CA2004270A1 - Perfume microcapsules for use in granular detergent compositions - Google Patents
Perfume microcapsules for use in granular detergent compositionsInfo
- Publication number
- CA2004270A1 CA2004270A1 CA002004270A CA2004270A CA2004270A1 CA 2004270 A1 CA2004270 A1 CA 2004270A1 CA 002004270 A CA002004270 A CA 002004270A CA 2004270 A CA2004270 A CA 2004270A CA 2004270 A1 CA2004270 A1 CA 2004270A1
- Authority
- CA
- Canada
- Prior art keywords
- microcapsules
- perfume
- composition according
- weight
- microns
- 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.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/08—Liquid soap, e.g. for dispensers; capsuled
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/62—Quaternary ammonium 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/50—Perfumes
- C11D3/502—Protected perfumes
- C11D3/505—Protected perfumes encapsulated or adsorbed on a carrier, e.g. zeolite or clay
Abstract
PERFUME MICROCAPSULES FOR USE IN
GRANULAR DETERGENT COMPOSITIONS
Abstract of The Disclosure Perfume-containing microcapsules coated with a water-in-soluble cationic fabric softener and used in granular detergent compositions effectively impart perfume to fabrics during the home laundering operation. A method for delivery of the perfume is also provided.
GRANULAR DETERGENT COMPOSITIONS
Abstract of The Disclosure Perfume-containing microcapsules coated with a water-in-soluble cationic fabric softener and used in granular detergent compositions effectively impart perfume to fabrics during the home laundering operation. A method for delivery of the perfume is also provided.
Description
42~ ,p~
PERFUME MICROCAPSULES FOR USE IN
GRANULAR DETERGENT COMPOS~TIONS
William R. Michael TECHNICAL FIELD
The present invention relates to certain coated perfume-containing microcapsules which when used in granular laundry detergent compositions effectively deliver perfume to fabrics during the home laundering operation. The microcapsules containing the perfume are coated with a water-insoluble cationic fabric softener to facilitate attachment of the capsules to fabrics during a presoak bath or in the washing machine. The capsules thereafter release the perfume by diffusion through the capsule wall and by rupturing of the capsules during manipulation of the fabrics.
BACKGROUND OF THE INVENTION
DeliYery of perfumes, particularly volatile and nonsubstantive perfumes, to fabrics during the laundering operation is difficult. Surfactants are generally employed during presoaking and washing steps for the purpose of removing materials (soil) from the fabrics. Simultaneous deposition onto fabrics of perfume can, therefore, prove troublesome. Moreover, retention of perfumes, particularly the volatile and nonsubstantive perfumes, on fabrics during the drying process remains difficult.
Although treatment of fabrics with microcapsules is known (see, for example, Ida et al, U.S. Patent 3,870,542, issued March 11, 1975; and Pandell et al, U.S. Patent 3,632,296, issued January 4, 1972), such prior art fabric treatment has generally required utilization of large numbers of microcapsules to provide effective capsule delivery.
U.S. Patent 4,234,627, Schilling, issued November 18, 1980, and U.S. Patent 4,145,184, Brain et al, issued March 20, 1979, disclose granular compositions containing friable microcapsules containing conditioning agents, including perfumes, to deliver such conditioning agents to fabrics during the presoaking/washing stage of the home laundry operation.
:. ::, . . . ~ , . . .
,; .; , .. ;; - ~ .. . .
... .. . . . . .
... : - . : . - .
:.. .. : . - ~
; ~ . . ~:: . . . . :
:. .
.. ,, : ~ .
~o()~
Despite these disclosures, l:here is a continuing need for improved compositions capable of more effectively delivering perfumes to fabrics.
Accordingly, it is an object of the present invention to provide improved perfume-containing microcapsules which when used in granular presoaking/washing detergent compositions deliver effective amounts of perfume to fabrics being laundered.
It is a further object of the present invention to provide an improved method for delivering perfume to fabrics during the presoak or wash stage of the laundering process.
It has been surprisingly discovered that by ut;lizing particular types of perfume-containiny microcapsules coated with water-insoluble cationic fabric softeners, the above objectives can be attained.
SUMMARY OF THEI NVENTION
The present invention relates to microcapsules having an average size of from about 5 to 500 microns, each microcapsule consisting essentially of:
(i~ a liquid core containing perfume; and (ii) a solid thin polymeric shell completely surrounding said core, said shell having an average thickness of from about 0.1 to 50 microns, and said shell being formed by complex coacervation of polycationic and polyanionic materials;
said microcapsules being coated with a substantially water-in-soluble cationic fabric softener having a melting point between about 40C and 150C, wherein the weight ratio of microcapsules to cationic softener is from about 3:1 to about 50:1.
The invention also relates to granular laundry detergent compositions comprising from about 0.1% to ~0% of the above coated perfume-containing microcapsules and from about 5% to 99% by . weight of a detergent adjuvant selected from the group consisting of water-soluble detersive surfactants, detergency builders, and mixtures thereof.
, ~. .:
-: : ' . , .
~ 7 0 Additionally, the present invention relates to a method of treating fabrics with compositions as described above.
DETAILE~ DESCRIPTION OF THE TNVENTIO~I
The present invention involves the home laundry application to fabrics of granular detergent compositions containing perfume microcapsules coated w;th a water-insoluble cationic softener.
The cationic fabric softener facilitates attachment of the capsules to fabrics during a presoak bath or in the washing machine. The capsules thereafter release the perfume by diffusion through the capsule wall and by manipulat;on of the treated fabr;cs so as to rupture the capsules. While not intending to be limited by theory, it is believed that the cationic softener complexes with the anionic polymer portion of the capsule wall so as to enhance diffusibility of the perfume during the fabric laundering process when the capsules are rehydrated by the laundering solution. This results in improved delivery of the perfume to fabrics during the washing and/or drying steps, as desired.
~15~953~Y~
The microcapsules useful in the present invention comprise a liquid core containing one or more perfumes and a thin polymeric shell, formed by complex coacervation of polycationic and polyanionic materials, completely surrounding the l;quid core. By encapsulating the perfume (in liquid form), the perfume is protected during the production, distribution and storage of the granular detergent composition and is thus preserved for most efficient application to fabrics during the laundering operation.
Perfume is actually appl;ed to the fabrics by diffusion through the capsule wall or when the microcapsules rupture during manipulation of the fabr;cs. This can occur either during the automatic washing or drying step of the home laundering operation or can actually occur after the fabrics are laundered and while they are being used.
.. ..
" - ,. : ~ ' : , - . ~ .. . . ... .
:.;:: :: : ;
.
7 ~) The perfume which can be used in the liquid cores of the microcapsules can be any water-insoluble (or substantially water-insoluble) odoriferous material and will be selected : S according to the desires of the formulator. (~later-soluble perfume components are difficult to encapsulate using the complex coacervation methods described hereinafter.) In general terms, such perfume materials are characterized by a vapor pressure above atmospheric pressure at ambient temperatures. The perfume materials employed herein will most often be liquid at ambient temperatures, but also can be solids such as the various camphor-aceous perfumes known in the art. A wide variety of chemicals are known for perfumery uses, including materials such as aldehydes, ketones, esters, and the like. More commonly, naturally-occurring plant and animal oils and exudates comprising complex mixtures of various chemical components are known for use as perfumes, and such materials can be used herein. The perfumes herein can be relatively simple in their composition, or can comprise highly ~ sophisticated, complex mixtures of natural and synthetic chemical components, all chosen to provide any desired odor.
Typical perfumes herein can comprise, for example, woody~earthy bases conta;ning exotic materials such as sandalwood oil, civet, patchouli oil, and the like. The perfumes herein can be of a light, floral fragrance, etc., rose extract, violet extract, and the like. The perfumes herein can be formulated to provide desirable fruity odors, e.g., lime, lemon, orange, and the like. In short, any material which exudes a pleasant or otherwise desirable odor can be used in the liquid microcapsule core to provide a desirable odor when applied to fabrics. Preferred, ::
perfumes inciude musk ambrette, musk ketone, musk tibetine, musk xylol, aurantiol, ethyl vanillin and mixtures thereof. Examples of such perfume matrials can be found in U.S. Patent 4,515,705, Moeddel, issued May 7, 1985,incorporated herein by reference. -~'' Perfumes will frequently be in liquid form and can be used as the sole materials in the microcapsule core. Perfulnes which are ,:.;. ,,, : . : , ; - , , ~ :
: ,: , : , : . ', , , :.
~O~ 7r~
normally solid can also be emp'loyed in the microcapsule core if they are admixed with a liquefying agent such as a solvent. Any organic solvent can be used to liquify normally solid perfume for use in the microcapsule core provided such a solvent is chemically S compatible with the microcapsule shel'l material described hereinafter. Preferred solvents for use herein are materials such as mineral oil and dodecane.
The shell material surrounding the liquid, perfume-containing core to form the microcapsule can be any suitable polymeric material formed by complex coacervation of polycationic and polyanionic materials. The shell is substantially impervious to the materials in the liquid core and to materials which may come in contact with the outer surface of the shell during storage.
When the microcapsules are rehydrated by the laundering solution, it is believed that pores in the microcapsules expand to allow diffusion of the perfume during the washing and drying steps, thereby improving perfume delivery to fabrics.
