CN1084560A - stable bleaching composition - Google Patents

Abstract

The invention provides and comprise peralcohol and quadrol-N, a kind of bleaching composition of N '-disuccinic acid or its salt.This bleaching composition demonstrates good bleach stability in the aqueous solution, and is used in particular at least partially in temperature greater than in the bleaching method that carries out under 60 ℃.Said composition also has good storage stability.This bleaching composition can be used for bleached fiber disposition fibrous matter and synthetic textiles, and also is the useful component of detergent composition.

Description

Stable bleaching composition

The present invention relates to comprise that the activity that contains stablizer discharges oxygen (peroxide) compound and without phosphorus bleaching composition, wherein when said composition was used as the aqueous solution in the bleaching process, this stablizer is feasible might control bleaching action.This stablizer also provides the good storage stability of product.This bleaching composition also is used as the component of detergent composition.

The application that is used to bleach the peralcohol of purpose is known in the art.So-called peralcohol refers to hydrogen peroxide or any other addition compound, and it comprises inorganic perhydrate salt such as perborate and percarbonate, or organic peroxide acid.The perborate conduct is used for for example doing washing and the component of the detergent composition that automatic tableware washs is known.Hydrogen peroxide is usually as for example SYNTHETIC OPTICAL WHITNER in fabric and pulp bleaching process.

In related bleaching process, preferably SYNTHETIC OPTICAL WHITNER is released in the mode of controlling in whole process.

The use that reaches the stablizer of minimum degree for the quick decomposition that makes peralcohol is confirmed in the peroxide bleaching technology well, because, compare with normal the decomposition automatically of the peralcohol that causes bleaching action, wherein, the oxygen that quick decomposition like this by peralcohol discharges does not have bleaching action usually, in fact, the quick decomposition of peralcohol may be deleterious.For example, the fiber disposition material in the strong basicity peroxide solution is corroded by the oxygen from quick decomposition, and the result is owing to this material has reduced intensity.For current laundry and dishwashing detergent condition, under the higher temperature conditions that the basic solution neutralization is stood in practice, stablizer should be preferably effective.This stablizer also should be and other component compatibility that are present in washing composition or the peroxide bleaching solution.

Well-knownly be, the decomposition that some heavy metal ion can the agent of catalysis peroxide bleaching, this heavy metal ion is present in the wash water solution of laundry and dishwashing detergent process inevitably, and the result becomes the component of numerous food product and/or object dirt.Heavy metal ion also is the component of the aqueous solution of wood pulp bleaching process usually, and this wood pulp often absorbs from those ions that are used to tear the machine of pinching spile and wood pulp.

Therefore heavy metal chelant is used, so that be controlled at the content of the free heavy metal ion of the aqueous solution peroxide solution that is used for bleaching process, is by preventing that the agent of heavy metal ion catalytic decomposition peroxide bleaching from playing the effect of bleaching stibilizer.

Discovery once for example is widely used as a kind of sequestrant of bleaching stibilizer in Betengent product be edetate (EDTA).Yet, because the relation of the environmental persistence of non-biodegradable this sequestrant, its present use of having slowed down.

Organic phosphonate and amino alkylidenyl many (alkylene phosphonic acids salt) sequestrant also is known as bleaching stibilizer (for example be described in United States Patent (USP) 3,860,391 and 4,239,643 in).In paper pulp and fabric bleaching method and the phosphine acid salt chelator that in detergent composition, uses be known.Yet common employed phosphine acid salt chelator also is non-biodegradable in these class methods now.

P contained compound also with the connection that links to each other with undesirable eutrophication effect in the river in the lake, and this has caused for example making the surprising minimizing of employed phosphorous washing assistant composition in the detergent composition.

Laundry detergent composition contains without phosphorus sequestrant, i.e. quadrol-N, and N '-disuccinic acid (EDDS) is disclosed among the EP-A-0267653.Thisly point out that openly in the time of in EDDS being incorporated into this class detergent composition, it can help in laundry processes food, beverage and some other organic dirt to be removed from fabric.The disclosure also points out, EDDS can be used to replace all or part of phosphine acid salt chelator that is generally used in many existing Betengent products.This application people is open, and when EDDS was used as the component of detergent composition, it can help to remove the degrease dirt.The EDDS molecule has two chiral centres.Point out openly that in EP-A-0267653 the biological degradation of EDDS can think to have special optically active isomer the fastest and [S, S] isomer that maximum range is degraded.

This application people has now confirmed the character of the biodegradable special optically active isomer of EDDS, and described [S, S] isomer is the optically active isomer of unique totally biodegradable, and it is decomposed in the residence time of the sewage treatment process of routine basically fully.

Beyond thoughtly be the also open EDDS that uses content with the form of special EDDS of this application people: the weight ratio of in containing the aqueous solution of some heavy metal ion, using the peralcohol that provides fabulous aspect the stabilizer function of peralcohol.Under elevated temperature (＞60 ℃), this stabilization has special significance.Surprisingly, under identical condition, EDDS provides the bleach stable effect more much better than its chemical isomerization body EDTA.This application people also finds, EDDS is incorporated into the improved storage-stable agent that the sort of composition is provided in the bleaching composition.

EP-A-0267653 points out that the EDDS of containing laundry detergent composition described herein also can contain as the SYNTHETIC OPTICAL WHITNER of selecting component, bleach activator, bleaching stibilizer etc., in the document, does not disclose peralcohol especially.EP-A-0267653 has also mentioned document [by J.Majer, V.Springer and B.Kopecka are disclosed in Chem.Zvesti.20(6): 414-422(1966) in (CAS make a summary 65:11738f)].This piece document has provided for EDDS and heavy metal ion Fe ³⁺, Cu ²⁺, Ni ²⁺, Co ²⁺, Zn ²⁺, Pb ²⁺, and Cd ²⁺The stability constant of title complex, and provided these stability constants with for the comparison of the corresponding stability constant of the title complex of EDAT.For removing Cu ²⁺Outside each these metal ion, the stability constant of the EDDS title complex all stability constant than EDTA title complex is low.In fact, for Cu ²⁺The stability constant of stability constant and EDTA title complex be identical.Therefore, under heating up, EDDS is that this discovery than the applicant of the better bleaching stibilizer of EDTA is more beyond thought in the disclosed document that this piece can be used to speak.

Therefore, the purpose of this invention is to provide the bleaching composition that comprises peralcohol and without phosphorus sequestrant, the EDDS in this composition has particularly shown good bleach stability under the situation of temperature＞60 of solution ℃ in the aqueous solution.

An aspect of of the present present invention has provided a kind of bleaching composition, and said composition comprises:

(a) peralcohol, it is selected from addition compound, organic peroxide acid and its mixture of hydrogen peroxide and hydrogen peroxide; With

(b) quadrol-N 0.05% to 2%(composition weight), N '-disuccinic acid, or the ammonium salt of an alkali metal salt, alkaline earth salt, ammonium salt or its replacement, or its mixture, wherein said peralcohol and said quadrol-N, the scope of the weight ratio of N '-disuccinic acid is 800: 1 to 10: 1.

Preferably, said peralcohol and said quadrol-N, the scope of the anharmonic ratio of N '-disuccinic acid is 400: 1 to 20: 1, is more preferably 200: 1 to 40: 1, and most preferably is 150: 1 to 50: 1.

The amount that peralcohol exists is preferably 0.5 to 60%, and more preferably 1% to 40%, most preferably be 2% to 25%(bleaching composition weight).

Bleaching composition of the present invention can be used in main any bleaching method.According to the present invention, be the basic solution that bleaching method will use the aqueous solution of bleaching composition on the one hand, the scope that has preferred pH value for said solution is 7.5-12.5, more preferably 9-12 most preferably is 9.5-11.5.

According to the present invention, be that bleaching method contains use the acid peralcohol of bleaching preparations on the other hand.Said preparation is generally used for bleaching in the application of additive or family expenses/hard surface detergent.It is 0.5 to 6 that this acid bleaching agent generally has pH value, is preferably 1 to 5.

Preferably, bleaching method of the present invention is higher than under 60 ℃ in temperature at least in part and carries out.

First basal component of bleaching composition of the present invention is a peralcohol.This peralcohol can be any addition compound or the organic peroxide acid of hydrogen peroxide or hydrogen peroxide, or its mixture.The addition compound of so-called hydrogen peroxide refers to by hydrogen peroxide and second kind of chemical compound (can be for example organic salt, urea or organic carboxylate) addition so that obtain the compound that addition compound forms.The example of the addition compound of hydrogen peroxide comprises the compound that inorganic perhydrate salt, hydrogen peroxide and organic carboxylate, urea form, and the compound that closed by cage of hydrogen peroxide.

The example of inorganic perhydrate salt comprises perborate, percarbonate, superphosphate, persulphate and persilicate.This inorganic perhydrate salt is an alkali metal salt normally.Hydrogen peroxide is described among the GB-A-1494953 by the salt that cage closes.

SPC-D is the preferred inorganic perhydrate salt that is included in the granular bleaching composition of the present invention.This can be with monohydrate or with empirical formula NaBO ₂H ₂O ₂3H ₂The form of O is introduced into.

Any composition that bleaching composition of the present invention and they can be introduced into can have for example solid of main any outward appearance, and it comprises powder, bar-shaped and granular, or fluid, and it comprises liquid, gel and mashed prod.Yet when peralcohol is hydrogen peroxide, bleaching composition will comprise hydrogen peroxide and EDDS concentrated solution together usually.When peralcohol is inorganic perhydrate salt, this bleaching composition will be solid usually, preferably be actually granulous.Said inorganic perhydrate salt can the form of the crystalline solid of protection be included in this class granular composition to have in addition.Yet for some perhydrate salt, the preferred method of this class granular composition is to use the coating form of material, and said material provides storage stability preferably for the perhydrate salt in granulated product.

SPC-D is the perhydrate salt very preferably that is included in the granular bleaching composition of the present invention, and it is to have corresponding to formula 2Na ₂CO ₃3H ₂O ₂Addition compound, and the form that it can crystalline solid has been bought from the market.Most preferably, percarbonate is introduced in this based composition with the form of coating.Most preferred coated substance comprises the mixture of alkali-metal vitriol and carbonate.This coating and coating process were described in GB-1 in the past, and 466,799(1977 March 9 authorized Interox) in.The mixing salt of coated substance is 1: 200 to 1: 4 with the scope of the weight ratio of percarbonate, is more preferably 1: 99 to 1: 9, and most preferred is 1: 49 to 1: 19.Preferably, mixing salt is to have general formula Na ₂SO ₄.n.Na ₂CO ₃Sodium sulfate and the mixing salt of yellow soda ash, in its formula, n is 0.1 to 3, preferred n is 0.3 to 1.0, and most preferably n is 0.2 to 0.5.

The coated substance of Shi Heing is that formula is SiO in addition ₂: Na ₂The water glass of O, its weight ratio are 1.6: 1 to 3.4: 1, and preferred 2.8: 1, it was to use with the form of the aqueous solution, is that 2% to 10%(of SPC-D weight is generally 3% to 5% to obtain content) silicate solid.Magnesium Silicate q-agent also can be included in the coating.Other coated substances that are fit to comprise the vitriol and the carbonate of basic metal and alkaline-earth metal.

Crossing a Potassium Persulphate is the inorganic perhydrate salt of useful especially another kind in the said composition.Corresponding organic peroxide acid, it also is useful promptly crossing a persulfuric acid.

