CA1284560C - Detergent compatible, dryer released fabric softening/antistatic agents - Google Patents

Abstract

DETERGENT COMPATIBLE, DRYER RELEASED FABRIC
SOFTENING/ANTISTATIC AGENTS
ABSTRACT

Fabric softener particles comprising an inner core of fabric softening composition and an outer coating completely surrounding said core. The outer coating is substantially water-insoluble and protects the inner core from dissolving when present in a typical fabric laundering operation, but releases the softener composition to the fabrics when the fabrics are dried in a heated dryer.

Description

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DETERGENT COMPATIBLE, DRYER RELEASED FABRIC
SOFTENING/ANTISTATIC AGENTS

Allen D. Clauss Gayle E. Culver David M. Piatt Thomas ~. Wierenga FIELD OF THE INVENTION
The invention pertains to coated particles of fabric softener which are included with detergent in the washing of fabrics. The particles survive the wash and release softener to the fabrics in a heated laundry dryer.
BACKGROUND OF THE INVENTION
The advantages obtained from the application of fabric conditioning agents (i.e., fabric softeners andlor antistatic agents) to laundered fabrics is well-known. The present inven-tion pertains to coated particulate softener/antistatic compositions which survive the wash process and release the active softeningl-antistatic agent to the laundered fabrics in the dryer.
Fabric softening and antistatic benefits are a desirable part of the laundry process. Softening and antistatic compounds are, in general, quaternary ammonium compounds that are not compatible with anionic surfactants. These compounds will be referred to hereinafter as fabric softening compounds or fabric softeners, although it is to be understood that they del iver both softening and antistatic benefits to fabrics. The opposite electrical charge of the anionic surfactant used in most detergents and the quaternary ammonium fabric softening compounds leads to a mutual attraction which causes precipitation. This, in effect, removes surfactant and fabric softener from solution and reduces 5~0 the cleaning capacity of the detergent while preventing effective fabric softener deposition on the fabric.
One solution to this incompatibility problem is the separate addition of the fabric softener during either the rinse cycle of the wash or while the fabrics are in the dryer. This increases the inconvenience of using fabric softeners because of the need to add them at a point in the laundering process which is different from that at which the detergent is added.
Various other solutions for this problem of incompatibility between detergent and softening compounds have been proposed in the art. U.S. Pat. No. 3,936,537, Baskerville Jr., issued Feb. 3, 1976, and U.S. Pat. No. 4,095,946, Jones, issued June 20, 1978, teach the use of intimate mixtures of organic dispersion inhibitors ~e.g., stearyl alcohol and fatty sorbitan esters) with solid fabric softener to improve the survival of the softener in the presence of detergent in the washer so the soft-ener can act on the fabrics when it melts in the dryer . U . S .
Pat. No. 4,234,627, Schilling, issued Nov. 18, 1980, teaches microencapsulation of fabric softener. The microcapsules survive the wash and adhere to the fabric surface. They are then ruptured by subsequent tumbling of the fabric in the dryer, thereby releasing softener to the fabrics. In spite of these developments, there is a continuing need for methods and com-positions which are suitable for conveniently and effectively delivering fabric softeners to fabrics during the home laundering process .
Accordingly, it is the object of the present invention to provi~e coated fabric softener compositions wherein the coating will be insoluble in a detergent solu~ion but ~-ill release the softener to the fabrics at dryer temperatures.

