CN1059930A

CN1059930A - Detergent composition

Info

Publication number: CN1059930A
Application number: CN91108855.5A
Authority: CN
Inventors: A·J·普雷蒂; D·G·弗雷泽; P·A·哈迪
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1990-08-17
Filing date: 1991-08-17
Publication date: 1992-04-01
Also published as: IE912924A1; NZ239436A; EP0543911B1; ES2100957T5; JP3615756B2; NO930528L; GR3035134T3; TW217420B; FI930673A; AU661826B2; AU8497091A; PT98654A; HU9300426D0; DE69125938T3; WO1992003525A1; MX9100708A; EP0543911A4; BR9106749A; CZ21693A3; EG19654A

Abstract

Disclose a kind of laundry granular detergent composition, it is in conjunction with the 5-50% tensio-active agent; A kind of three composition non-phosphorus Cleaning Aid Agent systems of 10-95%, this system comprises a kind of mixture, constitutes the sodium silicoaluminate zeolite, the water glass of water-soluble mono poly-or low polycarboxylate sequestrant and laminated crystalline; And the nonsurfactant of 0-40%, the detergent ingredient of non-washing assistant.Laminar crystal sodium silicate consist of NaMSi _XO _2x+1YH ₂O, wherein M is sodium or hydrogen, and x is the number of 1.9-4, and y is the number of 0-20.Preferred M is a sodium, x be 2 and y be 0.

Description

Detergent composition

The present invention relates to laundry detergent composition, particularly relate to the laundry detergent composition that those seldom contain or do not contain phosphorus containg substances.As a kind of at from environmental influence undressed or that cause through the waste liquid of the civil sewage that contains the dissolved phosphorus hydrochlorate of partially disposed, the result of social concerns and/or act of law constraint, this class laundry detergent composition is widely adopted.

For reach reduce the phosphoric acid salt load that produces by Betengent product in the environment basic purpose at commercial introducing phosphate-free detergent product, brought the complicacy of preparation, and improved the load of organic substance in the environment.No phosphoric acid salt composition adopts the complex body of material more than to replace phosphate builders, and main ingredient is generally a water-insoluble sodium silicoaluminate zeolite and adds mixture with water-soluble inorganic salt and polymerization organic salt.

Paid very big effort the staff of this area aspect this class polycomponent builder system of exploitation, the generation of this needs is a kind ofly to realize that be difficult by phosphate builders at the one matter of the preceding all functions that show because find.These functions (although not characterized fully) are included in Ca in the washing process ⁺⁺And Mg ⁺⁺The sequestering action of two kinds of hardness ionss and the dispergation of fabric decontaminating and suspension effect.

Find, in specific detergent builder compound component complex body, use the performance that crystalline or so-called layered silicate can obtain to strengthen in fact and allow and in gained granulated detergent product, reduce the content of some other material or it is eliminated fully.In preferable embodiment of the present invention, use the detergent builders component of suitable low levels can obtain the clean-up performance suitable with currently available products, reduced carrying capacity of environment thus.Other advantage comprises the allotment characteristic of reinforcement, as dispersion and/or solvency action, the minimizing of fabric on infusible precipitate (ash content) and the minimizing of fabric loss of shot shape product when the domestic washing machine washing phase begins automatically.

Comprise according to granular detergent composition provided by the invention:

(a) 5%-50%(weight) one or more are anionic, non-ionic, amphoteric, zwitterionic or cationic tensio-active agent, or by its any mixture of forming;

(b) the detergent builders system of 10%-95%, its mixture that comprises is;

ⅰ) account for this mixture 20%-60%(weight) the sodium silicoaluminate zeolite;

ⅱ) account for this mixture 10%-30%(weight) water-soluble monomer or oligomeric organic carboxylic ester salt sequestrant; And

ⅲ) account for this mixture 10%-65%(weight) consist of NaMSi _xO _2x+1YH ₂The O laminar crystal sodium silicate, wherein M is Na or H, and x is the number of 1.9-4, and y is the number of 0-20; And

(c) detergent ingredient of the nonsurfactant of 0-40%, non-washing assistant.

The component of preferable builder system (b) is α, β, γ or δ-Na (ⅲ) ₂Si ₂O ₅, and component (b) is Naz[(Alo for the single cell molecular formula (ⅰ) ₂) z(Sio ₂) y] .XH ₂The synthetic hydrated zeolite of O, wherein Z and y are at least 6, and Z is 1.0-0.5 with the ratio of r, and x is at least 5, is preferably 7.5-276.

In addition, preferably, the first carboxyl logarithm acidity constant (pK of this monomeric or oligomeric organic carboxylic ester salt sequestrant ₁) be lower than 9, be preferably 2-8.5.

The granular detergent composition that the present invention relates to comprises one or more tensio-active agents and detergent builders system, this builder system is made of three kinds of important component, i.e. the water glass of sodium silicoaluminate zeolite, water-soluble monomer or oligomeric organic carboxylic ester salt sequestrant and laminated crystalline.Preferred compositional of the present invention also contains other nonsurfactant, the detergent ingredient of non-washing assistant.

Can use large-scale tensio-active agent in this detergent composition.The situation of typically anionic, non-ionic, amphoteric and zwitter-ion type and the kind of these tensio-active agents are authorized on May 23rd, 1972 in the United States Patent (USP) 3,664,961 of Norris and are provided.

Suitable especially at this is the mixture of the mixture of anion surfactant, especially sulfonate and sulfate surfactant, and its weight ratio is 5: 1-1: 2, be preferably 3: 1-2: and 3, be more preferred from 3: 1-1: 1.Preferable sulfonate comprises alkylbenzene sulfonate, and its alkyl carbon atoms number is 9-15, particularly 11-13, and α-alpha-sulfonated fatty acid methyl ester, and fatty acid derived wherein is in C ₁₂-C ₁₈Fat source is preferably and is derived from C ₁₆-C ₁₈Fat source.Positively charged ion under every kind of situation is basic metal, with sodium for well.Preferable sulfate surfactant is an alkyl-sulphate, and the carbonatoms of its alkyl is 12-22, is preferably 14-18, and optional fusion ethoxy sulfate, and the carbonatoms of its alkyl is 10-20, is preferably 10-16, and average ethoxyquin degree is 1-6.Positively charged ion under every kind of situation still is an alkali metal cation, and with sodium for well.

Can be used for a class nonionogenic tenside of the present invention is the condenses of oxyethane, and its average hydrophilic-lipophilic balance (HLB) value scope that plays the hydrophobic part of Action of Surfactant is 8-17, is preferably 9.5-13.5, is more preferred from 10-12.5.The length that this hydrophobic (oleophylic) part can be aliphatic series or aromatics character and is condensed into the polyoxyethylene group of any specific hydrophobic grouping can easily be regulated, and has the water-soluble cpds of desired hydrophilic hydrophobic ingredient quality of balance with output.

The nonionogenic tenside of particularly preferred this type is the C that every mol of alcohol contains the ethoxylation of 3-8 moles of ethylene oxide ₉-C ₁₅Primary alconol, especially 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.

It is RO(C that another kind of nonionogenic tenside contains general formula _nH ₂NO) _tZ _xThe alkyl polyglucoside compound, wherein Z is by glucose deutero-part; R is the saturated hydrophobic alkyl group that contains 12-18 carbon atom; T is that 0-10 and n are 2 or 3, x is 1.3-4, and this compound comprises unreacted Fatty Alcohol(C12-C14 and C12-C18) that is lower than 10% and the short-chain alkyl polyglucoside that is lower than 50%.Compound of this type and the purposes in detergent composition thereof are disclosed among the EP-B0070074,0070077,0075996 and 0094118.

