CN1329660A - Process for delivering chelant agglomerate into detergergent composition for improving its storage stability, flowability and scoopability - Google Patents

Process for delivering chelant agglomerate into detergergent composition for improving its storage stability, flowability and scoopability Download PDF

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CN1329660A
CN1329660A CN 99814084 CN99814084A CN1329660A CN 1329660 A CN1329660 A CN 1329660A CN 99814084 CN99814084 CN 99814084 CN 99814084 A CN99814084 A CN 99814084A CN 1329660 A CN1329660 A CN 1329660A
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chelant
composition
agglomerate
transition metal
acid
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W·I·诺曼
D·L·珀金斯
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Procter and Gamble Ltd
Procter and Gamble Co
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/36—Organic compounds containing phosphorus
    • C11D3/364—Organic compounds containing phosphorus containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3245—Aminoacids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/36—Organic compounds containing phosphorus

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Glanulating (AREA)

Abstract

The present invention provides a process for preparation of a chelant composition by a non-spray-drying process, a process for improving one or more of flowability and scoopability of a laundry detergent composition, and a chelant agglomerate useful as an ad-mix in a particulate laundry detergent. In one aspect of the present invention, the process for preparation of a chelant composition by a non-spray-drying process includes the steps of admixing a transition metal chelant and an inorganic compound to form a mixture, agllomerating the mixture in an aqueous medium to form a chelant agglomerate and drying the chelant agglomerate.

Description

Delivering chelant agglomerate advances the method that detergent composition improves its stability in storage, flowability and scoopability
Technical field
The present invention relates to a kind of laundry detergent composition, relate more specifically to a kind of passing through significant quantity is concentrated in the chelant agglomerate adding laundry detergent composition, improve its stability in storage, and the method that makes it easy to bale-out.
Background of the present invention
Be starved of a kind of method that improves the detergent composition stability in storage and make it easy bale-out.This is the specific character that most consumers is all thirsted for very much, because the human consumer does not wish that opening the accidental water that absorbs for a long time because of detergent box " solidifies " detergent composition to have to situation about being handled together.
It has been recognized that transition metal chelator is added can promote the brilliant pin growth of interlocking in the base particle of laundry detergent composition, this estimates the flowability of gained granular laundry detergent compositions and scoopability are produced harmful effect.Therefore the present inventor recognizes, design a kind of method that transition metal chelator is separated be from the base particle of laundry detergent composition very favorable, the transition metal chelator of any significant quantity can be added like this in the finished product laundry detergent composition and can be to it mobile and scoopability not have a negative impact.Promptly be starved of a kind of technology or method, the chelant agglomerate of any significant quantity is sneaked in the laundry detergent composition, this chelant agglomerate can improve the solubleness and the stability in storage of gained cleaning composition composition formulation ideally like this, and can not produce harmful effect to the flowability and the scoopability of laundry detergent composition at least.The present invention has overcome above-mentioned problem.
United States Patent (USP) 5108646 discloses a kind of by detergent builder compound is mixed the method that formation unrestricted flow agglomerate comes the preparing washing builder agglomerates with selected binding agent.
International Patent Application WO 97/09415 discloses a kind of non-spray-dired granular detergent composition; by liquid and solids component being mixed in high-speed mixer/granulator and granulation is made; these compositions comprise washing assistant polymkeric substance and/or soil release polymer, wherein said polymkeric substance mix and the granulation process process in the form adding of the non-water pre-composition of non-diluent water.
The present invention's general introduction
The present invention is by providing a kind of method that is prepared chelant composite by non-drying process with atomizing; The method of one or more of a kind of all performances of stability in storage, flowability and scoopability that improve laundry detergent composition; And a kind ofly can be used as that the chelant agglomerate of compound satisfies the demand in the granular laundry detergent.
One aspect of the present invention, the method for preparing chelant composite by non-drying process with atomizing may further comprise the steps: transition metal chelator and mineral compound are mixed the formation mixture, the agglomeration in water medium of this mixture is formed chelant agglomerate, dry then this chelant agglomerate.
Another aspect of the present invention, the method of one or more in stability in storage, flowability and the scoopability of raising laundry detergent composition may further comprise the steps: provide chelant composite by non-drying process with atomizing, then this chelant composite is added in the granular laundry detergent material, wherein the weight ratio of chelant composite and granular laundry detergent material is about 0.05: about 2: 98 of 99.95-.This non-drying process with atomizing may further comprise the steps: transition metal chelator is mixed forming mixture with mineral compound, the agglomeration in water medium of this mixture is formed chelant agglomerate, dry then this chelant agglomerate.
Another aspect of the present invention discloses the chelant agglomerate that can be used as compound in the granular laundry detergent.The composition of this chelant agglomerate comprises transition metal chelator, mineral compound and water.This chelant agglomerate forms mixture by transition metal chelator is mixed with mineral compound, with this mixture agglomeration formation chelant agglomerate in water, and this chelant agglomerate of drying and forming then.
Those skilled in the art can obviously find out these and other purpose, characteristics and attendant advantages of the present invention below reading after the detailed description to preferred embodiment and claims.
The present invention describes in detail
In the preferred embodiments of the invention, the method for preparing chelant composite by non-drying process with atomizing may further comprise the steps: transition metal chelator and mineral compound are mixed the formation mixture, the agglomeration in water medium of this mixture is formed chelant agglomerate, dry then this chelant agglomerate.In this preferred embodiment, transition metal chelator is that dioxane Che1300 and mineral compound are selected from vitriol, carbonate, silicate, silico-aluminate and composition thereof.It is desirable to, this mineral compound is a silico-aluminate, and this mineral compound is preferably structural formula M M/n[(AlO 2) m(SiO 2) y] xH 2The aluminosilicate ion exchange material of O, wherein n is the valency of positively charged ion M, and x is the water molecule number of each structure cell, and m and y are the tetrahedron sums of each structure cell, and y/m is 1-100, and wherein M is selected from sodium, potassium, magnesium and calcium.Most preferably this mineral compound is a zeolite.
In this preferred embodiment; mixing step comprises; with transition metal chelator and mineral compound ideally with respectively about 10: the weight ratio that 90-is about 80: 20; preferably with respectively about 15: the weight ratio that 85-is about 60: 40; most preferably with respectively about 25: the weight ratio that 75-is about 35: 65, in one or more super mixers and tablets press, mix and granulation.
In this preferred embodiment, agglomeration step comprises, before agglomeration, ideally with respectively about 10: the weight ratio that 90-is about 80: 20, preferably with respectively about 15: the weight ratio that 85-is about 60: 40, most preferably with respectively about 25: the weight ratio that 75-is about 35: 65 forms the pre-composition of sequestrant-mineral compound.
Of the present invention in addition-preferred embodiment in, a kind of stability in storage of laundry detergent composition and method of scoopability of improving disclosed.In this preferred embodiment of the present invention, this method comprises the first step that forms chelant agglomerate.Very unexpectedly find, if the sequestrant particle is isolated the formation chelant agglomerate from remaining laundry detergent composition, and subsequently this chelant agglomerate is added in the granular laundry detergent compositions, so, when this chelant agglomerate and detergent powder the most at last with about 0.05: the ideal weight ratio that 99.95-is about 2: 98, preferably with about 0.03: 99.7 one about 1.5: 98.5 weight ratio, most preferably (chelant agglomerate: when laundry detergent composition) mixing, the stability in storage and the scoopability of gained laundry detergent composition are increased sharply with about 0.1: 99.9 weight ratio.Promptly, unexpectedly find, by the sequestrant particle is specially separated from laundry detergent composition, and only add in the laundry detergent composition with chelant agglomerate, the finished product so, be " caking " performance that laundry detergent composition has obvious improvement, the detergent composition that promptly has sequestrant has higher stability in storage and scoopability.Be bound to any specific theory though be reluctant, it is believed that this improvement realizes owing to the water absorbability transition metal chelator is separated from all the other " viscosity " laundry compositions.
With regard to this paper, its implication of term " caking " performance comprises the stability in storage of composition and the powder solubility in water.Its implication of term " viscosity " component comprises the mixture of one or more tensio-active agents, polyoxyethylene glycol, polyacrylic ester and water.Its implication of term " washing assistant " comprises that all can utilize ion exchange, complexing action, sequestering action or precipitating action remove the material of calcium ion from solution.Term " scoopability " definition is divided into 1-5 grade, represents that laundry composition is scooped out with spoon and the bale-out ability or the characteristic that can not be clamminess or lump, and wherein 1 is minimum ideal value, and 5 are ideal values.Sequestrant
Sequestrant can be selected from aromatic chelating agent that aminocarboxylate, amino phosphonates do, polyfunctional group replace, diethylenetriamine pentaacetic acid sodium and composition thereof.Though be reluctant to it is believed that bound by theory that the benefit part of these materials is passed through to form the soluble chelating thing owing to them, and from washing lotion, remove the unusual ability of iron and magnesium ion.