Carry out when temperature is lower than about 60 ℃ when bleaching method to the small part of using bleaching composition of the present invention, bleaching composition of the present invention also preferably contains the other SYNTHETIC OPTICAL WHITNER that is more suitable for cold bleaching.These SYNTHETIC OPTICAL WHITNER will comprise for example peroxyacid bleach precursor (bleach-activating agent).Yet, in bleaching composition of the present invention, exist the major advantage of EDDS to be the stabilization of peralcohol, when being used for high temperature (＞60 ℃) bleaching method, under lower solution temperature, it still plays effective sequestrant.Therefore, the sequestering action of the heavy metal ion that is provided by EDDS also can be stablized any organic peroxide acid bleaching components, and this component is that the form with active bleaching agent exists under these lower solution temperatures.

When EDDS was incorporated into the composition that contains SYNTHETIC OPTICAL WHITNER, it also provided the characteristic of improved storage stability.When the form of the composition that contains SYNTHETIC OPTICAL WHITNER, or, can observe the characteristic of this improved storage stability especially to have pH value when being the form preparation of 0.5 to 6 acidic formulation with alkaline detergent composition.The characteristic of the good storage stability that is reached for the acid bleaching preparation is a specific question known in the art.

This peroxyacid bleach precursor contains one or more N-or O-acyl group mostly, and above-mentioned precursor can be selected from various types of precursors.The precursor that is fit to kind comprises the derivative of the acidylate of acid anhydride, ester, imide and imidazole and oxime, and in the precursor of these kinds the case description of useful material in GB-A-1586789.Most preferably the precursor of kind is an ester, for example be disclosed among the GB-A-836988,864798,1147871 and 2143231, and imide, for example be disclosed in GB-A-855735 and 1246338.

Particularly preferred precursor compound is the N of following formula, N, N ', the compound of N ' tetrem acidylate

Wherein X can be 0 or 1 to 6 integer.

Example comprises wherein tetrem acyl methanediamine (TAMD), the tetraacetyl ethylene diamine (TAED) of X=2 and the tetrem acyl hexanediamine (TAHD) of X=6 of X=1.These compounds and similar compound are described among the GB-A-907356.Most preferred peroxyacid bleach precursor is TAED.

The compound that the acid amides that another kind of preferred peroxy acid bleach activator compound is following general formula replaces:

R wherein ¹For containing 1 aryl or the alkyl of having an appointment, R to about 14 carbon atoms ²For containing alkylidene group, arylidene and the alkarylene of 1 to 14 carbon atom of having an appointment, and R ⁵For H or contain alkyl, aryl or the alkaryl of 1 to 10 carbon atom, and L can be main any leavings group.Preferred R ¹Contain 6 to 12 carbon atoms of having an appointment, R ²Preferably contain 4 to 8 carbon atoms of having an appointment.R ¹Can be the aryl of alkyl, replacement of straight or branched or alkaryl or the both of containing substitution in side chain and exist, it can derive from synthetic source or comprise natural source as beef fat, for R ², the variation of similar structures allows.Replacement can comprise alkyl, aryl, halogen, nitrogen, sulphur and other general substituting group or organic compound.R ⁵Preferred H or methyl.R ¹And R ⁵Summation should not contain greater than 18 carbon atoms.The bleach activating immunomodulator compounds that this class acid amides replaces is described among the EP-A-0170386.

Other peroxyacid bleach precursor compounds comprise acyloxy benzene sulfonic acid sodium salt in the ninth of the ten Heavenly Stems, trimethyl acetyl oxygen base benzene sulfonic acid sodium salt, acetoxyl group benzene sulfonic acid sodium salt and benzoyloxy benzene sulfonic acid sodium salt, and it for example is disclosed among the EP-A-0341947.

Composition of the present invention contains just like the peralcohol organic peroxide acid, the peroxy acid that the acid amides that a wherein particularly preferred class is following general formula replaces:

R wherein ¹, R ²And R ⁵Aforementioned definitions as the peroxy acid bleach activator compound that replaces for corresponding amide.

Other organic peroxide acids comprise diacyl peroxide and dialkyl peroxide.What be fit to is diperoxy dodecandioic acid, diperoxy four sebacic acid, diperoxy 16 diacid, and one and two cross nonane diacids, one and two crosses undecane dicarboxylic acids, a peroxide phthalic acid, peroxybenzoic acid and their salt, and it for example is described among the EP-A-0341947.

When particularly the form of the component of the bleaching composition of acidic liquid was introduced with liquid, this peralcohol and particularly any organic peroxide acid can be dissolved or be disperseed, or are introduced into the form of emulsion or suspension.

It is 0.05% to 2%(composition weight that bleaching composition of the present invention contains second basal component), be preferably 0.05% to 1%(weight), most preferably be 0.1% to 0.5%(weight) quadrol-N, the ammonium salt of N '-disuccinic acid (EDDS) or an alkali metal salt, alkaline earth salt, ammonium salt or its replacement, or its mixture.Preferred EDDS compound is free acid form and sodium or magnesium salts or its title complex.This is that the sodium salt example of preferred EDDS comprises Na ₃EDDS.The example of the magnesium complex of the preferred EDDS of this class comprises MgEDDS and Mg ₂EDDS.

Magnesium complex is to be included in most preferred in the granular composition of the present invention.For example, these title complexs can be added in the said composition, perhaps by inertia magnesium salts such as MgCl ₂Or MgSO ₄With the EDDS compound reaction that exists with free acid or another kind of salt or complex form with the preparation said composition, in this process, can form these title complexs.When EDDS in this preparation process was added into the inertia magnesium salts, preferably, the mol ratio of magnesium salts and EDDS should be greater than 1: 1, more preferably greater than 3: 1, to guarantee to form required magnesium salts title complex.

The structure of the sour form of EDDS is as follows:

EDDS can be synthesized, and for example for example maleic anhydride and quadrol synthesize by the raw material of the following cheapness that obtains easily.

Synthesize by raw material available on the market EDDS method more fully openly can be at United States Patent (USP) 3,158,635(1964 issued in Kezerian and Ramsay November 24) in find.

Owing to have two unsymmetrical carbons, synthesize the mixture that EDDS produces three kinds of optically active isomers, i.e. [R, R], [S, S] and [S, R] type by maleic anhydride and quadrol.What the biological degradation of EDDS obtained is special optically active isomer, because [S, S] isomer carries out the fastest and degrade the most widely, therefore, [S, S] isomer is to be included in most preferred in the composition of the present invention.

[S, S] isomer of EDDS can be synthesized by following L-aspartic acid and glycol dibromide.

By L-aspartic acid and 1, the reaction of 2-ethylene dibromide is to form [the S of EDDS, S] isomer more fully openly can be at document (Neal and Rose, Stereospecific Ligands and Their Complexes of Ethylenediamine discuccinic Acid, Inorganic Chemistry, VO1.7(1968), find in PP.2405-2412).

Bleaching composition of the present invention is useful for bleached fiber disposition fibrous matter.Term as used herein fiber disposition fibrous matter relates to wood, cotton, flax, jute and other fiber disposition materials, and also comprise single fiber, for example wood pulp or cotton fibre, and other aggregates of yarn, hards, reticulation, fabric (weaving or nonwoven) and this fibrid.Bleaching composition of the present invention comprises that for bleaching the synthetic textiles of polymeric amide, viscose glue, regenerated fiber and polyester also is useful.

Bleaching composition of the present invention also is useful in cleaning composition.What these cleaning composition can be used on the needs bleaching mainly is in washing, laundry or the purging method.Therefore, this cleaning composition can be used as the detergent use of laundry additive composition, dirt pretreatment compositions, carpet and furniture in family or industry washing or automatic tableware washing methods, and can be used for comprising in any method of cleaning of washing, dairy farm of the cleaning of crust such as bottle, and comprise and be used for the method for cleaning as the kitchen of taking out toilet and bathroom.

In the method that is used for bleached fiber disposition fiber or synthetic textiles, bleaching composition of the present invention uses in the aqueous solution.The most preferred peralcohol that is used for these class methods is a hydrogen peroxide.The pH value of peroxide aqueous solution inorganic base metal alkaline matter commonly used such as sodium hydroxide, yellow soda ash, water glass and its mixture are regulated.Best pH value is 7.5 to 12.5.Usually, if pH value is higher than at about 12.5 o'clock, the very fast decomposition of peralcohol is not difficult to control suitable bleaching speed to cause having too to damage under the situation of fiber.Be lower than at about 7.5 o'clock at pH value, in most of the cases, making bleaching speed is uneconomic degree to reach for bleaching slowly.

When for provide alkalescence can use silicate particularly during water glass at the peroxide solutions that is used for bleached fiber disposition fiber, it tends to formed settling by on the fiber of bleaching, and that is to say, its use preferably remains on minimum.Most preferably, when using bleaching composition of the present invention, the peralcohol solution that is used for bleached fiber disposition fiber and synthetic textiles does not contain silicate.

The concentration of the EDDS stablizer in fiber disposition fiber or synthetic textiles bleaching peralcohol solution can change, it depends on kind, pH value, temperature of the concentration of peralcohol solution particularly, employed peralcohol etc., usually, use the concentration and the conventional fiber disposition fiber/synthetic textiles bleaching method of use of the peralcohol solution of regulation, the concentration that preferred EDDS exists is 0.0005% to 0.5%(weight), particularly preferred concentration is 0.001% to 0.1%(weight).

The method of bleaching that use contains the peralcohol solution of bleaching composition of the present invention can alter a great deal, for example use peralcohol solution down for about 70 ℃ to about 100 ℃ in temperature, time cycle is about 30 minutes to about 6-8 hour, and can use the continuous bleaching method, this method need be used peralcohol solution down for promptly about 25 ℃ at normal temperature, and contact with cellulosic material by state of saturation, promptly remove excessive moisture, and fiber disposition material is exposed to temperature is in about 100 ℃ to the 135 ℃ saturation steam, in some cases, time cycle is several seconds (about 20 seconds) extremely about 1 hour, even the longer time.United States Patent (USP) 2,839,353,2,960,383 and 2,983,568 can be used as the illustration of continuous peroxide bleaching method.

Bleaching composition of the present invention also can be incorporated into the composition that is used for main any laundry, washing or purging method, and the laundry composition of introducing bleaching composition of the present invention can be prepared and become granular composition and heavy duty detergent liquid composition.

In addition, said composition generally can contain those components that exist usually in Betengent product, it can comprise organic surface active agent, washing assistant, anti redeposition agent, soil-suspending agent, suds suppressor, enzyme, white dyes, photosensitization SYNTHETIC OPTICAL WHITNER, spices, filling salt, sanitas and pigment.

Laundry also can contain fabric softener and static inhibitor with cleaning composition.

Various tensio-active agents all can be used in this detergent composition.General listed negatively charged ion, nonionic, both sexes, zwitterionics, and various these tensio-active agents are at United States Patent (USP) 3,929,678(1975 issued in Laughlin and Heuring December 30) in provide.The listed cats product that is fit to is at United States Patent (USP) 4,259, and 217(1981 issued in Murphy March 31) in provide.

