is a layered crystal silicate.This situation is applicable to that also normality is a solid ingredient, but with the situation of fusion form as particle agglomeration/coating agent use.

Particle can be various profile, as extrudate, marumes, agglomerate, and flap or closely knit particulate matter.The preferred method that a kind of preparation contains the compact grain of layered crystal silicate and a kind of solid, water soluble ionizable material has been disclosed among the PCT application number WO92/06163 of common transfer.

Composition of the present invention contains and accounts for composition weight 0.05%-10% as basal component, preferred 0.05%-1% (wt), more preferably quadrol-N of 0.1%-0.5% (wt), the salt of N '-disuccinic acid (EDDS) or its basic metal, alkaline-earth metal, ammonium or its replacement ammonium, or their mixture.Concerning described granular detergent composition, preferred EDDS compound be free acid form or its sodium salt or magnesium salts.The sodium salt example of preferred EDDS comprises MgEDDS and Mg ₂EDDS.

For particulate composition of the present invention, the magnesium mixture is most preferred.These mixtures can former state be added in the composition, perhaps also can allow inertia magnesium salts such as MgCl in the process of preparation composition ₂Or MgSO ₄EDDS compound reaction with adding with the form of acid or salt or mixture makes above-mentioned mixture be shaped therefrom.When adding EDDS compound and inertia magnesium salts simultaneously in preparation process, the mol ratio of magnesium and EDDS was advisable greater than 1: 1, more preferably greater than 3: 1, so that guarantee to generate desired magnesium mixture.

The sour structural formula of EDDS is as follows:

Raw material that EDDS for example can be easy to get with cheapness such as maleic anhydride and quadrol are synthesized into by following reaction:

Relevant usefulness is purchased the more detailed explanation of the synthetic EDDS method of raw material can consult US3,158,635 (Kezerian and Ramsay), and 1964,11,24 authorize.

With maleic anhydride and the synthetic EDDS of quadrol, obtain the i.e. mixture of [R, R], [S, S] and [S, R] of three kinds of optically active isomers, this is owing to there are two unsymmetrical carbons to have event.The biological degradation of EDDS is that optically active isomer is specific, because the degraded of [S, S] isomer is very rapid and thorough, therefore, this isomer is preferred to composition of the present invention.

[S, S] isomer of EDDS can synthesize by following reaction with L-aspartic acid and glycol dibromide:

Reaction generates EDDS[S, S about L-aspartic acid and glycol dibromide] more detailed description of isomer can consult Neal and Rose " mixture of Stereoselective ligand and ethylenediamine disuccinic acid thereof ", inorganic chemistry, Vol.7, (1968), P2405-2412.

Generally speaking, detergent composition of the present invention also comprises those common in Betengent product compositions, can comprise organic surface active agent, other detergent builders, oxygen bleaching agent system and promoter material such as anti redeposition agent and outstanding dirty agent, suds suppressor, other heavy metal ion chelating agent, enzyme, white dyes, photosensitization SYNTHETIC OPTICAL WHITNER, spices and pigment.Some product can also comprise fabric-softening and static inhibitor.

Operable tensio-active agent scope is very wide in the detergent composition.US3,929,678 (Laughlin and Heuring, 1975,12,30 authorize) have provided these tensio-active agent species of the inventory of negatively charged ion, nonionic, both sexes and zwitter-ion type.The cats product example that is suitable for provides in 259,217 (Murphy is given in 1981,3,31 mandates) at US4.

The mixed type anion surfactant is applicable to the present invention, especially the mixture of vitriol, sulfonate and/or carboxylate surface active agent.

-as used sulfonate and vitriol mixed surfactant wherein sulfonate and the weight ratio of vitriol be 5: 1-1: 2, preferred 3: 1-2: 3, more preferably 3: 1-1: 1.Preferred sulfonate comprises alkylbenzene sulfonate and the α-sulfonation methyl soap that 9-15 carbon atom, an especially 11-13 carbon atom arranged in the alkyl, and wherein fatty acid derived has C ₁₂-C ₁₈Fat source, particularly C ₁₆-C ₁₈The fat source.In each example, positively charged ion is a basic metal, preferred sodium.Preferred sulfate surfactant has the alkyl-sulphate of 12-22, a particularly 16-18 carbon atom in alkyl in above-mentioned sulfonate sulfate mixture.

Another kind of useful surfactant system comprises two kinds of different alkyl-sulphate mixtures of material of mean chain length each other.A kind of C that contains in this system ₁₄-C ₁₅Alkyl-sulphate and C ₁₆-C ₁₈Alkyl-sulphate, wherein C ₁₄-C ₁₅: C ₁₆-C ₁₈Be 3: 1-1: 1 (weight ratio).Alkyl-sulphate also can also with alkyl in 10-20 is arranged, preferred 10-16 carbon atom and average degree of ethoxylation are that the alkyl ethoxy sulfate of 1-6 is used in combination.Positively charged ion in above-mentioned each example is basic metal equally, preferred sodium.

Another kind of preferred anionic surfactant system comprises C ₁₂-C ₂₀Alkyl-sulphate and water-soluble C ₁₁-C ₁₈The mixture of alkyl ethoxy sulfate, said alkyl ethoxy sulfate on average contains 1-7 oxyethyl group for every mole, and in the mixture, the weight ratio of alkyl-sulphate and alkyl ethoxy sulfate is 2: 1-19: 1, preferred 3: 1-12: 1, more preferably 3.5: 1-10: 1.

Alkyl-sulphate can derive from natural or the synthetic hydrocarbon feed.The preferred embodiment of this class salt comprises the C of collateralization basically ₁₄-C ₁₅Alkyl-sulphate, wherein C ₁₄-C ₁₅The collateralization degree of alkyl chain is greater than about 20%.The C of this basic collateralization ₁₄-C ₁₅Alkyl-sulphate is usually from synthesis material.C ₁₆-C ₂₀Alkyl-sulphate also is preferred, and they generally derive from natural matter such as shea butter and marine animal oil.

C ₁₁-C ₁₈Alkyl ethoxy sulfate comprises the primary alkyl ethoxy sulfate, and it is C ₁₁-C ₁₈The condensation product of pure and every mole of average 1-7 Oxyranyle.Preferred every mole on average contains 1-5, more preferably contains the C of 1-3 oxyethyl group ₁₂-C ₁₅Alkyl ethoxy sulfate.

C ₁₁-C ₁₈Alcohol itself can be from natural or synthesis material.Therefore, from neutral grease or Ziegler (Ziegler) method alkene, or OXO synthetic C ₁₁-C ₁₈Alcohol can generate suitable alkyl source.Synthesis method and the example of material comprise Dobanol25 (RTM), it is a kind of C ₁₂-C ₁₅The mixture of alcohol (selling) by shell chemical company (UK); Ethyl24 by the sale of Ethyl company; BASF GmbH company logo name is called the C of Lutensol and the Synperonic of ICI company (RTM) ₁₃-C ₁₅The mixture of alcohol, wherein C ₁₃Be 67% and C ₁₅Be 33%; And the Lial125 of LiquichimicaItaliana sale.The example that can obtain the natural materials of alcohol is Oleum Cocois and palm-kernel oil and corresponding lipid acid.C ₁₁-C ₁₈The alkyl ethoxy sulfate consumption preferably accounts for the 0.5%-10% of composition weight, more preferably accounts for 0.5%-5%, most preferably accounts for 1%-3%.

Other anion surfactant that is suitable for the object of the invention is that formula is R-CON (R ¹) CH ₂The basic metal sarcosinate of COOM, its R are C ₅-C ₁₇Straight or branched alkyl or alkenyl, R ¹Be C ₁-C ₄Alkyl, M are a kind of alkalimetal ion.Preferred examples is lauroyl, cocounut oil acyl (COCO _yL) (C ₁₂-C ₁₄), the Sodium sarcosinate of mnyristoyl and oil base methyl.