SUMMARY OF Tl~iE INVENTION
The present invention is directed to detergent-compatible, dryer-activated fabric softening particles having diameters of from about 5 microns to about 1,200 microns comprising an inner core of a fabric softener composition comprising a cationic fabric ~ - 3 -softener compound, and an outer coating comprised o~ water-insoluble material having a melting point above about 35C.
The particles can beincorporated intolaundry detergents.
In particular, the invention relates to a through-che-wash detergent and fabric softening composition comprising: ~A) from about 1% to about 50% of detersive surfactant; (B) from about 15% to about 60% of deter-gency builder; (C) from about 0.5% to about 10% of detergent-compatible, dryer activated fabric softener composition in particulate form, the said particles comprising: (a) an inner core of fabric softener compo-sition consisting essentially of at least about 10% of a cationic fabric softener, the said softener composi-tion having a melting point of from about 50 D C to about 80~C and the remainder of said inner core being materials which can be applied to fabrics along with said cationic fabric softener in a laundry dryer; ~b) a coating surrounding said core, said coating being a substantially water-insoluble material having a melting point above about 35~C, and a penetration value of about 0.6 mm or less as measured by ASTM Test D-1321, modified by using a 100 gram weight, said water-insoluble material being selected from the group consisting of:
cellulose ethers, cellulose esters, and mixtures thereof; the said coating comprising from about 3% to about 30% of said particle, the said inner core com-prising from about 97% to about 70% of said particle, and the said particles having a size of from about 5 to about 1,000 microns.

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- 3a -DE-TAILED DESCRIPTION OF THE INVENTION
The present invention relates to coated fabric softener particles which can be added to the wash step of the fabric laundering process and which release softener to fabrics in a laundry dryer. The invention also relates to laundry detergent compositions containing said particles.

A. The Particles The particles of the present invention comprise an inner core of a fabric softener composition which comprises a cationic fabric softener, and an outer coating which completely surrounds the core and comprises a substantially water-insoluble material having a melting point above 35C, preferably above 50C. By "sub-stantially water-insoluble" herein is meant having a solubility in 35C water of less than about 50 ppm. The particles have diameters of from about 5 microns to about 1,200 microns, pref-erably greater than about 500 microns, and most preferably ~reater than about 600 microns, with a number average of from about 900 to about 1,000 microns. The particles typically will be of a generally spherical shape, but can also have an irregular shape. The particle sizes quoted herein refer to the largest dimension (diameter or length) of the particle.
Typical cationic fabric softeners useful herein are quaternary ammonium salts of the formula [ Rl R2R3R4N ]

wherein one or two of R1, R2, R3 and R4 groups is an organic radical containing a group selected from a C12-C22 aliphatic radical or an alkyiphenyl or alkylbenzyl radical having from 10 to 16 carbon atoms in the alkyl chain, the remaining groups being selected from C1-C4 alkyl, C2-C4 hydroxyalkyl and cyclic ~,,. c ~i ;,;

structures in which the nitrogen atom in the above formula forms part of the ring, and Y constitutes an anionic radical such as halide, nitrate, bisulfate, methylsulfate, ethylsulfate and phos-phate, to balance the cationic charge.
I n the context of the above definition, the hydrophobic moiety ~i.e., the C12-C22 aliphatic, C10 C16 a y p alkylbenzyl radical) in the organic radical Rl or R2 may be directly attached to the quaternary nitrogen atom or may be indirectly attached thereto through an amide, ester, alkoxy, 10 ether, or like grouping.
The quaternary ammonium compounds useful herein include both water-soluble compounds and substantially water-insoluble compounds which are dispersible in water. For example, imidazolinium compounds of the structure C ~ ¦ _ + CH3504-wherein R is a C1 6 to C22 alkyl group, possess appreciable water solubility, but can be utilized in the present invention.
The quaternary ammonium softener compounds used in this invention can be prepared in various ways well-known in the art 30 and many such materials are commercially available. The quat-ernaries are often made from alkyl halide mixtures corresponding to the mixed alkyl chain lengths in fatty acids. For example, the ditallowalkyl quaternaries are made from alkyl halides having mixed C1 4-C1 8 chain lengths . Such mixed di-long chain quater-3~ naries are useful herein and are preferred from a cost stand-point .