Suitable polycationic' materials for use in forming the polymeric shell of the microcapsules herein include materials such as gelatin, poly(vinyl pyrrolidoneJ, poly(ethyleneimine) and albumin. Type A gelatin is preferred. Suitable polyanionic materials for forming the polymeric shell include materials such as ~um arabic, poly(ethylene/maleic anhydride), poly(vinyl methylethyl maleic anhydride), polyphosphate, polyacrylate, and gelatin. Polyphosphates, especially sodium hexametaphosphate, are particularly preferred.
Microcapsules as described above can be prepared by any conventional complex coacervation process. Such methods are described in U.S. Patent 2,800,457i 3,190,837; 3,317,434;
3,341,466; 3,533,958; 3,687,865, 3,697,437; and 3,840,467. All of the above patents are incorporated herein by reference.
The microcapsules should have an average size of between about 5 microns and 500 microns, preferably between about 40 microns and 250 microns, more preferably between about 80 and 150 ~ . .. . ;.. ; . :
.: , . ..
.. ..... . .
. .
:
: , .
o microns. Furthermore, the capsules utilized in the present invention have an average shell thickness ranging from about 0.1 to 50 microns, preferably from about 0.4 to 30 microns.
The microcapsules of the present invention are generally friable in nature. Friability refers to the propensity of the microcapsules to rupture or break open when subjected to direct external pressures or shear forces. For purposes of the present invention, the microcapsules utilized are "friable" if, while attached to fabrics treated therewith, they can be ruptured by the forces encountered when the capsule-containing fabrics are tumbled in an automatic laundry dryer or are manipulated by being worn or handled. Microcapsules made with the above-described shell materials will be "friable" if they fall within the capsule size and shell thickness limitations provided above.
Cationic Fabric Softener Attachment of the above-described microcapsules to the fabrics being treated therewith is facilitated by surrounding the microcapsules with the cationic fabric softener. These are substantially water-insoluble materials which are fabric substantive and which have a melting point with the range of from about 40C to 150C, preferably with the range of from about 49C
to 105C. 8y "substantially water-insoluble" herein is meant a water insolubility of 1% by weight, or less, at 30C.
Suitable cationic capsule transfer agents include any of the cationic (including imidazolinium) compounds listed in U.S.
Patent No. 3,686,025, Morton, issued August 22, 1972, incorporated herein by reference. Such materials are well known in the art and include, for example, the quaternary ammonium salts having at least one, preferably two, Clo-C20 fatty alkyl substituent groups;
alkyl imidazolinium salts wherein at least one alkyl group contains a C~-Czs carbon "chain"; the Clz-C20 alkyl pyridinium salts, and the like.
Preferred cationic softeners herein include the quaternary ammonium salts of the general formula RlR2R3R4N+,X-, wherein .: ., ; , .
:-: , . . . ~ .
:,, : .
~ O (~I L~ 2 7 () groups R1~R2~R3, and R4 are, for example, alkyl, and X~ is an anion, e.g., halide, methylsulfate, and the like, with e chloride and methylsulfate salts being preferred. Especially preferred capsule transfer agents are those wherein R1 and R2 are each C12-C20 fatty alkyl and R3 and R4 are each Cl-C4 alkyl. The fatty alkyl groups can be mixed, i.e., the mixed C14-CIg coconutalkyl and mixed C16-C1g tallowalkyl quaternary compounds.
Alkyl groups R3 and R4 are preferably methyl.
Exemplary quaternary ammonium softeners herein include ditallowalkyldimethylammonium methylsulfate, ditallowalkyldi-; methylammonium chloride, dicoconutalkyldimethylammonium methyl-sulfate, and dicoconutalkyldimethylammonium chloride.
The above-described microcapsules are coated with the fabric ; softener such that the weight ratio of microcapsules to softener15 generally varies between about 50:1 to 3:1, preferably between about 20:1 and 4:1, more preferably between about 10:1 and 5:1.
It is preferred that the fabric softener completely surround or envelop the individual microcapsules. This is generally accomplished by thoroughly admixing the microcapsules with the softener in some form of liquid medium, and then drying to solidify the coating. Any conventional coating technique can also be utilized including spray-on processes or fluidized bed coating methods, which are preferred for commercial scale operation.
The cationic fabric softener coating can optionally include minor amounts (e.g., less than 50%, preferably less than 20%) by weight of the nonionic capsule transfer agents described in U.S.
I Paent 4,234,627 to Schilling, incorporated herein by reFerence.
Granular peterqent Composition Granular laundry detergent presoaking and/or washing compositions herein contain from about 0.1% to 20%, preferably from about 0,3% to about 10%, more preferably from about 0.5% to about 5%, by weight of the above coated perfume-containing microcapsules. Such compositions also contain from about 5% to about 99%, preferably from about 10% to about 90%, more preferably r` ~ ` ~ , . , ; : ' ' ~
' ." ~ ~, . ': I i ""' "' I ' ' ' i .~ ' ' ~CO ~'7~
from about 20% to about 80%, by ~leight of a detergent adjuvant selected from the group consisting of water-soluble detersive surfactants, detergent builders, and mixtures thereof.
Water-soluble surfactants used in the presoaking/washing detergent compositions herein include any of the common anionic, nonionic, ampholytic and zwitterionic detersive surfactants well known in the detergency arts. Mixtures of surfactants can also be employed herein. More particularly, the surfactants listed in ; 10 Booth, U.S. Patent No. 3,717,630, issued February 20, 1973, and Kessler et al; U.S. Patent No. 3,332,880, issued July 25, 1967, each incorporated herein by re-Ference, can be used herein.
Non-limiting examples of surfactants suitable for use in the instant compositions are as follows.
Water-soluble salts of the higher fatty acids, i.e., "soaps", are useful anionic surfactants in the compositions herein. This includes alkali metal soaps such as the sodium, potassium, ammonium, and alkylolammonium salts of higher fatty acids containing from about 8 to about 24 carbon atoms, and preferably from about 12 to about 18 carbon atoms. Soaps can be made by direct saponification of fats and oils or by the neutralization of free fatty acids. Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap.
Useful anionic surfactants also include the water-soluble salts, preferably the alkali metal, ammonium and alkylolammonium salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 10 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group. (Included in the term "alkyl" is the alky portion of acyl groups). E~amples of this group of synthetic surfactants are the sodium and potassium alkyl sulf`ates, especially those obtained by sulfating the higher alcohols (Cg-C1g carbon atoms) such as those produced by reducing the glycerides of tallow or coconut oil; and ;. .: : :, ,:. .~ , - , : - .. ;.
, :; , .
'' :''' , ' , '' . : ' -. : , : . ~
;~oo~
the sodium and potassium alkylbenzene sulfonates in which the alkyl group contains from about 9 to about 15 carbon atoms, in straight chain or branched chain configuration, e.g., those of the type described in U.S. Patent Nos. 2,220,099, and 2,477,383.
Especially valuable are linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from about 11 to 13, abbreviated as Cll l3 LAS.
Other anionic surfactants herein are the sodium alkyl glyceryl ether sulfonates, especially those ethers of higher ~ alcohols derived from tallow and coconut oil; sodium coconut oil : fatty acid monoglyceride sulfonates and sulfates; sodium or potassium salts of alkyl phenol ethylene oxide ether sulfates containing from about 1 to about 10 units of ethylene oxide per molecule and wherein the alkyl groups contain from about 8 to about 12 carbon atoms; and sodium potassium salts of alkyl ethylene oxide ether sulfates containing about 1 to about 10 units of ethylene oxide per molecule and wherein the alkyl group contains from about 10 to about 20 carbon atoms.
Other useful anionic surfactants herein include the , water-soluble salts of esters of alpha-sulfonated fatty acids containing ~rom about 6 to 20 carbon atoms in the fatty acid group and from about 1 to 10 carbon atoms in the ester group;
water-soluble salts of 2-acyloxyalkane-1-sulfonic acids containing from about 2 to 9 carbon atoms in the acyl group and from about 9 to about 23 carbon atoms in the alkane moiety; water-soluble salts of olefin and paraffin sulfonates containing from abollt 12 to 20 carbon atoms; and beta-alkyloxy alkane sulfonates containing from 3 about 1 to 3 carbon atoms in the alkyl group and from about 8 to 20 carbon atoms in the alkane moiety.
Water-soluble nonionic surfactants are also useful in the compositions of the invention. Such nonionic materials include compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature. The length of ., . :: ,: . . . . . .
-; , :
,,: . : : ~ : . . , , ~ , .
.,~.. . . .. .
, . . . .
~,'092~70 the polyoxyalkylene group which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
Suitable nonionic surfactants include the polyethylene oxide condensates of alkyl phenols, e.g., the condensation products of alkyl phenols having an alkyl group containing from about 6 to 15 carbon atoms, in either a straight chain or branched chain configuration, with from about 3 to 12 moles of ethylene oxide per mole of alkyl phenol.
Preferred nonionic surfactants are the water-soluble and water-dispersible condensation products of aliphatic alcohols containing from 8 to 22 carbon atoms, in either straight chain or branched configuration, with from 3 to 12 moles of ethylene oxide per mole of alcohol. Particularly preferred are the condensation products of alcohols having an alkyl group containing from about 9 to 15 carbon atoms with from about 4 to 8 moles of ethylene oxide per mole of alcohol.