The aminocarboxylate that can optionally be used as sequestrant comprises edetate, N-hydroxyethyl-ethylenediamine tetraacetate, nitrilotriacetic acid(NTA) salt, ethylenediamine tetrapropionic acid(EDTP) salt, teiethylene tetramine-hexacetic acid salt, diethylenetriamine pentaacetic acid salt and ethanol Diglycocol, its basic metal, ammonium and substituted ammonium salt and composition thereof.
If allow carbamate additives for low phosphorus content in the detergent composition at least, amino phosphonates do also is suitable for the sequestrant of doing in the present composition so, comprises the ethylenediamine tetraacetic (methylene phosphonic acid salt) as DEQUEST.Preferably, these amino phosphonates do do not contain alkyl or the alkenyl that surpasses about 6 carbon atoms.
The aromatic chelating agent that polyfunctional group replaces also can be used for the present composition.Authorize people's such as Connor United States Patent (USP) 3812044 referring on April 21st, 1974.This class preferred compound of acid form is the dihydroxyl disulfobenzene, as 1, and 2-dihydroxyl-3,5-disulfobenzene.
The biodegradable cheating agent that this paper preferably uses is ethylenediamine disuccinate (" EDDS "), especially United States Patent (USP) 4704233 (authorizing Hartman and Perkin on November 3rd, 1987) described [S, S] isomer.
If use, these sequestrants generally account for about 10% weight of about 0.05-of detergent composition of the present invention, and more preferably sequestrant accounts for about 3.0% weight of about 0.05-of these compositions.
Most preferably being used for transition metal chelator of the present invention is diethylenetriamine pentaacetic acid sodium (DTPA).DTPA is preferably with about 0.1: about 1.5: 98.5 weight ratio (DTPA agglomerates: laundry detergent composition), most preferably use with 0.4: 99.6 weight ratio of 99.9-.Preferred this chelant agglomerate by DTPA and zeolite with about 15: the preferred weight ratio that 85-is about 25: 75 (DTPA: zeolite) form.Alumino-silicate materials
In the preferred embodiments of the invention, the structural formula of silico-aluminate is based on crystal structure cell unit, and the minimal structure unit is expressed as follows:
M m/n[(AlO 2) n(SiO 2) y]·xH 2O
Wherein n is the valency of positively charged ion M, and x is the unitary water molecule number of each structure cell, and m and y are the unitary tetrahedron sums of each structure cell, and y/m is 1-00.Most preferably y/m is 1-5.Positively charged ion M can be IA family and II family element, as sodium, potassium, magnesium and calcium.Most preferred alumino-silicate materials is a zeolite.Most preferred zeolite is zeolite A, X zeolite, zeolite Y, zeolite P, zeolite MAP and composition thereof.
The aluminosilicate ion exchange material that this paper is used for chelant agglomerate has high-calcium ionic exchange capacity and high rate of exchange.Though be reluctant bound by theory to it is believed that described high-calcium ionic rate of exchange and capacity are owing to producing correlation factors in the aluminosilicate ion exchange material method.Given this, aluminosilicate ion exchange material used herein is preferably according to people's such as Corkill United States Patent (USP) 4605509 (Procter﹠amp; Gamblee) produce, incorporate its disclosure into the present invention as a reference at this.
Preferably aluminosilicate salt ion exchange material is " sodium " form, because this silico-aluminate of potassium and hydrogen form can not have sodium high rate of exchange and capacity like that.In addition, aluminosilicate ion exchange material is preferably the super-dry form, helps to produce crisp chelant agglomerate as herein described like this.The particle diameter of aluminosilicate ion exchange material used herein preferably can be optimized its effectiveness as detergent builders.The average particulate diameter size of the given aluminosilicate ion exchange material of term used herein " particle diameter " expression by the routine analysis technology, is measured as microscope and scanning electronic microscope (SEM).The preferable particle size of silico-aluminate is about 10 microns of about 0.1-, and more preferably from about 0.5-is about 9 microns.Most preferably this particle diameter is about 8 microns of about 1-.
In a preferred embodiment, the crystal aluminosilicate ion-exchange material has following structural formula:
Na 12[(AlO 2) 12(SiO 2) 12]·xH 2O
Wherein x is about 20-about 30, especially about 27.This material is called zeolite A.This paper also can use dehydration zeolite (x=0-10).Preferably, the granularity of silico-aluminate is about 0.1-10 micron.Laundry detergent composition
In preferred embodiments, the composition of this laundry detergent composition comprises according to the present invention and makes and add chelant agglomerate in the laundry detergent composition.This laundry detergent composition also comprises washing assistant, yellow soda ash, sodium sulfate, tripoly phosphate sodium STPP, negatively charged ion and nonionogenic tenside and the excess water of making by agglomeration or drying process with atomizing.Laundry detergent composition is well known in the art, for example authorizes Scott W.Capeci and transfers Procter﹠amp; The United States Patent (USP) 5554587 of Gamble company discloses the various examples of various laundry detergent compositions.The chelant agglomerate of making by agglomeration process
In a preferred embodiment of the invention, chelant agglomerate is made by agglomeration process.Agglomeration process
This agglomeration process may further comprise the steps:
I) one or more compositions are mixed the formation mixture; Then
Ii) this mixture agglomeration is formed agglomerated particle or " agglomerate "; Then
Iii) dry this agglomerate.
Usually, this agglomeration process comprises: with each composition at one or more cyclone agglomerators, as disc type cyclone agglomerator, Z-blade mixer or more preferably in online mixing tank (preferred two), for example by Dutch Schugi (Holland) BV, 29 Chroomstraat, 8211 AS, Lelystad, with German Gebruder lodige Maschinenbau GmbH, D-4790 Paderborn1, Elsenestrasse 7-9, Potsfach 2050, and those machines of manufacturing mix.The preferred high-shear mixer that uses is as Lodige CB (trade mark).Most preferably with high-shear mixer and low sheared mixt, be used in combination as Lodige CB (trade mark) and Lodige KM (trade mark) or SchugiKM (trade mark).Optionally, use one or more low shear mixer.Preferably agglomerate is carried out drying and/or cooling subsequently.Authorize Scott W.Capeci and transfer Procter﹠amp; 5554587 pairs of agglomeration process of the United States Patent (USP) of Gamble company have carried out fabulous description.
Another agglomeration process comprises that the use fluidized-bed mixes each component of final agglomerate in different steps.For example, detergent powder can be by with tensio-active agent and on the wax that optionally adds or its mixture acid source that is sprayed to powder type and the composition that other optionally adds and agglomeration.Then, can add and comprise that perborate bleach and the alkaline source that optionally adds or part wait other component, and carry out agglomeration, form final agglomerated particle like this in one or more stages.
Agglomerate can be forms such as thin slice, piller, bead, bar, band, but is preferably particle form.The preferred method of processing granular is to make dry substance (as silico-aluminate, carbonate) agglomeration with the high active surfactant paste, and the particle diameter of gained agglomerate is controlled in the prescribed limit.Typical particle diameter is the 0.10-5.0 millimeter, preferred 0.25-3.0 millimeter, most preferably 0.40-1.00 millimeter.Usually, the bulk density of " agglomerate " preferably is at least 700 grams per liters, preferably about 700-900 grams per liter.The aucillary detergent composition
Ancillary component comprises other detergent builder compound, SYNTHETIC OPTICAL WHITNER, activator of bleaching agent, short infusion or suds suppressor, anti-loss of gloss pool and corrosion inhibitor, soil-suspending agent, stain remover, sterilant, pH value conditioning agent, non-washing assistant alkaline source, sequestrant, terre verte, enzyme, enzyme stabilizers and spices.Authorize people's such as Baskerville United States Patent (USP) 3936537 referring on February 3rd, 1976, incorporate it into the present invention as a reference at this.
SYNTHETIC OPTICAL WHITNER and activator are described in the United States Patent (USP) 4412934 of authorizing people such as Chung November 1 nineteen eighty-three and the United States Patent (USP) 4483781 of authorizing Hartman on November 20th, 1984, incorporate both into the present invention as a reference at this.Sequestrant also is described in people's such as Bush United States Patent (USP) 4663071 (17 hurdles 54 walk to 18 hurdles, 68 row), incorporates it into the present invention as a reference at this.Foam properties-correcting agent also is composition optionally, and be described in United States Patent (USP) 3933672 (authorizing people such as Bartoletta on January 20th, 1976) and United States Patent (USP) 4136045 (authorizing people such as Gault on January 23rd, 1979), incorporate both into the present invention as a reference at this.