The anionic group which can be the counter-ion in the quaternary compounds useful herein is typically a halide (e.g., chloride or bromide), nitrate, bisulfate, ethylsulfate, or methyl-sulfate. The methylsulfate and chloride ions are the preferred 5 counter-ions from an availability standpoint; while the methylsul-fate anion is most preferred because of its minimization of cor-rosive effects on the automatic clothes dryers in which it is used.
The following are representative examples of quaternary ammonium softening compounds suitable for use in the present 10 invention. ~ll the quaternary ammonium compounds listed can be included in the present invention, but the compilation of suitable quaternary compounds hereinafter is only by way of example and is not intended to be limiting of such compounds. Dioctadecyldi-methylammonium methylsulfate is an especially preferred fabric 15 softening compound for use herein, by virtue of its high anti-static, as well as fabric softening activity; ditallowalkyldi-methylammonium methylsulfate is equally preferred because of its ready availability and its good antistatic activity; other useful di-long chain quzternary compounds are dicetyldimethylammonium 20 chloride, didocosyldimethylammonium chloride, didodecyidimethyl-ammonium chloride, ditallowalkyldimethylarnmonium bromide, diole-oyldimethylammonium methylsulfate, ditallowalkyldiethylammonium chloride, ditallowalkyldipropylammonium bromide, ditallowalkyl-dibutylammonium fluoride, cetyldecylmethylethylammonium chloride, 25 bis-[ditallowalkyldimethylammonium] bisulfate, tris-[ditallowalkyl-d i methy lammon i um ] phos phate, 1 -methy l -1 -ta I lowam i doethy I - 2 -ta I low-imidazolinium methylsulfate, and the like. Particularly preferred quaternary ammonium fabric softening compounds are ditallowal-kyldimethylammonium chloride and ditallowalkyldimethylammonium 30 methylsulfate. The fabric softener core of the particles of the invention comprises from about 70% to about 97% and most prefer-ably about 859~ to about 9796 of the particle. All percentages herein are "by weight" unless otherwise indicated.
The core composition can consist entirely of cationic fabric 35 softeners, and will generally comprise at least 10%, usually 10% to 50% cationic fabric softener. Optionally, and preferably, the core V

can contain additional materials such as perfume, auxiliary fabric softening agents ~e.g., smectite clay, fatty alcohols and fatty amine, such as ditallowmethyl amine or 1-tallowamidoethyl-2-tallow-imidazoline), soil release agents, fabric brighteners, etc. Addi-5 tional disclosure of materials which can be applied to fabrics alongwith cationic fabric softening agents in a laundry dryer and, therefore, can be part of the core composition of the particles herein, are disclosed in U.S. Pat. Nos. 4,073,996, Bedenk et al., issued Feb. 14, 1978; 4,237,155, Kardouche, issued Dec. 2, t980 and 4,421,792, Rudy et al., issued December 20, 1983.
Preferred additional materials are the encapsulated fab-ric conditioning perfume microcapsules of U.S. Pat.
No. 4,234,627, Schilling, issued Nov. 18, 1980, and British Pat. No. 1,549,432. A particularly preferred process for 15 preparing such capsules is disclosed in U.S. Pat. No.
3,697,437, Fogle et al., issued Oct. 10, 1972. Particle sizes of from about 100 to about 200 microns are preferred.
The coating materials are substantially water-insoluble 20 materials, typically (but not necessarily) selected from waxy materials such as paraffinic waxes, microcrystalline waxes, animal waxes, vegetable waxes, saturated fatty acids and fatty alcohols having from 12 to 40 carbon atoms in their alkyl chain, and fatty esters such as fatty acid triglycerides, fatty acid esters of 25 sorbitan and fatty acid esters of fatty alcohols, or from sub-stantially water-insoluble polymers. Typical specific suitable waxy coating materials include lauric, myristic, palmitic, stearic, arachidic and behenic acids, stearyl and behenyl alcohol, micro-crystalline wax, beeswax, spermaceti wax, candelilla wax, sor-30 bitan tristearate, sorbitan tetralaurate, tripalrnitin, trimyristinand octacosane. A preferred waxy material is stearyl alcohol.
Examples of water~insoluble polymeric materials which may be used for the coating of the particles herein are cellulose ethers such as ethyl, propyl or butyl cellulose; cellulose esters such as 35 cellulose acetate, propionate, butyrate or acetate-butyrate; urea-formaldehyde resins, polyvinyl chloride, polyvinylidene chloride, ~t polyethylene, polypropyiene, polyacrylates, polymethacrylates, polymethyl-methacrylates and nylon. Such materials and their equivalents are described in greater detail in any conventional handbook of synthetic organic plastics, for example, in Modern Plastics Enc clopaedia Volume Vol. 62 No. 10A (for 1985-1986) Y _ , , at pages 768-787, published by McGraw-Hill, New York, N.Y.
(October 1g85). A preferred polymeric material is ethyl cellulose. The polymeric coating materials can be plasticized with known plasticizing agents such 10 as phthalate, adipate and sebacate esters, polyols (e.g., ethylene glycol), tricresyl phosphate, castor oil and camphor.
The coating surrounds the cationic fabric softener core and is present in an amount of from about 3% to about 3096, preferably from about 3% to about 15% by weight of the particle.
The coating material can comprise a mixture of waxy coating materials and polymeric coating materials. In such mixtures the waxy coating material will typically comprise from about 70% to about 90% of the mixture and the polymeric material about 30% to about 10%.
Typically, the coating material will have a hardness which corresponds to a needle penetration value of about 0.6 mm or less, and preferably less than about 0.1 mm, as measured by ASTM Test D-1321, modified by using a 100g weight instead of a 50g weight. The test is performed at 25-27C. In the case of 25 polymeric coating materials, sample preparation is accomplished by dissolving the polymer in a volatile solvent and then evaporating the solvent after the polymer solution has been placed in the test container. For waxy coating materials, sample preparation is done by melting the sample and then solidifying it in the test 30 container in the manner set forth in the ASTM method.
Penetration values of a number of suitable coating materials are shown in the following table.

