CN1088612A

CN1088612A - Coated peroxyacid bleach precursor compositions

Info

Publication number: CN1088612A
Application number: CN93117444.9A
Authority: CN
Inventors: A·多维; A·G·索里
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1992-12-22
Filing date: 1993-07-31
Publication date: 1994-06-29
Anticipated expiration: 2013-07-31
Also published as: TW227016B; ES2141770T3; CA2141584A1; EP0675978B1; EP0675978A1; JPH08504867A; DE69327797T2; WO1994015010A1; CN1069696C; AU4685193A; CA2141584C; DE69327797D1; MX9304666A; EP0675978A4; ATE189492T1

Abstract

The present invention discloses solid peroxygen acid blanching agent precursor composition, it comprises the peroxyacid bleach precursor material grains, wherein said composition contains particles of different sizes, said precursor applies through coating material, wherein said coating material is selected from water-soluble acid polymkeric substance, and wherein more little its coated weight of particulate size is big more.

Description

Coated peroxyacid bleach precursor compositions

The present invention relates to solid peroxygen acid blanching agent precursor granules and related to fusion to have the inorganic perhydrate SYNTHETIC OPTICAL WHITNER of N-or O-acyl group-contain the particulate detergent composition of the bleach precursor (so-called activator of bleaching agent) of peroxycarboxylic acid.

In recent years, bleach precursor compositions had been widely used as the cleaning product of heavy dirty fabric, in automatic washing machine.The growth that bleach-activating agent uses has caused the reduction of fabric washing temperature, and the growth that bleach-activating agent uses itself is accompanied by the increase of colored fabric ratio.

The result of this trend makes because the problem to the damage of the color of fabric and material that the appearance of the partial high density of SYNTHETIC OPTICAL WHITNER causes becomes more obvious.Owing to multiple reason, high SYNTHETIC OPTICAL WHITNER concentration can occur in any particulate SYNTHETIC OPTICAL WHITNER.SYNTHETIC OPTICAL WHITNER itself has the intrinsic low-solubility, and its solubleness can be because the existence of other materials such as heavy-gravity tensio-active agent phase or disperse owing to the agitated conditions of SYNTHETIC OPTICAL WHITNER in environment at once is not high enough to that the dissolved SYNTHETIC OPTICAL WHITNER is affected.If being a component in the composition then this potential problem, activator of bleaching agent just increases.Except because the potential problems of the perhydroxyl radical ionic high local concentrations that the dissolving of the inorganic perhydrate that contains usually causes, form crossing hydrolysis and also producing partial percarboxylate SYNTHETIC OPTICAL WHITNER concentration significantly of the cationic activator of bleaching agent of peroxycarboxyl groups in laundry detergent composition.

Develop so-called concentrated product and it only can be increased the weight of these problems with the input of fabric load by the diverting device that is contained in the machine.So exist a kind of needs, promptly provide such detergent composition wherein activator of bleaching agent with minimum form sneak into wherein and when it dissolves in washings and crosses hydrolysis, preferably eliminate fabric color and material damage.

Have in the prior art many examples about through apply or the agglomeration activator of bleaching agent so that its in detergent composition, increase stable and/or influence its solution property.

EP-A-0070474 has disclosed by the granular bleach agent activator that contains N-acyl group or O-acyl compounds and at least a water-soluble cellulose ether, starch or starch derivative with aqueous dispersion spraying drying preparation of can pump taking out, and wherein activator is 98: 2 to 90: 10 with the weight ratio that applies agent.

GB-A-1507312 has disclosed and has used basic metal C ₈-C ₂₂Its corresponding lipid acid phase of soap blended mixture applies activator of bleaching agent.GB-A-1381121 adopts a kind of fused to apply agent, especially C ₁₄-C ₁₈The coating agent of fatty acid mixt is with protection solid bleaching activator.GB-A-1441416 has disclosed a kind of similar method, and it adopts C ₁₂-C ₁₄Lipid acid and C ₁₀-C ₂₀The mixture of Fatty Alcohol(C12-C14 and C12-C18).EP-A-0375241 has described the activator of bleaching agent extrudate of stabilization, wherein with C ₅-C ₁₈The alkyl peroxycarboxylic acid precursors be selected from negatively charged ion and nonionogenic tenside, the tackiness agent of film-forming polymer lipid acid or their mixture mixes mutually.

EP-A-0356700 has disclosed and has contained activator of bleaching agent, water-soluble, film-forming polymers and 2-15% and be used to the C that increases stability and improve dispersiveness/dissolving power ₃-C ₆The composition of polycarboxylic acid or hydroxycarboxylic acid.With carboxylic acid, preferred example is a citric acid, mixes with activator of bleaching agent, then with the film-forming polymer granulation.Citric acid is believed to increase activator of bleaching agent particulate dissolution rate.

EP-A-0382464 relates to a kind of coating or encapsulation methods that comprises the solid particulate of bleaching compounds and activator of bleaching agent, the coating material that wherein particulate is formed disperse phase forms melt, this melt instability, cause that subsequently fragmentation becomes particulate material, disperse phase particulate wherein be embedded into (coating) continuously mutually in.Wherein disclosed various coating materials, some material such as polyacrylic acid and rhodia phthalic ester are useful when being pointed out to depend on pH value for the release of coating material.

What emphasized in the prior art is that the protection activator of bleaching agent tackles rugged environment when storing, and relatively almost seldom attention is placed on the dissolving characteristic of the coating of use or agglomeration material.The someone advises with poorly soluble material such as lipid acid applies and/or agglomeration, and this can cause the hydrolysis rate of crossing of activator of bleaching agent not adopt the slow of this protection than it.Use any rapider dissolved material such as citric acid as the agglomeration component so that reach the faster dissolved purpose of activator of bleaching agent.In both of these case, because crossing hydrolysis after beginning dissolving and forming alkaline hydrogen peroxide solution, Betengent product just begun at once, the problem of local peroxy acid bleach agent concentration still is undecided.

A kind of terms of settlement of this problem is to postpone beginning hydrolysis so that avoid the review of fabric color impaired problem relevant with the dissolving situation of other Betengent product components.Yet this point is very important, promptly crosses hydrolysis when beginning when bleach precursor, and this crosses that hydrolysis and percarboxylate SYNTHETIC OPTICAL WHITNER subsequently disperse should be fast as far as possible, because modern automatic washing machine washing time is short.Satisfying the problem that produces in these two purpose processes at the same time also is not realized in the prior art so far.

Known pH value along with medium reduces, and the crossing hydrolysis rate and can little by little reduce of the percarboxylic acids bleach precursor in oxidizing aqueous medium is particularly when the pH value of medium is brought down below the pKa value of parent acid of this precursor leavings group.But being considered in the prior art to can be used as applies lipid acid that agent uses to be used to provide low pH value environment in aqueous cleaning liquid is inapplicable, because their insoluble.And be found the hydrolysis rate of crossing that has reduced peroxyacid bleach precursor as the lipid acid of the coating of peroxyacid bleach precursor and/or agglomerant, therefore, reduced the efficient of total peroxycarboxylic acid SYNTHETIC OPTICAL WHITNER.

Another problem that prior art combinations runs into is storage and the transport properties about described composition, therefore, another object of the present invention provides a kind of free flowable powder bleach precursor compositions, and it was kept intact in storage period of whole prolongation.

Various water-soluble organic materialss are used in suggestion among the application GB-91-02507.2 of pending trial at the same time, and it comprises some monomer and the oligomeric carboxylate coating material as this bleach precursor compositions.

At the same time among the application EP-92202388.2 of pending trial, how the applicant can be as agglomeration and the coating material of peroxyacid bleach precursor if having described some acid polymeric materials with some specific characteristic, so that when the dissolving of this product, under the pressure stirring condition of the washing machine drum of loading, put off the beginning of hydrolysis, and when crossing the hydrolysis generation, do not play opposite blanketing, and provide stable in storage free flowable pulverous peroxyacid bleach precursor compositions.

Found further that the bleach precursor material of describing through applying can apply agent content by control according to the particulate size and be improved in EP-92202388.2.Its result has improved the SYNTHETIC OPTICAL WHITNER performance, has kept stability simultaneously, to fabric also safety.In other words, people can utilize discovery of the present invention and the bleachability that provides further reduces damage to fabric.

The invention relates to the peroxyacid bleach precursor grains of composition that contains through applying; wherein said composition contains various size particles; said precursor contains one or more N-; or O-acyl group and have Mpi＞30 ℃; said precursor applies with coating material; wherein said coating material is selected from water-soluble acid polymkeric substance; the water solubility of said polymkeric substance in the time of 20 ℃ is greater than 5g/l; molecular weight is 1000 to 250; 000; wherein the pH value of 1% solution of said polymkeric substance is less than 7, and preferably less than 5.5, wherein the said coated weight in said particle is bigger in less size particles.Preferably, said precursor is co-agglomerated with described water-soluble acid polymkeric substance before it is coated.