Another kind of tensio-active agent is that the semi-polarity tensio-active agent is such as amine oxide.Suitable amine oxide is selected from C ₈-C ₂₀, preferred C ₁₀-C ₁₄N-alkyl or alkenyl amine oxide and propylidene 1, the dioxide of 3-diamines, wherein remaining N can use methyl in the position, hydroxyethyl or hydroxypropyl replace.

Cats product also can be used in the detergent composition of this paper, and suitable quaternary ammonium surfactant is selected from C ₈-C ₁₆, be preferably C ₁₀-C ₁₄N-alkyl or alkenyl ammonium surfactant, wherein remaining N position is replaced by methyl, hydroxyethyl or hydroxypropyl group.

This detergent composition can contain 5%-50%(weight) tensio-active agent, but be generally 5%-30%, and be more preferred from 5%-15%(weight).It is preferred that dissimilar tensio-active agents are used in combination, particularly negatively charged ion-nonionic and negatively charged ion-nonionic-positively charged ion mixed type.Concrete preferred combination is disclosed in GB-A-2040987 and EP-A0087914.Although the form that tensio-active agent can mixture is mixed in the composition, but still each tensio-active agent of tendency control adds point, so that the physicals of optimum combination thing and avoid troublesome poeration.Add the preference pattern and the order of tensio-active agent and will do description hereinafter.

Second kind of basal component in the composition of the present invention is the detergent builder compound system, and this system contains the mixture of the sodium silicoaluminate zeolite, water-soluble monomer or oligomeric carboxylate's sequestrant and the laminar crystal sodium silicate that limit content.

In the time can using the silico-aluminate ion exchange material of certain limit, the unit cell molecular formula of preferable sodium silicoaluminate zeolite is:

Wherein z and y are at least 6; The mol ratio of z and y is 1.0-0.5, and x is at least 5, is preferably 7.5-276, is more preferred from 10-264.This silico-aluminate material is a hydrated form, is preferably crystalloid, moisture 10%-28%, the better 18%-22% that contains.

A feature again of above-mentioned silico-aluminate ion exchange material is that its grain size is the 0.1-10 micron, is preferably the 0.2-4 micron.In this term " grain size " expression with the routine analysis technology, the average particulate diameter of the given ion exchange material of measuring as the microscopy that adopts scanning electronic microscope.The another feature of silico-aluminate ion exchange material is its calcium ion exchange capacity, and its value is the CaCO of at least 200 milligrams of equivalences ₃The water hardness/every gram silico-aluminate is as the criterion in anhydride, and this is worth usually in the 300mgeq./g-352mgeq./g scope.The feature that the silico-aluminate ion exchange material of this paper also has in addition is its calcium ion exchange rate, and its value is at least the CaCO of 130 milligrams of equivalences ₃/ liter of/minute/(every gram silico-aluminate/liter) [i.e. 2 grain Ca++/gpms/(gram/gallon)] aluminosilicate (being as the criterion) with anhydride, and should value with the calcium ion sclerometer usually at the CaCO of 130 milligrams of equivalences ₃/ liter/minute/(grams per liter) [i.e. 2 grains/gpm/(gram/gallon)] be to the CaCO of 390 milligrams of equivalences ₃/ liter/minute/scope of (grams per liter) [i.e. 6 grains/gpm/(gram/gallon)] in.The calcium ion exchange rate that is used for the best silico-aluminate performance of washing assistant is at least the CaCO of 260 milligrams of equivalences ₃/ liter/minute/(grams per liter) [i.e. 4 grains/gpm/(gram/gallon)].

The silico-aluminate ion exchange material that can be used in the present invention's practice can be buied on market, and it can be naturally occurring material, but is produced as with synthetic.In U.S. Patent No. 3,985, a kind of method of producing the silico-aluminate ion exchange material has been discussed in 669.It is product of ZcoliteA, ZeoliteB, ZeoliteX, ZeoliteHS and composition thereof that synthetic crystallization type silico-aluminate ion exchange material that can be preferable as used herein is the trade mark that can buy.In optimum implementation, this crystal aluminosilicate ion exchange material is ZeoliteA, and its molecular formula is:

Wherein x is 20-30, is preferably 27, and molecular formula is Na ₈₆[(AlO ₂) ₈₆(SiO ₂) ₁₀₆] 276H ₂The ZeoliteX of O and molecular formula are Na ₆[(AlO ₂) ₆(SiO ₂) ₆] 7.5H ₂The ZeoliteHS of O also is suitable for.

The optional compound from a large scale of organic carboxylic ester sequestrant water-soluble monomer or oligomeric, but its first carboxyl logarithm acidity constant (pK ₁) be lower than 9 for well, preferable between 2-8.5, better between 4-7.5.

The definition of logarithm acidity constant is referring to this balance:

H ⁺+A ()/() H ⁺A

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

So this equilibrium constant is

K ₁= ((H+A))/((H ⁺)(A))

And pK ₁=log ₁₀K

With regard to the use occasion of this specification sheets, acidity constant is defined under the condition of 25 ℃ and zero ionic strength.Can take literature value (see Stability Constants of Motal-Ion Complexes, Special Publication No.25, THe Chemical Society, London); This value then wakes suspicion if adopt the potentiometric titration of glass electrode to determine.

Preferable carboxylicesters also can be according to its calcium ion stability constant (pK _Ca++) limit, be similar to pK ₁, this stability constant is determined by following reaction formula:

The pK of polycarboxylate _Ca++ preferable range is about 2-7, especially preferably about 3-6.Emphasize to take the literature value of stability constant once more.When will being limited to 25 ℃, the stability constant of measuring with glass electrode method under the condition of zero ionic strength, shows (1963) described among the Complexation in Analytical Chemistry as Anders Ringbom.

Carboxylicesters or polycarboxylate washing assistant can be monomer or oligomeric form, but, owing on cost and the performance, be good with monomeric polycarboxylates usually.

Monomeric or oligomeric washing assistant can be selected from acyclic, alicyclic ring, heterocycle and the aromatic carboxylic acid ester with following general formula:

R wherein ₁Represent H, can be randomly replace by hydroxyl, carboxyl, sulfo group or phosphono group or be connected C on the poly-inferior ethoxyl part that contains 20 inferior ethoxyl groups at the most _1-30Alkyl or alkenyl; R ₂Represent H, C _1-4Alkyl, alkenyl or hydroxyalkyl or alkaryl, sulfo group or phosphono group; X represents a singly-bound, O, S, SO, SO ₂Or NR ₁; The C that y represents H, carboxyl, hydroxyl, carboxymethoxyl or can randomly be replaced by hydroxyl or carboxylic group _1-30Alkyl or alkenyl; Z represents H or carboxyl; M is an integer between 1-10; N is an integer between 3-6; P, q are the integer between 0-6, and p+q is 1-6; Wherein, when x, y and z repeated in given molecular formula, every kind of representative can be identical or different, and have at least a Y or Z to contain a carboxylic group in a molecule.

The suitable carboxylicesters that contains a carboxyl comprises the derivative of lactic acid, oxyacetic acid and ether thereof, and as belgian patent Nos.831,368,821,369 and 821,370 is described.The polycarboxylate that contains two carboxyls comprises the water-soluble salt of succsinic acid, propanedioic acid, (ethylenedioxy) diacetic acid, toxilic acid, diglycollic acid, tartrate, tartronic acid and fumaric acid; and disclose 2 at German Patent; 446; 686,2; 446,687 and U.S. Patent No. 3,935; ethers carboxylicesters described in 257 and belgian patent No.840, the sulfinyl carboxylicesters described in 623.The polycarboxylate that contains three carboxyls especially comprises water miscible citrate, aconate and citraconate, and succinate derivative, as English Patent No.1,379, carboxy methoxy-succinic acid ester described in 241, English Patent No.1, the aminosuccinic acid ester described in newborn oxygen base succinate described in 389,732 and the Netherlands patent applications 7205873, with oxo polycarboxylate material, as English Patent No.1, the 2-oxa--1 described in 387,447,1,3-tricarballylic acid ester.