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Penetration Values of Representative Coating Materials Penetration Material in mm Stearyl alcohol 0. 57 Ethyl cellulose 0.09 Cellulose acetate 0.00 Ethyl cellulose + 10% dibutyl sebacate 0 . 00 70% Stearyl alcohol + 30% C30 alcohol 0. 32 10 90% Stearyl alcohol + 10% Elvax-431 ol 0.12 90~6 Stearyl alcohoi + 10% BE-Square-1952 0. 40 Trade mark for terpolymer of ethylene, vinyl acetate and acid from DuPont 2Trade mark for microcrystalline wax from Petrolite, Specialty Polymers Group The function of the coating which surrounds the fabric softener is to prevent the softener from becoming dissolved 20 and/or dispersed in the wash water when the particles are pres-ent during the wash step of a laundry process, and thereby prevent interaction between the fabric softener and the deter-gent. During the washing and rinsing of the fabrics, a substan-tial amount of the particles adhere to, or become entrapped within 25 folds of the fabrics. When the fabrics are dried in a heated automatic clothes dryer ~typically at temperatures of about 65 to 85C), the coating and the fabric softener core composition melt, thereby permitting the softener to spread throughout the fabric load and soften the fabrics.
I f the particles are incorporated into a granular detergent composition, it is preferred that the particle size of the softener particles be similar to the particle size of the detergent granule in order to minimize segregation. This will typically be in the range of from about 500 to about 1000 microns. Softener particles 35 which are smaller in size than the detergent granules can be .J

agglomerated to form larger particles to match the particle size of the detergent granules into which they will be incorporated. The agglomeration can be accomplished by using water-soluble or dispersible materials such as polyvinyl alcohol, sodium carboxy-S methyl cellulose, gelatin and polyoxyethylene waxes. The agglom-erates disintegrate when the detergent composition is added to water. Methods and agglomerating agents for agglomeration of fabric softener particles are described in U.S. Pat. No.
4,141,841, McDanald, issued Feb. 27, 1979.

