CN1343250A - Process for producing coated detergent particles - Google Patents

Process for producing coated detergent particles Download PDF

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Publication number
CN1343250A
CN1343250A CN00804703.0A CN00804703A CN1343250A CN 1343250 A CN1343250 A CN 1343250A CN 00804703 A CN00804703 A CN 00804703A CN 1343250 A CN1343250 A CN 1343250A
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CN
China
Prior art keywords
detergent
coating
mixing tank
particle
composition
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
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CN00804703.0A
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Chinese (zh)
Inventor
P·R·莫特三世
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 Ltd
Procter and Gamble Co
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Procter and Gamble Ltd
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Publication of CN1343250A publication Critical patent/CN1343250A/en
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/046—Salts
    • 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
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
    • C11D11/0088—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads the liquefied ingredients being sprayed or adsorbed onto solid particles
    • 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
    • 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
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • 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
    • 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
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • 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
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • 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
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols

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

Abstract

A process for preparing detergent particles having a coating layer of a water-soluble inorganic material is provided. The detergent particle comprises a particle core of a detergent active material. This particle core is then at least partially covered by a particle coating layer of a water soluble inorganic material. Particularly preferred are non-hydratable inorganic coating materials including double salt combinations of alkali metal carbonates and sulfates. The particle coating layer may also include detergent adjunct ingredients such as brighteners, chelants, nonionic surfactants, co-builders, etc. The process includes the steps of passing the particle core through a coating mixer such as a low speed mixer or fluid bed mixer and coating the particle core with a coating solution or slurry of the water soluble inorganic material. Upon drying, the resultant detergent particles have improved appearance and flow properties and may be packaged and sold as a detergent material or mixed with various other detergent ingredients to provide a fully formulated detergent composition.

Description

The method for preparing cated detergent particles
Invention field
The present invention relates to detergent particles and make this particulate method.More particularly, relate to the detergent particles that has the non-hydrated coating, and make described particulate method from mineral solution.
Background of invention
Recently, in detergent for washing clothes industry, people are for the advantage with liquid laundry cleaning product, as convenient, attractive in appearance and solvability is good, and keep the clean-up performance of granular detergent product and cheaply detergent for washing clothes be very much concern.But the problems such as relevant aesthstic performance, solvability and ease of use that the granular detergent composition in past exists also are difficult to solve.These problems, along with generally be insoluble to washing soln with and the appearance of " high-density " (or low dosage) granulated detergent product of liquid laundry detergent like product and seem even more serious.These low dosage washing composition current needs amounts are very big, because can save resource and selling with small packages, this is comparatively convenient in the human consumer before use, but compare with liquid laundry detergent, just it is so not convenient when it adds in the washing machine, because the latter is as long as directly pour out from bottle simply, opposite saccharoid just needs to be dispensed in the washing soln then from box " bale-out ".
The granular detergent product is generally made by one of two kinds of manufacture method.First method is to make aqueous detergent slurries spraying drying in spray-drying tower, produces detergent particles; And second method is that various compositions do are mixed, then with the binding agent agglomeration of itself and tensio-active agent and so on.Subsequently the gained detergent particles is dried to acceptable degree, in the time of promptly will making it to deliver in human consumer's hand, these the finished product are mobile, and do not lump in packing.In these two kinds of methods, the factor that influences described flowability comprises its chemical constitution and type, and drying process carries out the time.
Comprise many surfactant materials in the granulated detergent, as linear alkyl benzene sulfonate salt (LAS), ethoxylated alkyl sulfates and nonionogenic tenside, these materials are clamminess, and are difficult to complete drying and form piece, the group of formation, make its product the problem of mobile difference occur.Therefore people wish to solve in the Betengent product that makes, because the problem of " viscosity " flowability difference that tensio-active agent brought.
In addition, well-known, organic and/or inorganic materials adds in the washing composition production technique.For example US5576285 introduce to use inorganic double salt as the dry mixed composition in the agglomeration process, and with the dry paint of silico-aluminate, carbonate and silicate as flow control additive.In these methods, coating is coated onto on the particle as dry ingredients, perhaps just deposit or adhere to it in appearance, rather than real apply bond to particle originally on one's body.This patent also discloses in the mixing tank or fluidized-bed with liquid matrix material spirt washing composition technologies such as water, tensio-active agent, polymkeric substance.Some patent introduction will comprise that various materials such as alkalimetal silicate and tensio-active agent spray in the technology of making washing composition, and for example PCT applies for WO97/22685 and WO99/00475, and German patent application DE 4435743.But, to use under the situation of silicate coating, the water absorbability of silicate causes the washing composition lay up period to absorb moisture, and particularly under wet condition, the result makes and washs the agglomerating caking of lotion, makes it be difficult to bale-out, mobile poor, and damages its aesthstic performance.
Therefore, still need to open up a kind of method of producing the granulated detergent of mobile and aesthstic improved performance.
Summary of the invention
Described requirement can be satisfied by the present invention, and the inventive method improves surface, outward appearance and the flowability etc. of the detergent particles of production.Its surface property of particle of the present invention improves, and promptly smoother is more more even than prior art products surface and outward appearance.The improvement of this particle appearance in addition also is to seem brighter, whiter than the present product that can buy.And its flowability also improves, seldom agglomerating caking.