The polycarboxylate that contains four carboxyls comprises English Patent No.1, the oxo disuccinic acid ester, 1,1,2 described in 261,829,2-ethane tetracarboxylic ester, 1,1,3,3-propane tetracarboxylic acid ester and 1,1,2,3-propane tetracarboxylic acid ester.Containing the substituent polycarboxylate of sulfo group comprises and is disclosed in English Patent Nos.1; 398,421,1,398; 422 and U.S. Patent No. 3; sulfo-succinic acid ester derivative in 936,448 and English Patent No.1,082; sulphur described in 179 is for the pyrolysis citrate; contain the substituent polycarboxylate of phosphoryl and be disclosed in English Patent No.1, in 439,000.

Alicyclic ring and heterocycle polycarboxylate comprise pentamethylene-suitable, suitable, suitable-tetracarboxylic ester, cyclopentadiene pentacarboxylic acid ester, 2,3,4,5-tetrahydrofuran (THF)-suitable, suitable, suitable-tetracarboxylic ester, 2,5-tetrahydrofuran (THF)-suitable-dicarboxylic ester, 2,2,5,5-tetrahydrofuran (THF)-tetracarboxylic ester, 1,2,3,4,5,6-hexane-hexacarboxylic acid ester and polyvalent alcohol is as the carboxymethyl derivant of sorbyl alcohol, mannitol and Xylitol.Aromatic multi-carboxy acid's ester comprises and is disclosed in English Patent No.1, the mellitic acid in 425,343,1,2,4, the derivative of 5-pyromellitic acid and phthalic acid.

In the above-mentioned substance, preferable polycarboxylate contains the hydroxycarboxylic acid esters of three carboxyls, particularly citrate at the most for each molecule.

Also can consider with the parent acid of monomer or oligomeric polycarboxylate sequestrant or should acid and the mixture of its esters as the component of the builder system among the present invention, as, citric acid or Citrate trianion/citric acid mixture.

The third composition of builder system is a laminar crystal sodium silicate, and its general formula is:

Wherein M is Na or H, and x is the number between 1.9-4, and y is the number between 0-20.The laminar crystal sodium silicate of this type is disclosed among the EP-A-0164514, and its preparation method is disclosed among DE-A-3417649 and the DE-A-3742043.For use of the present invention, above x value in the general formula be 2,3 or 4, and with 2 for well.Preferably M is that Na and y are 0.The preferred embodiments of this molecular formula comprises Na ₂Si ₂O ₅α-, β-, γ-and δ-form.These materials all can be buied by HoechstAG FRG with NaSKS-5, NaSKS-7, NaSKS-11 and the NaSKS-6 trade mark respectively.Wherein the best is δ-Na ₂Si ₂O ₅, NaSKS-6.

Other detergent builders material also can become the integral part of this builder system, but not as its basal component.These materials can have machine or inorganic in nature.

Can become with the inorganic builders material of the optional component of builder system in the present invention and comprise alkali-metal carbonate, supercarbonate and silicate.Suitable organic substance comprises organophosphate and amino polyalkylene phosphoric acid ester, but in requiring composition under the situation of the P contained compound amount of minimizing, these materials are then not good enough.

Other suitable water-soluble organic salt is homopolymerization or copoly type poly carboxylic acid or its esters, and poly carboxylic acid wherein contains at least two carboxyls, and this carboxyl is separated from one another with the spacing of no more than two carbon atoms.The polymkeric substance of back one type is disclosed in GB-A-1, in 596,756.The example of this class salt be MWt2000-5000 polyacrylic ester and with the multipolymer of maleic anhydride, the molecular weight of this multipolymer is 20,000-70,000, particularly about 40,000.The consumption of these materials is generally the 0.5%-10% of composition weight, is preferably 0.75%-8%, and the best is 1%-6%.

This optional washing assistant composition is if exist, and its total amount must not surpass 25% of composition weight, normally is lower than 20%, is lower than 15% in most cases.

With regard to being used for the present composition, builder system accounts for the 10%-95% of said composition weight, is more preferred from 20%-60%(weight).In builder system, the sodium silicoaluminate zeolite accounts for the 20%-60% of this mixture weight, and monomer or low polycarboxylate account for the 10%-30% of this mixture weight, and crystalline layered silicate accounts for the 10%-65% of this mixture weight.More preferably, the amount of zeolite is 25%-50%, and monomer or low polycarboxylate account for the 15%-25% of builder system weight, and layered silicate accounts for the 20%-50% of builder system weight.Preferable also have, and its amount is at most inorganic and organic auxiliary washing assistant molectron (as yellow soda ash and maleic anhydride/acrylic copolymer) of 25% and is attached in the builder system.

Composition of the present invention also can contain 40% the nonsurfactant as optional component, non-detergent builder compound Synergist S-421 95 at the most.Anti redeposition agent and soil-suspending agent, white dyes, stain remover, dye well pigment are the example of this class optional component, and they can add with different amounts as requested.

Be applicable to that herein anti redeposition agent and soil-suspending agent comprise derivatived cellulose, as methylcellulose gum, carboxymethyl cellulose and Natvosol and homopolymerization or copolymerization poly carboxylic acid and salt thereof.This base polymer comprises maleic anhydride and ethene, methyl. the multipolymer of vinyl ether, acrylic or methacrylic acid, this maleic anhydride account for the 20%(molar percentage of this multipolymer at least).The normally used content of these compositions is the 0.5%-10% of composition weight, is more preferred from 0.75%-8%, and the best is 1%-6%.

Other available polymkeric substance is a polyoxyethylene glycol, and particularly those molecular weight are 1000-10000, is more preferred from 2000-8000 and best 4000 the polyoxyethylene glycol that is about.It uses content to be 0.20%-5%(Wt), be more preferred from 0.25%-2.5%(Wt).The polycarboxylate of these polymkeric substance and aforementioned homopolymerization or copolymerization is for improving retention of whiteness, fabric ash-deposition in the presence of the transition metal impurity and be valuable to the performance aspect the cleaning of shale, protein and oxidable dirt having.

Certainly, about an advantage of composition of the present invention be its to reduce aggretion type polycarboxylate washing assistant/anti redeposition agent of content, there is the ability of keeping insoluble particle solid (ash content) suspension in no aggretion type polycarboxylate perhaps even in preferred compositional of the present invention.Therefore in composition of the present invention, 5% aggretion type polycarboxylate content in the conventional products can be reduced by half, promptly reduce to 2.5%, and can not increase the ash oontent in the fabric.If all eliminate the aggretion type polycarboxylate, the fabric ash content only slightly increases, and by comparison, if this polymkeric substance is eliminated in conventional washing composition preparation, ash oontent then can double.

The inside inherent condition of composition of the present invention also shows certain intensity to Hardness Control, i.e. also existing whole mineral substance hardness of may command under the inadequate situation of detergent builder compound.Think that now the generation of this benefit is because the inside inherent condition of ternary builder system component has the ability that reallocation is stored in self calcium and magnesium hardness ions, promptly utilized the avidity of the reinforcement of crystalline layered silicate component and magnesium ion.