The terre verte that is applicable to this paper is described in the United States Patent (USP) 4762645 (6 hurdles 3 walk to 7 hurdles, 24 row) of authorizing people such as Tucker on August 9th, 1988, incorporates it into the present invention as a reference at this.Other detergent builder compound that is applicable to this paper is recited in Baskerville patent (13 hurdles 54 walk to 16 hurdles, 6 row) and authorized people's such as Bush United States Patent (USP) 4663071 on April 5th, 1987, incorporates both into the present invention as a reference at this.Tensio-active agent
Anion surfactant-preferred anionic surfactants tensio-active agent comprises C 11-C 18Alkylbenzene sulfonate (LAS) and primary, side chain and random C 10-C 20Alkyl-sulphate (AS), has structural formula CH 3(CH 2) x(CHOSO 3 -M +) CH 3And CH 3(CH 2) y(CHOSO 3 -M +) CH 2CH 3C 10-C 18Secondary (2,3) alkyl-sulphate, x and (y+1) be wherein at least about 7, preferably at least about 9 integer, and M is water solubilising positively charged ion, especially sodium, unsaturated vitriol, as oleyl sulfate, C 10-C 18Alkyl alkoxy sulfate (" AE xS "; Especially C EO1-7 ethoxy sulfate), 10-C 18Alkyl alkoxy carboxylate salt (especially EO1-5 ethoxy carboxylate), C 10-C 18Glyceryl ether, C 10-C 18Alkylpolyglycosides and poly-glycosides of corresponding sulfation and C 12-C 18α-sulfonated fatty acid ester.
In general, the anion surfactant that can be used for this paper is as being disclosed in the United States Patent (USP) 4285841 of authorizing people such as Barrar on August 25th, 1981 and authorizing on December 30th, 1975 as described in people's such as Laughlin the United States Patent (USP) 3919678.
Useful anion surfactant comprises water-soluble salt, especially basic metal, ammonium and alkanol ammonium (as monoethanolamine ammonium or the triethanol ammonium) salt (moieties of aryl is also included within the term " alkyl ") of the organosulfur acid-respons product that comprises about 10-20 carbon atom alkyl and sulfonic group or sulfate group in its molecular structure.The example of this class synthetic surfactant is an alkyl-sulphate, especially for example the glyceryl ester of butter or Oleum Cocois is reduced and the higher alcohols (C that makes 8-C 18Carbon atom) carry out sulfation and obtain those.
Other cats product of this paper is the water-soluble salt of the alkylphenol ethylene oxide ether sulfate of each molecule alkyl of comprising about 1-4 ethylene oxide unit and about 8-12 carbon atom.
Other the anion surfactant that can be used for this paper comprises comprising about 6-20 carbon atom in the fatty acid group, and comprises the water-soluble salt of the sulfonated fatty acid ester of about 1-10 carbon atom in the ester group; Comprise about 2-9 carbon atom in the acyl group, and comprise the water-soluble salt of the 2-acyloxy-alkane-1-sulfonic acid of about 9-23 carbon atom in the paraffin section; The water-soluble salt that comprises the alkene sulfonic acid of about 12-24 carbon atom; And comprise about 1-3 carbon atom in the alkyl, and comprise the b-alkoxy alkane sulfonate of about 8-20 carbon atom in the paraffin section.
Other the anion surfactant that can be used for this paper is the alkyl polyethoxylated vitriol of following structural formula:
RO(C 2H 4O) xSO 3 -M +
Wherein R is the saturated or undersaturated alkyl chain of about 10-22 carbon atom, and M makes this compound that water miscible positively charged ion be arranged, especially basic metal, ammonium or replace ammonium cation, and the about 1-15 of x average out to.
Other alkyl sulfate surfactant is non-ethoxylation C 12-15The primary and secondary alkyl-sulphate.In the cold water washing condition, promptly be lower than under about 65 °F (18.3 ℃), preferably the alkyl-sulphate with ethoxylation and non-ethoxylatedization mixes.The example of lipid acid comprises capric acid, lauric acid, tetradecanoic acid, palmitinic acid, stearic acid, eicosanoic acid and docosoic acid.Other lipid acid comprises physetoleic acid, oleic acid, linolic acid and ricinoleate acid.
The nonionic and the amphoterics of nonionogenic tenside-routine comprise C 12-C 18Alkylethoxylate (AE) comprises so-called narrow peak alkylethoxylate and C 6-C 12Alkyl phenolic alkoxy thing (especially ethoxylate and mixing oxyethyl group/propoxy-).Also can use C 10-C 18N-alkyl polyhydroxy fatty acid amide.Exemplary comprises C 10-C 18The N-methyl glucose amide.Referring to WO9206154.Other sugared deutero-tensio-active agent comprises N-alkoxyl group polyhydroxy fatty acid amide, as C 10-C 18N-(3-methoxy-propyl) glucamide.For low bubble, can use the N-propyl group to N-hexyl C 10-C 18Glucamide.Also can use C 10-C 20Conventional soap.High if desired bubble also can use side chain C 10-C 16Soap.The example of nonionogenic tenside is described in the United States Patent (USP) 4285841 of authorizing people such as Barrar on August 25th, 1981.
The example of tensio-active agent also comprises formula R (OC 2H 4) nThe pure and mild ethoxylated alkylphenol of the ethoxylation of OH, wherein R be selected from the aliphatic hydrocarbyl that comprises about 8-15 carbon atom and wherein alkyl comprise the alkyl phenyl of about 8-12 carbon atom, and the mean value of n is about 5-15.These tensio-active agents are described in more detail in the United States Patent (USP) 4284532 of authorizing people such as Leikhim on August 18th, 1981.Other tensio-active agent comprises 10-15 the carbon atom of on average having an appointment in the alcohol, and average degree of ethoxylation is the ethoxylated alcohol of about 6-12 mole ethylene oxide/mol of alcohol.Use the mixture of negatively charged ion and nonionogenic tenside especially favourable.
Other conventional surfactant is set forth in the standard textbook, comprises polyhydroxy fatty acid amide, alkylglycoside, many alkylglycosides, C 12-C 18Trimethyl-glycine and sultaine.Its example comprises C 10-C 18The N-methyl glucose amide is referring to WO9206154.Other sugared deutero-tensio-active agent comprises N-alkoxyl group polyhydroxy fatty acid amide, as C 10-C 18N-(3-methoxy-propyl) glucamide.For low bubble, can use the N-propyl group to N-hexyl C 10-C 18Glucamide.
Cats product-useful cats product is the monoalkyl quaternary ammonium surfactant, but any cats product that can be used for detergent composition all is applicable to this paper.
The cats product that can be used for this paper comprises the quaternary ammonium surfactant of following structural formula:
Figure A9981408400121
R wherein 1And R 2Be independently selected from C 1-C 4Alkyl, C 1-C 4Hydroxyalkyl, benzyl and-(C 2H 4O) xH, wherein x is the value of about 2-5; X is a negatively charged ion; And (1) R 3And R 4Be respectively C 6-C 14Alkyl, or (2) R 3Be C 6-C 18Alkyl, and R 4Be selected from C 1-C 10Alkyl, C 1-C 10Hydroxyalkyl, benzyl and-(C 2H 4O) xH, wherein x is the value of about 2-5.
Other useful quaternary ammonium surfactant is muriate, bromide and Methylsulfate.The example of ideal single-long-chain alkyl quaternary ammonium surfactant is R wherein 1, R 2And R 4Be respectively methyl and R 3Be C 8-C 16Alkyl; Or R wherein 3Be C 8-C 18Alkyl, and R 1, R 2And R 4Be selected from methyl and hydroxyalkyl the part those.Lauryl trimethyl ammonium chloride, myristyl trimethyl ammonium chloride, palmityl trimethyl ammonium chloride, coco group trimethyl ammonium chloride, coco group trimethylammonium methylsulfuric acid ammonium, coco group dimethyl list hydroxyethyl ammonium chloride, coco group dimethyl list hydroxyethyl methylsulfuric acid ammonium, stearyl dimethyl list hydroxyethyl ammonium chloride, stearyl dimethyl list hydroxyethyl methylsulfuric acid ammonium, two-C 12-C 14Alkyl dimethyl ammonium chloride, and composition thereof also be ideal.ADOGEN412 TM, also be ideal from the lauryl trimethyl ammonium chloride of Witco.Other ideal surfaced promoting agent is lauryl trimethyl ammonium chloride and myristyl trimethyl ammonium chloride.
Another kind of suitable cationic surfactants is the alkylolamide quaternary ammonium surfactant of following structural formula:
Figure A9981408400131
R wherein 1Can be C 10-18Alkyl or replacement or unsubstituted phenyl; R 2Can be C 1-4Alkyl, H or (EO) y, wherein y is about 1-5; Y be O or-N (R 3) (R 4U); R 3Can be H, C 1-4Alkyl or (EO) y, wherein y is about 1-5; If there is R 4Can be C 1-4Alkyl or (EO) y, wherein y is about 1-5; N is independently selected from about 1-6 respectively, preferably about 2-4; X be hydroxyl or-N (R 5) (R 6) (R 7), R wherein 5, R 6, R 7Be independently selected from C 1-4Alkyl, H or (EO) y, wherein y is about 1-5.