An available class ionic surfactant pack of the present invention is drawn together the condenses of an oxyethane and a hydrophobic part, and the average hydrophile-lipophile balance value of this tensio-active agent (HLB) that provides is 8-17, is preferably 9.5-13.5, preferably 10-12.5.Hydrophobic (oleophylic) part can be natural aliphatic series or aromatic, and can be easy to regulate with the polyoxyethylated length of arbitrary concrete hydrophobic grouping condensation, a kind ofly has institute and requires hydrophilic and the water-soluble cpds hydrophobic balance degree so that obtain.

Particularly preferred the type nonionogenic tenside is the C that every mol of alcohol on average contains the 3-8 moles of ethylene oxide ₉-C ₁₅Primary alcohol ethoxylate, especially every mol of alcohol on average contains the C of 6-8 moles of ethylene oxide ₁₄-C ₁₅Primary alconol and every mol of alcohol on average contain the C of 3-5 moles of ethylene oxide ₁₂-C ₁₅Primary alconol.

Another kind of ionic surfactant pack is drawn together the following alkyl polyglucoside compound of general formula.

RO (C _nH _2nO) _tZ _xZ is a Fructus Vins sugar deutero-part in the formula; R is the saturated hydrophobic alkyl that contains 6-18 carbon atom; T is that 0-10 and n are 2 or 3; X is 1.1-4, and said compound comprises the unreacted fatty alcohol less than 10%, and the short-chain alkyl polyglucoside is less than 50%.Such compound and the application in detergent composition thereof are disclosed among the EP-B0070074,0070077,0075996 and 0094118.

Another kind of preferred nonionic is the polyhydroxy fatty acid amide surfactant compound, and its structural formula is

Wherein: R ¹Be H, C ₁-C ₄Alkyl, 2-hydroxyethyl, 2-hydroxypropyl, or their mixture, preferred C ₁-C ₄Alkyl.More preferably C ₁Or C ₂Alkyl, most preferably C ₁Alkyl (being methyl); R ²Be C ₅-C ₃₁Alkyl, preferred C ₇-C ₁₉Straight chained alkyl or alkenyl, more preferably C ₉-C ₁₇Straight chained alkyl or alkenyl, most preferably C ₁₁-C ₁₇Straight chained alkyl or alkenyl perhaps are their mixture, and Z is many hydroxyl alkyls, and at least 3 direct coupled hydroxyls are arranged on its straight chain hydrocarbon chain, or are its alkoxy derivative (preferred ethoxylation or propoxylation).Z is preferably from the reducing sugar in the reductive amination reaction; Preferred Z is the wood sugar that the suitable reducing sugar of sugar alcohol base (glycity1) comprises glucose, fructose, maltose, lactose, semi-lactosi, seminose.As raw material, high glucose maize treacle, high-fructose corn syrup and high malt sugar maize treacle and the same can the utilization of above-mentioned listed every kind of sugar.These maize treacle can produce the mixing sugar composition and be used for Z.Should be appreciated that above-mentioned for example and do not mean that and get rid of other suitable raw material.Z preferably is selected from-CH ₂-(CHOH) n-CH ₂OH ,-CH (CH ₂OH)-(CHOH) _N-1-CH ₂OH ,-CH ₂-(CHOH) ₂-(CHOR ') (CHOH)-CH ₂The group of forming among the OH, wherein n is an integer among the 3-5, R ' is H or a ring-type or aliphatic monose, or its alkoxy derivative.The n sugar alcohol base (glycityls) that equals 4 most preferably, especially-CH ₂-(CHOH) ₄-CH ₂OH.

In formula (I), R ¹Can be, as N-methyl, N-ethyl, N-propyl group, N-sec.-propyl, N-butyl, N-2-hydroxyethyl or N-2-hydroxypropyl.

R ²-CO-N＜can be is as coconut monoethanolamide (Cocamide), stearylamide, oleylamide (Oleamide), laurylamide, myristic amide, decyl amide, palmitic amide and tallow acid amides etc.

Z can be 1-deoxy-glucose alcohol radical (1-deoxyglucityl), 2-deoxidation fructose alcohol radical, 1-deoxidation maltose alcohol radical, 1-deoxidation lactose alcohol radical, 1-deoxy-galactose alcohol radical, 1-deoxymannose alcohol radical, 1-deoxidation trisaccharide maltose alcohol radical etc.Preferred compound is N-methyl N-1-deoxy-glucose alcohol radical C ₁₄-C ₁₈Fatty acid amide.

Also having a class tensio-active agent is the semi-polarity tensio-active agent, as amine oxide.The amine oxide that is suitable for is selected from single C ₈-C ₂₀, C especially ₁₀-C ₁₄N-alkyl or alkenyl amine oxide compound and titanium dioxide propylidene-1, the 3-diamines, wherein the last surplus position of N also has substituting group methyl, hydroxyethyl or hydroxypropyl.

Detergent composition of the present invention can also use cats product, and suitable quaternary amine type tensio-active agent is for being selected from single C ₈-C ₁₆, C especially ₁₀-C ₁₄N-alkyl or alkenyl ammonium type tensio-active agent, wherein, the last surplus position of N also has substituting group methyl, hydroxyethyl or hydroxypropyl.

Detergent composition contains the tensio-active agent of 0%-30% (wt).Laundry detergent composition contains 5%-20% (wt) tensio-active agent usually, preferably accounts for the 7%-15% of composition weight.

The wash up machine with detergent composition-as contain the 0%-10% of composition weight, preferred 0.5%-10%, the more preferably tensio-active agent of 1%-5%.Tensio-active agent can be selected from negatively charged ion, positively charged ion, nonionic, both sexes or zwitterionics.Tensio-active agent preferably hangs down alveolitoid.In EP-A-0414549, provide with the used general tensio-active agent of detergent composition for the automatic dishwashing machine.Most preferably low alveolitoid nonionogenic tenside, especially water miscible ethoxylation C ₆-C ₁₆Fatty Alcohol(C12-C14 and C12-C18) and C ₆-C ₁₆Mixed type ethoxylated/propoxylated fatty alcohol, their mixture in addition.The preferred ethoxylation degree of ethoxylized fatty alcohol is the C of 5-50 ₁₀-C ₁₆Ethoxylized fatty alcohol, more preferably ethoxylation degree is the C of 8-40 ₁₂-C ₁₆Ethoxylized fatty alcohol.Preferred mixed type ethoxylated/propoxylated fatty alcohol wherein alkyl chain length is a 10-16 carbon atom, and ethoxylation degree is 3-30, and the propoxylation degree is 1-10.

It is preferred that dissimilar tensio-active agents is used in combination, especially anionic-cationic mixture and negatively charged ion-nonionic-cation mixt.Particularly preferred mixture is disclosed among GB-A-2040987 and the E P-A-0087914.Although tensio-active agent can add with the form of mixture in the composition, the joining day of preferably controlling every kind of tensio-active agent is so that the physicals of optimum combination thing and the problem for avoiding processing.

The interpolation order of preferable methods and tensio-active agent will be described later.

Particularly preferred component is some other non-phosphate detergent washing assistant in the detergent composition of the present invention, hereinafter is called the auxilliary non-phosphate detergent washing assistant that adds.It can include, but is not limited to the alkali metal aluminosilicate class, monomer multi-carboxylate, polycarboxylic acid homopolymer or multipolymer or their salt, wherein polycarboxylate comprises that at least two are no more than the carboxylic group that 2 carbon atoms separate each other, can also be carbonate, silicate and above-mentioned any mixture.

The aluminosilicate ion exchange material of certain limit also can use, and preferred sodium silicoaluminate zeolite has as the lower unit general formula

Na _z[(AlO ₂) _z(SiO ₂) _y] _xH ₂O wherein z and y is at least 6; The mol ratio of z and y is 1.0-0.5, and x is at least 5, preferred 7.5-276, more preferably 10-264.Alumino-silicate materials is hydrated form and preferred crystal, contains combination water 10%-28%, preferably 18-22%.