Semi-polar nonionic surfactants include water-soluble amine oxides containing one alkyl moiety of from about 10 to 18 carbon atoms and two moieties selected from the group of alkyl and hydroxyalkyl moieties of from about 1 to about 3 carbon atoms;
water-soluble phosphine oxides containing one alkyl moiety of about 10 to 18 carbon atoms and two moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of from about 10 to 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from about 1 to 3 carbon atoms.
Ampholytic surfactants include derivatives of aliphatic or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic moiety can be straight chain or branched and wherein one of the aliphatic substituents contains : ,.. , . ., - ,: . . . .
.,, : .:, : : -~
., ,- . . .
"~
.'; . : . :
.
z~o~
` from about a to l~ carbon atoms and at least one aliphatic substituent contains an anionic water-solubilizing group.
Zwitterionic surfactants include derivatives of aliphatic, S quaternary, ammonium, phosphonium, and sulfonium compounds in which one of the aliphatic substituents contains from about 8 to 18 carbon atoms.
When the present granular detergent compositions are used as presoaking or wash additive compositions in conjunction with other commercially available laundry detergent products, the detersive surfactant component generally comprises from about 0% to 20% by weight of the compositions, preferably from about 1% to 10% by weight. When the present compositions are to be used as the sole detergent product during the laundering process, the detersive surfactant component generally comprises from about 5% to about 75%, preferably from about 10% to 40%, by weight of the composition.
In addition to detergent surfactants, detergency builders can be employed in the final granular detergent product.
Water-soluble inorganic or organic electrolytes are suitable builders. The builder can also be water-insoluble calcium ion exchange materials; nonlimiting examples oF suitable water-soluble, inorganic detergent builders include: alkali metal carbonates, borates, phosphates, bicarbonates and silicates.
Specific examples of such salts include sodium and potassium tetraborates, bicarbonates, carbonates, orthophosphates, pyrophosphates, tripolyphosphates and metaphosphates.
Examples of suitable organic alkaline detergency builders include: (l) water-soluble amino carboxylates and aminopolyacetates, for example, nitrilotriacetates, glycinates, ethylenediamine, tetraacetates, N-(2-hydroxyethyl)nitrilo diacetates and diethylenetriamine pentaacetates; (2) water-soluble salts of phytic acid, for example, sodium and potassium phytates;
(3) water-solub1e polyphosphonates, including sodium, potassium, and lithium salts of ethane l-hydro~y-1, I-diphosphonic acid;
.
.
:
.
',: ~ .
. ~ .
ZO~2'7~:) sodium, potassium, and lithium salts of ethylene diphosphonic acid; and the like; (4) water-soluble polycarboxylates such as the salts of lactic acid, succinic acid, malonic acid, maleic acid, citric acid, carboxymethyloxysuccinic acid, 2-oxa-1,1,3-propane tricarboxylic acid, 1,1,2,2-ethane tetracarboxylic acid, mellitic acid and pyromellitic acid; and (5) water-soluble polyacetals as disclosed in U.S. Patent Nos. 4,1~,266 and 4,246,495 incorporated herein by reference.
Another type of detergency builder material useful in the final granular detergent product comprises a water-soluble material capable of forming a water-insoluble reaction product with water hardness cations preferably in combination with a crystallization seed which is capable of providing growth sites for said reaction product. Such "seeded builder" compositions are fully disclosed in British Patent No. 1,424,406.
A further class of detergency builder materials useful in the present invention are insoluble sodium aluminosilicates, particularly those described in Belgian Patent No. ~14,874, issued November 12, 1974, as having the formula:
Naz-(Alo2)-(sio2)yxH2o wherein z and y are integers equal to at least 6, the molar ratio of z to y is in the range of from 1.0:1 to about 0.5:1, and X is an integer from about 15 to about 264, said aluminosilicates having a calcium ion exchange capacity of at least 200 milligrams equivalent/gram and a calcium ion exchange rate of at least about 2 grain/gallon/minute/gram. A preferred material is Zeolite A
which is:
Nal2-(SiO2A102)l227H2o When the present granular detergent compositions are used as presoaking or wash additive compositions in conjunction with other commercially available laundry detergent products, the detergency builder component generally comprises from about 20% to 90% by weight of the compositions, preferably from about 30% to 75% by weight. When the present granular compositions are to be used as :: ~: . , , . .... . , . . .: .
~o~ n the sole detergent product during the laundering process, the detergency builder component generally comprises from about 10% to about 75%, preferably from about 20% to 50%, by weight of the composition.
Optional detergent composition components include enzymes (e.g., proteases and amylases), bleaches and bleach activators, soil release agents (e.g., methylcellulose), soil suspending agents (e.g., sodium carboxymethylcellulose), fabric brighteners, enzyme stabilizing agents, color speckles, suds boosters or suds suppressors, anticorrosion agents, dyes, fillers, germicides, pH
adjusting agents, nonbuilder alkalinity sources, and the like.
EXAMPLE I
A granular laundry detergent composition of the present 15 invention is as follows.
Inqredient Weiqht Percent ~:
Sodium C13 linear alkylbenzene sulfonate 8.5 Sodium C14 15 alkyl sulfate 8.4 Sodium tripolyphosphate 39.4 20 Sodium carbonate 12.3 i~.
Sodium silicate (1.6 ratio) 5.6 Water 7 0 Coated perfume microcapsules 0.9 Sodium sulfate & miscellaneous ~alance to 100 25The above granular detergent composition is made by mixing the ingredients (except the microcapsules) in a crutcher, and then spray-drying by conventional methods.
The coa~ed perfume microcapsules are made as follows: A
67/33 (by weight) perfume/light mineral oil (viscosity 125/135) mixture is heated to about 60C in a constant temperature controlled water bath. About 10 grams of Type A gelatin per 100 grams of perfume/mineral oil is dissolved in 250 ml of distilled water with stirring at 250 revolutions per minute (rpm). About O.S to 1.0 grams of sodium hexametaphosphate per 100 grams of perfume/mineral oil is dissolved in distilled water to a .~ ~, "
concentration of 5% by weight. The dissolve~ ge1atin solution is stirred at 600 rpm using a Lightin Stirrer Model RP1515 with a 5 cm high sheer stirring blade. The perfume/mineral oil mixture is added dropwise to the gelatin solution over a period of 10-15 minutes to form an emulsion with particle sizes ranging from 75-250 microns. An additional 200 ml of 60C water is added and the stirring speed reduced to 250 rpm. The pH of the mixture is adjusted to 4.92 with glacial acetic acid. The heating element of the water bath is turned off to allow the mixture to cool for from 6 to 2~ hours. When the oil droplets are completely covered with a layer of gelatin the reaction is cooled to 1-2C with external ice. The mixture is allowed to remain at that temperature for 10 to 30 minutes. At this point 4 ml of 25% glutaraldehyde is added to crosslink the gelatin capsule walls. The mixture is then stirred and allowed to warm to room temperature for from 6 to 24 hours. Approximately 4 grams of a syloid filter aid is added to the mixture after the reaction with glutaraldehyde is completed.
The mixture is then filtered to separate the capsules. The capsules are washed with 2 liters of water to remove residual glutaraldehyde. The capsules are then spread on a paper towel to dry. (Drying can also be accomplished in a fluid bed dryer when larger than 100 gram samples are used.) The capsules are then sieved to remove capsules and debris of a size larger than about 250 microns. The remaining capsules have an average size of about 100 to 150 microns and have a shell thickness averaging 0.1 to 50 microns.
The capsules are added to a solution of methylene dichloride containing ditallowdimethylammonium chloride (DTDMAC) in a ratio of 10 ml of methylene dichloride and 2 grams o~ DTDMAC per 10 grams of capsules. The methylene chloride is removed from the mixture using a stream of nitrogen. The coating solution is warmed gently in a steam bath to facilitate removal of the solvent. The resulting capsules are evenly coated with a thin layer (about 20-50 microns) of the DTDMAC. (For larger samples, a .: , ~ .. : :
~,,, ~. . - - .
,: : - . -; . : :, ;-~. .: ` : ` . `
:
: . . . -.
~ g~ 2 ~
Wurster Coater or any suitable fluid bed apparatus can be used to obtain an even coating of the microcapsules, after adjustment of all ratios to obtain an even flow of the capsules in the system.) The microcapsules are then admixed with the spray dried detergent ingredients to form a finished detergent composition.
When the composition is used in a washing machine to clean fabrics, the coated perfume-containing microcapsules effectively deliver perfume to the fabrics during the washing and drying steps and thereafter during handling of the fabrics.
Other compositions of the present invention are obtained when the perfume microcapsules are prepared by initially using a 50/50 (by weight) perfume/light mineral oil mixture, or 100% perfume tno mineral oil), or by replacing the sodium hexametaphosphate with gum arabic.
Other compositions herein are obtained when the DTDMAC used to coat the microcapsules is replaced with a 3:1 by weight ratio mixture of DTDMAC and tallow alcohol, or when the sodium tripolyphosphate in the detergent composition is replaced with a 3:1 by weight ratio mi~ture of hydrated sodium zeolite A and sodium carbonate.
EXAMPLE II
A granular laundry detergent composition of the present invention is as follows.