Amine oxide surfactant-this paper laundry detergent composition also can comprise the amine oxide surfactant of following structural formula;
R 1(EO) x(PO) y(BO) zN(O)(CH 2R’) 2·qH 2O (1)
Generally as can be seen, structural formula (I) provides a long-chain part R 1(EO) x(PO) y(BO) zWith two short chain portion C H 2R '.R ' be preferably selected from hydrogen atom, methyl and-CH 2OH.In general, R 1Being uncle or branched hydrocarbyl part, can be saturated or undersaturated, R 1Be preferably the primary alkyl part.If x+y+z=O, R 1Be that chain length is the hydrocarbyl portion of about 8-18.If x+y+z is not equal to O, R 1Can be more longer, the chain length scope is C 12-24This general formula also comprises wherein x+y+z=0, R 1=C 8-C 18, R ' is H and q=0-2, preferred 2 amine oxide.The example of these amine oxides is C 12-14Alkyl dimethyl amine oxide, cetyl dimethyl amine oxide, octadecyl amine oxide and hydrate thereof especially are disclosed in the dihydrate of United States Patent (USP) 5075501 and 5071594, incorporate it into the present invention as a reference at this.
The present invention comprises that also wherein x+y+z is not equal to 0, and especially x+y+z is about 1-10, R 1For comprising about 24 carbon atoms of 8-, the amine oxide of the primary alkyl of preferably about 12-16 carbon atom; In these embodiments, y+z be preferably 0 and x be preferably about 1-6, more preferably from about 2-4; EO represents oxyethyl group oxygen; PO represents propylidene oxygen; And BO represents butylene oxide.These amine oxides can be by conventional synthetic method, for example by the reaction of alkyl ethoxy sulfate and dimethyl amine, with hydrogen peroxide this ethoxylated amine is carried out oxidation subsequently and makes.
This paper ideal amine oxide is solid at ambient temperature, and more preferably their melting range is 30-90 ℃.The amine oxide that is applicable to this paper is by comprising Akzo Chemie, Ethyl Corp. and Procter﹠amp; Many suppliers of Gamble supply with.About other amine oxide manufacturers, referring to compilation and the Kirk-Othmer survey article of McCutcheon.Other desirable commercially available amine oxide is from Ethyl Corp.Solid dihydrate ADMOX 16 and ADMOX 18, ADMOX 12, especially ADMOX 14.
Other embodiment comprise dimethyl dodecyl amine oxide dihydrate, cetyl dimethyl amine oxide dihydrate, octadecyl dimethyl amine oxide dihydrate, hexadecyl three (ethyleneoxy group) dimethyl oxidation amine, CH3-(CH2)13N(CH3)2-O dihydrate, and composition thereof.In certain embodiments, R ' is H, but suitably allows R ' to be a bit larger tham H.Other embodiment comprises that wherein R ' is CH 2The amine oxide of OH is as hexadecyl two (2-hydroxyethyl) amine oxide, butter two (2-hydroxyethyl) amine oxide, stearyl two (2-hydroxyethyl) amine oxide and oil base two (2-hydroxyethyl) amine oxide.Enzyme
Enzyme can be included in this paper prescription, and it is used for various fabric washing occasions, comprises removing protein-based, carbohydrate-based or triglyceride level base spot; And be used for fabric and restore.The enzyme that adds comprise proteolytic enzyme, amylase, lipase and cellulase, and composition thereof.The enzyme that also can comprise other kind.They can have any suitable source, for example plant, animal, bacterium, fungi and yeast source.But their selection is influenced by Several Factors, as pH-activity and/or optimal stability state, thermostability with to stability of activated detergent, washing assistant etc.In this respect, bacterium or fungal enzyme are preferred, as bacterial amylase and proteolytic enzyme, and fungal cellulase.
The add-on of enzyme should be enough to provide every gram detergent composition, mostly is about 5mg most, more generally is the organized enzyme of about 0.01-3mg.Except other has explanation, the composition of this paper generally comprises 0.001-5%, is preferably the commercial enzyme preparation of 0.01-1% weight.Usually in article of commerce, the amount of proteolytic enzyme should be enough to provide the activity of 0.005-0.1 Anson unit (AU)/gram composition.
The suitable example of proteolytic enzyme is a subtilysin, and it is that specific bacterial strain by subtilis and Bacillus licheniformis produces.Another suitable proteolytic enzyme is produced by bacillus strain, and its activity in whole pH8-12 scope is the highest, sells by Novo Industries A/S exploitation, and with trade(brand)name ESPERASE.The preparation of this kind of enzyme and similar enzyme has description in the English Patent 1243784 of Novo.The commercially available proteolytic enzyme that is used to remove protein-based spot comprises: those that sold with trade(brand)name ALCALASE and SAVINASE by Novo Industries A/S (Denmark) and Dutch International Bio-Synthetic, the MAXATASE of Inc.Other proteolytic enzyme comprise protease A (referring to EPl30756, on January 9th, 1985 open) and proteolytic enzyme B (referring to the european patent application of submitting on April 28th, 1,987 87303761.8 and January in 1985 people such as disclosed Bott on the 9th european patent application 130756).
Amylase comprises for example GB1, the α-Dian Fenmei of describing among 296,839 (Novo), International Bio-Synthetics, the RAPIDASE of Inc. and the TERMAMYL of NovoIndustries.
The cellulase that can be used among the present invention comprises bacterium and fungal cellulase.Preferred its optimal ph is between 5-9.5.Suitable cellulase is disclosed in the United States Patent (USP) S 4 that authorized people such as Barbesgoard on March 6th, 1984,435,307, wherein disclose and derived from Humicola insolens and fungal strain DSM1800 is planted in corruption, or the mycetogenetic cellulase 212 of Aeromonas, and the cellulase that from extra large mollush (Dolabella AuriculaSolander) hepatopancreas, extracts.Suitable cellulase also is disclosed in GB-A-2, in 075,028, GB-A-2,095,275 and DE-OS-2,247,832.CAREZYME (Novo) is a particularly suitable.
The lipase that is applicable to washing composition comprises the microorganism of Rhodopseudomonas, as disclosed Situ Ci Shi Rhodopseudomonas ATCC 19154 among the GB1372034.In addition referring to disclosed Japanese patent application 5320487 on February 24th, 1978.This lipase can derive from the Amano Pharm Pur GmbH that is positioned at Japanese Nagoya, and commodity are called Lipase P " Amano ", below are called " Amano-P ".Other suitable commercial product lipase comprises: from the Amano-CES lipase of thickness look bacillus, as derive from Japanese Tagata Toyo Jozo company separate fat thickness chromobacterium variant NRRLB 3673; Derive from the thickness look bacillus lipase of U.S. U.S.Biochemicai company and Dutch Disoynth company; And the lipase of high calamus Rhodopseudomonas.Plant by dredging the corruption of cotton shape hair that to belong to the LIPOLASE  enzyme (in addition referring to EP341947) of deriving and can derive from Novo be to be used for a kind of preferred fat enzyme of the present invention.
The United States Patent (USP) 3553139 of authorizing people such as McCarty on January 5th, 1971 discloses the mode in various enzymes and the adding synthesis of detergent composition thereof.Authorize people's such as P1ace United States Patent (USP) 4101457 and the United States Patent (USP) 4507219 of authorizing Hughes on March 26th, 1985 on July 18th, 1978 and further disclose some enzymes.The United States Patent (USP) 4261868 of authorizing people such as Hora on April 14th, 1981 discloses enzyme that is used for liquid detergent formula and the method that adds this prescription thereof.The enzyme that is used for washing composition can adopt the whole bag of tricks to be stablized.Authorized on August 17th, 1971 people such as Gedge United States Patent (USP) 3600319 and October in 1986 Venegas on the 29th european patent application 0199405, open and enumerated various enzyme stabilization techniques.The enzyme stabilising system also has description, for example in United States Patent (USP) 3519570.
Enzyme used herein can make it stable by the water-soluble sources that has calcium and/or magnesium ion in final composition, described composition offers enzyme (if only use a kind of cationic words calcium ion generally more effective a little and preferred in this article than magnesium ion) with these ions.Additional stability can by exist various other this area disclosed stablizer, especially borate family and provide.United States Patent (USP) 4537706 referring to Severson.Typical washing composition, especially liquid comprise about 1-30, preferably about 2-20,5-15 more preferably from about, most preferably from about 8-12 mmole calcium ion/rise final product composition having.This can have certain variation according to the amount of enzyme and to the response of calcium or magnesium ion.The content of calcium or magnesium ion should be selected, and make after the complexings such as washing assistant in itself and the composition, lipid acid, always has only minimum quantity and enzyme to meet.Any water-soluble calcium or magnesium salts source be can use, calcium chloride, calcium sulfate, calcium malate, calcium maleate, calcium hydroxide, calcium formiate and lime acetate and corresponding magnesium salts included, but is not limited to as calcium or magnesium ion.Because there are calcium in enzyme slurry and prescription in the water, also have a spot of calcium ion usually in composition, be generally about 0.4 mmole of about 0.05-/liter.In solid detergent composition, prescription can comprise the water-soluble calcium ion source of q.s so that produce described calcium ion amount in the washing liquid.In addition, can satisfy neutral water hardness.
Should be clear and definite, aforesaid calcium and/or magnesium ion content are enough to produce enzyme stability.More calcium and/or magnesium ion can be added in the composition so that additional degrease performance to be provided.Therefore, general recommendations, the composition of this paper should comprise the calcium or the magnesium ion of about 0.05-2% weight, or both water-soluble sources.Certainly, this amount can change according to the amount and the kind of the used enzyme of said composition.
