CN1124494A - Secondary (2,3) alkyl sulfate surfactants to coat free-flowing granular detergent compositions - Google Patents

Secondary (2,3) alkyl sulfate surfactants to coat free-flowing granular detergent compositions Download PDF

Info

Publication number
CN1124494A
CN1124494A CN 94192196 CN94192196A CN1124494A CN 1124494 A CN1124494 A CN 1124494A CN 94192196 CN94192196 CN 94192196 CN 94192196 A CN94192196 A CN 94192196A CN 1124494 A CN1124494 A CN 1124494A
Authority
CN
China
Prior art keywords
alkyl
composition
detergent
acid
sulphate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN 94192196
Other languages
Chinese (zh)
Inventor
P·K·文森
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Publication of CN1124494A publication Critical patent/CN1124494A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules

Abstract

The present invention relates to granular detergent compositions which have a tendency to clump or cake are coated with finely-divided secondary (2,3) alkyl sulfate surfactant to improve free-flow properties. Thus, a typical granular laundry detergent comprising one or more conventional detersive surfactants, a builder, such as zeolite or layered silicate, and various detersive adjuncts such as enzymes, bleaches, and the like, is coated with a fine dust of dry secondary (2,3) alkyl sulfate. The resulting coated granules are especially useful as fabric laundry compositions.