The another benefit that the present composition brings is to have reduced the fabric loss that washing process produces.This minimizing is considered to be deposited in the washing process heavy metal ion and the oxygen bleaching agent results of interaction on the fabric.With the displaced composition of conventional amorphous silicon hydrochlorate, the fabric that washs in the present composition has shown the tensile strength loss that heavy metal ion to a certain degree deposits and reduces with respect to general's crystalline layered silicate component wherein.

Preferable white dyes is an anion characteristic, the example is 4,4 '-two-(2-diethanolamino-4-anilino-s-triazine-6-base-amino) stilbene 2: 2 '-the disulfonic acid disodium, 4,4 '-two-(2-morpholino-4-anilino-s-triazine-6-base-amino) stilbene-2: 2 '-the disulfonic acid disodium, 4 ', 4 " two-(2; 4-hexichol amido s-triazine-6 bases-amino) stilbene-2: 2 '-the disulfonic acid disodium; 4 ', 4 is " two-(2,4-hexichol amido s-triazine-6-base-amino) stilbene-2-sodium sulfonate, 4 ' 4 " two-(2-anilino-4-(N-methyl-N-2-hydroxyethylamino) s-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-hydroxyethylamino) s-triazine-6-base is amino) stilbene-2; 2 '-disulfonic acid disodium and 2(stilbene radicals-4 " (naphtho--1 ', 2 ': 4,5)-1,2,3-triazole-2 " sodium sulfonate.

Can be used for multipolymer or terpolymer that the stain remover in the present composition constitutes with different arrangements for habitual terephthalic acid and 1 and/or propylene glycol unit.The example of this base polymer be disclosed in the United States Patent(USP) Nos. 4116885 authorized and 4711730 and the open No.0272033 of european patent application in.The chemical formula of particularly preferred polymkeric substance is among the EP-A-0272033

Wherein PEG is-(OC ₂H ₄) O-, PO is (OC ₃H ₆O) and T be (pcOC ₆H ₄CO).

Some polymkeric substance is mainly 5000-20000 as MWt, and the polyvinylpyrrolidone that is preferably 10000-15000 also can form the effective medium that prevents that unstable dyestuff transmits between fabric in the washing process.

Another kind optionally but also be that highly preferred Synergist S-421 95 is a particulate inorganic perhydrate SYNTHETIC OPTICAL WHITNER.Can use any particulate inorganic perhydrate SYNTHETIC OPTICAL WHITNER, the amount of getting is the 3%-40%(weight of composition), be more preferred from 8%-25%(weight), and the best is a 12%-20%(weight).The preferred embodiments of this class SYNTHETIC OPTICAL WHITNER is the monohydrate of Sodium peroxoborate and tetrahydrate and composition thereof.

Another preferable Synergist S-421 95 is the percarboxylic acids bleach precursor of so-called bleach-activating agent, preferably it is added with a shot or a shape.This type suitable compounds example is disclosed in English Patent Nos.1586769 and 2143231, it is formed the granulous method of loosing describe to some extent in the open No.0062523 of european patent application.The preferred embodiments of this compounds is tetra-acetylated inferior quadrol and 3,5, and the 5-trimethylammonium is acyl-oxygen phenylbenzimidazole sulfonic acid sodium.

The common consumption of bleach-activating agent is the 0.5%-10%(weight of composition), the most frequently used amount is a 1%-8%(weight), be worth the good 2%-6%(weight that is).

Another kind of optional Synergist S-421 95 is a froth suppressor, and the example is siloxanes and silica-mixture of siloxanes.Siloxanes is representative with alkylation polysiloxane material usually, and with silica aerogel, the silica that xerogel and dissimilar hydrophobicity silica are example uses with finely divided form usually.These materials can be blended together particle, froth suppressor wherein is combined in water-soluble with can being convenient to disengage knot or water dispersible, real in the carrier of the impermeable washing composition of on-surface-active.Froth suppressor is solubilized or be scattered in the liquid vehicle and it is sprayed on one or more other components and use also.

As mentioned above, effectively the siloxane foams inhibitor can contain above the alkylation siloxanes of indication type and the mixture of solid silica.This class mixture makes by siloxanes being joined the solid silica surface.Preferable silicone suds suppressor is representative with the hydrophobic silaneization admixed fully with the dimethylsilane fluid (being preferably trimethyl silicone hydride) silica, and the particle size of silica is higher than 50m in 10nm-20nm scope and its specific surface area ²/ g, the molecular weight of this dimethyl siloxane be in about 200,000 scopes of about 500-, and siloxanes is about 1 to the weight ratio of silanization silica: 1-1: 2.

Preferable silicone foam control agent is disclosed in the United States Patent (USP) 3,933,672 of Bartollota etc.Other useful especially Foam Control is the self-emulsifying silicone foam control agent, and this is at disclosed German patent application DTOS2 on April 28th, 1977, describes to some extent in 646,126.An example of this compound is DC-544, a kind of siloxanes/glycol copolymer that can have been bought by Dow Corning.

The general content of above-mentioned suds suppressor is the 0.001%-0.5% of composition weight, is preferably 0.01%-0.1%(weight).

Preferable combination comprises that the suds suppressor with liquid form is sprayed on and forms individual particles on one or more components of composition or with suds suppressor and can mix with other solid ingredient of composition subsequently.Also allow the material of other control foam of admixture therein with individual particles in conjunction with foaming regulator, as C ₂₀-C ₂₄The high MWt multipolymer of lipid acid, microcrystalline wax and oxyethane and propylene oxide, otherwise these materials can have disadvantageous effect to the dispersiveness of matrix.Forming this class A foam A regulates particulate technology and is disclosed in the U.S. Patent No. 3,933,672 of aforementioned Bartolotta etc.

The composition that another choosing adds among the present invention is one or more enzymes.

The preferable enzyme material of sneaking into usually in the detergent composition comprises the amylase that market can be purchased, neutrality or Sumizyme MP, lipase, esterase and cellulase.Suitable enzyme is seen United States Patent (USP) 3,519,570 and 3,533,139.

According to the present invention, also fabric softener can be added in the detergent composition.This dose of material can be inorganic or organic type.The example of inorganic softening agent is for being disclosed in GB-A-1, the terre verte in 400,898.The organic fabric softening agent comprises as being disclosed in the water-insoluble tertiary amine among GB-A-1514276 and the EP-B-0011340.It has a C ₁₂-C ₁₄The combination of the quaternary ammonium salt of alkyl is disclosed in EP-B-0026527 and 528.The amide that other effective organic fabric softening agent is two long-chains is described in EP-B-0242919.The additional organic composition of fabric softener system comprises high-molecular weight polyethylene oxide material, as disclosed in EP-A-0299575 and 0313146.

Terre verte is done mixed component with conduct and is joined the content of the material in all the other batchings usually in 5%-15%(weight) scope, be more preferred from 8%-12%(weight).The organic fabric softening agent, as water-insoluble tertiary amine or long-chain diamines material, its add-on is in 0.5%-5%(weight), usually in 1%-3%(weight), and the add-on of high-molecular weight polyoxy ethane material and water-soluble cationic material is a 0.1-2%(weight), be generally 0.15%-1.5%(weight).

At composition partly is under the spray-dired situation, these materials can be added in the aqueous slurries of sending into spray-drying tower, but, in some occasion, with it as do to mix that particle adds or be sprayed on other solid ingredient of composition it more convenient with melting liquid.

Composition of the present invention can several different methods be made, comprise do to mix, spraying drying, agglomeration and granulating, and preferred methods comprises the combination of these technology.A preferred approach for preparing this composition comprises spraying drying, the agglomeration in super mixer and does a kind of combination that mixes.

