CN1104693A - Fabric care compositions - Google Patents

Fabric care compositions Download PDF

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Publication number
CN1104693A
CN1104693A CN94104208A CN94104208A CN1104693A CN 1104693 A CN1104693 A CN 1104693A CN 94104208 A CN94104208 A CN 94104208A CN 94104208 A CN94104208 A CN 94104208A CN 1104693 A CN1104693 A CN 1104693A
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CN
China
Prior art keywords
composition
spices
particle
mixture
clad
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
CN94104208A
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Chinese (zh)
Inventor
黛安·格洛·施米特
霍华德·约翰·巴特利
罗伯特·詹姆斯·诺布里
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
3M Co
Original Assignee
Procter and Gamble Co
Minnesota Mining and Manufacturing Co
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Filing date
Publication date
Application filed by Procter and Gamble Co, Minnesota Mining and Manufacturing Co filed Critical Procter and Gamble Co
Publication of CN1104693A publication Critical patent/CN1104693A/en
Pending legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/50Perfumes
    • C11D3/502Protected perfumes
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/50Perfumes
    • C11D3/502Protected perfumes
    • C11D3/505Protected perfumes encapsulated or adsorbed on a carrier, e.g. zeolite or clay
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039Coated compositions or coated components in the compositions, (micro)capsules
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047Detergents in the form of bars or tablets
    • C11D17/0065Solid detergents containing builders
    • C11D17/0069Laundry bars
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005Other compounding ingredients characterised by their effect
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005Other compounding ingredients characterised by their effect
    • C11D3/001Softening compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10Objects to be cleaned
    • C11D2111/12Soft surfaces, e.g. textile

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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)
  • Dispersion Chemistry (AREA)
  • Fats And Perfumes (AREA)
  • Detergent Compositions (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Manufacturing Of Micro-Capsules (AREA)
  • Cosmetics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Disinfection, Sterilisation Or Deodorisation Of Air (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

Perfume particles comprise perfume dispersed within certain water-insoluble polymeric carrier materials and encapsulated in a protective shell by coating with a friable coating material. The coated particles allow for preservation and protection of perfumes which are susceptible to degradation or loss in storage and in harsh cleaning conditions. In use, the surface coating fractures and the underlying carrier/perfume particles efficiently deliver a large variety of perfume types to fabrics or other surfaces.

Description

Fabric care compositions
The present invention relates to perfume particle, it contains and is scattered in the water-insoluble low-molecular-weight polymeric carrier mass and with the spices of frangible covering sealing.These coated pellet are useful in as washing and fabric-conditioning mixture.
The present invention is based on controlled spices and discharge this notion, promptly sometime and the spices under the condition of the fragrance effects that to require discharge, in general, this is a very old viewpoint, has proposed from spices being placed on simple idea the candle to the several different methods of the complex technology of little envelope method for obtaining this result.
An aspect of this notion of controlled release of spices is the release at a slow speed of keeping spices period all the time that continues.This generally can realize by spices is mixed with a kind of material, thereby this material can be collected spices basically and make a spot of spices to discharge from start to finish, and it is known that this heavy polymer matter that is mixed with spices is used to the delayed controlled release of spices is provided.See the people's such as Lindauer that authorize as on January 15th, 1980 United States Patent (USP) 4,184,099; May in 1981 disclosed Leonard on the 6th european patent application 0,028,118; And on August 29th, 1978 Newland that authorizes United States Patent (USP) 4,110,261, they have been told about spices combined with the control dissolution medium and make this mixture form solid product and have been used to purify air.
Fabric washing is also relevant with the controlled release of spices.Use this notion to make to slow down or stop spices release during long term storage on screen work to become possibility.Because the consumption of spices is quite few, this notion also makes uses quite low flavour content to become possibility in product.
Spices can adopt multiple mode in the preservation of duration of storage.Spices can be made into the part of mixture packing.United States Patent (USP) 4,540,721 as the Staller that authorized on September 10th, 1985 is described, and spices can combine with the plastics that are used to make bottle, or with polymer and the product that is used to coat the carton package composition mix.Spices all discharges from polymeric matrix in arbitrary mode from start to finish.
Spices/controlled release medium also can be the particle form of sneaking into purging compound.According to stating a kind of method that obtains this result is that spices is combined with water-soluble polymer.Make it to form particle and join in the purging compound, as the United States Patent (USP) 4,209,417 of the Whyte that authorizes on June 24th, 1980; Described in the people's such as Gould that the United States Patent (USP) of the Whyte that authorize July 13 nineteen eighty-two was authorized on April 27th, 4,339,356 and 1971 the United States Patent (USP) 3,576,760.