Composition of the present invention contains the particle of the peroxyacid bleach precursor through applying.Composition of the present invention contains various size particles, all particles, they can be different or, be preferably identical particle, for concrete component, they all contain a kind of solid peroxygen acid blanching agent precursor, a kind of coating material and, preferably contain a kind of jointing material.

As first kind of main component; this solid peroxygen acid blanching agent precursor composition of the present invention includes the precursor that contains one or more N-or O-carboxyl groups; this precursor can be selected from the multiclass material; suitable several classes comprise acid anhydrides, ester, imide and imidazoles and oxime acyl derivative, and examples of substances useful in these materials is disclosed in GB-A-1586789.Most preferred material is as ester that discloses among the GB-A-836988,864798,1147871 and 2143231 and the imide as disclosing in GB-A-855735 and 1246338.

Particularly preferred precursor compound be as shown in the formula N, N, N ', N '-tetra-acetylatedization compound:

Wherein x is the integer between 0 or 1 to 6.

Example comprises the wherein tetra-acetylated methanediamine (TAMD) of X=1, the wherein tetra acetyl ethylene diamine of X=2 (TAED) and the wherein tetra-acetylated hexanediamine (TAHD) of x=6.These and similar compounds are described in GB-A-907356.Most preferred peroxyacid bleach precursor is TAED.

Useful its Mpi of solid peroxygen acid blanching agent precursor among the present invention＞30 ℃, preferred Mpi＞40 ℃.This precursor is fine powder or crystallized form normally, wherein 90%(weight at least) particle diameter＜150 micron of powder.

The another kind of main component of composition of the present invention is water-soluble acid polymkeric substance.Said polymkeric substance has as coating material in composition of the present invention and applies said precursor.In one embodiment of the present invention, said precursor is co-agglomerated with jointing material before it is coated.Said jointing material is preferred but to need not all be said water-soluble acid polymkeric substance.Adhesive material is different water-soluble acid polymkeric substance with coating material in the preferred embodiment of the invention, also is in the most preferred embodiment of the present invention at another still, and adhesive material is identical water-soluble acid polymkeric substance with coating material.

The suitable polymkeric substance of Shi Yonging is water miscible in this article.So-called in this article water-soluble be meant polymkeric substance 20 ℃ solubleness greater than 5g/l.

The suitable polymkeric substance of Shi Yonging is a tart in this article.The pH value that so-called acidity in this article refers to its 1% solution of said polymkeric substance is less than 7, preferably less than 5.5.

The molecular weight ranges that has of the suitable polymkeric substance of Shi Yonging is 100 to 280000 in this article, and is preferred 1500 to 150000, and preferably, the suitable polymkeric substance of Shi Yonging has and is higher than 30 ℃ fusing point in this article.

Therefore meet above-mentioned standard and be that useful especially suitable polymkeric substance comprises that those have the compound of the formula I of following empirical formula in the present invention:

Wherein X is O or CH ₂; Y is comonomer or monomer mixture; R ¹And R ²Be the polymer terminal group of bleach stable: R ³Be H, CH or C _1-4Alkyl; M is H, and with basic metal, alkaline-earth metal, ammonium or replace the mixture of ammonium; P is 0 to 2; N is at least 10, and their mixture.M is that the ratio of H must be to guarantee that this polymkeric substance has enough acidity to satisfy the previously defined acid standard of this paper in this polymkeric substance.

Polymkeric substance according to the formula I is known in the cloth-washing detergent field, typically is used as sequestrant, as the situation in GB-A-1597756.Be divided into several classifications from preferred multi-carboxylate's polymkeric substance.The first kind belongs to copolymerization multi-carboxylate polymkeric substance, it at least in form, it is as first monomer and unsaturated monocarboxylic such as vinylformic acid or α-C by unsaturated poly carboxylic acid such as toxilic acid, citraconic acid, methylene-succinic acid, methylfumaric acid _1-4Alkyl acrylic forms as second monomer.Therefore, the preferred multi-carboxylate's polymkeric substance of the type is that X is CH in those formula I ₂, R ³Be H or C _1-4Alkyl, preferable methyl, p are about 0.1 to 1.9, and be preferred about 0.2 to 1.5, and the n average out to is about 10 to 1500, preferred about 50 to 1000, more preferably 100 to 800, most preferably 120 to 400 and Y contain the polymkeric substance of the monomeric unit of formula II,

Ⅱ

These polymkeric substance are according to trade(brand)name Sokalan

Among the CP5(and form) and Sokalan The CP45(acid form) can obtain from BASF.

Second class belongs to multi-carboxylate's polymkeric substance of formula I, and wherein X is CH ₂, R ³Be OH, p is 0 to 0.1, is preferably 0, n average out to about 50 to 1500, preferred 100 to 1000.Y if exist, can be poly carboxylic acid such as top II, or ethylene oxide moiety.

The 3rd class belongs to the acetal multi-carboxylate polymkeric substance of formula I, wherein, and the formula I, X is), R ³Be H, p is 0 to 0.1, preferably 0, and n average out to 10 to 500.If present, Y can also be the poly carboxylic acid or the ethylene oxide moiety of following formula II.

The 4th class belongs to multi-carboxylate's polymkeric substance of formula I, and wherein X is CH ₂, R ³Be H or C _1-4Alkyl, p are 0 and n average out to about 10 to 1500, preferably about 500 to 1000.

The 5th class be have a formula I multi-carboxylate's polymkeric substance wherein X be CH ₂, R ³Be H or C _1-4Alkyl, particularly methyl, p are 0.01 to 0.09, preferably 0.02 to 0.06, n average out to about 10 to 1500, preferably about 15 to 300, Y is the poly carboxylic acid that is formed by toxilic acid, citraconic acid, methylene-succinic acid or methylfumaric acid, extremely preferably the maleic acid derivatives comonomer of top formula II.

The end group of the polymkeric substance of anti-bleaching the in the suitable formula I comprises alkyl, alkoxyl group and alkyl carboxylic acid base and its salt and ester.

In the superincumbent formula I, M is H or itself and basic metal, alkaline-earth metal, ammonium or the mixture that replaces ammonium.M is that the ratio of H is to guarantee that this polymkeric substance satisfies the requirement of the above-described pH value of this paper.

Top n, promptly the polymerization degree of polymkeric substance can be determined divided by average monomer molecule amount by average polymer molecule weight.Therefore, be 15500 and contain the maleic acid-acrylic acid copolymer of the toxilic acid derived units of 30 moles of % that for molecular-weight average n is that 182(is 15500/(116 * 0.3+72 * 0.7).

If have a question, average polymer molecule weight can be measured by gel permeation chromatography, wherein uses Water[mu] Porasil(RTM) GPC60A ₂[Mu] Bondagel(RTM) E-125, E-500 and E-1000 series, measure under 40 ℃ with respect to sodium polystyrene sulfonate polymkeric substance standard substance control column temperature, this standard substance can be from Polymer Laboratories Ltd., ShropshireUK obtains, and the polymkeric substance standard substance is that PH is 7 0.15M SODIUM PHOSPHATE, MONOBASIC and 0.02M tetramethyl ammonium hydroxides in 80/20 water/acetonitrile.

Multi-carboxy acid copolymer's mixture here also is suitable for, contain particularly that to have the n value be 100 at least, preferably be at least 120 high molecular weight component and on have the n value and be lower than 100, preferably 10 to 90, be more preferably the mixture of 20 to 80 lower-molecular-weight component.It is optimum being used for zero phosphoric acid washing agent prescription from this mixture of viewpoint that good bleach stability and anti-surface hardening performance are provided.

In such mixture, the weight ratio of high molecular weight component and lower-molecular-weight component is 1: 1 usually at least, preferred about 1: 1 to about 20: 1, is more preferably about 1.5: 1 to 10: 1, particularly about 2: 1 to 8: 1.Multi-carboxylate's polymkeric substance of preferred lower molecular weight type is multi-carboxylate's polymkeric substance (the many acrylate polymers of homopolymerization) of the 4th class listed above.

In a word, those that extremely preferred herein multi-carboxylate's polymkeric substance is the first kind, wherein the n average out to 100 to 800, preferably 120 to 400 and with multi-carboxylate's polymkeric substance of the 4th class, wherein the n average out to 10 to 90, preferred 20 to 80 mixture.

Other suitable polymers that the present invention uses comprise by amino acid such as polyglutamic acid derived polymers, as what in the application GB-91-20653.2 of common pending trial, disclose, with by the poly aspartic acid derived polymers, as in EP305282 and EP351629, disclosing.

The particle of the present composition contains 30% to 93% 70% to 88% the said peroxyacid bleach precursor preferably that accounts for total composition weight, and the particle of the present composition contains 7% to 70% 12% to 30% the said tackiness agent preferably that accounts for composition total weight.

Composition of the present invention contains the particle of the above-described various size of this paper.Another principal character of the present invention is that the coated weight in the bigger particle of smaller particles is bigger.