Preferable detergent composition of the present invention also contains at least two kinds of granulated multicomponent Synergist S-421 95 components.First component account at least composition heavy 20%, account for 30%-70% usually, but better no more than 40%, and second component is the heavy 1%-50% of composition, is more preferred from 10%-40%.

The particle that first component has is mixed with the anion surfactant and its amount one or more inorganic and/or organic salts for powder heavy 99.25%-65% of its amount for the heavy 0.75%-35% of powder.Particle can have the shape of any suitable, as particulate state, flakey, coccoid, ball shape (marumes) or hollow ball-shape, but with granular for well, particle itself can be with dish type machine or cydariform machine agglomeration technique or the agglomerate that forms with line mixer, but it is preferably by the aqueous slurry of this Synergist S-421 95 of atomizing in hot steam and removes big juicy and the spray-dried granules made.In some technology, the spray-dried granules that forms first component carries out as using the high speed cutting mixing tank from experiencing a fine and close step to improve density before reagglomeration.For the purpose of illustrative, first component of spray-dried powders is hereinafter described, because of this constitutes a preferable embodiment of the present invention.

A key property of main anion surfactant is that it should have low dissolution rate in the water medium under the water temperature in first component, and this water temperature is to fill during the automatic washing machine cycles of washing to carry a general temperature of stage.According to European's washing habits, the water temperature of filling the stage of carrying is substantially 5 ℃ of-20 ℃ of scopes, and more normal is 7 ℃-12 ℃.

Find, the suitable anion surfactant that is used for first component for alkyl average carbon atom number wherein be the straight-chain alkyl sulfate of 10-22 and wherein the alkyl average carbon atom number be straight-chain alkyl carboxylic acid's salt of 16-24.The alkyl of this two classes tensio-active agent preferably is derived from natural fat, refers to as ox.Its alkyl is derived from has not too suitable than short-chain alkyl vitriol or carboxylate salt more than the source body of 40% mixture of the moieties that contains 14 or lower carbon atom, because of its breaking-in period chien shih first component produce jelly.

The anionic surfactant concentration that forms first component in spray-dried powders is a 0.75%-40%(weight), more normal is 2.5%-25%(weight), be preferably 3%-20%, the best is a 5%-15%(weight).Can be implicit typing or also can it be coated on the spray-dried powders subsequently as the water soluble surfactant active of linear alkylbenzene sulfonate by spraying.

The main Synergist S-421 95 of other of spray-dried powders is one or more inorganic or organic salts of this granule crystal structure of decision.These inorganic or organic salts can be water-soluble or water-insoluble, and back one class salt is comprised for the water-insoluble washing assistant under the situation that constitutes the builder system integral part or is that it is mainly formed.Suitable water-soluble inorganic salt comprises alkali-metal carbonate, supercarbonate, vitriol and borate.If silico-aluminate is not the integral part of spray-dried component, alkalimetal silicate also can be stored in the spray-dried granules.

Preferably, mix in the spray-dried granules to major general's part silico-aluminate washing assistant, and as above point out, in this occasion, silicate should not exist with the integral part of spray-dried component arbitrarily.In these cases, the adding of silicate can several modes realize, as manufactures and independently contain the silicate spray-dried granules, silicate sneaked in the agglomerate of other Synergist S-421 95 or more preferably, and silicate is mixed solids component and adds to do.

Above mentioned optional builder salt also can be added to and form first component in the spray-dried powders.Spray-dried powders also can comprise some or even whole water-soluble monomer or oligomeric carboxylicesters sequestrants, but because of this will be easy to suppress the quick dissolving of this composition, so not good enough.Organic and or inorganic salt account for the 60%-90% of first composition weight, be more preferred from 70%-90% and bestly be 75%-85%(weight).

Spray-dried powders also contains 15%(weight at the most usually) mix Synergist S-421 95.

In first component is in the preferred compositional of spray-dried powders, and the optional Synergist S-421 95 that is included in first component should be to a certain extent for heat-staple, to satisfy the needs of temperature of living in the opposing spray-drying process.In first component is under the situation of spray-dried powders, and being dried usually to water capacity is the 7%-11% of spray-dried powders weight, is more preferred from 8%-10%(weight).Powder water capacity with other method (as agglomeration technique) preparation can be lower, and can be in 1%-10%(weight) scope.

The particle size of first kind of component is a stock size, is preferably and wherein is not more than 5%(weight) should be more than 1.4mm, wherein be not more than 10%(weight simultaneously) out to out should be less than 0.15mm.Preferably at least 60% and the best 80%(weight at least) powder size drop between 0.7mm and the 0.25mm.To spray-drying powder, it is the 350-650 grams per liter that the particulate tap density falls into scope, and normal ranges is the 540-600 grams per liter.The upper limit of this scope is that the tap density of 600-650 grams per liter is particularly useful, and it is desirable preparing so-called enriched product herein.If make spray-drying powder stand further procedure of processing, compacted subsequently such as in high speed cutting device/mixing tank, reducing size, then can prepare the product of the above tap density of this scope.As selection, also can use spraying drying technology in addition to come powder process.

According to the present invention, second kind of component of preferred composition is kind of a particle that contains the water soluble surfactant active.

It can be a negatively charged ion, non-negatively charged ion, positively charged ion or half-shadow sexual type, or the mixed type of its any way.List before the suitable tensio-active agent, preferred surfactants is a straight chain C ₁₁-C ₁₅Alkylbenzene sulfonate and C ₁₄-C ₁₈The fatty acid methyl sulfonated ester.

Second kind of component can have any nonlimiting examples of suitable physical, that is the form that it can be taked is thin slice, bead, and marumes, hollow ball, ribbon, or particle shape, it can be by spraying drying or non-spraying drying agglomeration.Though second kind of component himself can comprise the water soluble surfactant active in theory, in fact it comprises at least a organic or inorganic salt so that promote processing.This just provides a kind of degree of crystallinity to particle, therefore acceptable flow characteristics is arranged, and can have any or multiple organic or inorganic salt in first kind of component.

The particle size range of second kind of component is not strict, but wants can avoid therefrom separating when mixing with first kind of component spray-dried granules.Therefore, what 1.4mm was above should be no more than 5%(weight), and overall dimension should be no more than 10%(weight less than 0.15mm).

The tap density of second kind of component should be relevant with its preparation mode.So in the spray-dried granules form, the density of second kind of component is the 350-650 grams per liter, and preferable range is the 500-630 grams per liter.Yet the preferred form of second kind of component is a kind of mechanically mixing agglomerate, the mode for preparing this thing can be with drying redients or with a kind of agglomerant and together is added to the agglomeration pot, Z type blade mixer, or preferred a kind of line mixer is such as Schugi(Holland) the 29chroomstraat8211AS type made of BV, Lelystad, Netherlands and Gebruder Lodige Maschinenban GmbH type, the D-4790Paderborn1 type, the Elsenerstrasse7-9 type is in the Postfach2050F.R.G. type mixing tank.Mode like this, second kind of available tap density scope of component is the 650-1190 grams per liter, preferred 750-850 grams per liter.The so-called enriched product of this knot preparation is particularly useful.

Preferred compositions contains alkaline carbonate to a certain degree in its second kind of component, its corresponding amount is the 3-15% of composition weight, and preferred amounts is 5-12%.This will make that the content of carbonate is 20-40%(weight in second kind of component).