Description

Free flowing granule detergent composition with secondary (2,3) alkyl sulfate surfactant coating
The field of the invention
The present invention relates to be coated with the detergent particles that reduces bonding and strengthen free-flowing property with secondary (2,3) alkyl sulfate surfactant particle.
Background of invention
The most conventional detergent composition contains the mixture of various detersive surfactants, in order that from various dirts of surface removal and spot.For example various anion surfactants, especially alkylbenzene sulfonate is used to remove dirt particles, and various nonionogenic tensides such as alkylethoxylate and alkyl phenol ethoxylate are used to remove the unctuousness dirt.Found to comprise secondary alkyl sulfate at the class tensio-active agent that needs carry out being limited to use in the various compositions of emulsifying effect.The random mixture of pasty state of the alkane of normally Sulfated straight chain of commercially available conventional secondary alkyl sulfate and/or part collateralization.This material can not be widely used in the detergent for washing clothes, because they can not provide than alkylbenzene sulfonate benefit more particularly.
Granular laundry detergent is configured to " concentrating " type now, and this provides great benefit for human consumer and manufacturing commercial city.For consumers, less being easy to of concentrated product packing material being housed uses and deposits.For manufacturers, unit carrying cost, trucking costs and Packing Fee are lowered.
The difficulty that himself is arranged about the preparation of acceptable concentrated granulated detergent.In general concentrated prescription, alleged 'inertia' component is to be excluded as sodium sulfate, yet this component but plays the deliquescent effect of enhancing detergent particles; Therefore usually there is solubility problem in the concentrated type washing composition.In addition, conventional low density detergent granule normally prepares with spray drying process, and what obtain like this is very to be easy to dissolved vesicular detergent particles in the laundry aqueous solution.Opposite concentrated prescription generally contains the high density detergent granules of basic atresia, and it is not easy to dissolving.In a word, because the concentrated type granulated detergent generally comprises the particle that contains high-load decontamination component and almost do not have solubilizing agent, and, because this particle has a mind to be made as high bulk density, thus net result exist with use in the relevant basic problem of solvability.
In addition, the spray-dried detergent particle for routine exists and " bonding " or " reunion " relevant problem with newer concentrated granular both.Developed various alleged free-flow agents, but the crisp granulated detergent with free-flowing property is still a challenge for the prescription teacher.
Have now found that a class secondary alkyl sulfate of special subordinate, this paper refers to the second month in a season (2,3) alkyl-sulphate (＂ SAS ＂), considerable benefit is provided for the prescription teacher and the user of detergent composition.Commercially available secondary alkyl (2,3) vitriol is the granular solids of doing, and it is dissolved in the water-bearing media than the primary alkyl sulphates corresponding with them is easier.In view of the above, use secondary alkyl (2, the 3) vitriol of particle form to coat granular laundry detergent, to strengthen its flowability.Except above-mentioned, now measured (2,3) alkyl-sulphate second month in a season degradable all under aerobic and anaerobism, this helps their decomposition in environment.
Background technology
The whole bag of tricks of suitable preparation high density granular and equipment open in the literature and some be used in the washing composition technology.Referring to, for example: U.S.5,133,924; EP-A-367,339; EP-A-390,251; EP-A-340,013; EP-A-327,963; EP-A-337,330; EP-B-229,671; EP-B2-191,396; JP-A-6,106,990; EP-A-342,043; GB-B-2,221,695; EP-B-240,356; EP-B-242,138; EP-A-242,141; U.S.4,846,409; EP-A-420,317; U.S.2,306,698; EP-A-264,049; U.S.4,238,199; DE4,021,476.
The detergent composition that contains various " second month in a season " and branched-chain alkyl vitriol is disclosed in the various patents, referring to: U.S.2,900,346, people such as Fowkes, August 18 nineteen fifty-nine; U.S.3,468,805, people such as Grifo, on September 23rd, 1969; U.S.3,480,556, people such as DeWitt, on November 25th, 1969; U.S.3,681,424, people such as Bloch, on August 1st, 1972, U.S.4,052,342, people such as Fernley, on October 4th, 1977; U.S.4,079,020, people such as Mills, on March 14th, 1978; U.S.4,235,752, people such as Rossall, on November 25th, 1980; U.S.4,529,541, people such as Wilms, on July 16th, 1985; U.S.4,614,612, people such as Reilly, on September 30th, 1986; U.S.4,880,569, people such as Leng, on November 14th, 1989; U.S.5,075,041, Lutz, on December 24th, 1991; U.K.818,367, Bataafsche Petroleum, August 12 nineteen fifty-nine; U.K.1,585,030, Shell, on February 18th, 1981; GB2,179,054A, people such as Leng, on February 25th, 1987 (referring to GB2,155,031).What the United States Patent (USP) of authorizing on February 8th, 1,966 3,234,258 of Morris related to is the sulfation alpha-olefin, use be H2SO4, alkene reactant and lower boiling nonionic organic crystal medium.
The present invention's general introduction
The present invention relates to use thin (general about 0.01 to about 20 microns) the granulous second month in a season (2,3) alkyl sulfate surfactant as the coating of detergent particles to reduce described particulate cohesiveness, the free-flowing property that is improved thus.
The invention provides granular detergent composition; it comprises and contains one or more detersive surfactants and annexing ingredient particle optionally; (2,3) the alkyl sulfate surfactant second month in a season that described particle is done basically, finely powdered (general about 0.01 to about 20 microns as mentioned above) coats.In preferred embodiments, the present composition also comprises one or more described annexing ingredients, as washing auxiliary detergent, detergency enzymes, SYNTHETIC OPTICAL WHITNER, fabric softener or the like.
The present invention also comprises the method for preparing free-pouring granulated detergent, it may further comprise the steps: the mixture that (a) prepares one or more detersive surfactants and selectivity annexing ingredient is to obtain granular detergent composition (i.e. " basic granules "), its mean particle size about 400 to about 1,200 micrometer range; (b) composition grain of the abundant encapsulation steps of (2,3) the alkyl sulfate surfactant exsiccant second month in a season (a) of usefulness finely powdered, (i.e. " coatedparticles ").
All herein percentage ratio, ratio and ratio are by weight calculation except as otherwise noted.All documents of quoting are as this paper reference.
Detailed description of the present invention
Secondary (2,3) alkyl sulfate surfactant
Be convenient prescription teacher, hereinafter confirm and illustrated the difference of employed in this article sulfated surfactants and other conventional alkyl sulfate surfactant.
Conventional primary alkyl sulphates tensio-active agent has general formula:
ROSO 3 -M +Wherein R is generally the C of straight chain 10～C 20Alkyl, M are water-soluble cationic.Chain primary alkyl sulfate tensio-active agent (being side chain " PAS ") with 10～20 carbon atoms also is known; Referring to for example: the european patent application 439,316 of people's such as Smith application in 21 days January in 1991.
Conventional secondary alkyl sulfate surfactant is those materials with sulfate radical part of the irregular distribution of alkyl " skeleton " along molecule.These materials can be used following structrual description:
CH 3(CH 2) n(CHOSO 3 -M +) (CH 2) mCH 3Wherein m and n are 2 or greater than 2 integer, and the summation of m+n is general about 9 to 17, and M is a water-soluble cationic.
With above contrast, the selected herein second month in a season, (2,3) alkyl sulfate surfactant comprised the material with formula A and B structure:
(A) CH 3(CH 2) x(CHOSO 3 -M +) CH 3With
(B) CH 3(CH 2) y(CHOSO 3 -M +) CH 2CH 3They are respectively 2-vitriol and 3-vitriol.Can use the mixture of 2-vitriol and 3-vitriol herein.In formula A and B, x and (y+1) be respectively to be at least about 6 integer, and can be about 7 to about 20 scopes, preferred about 10 to about 16 scopes.M is a positively charged ion, as basic metal, ammonium, alkanol ammonium, alkaline-earth metal etc.M is generally sodium water-soluble to prepare (2,3) alkyl-sulphate, but ethanol ammonium, di-alcohol ammonium, triethanol ammonium, potassium, ammonium etc. also can use.C 10～C 20Secondary (2,3) alkyl-sulphate can suit to use in this article this C 14～C 18Compound is preferred in the laundry cleaning operation.
The physical/chemical of having determined the alkyl sulfate surfactant of aforementioned type by the present invention has non-foresight difference each other aspect several, this prescription teacher for granular detergent composition is important.For example, primary alkyl sulphates interacts with metallic cation such as calcium and magnesium unfriendly, even can be precipitated by it.Therefore, water hardness to the comparison of the negative interaction of primary alkyl sulphates herein the second month in a season (2,3) alkyl-sulphate the negative interaction degree big.In view of the above, have now found that the second month in a season (2,3) alkyl-sulphate is in the presence of calcium ion and under the high water hardness condition or to use down at alleged " low help wash " environment (environment that produces when using nonphosphate builders) be preferred.
In addition, the solubleness of primary alkyl sulphates is good not as the solvability of secondary (2,3) alkyl-sulphate.Therefore, have now found that with secondary (2,3) alkyl-sulphate than simpler and more effective with primary alkyl sulphates preparation and coating high active surfactant particle.
About random secondary alkyl sulfate (being that sulfate groups is at for example locational secondary alkyl sulfate such as 4,5,6,7 secondary carbon(atom)s such as grade), it is the solid of viscosity that this material tends to, or more generally is paste.Therefore, this random alkyl-sulphate can not provide the technological advantage that brings with the solid second month in a season (2,3) alkyl-sulphate when by method preparation of the present invention and coating detergent particles.In addition, the second month in a season herein, (2,3) alkyl-sulphate had whipability preferably than corresponding random mixture.This random secondary alkyl sulfate of preferably secondary (2,3) alkyl-sulphate essentially no (promptly contain and be lower than approximately 20%, more preferably be lower than approximately 10%, most preferably be lower than about 5%).
The second month in a season (2 herein, 3) alkyl sulfate surfactant is about under the fabric washing operational circumstances than the another kind of advantage of other position or " random " alkyl-sulphate isomer, by the said second month in a season (2,3) alkyl-sulphate for the benefit of improving that soil redeposition provided.Detergent for washing clothes from the fabric that is washed remove dirt and with dirt be suspended in the laundry aqueous solution, this person of being to use crowd knows.Yet a part of dirt can deposit on the fabric again, and this is that the detergent formulation teacher is known.Therefore some dirts may take place to distribute and deposits on the fabrics all in the loaded article that is washed.Certainly this is undesirable, and this can cause known fabric " change ash " phenomenon.(make the simple experiment of deposit properties with any laundry detergent formulations of giving, clean white " spike " cloth can mix with the fabric of band dirt to be washed again.In the terminal of laundry operations, by the technology observer with photometric determination or with the naked eye estimate the degree that this white spike cloth departs from its initial whiteness.It is good more that the whiteness of spike cloth keeps, and soil redeposition does not take place more.)
As measuring, determined that now secondary (2,3) alkyl-sulphate has significant advantage at the soil redeposition aspect of performance than other position secondary alkyl sulfate isomer in detergent for washing clothes by aforesaid cloth tracing method.Therefore the choice of practice second month in a season (2, the 3) alkyl sulfate surfactant according to the present invention preferably wherein is substantially free of the secondary isomer of other position, unexpectedly helps to solve the soil redeposition problem with this method of understanding never.
Be noted that the second month in a season used among the present invention (2,3) alkyl-sulphate obviously is being different from secondary alkene sulfonate (people's such as Klisch United States Patent (USP) 4,064,076 for example aspect some key property, 12/20/77), such secondary sulfonate is not place, center of the present invention in view of the above.
Preparing the second month in a season used herein (2,3) alkyl-sulphate can be by with H 2SO 4Add in the alkene and carry out.The United States Patent (USP) that uses alpha-olefin and the general building-up reactions of vitriolic to be disclosed in Morris was authorized in the United States Patent (USP) 5,075,041 of Lutz on December 24th, 3,234,258 or 1991.This building-up reactions is carried out in solvent, obtains (2,3) the alkyl-sulphate second month in a season through cooling, and the product that obtains is removed unreacted matters, random sulfation material, not Sulfated by product such as C when making with extra care 10Or more when high-grade alcohol, secondary alkene sulfonate etc., be generally the 2-sulfation of 90+% purity and the mixture of 3-sulfation material (generally having about 10% sodium sulfate), and be the inviscid transparent crystallization of white polity.Also can exist some 2, the 3-dithionate, but the common no more than second month in a season of its content (2,3) alkyl-sulphate mixture 5%.This material can have been bought by " DAN " trade(brand)name, for example " DAN 200 " that can buy from Shell Oil company.
Secondary (2,3) alkyl sulfate surfactant of solvability " crystallization " that be enhanced if desired, prescription Shi Keneng wishes to use this surfactant mixtures with mixinglength alkyl chain.Like this, has C 12～C 18The mixture of alkyl chain is to that is to say all be C than alkyl chain aspect solvability 16(2,3) the alkyl-sulphate second month in a season good.By to secondary (2,3) add other tensio-active agent such as alkylethoxylate or other nonionogenic tenside or in the alkyl-sulphate with reducing the second month in a season (2,3) any other material of alkyl-sulphate degree of crystallinity also can increase the solvability of (2,3) the alkyl-sulphate second month in a season.The material of this interference degree of crystallinity generally its content be this second month in a season (2,3) alkyl-sulphate 20% or be effective when lower.
If desired, secondary (2,3) alkyl-sulphate is selectively further removed unwanted sodium sulfate by refining.Can make the sodium sulphate content in secondary (2, the 3) alkyl-sulphate of the reduction that ins all sorts of ways.For example, when in alkene, adding H 2SO 4After, before the second month in a season of sour form, (2,3) alkyl-sulphate was neutralized, remove unreacted H carefully 2SO 4In another approach, (2,3) the alkyl-sulphate water second month in a season that will contain the sodium-salt form of sodium sulfate is near or below the second month in a season in temperature under the Krafft temperature of (2,3) sodium alkyl sulfate and carries out drip washing.This will remove Na 2SO 4And only small loss required by the purified second month in a season (2,3) sodium alkyl sulfate.Certainly these two kinds of steps all can be used, and first kind is step before the neutralization, and second kind is neutralization back step.
Term used herein " Krafft temperature " is a kind of technical term, and it is that worker in the tensio-active agent scientific domain is known.The Krafft temperature is described in the ＂ Principles of Solution and Solubility ＂ article by K.Shinoda, with Paul Becher cooperation translation, is published 160-161 page or leaf in 1978 by Marcel Dekker Inc..Explanation in a capsule be tensio-active agent before rising to this point with temperature, promptly reach before the Krafft temperature, its solubleness increase in water is quite slow, and under the Krafft temperature, solubility table reveals rapid fast rise.When temperature was higher than about 4 ℃ of Krafft temperature, almost any composition solution all became homogeneous phase.General any tensio-active agent of giving type is as herein (2,3) the alkyl-sulphate second month in a season, and it contains anionic hydrophilic sulfate group and hydrophobic alkyl, and its Krafft temperature will be with the hydrocarbyl chain length variations.This be since the change of tensio-active agent solubleness in water along with the tensio-active agent hydrophobic part changes.
In the invention process, the prescription teacher can not be higher than in temperature and optionally washes (2, the 3) alkyl sulfate surfactant second month in a season that is polluted by sodium sulfate under the Krafft temperature with water, particularly for the second month in a season (2 that is washed, 3) sodium alkyl sulfate preferably carries out being lower than under the Krafft temperature.This makes sodium sulfate be washed water dissolution and washing water are removed together, keeps making the second month in a season (2,3) alkyl-sulphate to be lost to amount minimum in the washing water simultaneously.
The second month in a season in the present invention, (2,3) alkyl sulfate surfactant comprised under the situation of mixinglength alkyl chain, will recognize that the Krafft temperature is not a single point, but be represented as " Krafft scope ".This situation is that the technician in tensio-active agent/measured in solution sciemtifec and technical sphere is known.For this second month in a season (2,3) alkylsurfuric acid salt mixture, in any case, preferably the removal of sodium sulfate component is optionally operated in and be lower than under the Krafft range temperature, preferably be lower than under the Krafft temperature of tensio-active agent of the short chain that exists in this mixture and carry out, because this is avoided secondary (2,3) alkyl-sulphate too to be lost in the washing soln.For example for C 16Secondary alkyl (2,3) sodium sulfate tensio-active agent preferably being lower than about 30 ℃ of temperature, carries out washing operation under about 20 ℃.Certainly, Krafft temperature and this preferred wash temperature can change along with the cationic character relevant with secondary (2,3) alkyl-sulphate.
This washing process can be interrupted and carries out, promptly by will wet or the exsiccant second month in a season (2,3) alkyl-sulphate be suspended in the enough water to obtain 10～50% solids, generally be at least 10 minutes (for C in about 22 ℃ of following mixing times 16Secondary (2,3) alkyl-sulphate), then pressure filtration.In preferred embodiments, slurries will contain a little less than about 35% solid, and this is because such slurries are runny and easy stirring in washing process.
Another advantage is the content that this washing process has also reduced the organic pollutant that comprises above-mentioned random secondary alkyl sulfate.
Secondary (2,3) alkyl-sulphate is used for the inventive method with the form as following disclosed particle or composite grain.
Composite grain
Except including only the purified second month in a season (2,3) outside the particle of alkyl-sulphate, be substantially devoid of the second month in a season (2 of materials such as above-described unreacted alcohol, 3) alkyl-sulphate also has fabulous unrestricted flow character, this makes the prescription teacher prepare the detergent particles of high reactivity content, it comprises (2,3) alkyl-sulphate and the mixture of one or more cosurfactants second month in a season.This " high reactivity content " particle can comprise 35% (weight) and high-content more, preferred 50% and high-content more, most preferably 90% and the more high-load second month in a season (2,3) alkyl sulfate surfactant and the compound particles of cosurfactant.This mixture that uses in described particle generally comprises at least about 40% (weight), more preferably at least about (2, the 3) alkyl-sulphate and comprise cosurfactant or the surplus thing of the mixture of the cosurfactant second month in a season of 50% (weight).