Particles of different sizes in the composition of the present invention can be separated by utilizing sieve.Composition of the present invention contains 100 microns to 1700 microns particle, and promptly all particles have passed through 1700 microns sieve and can not pass through 100 microns sieve.Less and bigger particle all is not suitable for purposes of the present invention.

Composition of the present invention can be divided at least two kinds, and each contains the particle in the size range.Mean value for each its coated weight can be determined.Particle size is more little in the present composition, and its coated weight mean value is big more.

For each particle size, coating agent content mean value used herein is based on the amount of the coating material that the usefulness weight % of this kind particle gross weight represents, promptly the mean value of coated weight is not considered the difference in the particle size of given kind.As used in this article, the mean value of the coated weight of the present composition is meant the amount of the coating material that the usefulness weight % based on composition total weight represents.

According to the polymkeric substance that in composition of the present invention, is used for agglomeration and coating, can measure the amount and the coated weight of the polymkeric substance in particle with different analytical procedures.This method comprises uses sulphur cyanogen ferrous colorimetric titration, uses photometric titration, the vapor-phase chromatography of chromotrope, etc.Preferred and simple method is the acid base titration with this polymkeric substance calibration.Adhesive material is identical polymkeric substance with coating material in embodiment preferred of the present invention, applying agent content can be by measuring the amount of the polymkeric substance in the agglomerant but uncoated sample, the amount of the polymkeric substance in the agglomerant and sample that applies of measurement identical weight.The difference that calculates both is then determined.The average coated weight that suitable composition has among the present invention is 2% to 25%, preferably 5% to 20%, and most preferred is 5% to 15%.

Preferred compositions can be divided into three kinds by particle among the present invention.

First kind of particle that comprises 1700 to 850 microns.Said first kind of average coated weight of particulate be the average coated weight of composition more than 0% to 100%, preferably 0% to 50%.

Second kind of particle that comprises less than 850 to 500 microns.The average coated weight of this kind particulate is 0% to 150% of the average coated weight of composition, preferably 0% to 100%.

The third comprises the particle less than 500 to 250 microns.The average coated weight of this kind particulate is 50% to 300% of the average coated weight of composition, preferably 75% to 275, and most preferred is 100% to 250%.

According to the present invention, the method for producing preferred solid peroxygen acid blanching agent precursor comprises the following steps:

-with peroxyacid bleach precursor and co-agglomerated as the previously defined jointing material of this paper;

-at random dry said co-agglomerated thing;

-apply the co-agglomerated thing of said drying with the coating material of above-mentioned definition;

Co-agglomerated thing after the-dry said coating.

According to described method, the peroxyacid bleach precursor powder must co-agglomeratedly enter as in the previously defined water-soluble acid polymeric adhesive material of this paper.The known any agglomeration technique of those of skill in the art all is suitable in this article.

Itself can not provide benefit through co-agglomerated fine material, said co-agglomerated material require this paper water-soluble acid polymer-coated defined above to the present invention.Use coating material can be undertaken by several means to the coating of co-agglomerated material.

Coating material can melt substance or is sprayed with solution in solvents/carriers liquid or dispersion form, and solvent and carrier liq can be removed through evaporation subsequently.Coating material also can be used for powder coated for example to be used by electrostatic technique, though this method is not preferred, because the coating material of powdered attaches difficulty, and expensive.

Fusion coating is preferred technology to the coating material of Mpi＜80 ℃ in fact, but is inconvenient to the acid of higher melt (promptly＞100 ℃).For the coating material of Mpi＜80 ℃, it is preferred spraying with solution or dispersion form.Can need although it is so to reclaim solvent so that save ground and use them with an organic solvent as ethanol and Virahol wiring solution-forming or dispersion.But, with an organic solvent also can cause safety problem such as inflammableness and operational safety, so aqueous solution or dispersion are preferred.

Aqueous solution is particularly advantageous, because coating material of the present invention has high water solubility, the solution that is provided has enough low viscosity makes it be easy to handle.Preferably using the concentration of coating material in solvent is 25%(weight at least) so that after surface treatment, alleviate the burden of drying/evaporation.Treatment unit can be those any devices that are generally used for this purposes, as the inclination rotating disk, and rotor and fluidized-bed, high speed and slow-speed mixer (Lodige).

In the present invention, the most important thing is that control coating distributes to guarantee the more of particle coated that smaller particles is bigger.

Is the several grain flows that the particle of composition are divided into different size after agglomeration step being used for producing particulate method of the present invention according to the appropriate mode of particle size control coated weight, then each grain flow of coating processing individually.

Control applies agent and is to use particle fluidizing fluidized-bed in airflow in the mode more cleverly of the content on the particle.This fluidisation provides natural particle size gradient, smaller particles at bed top and bigger particle in the bottom.Then coating material is sprayed onto on the particle, places nozzle rightly and can obtain suitable coating effect.Particularly, be increased in a sprinkling on top higher coated weight can be provided on little particle.

Solid peroxygen acid blanching agent precursor composition according to the present invention can be used for various uses.Therefore this peroxyacid bleach composition itself can mix in other solids compositions such as tablet, extrudate and the agglomerate.Composition also can be suspended in the non-aqueous liquid compositions, and wherein organic acid surface treatment material is insoluble and inert.But, it is fine component as granular detergent composition that solid peroxygen bleach precursor composition of the present invention preferably uses, particularly by placing feeding device in the washing machine drum that is placed with dirty fabric to join the so-called concentrated cleaning compositions of washing machine.By charging device spissated granular detergent composition is dispensed into the dispersion cabin of comparing in the washing liq by washing machine and adds the domination that composition more is subjected to problems of dissolution, because at the initial stage of washing, the inhibition that the stirring of the instant environment of product is existed by fabric.And can bring benefit to the high instant concentration aspect that allows tackiness agent and tensio-active agent to occur like this.The appearance of the high instant concentration of peroxy acid as previously mentioned, can cause fabric and color impaired.Composition of the present invention in the time of in mixing the spissated Betengent product that is sent to by diverting device in the washings, had both made the words of not eliminating this problem.Also can relax this problem.

The detergent composition that has mixed the peroxyacid bleach precursor compositions that the present invention applies contains the detergent composition of this precursor composition of 0.5% to 20% usually, more frequent is 1% to 9%, most preferably 3% to 8%, the weight that top amount all is based on composition is meter.

Certainly, this detergent composition will contain in washing soln for the source that forms the necessary alkaline hydrogen peroxide of peroxy acid bleach species, preferably also can contain other conventional components that can be used in the detergent composition.Therefore preferred detergent composition should mix one or more tensio-active agents, organic and inorganic adhesive, soil-suspending agent and anti redeposition agent, froth suppressor, enzyme, white dyes, photoactivation SYNTHETIC OPTICAL WHITNER, spices and pigment.

The detergent composition that mixes the particulate peroxyacid precursor of coating of the present invention comprises inorganic perhydrate washing composition, and common form with sodium salt is as the alkaline hydrogen peroxide source in washings.This perhydrate is usually by 3% to 35%(weight of composition) amount mix 3% to 35%(weight more preferably) and 5% to 30%(weight most preferably).

This perhydrate can be any such inorganic salt such as perborate, percarbonate, superphosphate and persilicate, but commonly used be alkali metal perborate or percarbonate.The extent of damage of the review of fabric color that is caused by composition according to the present invention is low, no matter whether use peroxyboric acid or percarbonate, compare with the precursor particulate of uncoated, using the effect improved of percarbonate bleach is significantly, because the bleach precursor that does not have to apply can cause review of fabric color impaired bigger.

SPC-D, it is preferred perhydrate, is to have corresponding to 2Na ₂CO ₃3H ₂O ₂The adducts of molecular formula is the crystalline solid that can buy on the market.The material that can buy on most of market comprises a spot of heavy metal chelant such as EDTA, 1-hydroxy ethylene 1,1-bisphosphate (HEDP) or amino acid phosphoric acid salt, and they are impregnated in process of production.Concerning detergent composition of the present invention, percarbonate can mix in the detergent composition and need not other protection, but the preferred use-pattern of said composition is to utilize the coated form of this material.Suitable coating agent is SiO ₂: Na ₂The water glass of O, both ratios are 1.6: 1 to 3.4: 1, preferably 2.8: 1, use with the form of the aqueous solution to be generally 3% to 5% so that the amount of silicate solid accounts for 2% to 10%(of percarbonate weight).Another kind of coating agent is the mixing salt of alkali metal sulfates and carbonate.This class applies agent and coating method licenses to Interox at GB-1466799(on March 9th, 1977) in describe.The weight ratio of this mixing salt coating material and percarbonate in 1: 200 to 1: 4 scope, even more preferably 1: 99 to 1: 9, most preferably 1: 49 to 1: 19.Preferably, this mixing salt is that sodium sulfate and yellow soda ash are formed, and it has general formula Na ₂SO ₄.n.Na ₂CO ₃Wherein n is 0.1 to 3, and preferably n is 0.3 to 1.0, and most preferred n is 0.2 to 0.5.Magnesium Silicate q-agent also can be contained in such and applies in the agent.