Spices is also adsorbable to the porous carrier material, and this carrier mass can be a polymeric material.See as July in 1981 people such as disclosed Bares on the 15th BP disclose 2,066,839(is with Vysoka Skola Chemicko Technologika name application).These methods also can be used in the shield hybrid thing offensive odour or protection spices avoids being washed mixture moderate stimulation component degradation.These class methods only just can obtain these advantages for dry powder or particulate mixtures, because once discharging when polymer hydration spices.Therefore, these methods have guaranteed that one has the advantage of spices fragrance when opening the packing of product and packing washing machine into.Although wishing has these advantages, more wish to have a kind of can make undiluted, scatter and disappear and unaltered spices is passed to fabric and when washing process finishes the method for release spices so that on fabric, smell desirable fragrance.
Certainly, a kind of method that obtains this result is that spices is put into the product that directly enters drying machine.Like this, just spices has been passed to fabric in the drying machine on-stream period, this method is all to illustrate in the United States Patent (USP) 4,636,330 of the Melville that on January 13rd, 4,511,495 and 1987 authorized of the United States Patent (USP) of the Melville that authorizes on April 16th, 1985.Two pieces of patents all propose to make spices form particle with carrier, these particle formulation resulting mixtures, this mixture are used on the fabric before fabric is put into drying machine or before drying on the clothes-line then.
A kind of spices pass to the better method of laundering of textile fabrics be guarantee in washing process protection spices and subsequently with spices basically with its originally state transfer give fabric.
This method must be convenient to prevent dilution, degraded or the loss at the washing phase of laundry processes spices.This can be by using a system that discharges spices to realize in dry run or after spices is passed to fabric.Prevent spices lost very difference and more difficult technologies of relating in washing process.This protective effect not only must be stable under the wash conditions of heat temperature raising but also must be stable in the degradation of other harsh chemicals of anti-water and washing process such as bleaching agent, enzyme, surfactant etc.
A kind of method of these advantages of acquisition that now proposed is little envelope methods of spices.Here spices comprise one by can be polymeric material cover fully seal nuclear.The people's such as Brain that on March 20th, 1979 authorized United States Patent (USP) 4,145, the United States Patent (USP) 4 of the Schilling that on November 18th, 184 and 1980 authorized, 234,627 point out to use a kind of hard close coating material that can prevent to come from the diffusion of spices basically, spices through micro-capsule pass to fabric then when handling fabric contingent micro-capsule break and scatter and disappear.
The another kind of method of the transmission of spices comprises and guarantees to discharge spices at washing phase protection spices in the drying machine at heat temperature raising; the people's such as Brock that on June 20th, 1978 authorized United States Patent (USP) 4; 096; 072 has told about and a kind ofly by the particle that contains hydrogenated castor oil ﹠ fat quaternary ammonium salt fabric conditioner has been passed to the method for fabric in washing and dry period, can mix spices in these particles.Yet when particle was soft, the spices that so mixes was to discharge or more satisfactory be carried at that to enter drying machine in the particle and discharge be unclear in drying machine in the washing phase.
The people's such as Schnoring that authorize September 6 nineteen eighty-three United States Patent (USP) 4,402,856 has been told about a kind of little encapsulation technique, and it comprises a kind of can making from the spices in the packing only at the composition of holding the shell material that spreads under the fixed temperature.Be convenient to like this perfume particle store and other washing during preservation.Particle is attached to also being brought into drying machine on the fabric, so the diffusion of spices from packing only takes place under the heat temperature raising situation of drying machine.These particles are to be made by gelatin, a kind of anionic polymer and a kind of hardener,
The United States Patent (USP) 4 of the Young that on May 1st, 1979 authorized; 152; tell about in 272 spices mixed in the Wax particles so that in dry mixture, store and washing process in protect spices, thereby spices cerul body by particle under the heat temperature raising condition of drying machine is diffused on the fabric.
Wish to form and contain the mixture that to mix the perfume particle in liquid and dried particle or mixture of powders and keep long storage-stable.
Be desirable to provide and a kind of very large-scale fragrance material passed to fabric or other surperficial method in washing and fabric or fiber conbidioning process.
Especially wish to obtain a kind of fragrant washing or conditioning mixture of containing, this mixture can guarantee to improve the smell of product, improves the smell of the spices that discharges and improve smell and the intensity that passes to the spices that is washed the surface in washing process.
Be desirable to provide in fluid mixture stable especially but can discharge containing of spices of fragrant particle when using.