In addition, have now found that the second month in a season (2 herein, 3) alkyl-sulphate (SAS) obtains blended SAS/PFAS/AE/AS particle with the mixture fusion and the agglomeration of polyhydroxy fatty acid amide cosurfactant (PFAS), alkylethoxylate cosurfactant (AE) and primary alkyl sulphates cosurfactant (AS), and its solubleness in cold water greatly and is significantly improved as a result.Bound by theory not, obviously the increase of solubleness is because the destruction of SAS degree of crystallinity.No matter what reason, the solvability of improvement has very big benefit under cold water condition (for example temperature at 5 ℃ to about 30 ℃ of scopes) (having problem in the dissolution rate of detergent particles in wash water solution under this condition).Certainly, may be debatable concentrate now or during closely knit detergent particles, the solvability of resulting improvement herein also has very big benefit when the preparation solvability.
The prescription teacher will recognize that for some cosurfactant total solubleness of blended high-activity particle may slightly weaken, especially in cold water.In this case, can mix various solubilizing agents in particle, general content is being in particulate 5%～20% (weight) scope.For example, any high soluble substance is used for this purpose, harmless inorganic salt are to use always as sodium sulfate, sodium bicarbonate etc.
Composite grain herein can be used as basic granules of the present invention or coatedparticles, perhaps simultaneously as the two use.This blended particle for example can comprise: secondary (2,3) alkyl-sulphate and uncle C 10～C 18Alkyl-sulphate; Secondary (2,3) alkyl-sulphate and polyhydroxy fatty acid amide surfactant in greater detail hereinafter; Secondary (2,3) alkyl-sulphate and alkyl ethoxy sulfate; Secondary (2,3) alkyl-sulphate and alkyl ethoxy carboxylate; Secondary (2,3) alkyl-sulphate and primary alkyl sulphates and polyhydroxy fatty acid amide; Secondary (2,3) alkyl-sulphate and alkyl ethoxy sulfate and polyhydroxy fatty acid amide; Secondary (2,3) alkyl-sulphate and primary alkyl sulphates and alkyl ethoxy sulfate and polyhydroxy fatty acid amide; Secondary (2,3) alkyl-sulphate and α-sulfonated fatty acid methyl ester; Secondary (2,3) alkyl-sulphate and C 10～C 18Alkylpolyglycosides; And secondary (2,3) alkyl-sulphate and α-sulfonated fatty acid methyl ester and polyhydroxy fatty acid amide.Also can prepare comprise the second month in a season (2,3) alkyl-sulphate with conventional C 10～C 18The particle of soap.More than be not the limitative examples of this composite grain, the prescription teacher in present technique field also expects other example easily.For coating purpose herein, preferably use the independent second month in a season of (2,3) alkyl-sulphate, promptly there is not cosurfactant.C 10～C 18Alkylbenzene sulfonate (LAS) can be used in the basic granules of this paper, but preferred said composition is substantially devoid of LAS.Really, an advantage of the present invention has just provided the detergent for washing clothes that does not conform to LAS.
Particulate forms
In general, the particle of (2,3) the alkyl sulfate surfactant second month in a season that comprises used herein can prepare with various known methods.For example can form particle by agglomeration, wherein solid (comprising (2,3) the alkyl-sulphate second month in a season) pushes/piles up and stick together with binding agent by mechanically mixing.The suitable equipment of nodulizing comprises dry powder blend device, thermopnore and turbilizers, can be from Lodige, and Eric, Bepex and Aeromatic manufacturers have bought.
In another embodiment, particle can form by extruding.In the method, polity passes through with relatively high pressure and high-energy charging as secondary (2,3) alkyl-sulphate, and the powder of this damping of pumping is pressed together by the aperture on the template.This method has obtained bar-shaped particle, and it can be ground into required granularity arbitrarily.Equipment comprises axially or the radial extrusion machine, as can be from Fuji, and those that Bepex and Teledyne/Readco have bought.
In another embodiment, particle can form by granulation.In the method, the liquid mixture that contains required component (being that a kind of in them is secondary (2,3) alkyl sulfate particles) under high pressure is pumped and is sprayed in the freezing air.When drop cooled off, they became more firm, have so just formed particle.This solidification be owing to hot-melt adhesive transfers the solid phase transformation to or free-water is converted into the reason of the phase transformation that crystal water produces by some hydratable materials in the primary liquid mixture.
In another embodiment, particle can form by compacting.This method is similar to the compressing tablet manufacturing process, and wherein solid (promptly secondary (2,3) alkyl sulfate particles) is by being pressed together powder being pressed into mould/moulded product on the roller or on the flat board.
In another embodiment, particle can form by fusion/solidification.In the method, by with the second month in a season (2,3) alkyl-sulphate with arbitrarily required additional ingredients fusion, and make this melt cooling, for example in a mould or, and form particle with the form cooling of drop.
Alternative integrity and the intensity of using tackiness agent with enhanced granule in above method.Independent water is a kind of effective tackiness agent of secondary (2,3) alkyl-sulphate, because it can dissolve some second month in a season (2,3) alkyl-sulphates so that adhesive function to be provided.Other tackiness agent comprises, for example starch, polyacrylic ester, carboxymethyl cellulose or the like.Tackiness agent is known in granulation process.If you are using, the general usage quantity of tackiness agent is a final particulate 0.1%～5% (weight).
If desired, additive, but as hydration and salt non-hydrated, crystalline and vitreous solid, various decontamination component such as zeolite, or the like can be incorporated in the particle.If desired, this additive generally accounts for about 20% (weight) of particulate at the most.
According to prescription teacher's needs, the particle for preparing by preceding method can then be dried or cool off to regulate its intensity, physicals and final moisture content.
Comprise the single second month in a season (2; 3) alkyl-sulphate; or selectivity but very do not preferably include the second month in a season (2; 3) a kind of preparation scheme of the particulate of the mixture of alkyl sulfate surfactant and cosurfactant comprised the second month in a season (2; 3) alkyl-sulphate is optionally with one or more fused cosurfactant fusions, and the already solidified melt that obtains made the particle or the bead of any desired particle size.Be the mixing tank of OSTER for example, or be that WILEY grinds machine and can obtain required granularity with large-scale stone roller machine such as commercially available trade mark with mixing tank such as market ATTACH LABEL.
In another program, comprise that the melt of blended tensio-active agent forms drop by nozzle spray, when being cooled, obtained the particle of desired particle size.
In another program, the garden dish that can use rotation comprises (2,3) alkyl-sulphate and the melt drop of the required cosurfactant arbitrarily second month in a season with formation.This drop then also can be by suitable screen cloth to obtain the particle of any desired particle size by cooling curing.In another program, can use prilling tower to obtain the having particle that granularity distributes in the mean particle size range of being given.
In another program, the homogeneous melt of secondary (2,3) alkyl-sulphate and cosurfactant is cured and pulverizes and makes particle.Can use high-energy crushing operation such as hammering, rodding and ball milling.In a different scheme, can use the low-energy comminution operation, as carry out the grid filter by sieve with any required aperture.
When coating herein the final detergent particles of 400 to 1200 microns sizes with secondary alkyl sulfate, will be with the secondary alkyl sulfate of superfine size range, generally about 0.01 to about 5 microns.In all cases, the equal available standards sieve of size range is herein determined.
Densification equipment
Can in all sorts of ways and equipment with the preparation according to granular detergent composition of the present invention.In implementing, the common commercial of this area use spray-drying tower to produce the granular laundry detergent that bulk density is lower than about 550 grams per liters.Therefore conventional spraying drying can be used as the general approach of this paper.Teacher of the prescription can not adopt spray-drying process by using commercial commercially available mixing, density and granulating equipment in addition.Below be that the indefiniteness that is suitable for this equipment used herein is described.
In the methods of the invention, can use high-speed mixer/densifier.For example, the market ATTACH LABEL is the equipment of ＂ Lodige CB30 ＂ Recycler, and it comprises an attitude round shape mixing drum, and it has center rotating shaft, and mixing/cutting blade is housed on this axle.In use, in the component adding cylinder with detergent composition, axle/blade part rotates thoroughly to mix/the densification effect with the speed of 100～2500rpm scope.Other this equipment comprises that the market ATTACH LABEL is that ＂ Shugi Granulator ＂ and trade mark are the equipment of ＂ Drais K-TTP 80 ＂.
According to required densification effect and/or nodulizing degree, can comprise the procedure of processing of further densification effect.Can use the equipment of market ATTACH LABEL as ＂ LodigeKM300 Mixer ＂, it is that the people knows altogether with ＂ Lodige Ploughshare ＂ also.This equipment is generally operated under 40～160rpm.Other useful device comprises that commercially available trade mark is the equipment of ＂ Drais K-T 160 ＂.
In another program, granulation process can use fluidized bed for solid mixing to carry out.In the method, the various components in the final composition are blended in the aqueous slurry, and spray in the fluidized-bed that contains (2,3) the alkyl sulfate particles second month in a season, to obtain final detergent particles.In another program, slurry can be sprayed in the fluidized-bed of zeolite or layered silicate particle, perhaps sprays into the second month in a season in the mixture of (2,3) alkyl sulfate particles and zeolite and/or layered silicate particle.In this method, the first step alternative comprises " Lodige CB30 " or " Flexomix 160 " mixed slurry that use has been bought from Shugi.In these methods, can use fluidized-bed or the moving-bed equipment of commercially available trade mark for " Escher Wyss ".
The granulating equipment of other type used herein comprises the equipment in the United States Patent (USP) 2,306,898,1942,12,29 that is disclosed in G.L.Heller.
The densification operational condition
Should be appreciated that distinct advantages provided by the invention is that the particle properties of (2,3) the alkyl-sulphate institute tool second month in a season makes the prescription teacher can go to select multiple production unit and operational condition to prepare required high-density, high-dissolvability, free flowing detergent particle.
In a scheme, the composition that can prepare this paper by the combination of following steps: these steps comprise the spraying drying step, follow mixing/densification step, carry out encapsulation steps then, wherein detergent particles be with the fine grain second month in a season (2,3) alkyl-sulphate coat.In this step, the hydrous slurry with the various thermostability components that exist in final detergent composition forms single-size down by spray-drying tower, use routine techniques for about 175 ℃ to about 225 ℃ in temperature.Then the particle that obtains is mixed in rotation or spiral type mixing machine/densifier with secondary (2,3) alkyl sulfate particles, under operating speed 500～1500rpm, the residence time was generally 1～5 minute, to obtain the densification particle.The improvement of this method is that heat-labile component such as detergency enzymes and bleach-activating agent are joined in the composition in mixing machine/densifier equipment.
In another program, particle is to be produced with densification by two mixing machines of operation in order and densifier machine.For example required composition component is mixed and by the residence time be 0.1 to 1.0 minute Lodige mixing machine, be second Lodige mixing machine of 1 minute to 5 minutes then by the residence time.
In another program, the hydrous slurry (being generally 80% solids content) that will contain required recipe ingredient sprays into the second month in a season in the fluidized-bed of (2,3) alkyl sulfate particles (general granularity is 50～200 microns).The particle that obtains can be further by passing through Lodige equipment as mentioned above by densification.
Last encapsulation steps
How to prepare basic detergent particles or blended basic granules no matter make; the final step of all methods all comprises with secondary (2; 3) alkyl-sulphate fine powder; perhaps in not too preferred scheme; the mixing fine powders of (2,3) alkyl sulfate surfactant and cosurfactant coats described basic granules with the aforesaid second month in a season.This be near the end of any above-mentioned mixing step by with second month in a season (2,3) alkyl-sulphate fine powder add greatly in the detergent particles and simply finish.General fine powder and proportion of particles are in about 1: 25 to about 1: 5 scope.This guarantees to make all larger particles fully to be coated by secondary (2,3) alkyl-sulphate fine particle.
Annexing ingredient
Except second month in a season of coating layer outside (2, the 3) alkyl-sulphate, detergent composition particle herein optionally but generally comprises various other soil release characteristics components and increases the annexing ingredient of aesthetic feeling.The non-limiting example of these components is as follows.
Tensio-active agent---as mentioned above, the present composition can contain tensio-active agents such as various negatively charged ion, nonionic, zwitter-ion.The general amount of this additional surfactant is about 5% to about 35% of a composition.It should be noted that said composition can contain the second month in a season (2,3) alkyl-sulphate as the main detersive surfactant in basic granules and the coatedparticles.Other selective meter's surface-active agent also can be used as the main tensio-active agent in the detergent particles that is coated by secondary (2,3) alkyl-sulphate.
The unrestricted example of selective meter's surface-active agent used herein comprises conventional C 11～C 18Alkylbenzene sulfonate, C 10～C 18Uncle and random alkyl-sulphate, C 10～C 18Alkyl alkoxy sulfate (especially EO 1～5 ethoxy sulfate), C 10～C 18Alkyl alkoxy carboxylate salt (especially EO 1～5 ethoxy carboxylate), C 10～C 18The poly-glycosides of alkylpolyglycosides and its corresponding sulfation, C 12～C 18α-sulfonated fatty acid ester, C 12～C 18Alkyl and alkylphenol based alkoxylation thing (especially ethoxylate and blended oxyethyl group/propoxylated glycerine), C 12～C 18Trimethyl-glycine and sultaine (＂ sultaines ＂), C 10～C 18Amine oxide or the like.Other conventional useful tensio-active agent is listed in the standard textbook.
Especially in the present invention the special additional ionic surfactant pack of a useful class is drawn together the polyhydroxy fatty acid amide of following formula:
Figure A9419219600191
R wherein 1Be H, C 1～C 8Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or its mixture, preferred C 1～C 4Alkyl, C more preferably 1Or C 2Alkyl, C most preferably 1Alkyl (being methyl); R 2Be C 5～C 32Hydrocarbyl portion, preferred straight chain C 7～C 19Alkyl or alkenyl, straight chain C more preferably 9～C 17Alkyl or alkenyl, most preferably straight chain C 11～C 19Alkyl or alkenyl or its mixture; Z directly is connected in polyhydroxy alkyl part on the straight-chain alkyl chain or its ethoxylated derivative (preferred ethoxylation or propoxylation) for having at least 2 hydroxyls (in the situation of Glycerose) or at least 3 hydroxyls (in the situation of other reducing sugar).Z is preferably derived from the reducing sugar in the reductive amination reaction; More preferably Z is a glycosyl part.Suitable reducing sugar comprises glucose, fructose, maltose, lactose, semi-lactosi, seminose and wood sugar and Glycerose.High glucose maize treacle, high-fructose corn syrup and high malt sugar maize treacle and above listed single sugar can be used, the mixture of sugared composition Z can be obtained by these maize treacle as raw material.Will be appreciated that the meaning of not getting rid of other suitable raw material.Z is preferably selected from-CH 2-(CHOH) n-CH 2OH ,-CH (CH 2OH)-(CHOH) N-1CH 2OH ,-CH 2(CHOH) 2(CHOR 1) (CHOH)-CH 2OH, wherein n is 1 to 5 integer, comprises that 1 and 5 is own, R 1Be H or the single or many saccharidess of cyclic and its alkoxy derivative.Glycosyl most preferably, wherein n is 4, particularly-CH 2-(CHOH) 4-CH 2OH.
In formula (I), R 1Can be for example N-methyl, N-ethyl, N-propyl group, N-sec.-propyl, N-butyl, N-isobutyl-, N-2-hydroxyethyl or N-2-hydroxypropyl.For obtaining best whipability, R 1Be preferably methyl or hydroxyalkyl.Low if desired whipability, R 1Be preferably C 2～C 8Alkyl, especially n-propyl, sec.-propyl, normal-butyl, isobutyl-, amyl group, hexyl and 2-ethylhexyl.
R 2-CO-N＜can be is coconut monoethanolamide, stearylamide, oleylamide, laurylamide, myristic amide, decyl amide, palmitic amide, butter acid amides etc. for example.
Although polyhydroxy fatty acid amide can be used Schwartz, United States Patent (USP) 2,703, the method preparation in 798 might exist the by product that has cyclisation and the pollution problem of other coloring matter.As comprehensive method, at WO-9, the preparation method who describes in 206,154 and WO-9,206,984 will obtain the high quality polyhydroxy fatty acid amide.This method comprises the use alkoxide catalysis, under about 85 ℃ of temperature with N-alkylamino polyvalent alcohol with, the preferred fatty acid methyl esters reacts in solvent and obtains high yield (90%～98%) polyhydroxy fatty acid amide, it contains the degradable cyclisation by product of suboptimum of required low levels (generally being lower than about 1.0%), and have the colourity of improvement and a colour stability of improvement, for example Gardner Colors be lower than about 4, preferably in 0 to 2 scope.(for as butyl, isobutyl-and n-hexyl compound, the methyl alcohol of introducing or generating in reaction by catalyzer provides enough rheomorphisms, can optionally use other reaction solvent in addition).If desired, be retained in the product unreacted N-alkylamino polyvalent alcohol arbitrarily and can use acid anhydrides, for example acidylate such as diacetyl oxide, maleic anhydride is to reduce the total amount of this residual amine in product.The residual source of classical lipid acid, it can suppress foam, can be by being consumed with for example trolamine reaction.
The meaning of " by product of cyclisation " is a unwanted byproduct of reaction in the main reaction herein, and a plurality of hydroxyls in main reaction in the obvious polyhydroxy fatty acid amide can form ring structure, and it generally speaking is not easy to biological degradation.The technician of chemical field should know is to use two and more high-grade saccharides such as maltose preparation polyhydroxy fatty acid amide herein will cause generating wherein linear substituting group Z (it contains the multi-hydroxy substituting group) by the polyhydroxy fatty acid amide of poly-hydroxy ring structure nature " sealing ".This class material is not the cyclisation by product that defines herein.
Aforesaid polyhydroxy fatty acid amide also can be by sulfation, as with SO 3/ pyridine reaction, and obtain the sulfation material that uses as herein additional anion surfactant.