Its feature of above-mentioned aluminosilicate ion exchange material is that also particle diameter is 0.1-10 μ m, preferred 0.2-4 μ m.This paper term " particle diameter " is meant the average particulate diameter of given ion-exchange material, is measured by the routine analysis technology, as utilizes scanning electron microscope to carry out micro-mensuration or fixed with the laser particle size instrumentation.Aluminosilicate ion exchange material again-feature is its calcium ion exchange capacity, in moisture-free basis, is at least 200mg equivalent CaCO ₃The water hardness/g silico-aluminate is generally 300mg equivalent/g-352mg equivalent/g.It is that its calcium ion exchange rate is at least 130mg equivalent CaCO that aluminosilicate ion exchange material of the present invention also has a feature ₃/ liter/minute/(grams per liter) [2 grain Ca ⁺⁺/ gallon per minute/gram/gallon)] silico-aluminate (moisture-free basis) is generally 130mg equivalent CaCO ₃/ liter/minute/(grams per liter) [2 grains/gallon per minute/(gram/gallon)]-390mg equivalent CaCO ₃/ liter/minute/(grams per liter) [6 grains/gallon per minute/(gram/gallon)], be benchmark with calcium ion hardness.

Its calcium ion exchange rate of the suitableeest silico-aluminate that is used for the washing assistant purpose is at least 260mg equivalent CaCO ₃/ liter/minute/(grams per liter) [4 grains/gallon per minute/(gram/gallon)].

Implementing the used aluminosilicate ion exchange material of the present invention can be purchased, and can be naturally occurring material, but the material that preferably is synthesized into.The method of producing aluminosilicate ion exchange material is at US3, discussion arranged in 985,669.Can be used for preferred composite crystals aluminosilicate ion exchange material of the present invention and be purchased, product are called zeolite A, zeolite B, zeolite P, X zeolite, zeolite HS, zeolite MAP, zeolite MAB and their mixture.In particularly preferred embodiments, the crystalline silica-aluminate ion-exchange material is zeolite A, and its formula is:

Na ₁₂[(AlO ₂) ₁₂(SiO ₂) ₁₂] _xH ₂O wherein x is 20-30, especially 27.Formula is Na ₈₆[(AlO ₂) ₈₆(SiO) ₁₀₆] 276H ₂The X zeolite of O and formula Na ₆[(AlO ₂) ₆(SiO ₂) ₆] 7.5H ₂The zeolite HS of O also is suitable for.

The water-soluble monomer or the low poly carboxylic acid washing assistant that are suitable for can be selected from a lot of compounds, but the preferred best one-level carboxyl of compound logarithm acidity/constant (pK ₁) less than 9, between the preferred 2-8.5, more preferably between the 4-7.5.

The logarithm acidity constant is determined by following balanced type: H ⁺+ A- HA wherein A is the complete ionization carboxylate anion of builder salt.

The equilibrium constant of diluting soln is expressed as:

pK ₁＝log ₁₀K。

For the object of the invention, acidity constant is at 25 ℃, and ionic strength is to determine in 0 o'clock.If possible, both adopted literature value (referring to " stability constant of metal ion mixture ", Special Publication No.2 5, The Chemical Society London), if with suspicion, then by potentiometric titration, measures with glass electrode.

Carboxylate salt or polycarboxylate washing assistant can be monomer or oligomeric-type, but the monomer polycarboxylate generally is preferred because of the reason of price and performance.

Monomer and oligomeric washing assistant can be by selecting in acyclic, alicyclic ring, heterocycle and the aromatic carboxylic-acid salts, and general formula is:

R in the formula ₁Be H, not the C that replaces or replace ₁-C ₃₀Alkyl or alkenyl, substituting group are hydroxyl, carboxyl, sulfo group or phosphono, perhaps C ₁-C ₃₀Alkyl or alkenyl with contain 20 polyoxyethylene below the vinyloxy group and partly link to each other; R ₂Be H, C _1-4Alkyl, alkenyl or hydroxyalkyl, or alkaryl, sulfo group or phosphono: X represents a singly-bound; O; S; SO; SO ₂Or NR ₁Y represents H; Carboxyl; Hydroxyl; Carboxymethoxyl; Or it is unsubstituted or by the C of hydroxyl or carboxyl substituted _1-30Alkyl or alkenyl; Z is H or carboxyl; M is an integer among the 1-10; N is an integer among the 3-6; P, q are the integers among the 0-6, and p+q is 1-6: when repeating given molecular formula, and X, each can be identical or different for Y and Z, at least one Y or Z contain a carboxyl in the molecule.

The suitable carboxylate salt that contains a carboxyl comprises water miscible lactic acid salt, and glycollate and their ether derivant are described in belgian patent 831368,821369 and 821370.The polycarboxylate that contains two carboxyls comprises water-soluble succinate, malonate, (ethylene dioxy base) diacetin, maleate, di-alcohol hydrochlorate, tartrate, tartronate and fumarate, and DE2,446,686 and 2,446,687 and US3,935, ether carboxylate described in 257, the sulfinyl carboxylate salt of describing in the belgian patent 840,623.The polycarboxylate that contains three carboxyls specifically comprises water-soluble citrate, achilleic acid salt (acontitrates), Citrate trianion and succinate derivative such as GB patent 1,379,241 disclosed carboxy methoxy-succinic acid salt, GB patent 1,389,732 disclosed newborn acyloxy succinates and Netherlands patent applications 7205873 disclosed aminosuccinic acid salt, also aerobic joins polycarboxylic acid salt material such as GB patent 1,387,447 disclosed 2-oxa-s-1,1,3-tricarballylic acid salt.

The polycarboxylate that contains four carboxyls comprises GB patent 1,261,829 disclosed oxygen di-succinates, 1,1,2,2-second tetracarboxylic acid hydrochlorate, 1,1,3, the 3-third tetracarboxylic acid hydrochlorate and 1,1,2, the 3-third tetracarboxylic acid hydrochlorate.Contain the substituent polycarboxylate of sulfo group and comprise GB patent 1,398,421 and 1,398, disclosed sulfosuccinate and GB patent 1,439,000 disclosed sulfonation pyrolysis Citrate trianion in 422 and US3,936,448.

Alicyclic ring and heterocycle polycarboxylate comprise pentamethylene-suitable, suitable, suitable-tetracarboxylic acid hydrochlorate, cyclopentadiene pentacarboxylic acid salt, 2,3,4,5-tetrahydrofuran (THF)-suitable, suitable, suitable-the tetracarboxylic acid hydrochlorate, 2,5-tetrahydrofuran (THF)-suitable-dicarboxylate, 2,2,5,5-tetrahydrofuran (THF)-tetracarboxylic acid hydrochlorate, 1,2,3,4,5, the carboxymethyl derivant of 6-hexane hexacarboxylic acid salt and polyvalent alcohol such as sorbyl alcohol, mannitol and Xylitol.Aromatic polycarboxylic acid salt comprises mellitic acid, 1,2,4, disclosed phthalic acid derivative in 5-phenylformic acid and the GB patent 1,425,343.

In above-mentioned, preferred polycarboxylate is the hydroxycarboxylate who contains 3 following carboxyls in each molecule, special optimization citric acid salt.

The parent acid of monomer or oligomeric polycarboxylate sequestrant or with their mixture of salt, also can be with reference to as builder system and composition in the detergent composition of the present invention as citric acid or Citrate trianion/citric acid mixture.

Other water-soluble organic salt that is suitable for is polycarboxylic acid homopolymer or multipolymer or their salt, and wherein, said polycarboxylic acid comprises at least two and is no more than 2 disclosed carboxylic groups of carbon atom each other.The polymkeric substance of back type has in 596,756 open at GB-A-1.The example of described salt is the polyacrylate of MWt 2000-5000 and they and multipolymer maleic anhydride, this molecular weight of copolymer is 20,000-70,000, particularly about 40,000.The consumption of these materials is generally the 0.5%-10% of composition weight, preferred 0.75%-8%, more preferably 1%-6%.