B. Preparation of Particles In preparing the softener particles of the invention, the solid fabric softener composition which is to be the core of the 15 particles is formed into particles having a size of from about 4.5 to about 1100 microns. This can be accomplished, for example, by milling the solid softener composition or by melting the com-position and spraying it through appropriate sized nozzles into an atmosphere having a temperature below the melting point of the 20 softene;, thereby forming the softener composition into solid particles .
The particles of softener composition can then be coated with coating material which is either melted or dissolved in a volatile solvent. The coating is done at a temperature which is below the 25 melting point of the softener composition, and the coated particles are then cooled (or the solvent is evaporated) to solidify the coating, The coating is typically applied in a fluidized bed type apparatus. A suitable type of apparatus is that described in U.S. Pat. No. 3,196,827, Wurster et al., issued July 27, 1965.
30 In this apparatus, solid soft-ener core particles are suspended on an air stream which carries them in a smooth cycl ic flow past the coating nozzle, which sprays them with fluid coating material. Air atomizes and expels the coating fluid through the coating nozzle. The atomized 35 coating fluid covers the surfaces of the core particles. The coated particles are lifted on the air stream and the fluid coating solldifies on the surface of the particles as the air stream lifts them away from the nozzle. The particles then settle out of the air stream and begin another cycle which takes them past the 5 nozzle again. The process is repeated until the desired amount of coating has been deposited on the particles. The amount of coating applied to the softener core particles is typically from about 3% to about 30%, preferably about 3% to about t 5% by weight of total particle (i.e., core plus coating), Alternatively, other types of encapsulating processes such as described in an article by Nack entitled "Microencapsulation Techniques, Applications and Problems," J. Soc. Cos. Chem., Vol. 21, Pages 85-98 (Feb. 4, 1970) can be used. When perfume microencapsules are incorporated, the processes disclosed in U.S. Pat. No. 4,234,627, suPra, can be used.
If it is desired to aggomerate the softener particles, this can be accomplished in the following manner. The softener particles are fed to a highly efficient mixer (e.g., Schugi Flexomix'~ Model 160,335 or 400 from Schugi Process Engineers USA, 41-T
Tamarack Circle, Skillman, New Jersy 08558), or a pan agglom-erator. Aqueous solution or dispersion of agglomerating agent is sprayed onto the moving particles causing them to stick to each other. The water is evaporated and the dried agglomerated particles are sized by sieving. Suitable agglomerating agents include dextrin starches, Pluronic3Polyols (copolymers of ethylene oxide and/or propylene oxide with either ethylene glycol or propylene glycol) and hydratable salts such as sodium tripoly-phosphate or sodium sulfate.
The type of apparatus described in U . S . Pat. No. 3 ,196, 827 (Wurster et al. ), cited supra, can also be used for agglomerating particles .