Enzyme---for multiple laundering of textile fabrics purpose, comprise the spot of removing protein-based, carbohydrate-based or triglycerin ester group, and, in detergent formulation, can comprise detergency enzymes for example for the dye migration that suppresses to come off with for the recovery of fabric.The enzyme that is impregnated in comprises proteolytic enzyme, amylase, lipase, cellulase and peroxidase, with and composition thereof.The enzyme that also can comprise other type.They can come from the source of any suitable, as plant, animal, bacterium, mould and yeast source.Yet their selection determines by Several Factors, as pH-activity and/or optimal stability point, thermostability, to the stability of activated detergent, washing assistant or the like factor decision.On bacterium aspect this or fungous enzyme is preferred, as bacterial amylase and proteolytic enzyme and mould cellulase.
Enzyme is impregnated in enough amounts usually so that maximum about 5mg (weight) in every gram composition to be provided, and is generally the organized enzyme of about 0.01mg to about 3mg.Be noted that in addition herein composition generally comprises about 0.001% to about 5%, preferred 0.1%～1% (weight) commercial enzyme goods.The amount of proteolytic enzyme in this article of commerce is enough to usually guarantee that every gram composition has 0.005 to 0.1Anson unit (AV) activity.
Suitable examples of proteases is a subtilisin, and it is that special bacterial strain by subtilis and Bacillus licheniformis obtains.Another kind of suitable proteolytic enzyme is obtained by bacillus strain, and it has maximum activity in pH8～12 scopes, and by Novo Industries A/S exploitation and sale, the commodity of registration are called ESPERASE.The preparation of this kind of enzyme and similar enzyme is described in the british patent specification 1,243,784 of Novo.The commercial commercially available proteolytic ferment that is suitable for removing protein-based spot comprises the proteolytic ferment of the commodity of being sold by Novo Industries A/S (Denmark) ALCALASE by name and SAVINASE, with by InternationalBio-Synthetics, the MAXATASE that Inc. (Holland) sells.Other proteolytic enzyme comprises that protease A is (referring to european patent application 130, on January 9th, 756,1985 is open) and proteolytic enzyme B (applied on April 28th, 87303761.8,1987 referring to the european patent application sequence number, disclosed european patent application 130,756 in 9 days January in 1985 with people such as Bott).
Amylase for example comprises in british patent specification 1,296, the α-Dian Fenmei of describing among 839 (Novo), RAPIDASE (International Bio-Synthetics, Inc. sells) and TERMAMYL (Novo Industries sale).
The cellulase that can be used among the present invention comprises bacterium and mould cellulase.Preferably they have best pH scope 5～9.5.Suitable cellulase is disclosed in the United States Patent (USP) of authorizing in 6 days March in 1984 of people such as Barbesgoard 4,435, in 307, it discloses the mould cellulase that produced by Humicola insolens and humicola lanuginosa strain DSM 1800 or by the cellulase that extracts in the cellulase 212 of the mould preparation that belongs to Aeromonas and the hepatopancreas by extra large mollush (Dolabella Auricula Solander).Suitable cellulase also is disclosed in GB-A-2,075,028; GB-A-2 is in 095,275 and DE-OS-2,247,832.
The spendable suitable lipase of washing composition comprises by the microorganism in the Rhodopseudomonas family, and those lipase that produce as Situ Ci Shi aeruginosa atcc 19.154, as be disclosed in English Patent 1,372 are in 034.Also referring to the lipase on February 24th, 1978 disclosed Japanese patent application 53-20487.This lipase can be by AmanoPharmaceutical Co.Ltd., and Nagoya (Japan) has bought, and commodity are called lipase P ＂ Amano ＂, hereinafter referred to as ＂ Amano-P ＂.Other commercial lipase comprises Amano-CES, lipase ex Chromobacter viscosum, for example pigment bacillus (Chromobacter) viscosum var.Lipolyticum NRRLB 3673, commercial can be by Toyo Jozo company, Tagata, (Japan) has bought; With other Chromobacter viscosum lipase, by U.S, Biochemical Corp. (U.S.) and Disoynth Co. (Holland) have bought and lipase ex gladiolus pseudomonas.Plant Pseudomonas fetal hair bacterium and be the preferred enzyme that is used for herein from corruption at the commercial LIPOLASE enzyme that can buy by Novo (also referring to EPO341,947).
Peroxidase is and oxygen source that for example percarbonate, perborate, persulphate, hydrogen peroxide etc. are used in combination.They are used for " solution bleaching " and promptly are suppressed at dyestuff that washing operation comes off or pigment migration other basic thing to the washing soln from basic things.Peroxidase is being known in the art, comprises for example horseradish peroxidase, lignoenzyme and halo peroxidase such as chloro and bromoperoxidase.The detergent composition that contains peroxidase is disclosed in, and for example the international first of PCT is asked among the WO89/099813, and on October 19th, 1989 is open, by the O.Kirk invention, transfers Novo Industries A/S.
Far-ranging enzyme material and the method that they are mixed in the synthetic detergent particle also are disclosed in the United States Patent (USP) 3,553,139 that was presented to people such as McCarty on January 5th, 1971.Some enzymes are disclosed in the people's such as Place that authorized on July 18th, 1978 United States Patent (USP) 4,101,457 and the people's such as Hughes that authorized on March 26th, 1985 United States Patent (USP) 4,507,219 in the two.The method that useful enzyme material and they are incorporated in these prescriptions in the detergent formulation is disclosed in United States Patent (USP) 4,261, in 868, people's such as Hora, on April 14th, 1981 authorized.The enzyme that is used for washing composition can make its stabilization with various technology.The enzyme stabilization technology is open and exemplify people such as Horn is authorized in explanation on April 14th, 1981 United States Patent (USP) 4, authorized people's such as Gedge United States Patent (USP) 3 on August 17th, 261,868,1971,600,319 and European patent application publication No. 0,199,405, application number is open on October 29th, 86200586.5,1986, Venegas.The enzyme stabilization system for example also is described in the United States Patent (USP) 4,261,868,3,600,319 and 3,519,570.
Enzyme stabilizers---enzyme used herein can be by being stabilized in the presence of the water dissolvable calcium ion source (it provides calcium ion to enzyme) in final composition.Stability in addition can obtain under existing at various other prior aries disclosed stablizer, especially borate family material (referring to Severson United States Patent (USP) 4,537,706 cited above).General washing composition comprises by every liter of final composition about 1 to about 30, preferred about 2 to about 20, more preferably about 5 to about 15, and 8 calcium ions most preferably from about to about 12 mmoles.It can change to some extent according to the amount of the enzyme that exists and the enzyme responsive to calcium ion.Should select the amount of calcium ion like this, make its with composition in complexing such as auxiliary agent, lipid acid after, for enzyme, always have available minimum.Water-soluble Ca salt all can be used as calcium ion source arbitrarily, comprise, but non-limiting in this, calcium chloride, calcium sulfate, calcium malate, calcium hydroxide, calcium formiate and lime acetate.Because the calcium ion that enzyme slurries and prescription contain in the water, make this small amount of calcium ion, general about 0.05 to about 0.4 mmole/liter, also often be present in the composition.Solid detergent composition of the present invention can comprise that the water-soluble calcium ion source of q.s is to be provided at required amount in the laundry aqueous solution.On the other hand, natural water hardness may be enough.
The amount that should be appreciated that aforementioned calcium ion is enough to guarantee enzyme stability.More calcium ion can be added in the composition so that the supplementary means that realizes that grease is removed to be provided.Therefore, the present composition can comprise about 0.05% to about 2% (weight) water-soluble calcium ion thing source.Certainly this amount can change with the amount and the type of employed enzyme in the composition.
The present composition also optionally but preferably contains various other stablizer, especially stablizers of borate type.Generally, the consumption of this stablizer in composition is calculated as about 0.25% to 10% by the boric acid in the composition or other borate compound (calculating for base by boric acid) that can form boric acid, preferred about 0.5% to about 5%, more preferably about 0.75% to about 3% (weight).Though other compound such as boron oxide, borax and other alkali metal borate (for example ortho-boric acid sodium, sodium metaborate and sodium pyroborate and penta borate) suit, preferably boric acid.The boric acid that replaces (for example, phenyl-boron dihydroxide, butane boric acid and to bromophenyl boric acid) also can replace boric acid to use.
Except enzyme, present composition alternative include help or strengthen scourability, to the nursing of the basic thing that is washed or improve one or more other washing composition additional substances or other materials of the aesthetic feeling (for example spices, tinting material, dyestuff etc.) of detergent composition.It below is the example that exemplifies of these additional substancess.
Washing assistant---detergent builders optionally is included in the composition of the present invention to help the control hardness of minerals.Can use inorganic and organic washing-assisting detergent.Washing assistant generally is used for the fabric laundry composition to help removing dirt particles.
The amount of washing assistant can change in relative broad range according to end-use and its required physical form of composition.When it existed, composition generally contained at least about 1% washing assistant.The prescription of saccharoid generally comprises about 10% to about 80%, more general about 15% to about 50% (weight) detergent builders.Yet meaning that, this does not get rid of the washing assistant that uses lower or higher amount.
Inorganic detergent builders comprises, but be not restricted to this, basic metal, ammonium, the alkylammonium salt of poly-phosphate (exemplify and be tri-polyphosphate, pyrophosphate salt and glassy polymeric metaphosphate), phosphoric acid salt, phytinic acid, silicate, carbonate (comprising supercarbonate and sesquicarbonate), vitriol and silico-aluminate.Yet need use the washing assistant of nonphosphate in certain areas.Importantly the present composition in addition have so-called " weak " washing assistant (with phosphate ratio) also have beyond thought effect under as Citrate trianion or so-called " low helping washed " environment (zeolite or layered silicate washing assistant produce).In addition, in the presence of weak nonphosphate builders (not allowing to exist calcium ion), secondary (2,3) alkyl-sulphate adds that the enzyme component can bring into play optimal efficacy.
The example of silicate-like builder is alkalimetal silicate, particularly SiO 2: Na 2O is than those silicate in 1.6: 1 to 3.2: 1 scopes, and layered silicate, as is described in the lamina sodium silicate in the United States Patent (USP) 4,664,839 of authorizing H.P.Rieck on May 12nd, 1987.NaSKS-6 is the trade mark (being abbreviated as ＂ SKS-6 ＂ in this article usually) by the crystalline layered silicate of Hoechst sale.Do not resemble zeolite builders, the NaSKS-6 silicate-like builder does not contain aluminium.NaSKS-6 has δ-Na 2SiO 5The layered silicate of morphology configuration.It can by as be described in German DE-A-3, those methods preparations in 417,649 and DE-A-3,742,043.SKS-6 is the most preferred layered silicate that is used for herein, but other such layered silicate has general formula NaMSi as those xO 2x+1YH 2O, wherein M is that sodium or hydrogen, x are 1.9 to 4 numerical value, is preferably 2, y is 0 to 20 numerical value, is preferably 0, layered silicate also can be used for herein.Various other layered silicates of buying from Hoechst comprise NaSKS-5, and NaSKS-7 and NaSKS-11 respectively are the structure of α, β and γ.As mentioned above, δ-Na 2SiO 5(NaSKS-6 type) most preferably uses herein.Other silicate also is useful, for example Magnesium Silicate q-agent, it can be used as in the saccharoid prescription crisp dose, the stablizer of oxygen bleaching agent and the component of control foam system.
The example of carbonate builders is for being disclosed in alkaline-earth metal and the alkaline carbonate in the disclosed German patent application 2,321,001 on November 15th, 1973.
The silico-aluminate washing assistant is useful especially among the present invention.The silico-aluminate washing assistant has great importance in the most frequently used commercially available heavy dirty granular detergent composition.The silico-aluminate washing assistant comprises those with following empirical formula:
M z(zAlO 2YSiO 2) wherein M be the ammonium of sodium, potassium, ammonium or replacement.Z is about 0.5 to about 2; Y is 1; The magnesium ion exchange capacity that this material has is that the anhydrous silico-aluminate of every gram exchanges about 50 millinormal CaCO at least 3Hardness.Preferred silico-aluminate is a zeolite builders, and it has following formula:
Na z[(AlO 2) z(SiO 2) y] xH 2O wherein z and y is at least 6 integer, and the mol ratio of z and y is 1.0 to about 0.5 scope, and x is about 15 to about 264 integer.
Useful silico-aluminate ion exchange material is commercial commercially available.These silico-aluminates can be crystallization or amorphous structure, and can naturally occurring silico-aluminate or synthetic obtaining.The method for preparing the silico-aluminate ion exchange material is disclosed in the United States Patent (USP) 3,985,669 of authorizing people such as Krummel on October 12nd, 1976.The preferred synthetic crystallization silico-aluminate ion exchange material that is used for this paper is buied by Zeolite A, ZeoliteP (B) and Zeolite X title.In particularly preferred embodiments, the crystal aluminosilicate ion exchange material has formula:
Na 12[(AlO 2) 12(SiO 2) 12] xH 2O wherein x is about 20 to about 30, especially about 27.This material is known to the public with Zeolite A.It is about 0.1～10 micron granularity that preferably aluminosilicate salt has diameter.
Suitable organic detergent washing assistant of the present invention comprises, but is not restricted to this, multiple multi-carboxylate's compound." multi-carboxylate " used herein refers to the compound that has a plurality of carboxylate groups, preferably has 3 carboxylate groups at least.The multi-carboxy acid salt washing agent adds in the composition with the form of acid usually, but form that also can neutralized salt adds.When using the form of salt, basic metal is preferred as sodium, potassium and lithium or alkanol ammonium salt.
In the multi-carboxy acid salt washing agent, comprise polytype useful matter.An important class multi-carboxy acid salt washing agent comprises the ether multi-carboxylate, comprises the oxidation disuccinate, as is disclosed in Berg. United States Patent (USP) 3,128, authorized on April 7th, 287,1964 and people's such as Lamberti United States Patent (USP) 3, on January 18th, 635,830,1972 authorized.Also see also the ＂ TMS/TDS ＂ washing assistant in the people's such as Bush that authorized on May 5th, 1987 the United States Patent (USP) 4,663,071.Suitable ether multi-carboxylate also comprises ring compound, particularly alicyclic compound, as at US3, and 923,679; 3,835,163; 4,158,635; Those that describe in 4,120,874 and 4,102,903.
Other useful detergent builder compound comprises the multipolymer, 1 of ether hydroxypolycarboxylic acid salt, maleic anhydride and ethene or vinyl methyl ether, 3,5-trihydroxybenzene-2,4,6-trisulfonic acid and carboxymethyl oxosuccinic acid, various polyacetic acid, as basic metal, ammonium and the substituted ammonium salt of ethylenediamine tetraacetic acid (EDTA) and nitrilotriacetic acid(NTA) and multi-carboxylate such as mellitic acid, succsinic acid, oxidation disuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxy methoxy-succinic acid and its water-soluble salt.
The Citrate trianion washing assistant, for example citric acid and its soluble salt (particularly sodium salt) are the multi-carboxy acid salt washing agents of particularly important in the dirt-cleaning agent prescription, reason is that they can be obtained and their biological degradability by renewable resources.Citrate trianion also can be used in combination with zeolite and/or layered silicate washing assistant.The oxidation disuccinate also is useful especially in these compositions and mixture.
Also have that suitable in detergent composition of the present invention that use is the U.S.4 that authorizes people such as Bush on January 28th, 1986, disclosed 3 in 566,984,3-dicarboxyl-4-oxa--1,6-adipate and relevant compound.Useful succsinic acid washing assistant comprises C 5～C 20Alkyl and alkenyl succinic and its salt.Particularly preferred compound is the dodecenyl succinic succsinic acid in this type.The object lesson of succinate washing assistant comprises: lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinic succinate (preferably), 2-15 carbene base succinates etc.The lauryl succinate is a preferred washing assistant in such, and is described in the disclosed european patent application 86200690.5/0,200,263 on November 5th, 1986.
Other suitable multi-carboxylate is disclosed in the people's such as Crutchfield that issued on March 13rd, 1979 the United States Patent (USP) 4,144,226 and in the people's such as Diehl that issued on March 7th, 1967 the United States Patent (USP) 3,308,067.Also see also people's such as Diehl United States Patent (USP) 3,723,322.
Lipid acid, for example C 12～C 18Monocarboxylic acid also can mix in the composition separately, or mixes in the composition so that additional washing assistant activity to be provided with aforesaid washing assistant, especially Citrate trianion and/or the combination of succinate washing assistant.Use lipid acid generally to cause whipability to reduce, this prescription teacher should consider.
Using under the phosphorated washing assistant situation, can use various alkali metal phosphates, as everyone knows tripoly phosphate sodium STPP, trisodium phosphate and sodium orthophosphate.Phosphate builders such as ethane-1-hydroxyl-1,1-diphosphate and other known phosphate (referring to, U.S.3 for example, 159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137) also can be used.
Bleaching compounds-SYNTHETIC OPTICAL WHITNER and bleach-activating agent---detergent composition of the present invention optionally contains SYNTHETIC OPTICAL WHITNER or contains SYNTHETIC OPTICAL WHITNER and the bleaching composition of one or more bleach-activating agents.When having SYNTHETIC OPTICAL WHITNER, its amount is generally detergent composition, in particular for the detergent composition of laundering of textile fabrics about 1% to about 30%, be more generally about 5% to about 20%.If there is bleach-activating agent, its amount be generally the bleaching composition that contains SYNTHETIC OPTICAL WHITNER and bleach-activating agent about 0.1% to about 60%, be more generally about 0.5% to about 40%.
SYNTHETIC OPTICAL WHITNER used herein is in existing oneself the known any SYNTHETIC OPTICAL WHITNER used in maybe will be for the cleaning purpose known to the public of fabric cleaning, hard surface cleaning or other to detergent composition.Comprising oxygen bleaching agent and other SYNTHETIC OPTICAL WHITNER.Can use perborate bleach herein, for example Sodium peroxoborate (for example monohydrate or tetrahydrate).