Ingredient Weiqht Percent 1. SpraY-dried deterqent base granules:
Sodium 13 linear alkylbenzene sulfonate (70%)/
Sodium C14 15 alkyl sulfate (30%) 12.88 Sodium tripolyphosphate 4.56 30 Tetrasodium pyrophosphate 17.16 Sodium silicate (1.6 ratio) 7.20 Diethylenetriamine pentaacetic acid 0.38 Brightener 0.18 Sodium polyacrylate (MW 4500) 0.96 Polyethylene glycol (MW 8000) 0.29 . .
' '`:, ~ .
.... . . .
. ~ . .
~oo~z~
Water* 3.0 Sodium sulfate & miscellaneousBalance to 100 2. SDraY on base q_anules:
C12 13 alcohol polyethoxylate (6.5)** 0.44 ~. Admix with base qranules-Sodium carbonate 22.00 Enzyme-Savinase (NovoJ 0.37 Sodium perborate monohydrate (solids) 3.69 10 Nonanoyloxybenzene sulfonate 5.26 Coated perfume microcapsules 1.50 *Remaining water is brought in with admixes.
**Alcohol and monoexthoxylated alcohol removed.
The above granular detergent composition is made as follows.
The spray-dried detergent base granules are formed by mixing the ingredients of step 1 in a crutcher, and then spray-drying by conventional methods. The nonionic surfactant of step 2 is then sprayed onto the detergent base granules. The resulting product is admixed with the ingredients of step 3, including the coated perfume microcapsules made according to Example I, to form a finished detergent composition.
When the composition ;s used in a washing machine to clean fabrics, the coated perfume-containing microcapsules effectively deliver perfume to the fabrics during the washing and drying steps and thereafter during handling of the fabrics.
WHAT IS CLAIMED IS:
-. . .:
. ~ ; ~. : - . . , .. , . .. , :
.. . . -: , .: . .......................................................... ..
~ :
PERFUME MICROCAPSULES FOR USE IN
GRANULAR DETERGENT COMPOS~TIONS
William R. Michael TECHNICAL FIELD
The present invention relates to certain coated perfume-containing microcapsules which when used in granular laundry detergent compositions effectively deliver perfume to fabrics during the home laundering operation. The microcapsules containing the perfume are coated with a water-insoluble cationic fabric softener to facilitate attachment of the capsules to fabrics during a presoak bath or in the washing machine. The capsules thereafter release the perfume by diffusion through the capsule wall and by rupturing of the capsules during manipulation of the fabrics.
BACKGROUND OF THE INVENTION
DeliYery of perfumes, particularly volatile and nonsubstantive perfumes, to fabrics during the laundering operation is difficult. Surfactants are generally employed during presoaking and washing steps for the purpose of removing materials (soil) from the fabrics. Simultaneous deposition onto fabrics of perfume can, therefore, prove troublesome. Moreover, retention of perfumes, particularly the volatile and nonsubstantive perfumes, on fabrics during the drying process remains difficult.
Although treatment of fabrics with microcapsules is known (see, for example, Ida et al, U.S. Patent 3,870,542, issued March 11, 1975; and Pandell et al, U.S. Patent 3,632,296, issued January 4, 1972), such prior art fabric treatment has generally required utilization of large numbers of microcapsules to provide effective capsule delivery.
U.S. Patent 4,234,627, Schilling, issued November 18, 1980, and U.S. Patent 4,145,184, Brain et al, issued March 20, 1979, disclose granular compositions containing friable microcapsules containing conditioning agents, including perfumes, to deliver such conditioning agents to fabrics during the presoaking/washing stage of the home laundry operation.
:. ::, . . . ~ , . . .
,; .; , .. ;; - ~ .. . .
... .. . . . . .
... : - . : . - .
:.. .. : . - ~
; ~ . . ~:: . . . . :
:. .
.. ,, : ~ .
~o()~
Despite these disclosures, l:here is a continuing need for improved compositions capable of more effectively delivering perfumes to fabrics.
Accordingly, it is an object of the present invention to provide improved perfume-containing microcapsules which when used in granular presoaking/washing detergent compositions deliver effective amounts of perfume to fabrics being laundered.
It is a further object of the present invention to provide an improved method for delivering perfume to fabrics during the presoak or wash stage of the laundering process.
It has been surprisingly discovered that by ut;lizing particular types of perfume-containiny microcapsules coated with water-insoluble cationic fabric softeners, the above objectives can be attained.
SUMMARY OF THEI NVENTION
The present invention relates to microcapsules having an average size of from about 5 to 500 microns, each microcapsule consisting essentially of:
(i~ a liquid core containing perfume; and (ii) a solid thin polymeric shell completely surrounding said core, said shell having an average thickness of from about 0.1 to 50 microns, and said shell being formed by complex coacervation of polycationic and polyanionic materials;
said microcapsules being coated with a substantially water-in-soluble cationic fabric softener having a melting point between about 40C and 150C, wherein the weight ratio of microcapsules to cationic softener is from about 3:1 to about 50:1.
The invention also relates to granular laundry detergent compositions comprising from about 0.1% to ~0% of the above coated perfume-containing microcapsules and from about 5% to 99% by . weight of a detergent adjuvant selected from the group consisting of water-soluble detersive surfactants, detergency builders, and mixtures thereof.
, ~. .:
-: : ' . , .
~ 7 0 Additionally, the present invention relates to a method of treating fabrics with compositions as described above.
DETAILE~ DESCRIPTION OF THE TNVENTIO~I
The present invention involves the home laundry application to fabrics of granular detergent compositions containing perfume microcapsules coated w;th a water-insoluble cationic softener.
The cationic fabric softener facilitates attachment of the capsules to fabrics during a presoak bath or in the washing machine. The capsules thereafter release the perfume by diffusion through the capsule wall and by manipulat;on of the treated fabr;cs so as to rupture the capsules. While not intending to be limited by theory, it is believed that the cationic softener complexes with the anionic polymer portion of the capsule wall so as to enhance diffusibility of the perfume during the fabric laundering process when the capsules are rehydrated by the laundering solution. This results in improved delivery of the perfume to fabrics during the washing and/or drying steps, as desired.
~15~953~Y~
The microcapsules useful in the present invention comprise a liquid core containing one or more perfumes and a thin polymeric shell, formed by complex coacervation of polycationic and polyanionic materials, completely surrounding the l;quid core. By encapsulating the perfume (in liquid form), the perfume is protected during the production, distribution and storage of the granular detergent composition and is thus preserved for most efficient application to fabrics during the laundering operation.
Perfume is actually appl;ed to the fabrics by diffusion through the capsule wall or when the microcapsules rupture during manipulation of the fabr;cs. This can occur either during the automatic washing or drying step of the home laundering operation or can actually occur after the fabrics are laundered and while they are being used.
.. ..
" - ,. : ~ ' : , - . ~ .. . . ... .
:.;:: :: : ;
.
7 ~) The perfume which can be used in the liquid cores of the microcapsules can be any water-insoluble (or substantially water-insoluble) odoriferous material and will be selected : S according to the desires of the formulator. (~later-soluble perfume components are difficult to encapsulate using the complex coacervation methods described hereinafter.) In general terms, such perfume materials are characterized by a vapor pressure above atmospheric pressure at ambient temperatures. The perfume materials employed herein will most often be liquid at ambient temperatures, but also can be solids such as the various camphor-aceous perfumes known in the art. A wide variety of chemicals are known for perfumery uses, including materials such as aldehydes, ketones, esters, and the like. More commonly, naturally-occurring plant and animal oils and exudates comprising complex mixtures of various chemical components are known for use as perfumes, and such materials can be used herein. The perfumes herein can be relatively simple in their composition, or can comprise highly ~ sophisticated, complex mixtures of natural and synthetic chemical components, all chosen to provide any desired odor.
Typical perfumes herein can comprise, for example, woody~earthy bases conta;ning exotic materials such as sandalwood oil, civet, patchouli oil, and the like. The perfumes herein can be of a light, floral fragrance, etc., rose extract, violet extract, and the like. The perfumes herein can be formulated to provide desirable fruity odors, e.g., lime, lemon, orange, and the like. In short, any material which exudes a pleasant or otherwise desirable odor can be used in the liquid microcapsule core to provide a desirable odor when applied to fabrics. Preferred, ::
perfumes inciude musk ambrette, musk ketone, musk tibetine, musk xylol, aurantiol, ethyl vanillin and mixtures thereof. Examples of such perfume matrials can be found in U.S. Patent 4,515,705, Moeddel, issued May 7, 1985,incorporated herein by reference. -~'' Perfumes will frequently be in liquid form and can be used as the sole materials in the microcapsule core. Perfulnes which are ,:.;. ,,, : . : , ; - , , ~ :
: ,: , : , : . ', , , :.
~O~ 7r~
normally solid can also be emp'loyed in the microcapsule core if they are admixed with a liquefying agent such as a solvent. Any organic solvent can be used to liquify normally solid perfume for use in the microcapsule core provided such a solvent is chemically S compatible with the microcapsule shel'l material described hereinafter. Preferred solvents for use herein are materials such as mineral oil and dodecane.
The shell material surrounding the liquid, perfume-containing core to form the microcapsule can be any suitable polymeric material formed by complex coacervation of polycationic and polyanionic materials. The shell is substantially impervious to the materials in the liquid core and to materials which may come in contact with the outer surface of the shell during storage.