Second kind of highly preferred Synergist S-421 95 of component also is a kind of artificial zeolite's type water-insoluble hydrated aluminosilicate ion exchange material, and the front is stated, and its amount is the 10-35% of second kind of composition weight.The respective numbers of water-insoluble silico-aluminate is the 1-10% of composition weight in this pattern, preferred 2-8%.If second kind of component of spraying drying then importantly do not allow it contain silicate and two kinds of Synergist S-421 95s of silico-aluminate, its reason front illustrates.Under this situation, silicate can be attached in first kind of component, perhaps, if first component also contains silico-aluminate, then can solid form be added in first kind and the second kind of component with other exsiccant mixing materials.

In a kind of technology of second kind of component of preparation, surfactant salt forms in a kind of line mixer on the spot.Tensio-active agent is added in the composite grain of a kind of continuous high speed mixing tank such as anhydrous sodium carbonate in the Lodige KM mixing tank and hydrated sodium aluminosilicate with the liquid acids form, and generates surfactant salt, keep the particle characteristics of mixture simultaneously through neutralization.The agglomerant mixture of gained has formed second kind of component, joins then in other compositions of product.In a kind of variant of this technology, give in the elder generation and surfactant salt, be added to sticky form in the mixture of other Synergist S-421 95s.In this variant technology, mixing tank only is used for the agglomeration Synergist S-421 95 to generate second kind of component.

Prepare in the special selection process of composition according to the present invention, will comprise the part shunting of the spraying drying product of first kind of component particles, with make its nonionogenic tenside spraying before residuum mixes again through low levels.Prepare second kind of component particles and adopt aforesaid selection process.First and second kinds of components can be with other dry mixed Synergist S-421 95s, such as with the carboxylicesters sequestrant, the inorganic peroxy SYNTHETIC OPTICAL WHITNER, bleach-activating agent, soil release polymer, silicate and enzyme are thrown on the conveying belt together subsequently, be transferred in the horizontal rotary drum, therein to product spraying spices and silicone suds suppressor.In highly preferred composition, adopt further rotary drum mixing step, wherein add the segmentation silico-aluminate xln of low levels (about 2% weight), so that increase density and improve the particulate flow characteristics.

Also can do well out of transmission system according to composition of the present invention,, thereby also avoid incidental product loss problem in pipeline operations or the machine washing groove so beginning can temporarily provide the high local concentrations product during laundry operation in the automatic washing machine cylinder.

Utilization is contained composition into bag or the mode of container and is easy to realize when laundry operation begins, promptly composition to be disengaged transmission to cleaning-drum along with stirring, heat up or immersing washing water in cylinder from bag or container.Washing machine self also can be selected adaptive, directly is added in the cylinder so that allow composition, for example uses a distribution device at the entrance door place.

The product that contains detergent composition that is encapsulated in sack or the container is usually designed to a kind of like this form, be that integral container is kept drying regime, contained object disengages when preventing drying, but when being exposed to wash environment, normally when being immersed in the aqueous solution, the container contained object will be suitable for release.

Container is normally flexible, such as bag or box.Sack can be fibrous texture, applies the fluid-tight protecting materials of one deck so that keep contained object, and is disclosed such as EP0018678.As selection, also the synthesizing polymeric material of available insoluble in water is made, and has the edge sealing that a kind of design can disconnect or seal in water medium, and is as EP0011500, disclosed in 0011501,0011502 and 0011968.But the disconnected form that makes things convenient for of sealing of water comprises the water-soluble glue mixture of distribution along the line and an edge sealing of box, and box is to be made by impermeable polymeric film, such as polyethylene or polypropylene.

In a kind of variant form of sack or vessel prepd, can adopt the laminated shim goods, center flexible layer wherein is coated with one or more skins to produce the textile-like decorative effect then with a kind of composition dipping and/or coating.Interlayer can be sealed so that keep in use connecting, or separates when contacting with water so that the release of application substance or impregnation of matters.

A kind of laminate form of selection comprises an embossed or distortion, to form the layer of a series of case type container, contain the detergent ingredients of certain deal in each container, this layer has covering second thin layer thereon, and the two-layer contact area sealing-in between case type container, but the interior component particulate state of containing, the form of pasty state or fusing, lamination should prevent to run out of before the case type container contained object is in being added to water.When contacting with water, each layer is separable or keep connection, has only a requirement, and promptly this structure should allow the contained object of case type container when entering solution to disengage fast.The number of per unit area of base case type container can be selected, and common variation range is every square meter 500-25000.

The appropriate materials that can be used as the pliable and tough stratiform thing of this respect of the present invention also comprises sponge, paper among others, braiding and non-woven cloth.

Yet the optimal way of realizing technology of the present invention is: said composition by a reusable distribution device, is introduced in the liquid that surrounds fabric in the cleaning-drum, and the wall of this device can see through liquid but can not see through solid-state composition.

This device has been disclosed in EP0343069 and 0343070.What the device of back patent disclosure comprised a bag shape stretches the pliable and tough covering of coming out from a support ring that the regulation hole arranged, this hole is used to allow and fills enough products in the bag for a cycles of washing use in the laundry operation.The part washing medium enters dissolved product in the bag by this hole, and solution outwards flows to washing medium by this hole then.Support ring has the shade device and prevents that moistening not molten product from disengaging, and this device generally includes the wall that stretches circumferentially extending from a spoke wheel configuration central boss, or similar structures, and wall wherein is a spiral form.

Following non-limiting example is used for illustrating the present invention, wherein all percentage ratios weight percentage all unless otherwise indicated.

The dummy suffix notation meaning of each composition is as follows in the detergent composition:

C ₁₂LAS: straight chain C ₁₂Sodium alkyl benzene sulfonate

TAS: sulfuric acid tallow sodium alkoxide

C _14/15AS C ₁₄-C ₁₆Sodium alkyl sulfate

TAE _n: the tallow alcohol ethoxylate has the n oxyethane that rubs in every mol of alcohol

45E7: the basic straight chain C of average 7 moles of ethylene oxide condensations ₄-C ₁₅The alkyl lower alcohol

C _nAE _E6.5:6.5 moles of ethylene oxide and C ₁₂-C ₁₃Elementary pure condenses

PEG: polyoxyethylene glycol (back is often with MWt)

TAED: tetraacetyl ethylene diamine

Silicate: (back is normal with SiO for amorphous sodium silicate ₂/ Na ₂The O ratio)

NaSKS-6: crystalline layered silicate, molecular formula δ-Na ₂Si ₂O ₆

Carbonate: anhydrous sodium carbonate

CMC: carmethose

Zeolite A: hydrated sodium aluminosilicate Na ₁₂(Al ₂SiO ₂) ₁₂27H ₂O basic granules size range 1-10 micron

Polyacrylic ester: MWt is 4000 acrylate homopolymer

Citrate trianion: three water citric acid sodium

Photosensitization SYNTHETIC OPTICAL WHITNER: four sulfonation zinc phthalocyanine phthalocyanines

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

MVEMA: maleic anhydride/methoxy ethylene multipolymer, molecular-weight average about 240,000 these materials give hydrolysis with NaOH before interpolation

Perborate: four water sodium perborate, nominal molecular formula are NaBO ₂3H ₂OH ₂O ₂

Perborate list anhydrous sodium perborate SYNTHETIC OPTICAL WHITNER, empirical formula is NaBO ₂H ₂O ₂Compound

Enzyme: hydrolysising protease and amylolytic enzyme miscellany, Novo In-dustrie AS is on sale

Whitening agent: 4,4 '-two (2-morpholino-4-anilino-S type-triazine-6-base is amino) stilbene-2:2 '-disulfonic acid disodium

DETPMP: diethylenetriamine penta (methylene radical phosphoric acid), Monsanto company is on sale, trade name Depuest2060

Mixed type suds suppressor: the paraffin wax that 25% fusing point is 50 ℃, 17% hydrophobic silex and 58% Valelinum Liquidum

The embodiment I

The component that preparation detergent granules product has is expressed as follows, and each several part by weight.