The particle size range of crystallization percarbonate is 350 microns to 450 microns, and its mean value is about 400 microns.After applying, 60% to 80%(weight) this crystallization has the particle diameter greater than 425 microns, and its mean value is about 650 microns.

The heavy metal that is present in the yellow soda ash that is used for producing percarbonate can be controlled by be doped into sequestrant in reaction mixture, and percarbonate still needs to avoid heavy metal to have those impurity in other components at product.Therefore, in the detergent composition that utilizes percarbonate as perhydrate salt, iron, copper and the mn ion total content in product is should exceed 25ppm not, preferably is less than 20ppm, to avoid the unacceptable disadvantageous effect to percarbonate stability.By the alkali metal percarbonate SYNTHETIC OPTICAL WHITNER therein the detergent composition of enhanced stability at the UK Patent Application No.9021761.3(patent attorney registration number CM343 of common pending trial) in disclosed.

Many kinds of tensio-active agents may be used in this detergent composition.The typical tabulation of the kind of negatively charged ion, nonionic, zwitterionics and series thereof December 30 was authorized Laughlin and Heuring at U.S.P3929678(1975) in provide.The tabulation of the cats product that is fit to was authorized Murphy on March 31st, 1981 at U.S.P.4259217) in provide.

Anionic surfactant mixture suits in invention, particularly the mixture of vitriol, sulfonate and/or carboxylate surface active agent.Sulfonate and the normally used weight ratio of sulfate surfactant mixture are sulfonate and the ratio of vitriol is 5: 1 to 1: 2, and preferably 3: 1 to 2: 3 more preferably is 3: 1 to 1: 1.Preferred sulfonate is included in has 9 to 15 in the alkyl, the preferably alkylbenzene sulfonate of 11 to 13 carbon atoms and the sulfonated fatty acid methyl ester of α, and wherein lipid acid is by C ₁₂-C ₁₈Fat source is preferably from C ₁₆-C ₁₈Fat source is derived and is obtained.Positively charged ion is a basic metal in each case, preferably sodium.Preferred vitriol is to have 12 to 22 in alkyl in such sulfonate sulfate mixture, preferably the alkyl-sulphate of 16 to 18 carbon atoms.Another kind of useful surfactant system contains the mixture of two kinds of alkyl-sulphate materials, and their mean chain lengths separately are different.A kind of such system contains C ₁₄-C ₁₅Alkyl-sulphate and C ₁₆-C ₁₈Alkyl-sulphate is ratio C by weight ₁₄-C ₁₅: C ₁₆-C ₁₈It is 3: 1 to 1: 1 mixture.This alkyl-sulphate also can with alkyl in have 10 to 20, preferred 10 to 16 carbon atoms and average degree of ethoxylation are 1 to 6 alkyl ethoxy sulfate combination.Positively charged ion remains basic metal in each case, preferred sodium.Other anion surfactants that are used for purposes of the present invention are formula R-CON(R) CH ₂An alkali metal salt of the sarkosine of COOM, wherein R is C ₉-C ₁₇Straight or branched alkyl or alkenyl, R ' are C ₁-C ₄Alkyl, M are alkalimetal ions.Preferred example is lauroyl, the cocoa acyl (C with their sodium-salt form use ₁₂-C ₁₄), mnyristoyl and oleoyl methyl sarcosinate.

The effective ionic surfactant pack of a class contains the condenses of oxyethane and hydrophobic part among the present invention, it provides has average hydrophile-lipophile balance value (HLB) 8 to 17, preferred 9.5 to 13.5, preferred tensio-active agent in 10 to 12.5 scopes.Hydrophobic (oleophylic) part can be in nature aliphatic series or aromatics, can easily regulate with any special hydrophobic group mutually the polyoxyethylated chain length of condensation to obtain having the water-soluble cpds of the quality of balance between the required hydrophilic and hydrophobic factor.

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

Another kind of ionic surfactant pack contains by being the alkyl poly glucoside compound of following formula:

Wherein Z is to be the saturated hydrophobic alkyl that contains the 12-18 carbon atom by glucose deutero-part: R; T be 0 to 10 and n be 2 or 3; X is 1,3 to 4, and this compounds comprises unreacted Fatty Alcohol(C12-C14 and C12-C18) that is less than 10% and the short-chain alkyl poly glucoside that is less than 50%.This compounds and in detergent composition, be used in EP-B0070074, disclosed in 0070077,0075996 and 0084118.

Another kind of tensio-active agent is semi-polarity tensio-active agent such as amine oxide.Suitable amine oxide is selected from single C ₈-C ₂₀, preferred C ₁₀-C ₁₄N-alkyl or alkenyl amine oxide compound and propylidene-1,3-two amine oxides, the position on the wherein remaining N is replaced by methyl, hydroxyethyl or hydroxypropyl.

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

Detergent composition contains 5% to 20% the tensio-active agent that accounts for composition weight, but more generally contains 7% to 20%, more preferably contains 10% to 15% tensio-active agent.

The tensio-active agent of mixed type is preferred, more preferably the adulterant of negatively charged ion-nonionic and negatively charged ion-nonionic-anion surfactant.Particularly preferred combination is described in GB-A-2040987 and EP-A-0087914.Though tensio-active agent can mix in the composition with mixture, the interpolation point of preferably controlling every kind of tensio-active agent is so that the physical property of optimum combination thing and avoid operational issue.Preferred mode and program that tensio-active agent adds will be described below.

In the detergent composition of the peroxyacid precursor particulate that is mixed with coating of the present invention another more preferably component is to contain one or more nonphosphate washing auxiliary detergent systems.They comprise, but be not limited only to, alkali-metal carbonate, supercarbonate, silicate, silico-aluminate, the monomer multi-carboxylate, all or copolymerization poly carboxylic acid or their salt, wherein poly carboxylic acid contains at least two apart carboxylic acid groups that are no more than two carbon atoms, the mixture of organic phosphonate and amino alkylidenyl poly-(alkylene phosphonic acids salt) and above-mentioned any material.The amount of builder system in composition is 25% to 60%(weight of composition weight), be more preferably 30% to 60%(weight).

Preferred builder system is a boron-containing compound not, and is for any polymeric organic materials, preferably biodegradable.

Suitable silicate is to have SiO ₂: Na ₂O ratio those in 1.6 to 3.4 scopes, Si ₂O: Na ₂O is that 2.0 to 2.8 so-called amorphous silicic salt is preferred.These materials can add on the difference of production process, as in by spray-dired component slurries or with the agglomerant of aqueous solution form as other solid ingredients, or when silicate itself is fine-grained form, join as solid in other fine components of composition.But, be the composition that is lower than as 30% for the percentage composition of spray-dried component, preferably amorphous silicic salt is included in by in the spraying-exsiccant component.

In silicates, more preferably material is that general formula is the laminar crystal sodium silicate of following formula

NaMSi _xO _2x+1·yH ₂O

Wherein M is sodium or hydrogen, and x is 1.9 to 4, and Y is 0 to 20.Such laminar crystal sodium silicate discloses in EP-A-0164514, and its preparation method is in DE-A-3417649 and DE-A-3742043 or disclosure.For the present invention, above the numerical value of x in the general formula be 2,3 or 4, be preferably 2.Even more preferably M is a sodium, and Y is 0, and the preferred example of this formula comprises Na ₂Si ₂O ₅α, β, γ and δ form.These materials have been bought with trade name Na SKS-11 and Na SKS-6 respectively from Hoechst AG FRG.Most preferred material is δ-Na ₂Si ₂O ₅(Na SKS-6).Crystalline layered silicate as the exsiccant blended solid, is perhaps mixed with other components as agglomerant solid ingredient.

Can use a series of silico-aluminate ion exchange materials, preferred sodium silicoaluminate zeolite has the following formula cell cube:

Wherein z and y are 6 at least; Z and y mol ratio are 1.0 to 0.5, and x is 5 at least, preferably 7.5 to 276, be more preferably 10 to 264.This alumino-silicate materials is with hydrate forms, and preferably crystallization contains 10% to 28%, more preferably contains 18% to 22% the water with the binding form.