The present invention includes perfume particle, (preferable particle mean size is not more than 150 microns to particle mean size after it coats less than about 350 microns, best particle size range is the 40-150 micron), containing 5% to about 70% the spices of having an appointment is dispersed in from about 30% to about 95% the water-insoluble polymeric carrier material, the molecular weight of carrier mass from about 100 to about 30,000, fusing point from about 37 ℃ to about 190 ℃ and hardness number from about 0.1 to about 15, this particle has frangible clad (" granularity " is meant average particulate diameter to big extremely particle spherical in shape, and aspherical particle is meant maximum gauge or size) here at its outer surface.Grain graininess can produce more loss and can not guarantee relatively enough big surface area so that discharge spices under the speed that requires greater than this value from their deposition surface.In addition, can be easy to discover on processed surface greater than the particle of above-mentioned given granularity, this be undesirable, and the particle that is in above-mentioned scope lower bound tends to well attached on the processed surface but tend to very rapidly discharge spices.
The particle here is generally to contain 1% to 20%(weight) the clad that contains perfume particle be feature.For the general service of fabric washing and conditioning mixture, clad generally contains 1% to 10%(weight) contain perfume particle.
Here preferable particle is that wherein frangible clad is water-insoluble substantially.Such suitable coating material can be prepared by the product of aminoplast polymer such as amine and aldehyde.Typical frangible coating material package is drawn together, such as the product of the amine that is selected from urea and melamine with the mixture of the aldehyde that is selected from formaldehyde, acetaldehyde and glutaraldehyde and these amine and these aldehyde.This frangible clad will be described in the back.
The perfume particle of this coating can be used for this situation: destroyed or wear away (such as in automatic washing machine or washing dryer) particle is emitted at this particle clad, then particle discharges its spices again.Therefore, coated pellet can be used for containing in the typical purging compound such as cleanliness surfactant, selectivity builder.Particle can be used for again containing in the conditioning mixture of fiber and fabric conditioner.
Here all percentages unless otherwise indicated all are weight percentage.
The present invention can make the spices that is included in washing and the conditioning mixture be preserved, protect and discharge under long term storage and irritating wash conditions.This can realize by the spices that separation is in the carrier mass of granule shape, now go through each several part of the present invention.
The particle that contains spices
The particle that contains spices of the present invention comprises the spices that is scattered in the specific support material.The particle that contains spices is coated by frangible clad material, and this clad material breaks when using and emits the particle that contains spices, and this particle discharges its spices again.
In the scope of this paper, term " spices " refers to any dulcet material or any material that plays the counteractant effect.Usually, these materials have at room temperature vapour pressure greater than the feature of ambient pressure.Spices used herein or deodorant material be liquid normally at room temperature, but also can be that solid is such as various camphoraceous perfumes known in the art.Known have many kinds of chemicals to can be used as spices, comprises materials such as aldehydes, ketone, ester class.More common ground, known natural plant and animal oil and the exudate that comprises the complex mixture of number of chemical component can be used as spices, and these materials also can be used for the present invention.The spices here can be considerably simple on forming, and also can contain the highly doped complex mixture of natural and synthetic chemical constituent.The required smell of these all selected acquisitions.
Wherein typical perfumes can contain such as the wooden/soil property matrix that contains such as sandalwood oil, civetta, patchouli oil or the like foreign substance.Spices herein can be the faint fragrance of a flower, for example rose extract, violet extract or the like.Spices herein can be prepared so that the fruit aroma of hope to be provided, for example bitter orange, lemon, fragrant citrus or the like.Suitable spices comprises Musk ambrette, ketone musk, musk tibetene, mixed xylenes Moschus, aurantiol, Ethyl vanillin and composition thereof.
This class fragrance material is at the Perfume Flavors and Chemicals of S.Arctander work, Vols.I and II, Aurthor, Montclair, N.J., and Merck Index, 8th Edition, Merck ﹠amp; Co., Inc.Rahway has carried out detailed description among the N.J., is incorporated herein these two pieces of lists of references as a reference.
In brief, any chemically compatible, disperse a kind of material pleasant or other desirable smell and all can be used for containing and provide desired smell when making it be used for fabric in the perfume particle herein.
Generally be solid-state spices and also can be used for the present invention.They can be before mixing particle with liquefier such as solvent, perhaps as long as spices does not distil or decomposes during heating, just simply their fusings and mix.
The present invention also comprises the use of the material that is used as counteractant.Although these materials are called " spices " hereinafter, itself can have discernible fragrance and can hide or weaken any irritating smell.The example of suitable counteractant is disclosed in the people's such as Hawley that authorized on August 27th, 1963 the United States Patent (USP) 3,102,101.
Of the present inventionly contain perfume particle even comprise usually and be not used for fragrance is reached as the spices on the fabric face in the washing process.In being used for discharging the specific mixture of spices, be highly susceptible to volatilizing, unstable or soluble fragrance material can be used for the present invention because spices can be separated from the mixture of particle.The fragrance material of not perpetuity on fabric also can be used for the present invention because particle is passed to fabric face to spices and is released at this in laundry processes.Therefore, use the present invention that spices is reached the kind that the surface has enlarged operable fragrance material.