The laundry detergent composition of this paper also can be optionally (but preferred) comprises various other stablizer, especially borate type stablizers.Usually, the consumption of these stablizers in composition is about 0.25-10%, preferably about 0.5-5%, and the boric acid of 0.75-4% weight more preferably from about, or other can form the borate compound (is basic calculation with boric acid) of boric acid in composition.Boric acid is preferred, but other compound, as boron oxide, borax and other alkali metal borate (as, former-, partially-and sodium pyroborate and sodium pentaborate) also suitable.Substituted boracic acid (as phenyl-boron dihydroxide, fourth boric acid and right-bromophenyl boric acid) also can be used for substituting boric acid.The polymkeric substance stain remover
The known any polymkeric substance stain remover of those skilled in the art can optionally be used for the compositions and methods of the invention.The polymkeric substance stain remover is characterised in that, have hydrophilic segment (with surface hydrophilic) and hydrophobic segment (keep adhering on it to be deposited on the hydrophobic fiber and, promptly be used as the anchor of hydrophilic segment) simultaneously by washing and finishing of rinse cycle with hydrophobic fiber such as polyester and nylon.This makes after with detergent-treatment that the spot that occurs is easier and washes in washing step after a while.
The example that can be used for the polymkeric substance stain remover of this paper comprises that the United States Patent (USP) of authorizing Gosselink on January 26th, 1988 authorized the United States Patent (USP) 4968451 that people's such as Nicol United States Patent (USP) disclosed european patent application April 22 in 4721580,1987 was authorized the United States Patent (USP) 4702857 of Gosselink and authorized J.J.Scheibel November 6 nineteen ninety on October 27, in 0219048,1987 on December 28 in 4721580,1976.Commercially available stain remover comprises SOKALAN class material, as the SOKALANHP-22 that obtains from West Germany BASF AG.In addition referring to the United States Patent (USP) 3959230 of authorizing Hays on April 25th, 1976 with authorized the United States Patent (USP) 3893929 of Basadur on July 8th, 1975.The example of this polymkeric substance comprises commercially available material ZELCON (from DuPont) and MILEASE T (from ICI).Other suitable polymers stain remover comprise the United States Patent (USP) 4711730 of authorizing people such as Gosselink on December 8th, 1987 terephthalate polyester, authorized on January 26th, 1988 Gosselink United States Patent (USP) 4721580 the end capped oligomer ester of negatively charged ion and authorized the block polyester of the United States Patent (USP) 4702857 of Gosselink on October 27th, 1987.Preferred polymkeric substance stain remover also comprises the stain remover of the United States Patent (USP) 4877896 of authorizing people such as Maldonado on October 31st, 1989.
If use, stain remover generally accounts for about 0.01-10.0% weight of this paper detergent composition, about usually 0.1-5%, preferably about 0.2-3.0%.Dirt removal/anti redeposition agent
The present composition also can optionally comprise the water-soluble ethoxylated amine with dirt removal/antiredeposition performance.Liquid detergent compositions comprises 0.01-5% usually.
Most preferred dirt removal/anti redeposition agent is the ethoxylation tetracthylene pentamine.The United States Patent (USP) 4597898 that on July 1st, 1986 was authorized VanderMeer has further described representational ethoxylated amine.Preferred another kind of dirt removal/anti redeposition agent is a cation compound, and the Oh on June 27th, 1984 and the european patent application of Grosselink 111965 disclose this.Spendable other dirt removal/anti redeposition agent comprises: ethoxylated amine polymer, June in 1984 disclosed Grosselink on the 27th european patent application 111984 in description is arranged; Amphoteric ion polymer, July in 1984 disclosed Grosselink on the 4th european patent application 112592 in description is arranged; Amine oxide, authorizing on October 22nd, 1985 in the United States Patent (USP) 4548744 of Connor has description.Other dirt removal/anti redeposition agent known in the art also can be used for the present composition.Another kind of preferred anti redeposition agent comprises carboxymethyl cellulose (CMC) material.These materials are well known in the art.Polymeric dispersant
In the present composition, particularly in the presence of zeolite and/or layered silicate washing assistant, can preferably use the polymeric dispersant of content for about 7% weight of about 0.1-.Suitable dispersion agent comprises multi-carboxylate's polymkeric substance and polyoxyethylene glycol, although also can use other dispersion agent known in the art.Although do not want to be subjected to the limitation of any theory, but it is believed that when with other washing assistant (comprising the lower molecular weight polycarboxylate) when being used in combination, polymeric dispersant can improve the overall performance of detergent use washing assistant by crystal growth restraining effect, particulate stain removal peptization and anti-redeposition.
Multi-carboxylate's polymkeric substance can prepare by polymerization or the suitable unsaturated monomer (being preferably sour form) of copolymerization.The unsaturated monomer acid that polymerizable forms suitable multi-carboxylate's polymkeric substance comprises: vinylformic acid, toxilic acid (or maleic anhydride), fumaric acid, methylene-succinic acid, aconic acid, methylfumaric acid, citraconic acid and methylene radical propanedioic acid.In multi-carboxylate's polymkeric substance of the present invention, suitable existence does not contain the monomer segment of carboxylate group, as vinyl methyl ether, vinylbenzene, ethene etc., as long as this segmental content is not more than 40% weight.
But specially suitable multi-carboxylate's polymkeric substance derived from propylene acid.Can be used for this vinylformic acid of the present invention is that polymer based is the water-soluble salt of polymeric acrylic acid.The molecular-weight average of the polymkeric substance of this sour form is 2000-10000, and more preferably 4000-7000 most preferably is 4000-5000.The water-soluble salt of this acrylate copolymer can comprise basic metal, ammonium and substituted ammonium salt etc.This soluble polymer is known material.The application of this polyacrylate in cleaning composition is existing to be disclosed, and for example authorizes in the United States Patent (USP) 3308067 of Diehl on March 7th, 1967.
Vinylformic acid/toxilic acid is the preferred component that based copolymers also can be used as dispersion/anti redeposition agent.These materials comprise the water-soluble salt of vinylformic acid and maleic acid.The molecular-weight average of the multipolymer of this sour form is preferably at 2000-100000, more preferably at 5000-75000, most preferably in the scope of 7000-65000.In this multipolymer, acrylate segment and maleic acid ester segmental ratio are generally about 30: about 1: 1 of 1-, and more preferably about 10: 1-2: in 1 the scope.The water-soluble salt of this vinylformic acid/maleic acid can comprise basic metal, ammonium and substituted ammonium salt etc.This water miscible vinylformic acid/maleic acid is known material, this has among the disclosed EP193360 in December 15 nineteen eighty-two disclosed european patent application № 66915 and on September 3rd, 1986 and describes, and the latter has also described this polymkeric substance that comprises the vinylformic acid hydroxypropyl ester.Other useful dispersion agent comprises toxilic acid/vinylformic acid/vinyl alcohol terpolymer.This material also disclosed in EP193360, comprising 45/45/10 terpolymer of for example toxilic acid/vinylformic acid/vinyl alcohol.
The another kind of polymer materials that can comprise is polyoxyethylene glycol (PEG).PEG has dispersing agent performance and can be used as dirt removal-anti redeposition agent.It is about 100000 that the molecular weight ranges that is used for this purposes is generally about 500-, and preferably about 1000-is about 50000, and most preferably from about 1500-about 10000.
Also can use poly aspartic acid and polyglutamic acid dispersion agent, particularly be used in combination with zeolite builders.The molecular weight of poly aspartic acid dispersion agent (on average) preferred about 10000.Whitening agent
In cleaning composition of the present invention, can add the known in the art any white dyes or other whitening agent that are generally 0.05-1.2% weight.Can be used for commodity white dyes of the present invention and can be divided into several subgroups, include, but is not limited to derivative, pyrazoline, tonka bean camphor, carboxylic acid, inferior first cyanines, the dibenzothiophene-5 of Stilbene, 5-dioxide, pyrroles, 5-and 6-unit ring heterocyclization thing and other mixing whitening agent.The example of these whitening agent is disclosed in John Wiley﹠amp; Son. in the M.Zahradnik work " production of white dyes and application " that publish New York (1982).