The mixture of anion surfactant be suitable for of the present invention, the mixture of vitriol, sulfonate and/or carboxylate surface active agent particularly.Usually use the mixture of sulfonate and vitriol, wherein the weight ratio of sulfonate and vitriol is 5: 1 to 1: 2, is preferably 3: 1 to 2: 3, more preferably 3: 1 to 1: 1.Preferred sulfonate is included in the alkylbenzene sulfonate that has 9 to 15 preferred 11 to 13 carbon atoms in the alkyl, and α-sulfonation fatty acid methyl ester, and wherein lipid acid is by C ₁₂-C ₁₈The preferred C of fat source ₁₆-C ₁₈Fat source is derived.Under each situation, said positively charged ion is a basic metal, is preferably sodium.Preferred sulfate surfactant with the form of this class sulfonate sulfate mixture is the alkyl-sulphate that has 12 to 22 preferred 16 to 18 carbon atoms in alkyl.

Useful in addition surfactant system contains the mixture of two kinds of alkyl-sulphate materials, and these materials represent to have different chain lengths mutually separately.A kind of such system contains C ₁₄-C ₁₅Alkyl-sulphate and C ₁₆-C ₁₈The mixture of alkyl-sulphate, wherein C ₁₄-C ₁₅: C ₁₆-C ₁₈Weight ratio be 3: 1 to 1: 1.Alkyl-sulphate also can combine with alkyl ethoxy sulfate, and said alkyl ethoxy sulfate has 10 to 20 preferred 10 to 16 carbon atoms in its alkyl and average degree of ethoxylation is 1 to 6.The positively charged ion of every kind of situation is a basic metal still, is preferably sodium.

Particularly preferred in addition anionic surfactant system contains C ₁₂-C ₂₀Alkyl-sulphate and water miscible C ₁₁-C ₁₈The mixture of alkyl ethoxy sulfate, said alkyl ethoxy sulfate has average 1 to 7 oxyethyl group for every mole, wherein the scope of the weight ratio of alkyl-sulphate and alkyl ethoxy sulfate is 2: 1 to 19: 1, more preferably 3: 1 to 12: 1, and most preferably be 3.5: 1 to 10: 1.

Alkyl-sulphate can be derived by natural or synthetic hydrocarbon source.The preferred examples of this class salt comprises the C of basic collateralization ₁₄-C ₁₅Alkyl-sulphate, that is to say, C ₁₄-C ₁₅The collateralization degree of alkyl chain is greater than about 20%.The C of the basic collateralization of this class ₁₄-C ₁₅Alkyl-sulphate is derived by synthetic source usually.C equally preferably ₁₆-C ₂₀Alkyl-sulphate, it is derived by natural source such as beef fat and signalling oil peculiar to vessel usually.

C ₁₁-C ₁₈Alkyl ethoxy sulfate contains the primary alkyl ethoxy sulfate, and it is by C ₁₁-C ₁₈The condensation product that pure and every mole of average 1 to 7 Oxyranyle carries out condensation is derived, preferably, and C ₁₂-C ₁₅Alkyl ethoxy sulfate, itself and every mole of average 1 to 5 oxyethyl group condensation are most preferably with every mole of average 1 to 3 oxyethyl group condensation.

C ₁₁-C ₁₈Alcohol can so be obtained by natural or synthetic source itself.So, C ₁₁-C ₁₈Alcohol (derive obtain by natural fat), or the product formed of Ziegler alkene, or oxo process can form suitable alkyl source.Comprise Dobanol 25(RTM by the synthetic example of material deutero-) (by Shell Chemicals(UK) Ltd sale), it is C ₁₂-C ₁₅The mixture of alcohol, Ethyl 24(is sold by Ethyl Corporation), it is C ₁₃-C ₁₅The mixture of alcohol, wherein ratio is 67%C ₁₃, 33%C ₁₅(trade(brand)name is Lutensol, is sold and trade(brand)name is Synperoinc(RTM by BASF Gmbh) sold by ICI Ltd.) and Lial 125(by Liquichimica Italiana sale).The example of naturally occurring material (can obtain alcohol thus) is Oleum Cocois and palm kernel oil and corresponding lipid acid.C ₁₁-C ₁₈The content of alkyl ethoxy sulfate is preferably 0.5% to 10%, and more preferably 0.5% to 5%, and most preferably be 1% to 3%(composition weight).

Other are suitable for the basic metal sarcosinate (Sarcosinate) that anion surfactant of the present invention is a following formula:

R is C in the formula ₅-C ₁₇Straight or branched alkyl or alkenyl, R ¹Be C ₁-C ₄Alkyl and M are alkalimetal ions.Preferred examples is lauroyl, the coconut acyl (C with its sodium-salt form ₁₂-C ₁₄), myristoyl and oleoyl methyl sarcosinate.

One class is used for the condenses that anion surfactant of the present invention comprises oxyethane and hydrophobic part, the scope that its tensio-active agent that provides has average hydrophilic-lipophilic balance (HLB) is 8 to 17, be preferably 9.5 to 13.5, more preferably 10 to 12.5.In fact that hydrophobic (oleophylic) part can be aliphatic series or aromatics, and can be conditioned easily with the length of the polyoxyethylene groups of specific hydrophobic base condensation, a water-soluble cpds of the required balance degree between hydrophilic and hydrophobic units had with generation.

The particularly preferred anion surfactant of this class is C ₉-C ₁₅Primary alcohol ethoxylate, its every mole contains average 3-8 moles of ethylene oxide, particularly C ₁₄-C ₁₅Primary alcohol ethoxylate, its every mol of alcohol contains average 6-8 moles of ethylene oxide, and C ₁₂-C ₁₅Primary alcohol ethoxylate, its every mol of alcohol contains average 3-5 moles of ethylene oxide.

Another kind of anion surfactant comprises the alkyl polyglucoside compound of following general formula:

The part of Z for deriving and obtain in the formula by glucose; R is the saturated hydrophobic alkyl that contains 6 to 18 carbon atoms; T be 0 to 10 and n be 2 or 3; X is 1.1 to 4, and this compound comprises less than 10% unreacted fatty alcohol with less than 50% short-chain alkyl polyglucoside.This compounds and its application in detergent composition are disclosed among the EP-B-0070074,0070077,0075996 and 0094118.

Another kind of preferred anionic surfactants tensio-active agent is the polyhydroxy fatty acid amide with following structural formula:

In the formula: R ¹Be H, C ₁-C ₄Alkyl, 2-hydroxyethyl, 2-hydroxypropyl, or its mixture are preferably C ₁-C ₄Alkyl, more preferably C ₁Or C ₂Alkyl most preferably is C ₁Alkyl (being methyl); R ²Be C ₅-C ₃₁Alkyl is preferably straight chain C ₇-C ₁₉Alkyl or alkenyl, more preferably straight chain C ₉-C ₁₇Alkyl or alkenyl most preferably are straight chain C ₁₁-C ₁₇Alkyl or alkenyl, or its mixture; With Z be polyhydroxy alkyl (its have have the straight-chain alkyl of directly linking at least 3 hydroxyls on the chain), or its oxyalkylated derivative (being preferably ethoxylation or propoxylated derivative).Preferably, Z will be derived by the reducing sugar in reductive amination process and obtain; More preferably Z is glucosyl (glycityl).The reducing sugar that is fit to comprises glucose, fructose, maltose, lactose, semi-lactosi, seminose and wood sugar.As raw material, not only above-mentioned monose can use, and can use senior glucose maize treacle, senior fructose maize treacle and senior maltose maize treacle.These maize treacle can produce the mixture for the sugar component of Z.Should think that this does not also mean that other raw materials that are fit to of attempt eliminating.Z is preferably selected from-CH ₂-(CHOH) n-CH ₂OH-CH(CH ₂OH)-(CHOH) _N-1-CH ₂OH ,-CH ₂-(CHOH) ₂(CHOR ') (CHOH)-CH ₂OH(wherein n is 3 to 5 integer, and the R ' that is included is H or ring-type or aliphatic monose) and its alkoxy derivative, most preferred for n wherein be 4 glucosyl, particularly CH ₂-(CHOH) ₄-CH ₂OH.

In formula I, R ¹Can be for example N-methyl, N-ethyl, N-propyl group, N-sec.-propyl, N-butyl, N-2-hydroxyethyl, or the N-2-hydroxypropyl.

R ²-CO-N＜can be for example cocoamide, stearylamide, oleylamide, laurylamide, myristamide, decyl amide, palmitic amide, tallow acid amides etc.

Z can be 1-deoxy-glucose base, 2-deoxidation fructosyl, 1-deoxidation malt-base, 1-deoxidation lactose base, 1-deoxy-galactose base, 1-deoxymannose base, 1-deoxidation Fructus Hordei Germinatus three alcohol radicals (1-deoxy-mato-triotityl) etc., and preferred compound is N-methyl N-1 deoxy-glucose base C ₁₄-C ₁₈Fatty acid amide.

Another kind of tensio-active agent is semi-polarity tensio-active agent such as amine oxide.The amine oxide that is fit to is selected from single C ₆-C ₂₀, preferred C ₁₀-C ₁₄N-alkyl or alkenyl amine oxide and propylidene-1,3-titanium dioxide amine, wherein the position of remaining N is replaced by methyl, hydroxyethyl or hydroxypropyl.

Cats product also can be used in the detergent composition of the present invention, and the quaternary ammonium surfactant that is fit to is selected from single C ₈-C ₁₆, preferred C ₁₀-C ₁₄N-alkyl or alkenyl ammonium surfactant, wherein the position of remaining N is replaced by methyl, hydroxyethyl or hydroxypropyl.

The laundry detergent composition of introducing bleaching composition of the present invention contains 3% to 30% tensio-active agent, but more generally contains 5% to 20%, more preferably contains 7% to 15%(composition weight) tensio-active agent.

The automatic dishwashing detergent composition of introducing bleaching composition of the present invention contains 0% to 10%, and is preferred 0.5% to 10%, most preferably 1% to 5%(composition weight) tensio-active agent.This tensio-active agent can be selected from negatively charged ion, positively charged ion, nonionic, both sexes or zwitterionics.Most preferably, tensio-active agent is low foamy.The general listed tensio-active agent that is included in the automatic dishwashing detergent composition provides in EP-A-0414549.

Most preferably low foam nonionogenic tenside, particularly water miscible ethoxylation C ₆-C ₁₆Fatty Alcohol(C12-C14 and C12-C18) and C ₆-C ₁₆Blended ethoxylated/propoxylated fatty alcohol and composition thereof.Preferably, ethoxylized fatty alcohol is that to have ethoxylation degree be 5 to 50 C ₁₀-C ₁₆Ethoxylized fatty alcohol, most preferred ethoxylized fatty alcohol are that to have ethoxylation degree be 8 to 40 C ₁₂-C ₁₆Ethoxylized fatty alcohol.Preferably, the blended ethoxylated/propoxylated fatty alcohol has the alkyl chain length of 10 to 16 carbon atoms, and has ethoxylation degree 3 to 30 and the propoxylation degree is 1 to 10.

Various surfactant mixtures are preferred, and more preferably negatively charged ion-non-ionic mixture, and negatively charged ion-nonionic-cationic mixture also is preferred.Particularly preferred mixture is described among GB-A-2040987 and the EP-A-0087914.Although this tensio-active agent can be incorporated into the form of mixture in the composition, preferably control the degree of the adding of every kind of tensio-active agent, so that the physical property of preferred said composition and the problem of avoiding technological process to occur.

The order that preferred pattern and tensio-active agent add is described hereinafter.