Another feature of above-mentioned silico-aluminate ion exchange material is that its particle diameter is 0.1 to 10 micron, preferred 0.2 to 4 micron.The median size of the given ion exchange material measured with conventional method of analysis represented in this article in term " particle diameter ", and these analytical procedures are for example with the micro-mensuration of scanning electronic microscope or utilize laser particle determinator mensuration.Another feature of silico-aluminate ion exchange material is their calcium ion exchange capacity, and this ability is 200mg equivalent CaCl at least ₃The water hardness/every gram silico-aluminate (pressing moisture-free basis calculates), this is worth usually in 300mg eq./g to 352mg eq./g scope.It is their calcium ion exchange rate that the silico-aluminate ion exchange material also has a feature in this article, is 130mg equivalent CaCO at least ₃/ liter/minute/(g/ liter) [2 grain Ca ⁺⁺/ gpm/(gram/gallon)] silico-aluminate (moisture-free basis), this speed is usually at scope 130mg equivalent CaCO ₃/ liter/minute/(g/ liter) [2 grains/gpm/(gram/gallon)] be to 390mg equivalent CaCO ₃/ liter/minute/(g/ liter) [6 grains/gpm/(gram/gallon)], based on calcium ion hardness.The calcium ion exchange rate that best conduct helps the silico-aluminate of washing usefulness to have is 260mg equivalent CaCO at least ₃/ liter/minute/(grams per liter) [4 grains/gpm/(gram/gallon)].

The silico-aluminate ion exchange material that uses among the present invention can have been bought from the market, can be the material that nature produces, but is preferably obtained by synthetic deriving.A kind of method of producing the silico-aluminate ion exchange material has been discussed in US3985669.The preferred synthetic crystallization silico-aluminate ion exchange material of Shi Yonging can title zeolite A, zeolite B in the present invention, X zeolite, zeolite HS and composition thereof bought.In particularly preferred embodiments, crystalline silico-alumino acid ion exchange material is zeolite A, and it has following formula:

Wherein x is 20 to 30, especially 27.Molecular formula is

Na ₈₆[(AlO ₂) ₈₆(SiO ₂) ₁₀₆] 276H ₂The X zeolite of O and molecular formula are

Na ₆[(AlO ₂) ₆(SiO ₂) ₆] 7.5H ₂The zeolite HS of O also is fit to.

Suitable water-soluble monomer or oligomeric carboxylate's washing assistant are included in lactic acid, oxyacetic acid and the ether derivant thereof that discloses among the belgian patent No.831368,821369 and 821370.The multi-carboxylate who contains two carboxyls comprises the water-soluble salt of following acid, be succsinic acid, propylene glycol, (ethylenedioxy) diacetic acid, toxilic acid, diglycollic acid, tartrate, tartronic acid and fumaric acid, and the sulfinyl carboxylate salt of describing among ether carboxylate of in German Patent 2446686,2446687 and US3935257, describing and the belgian patent No.840623.The multi-carboxylate who contains three carboxyls comprises, particularly, the carboxyl methyl oxydisuccinic acid salt of describing among water miscible Citrate trianion, aconitrates and citraconate and succinate derivative such as the English Patent No.1379241, the newborn acyloxy succinate of describing among the English Patent No.1389732, with the aminosuccinic acid salt of describing in the Netherlands patent applications 7205873, with the 2-oxa-of describing among oxidation multi-carboxylate material such as the English Patent No.1387447-1,1,3-tricarballylic acid salt.

The multi-carboxylate who contains four carboxyls comprises the oxidation disuccinate that discloses among the English Patent No.1261829,1,1,2, and 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 comprise English Patent No.1398421 and 1398422 and US3936448 in the sulfonation pyrolysis Citrate trianion described among the sulfo-succinic acid salt derivative that discloses and the English Patent No.1439000.

Alicyclic ring and heterocycle multi-carboxylate comprise pentamethylene-suitable, suitable, suitable-tetracarboxylic acid hydrochlorate, cyclopentadiene pentacarboxylic acid salt, 2,3,4,5-tetrahydrofuran (THF)-suitable, suitable, suitable-tetracarboxylic acid hydrochlorate, 2,5-tetrahydrofuran (THF)-suitable-dicarboxylate, 2,2,5,5-tetrahydrofuran (THF)-tetracarboxylic acid hydrochlorate, 1,2,3,4,5, the carboxyl methyl-derivatives of 6-hexane-hexacarboxylic acid salt and polyhydroxy-alcohol such as sorbyl alcohol, mannitol and Xylitol.Aromatic multi-carboxy acid's salt comprises mellitic acid, pyromellitic acid and the phthalic acid derivative that discloses in the English Patent 1425343.In a word, preferred multi-carboxylate is that per molecule contains the hydroxycarboxylate up to three carboxyls, even more preferably Citrate trianion.

The mixture of female acid of monomer or oligomeric multi-carboxylate's sequestrant or itself and their salt, also being considered as the mixture of citric acid or Citrate trianion/citric acid is used as component in the builder system of detergent composition of the present invention.

Other suitable water-soluble organic salts are all or copolymerization poly carboxylic acid or their salt, and wherein poly carboxylic acid contains at least two and is separated by and is no more than the carboxyl of two carbon atoms.The polymkeric substance of latter's type is disclosed in GB-A-1596756.The example of this salt is that molecular weight is the multipolymer of the polyacrylate of 2000-5000 and they and maleic anhydride, and the molecular weight of this multipolymer is 20000 to 70000, particularly about 40000.This washing assistant polymeric material can be with identical as the polymeric material of adhesive material and coating material (described above as this paper).The common usage quantity of these materials is to account for 0.5% to 10% of composition weight, more preferably 0.75% to 8%, most preferably 1% to 6%.

Another kind of preferred multi-carboxy acid salt washing agent is ethylene diamine-N, the salt of N '-disuccinic acid (EDDS) or its basic metal, alkaline-earth metal, ammonium or replacement ammonium, or their mixture.Preferred EDDS compound is its free acid form and its sodium or magnesium salts.The example of this preferred sodium salt of EDDS comprises NaEDDS, Na ₂EDDS and Na ₄EDDS.The example of this preferred magnesium salts of EDDS comprises MgEDDS and Mg ₂EDDS.It is most preferred that this magnesium salts mixes in the composition of the present invention.

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

EDDS can be synthesized, and for example, facile, cheap calmly starting raw material such as following maleic anhydride and quadrol are synthetic:

Be to authorize on November 24th, 1964 the open method more completely that can find among the US3158635 of Kezerian and Ramsay by the synthetic EDDS of the starting raw material that can buy from the market.

Obtain three optical activity isomers from maleic anhydride and the synthetic EDDS of quadrol, the mixture of [R, R], [S, S] and [S, R] is because product has two unsymmetrical carbons.The biological degradation of EDDS is that optically active isomer is narrow spectrum, and the degraded of [S, S] isomer is the fastest and the strongest, and therefore, it is most preferred that [S, S] isomer mixes in the composition of the present invention.

[S, S] isomer of EDDS can be synthetic from L-aspartic acid and glycol dibromide, as shown in the formula:

At the three-dimensional single-minded part of the ethylenediamine disuccinic acid of Neal and Rose and their title complex, Inorganic Chemistry, Vol 7(1968), can find in the 2405-2412 page or leaf by L-aspartic acid and 1, the reaction of 2-ethylene dibromide generates the open reaction more completely of [S, S] isomer of EDDS.

Organic phosphonate and amino alkylidenyl poly-(alkylene phosphonic acids salt) comprise alkali-metal ethane 1-hydroxyl diphosphonate, nitrilo trimethylene phosphonic salt, ethylenediamine tetramethylene phosphonic acid salt and diethylenetriamine pentamethylenophosphonic acid(DTPP) salt, although these materials are not preferred, because need indivisible phosphorus compound in composition of the present invention.

With regard to the detergent composition that comprises the processed bleach precursor particulate in surface of the present invention, the nonphosphate builders component should account for 25% to 60% of composition weight, is more preferably 30% to 60%(weight).In preferred compositions, sodium silicoaluminate such as zeolite A should account for 20% to 60%(weight of washing assistant total amount), monomer or oligomeric carboxylate should account for 10% to 30%(weight of washing assistant total amount), crystalline layered silicate should account for 10% to 65%(weight of washing assistant total amount).Washing assistant preferably also can be mixed with auxiliary inorganic or organic washing-assisting detergent mixture such as yellow soda ash and maleic anhydride/acrylic copolymer in this based composition, and its amount is up to the 35%(weight of total washing assistant).

Anti redeposition agent that is suitable among the present invention and dirt suspension agent comprise derivatived cellulose such as methylcellulose gum, carboxymethyl cellulose and Natvosol and homogeneous or totally one poly-poly carboxylic acid or their salt.This base polymer comprises the multipolymer of maleic anhydride and ethene, methylvinylether or methacrylic acid, and maleic anhydride accounts for the 20%(mole of multipolymer at least).The common usage quantity of these materials is to account for 0.5% to 10% of composition weight, is more preferably 0.75% to 8%, and most preferred is 1% to 6%.

Other useful polymeric material is a polyoxyethylene glycol, and particularly those molecular weight are 1000-10000, is more preferably 2000 to 8000 and be most preferably 4000 polyoxyethylene glycol.Their usage quantity is 0.20% to 5%, more preferably 0.25% to 2.5%(weight).These polymkeric substance and above-mentioned homogeneous or totally one poly-multi-carboxylate in the presence of transition metal impurity, keep, the fabric dust deposit, all be valuable argillous cleaning performance, the cleaning performance that reaches proteinic and oxidable dirt to improving white.