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C. Detergent Compositions The particles of the present invention are preferably formu-lated into detergent compositions. Such composi~ions typically comprise detersive surfactants and detergency builders and, 5 optionally, additional ingredients such as bleaches, enzymes, fabric brighteners and the like. The particles are present in the detergent composition at a leve! sufficient to provide from about 0. 5% to about 10~, and preferably from about 1% to about 5% of quaternary ammonium fabric softener in the detergent composition.
10 The remainder of the detergent composition will comprise from about 1~ to about 50~, preferably from about 10% to about 25%
detersive surfactant, and from about 15% to about 60~, preferably from about 20% to about 45% of a detergency builder, and, if desired, other optional laundry detergent components.
1. The Surfactant Surfactants useful in the detergent compositions herein include well-known synthetic anionic, nonionic, amphoteric and zwitterionic surfactants. Typical of these are the alkyl benzene sulfonates, alkyl- and alkylether sulfates, paraffin sulfonates, 20 olefin sulfonates, alkoxylated ~especially ethoxylated) aicohols and alkyl phenols, amine oxides, alpha-sulfonates of fatty acids and of fatty acid esters, alkyl betaines, and the like, which are well known from the detergency art~ In general, such detersive surfactants contain an alkyl group in the Cg-Cl8 range. The 25 anionic detersive surfactants can be used in the form of their sodium, potassium or triethanolammonium salts; the nonionics generally contain from about 5 to about 17 ethylene oxide groups.
C -C16 alkyl benzene sulfonates, C12-C18 paraffin-sulfonates and alkyl sulfates are especially preferred in the compositions of the present type.
A detailed listing of suitable surfactants for the detergent compositions herein can be found in U.S. Pat. No. 3,936,537, Baskerville, issued Feb. 3, 1976.
Commercial sources of such surfactants can be found in McCutcheon's EMULSIFIERS AND DETERGENTS, Ncrth American Edition, 198L~, lAcCutcheon Division, MC Publishing Company, 2. Detergency Bullders Useful detergency builders for the detergent compositions 5 herein include any of the conventional inorganic and organic water-soluble builder salts, as well as various water-insoluble and so-called "seeded" builders.
Nonlimiting exampies of suitable water-soluble, inorganic alkaline detergent builder salts include the alkali metal carbo-10 nates, borates, phosphates, polyphosphates, tripolyphosphates,bicarbonates, silicates, and sulfates. Specific examples of such salts include the sodium and potassium tetraborates, bicarbonates, carbonates, tripolyphosphates, pyrophosphates, and hexameta-phosphates .
Examples of suitable organic alkaline detergency builder salts are: (1 ) water-soluble amino polyacetates, e.g., sodium and potassium ethylenediaminetetraacetates, nitrilotriacetates, and N-(2-hydroxyethyl)nitrilodiacetates; (2) water-soluble salts of phytic acid, e.g., sodium and potassium phytates; (3) water-20 soluble polyphosphonates, including sodium, potassium and lithium salts of ethene-1-hydroxy-1,1-diphosphonic acid, sodium, potas-sium, and lithium salts of methylenediphosphonic acid and the like .
Seeded builders include such materials as sodium carbonate 25 or sodiunn silicate, seeded with calcium carbonate or barium sul fate .
A detailed listing of suitable detergency builders can be found in U . S . Pat. No. 3, 936, 537, supra .

3. Optional Detergent Ingredients Optional detergent composition components include enzymes (e.g., proteases and amylases), haiogen bleaches (e.g., sodium and potassium dichloroisocyanurates), peroxyacid bleaches (e.g., diperoxydodecane-1,12-dioic acid), inorganic percompound bleach-35 es (e.g., sodium perborate), activators for perborate (e.g., ~,:

tetraacetylethylenediamine and sodium nonanoyloxybenzene sulfo-nate), soil release agents (e.g., methylcellulose) soil suspending agents (e.g., sodium carboxymethylcellulose) and fabric bright-eners .

C. Pouched Compositions When fabric softener particles of the invention are added to the wash step of a laundering process, it is inevitable that some of the particles will not adhere to or become trapped in the folds 10 of the fabrics and will, therefore, be lost in the discarded wash solution or rinse water. In order to avoid such loss, the par-ticles can be added to the wash solution in a sealed, porous water-insoluble pouch such as the type described in U . S . Pat.
No. 4,223,029, Mahler et al., issued Sept. 16, 1980.
15 Detergent granules can be included in the pouch with the softener particles. When the pouch is placed in water in the wash step of the laundering process, the detergent dissolves, but the softener particles remain in the pouch. The pouch remains with the fabrics through the wash and rinse.
20 When the pouch is tumbled with the fabrics in the dryer, the softener particles release the softener, which melts onto the pouch material and is transferred from the pouch material to the fabrics as the pouch comes into contact with the fabrics during the drying cycle. Preferred pouch structures are multi-pouch 25 porous sheet structures such as described in U . S .
Pat. Nos. 4,638,907, BedenklHarden, issued Jan. 27, 1987; and U.S. Pat. No. 4,259,383, Eggensperger et al., issued Mar. 31, 1981 . In a single pouch structure, the particles tend to collect in a relatively small area 30 of the structure, whereas in a multi-pouch sheet structure the softener particles are distributed over a larger area of the structure thereby facilitating more even transfer of softener to fabrics in the dryer.
Suitable pouch materials include, paper, nonwoven synthetics 35 such as spunbonded and wet laid polyester, and porous formed fi Im plastic sheet material .