When the microcapsules are rehydrated by the laundering solution, it is believed that pores in the microcapsules expand to allow diffusion of the perfume during the washing and drying steps, thereby improving perfume delivery to fabrics.
Suitable polycationic' materials for use in forming the polymeric shell of the microcapsules herein include materials such as gelatin, poly(vinyl pyrrolidoneJ, poly(ethyleneimine) and albumin. Type A gelatin is preferred. Suitable polyanionic materials for forming the polymeric shell include materials such as ~um arabic, poly(ethylene/maleic anhydride), poly(vinyl methylethyl maleic anhydride), polyphosphate, polyacrylate, and gelatin. Polyphosphates, especially sodium hexametaphosphate, are particularly preferred.
Microcapsules as described above can be prepared by any conventional complex coacervation process. Such methods are described in U.S. Patent 2,800,457i 3,190,837; 3,317,434;
3,341,466; 3,533,958; 3,687,865, 3,697,437; and 3,840,467. All of the above patents are incorporated herein by reference.
The microcapsules should have an average size of between about 5 microns and 500 microns, preferably between about 40 microns and 250 microns, more preferably between about 80 and 150 ~ . .. . ;.. ; . :
.: , . ..
.. ..... . .
. .
:
: , .
o microns. Furthermore, the capsules utilized in the present invention have an average shell thickness ranging from about 0.1 to 50 microns, preferably from about 0.4 to 30 microns.
The microcapsules of the present invention are generally friable in nature. Friability refers to the propensity of the microcapsules to rupture or break open when subjected to direct external pressures or shear forces. For purposes of the present invention, the microcapsules utilized are "friable" if, while attached to fabrics treated therewith, they can be ruptured by the forces encountered when the capsule-containing fabrics are tumbled in an automatic laundry dryer or are manipulated by being worn or handled. Microcapsules made with the above-described shell materials will be "friable" if they fall within the capsule size and shell thickness limitations provided above.
Cationic Fabric Softener Attachment of the above-described microcapsules to the fabrics being treated therewith is facilitated by surrounding the microcapsules with the cationic fabric softener. These are substantially water-insoluble materials which are fabric substantive and which have a melting point with the range of from about 40C to 150C, preferably with the range of from about 49C
to 105C. 8y "substantially water-insoluble" herein is meant a water insolubility of 1% by weight, or less, at 30C.
Suitable cationic capsule transfer agents include any of the cationic (including imidazolinium) compounds listed in U.S.
Patent No. 3,686,025, Morton, issued August 22, 1972, incorporated herein by reference. Such materials are well known in the art and include, for example, the quaternary ammonium salts having at least one, preferably two, Clo-C20 fatty alkyl substituent groups;
alkyl imidazolinium salts wherein at least one alkyl group contains a C~-Czs carbon "chain"; the Clz-C20 alkyl pyridinium salts, and the like.
Preferred cationic softeners herein include the quaternary ammonium salts of the general formula RlR2R3R4N+,X-, wherein .: ., ; , .
:-: , . . . ~ .
:,, : .
~ O (~I L~ 2 7 () groups R1~R2~R3, and R4 are, for example, alkyl, and X~ is an anion, e.g., halide, methylsulfate, and the like, with e chloride and methylsulfate salts being preferred. Especially preferred capsule transfer agents are those wherein R1 and R2 are each C12-C20 fatty alkyl and R3 and R4 are each Cl-C4 alkyl. The fatty alkyl groups can be mixed, i.e., the mixed C14-CIg coconutalkyl and mixed C16-C1g tallowalkyl quaternary compounds.
Alkyl groups R3 and R4 are preferably methyl.
Exemplary quaternary ammonium softeners herein include ditallowalkyldimethylammonium methylsulfate, ditallowalkyldi-; methylammonium chloride, dicoconutalkyldimethylammonium methyl-sulfate, and dicoconutalkyldimethylammonium chloride.
The above-described microcapsules are coated with the fabric ; softener such that the weight ratio of microcapsules to softener15 generally varies between about 50:1 to 3:1, preferably between about 20:1 and 4:1, more preferably between about 10:1 and 5:1.
It is preferred that the fabric softener completely surround or envelop the individual microcapsules. This is generally accomplished by thoroughly admixing the microcapsules with the softener in some form of liquid medium, and then drying to solidify the coating. Any conventional coating technique can also be utilized including spray-on processes or fluidized bed coating methods, which are preferred for commercial scale operation.
The cationic fabric softener coating can optionally include minor amounts (e.g., less than 50%, preferably less than 20%) by weight of the nonionic capsule transfer agents described in U.S.
I Paent 4,234,627 to Schilling, incorporated herein by reFerence.
Granular peterqent Composition Granular laundry detergent presoaking and/or washing compositions herein contain from about 0.1% to 20%, preferably from about 0,3% to about 10%, more preferably from about 0.5% to about 5%, by weight of the above coated perfume-containing microcapsules. Such compositions also contain from about 5% to about 99%, preferably from about 10% to about 90%, more preferably r` ~ ` ~ , . , ; : ' ' ~
' ." ~ ~, . ': I i ""' "' I ' ' ' i .~ ' ' ~CO ~'7~
from about 20% to about 80%, by ~leight of a detergent adjuvant selected from the group consisting of water-soluble detersive surfactants, detergent builders, and mixtures thereof.
Water-soluble surfactants used in the presoaking/washing detergent compositions herein include any of the common anionic, nonionic, ampholytic and zwitterionic detersive surfactants well known in the detergency arts. Mixtures of surfactants can also be employed herein. More particularly, the surfactants listed in ; 10 Booth, U.S. Patent No. 3,717,630, issued February 20, 1973, and Kessler et al; U.S. Patent No. 3,332,880, issued July 25, 1967, each incorporated herein by re-Ference, can be used herein.
Non-limiting examples of surfactants suitable for use in the instant compositions are as follows.
Water-soluble salts of the higher fatty acids, i.e., "soaps", are useful anionic surfactants in the compositions herein. This includes alkali metal soaps such as the sodium, potassium, ammonium, and alkylolammonium salts of higher fatty acids containing from about 8 to about 24 carbon atoms, and preferably from about 12 to about 18 carbon atoms. Soaps can be made by direct saponification of fats and oils or by the neutralization of free fatty acids. Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap.
Useful anionic surfactants also include the water-soluble salts, preferably the alkali metal, ammonium and alkylolammonium salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 10 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group. (Included in the term "alkyl" is the alky portion of acyl groups). E~amples of this group of synthetic surfactants are the sodium and potassium alkyl sulf`ates, especially those obtained by sulfating the higher alcohols (Cg-C1g carbon atoms) such as those produced by reducing the glycerides of tallow or coconut oil; and ;. .: : :, ,:. .~ , - , : - .. ;.
, :; , .
'' :''' , ' , '' . : ' -. : , : . ~
;~oo~
the sodium and potassium alkylbenzene sulfonates in which the alkyl group contains from about 9 to about 15 carbon atoms, in straight chain or branched chain configuration, e.g., those of the type described in U.S. Patent Nos. 2,220,099, and 2,477,383.
Especially valuable are linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from about 11 to 13, abbreviated as Cll l3 LAS.
Other anionic surfactants herein are the sodium alkyl glyceryl ether sulfonates, especially those ethers of higher ~ alcohols derived from tallow and coconut oil; sodium coconut oil : fatty acid monoglyceride sulfonates and sulfates; sodium or potassium salts of alkyl phenol ethylene oxide ether sulfates containing from about 1 to about 10 units of ethylene oxide per molecule and wherein the alkyl groups contain from about 8 to about 12 carbon atoms; and sodium potassium salts of alkyl ethylene oxide ether sulfates containing about 1 to about 10 units of ethylene oxide per molecule and wherein the alkyl group contains from about 10 to about 20 carbon atoms.
Other useful anionic surfactants herein include the , water-soluble salts of esters of alpha-sulfonated fatty acids containing ~rom about 6 to 20 carbon atoms in the fatty acid group and from about 1 to 10 carbon atoms in the ester group;
water-soluble salts of 2-acyloxyalkane-1-sulfonic acids containing from about 2 to 9 carbon atoms in the acyl group and from about 9 to about 23 carbon atoms in the alkane moiety; water-soluble salts of olefin and paraffin sulfonates containing from abollt 12 to 20 carbon atoms; and beta-alkyloxy alkane sulfonates containing from 3 about 1 to 3 carbon atoms in the alkyl group and from about 8 to 20 carbon atoms in the alkane moiety.
Water-soluble nonionic surfactants are also useful in the compositions of the invention. Such nonionic materials include compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature. The length of ., . :: ,: . . . . . .
-; , :
,,: . : : ~ : . . , , ~ , .
.,~.. . . .. .
, . . . .
~,'092~70 the polyoxyalkylene group which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
Suitable nonionic surfactants include the polyethylene oxide condensates of alkyl phenols, e.g., the condensation products of alkyl phenols having an alkyl group containing from about 6 to 15 carbon atoms, in either a straight chain or branched chain configuration, with from about 3 to 12 moles of ethylene oxide per mole of alkyl phenol.