According to the present invention, provide preparation to have the granulated detergent of water-soluble substances coating.This detergent particles contains the grain core of detergent active thing, the conventional detergent particles of tensio-active agent and carbonate blend for example, or contain independent detergent ingredients, for example particle of enzyme, SYNTHETIC OPTICAL WHITNER etc.This core is coated with to the particulate coating bag of small part by water-soluble substances, and this coating can be given its aforementioned performance of improving.Preferred especially non-hydrated inorganic paint comprises the double salt binding substances of alkaline carbonate and vitriol.This particulate coating can also comprise the detergent additives composition, for example whitening agent, sequestrant, nonionogenic tenside, washing assistant etc.
The step of the inventive method comprises enters in the coating mixing tank of slow-speed mixer or fluidized bed for solid mixing and so on grain defined above core, applies this core with the coating solution or the slurries of water-soluble non-hydrated inorganic materials.After the drying, gained detergent particle grain appearance and flowability all improve, and can be used as detergent materials packing and sell, or mixes with various other detergent ingredients the sale of full formula detergent composition packing is provided.
Therefore, the present invention seeks to by with water-soluble non-hydrated inorganic material coating coated detergent grain core, and the method for production outward appearance and the mobile detergent particles that improves is provided.Another purpose is by in mixing tank, applies with inorganic materials solution or slurries, and preparing washing agent particulate method is provided.From following detailed and appended claims, above-mentioned feature and advantage of the present invention, and further feature and advantage will be conspicuous concerning those skilled in the art.
The description of Preferred Embodiments definition
Among the present invention, so-called " particle " refers to comprise the whole size range of washing composition the finished product or composition, or refers to the whole size range of discrete particle, agglomerate or the particle of final cleaning product or constituents mixt.It does not refer in particular to certain granularity mark (representing whole size range below 100%) of any of these grain type, unless this granularity mark is represented 100% of discrete particle in the granular mixture.For all types of particulate components in the mixture, in the whole size range of certain type discrete particle, by identical or similar substantially forming, no matter whether these particles contact with other particle.For the agglomeration composition, itself can be regarded as discrete particle agglomerate, and each discrete particle can be made up of the complex body of less primary particle and binder constituents.
So-called " geometric mean diameter " herein refers to how much mass median diameters by one group of discrete particle of any standard particle size determination techniques based on quality (preferred dry sieve method) mensuration.The phrase of relevant size-grade distribution " geometric standard deviation " or " footpath at interval " are the geometric widths at the best-fit standard logarithmic function of above-mentioned granularity, can be by the particle diameter of the 84.13 hundredths ratio (D divided by the particle diameter of cumulative distribution the 50th hundredths 84.13/ D 50) expression, referring to people's such as Gotoh " powder technology handbook, 6-11 page or leaf, Marcel Dekker 1997.
So-called " washing assistant " refers to have in the detergent range any inorganic materials of wash-aid effect herein, particularly can remove the organic or inorganic material of the water hardness from washing soln.So-called herein " bulk density " refers to not compress, untamped powder accumulation density, its mensuration is that first powdered sample with surplus passes through in the slick metal vessel of funnel impouring (for example cylinder of 500ml volume), the superfluous powder that the container edge is piled up above scrapes off then, measures remaining powder quality and divided by container volume.
So-called " composition " and " granular detergent composition " desires to comprise the finished product and the various additive/composition of detergent composition herein.The composition of being produced by the method for the present invention protection in other words can be a laundry detergent composition completely, perhaps can be the additive that other cleaning ingredients with usefulness such as laundering of textile fabrics uses.
So-called herein " surface-area " but be the powder total surface area of supplied gas absorption, therefore comprise internal surface area (being in the crack) and outer surface area the two.Surface-area adopts BET multiple spot surface-area assay.The grain core
New-type detergent particle of the present invention contains the grain core that scribbles water soluble paint to small part.In preferred embodiments, described grain core can comprise detergent particles, agglomerate or sheet grain etc.Therefore, described grain core preferably contains tensio-active agent, anion surfactant particularly, with dry detergent ingredients, for example carbonate, silico-aluminate, silicate help the blend of washing material, alkali metal sulfates, sequestrant and a small amount of various other dry detergent compositions.In addition, the grain core also can contain indivedual detergent ingredients such as enzyme, SYNTHETIC OPTICAL WHITNER, spices and composition thereof.
Particularly preferred grain core comprises the washing composition agglomerate by the high viscosity tensio-active agent is stuck with paste or the liquid acid precursor of tensio-active agent and aforementioned dry detergent composition generation nodulizing form.The nodulizing of tensio-active agent and dry detergent material can carry out at a high speed or in the moderate-speed mixers, then can be optionally with low speed or the further agglomeration of moderate-speed mixers.