The another kind of particularly preferred component of detergent composition of the present invention is the builder system that contains one or more other nonphosphate builders.These components can comprise (but being not limited thereto), the mixture of the poly carboxylic acid of crystallization stratotype water glass, carbonate borate, alkali metal aluminosilicate, monomer polycarboxylate, homopolymerization or copolymerization or its salt (wherein poly carboxylic acid contains two carboxyls that separated by no more than two carbon atoms mutually at least), carbonate, silicate and above-mentioned any material.

Preferred nonphosphate builders salt is the crystallization stratotype water glass of following general formula:

M is sodium or hydrogen in the formula, and x is 1.9 to 4 numerical value, and y is 0 to 20 numerical value.This class crystallization stratotype silicate is disclosed among the EP-A-0164514, and their preparation method is disclosed among DE-A-3417649 and the DE-A-3742043.For the present invention, the x in the above-mentioned general formula has 2,3 or 4 numerical value, and is preferably 2.Most preferably M is that sodium and y are 0, and the preferred embodiment in this formula comprise α-, β-, γ-and δ-type Na ₂Si ₂O ₅These materials can be respectively obtained by Hoechst AG ERG with the form of NaSKS-5, NaSKS-7, NaSKS-11 and NaSKS-6.Most preferred material is δ-Na ₂Si ₂O ₅, NaSKS-6.

These materials are processed to free-pouring solid, and it has granularity is 150 to 1000 microns, and tap density is at least the 800g/ liter, preferably about 900g/ liter.Yet when when preparation, this crystal is frangible, and is broken into granularity easily less than 100 microns particle.

The content that the laundry detergent composition of introducing bleaching composition of the present invention preferably contains crystallization stratotype water glass is 1% to 80%, more preferably 5% to 40% and most preferably be 7% to 20%(composition weight).

Crystallization stratotype water glass preferably is present in the intimate mixture with the ionizable material of solid, water soluble with particle form.The ionizable material of said solid, water soluble is selected from organic acid, organic and inorganic acid salt and composition thereof.Important condition is, this material should contain at least a acidic functionality (wherein PKa should less than 9), and it provides the ability of the hydroxyl ion that is discharged by this crystallization stratotype silicic acid to the small part neutralization.Beyond thoughtly be, for the present invention, find, PH＜7 that ionizable material need be in solution, promptly the amount of Cun Zaiing can provide the hydroxyl ion that is produced by the dissolving of crystalline silicate with the amount that stoichiometric calculation equates to hydrogen ion.Yet in fact, the neutralizing effect of the ionizable material in the particle storage is not limited to this bring disadvantageous effect aspect the infringement of fabric.

Ionizable material also should have mean particle size and be not more than 300 microns, and preferably is not more than 100 microns.This helps the uniform distribution of ionizable material and crystalline silicate, and thinks.When this particle is dissolved in wash water solution, strengthened the variation of local pH value.

The organic acid that is fit to 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-di 2 ethylhexyl phosphonic acid (EHDP), amino polymethylene phosphonic acids such as NTMP, EDTMP and DETPMP, and the mixture of any above-mentioned substance.The acid salt that is fit to comprises the mixture of sodium bicarbonate, sodium bioxalate, sodium pyrosulfate, sodium acid pyrophosphate, acid sodium orthophosphate, sodium hydrotartrate or any above-mentioned substance.

The granular mixture of crystallization stratotype silicate and solid, water soluble ionizable species will have pH value be at least 10(as in 20 ℃ of distilled water with 1% measured in solution), more general will have pH value and be at least 11, routine is at least 11.5.

The composition that other are other is incorporated into and can be particularly conducive to this particulate processing in crystallization stratotype silicate and the ionizable water-soluble cpds, and also helps improving the stability that contains this particulate detergent composition.Particularly, the agglomerate of some kind can need to add one or more tackiness agents, so that help bonding said silicate and ionizable water-soluble substances, so that produces the particle with acceptable physical property.The amount that tackiness agent can exist is 0% to 20%(composition weight), preferably, tackiness agent will exist with the form of the intimate mixture that forms with silicate and ionizable water-soluble substances.Preferred adhesive has fusing point between 30 ℃～70 ℃.The amount that tackiness agent preferably exists is the 1-10%(composition weight), and most preferably be the 2-5%(composition weight).

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

Other preferred adhesive comprise some polymkeric substance.Polyvinylpyrrolidone with molecular-weight average 12,000 to 700,000 is the example of this base polymer with the polyoxyethylene glycol with molecular-weight average 600 to 10,000.The multipolymer of maleic anhydride and ethene, methylvinylether or methacrylic acid (maleic anhydride forms at least 20% moles of polymer) is the other example as the polymkeric substance of tackiness agent.This this polymkeric substance can use with the form of itself, or to contain the C of 5-100 moles of ethylene oxide with solvent such as water, propylene glycol and above-mentioned every mol of alcohol ₁₀-C ₂₀The form that alcohol ethoxylates combines is used.The other example of tackiness agent of the present invention comprises C ₁₀-C ₂₀One and two glyceryl ethers, also comprise C ₁₀-C ₂₀Lipid acid.The solution that contains some inorganic salt of water glass also uses for this purpose.

Derivatived cellulose is methylcellulose gum, carboxymethyl cellulose and Natvosol for example, and homopolymerization or copolymerization poly carboxylic acid or its salt are the other examples of tackiness agent of the present invention.

This particle also can be included in the detergent composition other components commonly used, and condition is, these components itself are not inconsistent, and does not influence helping of crystallization stratotype hydrochlorate and wash function.Therefore, this particle can comprise the particle weight until 50%() negatively charged ion, nonionic, both sexes or zwitterionics or the mixture of any of these material, and the example of some preferred particulates contains tensio-active agent.The example of this class tensio-active agent is described hereinafter more fully.Yet, importantly, be incorporated into a certain amount of free (unconjugated) moisture that any surfactant materials in this particle can not contain even can be partly dissolved crystalline silicate.Therefore, said tensio-active agent should be solid, and preferably should contain no more than about 5% free (unconjugated) moisture, and more preferably no more than 2% free water content most preferably is less than 1% free water content.

Also can add other components under the condition identical with above-mentioned adding tensio-active agent, its total amount reaches 50% of particle weight.Therefore, these optional components preferably should be solid under normal temperature (room temperature), and should comprise be not more than 5%(weight), preferably less than 1%(weight) free (unconjugated) moisture.

If crystallization stratotype silicate does not have very big solubleness in this class component, 20% the amount that then can reach particle weight adds the on-aqueous liquid component.This also is applicable to the commonly used solid ingredient of fusion form as particulate condensing agent/coating-forming agent.

Particle can adopt various profiles, as extrudate, marumes, agglomerate, thin slice or die mould particle.The die mould particulate preferred method that preparation comprises crystallization stratotype silicate and solid, water soluble ionization material has been disclosed in Britain's application 9108639.7 of common transfer (in application on April 23rd, 1991) (Attorney ' s Docket No.CM369 F).

Although can use various silicate ion exchange materials, preferred sodium silicoaluminate zeolite has the structure cell formula:

Wherein Z and Y are at least 6; The mol ratio of Z and Y is 1.0 to 0.5, and X is at least 5, is preferably 7.5 to 276, more preferably 10 to 264.The silico-aluminate material is a hydrated form, and preferred crystalline, contains 10% to 28%, the water of preferred 18% to 22% bonding scheme.

Above-mentioned silico-aluminate ion exchange material is characterised in that particle diameter is 0.1 to 10 μ m, preferred 0.2 to 4 μ m.The median size of the given ion exchange material of term " particle diameter " representative herein, its mensuration is by conventional method of analysis, as measurement microscope or the laser particle instrument with scanning electronic microscope.Another feature of silico-aluminate ion exchange material is that its calcium ion-exchanged capacity is every gram silico-aluminate 200mg equivalent CaCO at least ₃The water hardness (calculating) based on moisture-free basis, and this scope is 300mg equivalent/g to 352mg equivalent/g usually.To be its ion-exchange speed be 130mg equivalent CaCO at least to another feature of silico-aluminate ion exchange material herein ₃/ liter/minute/(g/ liter) [2 grain Ca ⁺⁺/ gallon per minute/gram/gallon] silico-aluminate (moisture-free basis), its scope is at 130mg equivalent CaCO usually ₃/ liter/minute/(grams per liter) [2 grains/gallon per minute/(gram/gallon)] be to 390mg equivalent CaCO ₃/ liter/minute/(grams per liter) [6 grains/gallon per minute/(gram/gallon)], based on calcium ion hardness.

The best silico-aluminate that is used for the washing assistant purposes has calcium ion exchange rate and is at least 260mg equivalent CaCO ₃/ liter/minute/(grams per liter) [4 grains/gallon per minute/(gram/gallon)].

It is commercially available being used to implement silico-aluminate ion exchange material of the present invention, and can be naturally occurring material, but preferably synthetic deutero-material.The method for preparing the silico-aluminate ion exchange material is disclosed in United States Patent (USP) 3,985, in 669.It is commercially available being used for preferred synthetic crystallization silico-aluminate ion exchange material of the present invention, and its name is called Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS, Zeolite MAP and composition thereof.In particularly preferred embodiments, the crystal aluminosilicate ion exchange material is Zeolite A, and it has following formula

Wherein X is 20 to 30, particularly 27.Formula Na ₈₆[(AlO ₂) ₈₆(SiO ₂) ₁₀₆] 276H ₂The ZeoliteX of O and formula Na ₆[(AlO ₆) ₆(SiO ₂) ₆] 7.5H ₂The Zeolite HS of O also suits.

Suitable water-soluble monomer or oligomeric carboxylate's washing assistant can be selected from all cpds, but these compounds preferably have the first carboxyl logarithm acidity constant (PK ₁) less than 9, preferred 2 to 8.5, more preferably 4 to 7.5.

The logarithm acidity constant defines according to following balance

H ⁺+A ^-()/() HA

Wherein A is the complete ionized carboxylate anion of builder salt.

The equilibrium constant of a little dilute solutions of cause is expressed from the next

K ₁= ([HA])/([H ⁺][A ^-])

And PK ₁=log ₁₀K.

With regard to this specification sheets, acidity constant is undefined with zero ionic strength at 25 ℃.Adopt literature value (to see Stability Constants Of Metal-Ion Complexes if possible, Special Publication No.2.5, The Chemical Society, London): can measure it by potentiometric titration with glass electrode when throwing doubt upon.

Carboxylate salt or multi-carboxy acid salt washing agent can be monomer or oligomeric-type, but because the cause of cost and performance, preferred monomers multi-carboxylate usually.

Monomer and oligomeric washing assistant can be selected from acyclic, alicyclic ring, heterocycle and the aromatic carboxylic-acid salts with following general formula

R wherein ₁Represent H, replaced arbitrarily by hydroxyl, carboxyl, sulfo group or phosphono or link C on the poly-ethyleneoxy group part that contains 20 ethyleneoxy group nearly _1-30Alkyl or alkenyl: R ₂Represent H, C _1-4Alkyl, alkenyl or hydroxyalkyl, or alkaryl, sulfo group or phosphono; X represents singly-bound; O; S; SO; SO ₂; Or NR ₁; Y represents H, carboxyl; Hydroxyl; The carboxyl methoxyl group; Or by hydroxyl or any C that replaces of carboxyl _1-30Alkyl or alkenyl; Z represents H; Or carboxyl; M is 1 to 10 integer; N is 3 to 6 integer; P, q are 0 to 6 integer, and p+q is 1 to 6; Wherein X, Y and Z have identical or different definition separately when repeating in given molecular formula, and wherein Y in the molecule or Z comprise carboxyl at least.