Preferred nonionic surfactants are the water-soluble and water-dispersible condensation products of aliphatic alcohols containing from 8 to 22 carbon atoms, in either straight chain or branched configuration, with from 3 to 12 moles of ethylene oxide per mole of alcohol. Particularly preferred are the condensation products of alcohols having an alkyl group containing from about 9 to 15 carbon atoms with from about 4 to 8 moles of ethylene oxide per mole of alcohol.
Semi-polar nonionic surfactants include water-soluble amine oxides containing one alkyl moiety of from about 10 to 18 carbon atoms and two moieties selected from the group of alkyl and hydroxyalkyl moieties of from about 1 to about 3 carbon atoms;
water-soluble phosphine oxides containing one alkyl moiety of about 10 to 18 carbon atoms and two moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of from about 10 to 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from about 1 to 3 carbon atoms.
Ampholytic surfactants include derivatives of aliphatic or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic moiety can be straight chain or branched and wherein one of the aliphatic substituents contains : ,.. , . ., - ,: . . . .
.,, : .:, : : -~
., ,- . . .
"~
.'; . : . :
.
z~o~
` from about a to l~ carbon atoms and at least one aliphatic substituent contains an anionic water-solubilizing group.
Zwitterionic surfactants include derivatives of aliphatic, S quaternary, ammonium, phosphonium, and sulfonium compounds in which one of the aliphatic substituents contains from about 8 to 18 carbon atoms.
When the present granular detergent compositions are used as presoaking or wash additive compositions in conjunction with other commercially available laundry detergent products, the detersive surfactant component generally comprises from about 0% to 20% by weight of the compositions, preferably from about 1% to 10% by weight. When the present compositions are to be used as the sole detergent product during the laundering process, the detersive surfactant component generally comprises from about 5% to about 75%, preferably from about 10% to 40%, by weight of the composition.
In addition to detergent surfactants, detergency builders can be employed in the final granular detergent product.
Water-soluble inorganic or organic electrolytes are suitable builders. The builder can also be water-insoluble calcium ion exchange materials; nonlimiting examples oF suitable water-soluble, inorganic detergent builders include: alkali metal carbonates, borates, phosphates, bicarbonates and silicates.
Specific examples of such salts include sodium and potassium tetraborates, bicarbonates, carbonates, orthophosphates, pyrophosphates, tripolyphosphates and metaphosphates.
Examples of suitable organic alkaline detergency builders include: (l) water-soluble amino carboxylates and aminopolyacetates, for example, nitrilotriacetates, glycinates, ethylenediamine, tetraacetates, N-(2-hydroxyethyl)nitrilo diacetates and diethylenetriamine pentaacetates; (2) water-soluble salts of phytic acid, for example, sodium and potassium phytates;
(3) water-solub1e polyphosphonates, including sodium, potassium, and lithium salts of ethane l-hydro~y-1, I-diphosphonic acid;
.
.
:
.
',: ~ .
. ~ .
ZO~2'7~:) sodium, potassium, and lithium salts of ethylene diphosphonic acid; and the like; (4) water-soluble polycarboxylates such as the salts of lactic acid, succinic acid, malonic acid, maleic acid, citric acid, carboxymethyloxysuccinic acid, 2-oxa-1,1,3-propane tricarboxylic acid, 1,1,2,2-ethane tetracarboxylic acid, mellitic acid and pyromellitic acid; and (5) water-soluble polyacetals as disclosed in U.S. Patent Nos. 4,1~,266 and 4,246,495 incorporated herein by reference.
Another type of detergency builder material useful in the final granular detergent product comprises a water-soluble material capable of forming a water-insoluble reaction product with water hardness cations preferably in combination with a crystallization seed which is capable of providing growth sites for said reaction product. Such "seeded builder" compositions are fully disclosed in British Patent No. 1,424,406.
A further class of detergency builder materials useful in the present invention are insoluble sodium aluminosilicates, particularly those described in Belgian Patent No. ~14,874, issued November 12, 1974, as having the formula:
Naz-(Alo2)-(sio2)yxH2o wherein z and y are integers equal to at least 6, the molar ratio of z to y is in the range of from 1.0:1 to about 0.5:1, and X is an integer from about 15 to about 264, said aluminosilicates having a calcium ion exchange capacity of at least 200 milligrams equivalent/gram and a calcium ion exchange rate of at least about 2 grain/gallon/minute/gram. A preferred material is Zeolite A
which is:
Nal2-(SiO2A102)l227H2o When the present granular detergent compositions are used as presoaking or wash additive compositions in conjunction with other commercially available laundry detergent products, the detergency builder component generally comprises from about 20% to 90% by weight of the compositions, preferably from about 30% to 75% by weight. When the present granular compositions are to be used as :: ~: . , , . .... . , . . .: .
~o~ n the sole detergent product during the laundering process, the detergency builder component generally comprises from about 10% to about 75%, preferably from about 20% to 50%, by weight of the composition.
Optional detergent composition components include enzymes (e.g., proteases and amylases), bleaches and bleach activators, soil release agents (e.g., methylcellulose), soil suspending agents (e.g., sodium carboxymethylcellulose), fabric brighteners, enzyme stabilizing agents, color speckles, suds boosters or suds suppressors, anticorrosion agents, dyes, fillers, germicides, pH
adjusting agents, nonbuilder alkalinity sources, and the like.
EXAMPLE I
A granular laundry detergent composition of the present 15 invention is as follows.
Inqredient Weiqht Percent ~:
Sodium C13 linear alkylbenzene sulfonate 8.5 Sodium C14 15 alkyl sulfate 8.4 Sodium tripolyphosphate 39.4 20 Sodium carbonate 12.3 i~.
Sodium silicate (1.6 ratio) 5.6 Water 7 0 Coated perfume microcapsules 0.9 Sodium sulfate & miscellaneous ~alance to 100 25The above granular detergent composition is made by mixing the ingredients (except the microcapsules) in a crutcher, and then spray-drying by conventional methods.
The coa~ed perfume microcapsules are made as follows: A
67/33 (by weight) perfume/light mineral oil (viscosity 125/135) mixture is heated to about 60C in a constant temperature controlled water bath. About 10 grams of Type A gelatin per 100 grams of perfume/mineral oil is dissolved in 250 ml of distilled water with stirring at 250 revolutions per minute (rpm). About O.S to 1.0 grams of sodium hexametaphosphate per 100 grams of perfume/mineral oil is dissolved in distilled water to a .~ ~, "
concentration of 5% by weight. The dissolve~ ge1atin solution is stirred at 600 rpm using a Lightin Stirrer Model RP1515 with a 5 cm high sheer stirring blade. The perfume/mineral oil mixture is added dropwise to the gelatin solution over a period of 10-15 minutes to form an emulsion with particle sizes ranging from 75-250 microns. An additional 200 ml of 60C water is added and the stirring speed reduced to 250 rpm. The pH of the mixture is adjusted to 4.92 with glacial acetic acid. The heating element of the water bath is turned off to allow the mixture to cool for from 6 to 2~ hours. When the oil droplets are completely covered with a layer of gelatin the reaction is cooled to 1-2C with external ice. The mixture is allowed to remain at that temperature for 10 to 30 minutes. At this point 4 ml of 25% glutaraldehyde is added to crosslink the gelatin capsule walls. The mixture is then stirred and allowed to warm to room temperature for from 6 to 24 hours. Approximately 4 grams of a syloid filter aid is added to the mixture after the reaction with glutaraldehyde is completed.
The mixture is then filtered to separate the capsules. The capsules are washed with 2 liters of water to remove residual glutaraldehyde. The capsules are then spread on a paper towel to dry. (Drying can also be accomplished in a fluid bed dryer when larger than 100 gram samples are used.) The capsules are then sieved to remove capsules and debris of a size larger than about 250 microns. The remaining capsules have an average size of about 100 to 150 microns and have a shell thickness averaging 0.1 to 50 microns.
The capsules are added to a solution of methylene dichloride containing ditallowdimethylammonium chloride (DTDMAC) in a ratio of 10 ml of methylene dichloride and 2 grams o~ DTDMAC per 10 grams of capsules. The methylene chloride is removed from the mixture using a stream of nitrogen. The coating solution is warmed gently in a steam bath to facilitate removal of the solvent. The resulting capsules are evenly coated with a thin layer (about 20-50 microns) of the DTDMAC. (For larger samples, a .: , ~ .. : :
~,,, ~. . - - .
,: : - . -; . : :, ;-~. .: ` : ` . `
:
: . . . -.
~ g~ 2 ~
Wurster Coater or any suitable fluid bed apparatus can be used to obtain an even coating of the microcapsules, after adjustment of all ratios to obtain an even flow of the capsules in the system.) The microcapsules are then admixed with the spray dried detergent ingredients to form a finished detergent composition.
When the composition is used in a washing machine to clean fabrics, the coated perfume-containing microcapsules effectively deliver perfume to the fabrics during the washing and drying steps and thereafter during handling of the fabrics.
Other compositions of the present invention are obtained when the perfume microcapsules are prepared by initially using a 50/50 (by weight) perfume/light mineral oil mixture, or 100% perfume tno mineral oil), or by replacing the sodium hexametaphosphate with gum arabic.
Other compositions herein are obtained when the DTDMAC used to coat the microcapsules is replaced with a 3:1 by weight ratio mixture of DTDMAC and tallow alcohol, or when the sodium tripolyphosphate in the detergent composition is replaced with a 3:1 by weight ratio mi~ture of hydrated sodium zeolite A and sodium carbonate.