In addition, removing poly-effect can also carry out in single low speed, middling speed or super mixer.The used given mixer of the inventive method should comprise and pulverize or grind and the agglomeration instrument that such two kinds of technologies can be carried out simultaneously in single mixing tank.For this purpose, find with machined parameters described herein, at Lodige KM TM(plough shovel) 600 moderate-speed mixers, Lodige CB TMSuper mixer or by Fukae, the mixing tank that Drais, Schugi make, or in the mixing tank of other trade mark, can successfully finish first processing step.The LodigeKM that the present invention preferably uses TM(plough shovel) 600 moderate-speed mixers comprise the stationary cylinder of a horizontal hollow, wherein feel at ease and adorn a rotating shaft, around rotating shaft several plow-shape blades are housed.The rotating speed of preferred rotating shaft is extremely about 140rpm of about 15rpm, and more preferably from about 80rpm is to about 120rpm.Grind or pulverize with cutting unit and finish, its size is generally less than rotating shaft, preferably with about 3600rpm speed running.Other is applicable to that mixing tank similar on the performance of this technology comprises Lodige Ploughshare TMMixing tank and Drais K-T 160 mixing tanks.
Preferred each detergent ingredients raw material low, in or mean residence time in the super mixer be about 0.05 minute to about 15 minutes, most preferably from about 0.5 to about 5 minutes.By this way, gained detergent agglomerate density can reach desired level.
After the agglomeration then is drying step, and this step can be carried out in wide variety of devices, includes, but is not limited to fluidized bed dryer etc.The moisture eliminator special case comprises fixed or oscillatory type, rectangle bed or circular bed, straight formula or coil tube type moisture eliminator etc.These moisture eliminator manufacturing firms comprise Niro, Bepex, Spray, System and Glant etc.For instance, the moisture eliminator of fluidized-bed and so on can be used for drying, and if desired the time, air lift can be used for cooling.Air lift also can be used to force to make " carefully " grain to blow out, and makes it to be recirculated in the particle agglomeration technology.
Have at least its geometric mean diameter of particle of 50% weight to be about 500 μ m to 1500 μ m in the particle of the present invention, and preferably its geometric standard deviation about 1 is to about 2, more preferably from about 1.0 to about 1.7, and most preferably from about 1.0 to about 1.4.The granular detergent composition that obtains from this method can contain particulate, what is called " particulate " and be defined as geometric mean diameter that its geometric mean diameter is lower than selected granular detergent composition, standard deviation less than 1.65 particle.Can also have macrobead, so-called " big grain " is defined as geometric mean diameter that its geometric mean diameter is higher than selected granular detergent composition, standard deviation greater than 1.65 particle.Preferably particulate is separated from granular detergent composition, and it is joined at least one mixing tank and/or the fluidized bed dryer, and it is got back in the technology, will describe in detail as following.Equally, also preferably big grain is separated from granular detergent composition, it is added in the shredder again, its geometric mean diameter is reduced, and then the big grain that median size has reduced added at least one mixing tank and/or the fluidized bed dryer and get back in the technology.
Agglomeration process can comprise the step of spraying additional adhesive in the mixing tank, helps to produce desirable detergent particles.The adding purpose of binding agent is to strengthen nodulizing by the reagent that detergent ingredients is provided bonding or adhesive effect.Described binding agent is preferably selected from water, anion surfactant, nonionogenic tenside, polyoxyethylene glycol, polyvinylpyrrolidone, polyacrylic ester, citric acid and composition thereof.Other suitable binder material comprises people's such as Beerse U.S. Pat 5108646 (Procter ﹠amp; Gamble company) described, this article is incorporated herein by reference.
Another optional step that forms grain core of the present invention comprises continuous adding coated agent, for example zeolite, above-mentioned recirculation particulate and forge the system silica and wait until in the mixing tank are to improve the particulate color, to improve the particle whiteness or the free-flowing property of the washing composition that helps to be generated and avoided nodulizing.When adopting particulate as coated agent, preferred described particulate granularity is about 0.1 to 0.5 times of larger particles mean particle size.This particulate coating also can improve the integrity of fine coatings, and the anti-friction anti-wear during transporting is provided.In addition, detergent raw material also can add premixer earlier, for example Lodige CB mixing tank or twin screw extruder, and then send into mixing tank.Though this step adopts according to circumstances, help nodulizing really.
The present invention also preferably includes tower spray particulate grain core especially, and in this method, the grain core is formed by the slurries of tensio-active agent, water and the dry detergent raw material of preparation.The gained slurries are sprayed in the airflow by tower, and general temperature is about 175 ℃ to about 225 ℃, makes this slurry dried formation washing composition grain.In general, the gained pellet density is about 200 to about 500g/l.Particulate coating
As previously mentioned, particulate coating of the present invention is a water soluble paint.This coating is given very novel surface of detergent particles of the present invention and apparent character.The cated particle of the present invention has vivider and/or whiter apparent character than prior art particle.This can win that the human consumer better estimates, because of they always like whiter product.In addition, particulate coating of the present invention is also given the great sensorial effect of improving to particle of the present invention, and the cated particle of the present invention has brighter, slick sensation than prior art cleaning product.This can try to please the human consumer more, because of they always like slick and sly product uniformly.The cated particle of the present invention also makes and contains the effects,sound that particulate Betengent product of the present invention has improvement in addition, and it has the more crisp sound than existing cleaning product, and the human consumer is more appreciated its overall impression.