A??B

C ₁₂LAS 4.4 4.4

TAS??4.0??4.0

45E7??3.7??3.7

TAE ₁₁1.1 1.1

Zeolite A 18.2 8.0

Na-SKS-6??-??11.0

Citrate trianion 9.25 6.0

MA/AA??4.9??4.9

TAED??5.0??5.0

Perborate 10.0 10.0

Perborate monohydrate 6.0 6.0

DETPMP??0.19??0.19

Enzyme 1.40 1.40

Silicate (ratio 2.0) 4.0-

Carbonate 15.5 9.0

Suds suppressor 0.55 0.55

CMC??0.8??0.8

Photosensitive bleaching agent 20ppm 20ppm

Spices 0.43 0.43

Whitening agent 0.24 0.24

Moisture content and mixable 10.34 6.29

In conjunction with spraying drying, agglomeration and dry mixed technology prepare this two kinds of products.The preparation spray-dried powders can be in conjunction with whole TAS, similar 1/4th LAS, whole maleic anhydride/acrylic copolymer, DETPMP, CMC and whitening agent, part carbonate and zeolite builders.To the A product, about 82% zeolite and 65% carbonate are included in the dry part of spraying; And to the B product, about 60% zeolite and 45% carbonate add in this way.Spray-dired product is passed through a Lodige KM type high-speed mixing/cutter, and the 45E7 nonionogenic tenside of on particle, spraying.The particle that to handle is delivered to travelling belt then.With LAS, the residuum of carbonate and zeolite is processed into agglomerant particle and is sent and is given to travelling belt in Lodige KM super mixer.Other dry solid-state Synergist S-421 95, promptly Citrate trianion, silicate, perborate and bleach activator also are added to travelling belt simultaneously.Make composite grain in mixed cylinder, stand low intensive combination treatment at last,, thereby make end product during this period to particle spray perfume and suds suppressor.

Then these products are compared in splitting bag washing test program, so that can estimate its cleaning and detergency ability.The design experiment program, it has competent repeatability takes statistics the result learn to handle.The consumption of product A is each load 95 gram, and the B product is each load 79 gram, and this difference has reflected the higher concentration of Synergist S-421 95 in per 100 parts of B products, therefore needs to reduce consumption so that non-washing assistant Synergist S-421 95 keeps same amount.Testing sequence be to adopt AEG Lavamat980 automatic washing machine, be arranged on No. 2 circulations.This airborne water that 25 ℃ of Deutschland hardnesss are arranged, Ca wherein: the Mg ratio is 3: 1.Test under three kinds of temperature, promptly 40 ℃, 60 ℃ and 95 ℃, correspondingly, fabric load is respectively 1.81Kg, 2.25Kg and 2.72Kg.Every kind of load comprises the soiled white cotton fabric products of nature and dyes multiple stain, promptly greasy dirt, dirt, enzyme catalysis is dirty and can bleach the mixture that dirty cloth specimen mixes, so that make the evaluation of whiteness and detergency ability.Every kind of cloth specimen only uses its half, and second half washs with the contrast product in same washing machine.Washing back, is evaluated by expert judgments the cloth drying then in envrionment temperature, adopts the 1-5Scheffe rank to distinguish A product and B product in the feature of selecting whiteness and detergency ability under the temperature.

Evaluation shows that dirty and 95 ℃ of dirty B products of clay have tangible advantage and surpass the A product to 40 ℃ of greasy dirts and clay, and the total detergency ability of product is that statistics is upward nondescript in other respects.Therefore, surpass prior art combinations according to the present invention in conjunction with the use properties advantage that the composition of builder system exists.Moreover obtain the content (13.0 parts) that these advantages can significantly reduce the washing assistant Synergist S-421 95 simultaneously.

The embodiment II

Contrast deposits the amount of inorganic materials on the cloth after repeatedly washing, comparison other is the B product and the nonphosphate scouring agent (the UKAriel Ultra of Britain Procter and Gamble company limited system) of embodiment I.

1) and 95% wash temperature wash conditions comprises that the master of Miele Hydromatic W698 washes circulation (Ca:Mg=3:.Use the load of each product washing to comprise the new cotton towel cloth of 2.72Kg and wash load is separately carried out other 14 complete cycles of washing.

Then the cloth sample of each load is weighed, the residue that burnouts and weigh obtains in the cycles of washing data of deposition inorganic substance.The result is as follows:

Product dosage/washing (gram) ash (Wt%)

B product 102 grams 0.483%

Ariel Ultra 125 grams 0.698%

The result shows, is lower than the deposition content of commercially available non-phosphate detergent product gained according to the deposition content of composition generation inorganic salt of the present invention.

The embodiment III

Be prepared as follows the composition of component according to the present invention, preparation method is with the mode of embodiment I B product

C ₁₂LAS 6.80

TAS??2.20

45E7??3.27

TAE ₁₁1.00

Zeolite A 13.00

NaSKS6??11.00

Citrate trianion 6.00

MA/AA??4.25

Carbonate 9.00

TAED??5.00

Perborate monohydrate 12.50

DETPMP??0.19

Enzyme 1.20

CMC??0.48

Photosensitive bleaching agent 20ppm

Whitening agent 0.24

Suds suppressor 0.49

Spices 0.43

Moisture content and mixable 8.70

The embodiment IV

Press three kinds of product C of preparation method preparation of embodiment I composition B, D and E washing composition, wherein each composition is identical with embodiment I B composition, but at builder system difference is arranged, and is expressed as follows (all in its value of composition weight part).

Product C D E

Zeolite A 13.0 13.0 13.0

Citrate trianion 6.0 6.0 6.0

NaSKS6??11.0??11.0??-

Silicate (2.0 ratio) ^*--13.75

MA/AA??4.25??2.0??2.0

* expression is as long as just can have 80% activity for 11.0 parts in anhydride.

Carry out the test of full scale washing machine with these products, comprising looped pile shape towel cotton sample and have the clean fabric load of 4Kg, make its through cycles of washing repeatedly so that form heavy metal ion (Fe and Mn) after measuring repeated washing thereon and the total content of ash (inorganic salt).The heavy metal ion spike is with FeCl ₃The 0.25PPmFe of form and with MnCl ₂The 0.2PPmMn of form is added to washing and sends into that water flows in the machine.

Wash conditions is as follows:

Type: Miele Hydromatic W698

95 ℃ of cotton fabrics of machine washing circulation

Water hardness Newcastle upon Type(UK) town water is transferred to 25 ℃

Deutschland hardness, its Ca: the Mg ratio is 3: 1.(logical in the water source

The Cu that often contains 0-3Ppm).

Each load of artificial dirt contains the mixture of the following formation of 20 grams

Palmitinic acid 250 grams

Stearic acid 250 grams

Garden clay 200 grams

Dirty motor oil 150 grams

Sweet ester 150 grams of three oleic acid

Ferric oxide (Fe ₂O ₃) 5.36 grams

Cloth specimen is stood 25 cycles of washing, then analysis heavy metal ion content (PPm) and inorganic salt total content (ash).After need weighing looped pile shape towel cloth cloth specimen, the latter on naked light, burnt 3 minutes, subsequently in 800 ℃ of burnings 2 1/2 hours.The element of ash content analysis is as follows, and with primary sample weight fraction record.