Composition of the present invention can contain sequestrant selectivity composition.This optionally sequestrant can include the machine phosphonic acid compound, it comprises amino alkylidenyl many (alkylene phosphonic acids salt), ethyl 1-hydroxyl di 2 ethylhexyl phosphonic acid an alkali metal salt, nitrilo trimethylene phosphonic salt, ethylenediamine tetramethylene phosphonic acid salt and diethylenetriamine pentamethylenophosphonic acid(DTPP) salt.Phosphonate compounds can its sour form or the form of basic metal or alkaline metal ions mixture exist, the mol ratio of said metal ion and said phosphonate compounds is at least 1: 1.This class mixture is at US-A-4, description arranged in 259,200.Organic phospho acid salt compound (if present) preferably exists with the form of its magnesium salts.The consumption of phosphorated chelating agent for well, does not contain the person for most preferably with low as far as possible fully in the present composition.

For different purposes, be added with soluble silicate in the conventional formulation, but also nonessential in composition of the present invention.Layered crystal silicate is as a part that constitutes builder system in the detergent composition, must add to do the form of mixing thing, as forming agent, the soluble silicon aluminate still can be used in the spray-dried granules, and said particle is generally the part of detergent composition.If spray-dired particle is the silicon aluminate washing assistant not, just only contain organic material, be special ideal.The silicate that is suitable for is SiO ₂: Na ₂O is those salt of 1.6-3.4, this ratio be 2.0-2.8 be preferred.

For being added with as for the detergent composition of the layered crystal silicate of a builder system part the auxilliary 0%-50% that nonphosphate builders accounts for composition weight, the preferred 10%-40% of adding.In preferred detergent composition, silico-aluminate such as zeolite A account for the 20%-60% of washing assistant gross weight, and monomer or oligomeric carboxylate account for the 5%-30% of washing assistant gross weight, and layered crystal silicate accounts for the 10%-65% of washing assistant gross weight.In these compositions, builder system preferably also comprises the mixture that contains inorganic and organic auxiliary washing assistant, and as yellow soda ash and maleic anhydride/acrylic copolymer, their consumption accounts for washing assistant gross weight 35% at most.

Detergent composition of the present invention generally comprises a kind of inorganic perhydrate (perhydrate) SYNTHETIC OPTICAL WHITNER, and is generally its sodium salt.The add-on of perhydrate generally accounts for the 3%-40% of composition weight, preferred 5%-30%, more preferably 10%-25%.

Perhydrate can be inorganic salt such as perborate, percarbonate, and superphosphate and persilicate, but be generally an alkali metal salt, be generally sodium salt, perborate or percarbonate.Sodium peroxoborate can be formula NaBO ₂H ₂O ₂Monohydrate form, or tetrahydrate NaBO ₂H ₂O ₂3H ₂O.

SPC-D is preferred perhydrate, is a kind of addition compound, and its formula is 2Na ₂CO ₃3H ₂O, its crystalline solids is commercially available to be arrived.Though percarbonate is supplementary protection and joining in the detergent composition not, the preferred composition of implementing is to utilize cated material.Most preferred coated material comprises the salt of alkali metal sulfates and carbonate.These materials and coating process are disclosed in GB-1 already, in 466,799 (1977,3,9 authorize Interox).The weight ratio of mixing salt coated material and percarbonate is 1: 200-1: 4, preferred 1: 99-1: 9, more preferably 1: 49-1: 19.Preferred mixing salt is sodium sulfate and yellow soda ash, and general formula is Na ₂SO ₄.nNa ₂CO ₃, wherein n is 0.1-3, and preferred n is 0.3-1.0, and more preferably n is 0.2-0.5.

The another kind of coated material that is suitable for is a water glass, its SiO ₂: Na ₂O is 1.6: 1-3.4: 1, and preferred 2.8: 1, to use with the form of the aqueous solution, the amount that makes silicate solid is the 2%-10% (being generally 3%-5%) of percarbonate weight.Can also magnesium silicate in the coating.Other suitable coating material comprises the vitriol and the carbonate of basic metal and alkaline-earth metal.

Can control by the sequestrant in the reaction mixture though be used for producing the heavy metal that the yellow soda ash of percarbonate exists, percarbonate still need be protected in order to avoid be subjected to the harm of the beavy metal impurity in other composition in the product.Therefore, in adopting the detergent composition of percarbonate as perhydrate salt, the total amount of iron ion, cupric ion and mn ion should not surpass 25ppm in the product, preferably is no more than 20ppm, can avoid the disadvantageous effect to percarbonate stability like this.Contain among the still autre action pendante PCT application number WO92/06163 that the detergent composition that has improved stable alkali metal percarbonate SYNTHETIC OPTICAL WHITNER is disclosed in the applicant.

The bleach systems that joins in the detergent composition of the present invention preferably contains solid peroxygen acid blanching agent precursor (SYNTHETIC OPTICAL WHITNER active body).Therefore the add-on of peroxyacid bleach precursor is generally the 1%-20% of composition weight, preferred 1%-15%, more preferably 1%-10%.

These precursors can contain one or more N-or O-acyl group, and alternative precursor-type is a lot.Suitable kind has the acid anhydride class, the acylated derivatives of ester class, acid imide and imidazoles and oxime, and the example of suitable material is disclosed among the GB-A-1586789 in these kinds.Most preferred type is the ester class, and as at GB-A-836988, disclosed and acid imide is as at GB-A-855735﹠amp in 864798,1147871 and 2143231; Disclosed in 1246338.

N in the particularly preferred precursor compound, N, N ', N ' tetrem acylated compounds, structural formula is

X can be 0 in the formula, can also be an integer among the 1-6.

Example comprises: X=1, tetrem acyl methylene diamine (TAMD); X=2, tetraacetyl ethylene diamine (TAED); X=6, tetrem acyl hexanediamine (TAHD).These and similar compound thereof are disclosed among the GB-A-907356, and most preferred peroxyacid bleach precursor is TAED.

Another kind of preferred peroxyacid bleach active body compound is the compound with acid amides replacement of following general formula:

R in the formula ¹Be to contain 1-14 carbon atom aryl or alkaryl, R ²Be the alkylidene group that contains 1-14 carbon atom, arylidene and alkyl arylene R ⁵Be the alkyl of a H or 1-10 carbon atom, aryl or alkaryl, L can be any leavings group R substantially ¹Preferably contain 6-12 carbon atom, R ²Preferably contain 4-8 carbon atom.R ¹Can be the straight or branched alkyl, the aryl of replacement or contain side chain, the alkaryl that substituting group or both contain can be taken from synthetic source or natural origin, as shea butter.R ²Can do similar structural changes.Said substituting group can be an alkyl, aryl, halogen, nitrogen, sulphur and other typical substituting group or organic compound.R ⁵Preferred H or methyl.R ¹And R ⁵The carbonatoms sum be no more than 18.The SYNTHETIC OPTICAL WHITNER active body compound that acid amides replaces is disclosed among the EP-A-0170386.

Other peroxyacid bleach precursor compound comprise as among the EP-A-0341947 disclosed ninth of the ten Heavenly Stems acyloxy benzene sulfonic acid sodium salt, front three hexylyloxy benzene sulfonic acid sodium salt, acetoxyl group benzene sulfonic acid sodium salt and benzoyloxy benzene sulfonic acid sodium salt.

The contained organic peroxide acid of the present composition can account for the 1%-15% of composition weight, preferred 1%-10%.A particularly preferred class is that the acid amides with following general formula replaces peroxy acid:

R wherein ¹, R ²And R ⁵Definition replace the identical of peroxyacid bleach active body compound with above-mentioned corresponding amide.

Other organic peroxide acid comprises as disclosed diperoxy dodecanedioic acid among the EP-A-0341947, diperoxy tetradecane diacid, diperoxy Thapsic acid, to be crossed and two crosses that nonane diacid, is crossed and two cross undecane dicarboxylic acids, a peroxide phthalic acid and a peroxybenzoic acid, and their salt.