Usually, the perfume particle that contains of the present invention contains and has an appointment 5% to about 70%, is preferably to contain about 5% to about 50% spices.The definite quantitative changeization of the spices that uses in the particle is very big, depends on the intensity and the desired fragrance effects of the specific fragrance of use.
The carrier mass that contains perfume particle must satisfy some standard for being used for the present invention.At first, carrier mass must be water-insoluble polymeric material.In addition, the molecular weight of material must be between about 100 to about 30000, and is preferable between about 500 to about 5000.The molecular weight of carrier mass can be determined with any standard method.The fusing point of material must be generally 37 ℃ to 130 ℃ between about 37 ℃ to about 190 ℃.Like this can be in the fusing of storing or in the rinsing maching of laundry usefulness, prevent particle.(optimal carrier mass is not exclusively fusing in automatic drier, with the obstruction of avoiding velveteen net in the drying machine and the undue accumulation of heat).The fusing point of carrier mass also should not be higher than the temperature of the spices decomposition of combination with it.The fusing point of carrier mass is measured with so-called drop melting point method.American Society for Testing and Materials(ASTM) Test Method D127-63(1982 ratifies once more, lists as a reference at this).In brief, this method comprises the steps.By making on the thermal bulb of tested sample attached to thermometer in the sample that the thermometer of cooling is inserted fusing.Then the thermometer that has sample is put into test tube and be heated to sample fusing and fall till first from thermometer bulb with water-bath.The mean temperature that sample drop falls is exactly the some melt drop temperature of sample.
Polymer also must have specific hardness.Hardness number can be measured with the standard method of test of pertroleum wax needle penetration.ASTM Test Method D1321-86(is incorporated herein for reference).In brief, this method comprises at first tested sample fusing is heated above 17 ℃ at its freezing point (30) then.Then sample is poured in the container and under controlled condition and cooled off with air.Then sample is adjusted under probe temperature in water-bath.Then, promptly standard pin was acted on for 5 seconds under 100 gram loads on sample with penetrometer surveyingpin in-degree.Needle penetration or hardness number are that standard pin thrusts the degree of depth in the wax under these qualifications, and with a few tenths of expression of millimeter, in order to be used for the present invention, the hardness number of carrier mass must be preferably between 0.1 to 8 between about 0.1 to about 15.So just can guarantee the particle of certain degree of hardness and make that the protection/preservation of spices reaches optimization in the carrier.
Carrier mass also must be also not tasteless comparatively speaking with the spices chemically reactive, and this material must be able to make spices pass through its diffusion.Carrier mass also must melt and not decompose.
The non-limiting example of spendable carrier mass comprises polyethylene kind, polyamide-based, polystyrene type, polyisoprene class, polycarbonate-based, polyesters, polyacrylate, polyvinyl class and polyurethanes and composition thereof, they satisfy above-mentioned standard, for example they are water-insoluble, molecular weight is about 100 to about 30, between 000, fusing point between about 37 ℃ to 190 ℃ and hardness number between 0.1 to 15.
The hardness number that best carrier has is 0.1 to 8, general 0.5; Molecular weight is 500 to 5, and 000(general 2,000); Fusing point be about 126 ℃-be generally polyethylene.
Satisfying a kind of carrier mass of all these limit standards is sold by Petrolite Speciality Polymers Group with commodity POLYWAX2000 by name.This material is a kind of polyethylene, and molecular weight is about 2,000, and fusing point is about 259 °F (126 ℃), and hardness number (recording as stated above) is about 0.5 at 77 °F (25 ℃).The another kind of material that satisfies these standards is that POLYWAX1000(is also sold by Petrolite Speciality Polymers Group).This material also is that a kind of molecular weight is about 1,000, about 237 of fusing point (114 ℃), and 77 °F (25 ℃) are the polyethylene of hardness number about 1.0 down.Another kind of such material is POLYWAX500.
In perfume particle of the present invention, wish to use the mixture of different carriers material, for example the mixture of polymer and a small amount of wax stock.The example of spendable wax stock comprises with commodity BOLER 1014 by name, the material that STARWAX 100 and VICTORY sell, and all these all can have been bought from Boler Petroleum Company.This mixture has adhesion property preferably, because have " more tacky " surface by its particle that forms.As long as the final mixture of carrier mass satisfies above-mentioned standard, the combination of a large amount of materials is possible and is hopeful to be contained among the present invention.
Be used for being chosen in of carrier mass that the present invention contains perfume particle and depend on employed specific spices on some degree.Some spices needs the protection of higher degree than other spices, and therefore the carrier mass that uses therewith can be done corresponding selection.
Usually, be used for the perfume particle that contains of the present invention and contain and have an appointment 30%, be preferably about 50% to about 95% carrier mass, and this can become with type and amount of employed specific spices to about 95%.