The result is as follows:

C??D??E

Fe??PPm??8.8??9.9??27.2

Mn??PPm??1.9??3.5??12.4

Cu??PPm??1.4??2.3??7.0

Ca+Mg%??0.42??0.46??1.05

Si and Al% 0.18 0.27 0.49

As can be seen, the cotton with the product C that contains the present composition and D washing has shown similar ash and heavy metal ion content.Even the polymeric polycarboxylate shop that composition D contains to a certain degree helps washing assistant, it less than routine used 50%, also show the intensity of using ternary builder system of the present invention can improve detergent composition.

E compares with the contrast product, and D and C product result also show the content that has reduced deposition inorganic salt (ash), compare with the builder system of prior art, and this is just owing to having used the ternary builder system.More particularly, the contrast of C and D product and E product shows, obviously lowers the content of heavy metal ion on the cloth of use present composition gained.The heavy metal ion content of cloth is directly connected to the tensile strength decay of cloth, is attributable to the inorganic ortizon SYNTHETIC OPTICAL WHITNER of catalytic decomposition on the cloth surface.

Claims

1, a kind of granular detergent composition is characterized in that it comprises:

(a) tensio-active agent that is selected from following material of about 5%-50% (weight); Negatively charged ion, nonionic, both sexes and cats product and any type of mixture thereof;

(b) the detergent builders system of about 10-95%, it comprises following mixture;

(i) the heavy sodium silicoaluminate zeolite of about 20-60% mixture;

The heavy water-soluble chelator that is selected from following material of (ii) about 10-30% mixture: monomer and oligomeric carboxylicesters and composition thereof; With

The water glass of the laminated crystalline that (iii) about 10-65% mixture is heavy, it consists of NaMSixO _2x+1YH ₂O, wherein M is sodium or hydrogen, x is the numerical value of 1.9-4 and y is the number of 0-20, and

(c) nonsurfactant of about 0-40%, the detergent ingredient of non-washing assistant.

2, according to the granular detergent composition of claim 1, (b) wherein (ⅲ) in the component x numerical value be 2.

3, according to the detergent composition of claim 2, wherein (b) (ⅲ) in the composition M be sodium.

4, according to the detergent composition of claim 3, wherein (b) (ⅲ) composition be α, β or δ-Na ₂Si ₂O ₆

5, according to the detergent composition of claim 1, sodium silicoaluminate zeolite wherein is the synthetic hydrated zeolite, is that base calculates with the anhydride, and every gram zeolite has about 200mgCaCO at least ₃The calcium ion exchange capacity of the water hardness.

6, according to the detergent composition of claim 5, wherein synthetic hydrated zeolite unit cell molecular formula is

Z and y are 6 at least herein, and the ratio of z and y is 1.0-0.5, and x is 5 at least, preferred 7.5-276.

7, according to the detergent composition of claim 6, sodium silicoaluminate zeolite wherein is hydrated zeolite Z, X, B or HS.

8, according to the detergent composition of claim 1, the first carboxyl logarithm acidity constant (pK that organic carboxylic ester sequestrant wherein has ₁) be less than about 9 greatly.

9, detergent composition according to Claim 8, the wherein pK that has of organic carboxylic ester sequestrant ₁Be about 2-8.5.

10, according to the detergent composition of claim 9, wherein the organic carboxylic ester sequestrant comprises a kind of polycarboxylate monomer, its pK ₁Be about 4-7.5.

11, according to the detergent composition of claim 10, wherein the polycarboxylate monomer comprises a kind of aliphatic polycarboxylate monomer, and its carboxyl number that contains is 2-4.

12, a kind of granular detergent composition comprises

(a) about 5-50%(weight) be selected from the organic surface active agent of following material: negatively charged ion, nonionic, both sexes and cats product and any mixture thereof;

(b) the detergent builders system of about 10-95%, it comprises following mixture:

(ⅰ) the heavy synthetic aluminosilicate natrolite of about 20-60% mixture, its unit cell molecular formula is

Wherein z and y are at least 6, and z is 1.0-0.5 with the ratio of y, and x is at least 5, preferred 7.5-276,

(ⅱ) the heavy water-soluble grease adoption carboxylic acid ester monomer sequestrant of about 10-30% mixture, it contains carboxyl 2-4 and its pK ₁Be about 4-7.5, and

(ⅲ) the heavy laminar crystal sodium silicate of about 10-65% mixture, its molecular formula is δ-Na ₂Si ₂O ₅And

(c) nonsurfactant of 0-about 40%, the detergent ingredient of non-washing assistant.

13,, comprise (a) component of about 5-30%, approximately (b) component of 20-60% and approximately other detergent ingredients of 20-40% according to the detergent composition of claim 12.

14, according to the detergent composition of claim 12, water-soluble grease adoption carboxylic acid ester monomer sequestrant wherein is selected from citric acid, water-soluble citrate and composition thereof.

15, according to the detergent composition of claim 14, (b) composition wherein also comprises the washing assistant auxiliary.

16, according to the detergent composition of claim 15, washing assistant auxiliary wherein is selected from; Water soluble amino polyalkylene phosphoric acid salt, alkaline carbonate and supercarbonate, homopolymerization/or the poly carboxylic acid and the salt thereof of copolymerization, poly carboxylic acid wherein comprise at least two that be separated from each other and by no more than two carboxyls that carbon atom separates, and the mixture of their any patterns.

17, according to the detergent composition of claim 16, (c) component wherein comprises a kind of oxygen bleaching agent.

18, according to the detergent composition of claim 17, oxygen bleaching agent wherein is a kind of inorganic perhydrate.

19, according to the detergent composition of claim 18, oxygen bleaching agent wherein comprises a kind of organic peroxy acid precursor.

20, according to the detergent composition of claim 12, (c) component wherein comprises a kind of detergent enzyme.

21, a kind of method for preparing granular detergent composition comprises

(b) about 10-95% detergent builders system, it comprises following mixture;

Here z and y are at least 6, and z is 1.0-0.5 with the ratio of y, and x is 5 at least, preferred 7.5-276,

(ⅱ) the heavy water-soluble grease adoption carboxylic acid ester monomer sequestrant of about 10-30% mixture, it contains carboxyl 2-4 and pK ₁Be about 4-7.5, and

(ⅲ) the heavy laminar crystal sodium silicate of about 10-65% mixture, its molecular formula is δ-Na ₂Si ₂O ₅; With

(c) nonsurfactant of about 0-40%, the detergent ingredient of non-washing assistant,

Laminar crystal sodium silicate wherein (b) (ⅲ) adds one or more to fine solid granulates form and comprises component (a), component (b) is if (ⅰ) and (ⅱ) and in the solid granulates of the component (c) that exists, at least a said solid granulates comprises a kind of multicomponent mixture, and its amount is about at least 20% of a composition weight.

22, the method for preparing granular detergent composition according to claim 21, the step that comprises is:

(ⅰ) first kind of solid particulate of spraying drying, it accounts for about 30-70% of composition, and the basic comprising of its component is about 0.75-35%(weight) anion surfactant and the about salt that is selected from following material of 65-99.25%; Synthetic aluminosilicate zeolite and other inorganic and organic detergent builder salt;

(ⅱ) second kind of solid particulate of preparation, it accounts for the heavily about 1-50% of composition, and it is substantially by a kind of agglomerant anion surfactant, and the mixture of synthetic aluminosilicate zeolite and other inorganic detergent builders salt constitutes;

(ⅲ) blend of a kind of said first and second kinds of solid granulates of generation; With

(ⅳ) in wherein adding water-soluble grease adoption carboxylic acid ester monomer sequestrant and as the layered crystalline sodium disilicate of individual particles form.