Disclose detergent composition in the still autre action pendante GB application number 9102507.2 of applicant (1991.2.6 application), the contained solid peroxygen bleach precursor of these compositions is protected by acid coated, so that reduce the infringement of fabric color to greatest extent.

Antiredeposition that the present invention is suitable for and outstanding dirty agent comprise derivatived cellulose, polycarboxylic acid homopolymer or multipolymer or their salt, and polyamino compounds, said fiber derivative such as methylcellulose gum, carboxymethyl cellulose and Natvosol.The polymkeric substance of said type comprises polyacrylate, and maleic anhydride and ethene, the multipolymer of ethylene methacrylic ether or methacrylic acid, maleic anhydride account for multipolymer at least 20% (mole), and is disclosed as EP-A-137669.Polyamino compounds is disclosed in EP-A-305282 as those polyamino compounds that obtained by aspartic acid, among EP-A-305283 and the EP-A-351629.These materials and consumption are generally the 0.5%-10% of composition weight, preferred 0.75%-8%, more preferably 1%-6%.

Other available polymeric material is a polyoxyethylene glycol, particularly molecular weight is those polyoxyethylene glycol of 1000-10000, more preferably 2000-8000 molecular weight, most preferably from about 4000 molecular weight.Consumption is 0.20%-5% (wt), more preferably 0.25%-2.5% (wt).These polymkeric substance and aforementioned polycarboxylate homopolymer and multipolymer are having in the presence of the transition metal impurity, for improving white persistence, improve the fabric ash-deposition and clean clay, and the performance of albumen thing and oxidable dirt is valuable.

Preferred white dyes is suitable negatively charged ion, the example has: 4,4 '-two-(2-diethanolamine-4-anilino-S-three azines-6-base is amino) stilbene-2:2 '-disulfonic acid disodium, 4,4 '-two (2-morpholinoes-4-anilino-2-three azines-amino stilbene-2:2 ' of 6-base-disulfonic acid disodium, 4,4 '-two-(2,4-hexichol amido-S-three azines-6-base is amino) stilbene-2:2 '-disulfonic acid disodium, 4 ', 4 ' '-two-(2,4-hexichol amido-S-three azines-6-base is amino) stilbene-2-sulfonic acid one sodium, 4,4 '-two-(2-anilino-4-(N-methyl-N-2-hydroxyethylamino)-2-three azines-6-base is amino) stilbene-2,2 '-the disulfonic acid disodium, 4,4 '-two-(4-phenyl-2,1,3-tripyrrole-2-yl) stilbene-2,2 '-the disulfonic acid disodium, 4,4 '-two-(2-anilino-4-(1-methyl-2-hydroxyethylamino)-S-three azines-6-base is amino) stilbene-2,2 '-disulfonic acid disodium and 2 (stilbene radicals-4 " naphtho--1 '; 2 ': 4; 5)-1,2,3-tripyrrole-2 " sodium sulfonate.

The stain remover that can be used for the present composition is conventional unitary multipolymer of the different arrangement modes with ethylene glycol and/or propylene glycol of terephthalic acid or terpolymer, the example of these polymkeric substance be disclosed in common transfer US4116885 and 4711730 and EP-A-0272033 in.According to EP-A-0272033, a kind of particularly preferred polymkeric substance has following formula:

(CH ₃(PEG) ₄₃) _0.75(POH) _0.25[(T-PO) _2.8(T-PEG) _0.4] T (PO-H) _0.25((PEG) ₄₃CH ₃) _0.75Wherein PEG is-(OC ₂H ₄)-O-, PO are (OC ₃H ₆O) and T be (PCOC ₆CO).

The polyvinylpyrrolidone of some polymeric material such as MWt5000-20000, especially 10000-15000 also is to prevent in the washing process the insecure useful preparation of scurrying look of dyestuff between fabric.

Another kind of cleaning composition selectivity composition is a suds suppressor, is specially siloxanes, silicon-dioxide-mixture of siloxanes.Siloxanes can be the alkylation silicone materials usually, and silicon-dioxide generally uses with the form of fine dispersion, is specially aerosil and xerogel and various types of water drain silica.These materials can add with the form of particulate matter, and in particulate matter, suds suppressor preferably is added in water-soluble with releasable form or water is dispersible does not have substantially in the surface-active washing composition impenetrability carrier.In addition, suds suppressor dissolves in or is scattered in a kind of liquid vehicle, is added to other one or more components by the mode of spraying again and gets on.

As mentioned above, the silicone suds suppressor of Shi Yonging can comprise the mixture of a kind of alkylation siloxanes (above-mentioned indication type) and solid silica.This mixture is by making siloxane stationary on the solid silica surface.A kind of preferred silicone suds suppressor is a kind of granularity 10-20nm, and specific surface area is greater than 50m ²The hydrophobic silaneization of/g (preferably trimethyl silicone hydride) silicon-dioxide and molecular weight are about 500-200, the intimate mixture of 000 dimethyl siloxane liquid, and wherein the weight ratio of siloxanes and silanized silica is about 1: 1-1: 2.

A kind of preferred silicone suds suppressor is disclosed in people's such as Bartollota US3, in 933,672.Wherein the suds suppressor of particularly suitable is the gala silicone suds suppressor, is disclosed in German patent application DTOS2, in 646,126 (1977,4,28 is open).Wherein this examples of compounds is DC0544, can be purchased by Dow Corning, i.e. siloxanes/glycol copolymer.

The consumption of above-mentioned suds suppressor is generally the 0.001%-5% of composition weight, preferred 0.1%-3%.

Preferred adding method comprises: suds suppressor is sprayed on one or more main components of composition with liquid form; Perhaps, suds suppressor is made dispersed particles, mix with other solid ingredient of composition again.What add that foam modifying agent dispersed particulate matter can consider to use other simultaneously presses down foam material such as C ₂₀-C ₂₄Lipid acid, the high MWt multipolymer of Microcrystalline Wax and oxyethane and propylene oxide, otherwise they have disadvantageous effect to the dispersiveness of base-material.Prepare the US3 of this foam modifying agent particulate technology, have in 933,672 open people such as above-mentioned Bartolotta.

It is a kind of or some kinds of enzymes that another kind can be used for selectivity composition of the present invention.

Preferred enzyme material comprises commercially available amylase, neutrality and Sumizyme MP, and lipase, esterase and cellulase, these all are the enzymes that often add in the detergent composition.The enzyme that is suitable for is at US3, has in 519,570 and 3,533,139 open.

Preferred commercially available protein enzyme comprises those enzymes of the Maxatase of the trade(brand)name Alcalase of Novo Indnstries A/S (Denmark) and Savinase and International Bio-Synthetics company (Holland).

Preferred amylase comprises the amylase that obtains as by the extraordinary bacterial classification of B lichens shape, and GB1 has more detailed description among 269,839 (Novo).The Termamyl of preferred commodity starch enzyme as comprising that Rapidase that International Bio-Synthetics company sells and NovoIndustries A/S sell.

A kind of particularly preferred lipase is by Novo Industries A/S (Denmark) production and selling, and commodity are called Lipolase (Biotechnology Newswatch, 1988,3,7, P6), above-mentioned fat and other lipase that is suitable for are open in EP-A-0258068 (Novo).

Detergent composition of the present invention also can add fabric softener.These preparations can be mineral-type or organic class.Inorganic softening agent is specially GB-A-1, disclosed terre verte in 400,898.The organic fabric softening agent comprises GB-A-1514276 and the disclosed water-insoluble tertiary amine of EP-B-0011340.

They and single C ₁₂-C ₁₄The mixture of quaternary amine is at EP-B-0026527﹠amp; Open in 528.Other available organic fabric softening agent is two long-chain acid amides, described in EP-B-0242919.Auxilliary in the fabric softener system adds organic composition and comprises the high molecular weight polyethylene oxide material, as described in EP-A-0299575 and 0313146.