The suitable carboxylate salt that contains a carboxyl comprises the water-soluble salt of lactic acid, oxyacetic acid and ether derivant thereof, as disclosed in belgian patent 831,368,821,369 and 821,370.The multi-carboxylate of containing two carboxyls comprises the water-soluble salt of succsinic acid, propanedioic acid, (ethylidene dioxy base) oxalic acid, toxilic acid, diethyl alkyd, tartrate, tartronic acid and fumaric acid; and ether carboxylate; they are described in German Patent 2,446, and 686 and 2; 446; 687 and United States Patent (USP) 3,935,257 in; and the sulfinyl carboxylate salt of in belgian patent 840,623, describing.The multi-carboxylate of containing three carboxyls particularly including water-soluble citrate, aconitate and citraconate and succinate derivative as in English Patent 1,379, the carboxymethyl oxygen base succinate of describing in 241, in English Patent 1, the newborn acyloxy succinate of describing in 389,732, the aminosuccinic acid salt of in Holland's application 7205873, describing, and oxygen Quito carboxylate salt material, as in English Patent 1,387, the 2-oxa-of describing in 447-1,1,3-tricarballylic acid salt.

The multi-carboxylate of containing four carboxyls is included in English Patent 1,261, disclosed oxygen base disuccinate in 829.1,1,2,2-ethane tetracarboxylic acid hydrochlorate, 1,1,3,3-propane tetracarboxylic acid salt and 1,1,2,3-propane tetracarboxylic acid salt.Contain the substituent multi-carboxylate of sulfo group and be included in English Patent 1,398,421 and 1,398,422 and United States Patent (USP) 3,936,448 in disclosed sulfo-succinic acid salt derivative, and in English Patent 1,439, the sulfonation pyrolysis Citrate trianion of describing in 000.

Alicyclic ring and heterocycle multi-carboxylate comprise that pentamethylene is suitable, and be suitable, suitable-the tetracarboxylic acid hydrochlorate, cyclopentadiene acid anhydride pentacarboxylic acid salt, 2,3,4, the 5-tetrahydrofuran (THF) is 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 Sorbitol Powder, mannitol and Xylitol.Aromatic polycarboxylic acids salt comprises and is disclosed in English Patent 1,425, the mellitic acid in 343,1,2,4,5-pyromellitic acid and phthalic acid derivative.

In above-claimed cpd, preferred multi-carboxylate is the hydroxycarboxylate of containing three carboxyls of as many as in each molecule, special optimization citric acid salt.

The mixture of the parent acid of monomeric or oligomeric multi-carboxylate's sequestrant or itself and its salt such as citric acid or Citrate trianion/citric acid mixture also are considered to the component of the builder system of detergent composition of the present invention.

Other suitable water-soluble organic salts are homopolymerization or copolymerization poly carboxylic acid or its salt, and wherein poly carboxylic acid comprises and is no more than at least two carboxyls that two carbon atoms separate each other.Back one base polymer is disclosed in GB-A-1, in 596,756.The example of this class salt be M Wt 2000-5000 polyacrylate and with the multipolymer of maleic anhydride, as the multipolymer of molecular weight 20,000 to 70,000 particularly about 40,000.The common consumption of these materials is 0.5% to a 10%(weight of composition), more preferably 0.75% to 8%, 1% to 6%(weight most preferably).

The detergent composition that adds bleaching composition of the present invention comprises the free phosphate detergent washing-aid compound, and its content is 1% to 80%(weight of composition), 10% to 60%(weight more preferably), 20% to 50%(weight most preferably).

In preferred laundry detergent composition, sodium silicoaluminate such as Zeolite A account for 20% to 60%(weight of washing assistant total amount), monomer or oligomeric carboxylate account for 5% to 30%(weight of washing assistant total amount), crystallization stratotype silicate accounts for 10% to 65%(weight of washing assistant total amount).Builder system also preferably comprises composition such as the yellow soda ash and the maleic anhydride/acrylic copolymer of auxiliary inorganic and organic washing-assisting detergent in this composition, its amount nearly the washing assistant total amount 35%.

Detergent composition can contain optional chelator component.These optional sequestrants include organic phosphonates, comprise amino alkylidenyl many (alkylene phosphonic acids salt), basic metal ethane 1-hydroxyl diphosphonate, nitrilo trimethylene phosphonic salt, ethylenediamine tetramethylene phosphonic acid salt and diethylenetriamine pentamethylenophosphonic acid(DTPP) salt.Phosphonate compounds or exist with its sour form, or exist as the title complex of basic metal or alkaline-earth metal ions, the mol ratio of described metal ion and described phosphonate compounds is at least 1: 1.This title complex is described in US-4, in 259,200.The organic phospho acid salt compound is preferably its magnesium salts form when existing.The phosphorus content that contains sequestrant in the present composition preferably is reduced to bottom line.Not phosphorous fully in the most preferred group compound.

Silicate is the useful component that is added with the automatic dishwashing detergent composition of bleaching composition of the present invention.Suitable silicate comprises having SiO ₂: Na ₂The O ratio is 1.0: 2.8 a water-soluble metasilicate.Silicate can be anhydrous salt or salt hydrate form.Most preferably has SiO ₂: Na ₂The O ratio is 2.0 water glass.Is 5% to 50%(weight of composition at the wash up machine with the amount that detergent composition mesosilicic acid salt exists), 10% to 40%(weight more preferably).

Although soluble silicate can be used for various purposes in the laundry detergent compositions of routine, its existence may be unnecessary in the detergent composition that is added with crystallization stratotype silicate material.Yet, must mix the component adding as doing owing to constitute the builder system crystalline layered silicate partly of detergent composition, so soluble silicate still can be used as constituent in the spraying drying granula that constitutes the laundry detergent composition part usually.If the spraying drying granula does not contain the silico-aluminate washing assistant and only comprises organic substance, this is suitable especially.Suitable silicate has SiO ₂: Na ₂O is than in 1.6 to 3.4 scopes, and preferably the two ratio is 2.0 to 2.8.

The detergent composition that adds bleaching composition of the present invention generally includes the inorganic perhydrate salt that is generally sodium-salt form, and suitable inorganic perhydrate salt is described in this paper front.Usually bleaching composition is added into 3% to the 40%(weight that the amount that makes perhydrate accounts for detergent composition), 5% to 30%(weight more preferably), 10% to 25%(weight most preferably).

The detergent composition that adds bleaching composition of the present invention generally also comprises peroxyacid bleach precursor (bleach-activating agent).Suitable peroxyacid bleach precursor is narrated hereinbefore.Usually the amount that adds peroxyacid bleach precursor accounts for 1% to 20% of composition weight, and more preferably 1% to 15%, most preferably 3% to 10%.

Detergent composition can also comprise organic peroxide acid, and its content is 1% to 15%(weight of composition), 1% to 10%(weight more preferably).

Common unsettled Britain application 9102507.2(1991 the applicant apply for February 6) in detergent composition is disclosed, wherein the solid peroxygen bleach precursor is protected by the acid protection be reduced to minimum level so that the color of fabric damaged.

Be applicable to that antiredeposition of the present invention and soil-suspending agent comprise derivatived cellulose, as methylcellulose gum, carboxymethyl cellulose and Natvosol, homopolymerization or copolymerization poly carboxylic acid or its salt and polyamino compound.This base polymer comprises the multipolymer of polyacrylic ester and maleic anhydride and ethene, methylvinylether or methacrylic acid, and maleic anhydride accounts for the mole of 20%(at least of multipolymer), they are disclosed among the EP-A-137669 in detail.The polyamino compound is disclosed in EP-A-305282, EP-A-305283 and EP-A-351629, as by aspartate-derived polyamino compound.Usually the consumption of these materials is 0.5% to a 10%(weight of composition), 0.75% to 8%(weight more preferably), 1% to 6%(weight most preferably).

Other useful polymeric materials are polyoxyethylene glycol, and its molecular weight is preferably 1000-10000,2000-8000 more preferably, most preferably from about 4000.Its consumption is 0.20% to 5%(weight), 0.25% to 2.5%(weight more preferably).These polymkeric substance and above-mentioned homopolymerization or copolymerization multi-carboxylate can improve whiteness effectively and keep, the fabric ash-deposition and in the presence of transition metal impurity to the scourability of clay, protein(aceous)soil and oxidable dirt.

Preferred window of tube whitening agent is suitable negatively charged ion, the example is 4,4 '-two (2-diethanolamino-4-anilino-S-triazine-6-base is amino) stilbene-2: 2 ' disulfonic acid disodium, 4,4 '-two-(2-morpholino 4-anilino-2-triazine-6-base amino stilbene-2: 2 '-the disulfonic acid disodium, 4,4 '-two-(2,4-hexichol amido-S-triazine-6-base is amino) stilbene-2: 2 '-the disulfonic acid disodium, 4 ', 4 " two-(2; 4-hexichol amido-S-triazine-6-base is amino) stilbene-2-sulfonic acid one sodium; 4,4 '-two-(2-anilino-4-(N-methyl-N-2-hydroxyl ethylamino)-2-triazine-6-base is amino) stilbene-2,2 '-the disulfonic acid disodium; 4; 4 '-two (4-phenyl-2,1,3-triazole-2-yl) stilbene-2; 2 '-the disulfonic acid disodium, 4,4 '-two-(2-anilino-4-(1-methyl-2-hydroxyl ethylamino)-S-triazine-6-base is amino) stilbene-2,2 '-the disulfonic acid disodium, and 2-(stilbene radicals-4 " (naphtho--1 '; 2 ': 4.5)-1,2,3-triazoles-2 " sodium sulfonate.

The stain remover that is used for detergent composition normally terephthalic acid and ethylene glycol and/or propylene glycol unit with the multipolymer or the terpolymer of various arrangements.The example of this base polymer be disclosed in common transfer United States Patent (USP) 4116885 and 4711730 and European publication application 0272033 in.The particularly preferred polymkeric substance of EP-A-0272033 has following formula:

(CH ₃(PEC) 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 is (OC ₃H ₆O) and T be (PCOC ₆H ₄CO).

Some polymeric material such as Polyvinylpyrolidone (PVP) (NWt is generally 5000-20000, preferred 10000-15000) have also constituted useful reagent to stop the transfer of unsettled dyestuff between fabric in the washing process.

Another optional detergent composition composition is a suds suppressor, and example has siloxanes and silicon-dioxide-mixture of siloxanes.Siloxanes generally can be provided by alkylation polysiloxane material, and silicon-dioxide uses with form in small, broken bits usually, and the example is aerosil and xerogel and various types of hydrophobic silex.These materials can be used as particle and add.Wherein suds suppressor is added in water-soluble or water dispersible and basically in the carrier of impermeable on-surface-active detergent with helping discharging.In addition, suds suppressor can be dissolved in or be scattered in the liquid vehicle, and uses by being sprayed on one or more other components.

As mentioned above, useful silicone suds suppressor can comprise the alkylation siloxanes of the above-mentioned type and the mixture of solid silica.This mixture prepares by siloxanes being attached to the solid silica surface.Preferred silicone suds suppressor is provided by hydrophobic silanization (most preferably trimethyl silicone hydride) silicon-dioxide, and the silanized silica size range is in 10 nanometer to 20 nanometers, and specific surface area is greater than 50m ²/ g, it and molecular weight about 500 mix fully to about 200,000 dimethyl silicone fluids, and the weight ratio of siloxanes and silanized silica is about 1: 1 to about 1: 2.