The most important thing is that the cated particle of the present invention provides caking and mobile improvement effect to containing this particulate Betengent product.This particulate coating provides crisp not sticking coating, when improving the whole prod flowability effectively, also make contain surfactant product avoid the caking effective especially, for the product that contains nonionogenic tenside, linear alkylbenzene sulfonate (LAS) and ethoxylated alkyl sulfates, or the cleaning product (being that surface active ingredient is higher than about 25wt%) of high level of surfactant is arranged, be dried to sticking state more difficult.
Particulate coating of the present invention to small part is coated a core, certainly, is coated with though wish that particle can be wrapped fully by particulate coating material, and, in the continuous high speed manufacturing processed, in all cases, realize that topped fully is impossible.Though the topped quite difficulty of quantitative extent that reaches of coating is found, improves the solid glue spread by solids concn in the raising solution or by spraying more solution, can improve applying effect and obtaining more uniform topped apparent.The effect and the cost that dry excess moisture consumes that improve cover ratio in this technology can reach balance.Therefore, in the preferred embodiment of the invention,,, can reach sufficient topped effect most preferably more than about 5wt% if the coating solid that applies is more than the about 3wt% of grain core quality.
Particulate coating of the present invention contains water soluble paint.In the preferred embodiment, described coating is not alkalimetal silicate, because there is stability problem in it in detergent composition, promptly in the washing composition course of processing, the trend that forms insoluble sludge is arranged.Described water soluble paint makes the gained detergent particles that more smooth uniform outward appearance be arranged.Described coating can be from variously giving that it is apparent, selecting the material of flowability and surface property.Preferred material comprises inorganic salt and organic salt, polymkeric substance and combines.Suitable organic salt comprises alkali metal carboxylate, for example Citrate trianion and acetate.Inorganic salt can comprise silicate, boron salt, phosphoric acid salt, magnesium salts and other glassy salt or crystalline inorganic salt.Non-hydrated material most preferably.As for the non-hydrated material, be meant not with environment in moisture, for example moisture in the composition or water in air branch have very strong reaction tendency, form the material of higher hydrates phase.Be the present invention's purpose, the non-hydrated dope layer refers in the coating that 40wt% coating is made up of the non-hydrated inorganic materials at least, preferably more than about 60wt%, most preferably more than about 80wt%.
Described non-hydrated material is preferably selected from basic metal and/or alkaline earth metal sulphate and carbonate or the two mixture.A kind of highly preferred material is formula M nX n: MSO 4: MCO 3Vitriol and the double salt of carbonate, MX is the salt compound of metal halide and so on, wherein MSO in the formula 4And MCO 3The molar fraction of the two accounts for the 10mol% in the formula at least.Preferred MSO 4: MCO 3Mol ratio is about 90: 10 to about 10: 90, and more preferably from about 75: 25 to about 60: 40, wherein M represented basic metal or alkaline-earth metal separately, and n is integer or the mark of 0-5.The example of these height preferred materials is anhydrous sulfate and Carbon Dioxide salt material, forms by the evaporation deposition method is natural, hanksite for example, KNa 22(SO 4) 9(CO 3) 2Cl, and tychite, Na 6Mg 2(CO 3) 4(SO 4).A kind of particularly preferred material is the double salt Na of 2: 1 mol ratios 2SO 4: Na 2CO 3, be the Na that is referred to as " yellow soda ash rock " in addition 6(CO 3) (SO 4) 2
Except particulate coating material, described particulate coating can also comprise the washing composition ancillary component, this comprises various composition of wide range, include, but is not limited to white dyes, pigment or dyestuff, sequestrant, nonionogenic tenside, pH control agent, detergent builder compound, and their mixture.Particularly preferred pigment or dyestuff for example are titanium dioxide, the blue reagent of copper sulfate, thiosulfuric acid zinc and ultramarine and so on; Preferred variegation toughener for example is a sheet mica; And preferred washing assistant, for example be Citrate trianion and nonionogenic tenside.Cated particle
As previously mentioned, particle of the present invention applies production with particulate coating material with the grain core in applying mixing tank.Described coating mixing tank can be that many mixing tanks are any, comprises high speed, middling speed and slow-speed mixer, for example Lodige KM TM(plough shovel form) 600 moderate-speed mixers, LodigeCB TMSuper mixer, or the mixing tank of making by Fukae, Drais, Schugi, or the mixing tank of similar brand.The present invention especially preferably uses low speed drum tumbler and the low fluidized bed for solid mixing of shearing.If adopt the low speed drum tumbler, mixing tank preferably is docile and obedient preface and is connect drying installation, and fluidized-bed for example makes the particle drying after the coating, obtains the coating particles that has of the present invention.
In the preferred embodiments of the invention, applying mixing tank is fluidized-bed.Preferably make washing composition agglomerated particle core, spray-dried granules or most preferably their mixture enter in the fluidized bed dryer of a plurality of inside " stage " or " section ".Described " stage " or " section " are the zones of separating in the moisture eliminator, and this two term is used interchangeably.The processing condition of certain section and other section can be identical or different in the moisture eliminator.Should be clear and definite, two adjacent moisture eliminators are equal to the single moisture eliminator that two sections are arranged.The different feeds logistics of grain core and coating can add at different sections, and this depends on the moisture content etc. of granularity and feed stream.Different streams is introduced at different sections, can make in the moisture eliminator thermal load reduce to minimum, granularity and shape the best that this paper is defined.