The consumption of terre verte-as be 5%-15% (wt), preferred 8%-12% (wt), this material adds in other composition in the prescription with the dried branch form that blendes together.The add-on of organic fabric softening agent such as water-insoluble tertiary amine or two long-chain acid amides materials is 0.5%-5% (wt), be generally 1%-3% (wt), and the add-on of high molecular weight polyethylene oxide material and water-soluble cationic material is 0.1%-2% (wt), is generally 0.15%-1.5% (wt).When a part of component spraying drying in the composition, these materials can be added in the water slurry of sending in the spray-drying tower, but in some cases, add, or they are sprayed on fused solution may be more more convenient on other solids component of composition do to mix the particulate form.

In general, granular detergent composition of the present invention can pass through several different methods, comprises dry blending, spraying drying, and agglomeration and process for granulating and make, preferable methods is the combined method of these technology.A kind of preferred method for preparing composition comprises spraying drying, agglomeration in high-speed mixer then, dry blending again.

As common laundry detergent composition such, the tap density of granular detergent composition of the present invention can be 400-600g/l.In addition, what granular detergent composition can concentrated type, it is characterized in that comparing and have higher density with common laundry detergent composition.The tap density of these high-density compositions is at least 650g/l, is generally 700g/l at least, preferred 800-1100g/l.

Tap density is measured by a simple funnel and cup device, said device is: a rigid molded conical hopper is arranged on a pedestal, in its bottom one flap valve is housed, material turned letter in the funnel is entered be placed on below the funnel and the tubular cup of axis centering in.This funnel is respectively 130mm and 40mm in two ends up and down, and the bottom is installed in 140mm place, pedestal upper surface top.Tube cup height overall 90mm, interior high 87mm, internal diameter 84mm.Normal volume 500ml.

In order to measure, from filling powder in the funnel, open flap valve, allow powder pour in the cup.Take out the tube cup of filling from shelf,, remove powder unnecessary in the cup with a straight flange instrument such as the horizontal upper limb of scraping cup of cutter.Then brimmer is weighed, gained powder weight on duty 2 promptly gets tap density g/l.If desired, can carry out replication.

The concentrated type detergent composition generally also is added with at least a multicomponent component, and promptly they do not comprise the composition of only making by dry each single composition.The composition of making by dried mixed each composition generally is a powdered, in slowly dissolving of duration of storage, also can lump, and makes particulate flowability variation.

According to the present invention, preferred granular detergent composition contains at least two kinds of particulate state multicomponent components.At least 15% of first kind of ingredients constitute composition weight.Be generally 25%-50%, but preferably be no more than 35%, the second kind of ingredients constitute composition weight 1%-50%, preferred 10%-40%.

First kind of component comprises a kind of by the anion surfactant that accounts for the heavy 0.75%-40% of powder and one or more inorganic and/or organic salt is formed particulate matter of 99.25%-60%.Particulate matter can be any suitable form such as granular, and sheet is spherical, ball shape or noodles shape, but preferably granular.Saccharoid can be by disc type or rotating cylinder agglomeration or the agglomerate that is shaped by a string mixing tank, but normally spray-dired particle, and the water slurry that is about to contain described composition atomizes in the hot blast that can remove its most of moisture content and the particle made.Then, spray-dired particle is carried out densification steps handle,, after this carry out agglomeration once more as handling to increase density by high-speed cutting mixing machine and/or grinder.In order to describe in detail, hereinafter first kind of component to the spray-dried powders form is described.

Have now found that the anion surfactant that first kind of component is suitable for is to dissolve straight-chain alkyl sulfate and straight-chain alkyl carboxylic acid's salt slowly, the former its alkyl on average contains 16-22 carbon atom, and the alkyl among the latter on average contains 16-24 carbon atom.The alkyl that is used for these two types of tensio-active agents is natural origin preferably, as shea butter and marine animal oil.

In the spray-dried powders that constitutes first component, the consumption of anion surfactant is 0.75%-40% (wt), and that more commonly used is 2.5%-25% (wt), preferred 3%-20% (wt), most preferably 5%-15% (wt).Can also comprise the water soluble surfactant active, as linear alkylbenzene sulfonate or C ₁₄-C ₁₅Alkyl-sulphate perhaps can be added to them on the spray-dired powder by spray subsequently.

Another main component in the spray-dried powders is one or more inorganic or organic salt, and these salt make particulate matter have crystalline structure.Inorganic and/or organic salt can be water-soluble or water-insoluble, and when the water-insoluble washing assistant had constituted washing assistant composition a part of, water-insoluble salt then was insoluble washing assistant or most ofly is the water-insoluble washing assistant.The water-soluble inorganic salt that is suitable for comprises alkaline carbonate and supercarbonate, if when silico-aluminate is not spray-dried component a part of, can use amorphous alkali metal silicate to make spray-dried granules have a fixed structure.

But, in the concentrated type detergent composition, preferably do not add sodium sulfate as the separant composition, as should reduce to greatest extent with sulfation (sulfonation) tensio-active agent bonded by product.

When with aluminosilicate zeolite as the washing assistant composition or when forming washing assistant composition a part of, it directly had better not be added in other component by dry blending, but be added in the multicomponent component.

Can also contain 15% (wt) following various compositions such as whitening agent, anti redeposition agent, photosensitization SYNTHETIC OPTICAL WHITNER (as tetrasulfonic acid zinc phthalocyanine) and sequestrant in first kind of component.When first kind of component is spray-dried powders, it typically is and be dried to the 7%-11% that moisture content is a spray-dried powders weight, preferably 8%-10%.The powder moisture content of producing by other method such as agglomeration technique can be lower, can be 1-10% (wt).

The granularity of first kind of component is conventional, and preferably, overall dimension is no more than 5% (wt) more than 1.4mm, and overall dimension is less than 10% (wt) that be no more than of 0.15mm simultaneously.Preferred at least 60% (wt), more preferably the powder size of at least 80% (wt) is between 0.7mm-0.25mm.For spray-dried powders, the packing density of particle that comes out from spray-drying tower is generally 540-600g/l, adds compacting tap density is improved as reduce granularity in high-speed cutting machine/mixing machine by other treatment steps then.In addition, except spraying drying, can directly form high density granular with other method.

Second kind of component in the preferred composition of the present invention is the another kind of multicomponent component that contains the water soluble surfactant active.

Tensio-active agent can be anionic, non-ionic type, cationic or half-shadow sexual type, or their any mixture.The tensio-active agent that is suitable for is listed at preamble, but preferred surfactants is C ₁₄-C ₁₅Alkyl-sulphate, C ₁₁-C ₁₅Linear alkylbenzene sulfonate and aliphatic C ₁₄-C ₁₈Methylmesylate.

Second kind of component can have any suitable profile,, can adopt sheet, spherical, ball shape, noodles shape, band shape or by spraying drying or non-spraying drying agglomeration and the particulate state that forms that is.Though in theory, second kind of component can only contain the water soluble surfactant active, in fact, should comprise at least a organic or inorganic salt so that processing.Said salt can make particle have certain degree of crystallinity, acceptable flow characteristics, and can be existing any or more than one the organic or inorganic salt of first kind of component.

The size range of second kind of component should be not contain the scope that forms boundary with the particle of first kind of component of its blended.Therefore, overall dimension should not surpass 5% (wt) more than 1.4mm, and simultaneously, the maximum value footpath should be no more than 10% (wt) less than 0.15mm.

The tap density of second kind of component, relevant with its preparation method.But preferred second kind of component forms the agglomerate of mechanically mixing, this agglomerate can prepare like this: be added to a disc type agglomeration machine with dry ingredients or with agglomerant, Z paddle stirrer or a line style mixing machine (Schugi (Holland) BV preferably, 29, Chroomstraat 8211AS, Lelystad, Netherlanda and Gebruder Lodige Maschinenban GmbH, D-4790 Padeyborn 1, Elsenerstrasse 7-9, those mixing machines that Postfach 2050 F.R.G. make).According to said method, the tap density of second kind of component can reach 650-1190g/l, is preferably 750g/l-850g/l.