Preferred white dyes has the negatively charged ion feature, the example is 4,4 '-two-(2-diethanolamino-4-anilino-5-triazine-6-base is amino) stilbene-2: 2 '-the disulfonic acid disodium, 4,4 '-two-(the amino stilbene-2: 2 of 2-morpholino-4-anilino-2-triazine-6-'-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 list sodium; 4; 4 '-two-(2-anilino-4-(N-methyl-N-2-hydroxyethylamino-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-hydroxyethyl amino)-5-triazines-6-base is amino) stilbene-2,2 '-the disulfonic acid disodium, with 2-(stilbene radicals-4 " (naphtho--1 '; 2 ': 4; 5)-1,2,3-triazoles-2 " sodium sulfonate.

The stain remover that is used for the present composition normally terephthalic acid and ethylene glycol and/or propylene glycol unit with the multipolymer or the terpolymer of various rearrangement modes.The example of this base polymer the common US4116885 that transfers the possession of and 4711730 and European publication application No.0272033 in disclose.Particularly preferred polymkeric substance according to EP-A-0272033 has following formula

（CH ₃（PEG） ₄₃） _0.75（POH） _0.25（T-PO） _2.8（T-PEG） _0.4]T（POH） _0.25（（PEG） ₄₃CH ₃） _0.75

where PEG is-（OC ₂H ₄）O-，PO is（OC ₃H ₆O）and T is（pCOC ₆H ₄CO）.

Some polymeric material such as typical molecular weight are 5000-20000, and preferably the polyvinylpyrrolidone of 10000-15000 also can form useful reagent unsettled pigment shifts between fabric in washing process to avoid.

Another optional detergent composition component is a froth suppressor, for example siloxanes, and silicon-dioxide-mixture of siloxanes.Siloxanes can be represented by the alkylation silicone materials usually, and silicon-dioxide uses with fine powder form usually, for example aerosil and xerogel and various types of water drain silica.These materials can be used as particulate and mix, and wherein froth suppressor advantageously is impregnated in water misciblely or water dispersible releasedly, is actually in the non-surface active impermeable washing composition carrier.In other words, froth suppressor can dissolve or be distributed in the liquid vehicle.Be applied on one or more other components by spraying.

As previously mentioned, useful silicone foam control agent can contain the alkylation siloxanes with the above-mentioned preferred type of this paper and the mixture of solid silica.This mixture prepares by siloxanes is added on the solid silica surface.Preferred silicone foam control agent is that to have particle size range be that 10 millimicrons to 20 millimicrons and specific surface area are greater than 50m ²The silicon-dioxide of the hydrophobic silanization of/g (most preferably trimethyl silicone hydride) is directly to mix to about 1: 2 ratio in about 1: 1 to obtain with to have molecular weight ranges be about dimethyl silicone fluids of 500 to 200000 in the siloxanes and the weight ratio of silanized silica.

Preferred silicone foam control agent discloses in people's such as Bartollota US 3933672, other useful especially froth suppressor are self-emulsifying siloxane foams inhibitor, and it was described among the disclosed German patent application DTOS 2646126 on April 28th, 1977.This examples for compounds is DC0544, can buy from Dow Corning, and it is the multipolymer of siloxanes/H alcohol.

The common usage quantity of above-described froth suppressor is to account for 0.001% to 0.5% of composition weight, preferably 0.01% to 0.1%.

Preferred fusion mode comprises froth suppressor is applied on the main component of one or more present compositions by spraying with liquid form.Or another kind of method is that froth suppressor is formed the dispersive particulate, mixes with other solids components in the composition then.Fusion allows also that other foam control are material doped goes into wherein this material such as C to foaming regulator as the dispersive particulate ₂₀-C ₂₄The high-molecular weight multipolymer of lipid acid, Microcrystalline Wax and oxyethane and propylene oxide, otherwise can influence the dispersive ability of matrix on the contrary.Forming this foam regulates among the people's such as Bartolotta that the method for particulate mentions in front the US3933672 and discloses.

Another optional composition of the present invention that is used for is one or more enzymes.

Preferred enzyme material comprise can buy on the market advanced amylase, neutrality and Sumizyme MP, lipase, esterase and cellulase in the detergent composition by fusion usually.The enzyme that is suitable for is discussed in US3519570 and 3533139.

Fabric softener also can mix in the detergent composition of the present invention.These reagent can be inorganic or organic types.The edge soil clay of the example of inorganic tenderizer in GB-A-1400898, disclosing.The organic fabric tenderizer comprises the water-fast tertiary amine as disclosing in GB-A-1514276 and EP-B-0011340.

They and single C ₁₂-C ₁₄Being combined in EP-B-0026527 and 0026528 of quaternary amine discloses.The dilong chain acid amides of other useful organic fabric tenderizers as in EP-B-0242919, disclosing.The organic composition that adds in the fabric-softening system comprises the high molecular weight polyethylene oxide that discloses as in EP-A-0299575 and 0313146.

The content of edge soil clay is usually in 5% to 15%(weight) scope in 8% to 12%(weight more preferably), this material is joined in the residuum of preparation with the dry mixed component.Organic fabric tenderizer such as water-fast tertiary amine or dilong chain acid amides material are 0.5% to 5%(weight by content), be generally 1% to 3%(weight) be impregnated in and high molecular weight polyethylene oxide material and water-soluble cationic material are 0.1% to 2% by content, be generally 0.15 to 1.5%(weight) be added into.Some part of composition is by spraying drying, these materials can be added in the aqueous slurry that is added to spray-drying tower, though in some cases, their particulates with dry mixed are added to, or to be sprayed onto them on other solid ingredients in the composition with fusing fluid will be more easily.

Peroxyacid bleach precursor particulate through applying of the present invention is useful especially in spissated granular detergent composition, and said composition is characterised in that comparing it with laundry detergent composition commonly used has relative high density.The loose density that this high-density composition has is at least the 650g/ liter, more generally be 700g/ liter at least, more preferably greater than the 800g/ liter.

Simple funnel of loose density utilization and cup measurement device, the conical hopper of this device are embossed on the base plate securely, and its lower end is equipped with a valve and is flowed in the cylindrical cup-shaped thing that axially sets be placed on below the funnel by the thing in the funnel.These funnel top and bottom correspondingly are 130mm and 40mm.It is installed in the total height that makes its lower end be higher than plate upper surface 140mm cup is 90mm, interior high 87mm, internal diameter 84mm.Its nominal volume is 500ml.

When measuring, fill up funnel, open valve by excessive this cup that fills up of powder with the hand pouring powders.The cup that fills up is taken away from framework, excessive powder is removed from this cup by streaking from the upper edge of cup with edge instrument always such as pocket knife.The cup that fills up of weighing then, the gravimetric value of the powder that obtains double promptly to obtain the loose density with the g/ unit of being upgraded to.Carry out replicate measurement as required.

The common also at least a multicomponent component of fusion of spissated detergent composition is that they do not contain the composition that only forms by each composition of dry mixed.Each composition wherein all be dried the blended composition normally many dirt, dissolved slowly, in storage, also be easy to lump and cause poor mobility of particle.

Be subjected to the domination of top loose density and component concentration restriction, composition of the present invention can comprise that dry mixed, spraying drying, agglomeration and granulation prepare by the whole bag of tricks, and preferable methods is the combination of these methods.A kind of preferable methods for preparing this composition comprises the combination of spraying drying and agglomeration in super mixer and dry mixed.

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

First component comprises one or more particle powders inorganic or organic salt of 99.25% to 60% that 0.75% to 40% anion surfactant that fusion content is powder weight and content are powder weight.This particulate can adopt suitable form such as small-particle, plate, bead, marumes or soap noodles, but granulous preferably.Particle itself can be an agglomerate, and it forms by basin or cylinder agglomeration or by inline mixer, but the normally spray-dired particle of small-particle, its by in hot blast with the aqueous slurry atomizing of component and remove most of water preparation.Then with spray-dried granules through densification steps, for example utilize high-speed shearing machine mixing tank and/or compacting shredder, before reagglomeration, increase density.For illustration purpose, first component is described as spray-dried powders in this paper back.

Have been found that suitable anion surfactant as the first component purposes be slow dissolved alkyl wherein have the straight-chain alkyl sulfate of 16 to 22 carbon atoms of average out to and wherein alkyl have straight-chain alkyl carboxylic acid's salt of 16 to 24 carbon atoms of average out to.The alkyl of this tensio-active agent of two types is preferably derived from natural source such as butter fat and marine animal oil and is obtained.

The content of anion surfactant in forming the spray-dried powders of first component is 0.75% to 40%(weight), more common is 2.5% to 25%, preferably 3% to 20% and most preferred be 5% to 15%(weight).Water miscible tensio-active agent can comprise as linear alkylbenzene sulfonate or C ₁₄-C ₁₅Alkyl-sulphate or can then be applied on the spray-dired powder by spraying.