The object lesson that can be used for the white dyes of the present composition has been authorized in the United States Patent (USP) 4790856 of Wixon on December 13rd, 1988 and has been assert.These whitening agent comprise, derive from the PHORWHITE series of Verona.Disclosed other whitening agent comprises in this reference: Tinopal UNPA, the Tinopal CBS and the Tinopal SMB that derive from Ciba-geigy; Actic White CC and Actic White CWD available from Italian Hilton-Dayis; 2-(4-styryl-phenyl)-2H-naphthols [1,2-d] triazole; 4,4 '-two (1,2,3-triazoles-2 base)-Stilbene; 4,4 '-two (styryl) biphenyl; And aminocoumarin.The object lesson of these whitening agent comprises: 4-methyl-7-diethyl-aminocoumarin, 1,2-pair (benzimidazolyl-2 radicals-yl)-ethene, 1,3-phenylbenzene-pyrazoline; 2, the two (benzoxazoles of 5--2-yl) thiophene; 2-styryl-naphtho-[1,2-d] oxazole; And 2-(Stilbene-4-yl)-2H-naphtho-[1,2-d] triazole.Authorize the United States Patent (USP) 3646015 of Hamilton in addition referring on February 29th, 1972.The negatively charged ion whitening agent is preferred in this article.Suds suppressor
Can add in the present composition and be used to reduce or suppress the compound that foam forms.In preceding year European washing machine of formula and the what is called " high density was cleaned method " described in United States Patent (USP) 4489455 and 4489574, foam inhibition effect is a particularly important.
A variety of materials all can be used as suds suppressor, and suds suppressor is well-known to those skilled in the art.Referring to for example " Kirk Othmer encyclopedia of chemical technology ", the third edition, the 7th volume, 430-447 page or leaf (John Wiley﹠amp; Son.Inc., 1979).A kind of valuable especially suds suppressor comprises monoester fat carboxylic acid and water-soluble salt thereof.Authorize the United States Patent (USP) 2954347 of WayneSt.John referring to September 27 nineteen sixty.Monoester fat carboxylic acid and water-soluble salt thereof as suds suppressor generally have 10-24 carbon atom, the hydrocarbyl chain of preferred 12-18 carbon atom.Suitable salt comprises an alkali metal salt, as sodium, potassium and lithium salts, and ammonium and alkanol ammonium salt.
Detergent composition of the present invention also can comprise the nonsurfactant suds suppressor.These materials for example comprise: high-molecular weight hydrocarbon, and as the fatty acid ester of paraffin, fatty acid ester (as, fatty acid triglycercide), monovalent alcohol, aliphatic C 18-C 40Ketone (as stearone) etc.Other suds suppressor comprises: N-alkylation aminotriazine, as three-to six-alkyl melamine or two-to four-alkyl diamine chlorotriazine (cyanuryl chloride and two or three moles have the product that the uncle of 1-24 carbon atom or secondary amine, propylene oxide form); And single stearyl phosphate ester salt, as single stearyl alcohol phosphoric acid ester and single stearyl two basic metal (as K, Na and Li) phosphoric acid salt and phosphoric acid ester.Hydrocarbons can use by liquid form as paraffin and halo paraffin.Liquid hydrocarbon is liquid under room temperature and normal atmosphere, and its pour point scope is-40 ℃ to about 50 ℃ approximately, and its minimum boiling point is not less than about 110 ℃ (under normal atmosphere).The known in addition fusing point that can use is preferably lower than about 100 ℃ wax shape hydrocarbon.Hydrocarbons has constituted the preferred suds suppressor that is used for cleaning composition.The hydro carbons suds suppressor, for example authorizing on May 5th, 1981 in people's such as Gando1fo the United States Patent (USP) 4265779 has description.Therefore, this hydrocarbons comprises the saturated or unsaturated hydrocarbons of aliphatic series, alicyclic ring, aromatics and heterocycle of about 12-70 carbon atom.In the discussion to this suds suppressor, used term " paraffin " means the mixture that comprises true paraffin and cyclic hydrocarbon.
Another kind of preferred nonsurfactant suds suppressor comprises silicone suds suppressor.This field comprises uses poly organic silicon oil, as the dispersion liquid of polydimethylsiloxane, poly organic silicon oil or resin or the mixture of emulsion and organopolysiloxane and silica granule, and organopolysiloxane chemisorption or be fused in the silica wherein.Silicone suds suppressor is well known in the art, for example authorize on May 5th, 1981 people such as Gandolfo United States Patent (USP) 4265779 and February 7 nineteen ninety disclosed Starch.M.S. european patent application № 89307851.9 in existing the description.
Other silicone suds suppressor is disclosed in the United States Patent (USP) 3455839, and it relates to by adding a small amount of polydimethylsiloxane fluid to the aqueous solution to eliminate its foamy composition and method.
For example German patent application DOS 2124526 has described the mixture of siloxanes and silanization silica.
Be used for the preferred silicone suds suppressor of this paper, the solvent that is used for external phase is made up of some polyoxyethylene glycol or polyethylene glycol-propylene glycol copolymers or its mixture (preferably) or polypropylene glycol.Main silicone suds suppressor is a branching/crosslinked, and preferred non-linearity.
In order to further specify this point, have that controlled foamy typical liquid laundry detergent composition is optional optionally to comprise about 0.001-1, preferred about 0.01-0.7, the described silicone suds suppressor of 0.05-0.5% weight most preferably from about, comprising: the nonaqueous emulsion of (1) main defoamer, this defoamer is the mixture of following component: (a) organopolysiloxane, (b) silicone compounds of arborescens siloxanes or generation silicone resin, (c) finely divided filler and (d) be used to promote constituents of a mixture (a), (b) and (c) reaction forms the catalyzer of silanol; (2) at least a nonionic siloxane tensio-active agent; (3) polyoxyethylene glycol or polyethylene glycol-propylene glycol copolymers, its water solubility at room temperature be greater than about 2% weight, and do not have polypropylene glycol.In addition, referring to the United States Patent (USP) 4978471 of authorizing Starch December 18 nineteen ninety with authorized the United States Patent (USP) 4983316 of Starch on January 8th, 1991, authorized people's such as people's such as Huber United States Patent (USP) 5288431 and Aizawa United States Patent (USP) 4639489 and 4749740 the 46th row-Di four hurdles, first hurdle the 35th row on February 22nd, 1994.
The silicone suds suppressor of this paper preferably includes the multipolymer of polyoxyethylene glycol and polyethylene/polypropylene glycol, and their molecular-weight average is all less than about 1000, preferably about 100-800.For polyoxyethylene glycol among the present invention or polyethylene glycol-propylene glycol copolymers, their water solubilities at room temperature are preferably greater than about 5% weight greater than about 2% weight.
The preferred solvent of this paper is a molecular-weight average less than about 1000,100-800 more preferably from about, the multipolymer of the most preferably polyoxyethylene glycol of 200-400, and polyethylene glycol-propylene glycol, preferred PPG 200/PEG 300.Polyoxyethylene glycol: the weight ratio of polyethylene glycol-propylene glycol copolymers preferably about 1: 1-1: 10, most preferably 1: 3-1: 6.
It is 4000 that preferred silicone suds suppressor used herein does not contain polypropylene glycol, particularly molecular weight.The segmented copolymer of their also preferred oxygen-free ethene and propylene oxide is as PLURONIL L101.
Can be used for the mixture that other suds suppressor of the present invention comprises secondary alcohol (as 2-alkyl alkanol) and this alcohol and silicone oil, as disclosed siloxanes among United States Patent (USP) 47984075 and the EP150872.Secondary alcohol comprises having C 1-C 16The C of chain 6-C 16Alkyl alcohol.Preferred alcohol is 2-butyl octanol, can derive from Condea, and commodity are called ISOFOL 12.The mixture of secondary alcohol can derive from Enichem, and commodity are called ISALCHEM 123.It is 1 that the mixing suds suppressor comprises weight ratio usually: 5-5: 1 the alcohol and the mixture of siloxanes.
Concerning any detergent composition that is used for automatic washing machine, formed foam should not overflow washing machine.If the use suds suppressor preferably uses with " foam inhibition amount "." foam inhibition amount " is meant that the prescription teacher of said composition can select to be enough to the suds suppressor amount of complete control foam, obtains being used for the low foam detergent for washing clothes of automatic washing machine like this.
The laundry detergent composition of this paper generally comprises the suds suppressor of 0-about 5%.If as giving as security infusion, the amount of mono carboxylic lipid acid and salt thereof is the highest 5% weight that accounts for detergent composition usually.The usage quantity of silicone suds suppressor can the highlyest account for 2.0% weight of cleaning composition, also can use higher amount certainly.This upper limit is decided according to practical situation substantially, main consider to make cost minimum, and when low amount effective control foam.The preferred silicone suds suppressor that uses about 0.01-1%, more preferably from about 0.25-0.5%.These weight percentage used herein comprise all silicas that can be used in combination with organopolysiloxane, and spendable any additives.The usage quantity that single stearyl phosphate ester salt is given as security infusion is generally about 2% weight of about 0.1-of composition.The usage quantity of hydro carbons suds suppressor is generally the 0.01-5.0% weight of composition, although also can use high level.The usage quantity of alcohols suds suppressor is generally the 0.2-3% weight of final product composition having.Dye transfer inhibitor
Laundry detergent composition of the present invention also can comprise one or more can effectively suppress dyestuff is transferred to another fabric from a kind of fabric material in washing process.In general, described dye transfer inhibitor comprise polyvinylpyrrolidonepolymers polymers, polyamine N-oxide, N-vinyl pyrrolidone and N-vinyl imidazole multipolymer, manganese phthalocyanine, peroxidase, and composition thereof.If use, these inhibitor account for the 0.01-10% of composition weight usually, preferred 0.01-5%, most preferably 0.05-2%.