In preferred laundry composition, the amount of the alkaline carbonate that second kind of component is contained is 3%-15% corresponding to the weight of composition, 5%-12% preferably, and therefore, the amount of carbonate is 20%-40% (wt) in second kind of component.

A kind of preferred composition is aforementioned synthetic zeolite type water-insoluble aluminosilicate ion exchange material in second kind of component, and its amount accounts for the 10%-35% of second kind of composition weight.The amount of the water-insoluble alumino-silicate materials that is added in this way is the 1%-10% (wt) of composition weight, preferably 2%-8% (wt).

In the method for second kind of component of a kind of preparation, surfactant salt is instant the generation in a line style mixing tank.Tensio-active agent joins one with the form of liquid acid and exceeds continuously in the mixture of particulate state anhydrous sodium carbonate in mixing machine such as the Lodige C6 mixing machine and hydrated sodium aluminosilicate, and be neutralized the generation surfactant salt, keep the particle properties of mixture simultaneously.The agglomerant mixture of gained becomes second kind of component, is added into then in other component of product.

In the aforesaid method of change to some extent, surfactant salt is earlier by pre-neutralization, and the form with mucilage is added in other mixing element again.By this variation, mixing machine only plays nodulizing makes described composition form second kind of component.

In a kind of preferred method for preparing granular detergent composition of the present invention, take out first kind of grain fraction that a part contains the spraying drying product, with a spot of nonionogenic tenside spray thereon, and then mix with residuum.Second kind of grain fraction made with above-mentioned preferred method equally.Then, with first kind and second kind of component and layered crystal silicate granules composition, perhydrate SYNTHETIC OPTICAL WHITNER and peroxyacid bleach precursor particle, other is dried to blend together branch as carboxy acid salt chelator arbitrarily, soil release polymer and enzyme are sent on the travelling belt together, send into thus again in the horizontal swing roller, in cylinder, spices and silicone suds suppressor are sprayed on the product.For particularly preferred composition, also to adopt another cylinder mixing step, in this step, the crystalline material of the fine dispersion of introducing a small amount of (about 2%wt) is to increase particulate density and the flowing property that improves product.

In preferably containing with the concentrated type Betengent product of alkali metal percarbonate as perhydrate salt, the existing discovery must the several product indexs of control such as its heavy metal ion content and equilibrium relative humidity.This composition that contains SPC-D that has improved stability is disclosed among the PCT application number WO92/06163 of common transfer.

Laundry composition of the present invention can also have benefited from release system, and this system can make the product partial concn in the automatic washing machine rotating cylinder temporarily higher when begin wash(ing)cycle.Avoided thus with pipe washer or dirt box in the relevant problem of product loss.

Packing into composition in one bag or can being easy in the container discharges to rotating cylinder, when composition began in wash(ing)cycle, along with stirring, heat up or immerse in the washing water in the rotating cylinder can be very fast from above-mentioned bag or discharge in the container.In addition, washing machine itself can be suitable for composition directly is added in the rotating cylinder, adds as the distribution device by ingress.

Comprise and be contained in one bag or the normally so design of the product of the detergent composition in the container: promptly during drying regime, container is in drying regime fully and goes out to prevent content, but, generally be that this product is suitable for discharging the content in the container when being immersed in the aqueous solution when placing wash environment.

Container generally is a softish, as bag (bag or pouch).Said bag can be to scribble the fibrous structure of impervious material so that store content, and is disclosed as EP-A-0018678.In addition, the insoluble synthetic polymeric material of its used water is made, edge sealing or closed, but can in hydration medium, split, as EP-A-0011500,0011501,0011502 and 0011968 is disclosed.A kind ofly be easy in water disruptive sealing mode easily and comprise a limit coating, the involution of water-soluble adhesive glue along bag, said bag is made by impermeable polymer thin film such as polyethylene or polypropylene.In the form of various bags or container, can adopt the lamination flake products, wherein the center flexible layers is flooded and/or is scribbled composition, and then adds one deck and multilayer skin, to produce the fabric aesthetic effect.Layer can perhaps contact with water and can separate hermetically so that still be in tacky state in use with layer, to promote the release of coating or impreg.

Another kind of lamination form comprises a convex-concave layer or reshapes layer so that a series of bags of sample containers to be provided, detergent component is promptly quantitatively deposited in each container, the first layer is placed on the second layer, makes that two-layer those area places that come in contact are sealed between bag sample container.Said component can particle, pulpous state or fused form are deposited, and before putting into them in the water, lamination would not make the content in bag sample container leak outside.When contacting with water, layer with layer can separate, also can still be in the state that is bonded together, unique requirement is, its structure should allow content snap-out release in bag sample container in solution.Bag number on the per unit area base is selectable, but generally at 500-25,000/m ²Between change.

Be applicable to that flexible laminar material of the present invention especially comprises sponge, paper and textiles and nonwoven fabric.

Yet preferred clothes washing method is that composition is incorporated in the rotating cylinder in the liquid around the fabric by a recycling distribution device, and said distribution device has can make liquid see through but the wall of porous solid ingredient not.

This class device is disclosed in EP-A-0343069 and 0343070.The back disclosed device of one application comprises one bag of flexible cover of shape, and it stretches out on supporting ring of hole by deciding, and said hole is suitable for this bag for enough products are provided a wash(ing)cycle.Part washing medium circulation via hole flows in the bag, dissolved product, and solution is outwards flowed out by the hole and enters washing medium then.Be furnished with shield cap on the supporting ring, with damp proof undissolved product outflow, this shield cap is generally, and stretch out some radial walls by the center hub of spoke wheel structure, or its mesospore is the similar structures of helicoidal surface.

J.Bland be disclosed in article among the Manufacturing Chemist (1989,11, P41-46) distribution device of particularly preferred particulate product has been described also, this particulate product is a kind of known particle (granulette) product.

Describe the present invention in detail in following non-limiting example, wherein all percentage all refer to weight, except as otherwise noted.

In cleaning composition, the abbreviation component is represented following meaning: LAS:C ₁₂Linear alkylbenzene sulphonic acid TAS: tallow alkyl sodium sulfate TAEn: every mol of alcohol is with the tallow alcohol 25EY of n moles of ethylene oxide ethoxylation: with the C that is mainly of average Y moles of ethylene oxide condensation _12-15Straight chain primary alcohol TAED: tetraacetyl ethylene diamine silicate: non-crystalline state silicic acid sodium (SiO ₂: Na ₂O ratio normal range) NaSKS-6: formula is δ-Na ₂Si ₂O ₅The layered crystal silicate carbonate: anhydrous sodium carbonate CMC: Xylo-Mucine zeolite A: formula is Na ₁₂(AlO ₂Si ₂O ₂) ₁₂27H ₂O's

Hydrated sodium aluminosilicate, initial particle size 1-10 μ m polyacrylate: the acrylate homopolymer Citrate trianion of MW14000: citrate trisodium dihydrate MA/AA:1: 4 toxilic acids/acrylic copolymer, molecular-weight average 80,000 perborate: anhydrous sodium perborate monohydrate SYNTHETIC OPTICAL WHITNER, empirical formula:

NaBO ₂H ₂O ₂Enzyme: proteolytic ferment and starch water that Novo Industries AS sells

Separate enzyme mixture DETPMP: diethylenetriamine five (methylene phosphonic acid), Monsanto sells,

Commodity are called Daquest 2060 suds suppressors: 25% paraffin (Mpt50 ℃), and 17% water drain silica,

58% paraffin oil ADDS: quadrol-N, N '-disuccinic acid, [S, S] its sodium salt shape

The isomer of formula

Example 1

Prepared following detergent composition (weight part).Composition A-D is a prior art, and composition E is the present invention.