The class SYNTHETIC OPTICAL WHITNER that can use without limits comprises percarboxylic acids SYNTHETIC OPTICAL WHITNER and its salt.The suitable example of this class SYNTHETIC OPTICAL WHITNER comprises monoperphthalic acid magnesium hexahydrate, metachloroperbenzoic acid magnesium, 4-chloro in the ninth of the ten Heavenly Stems-4-oxo Perbutyric Acid magnesium and diperoxy dodecanedioic acid magnesium.These SYNTHETIC OPTICAL WHITNER are disclosed in the United States Patent (USP) 4 of the Hartman that issued on November 20th, 1984,483,781, the people's such as Burns of application on June 3rd, 1985 U.S. Patent application 740,446, February in 1985 people such as disclosed Banks on the 20th european patent application 0,133,354 and the people's such as Chung that issue November 1 nineteen eighty-three United States Patent (USP) 4, in 412,934.Most preferred SYNTHETIC OPTICAL WHITNER also comprises 6-amino in the ninth of the ten Heavenly Stems-6-oxo-mistake oxy hexanoic acid of describing as in the United States Patent (USP) 4,634,551 that is presented to people such as Burns on January 6th, 1987.
Also can use peroxygen bleach.Suitable peroxy bleaching compound comprises yellow soda ash peroxyhydrate (" percarbonate " SYNTHETIC OPTICAL WHITNER), trisodium phosphate peroxyhydrate, urea peroxyhydrate and sodium peroxide.Also can use persulphate SYNTHETIC OPTICAL WHITNER (for example, OXONE is made by Du Pont commercial).
Also can use the mixture of SYNTHETIC OPTICAL WHITNER.
Peroxygen bleach, perborate, percarbonate etc. preferably are used in combination with bleach-activating agent, and this causes producing on the spot the peroxy acid corresponding to bleach-activating agent in the aqueous solution (promptly in washing process).The various non-limiting examples of activator are disclosed in the United States Patent (USP) 4,915,854 and United States Patent (USP) 4,412,934 that is presented to people such as Mao April 10 nineteen ninety.Nonanoly acyloxy benzene sulfonate (NOBS) and Tetrahydroxyethyl ethylenediamine (TAED) activator are normally used, also can use their mixture.Representative SYNTHETIC OPTICAL WHITNER of useful herein other and activator be referring to U.S.4, and 634,551.
Those SYNTHETIC OPTICAL WHITNER of non-oxygen type SYNTHETIC OPTICAL WHITNER also are known in the art and can use in the present invention.The non-oxygen type of class SYNTHETIC OPTICAL WHITNER with specific benefits comprises the SYNTHETIC OPTICAL WHITNER of photoactivation, as sulfonation phthalocyanine phthalocyanine zinc and/or aluminium.Be presented to people's such as Holcombe U.S.4 referring on July 5th, 1977,033,718.If generally containing, use SYNTHETIC OPTICAL WHITNER, detergent composition have an appointment 0.025% to about 1.25% (weight) this SYNTHETIC OPTICAL WHITNER, especially sulfonation phthalocyanine phthalocyanine zinc.
The polymerization dirt release agent
Well known to a person skilled in the art that any polymerization dirt release agent alternative is used for the compositions and methods of the invention.The polymerization dirt release agent is characterised in that and contains hydrophilic segment simultaneously that this part makes hydrophobic fiber, as the surface hydrophilic of polyester and nylon; With the hydrophobic part, this part anchors at the surface of hydrophobic fiber and still anchors on the fiber surface after whole washing, rinse cycle are finished, and thus hydrophilic segment is played fixed action.This makes after dirt release agent is handled, and is easier in the spot of the generation washing process afterwards remove.
The polymerization dirt release agent that the present invention uses especially comprises those dirt release agents with following composition: (a) mainly by (ⅰ), (ⅱ) or one or more nonionic hydrophilic components of (ⅲ) forming, wherein (ⅰ) is that the polymerization degree is at least 2 polyoxyethylene part, be that the propylene oxide or the polymerization degree are at least 2～10 polyoxypropylene part (ⅱ), hydrophilic segment does not wherein comprise any propylene oxide unit, unless this unit is attached at the two ends of adjacent part by ehter bond; Be to comprise ethylene oxide and 1 the unitary mixture of oxidation alkene (ⅲ) to about 30 propylene oxide units, wherein said mixture contains abundant ethylene oxide unit, thereby makes the wetting ability of hydrophilic component big to the wetting ability that can increase normal polyester synthon surface (dirt release agent is deposited on this surface).Described hydrophilic segment preferably contains the ethylene oxide unit at least about 25%, contains 20～30 propylene oxide units and be particularly preferred at least about the composition of 50% ethylene oxide unit of having an appointment; Or (b) by (ⅰ), (ⅱ), (ⅲ) or (ⅳ) one or more hydrophobic compositions of forming, wherein (ⅰ) is C 3Oxidation alkene terephthalate part, if wherein described hydrophobic composition also comprises the ethylene oxide terephthalate, then ethylene oxide terephthalate and C 3The ratio of oxidation alkene terephthalate units is about 2: 1 or is lower, (ⅱ) is C 4～C 6Alkene or oxidation C 4～C 6Alkene part, or their mixture (ⅲ) are poly-(vinyl ester) part, and preferred degree of polymerization is at least 2 poly-(vinyl-acetic ester), (ⅳ) is C 1～C 4Alkyl oxide or C 4Hydroxyalkyl ether substituting group, or their mixture, substituting group wherein is with C 1～C 4Alkyl oxide or C 4Hydroxyalkyl ether derivatived cellulose or its form of mixtures exist, and this derivatived cellulose is an amphipathic, makes them have competent C thus 1～C 4Alkyl oxide and/or C 4The hydroxyalkyl ether unit anchors on the conventional polyethylene terephthalate surface, and keeps the hydroxyl of q.s, in case be adsorbed on these conventional synthon when surperficial when it, wetting ability that can the increased fiber surface; Or (a) and (b) make up.
Generally speaking, (a) polymerization degree of the polyoxyethylene in (ⅰ) part be 2～about 200, although also can use the higher polymerization degree, preferred 3～about 150; 6～about 100 is more preferred.Suitable oxidation C 4～C 6The alkene hydrophobic comprises that partly (but be not limited to this) is as MO 3S (CH 2) nOCH 2CH 2The polymerization dirt release agent end-blocking part of O-, M is a sodium in the formula, n is 4～6 integer, and is as Gosselink, disclosed in the United States Patent (USP) 4,721,580 that on January 26th, 1988 authorized.
The polymerization dirt release agent that uses among the present invention also comprises derivatived cellulose, hydroxy ethers cellulose polymer compound for example, the copolymerization block thing of glycol terephthalate or propylene glycol terephthalate and polyoxyethylene terephthalate or polyoxypropylene terephthalate etc.These reagent all have commercially available, comprising the cellulosic hydroxy ethers as METHOCEL (Dow).The Mierocrystalline cellulose dirt release agent that the present invention uses also comprises C 1～C 4Alkyl and C 4Hydroxy alkyl cellulose; United States Patent (USP) 4,000,093 referring to the people such as Nicol that authorized on December 28th, 1976.
The dirt release agent that is characterised in that poly-(vinyl ester) hydrophobic part comprises that poly-(vinyl ester) is as, C 1～C 6The graft copolymer of vinyl ester preferably grafts on poly-(vinyl-acetic ester) on polyoxygenated alkene skeleton such as the polyoxyethylene skeleton.Be illustrated in people's such as disclosed Kud on the 4th and 22 in 1987 european patent application 0,219,048.This commercially available class dirt release agent comprises SOKALAN type material, SOKALAN HP-22 for example, and BASF (West Germany) produces.
The preferred dirt release agent of one class is the multipolymer with glycol terephthalate and the random block of polyoxyethylene (PEO) terephthalate.The molecular weight of this polymerization dirt release agent is about 25,000～about 55,000.Be issued to the United States Patent (USP) 3,893,929 of Basadur on July 8th, 3,959,230 and 1975 referring to the United States Patent (USP) that was issued to Hays on May 25th, 1976.
Another kind of preferred polymerization dirt release agent is the polyester that has the glycol terephthalate repeating unit, wherein contain the polyoxyethylene terephthalate unit of the glycol terephthalate unit and 90%～80% (wt) of 10～15% (wt), it comes from the polyoxyethylene glycol of molecular-weight average 300～5000.The example of this polymkeric substance comprises commercially available ZELCON5126 (Dupont product) and MILEASE T (ICI product).Be issued to the United States Patent (USP) 4,702,857 of Gosselink referring on October 27th, 1987.
Also having a kind of preferred polymerization dirt release agent is to be the sulfonated products of the ester oligomer of straight chain substantially, and this oligopolymer contains terephthaloyl and the multiple unitary oligomer ester skeleton of oxyalkylene oxygen basic weight, and the terminal portions that links to each other with this skeleton covalency.Authorize November 6 nineteen ninety in the United States Patent (USP) 4,968,451 of J.J.Scheibel and E.P.Gosselink these dirt release agents are had complete description.
Other suitable polymerization dirt release agent comprises the United States Patent (USP) 4 of authorizing people such as Gosselink on December 8th, 1987,711, terephthalate polyester in 730, authorized the United States Patent (USP) 4 of Gosselink on January 26th, 1988,721, the oligomer ester of negatively charged ion end in 580 envelope and authorized block polyester oligopolymer in the United States Patent (USP) 4,702,857 of Gosselink on October 27th, 1987.
Preferred polymerization dirt release agent also comprises the dirt release agent in the United States Patent (USP) 4,877,896 of authorizing people such as Maldonado on October 31st, 1989, this patent disclosure negatively charged ion, the particularly end capped terephthalate of sulfo group aroyl.
If the use dirt release agent, then its consumption for detergent composition weight of the present invention about 0.01%～about 10.0%, be generally about 0.1%～about 5%, preferred about 0.2%～about 30%.
Sequestrant
Detergent composition of the present invention can also selectivity contains the sequestrant of one or more iron and/or manganese.This class sequestrant can be selected from aminocarboxylate, phosphoro-amidate, and fragrant chelating agent of multifunctional replacement and composition thereof, whole definition is all hereinafter.Without being limited by theory, the benefit that it is believed that these materials is that partly they remove the outstanding performance of magnesium and iron by forming soluble inner complex from washing soln.
Aminocarboxylate as selectivity chelator comprises edetate, N-hydroxyethyl-ethylenediamine triacetate, nitrilotriacetic acid salt, ethylenediamine tetrapropionic acid(EDTP) salt, triethylenetetraaminehexaacetic acid salt, diethylentriamine pentacetate and ethanol Diglycocol, and they are an alkali metal salt, ammonium salt and substituted ammonium salt and composition thereof.
When allowing at least in detergent composition, to have a spot of total phosphorus, phosphoro-amidate also is fit to be used as sequestrant of the present invention, comprising: ethylenediamine tetraacetic (methylene radical phosphoric acid salt), nitrilo three (methylene radical phosphoric acid salt) and diethylenetriamine five (methylene radical phosphoric acid salt) are (DEQUEST).Preferably these phosphoro-amidates do not contain alkyl or the alkenyl above six carbon atom.
In the present composition, also can use the aromatic chelating agent of multifunctional replacement.Authorize people's such as Connor United States Patent (USP) 3,812,044 referring on May 21st, 1974.The compound of preferred this class acid form is the dihydroxyl disulfobenzene, for example: 1,2-dihydroxyl-3,5-disulfobenzene.
The biodegradable cheating agent of most preferably using was ethylenediamine disuccinate (＂ EDDS ＂) in the present invention, authorized the United States Patent (USP) 4,704,233 of Hartman and Perkins referring on November 3rd, 1 987.
If the use sequestrant, then its consumption is about 0.1%～about 10% of detergent composition weight of the present invention.Preferred amount of chelant is about 0.1%～about 3.0% of a said composition weight.
Remove clay soil/anti redeposition agent
Composition of the present invention also can contain the water-soluble ethoxylated amine with removal clay soil and antiredeposition performance.The granular detergent composition that contains these compounds generally contains the water-soluble ethoxylated amine of 0.01% about 10.0 (wt) that have an appointment.
Most preferred removal dirt and anti redeposition agent are the tetrens of ethoxylation.The example of ethoxylated amine is invested on July 1st, 1986 in the United States Patent (USP) 4,597,898 of VanderMeer description.Another kind of preferred removal clay soil/anti redeposition agent be on June 27th, 1984 disclosed Oh and the european patent application 111,965 of Gosselink in the cation compound of report.Other removal clay soil/anti redeposition agent that can use in the present invention comprises the ethoxylated amine polymer of reporting in the european patent application 111,984 of disclosed Gosselink on the 27th June in 1984; July in 1984 disclosed Gosselink on the 4th european patent application 112,592 in the report amphiphilic polymers; With the amine oxide of authorizing the United States Patent (USP) 4,548,744 of Connor on October 22nd, 1985.As known in the art other removes clay soil and/or anti redeposition agent also can be used in the composition of the present invention.Another kind of preferred anti redeposition agent comprises carboxymethyl cellulose (CMC).This class material is well known in the art.
Polymeric dispersant
Consumption is that about polymeric dispersant of 0.1%～about 7% (wt) of the present composition is favourable, and is especially more favourable when having zeolite and/or layered silicate washing assistant to exist.Suitable polymeric dispersant comprises polymeric polycarboxylate and polyoxyethylene glycol, and the known polymeric dispersant of other of this area also can use.Do not limited by theoretical although do not wish, but can be sure of when polymeric dispersant with other washing assistant (comprising low-molecular-weight polycarboxylate) when using, generate restraining effect by crystal, especially free the peptization and the anti-redeposition of dirt, can improve the performance of all detergent builder compounds.
By making suitable unsaturated monomer, the polymerization of unsaturated monomers of especially sour form or copolymerization multi-carboxylate polymer.Can comprise through the unsaturated monomer acid that polymerization prepares suitable multi-carboxylate polymer: vinylformic acid, toxilic acid (or maleic anhydride), fumaric acid, methylene-succinic acid, equisetic acid, methylfumaric acid, citraconic acid and methylene radical propanedioic acid.In polymer poly-carboxylate of the present invention, do not have the monomer segment of hydroxy-acid group, as vinyl methyl ether, vinylbenzene, ethene, as long as its content is no more than about 40% (wt) and suits.
Can be particularly suitable by the multi-carboxylate polymer that vinylformic acid obtains.Such that uses among the present invention is that the polymkeric substance of base is the water-soluble salt of polymeric acrylic acid with vinylformic acid.The molecular-weight average preferably about 2,000～10,000,4,000～7,000 of this base polymer of acid form is more preferred, and 4,000～5,000 is the most preferred.The example of the water-soluble salt of such acrylate copolymer comprises for example ammonium salt of an alkali metal salt, ammonium salt and replacement.Such polymer soluble is known.Authorize on March 7th, 1967 in the United States Patent (USP) 3,308,067 of Diehl and disclose this application of class polymerization acrylate in detergent composition.
With vinylformic acid/toxilic acid is that the multipolymer of base also can use as the preferred ingredient of dispersion/anti redeposition agent.This class material comprises the water-soluble salt of vinylformic acid and maleic acid.The molecular-weight average of this analog copolymer of acid form is preferably about 2,000～10,000; The 5,000～75, the 000th, preferred, 7,000～65,000 is the most preferred.The ratio of acrylate moiety and toxilic acid part was generally about 30: 1～about 1: 1 in this analog copolymer, and is about 10: 1～2: 1st, comparatively preferred.The water-soluble salt of this class vinylformic acid/maleic acid can comprise, for example: the ammonium salt of an alkali metal salt, ammonium salt and replacement.Such vinylformic acid/maleic acid is the known substance described in the disclosed european patent application 66915 on December 15 nineteen eighty-two.
Included another kind of polymeric material is polyoxyethylene glycol (PEG).PEG is except can be as removing the performance that also has dispersion agent clay soil/anti redeposition agent.That the molecular weight that is used for this purpose polyoxyethylene glycol is generally is about 500～about 100,000, about 1,000～about 50,000th, preferred, about 1,500～about 10,000 is more preferred.
Also can use polyaspartic acid salts and polyglutamate, especially together use with zeolite builders.
Whitening agent
Can in detergent composition of the present invention, mix well known in the prior art any white dyes or other whitening agent of general about 0.05%～about 1.2% (wt).Can be used for commercially available white dyes of the present invention and can be divided into following group, but not only be restricted to this: stilbene, pyrazoline, tonka bean camphor, carboxylic acid, methyne cyanines, dibenzothiophen-5,5-dioxide, pyrroles, 5-and 6-unit heterocyclic derivative, and other variegated dose.The example of these whitening agent is disclosed in ＂ The Production and Application of Fluorescent BrighteningAgent ＂, M.Zahradnik, John Wiley﹠amp; Sons publishes, among the New York (1982).
The specific examples of the white dyes that in the present composition, uses be same as in the United States Patent (USP) 4,790,856 that was issued to Wixon on December 13rd, 1988 disclosed those.These whitening agent comprise the PHORWHITE whitening agent series that Verona produces.Disclosed other whitening agent comprises in this reference: the TinopalUNPA that Ciba-Geigy produces, Tinopal CBS and Tinopal 5BM; (place of production Italy) Arctic White CC and Artic White CWD that Hilton-Davis produces; 2-(4-styryl phenyl)-2H-naphthalene alcohol [1,2-d] triazole; 4,4 '-two (1,2,3-triazoles-2-yl) stilbene; 4,4 '-bis-styrylbiphenyl and aminocoumarin.The object lesson of these whitening agent has: 4-methyl-7-diethyl amino coumarin; 1, the two (ethene of benzimidazolyl-2 radicals-yl) of 2-; 1, the 3-diphenylpyrazoline; 2, the two (benzoxazoles of 5--2-yl) thiophene; 2-styryl-naphthalene-[1,2-d] oxazole and 2-(stilbene-4-yl)-2H-naphtho--[1,2-d] triazole.Also can authorize the United States Patent (USP) 3,646,015 of Hamilton referring on February 29th, 1972.
Suds suppressor
Can in the present composition, mix and to reduce or to suppress the compound that foam forms.Foamy is suppressed at and uses in the preceding material filling type washing machine of European plan, or at United States Patent (USP) 4,489, in 455 and 4,489,574 the thickening and washing method, or under the condition in detergent composition of the present invention, particularly important when selectivity contains height bubble cosurfactant.
Can use multiple material as suds suppressor, suds suppressor is known in those skilled in the art.Referring to, as: Kirk Othmer Encyclopedia of Chemical Technology, the third edition, 7 volumes, 430～447 pages of (John Wiley﹠amp; Sons, Inc., 1979).The suds suppressor of one class particularly important comprises mono carboxylic lipid acid and its soluble salt.Authorize the United States Patent (USP) 2,954,347 of wavne St.John referring to September 27 nineteen sixty.Be used as the mono carboxylic lipid acid of suds suppressor and salt thereof and generally have and contain 10～about 24 carbon atoms, preferably contain the hydrocarbyl chain of 12～18 carbon atoms.Suitable salt comprises an alkali metal salt, for example sodium salt, sylvite and lithium salts; Ammonium salt and alkanol ammonium salts.