Preferred silicone suds suppressor is disclosed in people's such as Bartollota the United States Patent (USP) 3,933,672.Other useful especially suds suppressors are self-emulsifying silicone suds suppressors, record and narrate at German patent application DTOS2, and 646,126(1977 is open April 28).An example of this compound is DCO544, and it is siloxanes/glycol copolymer, can have been bought by Dow Corning.

The common consumption of above-mentioned suds suppressor is 0.001% to a 5%(weight of composition), preferred 0.1% to 3%(weight).

Preferred adding method comprises the suds suppressor by applicating liquid form on one or more main ingredients that are sprayed to composition, perhaps in addition suds suppressor is made independent particle, and it is mixed with other solid ingredients of composition.The foaming regulator that adds as independent particle also can comprise other and press down the bubble material, as C ₂₀-C ₂₄Lipid acid, Microcrystalline Wax and the oxyethane that the dispersiveness of matrix is had no adverse effect and the high MWt multipolymer of propylene oxide.Preparing this class A foam A regulates in the United States Patent (USP) 3,933,672 that the method for granula is disclosed in people such as above-mentioned Bartolotta.

Another the optional composition that is used for detergent composition is one or more enzymes.The amount that they add is 0.1% to 10% of a detergent composition, more preferably 0.5% to 5%(weight).

Preferred enzyme material comprises commercially available amylase, neutrality and Sumizyme MP, lipase, esterase and the cellulase that often is added in the detergent composition.Suitable enzyme is disclosed in United States Patent (USP) 3,519, in 570 and 3,533,139.

Preferred commercially available proteolytic enzyme comprises with trade(brand)name Alcalase and Savinase by Novo Industries A/S(Denmark) proteolytic enzyme sold, and with the Maxatase trade(brand)name by International Bio-Synthesis, Inc(Holland) proteolytic enzyme sold.

Preferred amylase comprises the amylase that is for example obtained by the special bacterial strain of B lichenoid form, and they are described in greater detail in GB-1,269,839(Novo) in.Preferred commercially available amylase comprises for example by the Rapidase of International Bio-Synthetics Inc sale and the Termamyl that is sold by Novo Indnstries A/S.

Particularly preferred lipase is by Novo Industries A/S(Denmark) with trade(brand)name Lipolase(Biotechnology Newswatch, on March 7th, 1988, the 6th page) produce and sell, at EP-A-0258068(Novo) in it is referred with other suitable lipase.

Another optional member that is used for detergent composition is a corrosion inhibitor, C ₁₄-C ₂₀Lipid acid is the preferred embodiment of this class corrosion inhibitor.

Fabric softener also can add in the laundry detergent composition.These reagent can be inorganic or organic types.The example of inorganic softening agent has at GB-A-1, disclosed smectic clays in 400,898.Other suitable inorganic soft systems (comprising hectorite and polynite) that comprise smectic clays also are disclosed among the EP-A-0522206.The organic fabric softening agent comprises as disclosed water-insoluble tertiary amine among GB-A-1514276 and the EP-B-0011340.

Itself and single C ₁₂-C ₁₄The combination of quaternary ammonium salt is disclosed in EP-B-0026527 and 528.Other useful organic fabric softening agents are as being disclosed in the two long-chain acid amides among the EP-B-0242919.Other organic compositions of fabric sofetening system comprise high-molecular weight polyethylene oxide material, and they are disclosed in EP-A-0299575 and 0313146.

The content of smectic clays is generally in 5% to 15%(weight) scope in, 8% to 12%(weight more preferably), this material mixes the rest part that component is added into preparation as doing.Organic fabric softening agent such as water-insoluble tertiary amine or two long-chain acid amides material are with 0.5% to 5%(weight), usually with 1% to 3%(weight) amount add, and high molecular weight polyethylene oxide material and water-soluble cationic material are with 0.1% to 2%, usually with 0.15% to 1.5%(weight) amount add.When part composition during by spraying drying, these materials can be added into aqueous slurry and be fed in the spray-drying tower, but in some cases, be more suitable for it is mixed the particle adding as doing, or it is sprayed on other solid ingredients of composition as melt liquid.

Usually detergent composition can pass through prepared in various methods, comprise drying, spraying drying, agglomeration and granulation, and preferable methods comprises the combination of these technology.The preparation granular laundry with the preferred method of detergent composition comprise spraying drying, in high-speed mixer agglomeration and do mixed combination.

The volume density that adds the granular detergent composition of bleaching composition of the present invention can be about 450 to 600g/l, and this is that conventional laundry detergent composition is used always.In addition, granular detergent composition can be to concentrate granular detergent composition, it is characterized in that comparing it with conventional detergent composition has higher density.This high-density composition has volume density and is at least 650g/l, more generally is at least 700g/l, more preferably 800g/l to 1100g/l.

Volume density is measured by simple and easy funnel and ring device, the formation of this device is the conical funnel of casting securely on pedestal, has a lobe flap valve than low side so that the thing in the funnel is drained enters in the cylindrical cup that is positioned on the axes alignment below the funnel at funnel.The top and bottom of this funnel are respectively 130mm and 40mm.Fix this funnel and make 140mm place on the upper surface of pedestal, its lower end.The cup total height is 90mm, interior high 87mm, internal diameter 84mm.Its nominal volume is 500ml.

For measuring, make funnel be full of powder by toppling over by hand, open the lobe flap valve and make powder overfill cup.The cup that fills up is by shifting out in the framework, makes straight utensil in edge such as the knife upper limb by cup to remove excessive powder from cup.Then the cup that fills up is weighed and the powder weight value that obtains doubled and just obtain volume density (g/l).Can carry out replicate measurement if need.

Spissated laundry detergent composition also adds at least a multicomponent component usually, and promptly they do not comprise only by doing the mixed formed composition of single component.Wherein each single component composition of all do being mixed generally is powdered, slowly dissolving and usually lump and increased particle flow characteristics very poor in the storage process.

Preferred laundry detergent composition comprises at least two kinds of granular multicomponent components.At least 15% of the first ingredients constitute composition weight is suitably 25% to 50%, but more preferably is no more than 1% to 50% of 35%, the second ingredients constitute composition weight, and more preferably 10% to 40%.

First component comprises the anion surfactant that adds with 0.75% to 40% the amount that accounts for powder weight and one or more particles inorganic and/or organic salt that add with 99.25% to 60% the amount that accounts for powder weight.This particle can have any suitable form such as particle, thin slice, granule, marume or slice, but preferred particulates.Particle itself can be by groove or cylinder nodulizing or the agglomerate by the preparation of list type mixing machine, but normally by the aqueous slurry of each composition is sprayed in hot blast to remove the spray-dried granules that most of water makes.Make spray-dried granules through the enrichment step, for example by high-speed cutting mixing machine and/or press, so that before reagglomeration, increase density then.In order to illustrate, hereinafter first component is described as spray-dried powders.

Suitable anion surfactant has been found and can have dissolved straight-chain alkyl sulfate lentamente for first component, and wherein alkyl on average has 16 to 22 carbon atoms and straight-chain alkyl carboxylic acid's base, and wherein alkyl on average has 16 to 24 carbon atoms.The alkyl of this two classes tensio-active agent is preferably taken from natural resource such as beef fat and marine animal oil.

The content of anion surfactant is 0.75% to 40%(weight in constituting the spray-dried powders of first component), more generally be 2.5% to 25%, preferred 3% to 20%, 5% to 15%(weight most preferably).Can comprise water soluble surfactant active such as linear alkylbenzene sulfonate or C ₁₄-C ₁₅Alkyl-sulphate maybe can provide it subsequently by spraying and give spray-dried powders.

Another main component of spray-dried powders is one or more inorganic or organic salts, and they give the particle crystal structure.Inorganic and/or organic salt can be water miscible or water-insoluble, and the salt of back one type is made up of water-insoluble washing assistant or its major portion when its formation washing assistant composition a part of.Suitable water-soluble inorganic salt comprises alkaline carbonate and supercarbonate.The amorphous alkali metal silicate also can be used for providing structure to spray-dried granules, as long as silico-aluminate does not constitute the part of spray-dried component.

Yet, in spissated detergent composition, preferably sodium sulfate is not added as separate constituent, and it should be reduced to minimum level as by product such as mixing of sulfation (sulfonation) tensio-active agent.

When aluminosilicate zeolite constituted washing assistant composition or its part, preferably aluminosilicate zeolite was not directly to add other components by doing to mix, but adds in the multicomponent component.

First component can also comprise nearly 15%(weight) assorted composition, as whitening agent, anti redeposition agent, photoactivation SYNTHETIC OPTICAL WHITNER (as four sulfonation zinc phthalocyanine phthalocyanines) and sequestrant.When first component was spray-dried powders, being dried water capacity usually was 7% to 11%(weight of spray-dried powders), 8% to 10%(weight more preferably).Water capacity by the powder that additive method such as nodulizing produced may be lower, and can be in 1-10%(weight) in the scope.

The granularity of first component is conventional, and preferably is no more than 5%(weight in overall dimension) particle should be greater than 1.4mm, and be no more than 10%(weight) particle should be less than 0.15mm.Preferably at least 60%, 80%(weight at least most preferably) its size of powder is between the 0.7mm to 0.25mm.For spray-dried powders, the volume density of the particle that is obtained by spray-drying tower is suitable in 540 to 600g/l scope, suppresses subsequently volume density is increased as reduce volume in high-speed cutting machine/mixing machine by other procedure of processings then.In addition, the method except that spraying drying can be used for directly forming high density granular.

Second component of preferred detergent composition is another multicomponent particle that contains the water soluble surfactant active.

This tensio-active agent can be negatively charged ion, nonionic, positively charged ion or semi-polarity type or its mixture arbitrarily.Above listed suitable tensio-active agent, but preferred surfactants is C ₁₄-C ₁₅Alkyl-sulphate, straight chain C ₁₁-C ₁₅Alkylbenzene sulfonate and aliphatics C ₁₄-C ₁₈Methyl ester sulfonate.

Second component can have suitable physical form arbitrarily, and promptly it can take thin slice, granule, marume, slice, ring or particulate form, and they can be spraying drying or non-spraying drying agglomerate.Although second component itself can comprise the water soluble surfactant active in theory, in fact second component comprises that at least a organic or inorganic salt is to do well out of processing.This provides crystallinity and acceptable flow characteristics to a certain degree to particle, and described organic or inorganic salt can be any one or the multiple organic or inorganic salt that is present in first component.

The size range of second component should be the granularity of avoiding when it mixes with first component with the separate particles of first component.Therefore, in overall dimension, be no more than 5%(weight) particle should be greater than 1.4mm, and be no more than 10%(weight) particle should be less than 0.15mm.

The volume density of second component changes with its preparation method.Yet, the preferred form of second component is the agglomerate of mechanically mixing, its preparation is by being added in slot type agglomeration machine, Z paddle agitator or the preferred list type stirrer with dried composition or with agglomerant, as by Schugi(Holland) BV, 29 Chroomstraat, 8211 AS, Lelystad, Netherland and Gebruder Lodige Maschinenban GmbH, D-4790 Paderborn 1, Elsenerstrasse 7-9, this class machine that Postfach 2050 F.R.G produce.The volume density scope that can obtain second component by this method is 650g/l to 1190g/l, more preferably 750g/l to 850g/l.