A B C D ELAS 7.7 7.7 7.7 7.7 7.7TAS 2.4 2.4 2.4 2.4 2.4TAE11 1.1 1.1 1.1 1.1 1.125E3 3.3 3.3 3.3 3.3 3.3 Wessalith CSs 19.5 19.5 19.5 13.0 13.0 citrates 6.5 6.5 6.5--MA/AA 4.3 4.3 4.3 4.3 4.3NaSKS-6^*---10.0 10.0 citric acids ^*2.7 2.7TAE50 of--- ^*---0.3 0.3 carbonate, 11.1 11.1 11.1 9.8 9.8 perborate, 16.0 16.0 16.0 16.0 16.0TAED, 5.0 5.0 5.0 5.0 5.0EDDS--0.2-0.2CMC 0.5 0.5 0.5 0.5 0.5 foam inhibitors 0.5 0.5 0.5 0.5 0.5 enzymes 1.4 1.4 1.4 1.4 1.4 silicate (2.0 ratio) 4.4 4.4 4.4--MgSO₄0.4 0.4 0.4 0.4 0.4DETPMP-0.4---water and micro-thing be to equal amount

^*Exist with the layered crystal silicate granules.

Carry out 25 circulation washing machine tests of whole process to compare the performance of three kinds of compositions with Miele 701 washing machines.The cycle of washing comprises that prewashing and master wash circulation entirely for each.Each cycles of washing selected to boil wash setting (temperature=95 ℃), use 25 ° of Deutschland hardness (Ca: Mg=3: water 1), each washing loads is the white heavy fleece towel of 4 15cm * 30cm, knitting cotton and cotton fabric, first wash circulation entirely before, washes and 20g people are put into the washing machine rotary drum for dirt and " granulette " type distribution device of containing the 100g Betengent product.To subsequently 24 wash round-robin entirely each time, use the Betengent product and the artificial dirt of same amount.Artificial dirt comprises: 5g palmitinic acid, the clay that 5g stearic acid, 4g sieve, the dirty engine oil of 3g glycerine/trioleate and 3g.When washing loop ends entirely for 25, from washing machine, take out washes, drying, every to four fabrics of three classes measures whiteness/filth and heavy metal ion content then.

Keeping of whiteness

By the whiteness/pollution level of panel of experts with every fabric of 5 fens system Scheffe scale assessments.Three groups of comprehensive average results that contrast every group are set as follows, with the common object of reference of prior art composition A conduct that does not contain crystal layered silicate or sequestrant.

B/A C/A D/A E/A

0.89 0.04 0.39 1.75ss=confidence level is 95% statistics symbol.

Relatively B/A has illustrated the advantage that comprises the phosphoric acid salt sequestrant in composition A.Relatively C/A explanation is when there is not what advantage (NB: 0.2% (weight) EDDS is equivalent to 0.4% (weight) DETPMP) similarly when composition A adds EDDS.Few advantages when comparison D/A has illustrated with the part zeolite A of the layered crystal silicate granules replacement composition A that contains SKS-6, citric acid and TAE50 and whole lemon silicate.Obtained great advantage when relatively composition E of the present invention is used in the E/A explanation.

Heavy metal ion content

Stick to the incrustive heavy metal ion content of inorganic salt on every fabric in order to following method measurement.Scrape the sample that weighs 2 grams at least from every the fabric that obtains by above-mentioned 25 periodic tests.Then sample is placed in the clean ceramic crucible and in a fuming cupboard, heats with a Bunsen burner, up to fabric fight burnout fully till, in crucible, stay the inorganic salt residue.With exact chemical balance this inorganic salt residue of weighing, make it then to be dissolved in the 1M sulphuric acid soln of known volume.Then, utilize atomic absorption spectrometer to determine the iron of this solution, copper, zinc and mn ion content, like this, just obtained iron, copper, zinc and the manganese content of inorganic residues.

The overall average iron, copper, zinc and the manganese content that carry out the resulting inorganic residues of cloth testing with composition C, D and E are following listed.

C D E

2400ppm 950ppm 690ppm

Claims (15)

1. detergent composition, containing (a) 1% to 80% (weight) molecular formula is LMSi _xO _2x+1YH ₂O

Layered crystal silicate-like builder material, L is a basic metal in the formula, M be sodium or

Hydrogen, x are a number of 1.9 to 4, and y is a number of 0 to 20; (b) 0.05% to 10% (weight) quadrol-N, N '-disuccinic acid,

Or the ammonium salt of its an alkali metal salt, alkaline earth salt, ammonium salt or replacement or its mixing

Thing; (c) 0% to 30% (weight) is selected from anion surfactant, non-ionic surface

Promoting agent, zwitterionics, amphoterics, cation form

The detergent surfactant of surface-active agent and their mixture; (d) the auxilliary non-phosphate detergent that adds of 0% to 50% (weight) helps and washes compound.

2. by the described detergent composition of claim 1, it is characterized in that quadrol-N, N '-disuccinic acid component is its [S, S] isomeric forms.

3. by claim 1 or 2 described detergent composition, it is characterized in that quadrol-N, N '-disuccinic acid component is the magnesium composite form.

4. by claim 1,2 or 3 described detergent composition, it is characterized in that the layered crystal silicate material is δ-Na ₂Si ₂O ₅

5. by the described detergent composition of claim 1, it is characterized in that anion surfactant comprises a kind of C ₁₂-C ₂₀Alkyl-sulphate and every mole of water-soluble C that on average contains 1-7 oxyethyl group group ₁₁-C ₁₈The mixture of alkyl ethoxy sulfate, the weight ratio of the described alkyl ethoxy sulfate of wherein said alkylsurfuric acid salt pair is 2: 1 to 19: 1.

6. by the described detergent composition of claim 5, it is characterized in that alkyl-sulphate is C ₁₄-C ₁₅Alkyl-sulphate, alkyl ethoxy sulfate are every mole of C that on average contains three oxyethyl groups ₁₂-C ₁₅Alkyl ethoxy sulfate, wherein said weight ratio are 3.5: 1 to 10: 1.

7. by the described detergent composition of claim 1, it is characterized in that nonionogenic tenside is polyhydroxy fatty acid amide or its alkoxy derivative of following formula, R in the formula ¹Be H, C ₁-C ₄Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or their mixture, R ²Be C ₅-C ₃₁Alkyl, Z are the polyhydroxy alkyls with the straight chain hydrocarbon chain that directly is connected with at least 3 hydroxyls.

8. by the described detergent composition of claim 1, it is characterized in that nonionogenic tenside is the C that every mol of alcohol on average contains 3 to 8 moles of ethylene oxide ₉-C ₁₅Primary alcohol ethoxylate.

9. by the described detergent composition of claim 8, it is characterized in that primary alcohol ethoxylate is the C that every mol of alcohol on average contains 3 to 5 moles of ethylene oxide ₁₂-C ₁₅Primary alconol.

10. by the described detergent composition of claim 1, it is characterized in that the auxilliary nonphosphate builders compound that adds is selected from sodium silicoaluminate zeolite, alkaline carbonate and supercarbonate, carboxylate salt and polycarboxylate and maleic anhydride/acrylic copolymer.

11., it is characterized in that containing the auxilliary nonphosphate builders compound that adds of 7%-20% (weight) layered crystal silicate-like builder material and 10% to 40% (weight) by the described detergent composition of claim 1.

12., it is characterized in that containing the inorganic perhydrate SYNTHETIC OPTICAL WHITNER of 3% to 40% (weight) and 1% to 20% (weight) solid peroxygen acid blanching agent precursor by the described detergent composition of claim 1.

13. by the described detergent composition of claim 12, it is characterized in that inorganic salt hydrate excessively is a SPC-D, content is 5% to 30% of composition weight, solid peroxygen acid blanching agent precursor is TAED, and content is 1% to 10% of composition weight.

14., it is characterized in that containing the organic peroxide acid of 1% to 10% (weight) by the described detergent composition of claim 1.

15., it is characterized in that containing the auxilliary detergent ingredients that adds that is selected from detergent enzyme, outstanding dirty agent and anti-redeposition agent, white dyes, suds suppressor, spices and its mixture by the described detergent composition of claim 1.