In general, fluidized bed for solid mixing of the present invention comprises that first applies section, wherein introduces particulate coating material of the present invention.Described coating section comprises coating with in water liquid or the slurries form spraying influent stream particle.Generally make its fluidisation, so that moisture can dry or part drying in the coating after the spraying with warm air.Spray by shower nozzle, make it carry coating jet flow superfine or atomizing, to reach complete topped particulate effect.In general Wu Hua drop size is less than about 100 μ m.This atomizing can reach by the two-fluid nozzle of conventional belt atomizing air, or reaches by conventional pressure nozzle.For realizing such atomizing, the rheological charactristics of described solution or slurries generally is that viscosity is less than about 500 centipoises, preferably less than about 200 centipoises.Though nozzle can be arranged in any position of fluidized-bed, optimum position is that coating compound is sprayed vertically downward, for example top spray configuration.For reaching best result, the position of nozzle is in particulate fluid height place in the fluidized-bed, or on it.Described fluid height is generally decided by weir lock or overflow lock height.Behind the coating section generally then is arid region or cooling section.Certainly, those skilled in the art are clear and definite, with other structure equipment, also can obtain coating particles required for the present invention.
Another embodiment is used the fluidized-bed that stirs, wherein except comprising that the conventional fluidization air that has passes through the fluidized-bed of dispenser panel, also comprise machinery and/or pneumatic hybrid element, the advantage of this agitated bed is when applying operation, can be used as the means that apply shearing force, control particle shape and slickness.
General condition in fluidized-bed of the present invention or the forced fluidized bed equipment comprises: (i) mean residence time about 1 was to about 20 minutes, (ii) not the degree of depth of fluidized-bed about 100 to about 600mm, (iii) Pen Wu drop size preferably is not more than about 50 μ m, (iv) spray height about 175 is to about 250mm, (v) fluidizing velocity about 0.4 is to about 2.0m/s, and (vi) bed temperature is about 12 to 100 ℃.Equally, those of skill in the art will recognize that these conditions in the fluidized-bed can change according to several factors.
The coated particle that from apply mixing tank, comes out, it can be the full formula detergent composition, promptly itself forms the full formula detergent composition, or in preferred embodiments can with supplementary component, for example SYNTHETIC OPTICAL WHITNER, enzyme, spices, non-coated particle washing composition, and other composition mixing, make the full formula detergent composition.
As previously mentioned, the cated particle surface performance of the present invention improves, and promptly compares with uncoated spray-dried granules or agglomerate detergent granules, and its particle is more even, the surface is more smooth.These features can show from its total surface area minimizing of the cated particle of the present invention, and this is just opposite with the particle that does not have coating of the present invention.Because irregular place on the particulate surface has been glossed, and the space filling is last, so coating of the present invention has reduced total surface area.Can measure the total surface area decrement that coating of the present invention provides by following formula: This per-cent is at least about 10%, more preferably at least about 20%, and most preferably at least 30%.
Surface-area provided by the present invention reduces to cause mobile the improvement, and the highly reflective surface improves the overall aesthetic performance owing to it has more.The surface-area testing method
Measure particulate surface-area of the present invention according to following method.Detergent particles is put into powder technology VacPrep 061 instrument, the processing before testing, described equipment is available from the micromeritics company of Georgia Norcross.This particle is put under about 500 little torr vacuum, and be heated to 80-100 ℃ about 16 hours.Use helium and nitrogen mixture, follow following general condition: vacuum pumping rate-500.0mmHg/ branch; Analytical model-balance; Pumpdown time-1.0 minute; Saturation pressure-771.77mmHg; Starting time-5 second; Helium/nitrogen pressure-15psig; Helium and nitrogen purity-99.9% are measured BET multiple spot surface-area in powder technology Gemini 2375 surface-area analysers, measure freeboard, make topped 0.05 to 0.3 scope of P/Po point with 5 data points of being got.
In addition, there is uniform shape to distribute in the preferably combination composition granule.Specifically, the standard deviation of the circularity distribution value of granular detergent composition of the present invention is less than about 20, preferably less than about 10, be more preferably less than about 7, most preferably less than about 4.And the standard deviation of radius-thickness ratio distribution value is preferably less than about 1, be more preferably less than about 0.5, further preferably less than about 0.3, most preferably less than about 0.2.
In the particularly preferred method of the present invention, the granular detergent composition of being produced, its circularity and radius-thickness ratio long-pending less than about 100, preferably less than about 50, be more preferably less than about 30, most preferably less than about 20.The long-pending distribution value standard deviation of also preferred its circularity and radius-thickness ratio is less than about 45, preferably less than 20, be more preferably less than about 7, most preferably less than about 2.
In the optional embodiments of the present invention, the cated particle of the present invention can carry out the back and apply the light processing, promptly provides bright layer on the particle that has applied.Described bright layer can comprise inorganic salt, sequestrant material, macromolecular material and composition thereof.Preferred inorganic salt material is the vitriol of sal epsom and so on, and preferred sequestrant is the diamines of ethylenediamine disuccinic acid (EDDS) and so on, and preferred macromolecular compound comprises the multipolymer of acrylate copolymer and vinylformic acid/maleic acid and so on.