Other main components of spray-dired powder are one or more inorganic or organic salts that crystalline texture is provided for particle.This inorganic and/or organic salt can be water miscible or water-insoluble, and back one type is comprised in the water-fast washing assistant, and wherein they have formed washing assistant composition or most washing assistant composition, or the major portion of this washing assistant.Suitable water-soluble inorganic salt comprises alkali-metal carbonate and supercarbonate.Alkalimetal silicate also may reside in the spray-dired particle as long as silico-aluminate is not the part of spray-dried component except crystalline layered silicate.

But in spissated detergent composition, preferably water soluble sulfate, particularly sodium sulfate exist with 2.5% the amount that is no more than composition weight.Preferred sodium sulfate does not add with independent composition, and it for example should reduce to minimum with the hybrid that sulphur (sulphur) is changed tensio-active agent as by product.

Form at aluminosilicate zeolite, or when forming part washing assistant composition, preferably its not by directly by dry-be mixed to join during other form, but be impregnated in the multicomponent component.Being blended in the spray-dired particle of zeolite takes place, and the existence of any silicate should not constitute the part of spray-dried granules.In these cases, can realize the fusion of silicate in several ways, for example, by preparing the independent spray-dired particulate that contains silicate, by silicate is mixed in the agglomerate of other compositions, or more preferably by the solids component of silicate as dry mixed added.

First component can also comprise the weight up to 15%() miscellaneous composition such as whitening agent, anti redeposition agent, photoactivation SYNTHETIC OPTICAL WHITNER (as four sulphating zinc phthalocyanines) and heavy metal sequestering agent.When first component was spray-dired powder, it was dried to moisture content usually and accounts for 7% to 11% of spray-dired powder weight, and more preferably 8% to 10%.Moisture content with the powder of additive method such as agglomeration preparation is lower, can be in 1-10%(weight) in the scope.

The particulate size of first component usually and preferably is no more than 5%(weight greater than 1.4mm), and on overall dimension, be no more than 10% less than 0.15mm.Preferably at least 60% most preferably the size of at least 80% powder between 0.7mm to 0.25mm.For spray-dired powder, from the particulate loose density of spray-drying tower normally 540 to 600g/ rise between, through further handling as reduce then compacting again of size in high-speed shearing machine/mixing tank, its loose density can also increase.In other words, the method except spraying drying also can be directly used in and form the high-density particulate.

Second component of preferred compositions of the present invention is another polycomponent particulate that contains the water soluble surfactant active.

This component can be negatively charged ion, nonionic, positively charged ion or half-shadow sexual type or their any mixtures on type.Suitable tensio-active agent is listed in this paper front, but preferred surfactants is C ₁₄-C ₁₅Alkyl-sulphate, straight chain C ₁₁-C ₁₅Alkylbenzene phosphoric acid salt and fatty C ₁₄-C ₁₈Methyl ester sulfonate.

Second component can have any suitable physical form, and promptly it can adopt plate, coccoid, marumes, soap noodles, band shape or particle form, and particle can be spraying drying or non-spray-dired agglomerate.Though second component can contain the water soluble surfactant active on himself in theory, in fact at least a organic or inorganic salt is included in wherein to simplify treating processes.This salt provides degree of crystallinity to a certain degree to particulate, therefore has acceptable flow performance, and this salt can be any or multiple organic salt or the inorganic salt that are present in first component.

The granular size scope of second component should be to avoid isolation when making particle fusion when itself and first component.Therefore, be no more than 5%(weight greater than 1.4mm in the size of particulate), and be no more than 10% less than 0.15mm.

The loose density of second component is relevant with its preparation method.But, the preferred form of second component is the agglomerate of mechanically mixing, it can prepare by being added in plate-like reunion machine, Z blade mixer or the preferred inline mixer with dry ingredient or with agglomerant, mixing tank is as by Schugi(Holland) BV, 29 Chroomstraat 8211AS, Lelystad, Netherladns and Gebruder Lodige Maschinenbau GmbH, D-4790 Paderborn 1, Elsenerstrasse 7-9, Postfach 2050F.R.G. makes.By this method, the available loose density scope of second component is that 650g/ rises to the 1190g/ liter, and more preferably 750g/ rises to the 850g/ liter.

Preferred compositions comprises the alkaline carbonate of certain content in second component, its content corresponding to composition is 3% to 15%(weight of composition weight), 5% to 12%(weight more preferably).This will make the content of carbonate in second component is 20% to 40%(weight).

The composition very preferably of second component can also be the hydrated aluminosilicate ion exchange material of water-fast permutite type, and as described earlier in this article, its amount is 10% to a 35%(weight of second component).The water-fast silico-aluminate amount of substance of fusion 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, tensio-active agent forms in inline mixer on the spot.The tensio-active agent of liquid acid form is added to the successive high speed mixer, in the mixture as particulate anhydrous sodium carbonate in the Lodige KM mixing tank and hydrated sodium aluminosilicate, makes its neutralization, keep the particulate character of mixture simultaneously to form surfactant salt.The agglomeration mixture of gained has formed second component as a result, it is added in other components of product then.In the variation pattern of this method, surfactant salt is neutralized in advance and be added in other mixture of ingredients as the viscosity paste.In this variation pattern, mixing tank only is used for these compositions of agglomeration to form second component.

Have in preparation fusion of the present invention in the particularly preferred method of detergent composition of peroxyacid bleach precursor particulate through applying, with the residuum fusion before, the spray-dired product that part contains first grain fraction is changed and through the nonionogenic tenside spraying of low levels.Use above-described preferable methods to prepare second grain fraction.Then with first and second components and bleach precursor particulate and perhydrate SYNTHETIC OPTICAL WHITNER through applying, other dry mixed compositions such as any carboxy acid salt chelator, soil release polymer, silicate and enzyme conventional or the laminated crystalline type are added on the conveyer belt together, they are transferred in the cylinder that horizontally rotates, here spices and siloxane foams inhibitor are sprayed onto on the product.In composition very preferably, adopt another cylinder mixing step, add crystalline material that the quilt of low (about 2%(weight) content segments here to increase density and to improve the particle flow feature.

In fusion has preferred washing composition product as the alkali metal percarbonate of crossing salt hydrate, have now found that the several aspects such as its heavy metal ion content and its relative humidity balance that need this product of control.The composition that contains SPC-D of the type with enhanced stability is at the common UK Patent Application No.9021761.3(patent attorney registration number CM343 that transfers the possession of, application on October 6 nineteen ninety) in disclose.

Composition of the present invention also can obtain an advantage from delivery system, and this system provides instant partial high production concentration in when beginning washing in the automatic washing machine cylinder, has therefore also avoided and the relevant problem of product loss in the pipeline of machine or sump.

The hybrid of the composition of utilization in bag or in the container can be realized delivery of composition easily in cylinder, stirs beginning along with washing, the dipping of temperature rising or the washing water in cylinder, and composition discharges from bag or container soon.On the other hand, washing machine itself can be suitable for allowing directly composition is added in the cylinder, for example by the diverting device at the entrance door place.

Be sealed in the product that the contains detergent composition design by this way usually in the bag or in the container, be that integral container remains on drying regime inclusion outflow when avoiding drying, but be exposed to wash environment, will be suitable for container contents when normally in aqueous solution, flooding and discharge.

Common container is deformable, as sack.This sack has by the fibrous texture through having applied fluid-tight protecting materials to maintain inclusion, as disclosing among the European publication application No.0018678.On the other hand, sack can be formed by water-fast artificial polymeric material, and has the edge sealing that is designed to split or seal in water-bearing media, as disclosing in European publication application No.0011500,0011501,0011502 and 0011968.A kind of common form of sealing of splitting in water comprises the one side that water-soluble binder is coated in and seals sack, and this sack is formed by fluid-tight polymeric membrane such as polyethylene or polypropylene.

In the version of sack or container, can use the lamination flaked product, wherein the deformable layer in center is combined, and thing floods and/or coating, then one or more layers upper layer is used to produce the aesthetic effect of textile-like.These layers can be enclosed in together in use so that keep adhering to, and maybe can separate, and are convenient to discharge material coated or dipping when contacting with water.

Another kind of laminate form comprise layer of surface by projection or distortion to produce a series of containers as bag, in each container, detergent component is put into by determined quantity, the second layer is placed on above the first layer and between the container of bag in two-layer contacted local sealing-in.Component can be put into particulate, paste or fusing form, and laminate layer should be avoided the inclusion outflow in the container of bag before adding them in the entry.The stratiform thing when contacting with water, can separate or remain adhered to only need together be this structure should allow as the bag container in inclusion be discharged in the solution rapidly.Be to need the thing selected as the number of container of bag in the per unit area substrate, but the variation between every square metre 500 to 25000 usually of this number.