The amount of the alkaline carbonate that preferred laundry detergent composition comprises in second component is corresponding to being 3% to 15%(weight of composition), 5% to 12%(weight more preferably) amount.This content that carbonate in second component is provided is 20% to 40%(weight).

The composition of particularly preferred second component also has the water-insoluble silico-aluminate ion exchange material of foregoing synthetic zeolite type hydration, and the amount of its existence is 10% to a 35%(weight of second component).The water-insoluble silico-aluminate amount of substance of Jia Ruing is 1% to a 10%(weight of composition in this way), 2% to 8%(weight more preferably).

In a kind of method of preparation second component, surfactant salt is to generate on the spot in the list type mixing machine.In continuous high-speed mixing machine such as Lodige C6 mixing machine, liquid acid shape tensio-active agent is added in the mixture of granular anhydrous yellow soda ash and hydrated sodium aluminosilicate, and neutralization generation surfactant salt, and the granular character of maintenance mixture.The agglomeration mixture that obtains has constituted second component, it is added in another component of product then.In the variant of this method, surfactant salt is neutralized in advance, and be added in other mixture of ingredients with the thickness paste.In this variant, only make each composition agglomeration to form second component with mixing machine.

At the preparation granular laundry with in the particularly preferred method of detergent composition, will comprise the first granular component spray dried prod part with the rest part remix before shift and handle through the nonionogenic tenside spraying of low levels.Prepare the second granular component with above-mentioned preferred method.Then with first and second components and crystallization stratotype silicate granular composition, perhydrate SYNTHETIC OPTICAL WHITNER and peroxyacid bleach precursor particle arbitrarily, other dried branches that blend together are as carboxy acid salt chelator, soil release polymer and enzyme are fed on the travelling belt arbitrarily, they are transferred in the cylinder that horizontally rotates thus, in cylinder, spices and silicone suds suppressor are sprayed on the product.Use another cylinder mixing step in particularly preferred composition, the crystalline material in small, broken bits that adds low levels (about 2% weight) in this step is to increase density and to improve the particulate flow characteristics.

In being added with the preferred thickening and washing product of alkali metal percarbonate such as perhydrate salt, having been found that and to control the several aspects of product such as the content and the equilibrium relative humidity thereof of its heavy metal ion.Applied for October 6 at the common Britain application 9021761.3(1990 that transfers the possession of) disclose the composition that this class contains SPC-D in (Attorney's Docket No.CM 343) and had enhanced stability.

Laundry detergent composition of the present invention also has benefited from delivery systme, in the cylinder of automatic washing machine when cycles of washing begins, this delivery systme provides the product of transparent high local concentrations, has therefore also avoided in the pipeline of washing machine or storage tank the problem by product loss brought.

Providing composition to cylinder the most easily is to finish by the composition that is added in the band or in the packing material, the stirring when cycles of washing begins because in cylinder, and temperature rise or the immersion in washing water make the composition snap-out release in the band or in the packing material.Can regulate washing machine itself in addition so that composition is directly added in the cylinder, for example by the dispensing devices in inlet.

Comprise the product that is contained in the laundry detergent composition in the band or in the packing material be designed under drying regime to keep packing material complete when avoiding drying the overflowing of its content, but when it is in wash environment (generally being to soak) in the aqueous solution, be suitable for discharging the content of packing material.

Usually bag shape thing is mobilizable, as bag or bag.Bag can be to scribble the fibrous texture of protection material of impermeable water to keep its content, as disclosed in European publication application 0018678.In addition, bag can be made of water-insoluble synthesized polymer material, and has sealing or closed edge, and it is designed to break in water-bearing media, as disclosed in European publication application 0011500,0011501,0011502 and 0011968.The easy disruptive of the water of appropriate form seals the water-soluble binder on one side that comprises the sealing that places bag, and it is made of the polymeric film of impermeable water such as polyethylene or polypropylene.In the variant of bag or packing material form, can use the lamination flaked product, wherein the central movable layer adds then that with composition dipping and/or coating one or more skins are to produce the appearance effect of fibrid.These layers can be sealed so that in use keep connecting, perhaps can when contacting, separate to promote the release of coating or impregnation of matters with water.

Another kind of laminate form comprises that one deck of embossing or distortion is to provide a series of class bag shaped packages, go into detergent component with quantitative deposition in each packing material, the second layer covers on the first layer and it is sealed in zone between the class bag shaped package of two-layer contact.Component can particle, sticks with paste or fusion form deposition, and laminate layers should be avoided content excessive of class bag shaped package before adding water.These layers can be independent maybe can remaining attached to when contacting with water, and unique requirement is that this structure should make the content snap-out release of class bag shaped package in solution.The problem that the quantity of the class bag shaped package of per unit area matrix is just selected, but in every square metre 500 to 25000 scope, change usually.

The suitable material that can be used for movable laminate layers of the present invention especially comprises sponge, paper and weaving and non-textile fiber.

Yet the preferred method that carries out laundry processes is that composition is introduced in the cylinder in the liquid around fabric by reusable dispensing devices, the wall liquid permeable of described dispensing devices but impermeable solids composition.

This class device is disclosed in European patent application publication No. 0343069 and 0343070.The back disclosed device of one application comprises the mobilizable skin of bag shape, and described satchel is suitable for supplying with bag enough products of once washing round-robin by the support ring of the having determined aperture aperture that trails.The part washing medium flows into bag by aperture, dissolved product, and solution flows in the washing medium outward by aperture then.It is excessive to prevent soaking the dissolved product that support ring has shading unit, and this device generally comprises the wall of circumferentially extending, and wall is to stretch out with the spoke wheel configuration from centre strut, or stretch out with the similar structures that wall has a spiral type.

At Manufacturing Chemist, disclosed paper has been described the particularly preferred dispensing devices that is used for the granular laundry detergent product in the November 1989 41-46 pages or leaves by J.Bland, and this class device is commonly referred to as " granulette ".

In following indefiniteness embodiment the present invention has been described, wherein all per-cents are all by weight unless otherwise indicated.

In detergent composition, abbreviation component symbol has following meaning:

LAS: straight chain C ₁₂Sodium alkyl benzene sulfonate

TAS: tallow alkyl sodium sulfate

TAEn: every mol of alcohol tallow alcohol of n moles of ethylene oxide ethoxylation

23EY: with the ZC of average Y moles of ethylene oxide condensation _12-13Primary alconol

25EY: with the C that is mainly straight chain of average Y moles of ethylene oxide condensation _12-15Primary alconol

45EY: with the C that is mainly side chain of average Y moles of ethylene oxide condensation _14-15Primary alconol

TAED: tetra acetyl ethylene diamine

Silicate: anhydrous sodium metasilicate (SiO ₂: Na ₂O can be according to common ratio)

NaSKS-6: formula 8-Na ₂Si ₂O ₅Crystallization stratotype silicate

Carbonate: anhydrous sodium carbonate

CMC: Xylo-Mucine

Zeolite A: formula Na ₁₂(AlO ₂SiO ₂) ₁₂27H ₂The hydrated sodium aluminosilicate of O, it has main granularity in 1 to 10 mu m range.

The acrylate homopolymer of Polyacrylate:MWt4000

Citrate: citrate trisodium dihydrate

MA/AA:1: 4 toxilic acids/acrylic acid multipolymer, molecular-weight average about 80,000.

Perborate: anhydrous sodium perborate-hydrate SYNTHETIC OPTICAL WHITNER, its empirical formula are NaBO ₂H ₂O ₂

PB ₄: anhydrous sodium perborate tetrahydrate SYNTHETIC OPTICAL WHITNER, its empirical formula are NaBO ₂H ₂O ₂3H ₂O

Enzyme: by the blended proteolytic ferment and the amylolytic enzyme of Novo Industries AS sale.

DETPMP: by the diethylenetriamine five (methylene phosphonic acid) of Monsanto with trade(brand)name Dequest 2060 sales

Suds Suppressor:25% paraffin, 50 ℃ of Mpt, 17% water drain silica, 58% paraffin oil

EDDS: quadrol-N, N '-Succinic Acid (S, S isomer)

Sulphate: anhydrous sodium sulphate

EDTA: edetate

Amylase: by the amylolytic enzyme of Novo Industries A/S with trade(brand)name Termamyl sale

Protease: by the proteolytic ferment of Novo Industries A/S with trade(brand)name Savinase sale

NaCl: anhydrous chlorides of rase sodium

Nonionic: the ethoxylation degree of selling with trade(brand)name Plurafac LE404 by BASF GmbH 3.8 and the C of propoxylation degree 4.5 ₁₃-C ₁₅Ethoxylated/propoxylated fatty alcohol.

Montmorillonite: smectite-type clay softening agent

Hectorite: smectite-type clay softening agent

CAS: coconut sodium alkyl sulfate

PEPA: poly-ethyl propoxy-alcohol

Sulphuric: sulfuric acid

Embodiment 1

Prepare the following detergent for washing clothes product (parts by weight) that contains peroxygen bleach.Product A and B are prior art compositions, and products C and D are the present compositions.

A??B??C??D

LAS??7.8??7.8??7.8??7.8

TAS??2.4??2.4??2.4??2.4

TAE11??1.1??1.1??1.1??1.1

25E3??3.3??3.3??3.3??3.3

Zeolite?A??19.5??19.5??19.5??19.5

Citrate??6.5??6.5??6.5??6.5

MA/AA??4.3??4.3??4.3??4.3

Carbonate??11.1??11.1??11.1??11.1

Perborate??16.0??16.0??16.0??16.0

TAED??5.0??5.0??5.0??5.0

EDTA??0.4??-??-??-

DETPMP??-??0.4??-??-

EDDS??-??-??0.4??0.2

CMC??0.5??0.5??0.5??0.5

Suds?Suppressor??0.5??0.5??0.5??0.5

Enzyme??1.4??1.4??1.4??1.4

Silicate (2.0 ratio) 4.4 4.4 4.4 4.4

MgSO ₄0.4 0.4 0.4 0.4

Sulphat??4.1??4.1??4.1??4.1

Yi Shui and assorted composition reach balance

To contain 1000ml17 ° of German Hardness(243 ppm CaCO ₃) beaker of water is placed in the thermostatic bath that is in 90 ℃, it reached bathe temperature.In this type of beaker, add the heavy metal ion of solubility inert inorganic salt form, make concentration of heavy metal ion (weight) reach 1.1ppm Cu.2ppm Fe, 2.3ppm Zn and 0.12ppm.These concentration of Cu, Fe, Zn and Mn are considered to representative concentration, and the heavy metal ion of these concentration can be present in the washings of automatic washing machine when washing the dirt of general load.Amount with 0.7% Betengent product of solution weight adds a kind of Betengent product in this beaker.At interval from beaker, shift out five equilibrium solution with regular time, measure remaining %H ₂O ₂(from perborate bleach).Be present in H in the Betengent product before promptly accounting for washing composition adding solution ₂O ₂The per-cent of amount.Residue %H ₂O ₂Mensuration be that solution such as branch such as grade is added 20% sulphuric acid soln, sulphuric acid soln stops H ₂O ₂Further decomposition, use 0.1N KMnO then ₄Stop the standard permanganate titration.Same method is used to each product A, B, C and D.Repeat until obtaining consistent result.