Detergent composition
The surfactant system of this detergent composition can comprise negatively charged ion, nonionic, zwitter-ion, both sexes and surfactant systems such as positively charged ion and compatibility mixture.Detergent surfactant is described in US 3664961 (granting Norris on May 23rd, 1972), US3919678 (granting people such as Laughlin on December 30th, 1975) to some extent, and this two literary composition is incorporated herein by reference.Cats product comprise described in US 4222905 (granting Cockrell on September 16th, 1980) and the US 4239659 (granting Murphy on December 16th, 1980) those, this two literary composition is incorporated herein by reference.
The non-limitative example of surfactant system comprises conventional C 11-C 18Alkylbenzene sulfonate (LAS) and primary, side chain and random G 10-C 20Alkyl-sulphate (AS), formula CH 3(CH 2) x(CHOSO 3 -M +) CH 3And CH 3(CH 2) y(CHOSO 3 -M +) CH 2CH 3C 10-C 18Secondary (2,3) alkyl-sulphate, x and (y+1) be integer in the formula at least about 7, preferably at least about 9, and M is a water lyotropy positively charged ion, especially sodium also comprises unsaturated vitriol, oleyl sulfate for example, C 10-C 18Alkyl alkoxy sulfate (" AE xS ", EO 1-7 ethoxylated sulfate especially), C 10-C 18Alkyl alkoxy carboxylate salt (the especially ethoxy carboxylate of EO 1-5), C 10-C 18Glyceryl ether, C 10-C 18Alkylpolyglycosides and the poly-glycosides of corresponding sulfation thereof, and C 12-C 18α-sulfonated fatty acid ester.If desired, conventional nonionic and amphoterics, for example C 12-C 18Alkylethoxylate (AE) comprises so-called narrow peak alkylethoxylate and C 6-C 12Alkyl phenolic alkoxy thing (especially ethoxylate and oxyethyl group/propoxylated glycerine mixture), C 12-C 18Trimethyl-glycine and sultaine (Sultaines), C 10-C 18Amine oxides etc. also can be included in this surfactant system.Can also use C 10-C 18N-alkyl polyhydroxy fatty acid amide.Typical example comprises C 12-C 18The N-methyl glucose amide, referring to WO9,206,154.Other sugared deutero-tensio-active agent comprises N-alkoxyl group polyhydroxy fatty acid amide, for example C 10-C 18N (3-methoxy-propyl) glucamide.The N-propyl group is to N-hexyl C 12-C 18Glucamide can be used under the low bubble situation.Also available C 10-C 20Conventional soap class.High if desired foam then can use side chain C 10-C 16Soap.Negatively charged ion and nonionogenic tenside particularly suitable.Other conventional tensio-active agent that uses is listed in the standard textbook.
Detergent composition can (preferably) comprise detergent builder compound.Washing assistant generally is selected from various water-soluble alkalis, ammonium or replaces phosphoric acid salt, polyphosphate, phosphonate, polyphosphonic acid salt, the multi-carboxylate of ammonium.The above-mentioned salt of preferred as alkali, particularly sodium.Preferably use phosphoric acid salt, carbonate, silicate, C herein 10-C 18Lipid acid, multi-carboxylate and composition thereof.Tripoly phosphate sodium STPP, Trisodium pyrophosphate, Citrate trianion, tartrate list-and two-succinate, water glass and its mixture (face as follows) most preferably.
The object lesson of inorganic phosphate builders is tri-polyphosphate, the pyrophosphate salt of sodium and potassium, polymkeric substance metaphosphate and the orthophosphoric acid salt of the about 6-21 of the polymerization degree.The example of multi-phosphate detergent builders is the sodium of ethylene phosphoric acid and sylvite, ethane 1-hydroxyl-1, the sodium of 1-bisphosphate and sylvite, ethane 1,1, the sodium of 2-triphosphoric acid and sylvite.Other phosphorus washing-aid compound is disclosed in US 3,159, and 581, among US 3,213,030, US 3,420,021, the US 3,422,137,3,400,176, all these patents all are incorporated herein by reference.
The example of non-phosphorus inorganic builders is carbonate, supercarbonate, sesquicarbonate, tetraborate decahydrate and the SiO of sodium and potassium 2With alkali metal oxide weight ratio about 0.5 to about 4.0, preferred about 1.0 to about 2.4 silicate.Be applicable to that water-soluble non-phosphorus organic washing-assisting detergent of the present invention comprises polyacetic acid salt, carboxylate salt, multi-carboxylate and many carboxyls sulfonate of various basic metal, ammonium and replacement ammonium.Polyacetic acid salt and multi-carboxy acid salt washing agent's example is sodium salt, sylvite, lithium salts, ammonium salt and the substituted ammonium salt of ethylene diaminetetraacetic acid, nitrilotriacetic acid(NTA), oxygen di-succsinic acid, mellitic acid, benzene polycarboxylic acid and citric acid.
The polymkeric substance multi-carboxy acid salt washing agent is recorded among the US 3308067 (granting Diehl on March 7th, 1967), and the disclosure content is incorporated herein by reference.These materials comprise the homopolymerization and the multipolymer water-soluble salt of aliphatic carboxylic acid, for example toxilic acid, methylene-succinic acid, methylfumaric acid, fumaric acid, equisetic acid, citraconic acid and methylene radical propanedioic acid.Some uses as following described water-soluble anionic polymer in these materials, but only is can when closely mixing with non-soap anionic surfactant.