More particularly, being preferred for polyamine N-oxide of the present invention comprises and has formula R-A xThe unit of-P, wherein P can connect polymerizable unit on it for the N-O group, or the N-O group can become the part of this polymerizable unit, or the N-O group can be connected on these two unit; A be a kind of following structure :-NC (O)-,-C (O) O-,-S-,-O-,-N=; X is 0 or 1; And R is aliphatic series, aliphatic, the aromatics of ethoxylation, heterocycle or alicyclic group or its any mixed group, and the nitrogen-atoms of N-O group can connect on it, or the N-O group becomes the part of these groups.For preferred polyamine N-oxide compound, wherein R is a heterocyclic group, as pyridine, pyrroles, imidazoles, tetramethyleneimine, piperidines and derivative thereof.
The N-O group can be represented with following general formula:
Figure A9981408400231
R wherein 1, R 2, R 3Be aliphatic series, aromatics, heterocycle or alicyclic group or its mixed group; X, y and z are 0 or 1; And the nitrogen-atoms of N-O group can be connected on any aforementioned group or become its part.For the amine oxide unit of polyamine N-oxide, its pKa＜10, preferred pKa＜7, more preferably pKa＜6.
As long as formed amine oxide polymers is water miscible and has the dye transfer rejection, so just can use any main polymer chain.The example of suitable polymers main chain be polyethylene base class, polyalkenes base class, polyester, polyethers, polyamide-based, polyimide, polyacrylate(s), and composition thereof.These polymkeric substance comprise random or segmented copolymer, and wherein a kind of monomer is an amine n-oxide, and another kind of monomer is the N-oxide compound.For the polymkeric substance of amine n-oxide, the ratio of amine and amine n-oxide is generally 10: 1-1: 1000000.But in the polyamine oxide compound, the number of amine oxide group can change by suitable copolyreaction or by suitable N-degree of oxidation.Almost can access polyamine oxide compound with any polymerization degree.Usually, the scope of its molecular-weight average is 500-1000000, more preferably 1000-500000, most preferably 5000-100000.This preferred substance can be described as " PVNO ".
The most preferably polyamine N-oxide that is used for this paper cleaning composition is poly-(4-vinylpridine-N-oxide compound), and its molecular-weight average is about 50000, and the ratio of amine and amine n-oxide is 1: 4.
Be preferred for the multipolymer (being called " PVPVI " class) that also has N-vinyl pyrrolidone and N-vinyl imidazole of the present invention.The average molecular weight range of PVPVI is preferably 5000-1000000, more preferably 5000-200000, most preferably (average molecular weight range passes through light scattering determining to 10000-20000, be described in people's such as Barth chemical analysis, Vol 113. " modernism of polymer characterization ", content disclosed in it is incorporated the present invention into as a reference at this).For the PVPVI multipolymer, the mol ratio of N-vinyl imidazole and N-vinyl pyrrolidone is generally 1: 1-0.2: 1, more preferably 0.8: 1-0.3: 1, most preferably 0.6: 1-0.4: 1.These multipolymers can be line style or branching.
The present composition also can use molecular-weight average to be 5000-400000, preferred 5000-200000, the more preferably Polyvinylpyrolidone (PVP) of 5000-50000 (" PVP ").PVP is that detergent applications is known to the skilled; Referring to for example at this EP-A-262897 that incorporates into as a reference and EP-A-256696.It is 500-100000 that the composition that contains PVP also can comprise molecular-weight average, the polyoxyethylene glycol (" PEG ") of preferred 1000-10000.In washing lotion, in the PEG/PVP ratio preferably about 2 of ppm: about 50: 1 of 1-, more preferably from about 3: about 10: 1 of 1-.
The laundry detergent composition of this paper also can optionally comprise certain hydrophilic white dyes of about 0.005-5% weight, and it also has the effect that suppresses dye transfer.If use, the present composition preferably comprises this white dyes of 0.0-1% weight.
Can be used for hydrophilic white dyes of the present invention and have following structural formula: R wherein 1Be selected from anilino, N-2-two-hydroxyethyl and NH-2-hydroxyethyl; R 2Be selected from N-2-pair-hydroxyethyl, N-2-hydroxyethyl-N-methylamino-, morpholino, chlorine and amino; And M is a salt-forming cation, as sodium or potassium.
In the following formula, work as R 1Be anilino, R 2For N-2-two-hydroxyethyl and M are positively charged ion, during as sodium, this whitening agent is 4,4 '-two [(4-anilino-6-(N-2-two-hydroxyethyl)-s-triazine-2-yl) amino]-2,2 '-Stilbene disulfonic acid and its disodium salt.This specific whitening agent can have been bought from Ciba-geigy company, and commodity are called Tinopal-UNPA-GX., Tinopal-UNPA-GX is the hydrophilic white dyes that is preferred for detergent composition of the present invention.
In the following formula, work as R 1Be anilino, R 2For N-2-hydroxyethyl-N-2-methylamino and M are positively charged ion, during as sodium, this whitening agent is 4,4 '-two [(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl) amino]-2,2 '-the Stilbene disulfonic acid disodium salt.This specific whitening agent can have been bought from Ciba-geigy company, and commodity are called Tinopal 5BM-GX.
In the following formula, work as R 1Be anilino, R 2For morpholino and M are positively charged ion, during as sodium, this whitening agent is 4,4 '-two [(4-anilino-6-morpholino-s-triazine-2-yl) amino]-2,2 '-the Stilbene disulfonic acid disodium salt.This specific whitening agent can have been bought from Ciba-geigy company, and commodity are called Tinopal AMS-GX.
Concerning being selected to specific fluorescent whitening agent of the present invention, if use with above-mentioned selected dye transfer inhibitor mixed with polymers, producing especially effectively, dye transfer suppresses effect.By mixing the selected polymkeric substance of use (for example PVNO and/or PVPVI) and this selected white dyes (for example Tinopal-UNPA-GX, Tinopal 5BM-GX and/or Tinopal AMS-GX), can in wash water solution, produce than a kind of obviously dye transfer inhibition preferably effect of using these two kinds of detergent components separately.Though be reluctant bound by theory, it is believed that described whitening agent is based on the following mechanism of action:, therefore can deposit to quickly on these fabrics because they have very high affinity to the fabric in the washings.In washing lotion, the deposition degree of whitening agent on fabric can define with the parameter that is called " consumption coefficient ".Consumption coefficient be commonly defined as the whitening agent that deposits on the fabric a) with washings in initial whitening agent concentration b) ratio.Among the present invention, the whitening agent with higher consumption coefficient is suitable for suppressing dye transfer most.
Certainly, also can consider in the present composition, optionally to use other conventional optical brightener compounds, " brighten " effect to produce conventional fabric, rather than real dye transfer suppress effect.This is conventional and know in detergent formulation.Bleaching compounds-SYNTHETIC OPTICAL WHITNER and bleach-activating agent
The laundry detergent composition of this paper can optionally comprise SYNTHETIC OPTICAL WHITNER or contain SYNTHETIC OPTICAL WHITNER and the bleaching composition of one or more bleach-activating agents.If exist, it is about 30% that the content of SYNTHETIC OPTICAL WHITNER is generally about 1-of detergent composition (specifically being used for laundering of textile fabrics), and more preferably from about 5-about 20%.If exist, it is about 60% that the amount of bleach-activating agent is generally about 0.1-of the bleaching composition that contains SYNTHETIC OPTICAL WHITNER and bleach-activating agent, and more preferably from about 0.5-about 40%.
SYNTHETIC OPTICAL WHITNER used herein can be to be applicable to cleaning fabric, to clean any SYNTHETIC OPTICAL WHITNER in crust or other is known now or known cleaning in the future the is used detergent composition.These materials comprise oxygen bleaching agent and other SYNTHETIC OPTICAL WHITNER.This paper can use perborate bleach, for example Sodium peroxoborate (for example, monohydrate or tetrahydrate).
Another kind of SYNTHETIC OPTICAL WHITNER that can unrestricted use comprises percarboxylic acids SYNTHETIC OPTICAL WHITNER and salt thereof.The suitable example of this class SYNTHETIC OPTICAL WHITNER comprises magnesium salts, 4-nonyl amino-4-oxo Perbutyric Acid and the diperoxy dodecanedioic acid of six hydration monoperphthalic acid magnesium, metachloroperbenzoic acid.These SYNTHETIC OPTICAL WHITNER are disclosed in the United States Patent (USP) 4483781 of the Hartman that authorized on November 20th, 1984, the people's such as Burns of application on June 3rd, 1985 U.S. Patent application 740446, February in 1985 people such as disclosed Banks on the 20th european patent application 0133354 and the people's such as Chung that authorize November 1 nineteen eighty-three United States Patent (USP) 4412934 in.Most preferred SYNTHETIC OPTICAL WHITNER also comprises 6-nonyl amino-6-oxo-mistake oxy hexanoic acid of describing in the United States Patent (USP) 4634651 that licenses to people such as Burns as on January 6th, 1987.