In a typical process, containing perfume particle can prepare as follows.At first carrier mass slowly is heated to its fusing point.With this material be heated to just in time melt temperature required promptly need not continue the heating.At room temperature promptly the spices that is generally oily or liquid is joined in the carrier mass that has melted then.These two is mixed into uniform mixture rapidly uses liquid nitrogen (or method of dry ice or the rapid cooling mixture of any energy) to cool off rapidly up to solidifying fully then.Then usually to pulverize or to grind the particle that the finely-divided solid material prepares the particle mean size that requires.Other method also can be used for finely divided particulate such as spraying cooling or extruding.
For the further spices of stable volatilization especially easily or rapid wear, wish spices with spices (for example, potpourri) is added on silica gel or the clay in advance before carrier mass mixes.Some not too volatile spices does not need this special treatment because can suppress their release from carrier mass widely.Purpose is the speed optimization that spices is discharged from carrier, and this selectable additional step is convenient to some more volatile spices and is obtained better speed control.
Clad
The above-mentioned frangible clad of perfume particle sealing formation that contains.This clad prevents that spices from freely spreading from particle at long-term lay up period.Moreover this covering helps to keep having original " feature " of the spices of volatile especially main feature.In addition, this clad helps to protect sneaking into of other component of containing in the composition that perfume particle avoids being furnished with spices.
Coating material used herein is frangible, and purpose is when using the prescription sneak into spices it to be broken, and contains perfume particle thereby discharge.
Thereby can being coated more than a kind of frangible coating material, this particle produces the particle that has more than a clad.As long as one of them clad (generally being outermost layer) is frangible, can select different clad materials to reach different spices protection effects as required.
The single perfume particle that contains also can contain many single larger particles that contain perfume particle with the coalescent acquisition of coating material.The particles coalesce material of this parcel is that the diffusion of spices from particle brought additional barrier, and this method also makes and is easy to make the free particle surface area of spices diffusion to reduce to minimum.The ratio of perfume particle and coalescent material alters a great deal according to the degree of desired supplementary protection.This coalescent method for the spices that is highly susceptible to volatilizing or the spices that is easy to degrade especially is and is useful.And coalescent being combined into of very little perfume particle stops the too early diffusion of spices that the additional protection effect is provided.
The particles coalesce of this form is useful for preventing that little perfume particle from separating (for example being in the dried detergent granules product) with big detergent particles.
The preparation method
For frangible clad, the preparation method is based on clad is used to contain perfume particle as a kind of " shell ".Be lower than for the fusing point of its carrier mass the employed solvent of this method boiling point contain perfume particle, this method comprises carrier and spices melts together and molten mixture is added in a kind of dissolving or a kind of suitable precursor of " shell " material, be kept above the carrier fusion temperature, fully stir this system in shell solution, to form the carrier/spices emulsion of drop size with requirement.Thereby set up the necessary condition of deposition encapsulating substance.The sealing solid particle that the whole cooling of emulsion is had frangible " shell " of requirement with acquisition.The water-insoluble of shell or the depositional phase form or separating or use particle before through suitably handling and forming.
Although method described herein is a step fusion drop shaping/seal process, those of ordinary skill in the art it is evident that the also available similar fashion of the sealing of preformed perfume particle realizes.The preform particle can prepare with multiple mode, comprises " the Microencapsulation as P.B.Deasy(; Related Drug Processes ", Dekker, N.Y.; 1986) and A.Kondo(" Microcapsule Processing and Technology ", Dekker, N.Y.; 1979) cryogrinding described in its book, spray drying, spraying is condensed and fusible dispersion technology.These technology are needs for the carrier mass that fusing point is higher than solvent boiling point.
Can use various suitable seal technology, such as above-mentioned by described in the book of Deasy and Kondo work.According to employed material, shell can make particle possess hydrophilic property or hydrophobicity.The non-limiting example of sealing substance and method comprises, to the Arabic gelatin-gummy concentrate of hydrophily shell for depositing with complicated coacervation process, such as United States Patent (USP) 2,800,457, be the ureaformaldehyde that deposits with polycondensation method to the hydrophobicity shell, such as United States Patent (USP) 3,516,941.
The water-insoluble of shell matter may be crosslinked and produce with suitable aldehydes or other known gelatin hardener after deposition by Arabic gelatin-gummy coacervate.The polymerization of ureaformaldehyde precondensate can produce water-insoluble in seal process.
The slurry that contains perfume particle can directly use, and for example other component spray drying in prescription is perhaps particle washing and separation, dry more if desired.
The embodiment I
The perfume particle that contains the hydrophilic clad that is deposited by complex coacervation is prepared as follows.
The polyethylene of 132 gram POLYWAX500(molecular weight 500) in the beaker on being placed on about 100 ℃ of hot plates heating up to firm fusing.44 gram spices are joined among the POLYWAX500 of fusing and keep heating in room temperature make this contain the core mixture to be returned to 100 ℃.