Detergent composition of the present invention also can contain the nonsurfactant suds suppressor.The example of this class suds suppressor has: high-molecular-weight hydrocarbons, for example paraffin, fatty acid ester (as fatty acid triglyceride), the fatty acid ester of MHA, aliphatic C 18～C 40Ketone (as stearone) etc.Other suds suppressor comprises the alkylating aminotriazine of N-, for example three-to six-alkyl melamine or two-to four-alkyl diamine chloro triazine, this compound is cyanuryl chloride and 2 or 3 moles of uncle or secondary amine, propylene oxide and single stearic alkyl phosphate salts that have 1～24 carbon atom, as the product of single stearic alkanol phosphoric acid ester and single stearic alkylphosphonic acid carboxylic acid two basic metal (as K, Na and Li) salt and phosphoric acid ester.Can use by liquid form as paraffin and halowax hydrocarbon.It is liquid that this liquid hydrocarbon should be under room temperature and normal atmosphere, and should have-40 ℃～about 5 ℃ pour point approximately, and minimum boiling point is not less than about 110 ℃ (normal atmosphere).Known use waxy hydrocarbon, preferably this hydrocarbon has and is lower than about 100 ℃ fusing point.This class hydrocarbon is the preferred suds suppressor of a class of detergent composition.For example authorize in people's such as Gandolfo the United States Patent (USP) 4,265,779 and described the hydrocarbon suds suppressor on May 5th, 1981.This hydrocarbon comprises the aliphatic series that contains 12～about 70 carbon atoms of having an appointment, alicyclic, aromatics and heterocycle is saturated or unsaturated hydrocarbons.The term that uses in the discussion about such suds suppressor " paraffin " meaning is to comprise the real paraffin and the mixture of cyclic hydrocarbon.
Another kind of preferred nonsurfactant suds suppressor comprises the polysiloxane suds suppressor.Comprising using organopolysiloxane oil, the for example dispersion agent or the emulsifying agent of polydimethylsiloxane, organopolysiloxane oil or resin, and the mixture of organopolysiloxane and silica dioxide granule, organopolysiloxane wherein condenses on silicon-dioxide through chemisorption.The polysiloxane suds suppressor is known in the art, for example is disclosed in the United States Patent (USP) 4,265,779 and the Starch that authorized people such as Gandolfo on May 5th, 1981, M.S. in February 7 nineteen ninety disclosed european patent application 89307851.9.
Other polysiloxane suds suppressor is disclosed in United States Patent (USP) 3,455, and in 839, this patent relates to by mixing a small amount of polydimethylsiloxane fluid to eliminate aqueous solution foamy composition and method in composition.
The mixture of polysiloxane and silanized silica is as German patent application DOS2, describes to some extent in 124,526.Polysiloxane defoamers in the granulated detergent and froth suppressor are disclosed in U.S. Patent application 3,933, and in 672 people such as () Bartolotta and the United States Patent (USP) 4,652,392 people such as () Baginski, on March 24th, 1987 authorized.
What use in the present invention is that the example of the suds suppressor of base is the froth suppressor that presses down the bubble amount that mainly has following composition with the polysiloxane:
(ⅰ) polydimethylsiloxane fluid of the 25 ℃ of about 20cs of following viscosity～about 1500cs;
(ⅱ) about 5～about 50 parts of (wt) polyorganosiloxane resins/100 parts (wt) (ⅰ), this resin
By (CH 3) 3SiO 1/2Unit and SiO 2The unit, with about 0.6: 1～about 1.2: 1
Ratio is formed; With
(ⅲ) about 1～about 20 parts of solid silicones (wt)/100 part (ⅰ) (wt);
In the present invention in the preferred polysiloxane suds suppressor of Shi Yonging, 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) (but not comprising polypropylene glycol).Based on the suds suppressor of polysiloxane is side chain/crosslinked and nonlinear.
Be exemplified below in order to further specify this viewpoint, cloth-washing detergent with the effect of control bubble generally can contain 0.001%～about 1% (wt) that have an appointment, preferred about 0.01%～0.7% (wt), the described polysiloxane suds suppressor of 0.05%～about 0.5% (wt) most preferably from about, this suds suppressor contains: (1) is the nonaqueous emulsion of main suds suppressor, this suds suppressor is following (a), (b), (c) and mixture (d), (a) organopolysiloxane, (b) arborescens polysiloxane or can produce the polysiloxane compound of polyorganosiloxane resin, (c) pulverizing filler and (d) promote component (a), (b) and (c) mixture reaction is to generate the catalyzer of silane alkoxide; (2) at least a nonionic silicones tensio-active agent; (3) solubleness in water surpasses the polyoxyethylene glycol of 2% (wt) or the multipolymer of polyethylene glycol-propylene glycol under the room temperature; Wherein do not contain polypropylene glycol.In granular composition, gel etc., also can use similar quantity.Authorize the United States Patent (USP) 4,978,471 of Starch referring to December 18 nineteen ninety; Authorized United States Patent (USP) 4,983,316 and the United States Patent (USP) 4,639,489 and 4,749,740 of Starch on January 8th, 1991, people such as Aizawa, 46 row～the 4 hurdle, the 1st hurdle, 35 row.
Preferred polysiloxane suds suppressor comprises among the present invention: the multipolymer of polyoxyethylene glycol and polyethylene/polypropylene glycol, their molecular-weight average should be lower than about 1,000, preferably between about 100～800.Polyoxyethylene glycol of the present invention and polyethylene/polypropylene glycol multipolymer solubleness in the water of room temperature should be higher than 2% (wt), preferably is higher than about 5% (wt).
The preferred solvent of the present invention is a molecular-weight average less than about 1,000, more preferably is about 100～800, most preferably is 200～400 polyoxyethylene glycol and polyethylene/polypropylene glycol multipolymer, preferred PPG 200/PEG 300.Preferred 1: 1～1: 10 of the weight ratio of polyoxyethylene glycol and polyethylene glycol-propylene glycol copolymers; 1: 3～1: 6 the most preferred.
The polysiloxane suds suppressor that the present invention preferably uses does not contain polypropylene glycol, does not especially conform to the polypropylene glycol that molecular weight 4,000 is arranged.The preferred segmented copolymer that does not also contain oxyethane and propylene oxide, for example PLURONIC L101.
Other suds suppressor that the present invention uses comprises the mixture of secondary alcohol (as the 2-alkyl chain triacontanol) and these alcohol and polysiloxane oil, and this polysiloxane oil is as U.S.4, disclosed polysiloxane in 798,679,4,075,118 and EP150,872.Secondary alcohol comprises and has C 6～C 16The C of chain 6～C 16Alkyl alcohol.Preferred alcohol is 2-butyl octanol, and the trade mark that this alcohol can ISOFOL 12 is buied from Condea.The secondary alcohol mixture can be buied from Enichem with the trade mark of ISALCHEM 123.Mix suds suppressor and generally contain the mixture that weight ratio is 1: 5～5: 1 a pure and mild polysiloxane.
For any detergent composition that is used for automatic washing machine, the foam of formation all should not overflow washing machine.Preferred its exists with " foam inhibition amount " when using suds suppressor.The implication of " foam inhibition amount " is the consumption of suds suppressor of the prescription Shi Xuanding of composition, this amount fully control foam to obtain can be used for the low foam laundry washing composition of automatic washing machine.
Composition of the present invention contains 0%～about 5% suds suppressor usually.When using mono carboxylic lipid acid and its salt as suds suppressor, its consumption is the highest 5% of the detergent composition weight that is about usually.Preferred about 0.5%～about 3% the fatty monocarboxylate suds suppressor that uses.Although also can adopt higher consumption, the consumption of polysiloxane suds suppressor the highest general about 2.0% of the detergent composition weight that is about.Because at first will consider to make cost to keep the efficient of the low consumption of minimum and effective control foam, this upper limit is practical from its character.About 0.01%～about 1% the polysiloxane suds suppressor of preferred use, about 0.25%～about 0.5% is more preferred.In the present invention, comprise the whole silicon-dioxide and the operable any additives material that can use with organopolysiloxane in these weight percent numerical value.The consumption of single stearic alkylphosphonic suds suppressor is generally about 0.1～about 2% of composition weight.Although can use the hydrocarbon suds suppressor of higher consumption, its consumption is generally about 0.01%～about 5.0%.The consumption of alcohol suds suppressor is generally 0.2%～3% of final product composition having weight.
Except that said components, composition of the present invention can also bring multiple other binder component of other benefit to be used in combination with giving the various compositions in the scope of the invention.Enumerate the example of multiple such binder component below, but be not limited only to this.
Fabric softener
The also alternative fabric softener that uses various experience washing whole processes in the present composition, particularly authorized the United States Patent (USP) 4 of Storm and Nirschl on December 13rd, 1977,062, disclosed microgranular montmorillonitic clay and other softening agent well known in the prior art in 647, thereby make the effect that obtains soft fabric in clean textile, the consumption of softening agent is generally about 0.5%～10% (wt).Also can authorize people's such as Crisp United States Patent (USP) 4,375,416 as March 1 nineteen eighty-three and authorize people's such as Harris United States Patent (USP) 4,291,071 on September 22nd, 1981 disclosed like that, clay softening agent and amine and cationic softener are together used.
Other component
In the present composition, can also contain other useful in multiple detergent composition component, comprising other active ingredient, carrier, processing aid, dyestuff or pigment.High if desired bubble then can mix as C in said composition 10～C 16The suds booster of alkanolamide, its consumption is generally 1%～10%.C 10～C 14Monoethanolamine and diglycollic amide are the representative instances of such suds booster.It also is favourable that this class suds booster is used as above-mentioned amine oxide, trimethyl-glycine, sultaine with height bubble cosurfactant.If desired, also can add as MgCl 2, MgSO 4The solubility magnesium salts obtain more foam, the consumption of this magnesium salts is generally 0.1%～2%.
The various decontamination components of using in the present composition can also be by being adsorbed on these components on the porous hydrophobic matrix, and then wrap up in application with hydrophobic and this matrix is wrapped up in to apply further make its stabilization.Preferably before adsorbing, this decontamination component is mixed with tensio-active agent with porous matrix.In use, this decontamination component is discharged into the wash water solution from matrix, and finishes the washing functions of its expection in this washings.
Following Example is understood this technology in more detail: with the porous hydrophobic silicon dioxide (trade mark SIPERNAT D10, DeGussa) with contain 3%～5%C 13～15The proteolysis enzyme solution of the nonionogenic tenside of ethoxylated alcohol EO (7) mixes.The amount of this enzyme/surfactant soln generally is 2.5 times of silica weight.The gained powder (can use viscosity 500～12,500 various polysiloxane oils) through dispersed with stirring in polysiloxane oil.Add in the last washing composition matrix with the polysiloxane oil dispersion thing emulsification of gained or with it.By this method, enzyme, SYNTHETIC OPTICAL WHITNER, bleach-activating agent, bleaching catalyst, photosensitizers, dyestuff, white dyes, fabric regulator and hydrolyzable tensio-active agent can " protected form " be used in the washing composition as the aforementioned.
Detergent composition of the present invention preferably be formulated into the pH that is adapted at washing water about 6.5～about 11, use in preferred about 7.5～about 10.5 aqueous cleaning operation.The method that the pH value is controlled at the use value of requirement comprises use buffer reagent, alkali, acid etc., and all methods known in those skilled in the art.
Hereinafter be illustrate detergent composition of the present invention and the second month in a season of the present invention (2,3) alkyl-sulphate coating purposes typical, but the example of indefiniteness.
Whole steps that preferably include three uniquenesses of making of particulate product of the present invention: (1) forms base-material with the component agglomeration, then; (2) agglomerate (as percarbonate bleach, bleach-activating agent etc.) that step (1) is formed mixes with various components; Can also comprise in addition, but also be simultaneously that preferred (3) spray into the material as spices in final mixture.
Base-material is agglomerant rather than spray-dired, is in order to prevent the tensio-active agent degraded of some thermo-sensitivity.The product of gained is that (the free flowing detergent mixture of 600g/l～800g/l), it can substitute existing spraying drying cloth-washing detergent and use high-density.
For the agglomeration (above-mentioned steps 1) of base-material, this process comprises following 4 steps: (A) use as Readco Standard Sigma Mixer, the mixing machine of T-series prepares the tensio-active agent paste; (B) use as Eirich Mixer, the mixing machine of R-series makes tensio-active agent paste and powdery components agglomeration; (C) as intermittent type Aeromatic fluidized-bed continous way is fixed or vibrated fluidized bed (NIRO, Bepex or Carrier Companics) in dry this agglomerate and (D) use as Eirich Mixer, R-series mixing machine is wrapped up in deposited this agglomerate.
Specifically describe agglomeration step below.
Steps A: the preparation of tensio-active agent paste
The purpose of this step be with the tensio-active agent in the composition and liquid mixing make dissolving that blend is beneficial to tensio-active agent turn into and nodulizing.In this step, with the tensio-active agent in the composition and other liquid ingredient together in Sigma Mixer in 140 (60 ℃), mixing about 15 minutes～about 30 minutes under about 40rpm～about 75rpm, make the paste that viscosity is 20,000～40,000 centipoise.After thoroughly mixing, when storage is extremely prepared to carry out the nodulizing of step (B) under 140F (60 ℃) with this mashed prod.The component of using in this step comprises tensio-active agent, vinylformic acid/toxilic acid polymkeric substance (m.w, 70,000) and polyoxyethylene glycol ＂ PEG ＂ 4000～8000.
Step B: the nodulizing of powder and tensio-active agent paste
The purpose of this step is the flowed detergent particles that base ingredient is gone to the about 300 μ m of median size～about 600 μ m.In this step, powder (is comprised as zeolite, Citrate trianion, citric acid washing assistant, stratiform silicon-dioxide washing assistant (as SKS-6), yellow soda ash, ethylenediamine disuccinate, sal epsom and white dyes) feed intake in Einich Mixer (R-series), and under about 1500rpm～about 3000rpm, carry out of short duration stirring (about 5～10 seconds), make various dry powder thorough mixing.Tensio-active agent paste with steps A feeds intake in mixing machine then; And under about 1500rpm～about 3000rpm and room temperature, mixed about 1 minute～about 10 minutes preferred 1～3 minute continuously.When forming thick agglomerate (median size 800～1600 μ m), stop mixing.
Step C:
The purpose of this step be by remove/dry moisture content reduces the viscosity of agglomerate, and helps particle diameter is reduced to target grain size (measuring its median size with sieve analysis is about 300～about 600 μ m).In this step, it is dry in the fluidized-bed of about 41 ℃ of airflow temperature～about 60 ℃ that wet agglomerate is fed intake, to the final water content of this particulate be about 4%～about 10%.
Step D: wrap up in and apply agglomerate and add free-flow agent
The purpose of this step is to obtain the ultimate aim particle diameter of about 300 μ m～about 600 μ m, mixes wrapping up in the material that applies agglomerate, reduces particulate caking trend and helps to keep acceptable flowability.In this step, the dry agglomerates that obtains among the step C is fed intake in Eirich Mixer (R-series), under about 1500～about 3000rpm speed, mix, in mixing, add 2～6% zeolite A (median size 2～5 μ m) simultaneously.Be mixed to continuously and obtain required about 1200～about 400 μ m median sizes (generally being about 5 seconds～about 45 seconds).Add secondary (23) alkyl-sulphate (median size 1～3 μ m) of about 0.1%～about 1.5% (wt) this moment, stop mixing as flow promotor.In another embodiment, the thin second month in a season (2,3) alkyl-sulphate and other automatic flowing agent can be used in combination as 1～3 micron silica.
Illustrate cloth-washing detergent below by the preceding method preparation.
Embodiment 1
Agglomerate
％(wt) ％(wt)
In final product in agglomerate C 14～15Sodium alkyl sulfate 5.8 6.8C 16Secondary (2,3) sodium alkyl sulfate 17.3 20.4C 12～C 13The alcohol of ethoxylation (EO3) 4.7 5.5C 12～14N-methyl glucose amide 4.7 5.5 acrylate/maleate copolymer 6.2 7.3 polyoxyethylene glycol, 1.4 1.7 silico-aluminates (zeolite) 8.8 10.3 Trisodium Citrates 1.9 2.2 citric acids/SKS-6 111.5 13.5 yellow soda ash, 12.2 14.4EDDS 20.4 0.5 sal epsom, 0.4 0.5 white dyes 0.1 0.1 moisture, 7.6 8.9 second month in a season (2,3) alkyl-sulphates (fine powder) 30.4 0.5 surplus (unreacted and Na 2SO 4) 1.6 1.9
Agglomerate amounts to 85.0 100.0
Dried yellow soda ash (400-600 micron) 7.8NORS that sneaks out 45.9 siloxanes/PEG defoamer 0.3 lipase 0.3Savinase 0.3
Spray spices 0.4
The finished product amount to 100.0 1The blended particles of citric acid and layered silicate (ratio 2.0) 2Ethylenediamine disuccinate 31～3 micron of granularity 4The ninth of the ten Heavenly Stems acyloxy benzene sulfonic acid sodium salt
Use above-mentioned conventional spraying drying and/or mixing/density technology to prepare the granular laundry detergent of following examples II-III.According to their prescription, with particle and about 2 microns second month in a season (2,3) alkyl-sulphate particle thorough mixing coating layer is arranged in the above the to make free flowing granule of (be about total composition 1%).
Example II
Granulated detergent of the present invention comprises following component:
Secondary (2,3) alkyl-sulphate * 10.0 zeolite A (1～10 micron) 26.0C of component % (weight) 12～14Primary alkyl sodium sulfate salt 5.0 Trisodium Citrates 5.0 yellow soda ash 20.0 white dyess, 0.1 detergency enzymes * * 1.0 sodium sulfate, 15.0 water and minor component surplus * C 14～C 18The mean chain length degree; 1: 1 mixture LIPOLASE/ESPERASE of sodium salt * *
Example II
Surfactant A B C
% (weight) % (weight) % (weight) C 16Secondary (2,3) sodium alkyl sulfate 6.92 9.00 7.60C 16/18Primary alkyl sulphates 2.05 3.00 1.30C 12～C 15Alkyl ethoxy (1-3) sulfuric acid 0.17 0.40 0.10 salt C 14～C 15Alkylethoxylate (EO7) 4.02 5.00 1.30C 16～C 18AE11 alkylethoxylate 1.10 1.40 1.10 (EO11) C 16～C 18AE25 alkylethoxylate 0.85--0.66 (EO25) dimethyl monosubstituted ethoxy C 12～14Alkylammonium----1.40 muriates
Washing assistant Citrate trianion 5.20 10.00 5.00 zeolite 4A 20.50 37.20 17.90 carbonate (Na) 15.00 5.50 12.10 amorphous silicates 2.0 3.00 2.00 3.10SOKALAN CP5 14.00 4.90 3.20 carboxymethyl celluloses 0.31 0.39 0.20
SYNTHETIC OPTICAL WHITNER perborate-hydrate 8.77--5.80 perborate tetrahydrate 11.64--7.40CO 3/ SO 4Percarbonate--12.0--TAED that coats 2--5.00 3.40 Phthalocyanine Zinc 20ppm--20ppmDEQUEST 2060 (Monsanto) 0.36 0.60 0.38MgSO 40.40 0.40 0.40LIPOLASE (100,000LU/g) 0.36 0.25 0.15Savinase (4.0 KNPU), 1.40 1.60 1.40 cellulases (1000CEVU/g), 0.13 0.13 0.26 dirt release agent polymkeric substance 30.20 0.20 0.15 anionic optical brighteners 0.19--0.15 Polyvinylpyrolidone (PVP)--0.15--wilkinite----, 12.50 polyoxyethylene glycol 4----0.30 glycerine----, 0.62 spices, 0.43 0.43 0.43 siloxanes+dispersion agent (defoamer), 0.49 0.60 0.49 moisture content, minor component----surplus---- 1Vinylformic acid/maleic acid; Molecular weight 70,000; Sodium salt 2Tetraacetyl ethylene diamine 3Sulfosalicylic acid, terephthalic acid, 1, the negatively charged ion pet reaction product of 2-propylene glycol, ethylene glycol, sulfoisophthalic acid, Maldonado, the place of production is the same. 4Molecular weight ranges 4,000,000
Previous exemplary use secondary (2,3) alkyl sulfate surfactant and other, mainly be the example of the present invention of anionic additional surfactants, the also alternative mixture that contains various additional cats products and positively charged ion and nonionic additional surfactants of said composition.Useful cats product comprises C 10～C 18Alkyl trimethyl ammonium halogenide, C 10～C 18Alkyl dimethyl (C 1～C 6) hydroxyalkyl ammonium halogenide, C 10～C 18Cholinesterase or the like.If use cats product, its content are 1%～15% of present composition weight.