The present invention also can use peroxygen bleach.Suitable peroxy bleaching agent compound comprises yellow soda ash peroxyhydrate and equivalent " percarbonate " SYNTHETIC OPTICAL WHITNER, trisodium phosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide.Also can use persulphate SYNTHETIC OPTICAL WHITNER (for example 0XONE is sold by DuPont merchant).
The present invention also can use the mixture of SYNTHETIC OPTICAL WHITNER.
Peroxygen bleach, perborate, percarbonate etc. preferably are used in combination with bleach-activating agent, can make the peroxy acid that produces corresponding bleach-activating agent in the aqueous solution (promptly at washing process) on the spot.The various indefiniteness examples of activator are disclosed in the United States Patent (USP) 4915854 and United States Patent (USP) 4412934 that licenses to people such as Mao April 10 nineteen ninety.Nonanoly acyloxy benzene sulfonate (NOBS) and tetra acetyl ethylene diamine (TAED) activator are typical activators, also can use their mixture.Typical SYNTHETIC OPTICAL WHITNER of useful herein other and activator are in addition referring to United States Patent (USP) 4634551.
Amido deutero-bleach-activating agent very preferably as shown in the formula:
R 1N (R 5) C (O) R 2C (O) L or R 1C (O) N (R 5) R 2C (O) L is R wherein 1Be to contain 6 the alkyl of having an appointment, R to about 12 carbon atoms 2Be to contain 1 alkylidene group, R to about 6 carbon atoms 5Be H or contain have an appointment 1 alkyl, aryl or alkaryl, and L is any suitable leavings group to about 10 carbon atoms.Leavings group be since cross the hydrolysis negatively charged ion on bleach-activating agent nucleophilic attack and from bleach-activating agent by any group of metathetical.Preferred leavings group is a phenylbenzimidazole sulfonic acid salt.
The preferred embodiment of following formula bleach-activating agent comprise (the amino caproyl of 6-decoyl) oxygen benzene sulfonate of describing in the United States Patent (USP) 4634551 (document is quoted as a reference by this paper), (the amino caproyl of 6-nonanoyl) oxygen benzene sulfonate, (the amino caproyl of 6-caprinoyl) oxygen benzene sulfonate, and composition thereof.
Another kind of bleach-activating agent comprises (this patent is quoted as a reference by this paper) disclosed benzo oxazinyl activator in the people's such as Hodge that authorize October 30 nineteen ninety the United States Patent (USP) 4966723.Another kind of preferred bleach-activating agent comprises the acyl lactam activator, especially acyl caprolactam and acyl group Valerolactim.Lactan activator very preferably comprises benzoyl caprolactam, capryloyl hexanolactam, 3; 5,5-trimethyl acetyl base hexanolactam, nonanoyl hexanolactam; the decanoyl hexanolactam, undecanoyl hexanolactam, benzoyl Valerolactim; the capryloyl Valerolactim, decanoyl Valerolactim, undecanoyl Valerolactim; the nonanoyl Valerolactim; 3,5, the 5-trimethylammonium is acyl group Valerolactim and composition thereof.Referring to the United States Patent (USP) 4545784 of the Sanderson that authorized on October 8th, 1985, this patent is quoted as a reference by this paper, wherein discloses acyl caprolactam, comprises the benzoyl caprolactam in addition, and they are adsorbed in the Sodium peroxoborate.
SYNTHETIC OPTICAL WHITNER except that oxygen bleaching agent also is known in the art and can be used for this paper.A kind of valuable especially non-oxygen bleaching agent comprises the photoactivation SYNTHETIC OPTICAL WHITNER, as sulfonation phthalocyanine phthalocyanine zinc and/or aluminium.License to people's such as Holcombe United States Patent (USP) 4033718 referring on July 5th, 1977.If use, detergent composition contains this class SYNTHETIC OPTICAL WHITNER, especially the Phthalocyanine Zinc sulfonate of the 0.025-1.25% that has an appointment (weight) usually.
If desired, bleaching compounds can utilize manganic compound catalysis.This compounds is a compound known in the art, for example comprises disclosed manganese in the United States Patent (USP) 5246621,5244594,5194416,5114606 and European patent EP 549271A1, EP549272A1, EP544440A2 and EP544490A1-catalyst based.Just practice, but not limited, the composition of this paper and technology can be regulated, so that the active bleaching catalyst at least about a ten million/order of magnitude is provided in containing water lotion, preferably in washing lotion, provide about 0.1-about 700ppm, more preferably from about this class catalyst substance of the about 500ppm of 1-.Static inhibitor
This laundry detergent composition also can comprise the static inhibitor that is described in United States Patent (USP) 4861502.The preferred example of static inhibitor comprises alkylamine-anion surfactant ion pair, as distearyl amine-cumene sulfonate ion pair.If exist, the amount of static inhibitor is about 0.5-20% of detergent composition, preferably about 1-10%, more preferably from about 1-5% weight.
In following examples A, exemplified an embodiment of chelant agglomerate of the present invention:
Embodiment A
Composition % weight
Zeolite 85.00
DTPA 15.00
Amount to 100.0%
Therefore, after so describing the present invention in detail, those skilled in the art obviously can carry out various variations and can not deviate from scope of the present invention, and can not think that the present invention only is confined to the described content of specification sheets.

Claims (10)

1. prepare the method for chelant composite by non-drying process with atomizing, it is characterized in that, may further comprise the steps:
A) transition metal chelator and mineral compound are mixed the formation mixture;
B) agglomeration in water medium of this mixture is formed chelant agglomerate; Then
C) dry this chelant agglomerate.
2. according to the process of claim 1 wherein that described transition metal chelator is selected from the aromatic chelating agent of aminocarboxylate, amino phosphonates do, polyfunctional group replacement, dioxane Che1300 and composition thereof.
3. according to the process of claim 1 wherein that described transition metal chelator is the dioxane Che1300.
4. according to the process of claim 1 wherein that described mineral compound is selected from vitriol, carbonate, silicate, silico-aluminate and composition thereof.
5. according to the method for claim 4, wherein said mineral compound is structural formula M M/n[(AlO 2) m(SiO 2) y] xH 2The aluminosilicate ion exchange material of O, wherein n is the valency of positively charged ion M, and x is the unitary water molecule number of each structure cell, and m and y are the unitary tetrahedron sums of each structure cell, and y/m is 1-100, and wherein M is selected from sodium, potassium, magnesium and calcium.
6. according to the process of claim 1 wherein that described mixing step comprises, described transition metal chelator and mineral compound are mixed also granulation in one or more super mixers and tablets press.
7. according to the process of claim 1 wherein that described agglomeration step comprises, water forms sequestrant-mineral compound pre-composition.
8. according to the process of claim 1 wherein that described transition metal chelator and described mineral compound are with weight ratio scope 10: 90-80: 20 mix mutually.
9. improve one or more the method in laundry detergent composition stability in storage, flowability and the scoopability, it is characterized in that according to the following steps:
(a) provide chelant composite by non-drying process with atomizing, be characterised in that according to the following steps:
(i) transition metal chelator is mixed the formation mixture with mineral compound;
(ii) the agglomeration in water medium of this mixture is formed chelant agglomerate; Then
(iii) dry this chelant agglomerate; Then
(b) this chelant composite is added in the granular laundry detergent material, wherein the weight ratio of chelant composite and granular laundry detergent material is about 0.05: 99.95-2: 98.
10. chelant agglomerate that can be used as compound in the granular laundry detergent, its composition characteristic is:
Transition metal chelator;
Mineral compound; With
Water; This chelant agglomerate forms mixture by transition metal chelator is mixed with mineral compound, with this mixture agglomeration formation chelant agglomerate in water, and this chelant agglomerate of drying and forming then.
CN 99814084 1998-10-05 1999-10-01 Process for delivering chelant agglomerate into detergergent composition for improving its storage stability, flowability and scoopability Pending CN1329660A (en)

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SE374762B (en) * 1968-03-04 1975-03-17 Monsanto Co
DE3120744A1 (en) * 1981-05-25 1982-12-09 Joh. A. Benckiser Gmbh, 6700 Ludwigshafen Non-friable granules based on alkali metal aluminium silicate with good dispersibility in aqueous liquor
JPS59157194A (en) * 1983-02-28 1984-09-06 ライオン株式会社 Manufacture of small bulk density detergent builder granules
GB8918984D0 (en) * 1989-08-21 1989-10-04 Unilever Plc Detergent compositions
ATE121129T1 (en) * 1990-11-14 1995-04-15 Procter & Gamble METHOD FOR PRODUCING OXYGEN BLEACHING SYSTEMS CONTAINING PHOSPHATE-FREE DISHWASHING DETERGENT COMPOSITIONS.
DE4311440A1 (en) * 1993-04-07 1994-10-13 Henkel Kgaa Builder for detergents or cleaners
PT796911E (en) * 1996-03-23 2002-10-31 Procter & Gamble A DETERGENT DRY DETERGENT COMPONENT FOR SPRAY SPRAY CONTAINING A QUELATING AGENT
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