EXAMPLE II
A granular laundry detergent composition of the present invention is as follows.
Ingredient Weiqht Percent 1. SpraY-dried deterqent base granules:
Sodium 13 linear alkylbenzene sulfonate (70%)/
Sodium C14 15 alkyl sulfate (30%) 12.88 Sodium tripolyphosphate 4.56 30 Tetrasodium pyrophosphate 17.16 Sodium silicate (1.6 ratio) 7.20 Diethylenetriamine pentaacetic acid 0.38 Brightener 0.18 Sodium polyacrylate (MW 4500) 0.96 Polyethylene glycol (MW 8000) 0.29 . .
' '`:, ~ .
.... . . .
. ~ . .
~oo~z~
Water* 3.0 Sodium sulfate & miscellaneousBalance to 100 2. SDraY on base q_anules:
C12 13 alcohol polyethoxylate (6.5)** 0.44 ~. Admix with base qranules-Sodium carbonate 22.00 Enzyme-Savinase (NovoJ 0.37 Sodium perborate monohydrate (solids) 3.69 10 Nonanoyloxybenzene sulfonate 5.26 Coated perfume microcapsules 1.50 *Remaining water is brought in with admixes.
**Alcohol and monoexthoxylated alcohol removed.
The above granular detergent composition is made as follows.
The spray-dried detergent base granules are formed by mixing the ingredients of step 1 in a crutcher, and then spray-drying by conventional methods. The nonionic surfactant of step 2 is then sprayed onto the detergent base granules. The resulting product is admixed with the ingredients of step 3, including the coated perfume microcapsules made according to Example I, to form a finished detergent composition.
When the composition ;s used in a washing machine to clean fabrics, the coated perfume-containing microcapsules effectively deliver perfume to the fabrics during the washing and drying steps and thereafter during handling of the fabrics.
WHAT IS CLAIMED IS:
-. . .:
. ~ ; ~. : - . . , .. , . .. , :
.. . . -: , .: . .......................................................... ..
~ :
Claims (18)
1. Microcapsules having an average size of from about 5 to 500 microns, each microcapsule consisting essentially of:
(i) a liquid core containing perfume; and (ii) a solid thin polymeric shell completely surrounding said core, said shell having an average thickness of from about 0.1 to 50 microns, and said shell being formed by complex coacervation of polycationic and polyanionic materials;
said microcapsules being coated with a substantially water-in-soluble cationic fabric softener having a melting point between about 40°C and 150°C, wherein the weight ratio of microcapsules tocationic softener is from about 3:1 to about 50:1.
(i) a liquid core containing perfume; and (ii) a solid thin polymeric shell completely surrounding said core, said shell having an average thickness of from about 0.1 to 50 microns, and said shell being formed by complex coacervation of polycationic and polyanionic materials;
said microcapsules being coated with a substantially water-in-soluble cationic fabric softener having a melting point between about 40°C and 150°C, wherein the weight ratio of microcapsules tocationic softener is from about 3:1 to about 50:1.
2. Microcapsules according to Claim 1 wherein the microcapsule shell wall material is formed by complex coacervation of Type A
gelatin and gum arabic or polyphosphate materials.
gelatin and gum arabic or polyphosphate materials.
3. Microcapsules according to Claim 1 wherein the cationic fabric softener is a C12-C20 dialkyldimethylammonium salt.
4. Microcapsules according to Claim 3 wherein the weight ratio of the microcapsules to the cationic fabric softener is from about 4:1 to about 20:1.
5. Microcapsules according to Claim 4 wherein the weight ratio of the microcapsules to the cationic fabric softener is from about 5:1 to about 10:1.
6. Microcapsules according to Claim 5 wherein the microcapsule shell wall material is formed by complex coacervation of Type A
gelatin and gum arabic or polyphosphate materials.
gelatin and gum arabic or polyphosphate materials.
7. Microcapsu1es according to Claim 6 having an average size of from about 80 to about 150 microns.
8. A granular laundry detergent composition comprising:
(a) from about 0.1% to 20% by weight of perfume microcapsules having an average size of from about 5 to 500 microns, each microcapsule consisting essentially of:
(i) a liquid core containing perfume; and (ii) a solid thin polymeric shell completely surrounding said core, said shell having an average thickness of from about 0.1 to 50 microns, and said shell being formed by complex coacervation of poly-cationic and polyanionic materials;
said microcapsules being coated with a substantially water-insoluble cationic fabric softener having a melting point between about 40°C and 150°C, wherein the weight ration of microcapsules to cationic softener is from about 3:1 to about 50:1; and b. from about 5% to 99% by weight of a detergent adjuvant selected from the group consisting of water-soluble detersive surfactants, detergency builders, and mixtures thereof.
(a) from about 0.1% to 20% by weight of perfume microcapsules having an average size of from about 5 to 500 microns, each microcapsule consisting essentially of:
(i) a liquid core containing perfume; and (ii) a solid thin polymeric shell completely surrounding said core, said shell having an average thickness of from about 0.1 to 50 microns, and said shell being formed by complex coacervation of poly-cationic and polyanionic materials;
said microcapsules being coated with a substantially water-insoluble cationic fabric softener having a melting point between about 40°C and 150°C, wherein the weight ration of microcapsules to cationic softener is from about 3:1 to about 50:1; and b. from about 5% to 99% by weight of a detergent adjuvant selected from the group consisting of water-soluble detersive surfactants, detergency builders, and mixtures thereof.
9. A composition according to Claim 8 wherein the microcapsule shell wall material is formed by complex coacervation of Type A
gelatin and gum arabic or polyphosphate materials.
gelatin and gum arabic or polyphosphate materials.
10. A composition according to Claim 9 wherein the cationic fabric softener is a C12-C22 dialkyldimethylammonium salt.
11. A composition according to Claim 10 wherein the weight ratio of the microcapsules the cationic fabric softener is from about 20:1 to about 4:1.
12. A composition according to Claim 11 wherein the microcapsule shell wall material is formed by complex coacervation of Type A
gelatin and gum arabic or polyphosphate materials.
gelatin and gum arabic or polyphosphate materials.
13. A composition according to Claim 12 wherein the microcapsules have an average size of from about 80 to about 150 microns.
14. A composition according to Claim 13 comprising from about 0.5% to about 5% by weight of the microcapsules.
15. A composition according to Claim 14 comprising from about 20%
to about 80% by weight of the detergent adjuvant.
to about 80% by weight of the detergent adjuvant.
16. A composition according to Claim 15 comprising from about 10%
to about 40% by weight of the detergent surfactant and from about 20% to about 50% by weight of the detergent builder.
to about 40% by weight of the detergent surfactant and from about 20% to about 50% by weight of the detergent builder.
17. A process for treating fabrics comprising contacting said fabrics with a laundering solution comprising an effective amount of a composition according to Claim 8.