At this respect of the present invention, can comprise porous material, paper and cloth and non-woven fabric as the suitable material of deformable laminate layer.

Yet the preferred mode of carrying out washing process is to utilize the diverting device of reusing have thin-walled, and this wall can see through liquid but can not see through solids composition, and composition is added in the liquid that surrounds fabric in the cylinder.

This device discloses in european patent application prospectus No.0343069 and 0343070.Back one application has disclosed a kind of device, and it comprises the yielding overcoat of a sack form, extends from a support ring that is defined as aperture, and this aperture is suitable for allowing this sack to have once washing round-robin product in enough cycles of washing.The part washing medium flows in the pouch by this aperture, and with the product dissolving, this solution enters washing medium by aperture from the outside then.This support ring is furnished with mask device, and is wetting to prevent, undissolved product is excessive, and this device typically comprises the thin-walled that radially extends, and this wall is from the spoke wheel structure, or a kind of wherein wall has in the center hub in the similar structures of spirrillum form and extends.

Embodiment

Use Sokalan as described above

CP45 is with TAED dust agglomeration and drying.Then gained exsiccant agglomerate is used again a certain amount of (25%(weight) in fluidized-bed) Sokalan

The P45 spray application.The altitude mixture control of nozzle is to making it be positioned at by the highest particulate top of airflow fluidizing.Rise to about 85 ℃ in order to reduce caking tendency with the temperature of being convenient to dry fluidization air.When spraying is finished, use warm air to proceed fluidisation and be lower than 5%(weight up to remaining moisture) then with said the sieving in finally dried agglomeration image front, have material between 1700 to 425 microns to obtain 95% particle.

Agglomerate has following composition:

TAED：??76.8%

Sokalan

CP45:18.6%, average coated weight is measured by acid-base titration, and the difference of calculating is 10.4%

Water/Misc: to 100%

Then composition is divided into four kinds of particles, average coated weight is measured and calculated difference with acid base titration.

Particle size (micron)〉1200〉850〉425〉425

Average coated weight 6.4 10.0 12.4 14.9

As above identical mixing device in will identical TAED powder and prepare a kind of TAED agglomerate of reference as the TAE25 agglomeration of the fusing of tackiness agent.With the particle cooling and with sieving as top identical standard.The agglomerate composition is:

TAED??87.0%

TAE25??13%

Detergent agglomerate is sneaked in the following washing composition matrix, detects it decreases ring to color potentiality (component is meter by weight):

C ₁₂Alkyl group benzene sulfonate 9.0

Tallow alkyl vitriol 2.8

Dobanol??45E7??3.8

Zeolite A 20

Citrate trianion 6.5

Carbonate 15.0

Silicate (SiO ₂: Na ₂O=2: 1) 3.5

Perborate monohydrate 16.0

Sokalan CP45 ^＊4.0

Miscellaneously add to 100

* washing composition matrix contained as altogether-washing assistant, independently from the Sokalan that is present in the agglomerate

CP45.

The amount of agglomerate in composition should be to make it provide active quantities TAED to account for 5% of total composition weight.

The preparation that will contain the TAED agglomerate carries out complete washing machine test, uses Miele automatic washing machine (Model W754) and is transferred to 40 ℃ short washing retainings.

Use is to the painted fabric sample cloth of SYNTHETIC OPTICAL WHITNER sensitivity, with 43cm ²The sample cloth be looped around on the diverting device, be added with the 100g said preparation in the diverting device.In each washing machine, add 3.3g white cotton sheet as ballasting.Injecting hardness in each loom is 150ppm(CaCO ₃Expression) Ca: the Mg ratio is 3: 1 12 liters in a water.The sample cloth is made by 100% lamb's wool cloth with purple 48 dyestuffs (registration number W3970), and it is by Borval Fabrics, Albert Street, and Hrddersfield, West Yorkshire, England provides.Repeated experiments is carried out in every kind of processing 24 times, with following hierarchy system the color damage intensity of fabric is with the naked eye carried out classification by panel of experts then.

Use prove three painted sample cloths that color is subjected to damaging in various degree as standard specimen to set up 4 grade standards, wherein " badly damaged " represented in 1 expression " in fact not being damaged " and 4.Three standard specimens are used to determine the intermediate point between the various descriptions that following color is damaged.

In fact 1 be not damaged

2 are damaged slightly

3 are damaged

4 be badly damaged bad

Use two panel of experts and with their equalization as a result.

Utilize this method to compare, obtain following result using the top color that preparation caused to damage:

It is overall that the formulation samples cloth has the % of grade

Grade 1234

(reference) TAE25 13 17 58 12 2.69

/TAED

(invention): 33 33 30 4 2.05

Sokalan

CP45/TAED

As can be seen, the preparation of fusion agglomerate of the present invention causes less fabric color to damage than the agglomerate of reference significantly.Further test confirms that also the bleachability of the product of optimization does not reduce.

Claims

1; a kind of solid peroxygen acid blanching agent precursor composition; it contains the peroxyacid bleach precursor particle through applying; wherein said composition contains particles of different sizes; wherein said precursor contains one or more N-; or O-acyl group and fusing point＞30 ℃; wherein said precursor applies with the coating material that is selected from water-soluble acid polymkeric substance; said polymkeric substance has at 20 ℃ water solubility greater than 5g/1; molecular weight is 1000 to 250000; wherein the pH value of 1% of the said polymer solution is less than 7, and the coated weight in the said particle of reduced size is bigger.

2, according to the composition of claim 1, average coated weight wherein is 2% to 25%.

3, according to the composition of claim 1, wherein said precursor is co-agglomerated with adhesive material before with said polymer-coated.

4, according to the composition of claim 3, wherein said adhesive material amount is said water-soluble acid polymkeric substance.

5, according to the composition of claim 1, it comprises:

Contain 1700 to 850 microns the said particle of particulate class, wherein the average coated weight in the particle of said kind be composition on average apply agent content 0% to 100%; Said particulate second class comprises the particle less than 850 microns to 500 microns, wherein the average coated weight in the particle of said kind be the average coated weight of composition 0% to 150% and

The 3rd class comprises the particle less than 500 microns to 100 microns, and wherein the average coated weight in said class particle is 50% to 300% of the average coated weight of composition.

6, according to the solid peroxygen acid blanching agent precursor composition of claim 4, wherein said adhesive material is identical with said coating material.

7, according to the solid peroxygen acid blanching agent precursor composition of claim 1, wherein the molecular weight of said water-soluble acid polymkeric substance is in 1500 to 150000 scopes.

8, according to the solid peroxygen acid blanching agent precursor composition of claim 1, wherein the pH value of 1% solution of said polymkeric substance is less than 5.5.

9, according to the solid peroxygen acid blanching agent precursor composition of claim 1, the fusing point that wherein said polymkeric substance has is higher than 30 ℃.

10, according to the solid peroxygen acid blanching agent precursor composition of claim 1, it contains 30% to 93%(weight) the said composition and 7% to the 70%(weight of said peroxyacid bleach precursor) the said composition of the said polymer.

11, according to the solid peroxygen acid blanching agent precursor composition of claim 1, polymkeric substance that wherein said polymkeric substance is a formula 1 or their mixture

Wherein X is O or CH ₂, Y is comonomer or copolymerized monomer mixture; R ¹And R ²Be bleaching base and alkali stable polymer terminal group; R ³Be H, OH or C _1-4Alkyl; M is H or itself and basic metal, alkaline-earth metal, ammonium or the mixture that replaces ammonium; P is 0 to 2; N is 10 at least,

12, according to the solid peroxygen acid blanching agent precursor composition of claim 11, wherein, in the formula I, p is 0.1 to 1.9, and x is CH ₂, R ³Be H or C _1-4Alkyl, M are H, and n on average is 100 to 800, preferably 120 to 400, and Y comprises the monomeric unit of formula II

13, according to the solid peroxygen acid blanching agent precursor composition of claim 1, wherein said peroxyacid bleach precursor is a tetra acetyl ethylene diamine.

14, a kind of fusion the whitener composition of solid peroxygen acid blanching agent precursor composition of claim 1, wherein said whitener composition also contains a kind of inorganic perhydrate SYNTHETIC OPTICAL WHITNER.

15, according to the whitener composition of claim 14, wherein the perhydrate SYNTHETIC OPTICAL WHITNER is Sodium peroxoborate or SPC-D.

16, a kind of laundry detergent composition that contains according to the composition of claim 1.

17, a kind of production claim 3 method for compositions comprises the following step:

With said peroxyacid bleach precursor and totally one agglomeration of said adhesive material;

Apply said exsiccant totally one agglomerate with said coating material;

Dry said totally one agglomerate through applying.

18, according to the method for claim 17, wherein said particle is being divided into several grain flows by different sizes after said agglomeration step, and with the independent coating processing of said grain flow.

19, according to the method for claim 17, wherein said particle after said agglomeration step in airflow fluidisation, said coating material is sprayed onto on the said particle that is fluidized.