The multi-carboxylate that other suitable this paper uses is the polyacetal carboxylation, as described in US4144226 (granting people such as Crutchfield on March 13rd, 1979) and US4246495 (granting people such as Crutchfield on March 27th, 1979), two Wen Jun are incorporated herein by reference.These polyacetal carboxylations' preparation method places the ester of Glyoxylic acid hydrate and polymerization starter under the polymerizing condition to react.Then the gained polyacetal carboxylic acid ester is connected on the chemical stability end group, makes it stable, avoid very fast degraded in basic solution, convert corresponding salt to, and join in the detergent composition.Particularly preferred multi-carboxy acid salt washing agent is the ether carboxylate composition that contains tartrate monosuccinic acid salt and tartrate disuccinic acid salt mixture, and described in US 4663071 (granting people such as Bush on May 5th, 1987), the disclosure document is incorporated herein by reference.
Formula SiO 2M 2The water-soluble silicate solid of O (M is a basic metal) representative, wherein SiO 2: M 2O weight ratio about 0.5 is the salt that detergent particles of the present invention is suitable for to about 4.0, and its consumption counts about 2% to about 15%, preferred about 3% to about 8% with moisture free weight.Anhydrous or hydration granular silicon hydrochlorate is all available.
Some kinds of supplementary components also can add in this granular detergent composition, comprise that other helps washing, SYNTHETIC OPTICAL WHITNER, bleach-activating agent, short infusion or suds suppressor, resistant to tarnishing agent and corrosion inhibitor, soil-suspending agent, scale remover, sterilant, pH regulator agent, non-washing assistant alkali source, sequestrant, terre verte, enzyme, enzyme stabilizers and spices.See US 3936537 (granting people such as Baskerville, Jr. on February 3rd, 1976), this article is incorporated herein by reference.
SYNTHETIC OPTICAL WHITNER and activator were introduced in US 4412934 (granting people such as Chung November 1 nineteen eighty-three), US 4483781 (granting Hartman on December 20th, 1984), and two Wen Jun are incorporated herein by reference.Sequestrant is recorded in US 4663071 (people such as Bush sees that this article the 17th hurdle, the 54th walks to the 18th hurdle, the 68th row, is incorporated herein by reference).The foam modifying agent also is the composition that optionally adds, and among US 3933672 (granting people such as Bartoletta on February 20th, 1976) and the US 4136045 (authorizing people such as Gault on January 23rd, 1979) description is arranged, and two Wen Jun are incorporated herein by reference.
Suitable terre verte walks to the 7th hurdle the 24th row (being incorporated herein by reference) referring to the 6th hurdle the 3rd among the US 4762645 (authorizing people such as Tucker on August 9th, 1988).Patent the 13rd hurdle, the 54th that other suitable detergent builder compound is recited in above-mentioned Baskerville walks among the 16th hurdle, the 16th row and the US 4663071 (authorizing people such as Buch on May 5th, 1987), and two Wen Jun are incorporated herein by reference.
The following examples are the purpose for illustrating only, does not constitute the restriction to the present invention.
All content are all with the weight percent meter of composition among the following embodiment.
Example I
In the present embodiment, washing composition agglomerate composition by the coating of non-hydrated inorganic salt, use following formulation as follows: in super mixer, to carry out the dry neutralization effect of HLAS, then in second moderate-speed mixers, carry out the paste nodulizing with pre-neutralization NaLAS, that continues sprays yellow soda ash rock solution (5% solid) in fluidized bed dryer.Super mixer (dry neutralization) Na 2CO 3Intermediate 82%NaLAS paste 18% agglomeration grain core 100% fluidized-bed after intermediate 82% moderate-speed mixers (paste agglomeration) dry neutralization after 59%HLAS 23% dry neutralization applies and dry agglomeration grain core 100% particulate " dirt ash " (zeolite, Na 2CO 3) 2% the spraying on solution *5% cated this solution composition of product 107%* of (with the wet basis restatement) 17.5% evaporation-12.5% solid net weight of coating (burkeite) is 1.5wt%Na 2CO 3, 3.5wt%Na 2SO 4And 12.5wt%H 2O.
Spray solution can be by the burkeite preparation of raw material among this embodiment, and promptly water-soluble with about 28.5wt% solid, perhaps with yellow soda ash and sodium sulfate, the mixed thing of pressing about 30: 70 is water-soluble, makes total salt solid reach about 28.5wt% in water.This solution is sprayed into drop, be coated on the core agglomerate, or part applies on it.In about 40-80 ℃ bed, make moisture evaporation then.After the evaporation, the salt co-precipitation forms the burkeite coating.
Example II
The granular detergent composition that this example applies with organic salt, as follows by following formulation: as to adopt spraying drying grain core, in fluidized bed dryer, spray potassium citrate solution (5% solid).Solution (with the wet basis restatement) 9% evaporation-3% solid net weight of coating (Tripotassium Citrate) 6% cated this solution composition of product 106%* that fluidized-bed applies and dry spraying drying grain core 100% is sprayed is 3.1wt%K 2CO 3, 2.9% citric acid and 3wt%H 2O.