Claims (6)

1. granular detergent composition, it comprises the particle of the particle that contains one or more detersive surfactants and optional granular annexing ingredient, said particle by the second month in a season of dry powder (2,3) alkyl sulfate surfactant coat substantially.
2. according to the composition of claim 1, wherein detergent composition comprises one or more detergent builder compounds as annexing ingredient.
3. according to the composition of claim 1 or 2, it also comprises one or more detergency enzymes as annexing ingredient in addition.
4. according to the composition of arbitrary claim in the claim 1～3, it also contains in addition and comprises one or more SYNTHETIC OPTICAL WHITNER as annexing ingredient.
5. according to the composition of the arbitrary claim in the claim 1～4, it also comprises one or more fabric softeners as annexing ingredient in addition.
6. method for preparing free-pouring granulated detergent may further comprise the steps:
(a) preparation contains the mixture of one or more detersive surfactants and the annexing ingredient of choosing wantonly, has the granular detergent composition of mean particle size in 400 to 1200 micrometer ranges to provide; With
(b) composition grain of the usefulness basic encapsulation steps of the finely powdered exsiccant second month in a season (2,3) alkyl sulfate surfactant (a).
CN 94192196 1993-04-08 1994-04-05 Secondary (2,3) alkyl sulfate surfactants to coat free-flowing granular detergent compositions Pending CN1124494A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US4550193A 1993-04-08 1993-04-08
US08/045,501 1993-04-08