That list below is remaining %H down at interval at a fixed time from the beaker that Betengent product is added each product A, B, C and D the time ₂O ₂

Time (minute) residue %H ₂O ₂

A??B??C??D

0??100??100??100??100

5??92.6??98.9??96.3??91.7

10??82.6??98.9??94.2??92.1

20??67.4??94.4??93.2??91.7

30??47.4??87.6??85.8??84.4

50??29.0??78.7??77.4??78.3

With the result as seen, contain composition C and the D that bleach stability that the composition A of EDTA provides contains the composition B of phosphonate far from or contains EDDS.Can find when EDDS and DETPMP with equivalent (0.4%) and etc. mole (0.2%) when base is used for phosphine acid salt chelator, the two provides much the same bleach stability.

Embodiment 2

Prepare following automatic dishwashing detergent composition (parts by weight).Product E and F are prior art compositions, and product G is the present composition.

A??B??C

Citrate??42.4??42.4??42.4

MA/AA??4.0??4.0??4.0

Silicate (2.0 ratio) 33.0 33.0 33.0

Nonionic??1.5??1.5??1.5

Perborate??10.4??10.4??10.4

TAED??2.6??2.6??2.6

Amylase??1.5??1.5??1.5

Protease??2.2??2.2??2.2

Sulphate??0.7??0.7??0.7

NaCl??1.3??1.3??1.3

EDTA??0.3??-??-

DETPMP??-??0.6??-

EDDS??-??-??0.3

Reach balance with moisture/assorted composition

Test with embodiment 1 described similar approach, but done some changes so that test more can be represented the condition of family expenses automatic tableware washing process.To contain 1000ml17 ° of German Hardness(243ppm CaCO ₃) beaker of water is placed in the water bath with thermostatic control that is initially located in 20 ℃.Add the heavy metal ion of the soluble inorganic salt form of inertia in this beaker, obtaining concentration of heavy metal ion (weight) is 1.5ppm Cu and 0.67ppm Fe.These concentration of Cu and Fe are considered to typical concn, and the Cu of above-mentioned concentration and Fe are present in the washing lotion of family expenses automatic tableware washing machine in having the general cycles of washing of common wash load.Take out in this beaker and to add a kind of Betengent product, obtaining concentration is 0.4%(weight) solution of Betengent product.With this solution heating, make solution temperature reach 65 ℃ with constant rate of speed after 15 minutes, shift out five equilibrium solution this moment and measure residue %H as stated above ₂O ₂Then solution was kept 10 minutes at 65 ℃ again, shift out second part this moment and wait branch solution and measure residue %H similarly ₂O ₂Repeat until obtaining consistent result.Provided the residue %H of each product E, F and G below ₂O ₂

Time (minute) residue %H ₂O ₂

E??F??G

0??100??100??100

15??56.8??-??81.3

25??42.6??69.7??71.0

Embodiment 3

Prepare the following detergent for washing clothes product that contains peroxygen bleach and smectic clays class softening agent of the present invention.

H??I

LAS??7.8??7.8

TAS??1.5??1.5

45E7??1.3??1.3

Zeolite?A??19.5??19.5

Citrate??5.0??5.0

MA/AA??3.2??3.2

Carbonate??12.0??12.0

Perborate??5.8??5.8

PB4??7.8??7.8

TAED??5.0??5.0

EDDS??0.2??0.2

CMC??0.48??0.48

Suds?Suppressor??0.5??0.5

Enxyme??1.4??1.4

Silicate (2.0 ratio) 3.0 3.0

MgSO ₄0.43 0.43

Sulphate??4.1??4.1

Montmorillonite??12.5??-

Hectorite??-??12.5

Reach balance with water, minor component and assorted composition

Embodiment 4

Prepare the following preparation that contains the liquid peroxy SYNTHETIC OPTICAL WHITNER of the present invention, they are suitable for use as the family expenses detergent or are used as the SYNTHETIC OPTICAL WHITNER additive:

J??K

Hydrogen?Peroxide??8.50??3.5

CAS??0.8??12.0

PEPA??1.1??-

23E3??-??1.8

Sulphuric to pH4-

Monoethanolamine-to pH2.5

EDDS??0.1??0.1

Water and minor component to 100 are to 100

Minor component comprises spices, whitening agent and dyestuff

Claims (31)

1, a kind of bleaching composition, said composition comprises:

(a) peralcohol, it is selected from addition compound, the organic peroxide acid of hydrogen peroxide and hydrogen peroxide, and composition thereof; With

(b) quadrol-N of 0.05% to 2% (composition weight), N '-disuccinic acid, or the ammonium salt of an alkali metal salt or alkaline earth salt, ammonium salt or its replacement, or its mixture, wherein said peralcohol and said quadrol-N, the scope of the weight ratio of N '-disuccinic acid is 800: 1 to 10: 1.

2, according to the bleaching composition of claim 1, quadrol-N wherein, N '-disuccinic acid exists with the form of [S, S] isomer.

3, according to the bleaching composition of claim 1 or 2, quadrol-N wherein, the amount that N '-disuccinic acid component exists is 0.05% to 1%(composition weight) and wherein said weight ratio be 400: 1 to 20: 1.

4, according to the bleaching composition of claim 1 or 2, quadrol-N wherein, the amount that N '-disuccinic acid component exists is 0.1% to 0.5%(composition weight) and wherein said weight ratio be 200: 1 to 40: 1.

5, according to the bleaching composition of claim 1, wherein introduce peroxyacid bleach precursor.

6, according to the bleaching composition that is used for bleached fiber disposition fiber and synthetic textiles of claim 1 or 5, wherein peralcohol is a hydrogen peroxide.

7, according to the bleaching composition of claim 6, wherein bleaching composition does not contain water glass.

8, the cleaning composition that contains the bleaching composition of with good grounds claim 1 or 5, wherein said peralcohol is inorganic perhydrate salt, and its amount is 3% to 40%(detergent composition weight), wherein said detergent composition comprises 1% to 80%(cleaning composition weight in addition) the washing-aid compound of no phosphoric acid salt, and composition thereof.

9, detergent composition according to Claim 8, quadrol-N wherein, N '-disuccinic acid component exists with the form of magnesium salts.

10, according to the automatic dishwashing detergent composition of claim 9, it introduces 0.5% to 10%(weight) low foam surface activity agent, this tensio-active agent is selected from negatively charged ion, positively charged ion, nonionic, both sexes and zwitterionics, and composition thereof.

11, according to the automatic dishwashing detergent composition of claim 10 or 27, it introduces enzyme, and this enzyme is selected from amylase, proteolytic enzyme and lipolytic enzyme and composition thereof.

12, according to the laundry detergent composition of claim 9, it contains 3% to 30%(weight) tensio-active agent, this tensio-active agent is selected from negatively charged ion, positively charged ion, nonionic, both sexes and zwitterionics and composition thereof.

13, according to the laundry detergent composition of claim 12 or 28, wherein do not have the phosphoric acid salt washing-aid compound and be selected from knot stratotype water glass, sodium silicoaluminate zeolite, alkaline carbonate and supercarbonate, carboxylate salt and multi-carboxylate, and maleic anhydride/acrylate copolymer.

14, according to the laundry detergent composition of claim 13, wherein crystallization stratotype sodium silicate drug builder compound is formula NaMSixO _2X+1YH ₂The material of O, M is sodium or hydrogen in the formula, X is that 1.9 to 4 numerical value and Y are 0 to 20 numerical value.

15, according to the laundry detergent composition of claim 13, wherein crystallization stratotype silicate material is δ-Na ₂Si ₂O ₅(NaSKS-6).

16, according to the laundry detergent composition of claim 13, wherein anion surfactant comprises C ₁₂-C ₂₀Alkyl-sulphate and every mole of water miscible C that contains average 1 to 7 oxyethyl group ₁₁-C ₁₉The mixture of alkyl ethoxy sulfate, the scope of the weight ratio of wherein said alkyl-sulphate and said alkyl ethoxy sulfate are 2: 1 to 19: 1.

17, according to the laundry detergent composition of claim 16, wherein alkyl-sulphate is C ₁₄-C ₁₅Alkyl-sulphate, alkyl ethoxy sulfate are every mole of C that contains average 3 oxyethyl groups ₁₂-C ₁₅Alkyl ethoxy sulfate, wherein the scope of said weight ratio is 3.5: 1 to 10: 1.

18, according to the laundry detergent composition of claim 12 or 28, wherein nonionogenic tenside is the polyhydroxy fatty acid amide of following formula

R in the formula ¹Be H, C ₁-C ₄Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or its mixture, R ²Be C ₅-C ₃₁Alkyl and second are the polyhydroxy alkyl with the straight-chain alkyl chain that has at least 3 hydroxyls directly linking on the said chain, or its alkoxy derivative.

19, according to the laundry detergent composition of claim 12 or 28, wherein nonionogenic tenside is the C that every mol of alcohol contains average 3 to 8 moles of ethylene oxide ₉-C ₁₅Primary alcohol ethoxylate.

20, according to the laundry detergent composition of claim 19, wherein primary alcohol ethoxylate is the C that every mol of alcohol contains average 3 to 5 moles of ethylene oxide ₁₂-C ₁₅Primary alconol.

21, according to the laundry detergent composition of claim 12 or 28, it introduces 1% to 20%(weight) solid peroxygen acid blanching agent precursor.

22, according to the laundry detergent composition of claim 21 or 29, wherein inorganic perhydrate salt is SPC-D, its amount is 5% to 30%(weight) and solid peroxygen acid blanching agent precursor be TAED, its amount is 1% to 10%(composition weight).

23, according to the laundry detergent composition of claim 12 or 28, it comprises other scrubbed component, and this component is selected from detersive enzyme, soil-suspending agent and anti redeposition agent, white dyes, suds suppressor, spices and its mixture.

24, the composition that contains the bleaching composition of with good grounds claim 1, wherein said composition be liquid and wherein peralcohol be selected from hydrogen peroxide, organic peroxide acid and its mixture, and wherein composition to have pH value be 0.5 to 6.

25, according to the composition of claim 24, wherein peralcohol is dissolved in or is scattered in the liquid composition, or introduces with the form of emulsion or suspension.

26, according to the composition of the introducing peroxyacid bleach precursor of claim 24 or 25, the wherein said oxygen acid blanching agent precursor that reaches is dissolved in or is scattered in this liquid composition, or introduces with the form of emulsion or suspension.

27, according to the composition of claim 24, wherein said composition is prepared as hard surface detergent compositions, or as laundry additive composition, or as the dirt pretreatment compositions, or as the washing composition of carpet and furniture.

28, automatic dishwashing detergent composition according to Claim 8, it introduces 0.5% to 10%(weight) low foam surface activity agent, this tensio-active agent is selected from negatively charged ion, positively charged ion, nonionic, both sexes and zwitterionics, and composition thereof.

29, laundry detergent composition according to Claim 8, it comprises 3% to 30%(weight) tensio-active agent, this tensio-active agent is selected from negatively charged ion, positively charged ion, nonionic, both sexes and zwitterionics, and composition thereof.

30, according to the laundry detergent composition of claim 13, it introduces 1% to 20%(weight) solid peroxygen acid blanching agent precursor.

31, according to the laundry detergent composition of claim 13, it comprises other detergent component, and this component is selected from detersive enzyme, soil-suspending agent and anti redeposition agent, white dyes, suds suppressor, spices, and composition thereof.