The core material that contains of fusing is added in 400 grams, 5% the aqueous gelatin solution (Sanafi Type A, 275 Bloom intensity), in 1 liter of steel beaker, remains on and be higher than 15-20 ℃ of core fusing point, through stirring and grain is dripped in emulsification to the requirement that obtains about 100 μ.Add 11% Arabic gelatin solution of 200 gram heat then and continue to stir about 30 minutes.
That PH is dropped to is about 4.2 through dripping glacial acetic acid, then thing in the beaker device is poured in 1 premium on currency that at room temperature stirs.This just makes and contains the deposition that the core mixture solidifies and be accompanied by Arabic gelatin-gummy coacervate.
Through frozen water slurry is cooled to about 5 ℃ and form clad.Can be used for slurry herein, perhaps through adding about isopyknic 10% sodium chloride and removing clad and make particle in slurry, not contain any not coacervate of deposition with separatory funnel.If necessary can repeat this step to remove free coacervate fully.After filtration, water is subsequently with the inopiopanol washing leaching cake, make particle drying at 25 ℃ then with air-dry overnight.
Can make particle meet the requirements of particle size range through screening then.
The embodiment II
Perfume particle with hydrophilic clad of poorly water-soluble can be prepared as follows.
The slurry that contains the perfume particle of Arabic gelatin-gummy clad prepares by the embodiment I.After the cooling, allow slurry rise to room temperature and also under agitation add the 8.0m125% glutaraldehyde water solution.Add 2.5% sodium hydrate aqueous solution and make PH rise to 5.0, and the slurry stirring is spent the night.
Can use slurry herein, perhaps separate as the embodiment I.
Clad after adding glutaraldehyde and handling can stand long-time immersion in 60 ℃ of water, and untreated clad is heated to 50 ℃ and will comes off.
The embodiment III
The perfume particle that contains the hydrophobic water-insoluble clad that is deposited by polycondensation is prepared as follows.
The mixture of 162 gram 37% water-containing acetals and 60-65 gram urea is adjusted to PH8.0 with 0.53 gram sodium tetraborate,, at first forms urea-formaldehyde pre-condensation compound thereby add 276.85 gram water then 70 ℃ of heating 1 hour.
Then 429 milliliters of these precondensates and 142 ml waters are stirred in 1 liter of steel reactor and add 57.14 gram sodium chloride and 0.57 gram sodium carboxymethylcellulose.Add the core component that contains that contains 161.3 gram POLYWAX500 carriers and 60.7 milliliters of spices then, reactor is heated to above about 10 ℃ of core fusing point.Adjust stirring and make it emulsification and make molten core remain on the particle size that drips of requirement, its PH is adjusted to about 5.0 with watery hydrochloric acid.
Allow then reactor cooled to room temperature simultaneously in 2 hours PH reduce to 2.2 gradually.And then reactor is increased to about 50 ℃ with 2 hours, and be cooled to room temperature then, with 10% sodium hydroxide solution PH is adjusted to 7.0 afterwards.
Can directly use the product slurry of the solid core particle that contains useful agroform sealing, or on request its sorting, washing and air drying be separated.
In hope in processed surface attachment fragrance be applied in enough stirrings and pressure and occasion that frangible clad is destroyed, containing perfume particle and can use with the coating of aforementioned manner preparation with any product type.The representative instance of these products is laundry detergent compositions and fabric softener.Set forth the use of mixture of the present invention in these products below.
The clothes washing product comprises: the cleanliness surfactant; Common one or more decontamination lotion promoters; Can select various enzymes, bleaching agent, carrier of usefulness or the like, all these can be understood thoroughly from general textbook and washing agent formulator right and wrong Changshu is known.Surfactant comprises soap, alkyl benzene sulfonate, ethoxyquin alcohols, alkylsurfuric acid salt or the like.Builder comprises various phosphoric acid salts, zeolites, polycarboxylate class or the like.United States Patent (USP) 3,985,669; 4,379,080 and 4,605,609 have provided typical these components can be for referencial use.
Current fabric softener mainly comprises one or more quaternary ammonium salts or imidazoline or imidazolinium compounds.Softener (and antistatic additive) generally contains one, or more preferably contains two C 12-C 18Alkyl substituent and two or three short-chain alkyl groups.In addition, these materials are common to the softener formulator and know.