Publications (1)

Publication Number Publication Date
CN1124494A true CN1124494A (en) 1996-06-12

Family

ID=21938254

Family Applications (1)

Application Number Title Priority Date Filing Date
CN 94192196 Pending CN1124494A (en) 1993-04-08 1994-04-05 Secondary (2,3) alkyl sulfate surfactants to coat free-flowing granular detergent compositions

Country Status (5)

Country Link
EP (1) EP0693106A1 (en)
JP (1) JPH08509014A (en)
CN (1) CN1124494A (en)
CA (1) CA2160109A1 (en)
WO (1) WO1994024243A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100422301C (en) * 2003-10-16 2008-10-01 雷克特本克斯尔荷兰有限公司 Coated bleach particle

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022122474A1 (en) * 2020-12-07 2022-06-16 Unilever Ip Holdings B.V. Composition
EP4108756A1 (en) * 2021-06-25 2022-12-28 The Procter & Gamble Company A laundry detergent powder

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3329616A (en) * 1963-07-31 1967-07-04 Monsanto Co Process for preparing detergents
GB1585030A (en) * 1978-05-22 1981-02-18 Shell Int Research Preparation of salts of secondary monoalkyl sulphuric acids

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100422301C (en) * 2003-10-16 2008-10-01 雷克特本克斯尔荷兰有限公司 Coated bleach particle

Also Published As

Publication number Publication date
WO1994024243A1 (en) 1994-10-27
EP0693106A1 (en) 1996-01-24
JPH08509014A (en) 1996-09-24
CA2160109A1 (en) 1994-10-27

Similar Documents

Publication Publication Date Title
CN1115404C (en) Detergent composition containing optimum proportions of agglomerates and spray dried granules
CN1085247C (en) Secondary alkyl sulfate surfactant with improved solubility by compacting/coating process
CN1037453C (en) Particulate detergent compositions
CN1187432C (en) Particulate laundry detergent compositions containing nonionic surfactant granules
JP3217277B2 (en) Detergent composition
CN1085245C (en) Preparation of secondary alkyl sulfate particles with improved solubility
JPH045080B2 (en)
AU661826B2 (en) Laundry detergent compositions containing crystalling/layeredsilicates
CN1124498A (en) Secondary (2,3) alkyl sulfate surfactants in mixed surfactant particles
CA1303939C (en) Detergent granules and a process for their preparation
CN1046954C (en) Secondary (2,3) alkyl sulfate surfactants in stable enzyme-containing detergent compositions
CN1151158A (en) Cationic bleach activators
JPH0680160B2 (en) Process for making high density granular detergents with improved fluidity.
CN1218500A (en) Agglomerated high density detergent composition containing secondary alkyl sulfate surfactant and processes for making same
CN1142850A (en) Stabilization of oxidation-sensitive ingredients in percarbonate detergent compositions
CN1111594C (en) Make the method for detergent composition
CN1124494A (en) Secondary (2,3) alkyl sulfate surfactants to coat free-flowing granular detergent compositions
CN1124975A (en) Detergent compositions
CN1102954C (en) Percarbonate bleach particles coated with partially hydrated crystalline aluminosilicate flow aid
CN1124495A (en) Secondary (2,3) alkyl sulfate surfactants in high density granular detergent compositions
JPH0672237B2 (en) Process for making high density granular detergents with improved fluidity.
JPH07122079B2 (en) Process for making high density granular detergents with improved fluidity.
CN1230505C (en) Granular detergent component containing zeolite MAP
CN1124499A (en) Secondary (2,3) alkyl sulfate surfactants in detergent compositions with polyhydroxy fatty acid amides
CN1085246C (en) Secondary alkyl sulfate surfactant with improved solubility by kneading/extruding process

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C01 Deemed withdrawal of patent application (patent law 1993)
WD01 Invention patent application deemed withdrawn after publication