In this example, spray solution dissolves altogether in water with salt of wormwood and citric acid and is made into.This solution is sprayed into that drop-coated is overlying on the agglomerate grain core or part applies on it.Transpiring moisture in 40-80 ℃ of bed then.After the evaporation, organic salt, promptly Tripotassium Citrate forms coating or partial coating on the spray-dried granules surface.

Claims (10)

1. preparing washing agent particulate method is characterized in that comprising the steps:
I) providing with the detergent active material is the grain core of feature;
Ii) described grain core is sent into and applied in the mixing tank;
The coating solution of water-soluble non-hydrated inorganics iii) is provided for described coating mixing tank; With
Iv) in described coating mixing tank, make a core, form detergent particles to the small part coated.
2. the process of claim 1 wherein described grain core is characterized in that it being the blend of anion surfactant and dry detergent ingredients.
3. each method of claim 1-2, the blend of wherein said anion surfactant and dry detergent ingredients is selected from detergent agglomerate, spray-dried granules, detergent tablet, and composition thereof.
4. each method of claim 1-3, wherein said coating mixing tank are selected from slow-speed mixer, fluidized bed for solid mixing and they combine.
5. each method of claim 1-4, wherein said coating mixing tank is a fluidized bed for solid mixing.
6. each method of claim 1-5, wherein said water-soluble non-hydrated inorganics is selected from alkaline carbonate, alkali metal sulfates and composition thereof.
7. each method of claim 1-6, wherein said water-soluble non-hydrated inorganics is double salt Na 2SO 4: Na 2CO 3, Na wherein 2CO 3With Na 2CO 3Weight ratio be 80: 20 to 20: 80.
8. each method of claim 1-7, the wherein said step that aqueous coating solution is provided, its further feature are that described coating solution is sprayed in the into described coating mixing tank.
9. each method of claim 1-8, wherein said coating mixing tank is to have phase-splitting planar fluidized-bed, and described coating solution is on described minute phase plane the described fluidized-bed of spirt.
10. preparing washing agent particulate method is characterized in that comprising the steps:
A) provide the surfactant materials and the dry detergent raw material of paste shape or liquid form;
B), form the grain core with described surfactant materials and dry detergent raw material blend;
C) described grain core is sent in the coating mixing tank;
D) provide the coating solution of water-soluble non-hydrated inorganics for described coating mixing tank; With
E) in described coating mixing tank, make described grain core to the small part coated, form detergent particles.
CN00804703.0A 1999-03-09 2000-03-08 Process for producing coated detergent particles Pending CN1343250A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105473699A (en) * 2013-08-28 2016-04-06 诺维信公司 Enzyme granule with fluorescent whitening agent
CN111893008A (en) * 2020-08-10 2020-11-06 纳爱斯集团有限公司 Washing preparation and preparation method thereof

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10221742A1 (en) * 2002-05-16 2003-12-04 Henkel Kgaa Builder granules
EP2584028B1 (en) * 2011-10-19 2017-05-10 The Procter & Gamble Company Particle
EP2639291A1 (en) * 2012-03-13 2013-09-18 Unilever PLC Packaged particulate detergent composition
WO2013139702A1 (en) * 2012-03-21 2013-09-26 Unilever Plc Laundry detergent particles
EP3140386B1 (en) * 2014-04-10 2024-02-28 The Procter & Gamble Company Composite detergent granules and laundry compositions comprising the same

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4105827A (en) * 1973-04-20 1978-08-08 Interox Particulate peroxygen compounds coated with sodium sesquicarbonate or Na2 SO4 mNa2 CO3
FR2226460B1 (en) † 1973-04-20 1976-12-17 Interox
DE2652776A1 (en) † 1975-05-13 1978-05-24 Interox Chemicals Ltd Stabilised sodium percarbonate mfr. - by precipitating in presence of silicate, then increasing the silicate content of the mother liquor
LU72575A1 (en) † 1975-05-23 1977-02-10
CA2160900A1 (en) * 1993-04-19 1994-10-27 Cornelis Marinus Van't Land Fluidized bed coated amidoperozyacid bleach composition
EP0623553B1 (en) † 1993-05-06 1997-07-30 Mitsubishi Gas Chemical Company, Inc. Stabilized particle of sodium percarbonate
DE69326833D1 (en) † 1993-07-14 1999-11-25 Procter & Gamble Stabilized detergent compositions
US5576285A (en) * 1995-10-04 1996-11-19 The Procter & Gamble Company Process for making a low density detergent composition by agglomeration with an inorganic double salt
IL126368A (en) † 1996-03-27 2001-12-23 Solvay Interox Sa Process for producing a percarbonate
DE19713328A1 (en) * 1997-03-29 1998-10-01 Henkel Kgaa Stabilisation of granular materials to prevent clumping
ATE250661T1 (en) † 1998-07-17 2003-10-15 Procter & Gamble DETERGENT TABLET

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105473699A (en) * 2013-08-28 2016-04-06 诺维信公司 Enzyme granule with fluorescent whitening agent
CN111893008A (en) * 2020-08-10 2020-11-06 纳爱斯集团有限公司 Washing preparation and preparation method thereof

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