The embodiment IV
Particulate laundry detergent is as follows:
Composition weight %
C 13Sodium alkyl benzene sulfonate 7.5
C 14-C 15Sodium alkyl sulfate 7.5
Remove the not C of the pure and mild rudimentary ethoxylate of ethoxyquin 12-13
Alkyl polyethoxylate (6.5) 2.0
C 12Alkyl trimethyl ammonium chloride 1.0
Sodium phosphate trimer 32.0
Sodium carbonate 10.0
Sodium perborate-hydrate 5.3
Decoyl oxo benzene sulfonic acid sodium salt 5.8
Diethylene-triamine pentaacetic acid sodium 0.5
Sodium sulphate, H 2O and accessory constituent surplus
Use conventional method preparation said mixture.This mixture combines as follows with the perfume particle of embodiment 1.Perfume particle among the embodiment 1 combines with detergent mixture, and its amount should make detergent mixture contain about 0.3% spices.
This particle can simply mix with detergent particles.For preventing that perfume particle from the time separating (owing to its granularity is little with respect to detergent particles) in packing with transportation, this particle with can choose a coating mode or coalescent before detergent particles combines with water-soluble coating material (on frangible clad).This can carry out in Schugi blender (Flexomix 160), in this blender the dextrin glue of q.s (2% dextrin, 3% water) is sprayed at formation and the perfume particle agglomerated thing of other detergent particles in same particle size range on the particle.
Spices is protected the bleaching agent degraded that makes it to avoid to be washed in the agent composition when the experience long term storage in particle.When being used for the washing process of automatic washing machine, this detergent mixture can make the spices taste be provided on the fabric by washing process from product with its ortho states basically.
A large amount of spices can be used in this mixture, and this spices is not suitable for again in this class clothes washing agent composition on the other hand.
The embodiment V
It is a kind of that to be used for the liquid fabric softener that the aqueous laundry rinsing bathes as follows:
Composition weight %
Softener A *3.00
Softener B *5.00
HCl 0.29
Dimethyl silicone polymer 0.15
Polyethylene glycol (4000) 0.30
The Bronopol(sterilization) 100ppm
Calcium chloride 30ppm
Dyestuff 30ppm
The perfume particle that coats * *4.0
Water surplus
* softener A is
Figure 941042081_IMG1
Wherein each R group is at C 15-C 18In the alkyl scope.
The * softener B is
Figure 941042081_IMG2
Wherein each R group is at C 15-C 18The alkyl scope
* * presses the particle of embodiment II preparation.100 micron granularities; 5% clad weight.
In the time of in the rinsing that is used in automatic washing machine is bathed, the clad that contains perfume particle of embodiment V just breaks, and these particles promptly provide fragrance to processed fabric.
The embodiment VI
A kind of liquid laundry detergent mixture is as follows:
Composition weight %
C 13Linear alkyl benzene sulphonic acid 7.2
C 14-15The poly-ethoxy of alkyl generation (2.25) sulfuric acid 10.8
C 12-13Alcohol polyethoxylate (6.5) *6.5
C 12Alkyl trimethyl ammonium chloride 1.2
C 12-14Aliphatic acid 13.0
Oleic acid 2.0
Citric acid (anhydrous) 4.0
Diethylene-triamine pentaacetic acid 0.23
Protease (2.0AU/g) 0.75
Amylase (375Am.U/g) 0.16
TEPA-E 15-18 **1.5
Monoethanolamine 2.0
(molal quantity of alkanolamine) (0.033)
Sodium ion 1.66
Potassium ion 2.65
(mol ratio K +: Na +) (0.94)
Propylene glycol 6.8
Ethanol 7.8
Formic acid 0.66
Calcium ion 0.03
Accessory constituent and water percentage surplus
In 68 (20 ℃) water, concentration is 10% PH 8.65
* removing alcohol reaches-ethoxylated alcohol.
* uses 15-18 mole (on average) oxirane ethoxylation tetren in each hydrogen position.
Washing agent can add each component preparation with following order under continuous stirring: the pulpous state premix of alkyl benzene sulphonate, NaOH, propylene glycol and ethanol; The pulpous state premix of alkyl poly-ethoxyquin sulfuric acid, NaOH and ethanol; Pentaacetic acid; The alcohol polyethoxylate; The premix of water, brightening agent, alkanolamine and pure polyethoxylate; Ethanol; NaOH and potassium hydroxide; Aliphatic acid; Citric acid; Formic acid and calcium; Alkyl trimethyl ammonium chloride; TEPA-E 15-18; Regulate PH to about 8.1; And surplus component.
Said mixture is combined as follows with the perfume particle that contains for preparing by the embodiment II.The perfume particle of embodiment II (mean particle size range 40-150 micron; 5% clad) fully sneak in the liquid scrubbing agent composition, its amount should make detergent mixture contain to have an appointment 0.3% spices (about 1% detergent mixture contains perfume particle).
The embodiment VII
A kind of fiber and fabric sofetening agent composition are as follows.