18. A process according to Claim 17 comprising contacting said fabrics with a laundering solution comprising an effective amount of a composition according to Claim 16.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US29188288A | 1988-12-29 | 1988-12-29 | |
| US291,882 | 1988-12-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2004270A1 true CA2004270A1 (en) | 1990-06-29 |
Family
ID=23122264
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002004270A Abandoned CA2004270A1 (en) | 1988-12-29 | 1989-11-30 | Perfume microcapsules for use in granular detergent compositions |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0376385A3 (en) |
| JP (1) | JPH02258900A (en) |
| KR (1) | KR900009951A (en) |
| CN (1) | CN1044295A (en) |
| AU (1) | AU4732389A (en) |
| BR (1) | BR8906831A (en) |
| CA (1) | CA2004270A1 (en) |
| DK (1) | DK672689A (en) |
Families Citing this family (44)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5066419A (en) * | 1990-02-20 | 1991-11-19 | The Procter & Gamble Company | Coated perfume particles |
| US5236615A (en) * | 1991-08-28 | 1993-08-17 | The Procter & Gamble Company | Solid, particulate detergent composition with protected, dryer-activated, water sensitive material |
| EP0617735B1 (en) * | 1991-12-20 | 1996-09-04 | The Procter & Gamble Company | A process for preparing a perfume capsule composition |
| EP0622453A1 (en) * | 1993-04-26 | 1994-11-02 | Setric International S.A. | Process for particulate protection of a combustible product against the action of a chlorinated product mixed therewith |
| CA2248065A1 (en) * | 1996-03-06 | 1997-09-12 | Novo Nordisk A/S | A method of killing or inhibiting microbial cells |
| JP2000503708A (en) * | 1996-09-18 | 2000-03-28 | ザ、プロクター、エンド、ギャンブル、カンパニー | Dual coating method for the production of granular laundry additive compositions for delivery of fragrances having improved physical properties |
| GB9700624D0 (en) | 1997-01-14 | 1997-03-05 | Danbiosyst Uk | Drug delivery composition |
| KR100495027B1 (en) * | 1997-05-06 | 2005-09-16 | 주식회사 엘지생활건강 | Powder detergent composition with microencapsulated fragrance |
| US6624136B2 (en) * | 1998-02-02 | 2003-09-23 | Rhodia Chimie | Water-dispersible granules comprising a fragrance in a water-soluble or water-dispersible matrix, and process for their preparation |
| FR2774389B1 (en) * | 1998-02-02 | 2001-07-27 | Rhodia Chimie Sa | WATER-DISPERSABLE GRANULES COMPRISING A PERFUME IN A WATER-SOLUBLE OR HYDRODISPERSABLE MATRIX AND THEIR PREPARATION METHOD |
| KR100497521B1 (en) * | 1998-04-08 | 2005-09-14 | 주식회사 엘지생활건강 | Manufacturing method of capsule laundry detergent |
| GB2336848A (en) * | 1998-04-30 | 1999-11-03 | Mcbride Robert Ltd | Liquids release from particulate surface cleaners |
| DE19855347C1 (en) * | 1998-12-01 | 2000-09-21 | Henkel Kgaa | Preparations containing active chlorine with stabilized fragrances |
| KR20010039226A (en) * | 1999-10-29 | 2001-05-15 | 이원목 | Fabric Softner Composition Containing Microcapsulated Perfume |
| US6531444B1 (en) | 2000-11-09 | 2003-03-11 | Salvona, Llc | Controlled delivery system for fabric care products |
| KR100411730B1 (en) * | 2000-12-06 | 2003-12-18 | 주식회사 엘지생활건강 | Fabric softner composition |
| DE10100689A1 (en) * | 2001-01-09 | 2002-07-18 | Henkel Kgaa | Microcapsules containing washing and cleaning active substances |
| DE10105801B4 (en) * | 2001-02-07 | 2004-07-08 | Henkel Kgaa | Detergents and cleaning agents comprising fine microparticles with detergent components |
| KR20020023694A (en) * | 2001-12-06 | 2002-03-29 | 이재식 | Microcapsule-type toilet cleaner |
| KR20030064502A (en) * | 2002-01-28 | 2003-08-02 | 주식회사 폴리크롬 | A Fiber Softener Composition Containing Functional Microcapsule And Method For Preparation Thereof |
| US7125835B2 (en) | 2002-10-10 | 2006-10-24 | International Flavors & Fragrances Inc | Encapsulated fragrance chemicals |
| US7585824B2 (en) * | 2002-10-10 | 2009-09-08 | International Flavors & Fragrances Inc. | Encapsulated fragrance chemicals |
| BR0303954A (en) * | 2002-10-10 | 2004-09-08 | Int Flavors & Fragrances Inc | Composition, fragrance, method for dividing an olfactory effective amount of fragrance into a non-rinse and non-rinse product |
| DE10247583C5 (en) * | 2002-10-11 | 2009-04-30 | Bell Flavors & Fragrances Duft Und Aroma Gmbh | Process for the preparation of a solid perfume concentrate |
| US7670627B2 (en) | 2002-12-09 | 2010-03-02 | Salvona Ip Llc | pH triggered targeted controlled release systems for the delivery of pharmaceutical active ingredients |
| ATE355357T1 (en) * | 2003-08-01 | 2006-03-15 | Procter & Gamble | AQUEOUS LIQUID DETERGENT CONTAINING VISIBLE PARTICLES |
| GB0326815D0 (en) * | 2003-11-18 | 2003-12-24 | Regency Chemical Company Ltd | Composition |
| MXPA04011520A (en) * | 2003-11-20 | 2005-08-16 | Int Flavors & Fragrances Inc | Encapsulated materials. |
| US20050112152A1 (en) * | 2003-11-20 | 2005-05-26 | Popplewell Lewis M. | Encapsulated materials |
| GB0328186D0 (en) | 2003-12-05 | 2004-01-07 | West Pharm Serv Drug Res Ltd | Intranasal compositions |
| CN100393859C (en) * | 2004-04-05 | 2008-06-11 | 新疆芳香植物科技开发股份有限公司 | Microcapsules of essential oil from fragrant plants and preparation thereof |
| EP1632560B1 (en) * | 2004-08-23 | 2011-01-05 | The Procter & Gamble Company | Microcapsules |
| DE602005025718D1 (en) | 2004-08-23 | 2011-02-17 | Procter & Gamble | microcapsules |
| EP1634944A1 (en) * | 2004-08-23 | 2006-03-15 | The Procter & Gamble Company | Microcapsules |
| EP1669437A1 (en) * | 2004-12-03 | 2006-06-14 | The Procter & Gamble Company | Microcapsules |
| ES2360293T5 (en) * | 2004-10-01 | 2014-06-02 | Firmenich Sa | Perfume or flavoring microcapsules comprising an explosion suppressor |
| KR100758786B1 (en) * | 2006-02-16 | 2007-09-14 | 주식회사 엘지생활건강 | Oral compositions containing capsules |
| WO2007143869A2 (en) * | 2006-06-13 | 2007-12-21 | Givaudan Sa | Encapsulation compositions |
| HUE029942T2 (en) | 2009-08-13 | 2017-04-28 | Procter & Gamble | Method of laundering fabrics at low temperature |
| WO2011056935A1 (en) * | 2009-11-06 | 2011-05-12 | The Procter & Gamble Company | Delivery particle |
| EP3109309B1 (en) * | 2012-01-18 | 2022-06-08 | The Procter & Gamble Company | Perfume systems |
| PT108665B (en) | 2015-07-05 | 2020-11-02 | Universidade Do Minho | MICRO OR NANOCAPSULES WITH PHOTOCATALYTIC PROPERTIES FOR CONTROLLED RELEASE OF DIFFUSING AGENTS AND THEIR METHOD OF OBTAINING |
| RS63086B1 (en) | 2016-04-18 | 2022-04-29 | Monosol Llc | Film comprising perfume microcapsules and a container comprising such a film and a detergent |
| EP3775140A1 (en) * | 2018-09-26 | 2021-02-17 | Firmenich SA | Powder detergent composition |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3798179A (en) * | 1971-06-29 | 1974-03-19 | Procter & Gamble | Granular free-flowing detergent bath composition |
| DE2653259A1 (en) * | 1975-11-28 | 1977-06-02 | Procter & Gamble | SOFTENING AND DETERGENT MIXTURES |
| DE3016170A1 (en) * | 1980-04-26 | 1981-10-29 | Bayer Ag, 5090 Leverkusen | MICROCAPSULES WITH A DEFINED OPENING TEMPERATURE, METHOD FOR THE PRODUCTION AND USE THEREOF |
| DE3621458A1 (en) * | 1985-06-27 | 1987-01-08 | Lion Corp | SOLID SOAP |
-
1989
- 1989-11-30 CA CA002004270A patent/CA2004270A1/en not_active Abandoned
- 1989-12-20 EP EP19890203260 patent/EP0376385A3/en not_active Withdrawn
- 1989-12-27 JP JP1339924A patent/JPH02258900A/en active Pending
- 1989-12-28 KR KR1019890019830A patent/KR900009951A/en not_active Application Discontinuation
- 1989-12-28 BR BR898906831A patent/BR8906831A/en not_active Application Discontinuation
- 1989-12-28 AU AU47323/89A patent/AU4732389A/en not_active Abandoned
- 1989-12-29 CN CN89109840A patent/CN1044295A/en active Pending
- 1989-12-29 DK DK672689A patent/DK672689A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| DK672689D0 (en) | 1989-12-29 |
| EP0376385A2 (en) | 1990-07-04 |
| EP0376385A3 (en) | 1990-10-10 |
| BR8906831A (en) | 1990-09-18 |
| CN1044295A (en) | 1990-08-01 |
| AU4732389A (en) | 1990-07-05 |
| DK672689A (en) | 1990-06-30 |
| JPH02258900A (en) | 1990-10-19 |
| KR900009951A (en) | 1990-07-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2004270A1 (en) | Perfume microcapsules for use in granular detergent compositions | |
| US4234627A (en) | Fabric conditioning compositions | |
| US4145184A (en) | Detergent composition containing encapsulated perfume | |
| US6531444B1 (en) | Controlled delivery system for fabric care products | |
| US4973422A (en) | Perfume particles for use in cleaning and conditioning compositions | |
| EP0397245B1 (en) | Perfume particles for use in cleaning and conditioning compositions | |
| US5154842A (en) | Coated perfume particles | |
| US5066419A (en) | Coated perfume particles | |
| US20050176599A1 (en) | Controlled delivery system for household products | |
| US20030045446A1 (en) | Delivery system having encapsulated porous carrier loaded with additives | |
| US20080234172A1 (en) | Substrate Care Product | |
| JPH03180575A (en) | Superlarge particle softener composition for use for cloth | |
| WO1992018601A1 (en) | Improvements in coated perfume particles | |
| US4828746A (en) | Detergent compatible, dryer released fabric softening/antistatic agents in a sealed pouch | |
| US4615814A (en) | Porous substrate with absorbed antistat or softener, used with detergent | |
| CA2146686C (en) | Granular detergent composition | |
| GB1561389A (en) | Fabric treatmetn compositions and method | |
| GB2212179A (en) | Detergent compatible, dryer released fabric softening/antistatic agents | |
| CA1284560C (en) | Detergent compatible, dryer released fabric softening/antistatic agents | |
| NZ228459A (en) | Particulate fabric softening composition wherein the particles have a smooth surface | |
| EP0334430A2 (en) | Quench cooled particulate fabric softening composition | |
| MXPA00012501A (en) | Perfume compositions |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Dead |