Composition weight %
Softener C *3.7
TAMET **0.3
GMS ***1.20
Phosphoric acid 0.023
Dimethyl silicone polymer (350) 0.10
Glutaraldehyde 550ppm
Blue dye 10ppm
The perfume particle that coats * * *3.0
* (R 1) 2(CH 3) 2N +, Br -, R wherein 1Be the C that mixes 12-C 18Alkyl (i.e. " tallow alkyl ").
* TAMET is tallow alkyl N(CH 2CH 2OH) 2
* * GMS is a glyceryl monostearate.
* * * sieves particle mean size less than 150 microns by the perfume particle of the coating of embodiment III preparation.Clad weighs 3%.
Those of ordinary skill in the art as can be seen, the anion X that uses with any cationic fabric softener is the material of selecting for use usually here, this X for example can be chloride bromide, sulfuric acid-methyl esters or the like.The mixture of fabric softener can use as anion mixture.
The embodiment VIII
Use has clad weight and is respectively frangible clad (melamine/urea/formaldehyde of 1% and 20%; 0.1/1/1.1 mol ratio; 300 micron granularities) the particle that is mixed with spices is to the processing of going bad respectively of the detergent mixture of embodiment VI.
The embodiment IX
2%(weight) perfume particle (7% clad of coating in the embodiment I; All particles are all by 150 tm screen) lentamente (so that clad is broken) be mixed in the 99.44% tallow soap mixture (Na salt) preparing washing rod mixture and in the bar shaped mould, form rod.
The mixture here also can combine with abrasive material.As everyone knows, abrasive cleaner mainly comprises 10% to 90+% abrasive material, such as float stone, silica, calcium carbonate or the like.The perfume particle that is used for the coating of these abrasive cleaners breaks in use and discharges spices.
The embodiment X
A kind of abrasive cleaner is as follows.
Composition weight %
Tallow sodium sulphate 1.0
Calcium carbonate 40.0
Float stone (by 60 tm screen) 45.0
Sodium sulphate 10.0
The perfume particle that coats *3.0
Efficacious Disinfeitant 1.0
* according to the embodiment III; 10% clad; Particle is by 100 tm screen.
Through slowly being done, component mixes the mixture for preparing embodiment X.
Formulator knows that the weight (or thickness) of practical frangible clad can purposes on the estimation adjust.For example, even quite thick clad also can break and discharge its perfume particle under the machine washing condition in Europe, and this machine washing condition can comprise many minutes wash time and high temperature and strong stirring.Comparatively speaking, the machine washing condition of the U.S. is quite to lack the time and act on mitigation therefore should use less coating layer material.For fabric softener, stirring and mixing time lower to some extent than washing usually.

Claims (12)

1, be selected from the Fabrid care composition of composition of detergent or softener composition, it is characterized in that described composition contains a kind of perfume composition, described perfume composition contains the perfume particle of coating, its particle mean size is 40 microns to 350 microns, the spices that contains 5% to 70% (weight), it is 100 to 30 that this spices is scattered in 30% to 95% (weight) molecular weight, 000, fusing point is that 37 ℃ to 190 ℃ and hardness number are in 0.1 to 15 the water-insoluble polymeric carrier material, described particle has the water-insoluble basically frangible clad of 1% to 20% (weight) on its outer surface, and described clad comprises the aminoplast polymer.
2, according to the composition of claim 1, wherein said composition is a kind of composition of detergent, also contains one or more cleanliness surfactants and one or more optional builders.
3, according to the composition of claim 2, wherein clad is amine or its mixture and the product that is selected from aldehyde or its mixture of formaldehyde, acetaldehyde, glutaraldehyde that is selected from urea and melamine.
4, according to the composition of claim 3, wherein carrier mass is selected from polyethylene kind, polyamide-based, polystyrene type, polyisoprene class, polycarbonate-based, polyesters, polyacrylate, polyvinyl class, polyurethanes and composition thereof.
5, according to the composition of claim 4, wherein carrier mass contains polyethylene.
6, according to the composition that is clavate of claim 2.
7, according to the composition of claim 2, said composition also contains abrasive material.
8, according to the composition of claim 1, wherein said composition is a kind of softener composition, also contains one or more fabrics or softening agent for fibres or antistatic additive.
9, according to the composition of claim 8, wherein clad is amine or its mixture and the product that is selected from aldehyde or its mixture of formaldehyde, acetaldehyde, glutaraldehyde that is selected from urea and melamine.
10, according to the composition of claim 9, wherein carrier mass is selected from polyethylene kind, polyamide-based, polystyrene type, polyisoprene class, polycarbonate-based, polyesters, polyacrylate, polyvinyl class, polyurethanes and composition thereof.
11, according to the composition of claim 10, wherein carrier mass contains polyethylene.
12, according to each composition in the aforementioned claim, the particle mean size of wherein said particle is 40 microns to 150 microns.
CN94104208A 1989-05-11 1994-04-12 Fabric care compositions Pending CN1104693A (en)

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