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In a further improvement of the multi-pouch type of struc-ture, the individual pouches have a water-insoluble baffling means which provides some standoff between the interior major surfaces of the pouches while the multi-pouch sheet is being tumbled in the clothes dryer. The standoff prevents the interior major surfaces of each pouch from coming into intimate contact with each other during the drying cycle, thereby reducing the ten-dency of the molten softener to be squeezed out of the pouch during the drying cycle, which can cause fabric staining. It is preferred that the molten softener be permitted to gradually wick through the substrate and thereby gradually transfer to the tumbling fabrics. The baffling can be produced, for example, by printing a cross hatched glue pattern on one of the interior surfaces of the pouch material or by including a layer of poly-meric net material between the interior major surfaces of the pouches .
~he invention will be illustrated by the following examples.

EXAMPLE I
Fabric softener core particles are prepared according to the fol lowing formula:

Ingredient Wt. %
Ditallowdimethylammonium methylsulfate (DTDMAMS) 42.4 Sorbitan monostearate21 . 3 Cetyl alcohol 21. 3 Bentonite clay 12.0 Perfume 3 . 0 Total l O0 . 0 The DTl)MAMS is heated in a reaction vessel at 71C under vacuum (Ca. 710 mm Hg) for 4 hours to remove residual moisture and/or isopropanol. The cetyl alcohol and sorbitan monostearate 35 are then added, and the molten "triblend" is mixed for one hour at about 71 C .

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The triblend is transferred into a PVM 40 Ross~ mixer (Charles Ross ~ Sons Company, Hauppauge, New York 11788) .
The temperature of the triblend is then raised to 79C - 85C
under vacuum (about 330-430 mm Hg). When the temperature has stabilized in this range, the Ros~s' anchor and disperser are turned on and the clay is added. The mixture is blended for 5 minutes and then sheared with the Ross' colloid mixer for 20 minutes. The perfume is then added and the mixture is blended ~or 5 minutes with the anchor, disperser and colloid mill still on.
The softener composition is then poured into trays and cooled overnight at about 4C.
The solid softener core composition is then converted to particles by milling in a Fitzmill, Model DA506 ~The Fitzpatrick Company, Elmhurst, Illinois 60126) at 4740 rpm's through a 4 mesh screen . The particles are then sized through 12 on 30 (U.S. Standard screens, 1.7 - 0.6 mm particle size).
The particles are then coated with a hot melt of fatty alcohol-based coating. The coating is a mixture of 90% stearyl alcohol and 10% Elvax-4310 ~ a terpolymer of ethylene, vinyl acetate and acid from E. l . du Pont de Nemours ~ Co., Polymer Products Dept., 1007 Market St., Wilmington, i?elaware 19898.
The coating is applied in an 18 Inch Wurster~'coater (Coating Place, Inc., P.O. Box 248, Verona, Wisconsin 53593). A de-tailed description of this type of equipment can be found in U . S.
Pat . No . 3,196,827, supra .
i3riefly, the Wurste~9 Coater consists of an apparatus that is capable of suspending the softener core particles on a rapidly moving warm air stream. Encapsulation is accomplished by pass-ing the softener particles through a zone of finely atomized droplets of coating. As the particles move up and away from the coa~ing nozzle, the coating begins to solidify as the particles cool. When the particles can no longer be fluidized by the air stream, they move down in the opposite direction of the fiuidizing air. The coated particles then reenter the coating zone and are recycled until the desired amount of coating is applied. The ~,~ .r ~

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coating cycle takes p~ace within a single chamber which preferably has a partition to separate the particles moving up through the coating zone from those moving down through the cooling zone.
The following conditions are used to apply a hot melt coating:

Stearyl Alcohol / Elvax Temperature 79C
Fluidizing Air 15.8 Cu.M/min. at 40.5C
Atomizing Air Volume 0.25 Cu.M/min.
Atomizing Air Rate 4218 g/s~.cm.
Inlet Air Temperature 20~C - 38C
Outlet Air Temperature 20CC - 38C
Pump Rate 0.2 Kg / min .
Nozzle Size CPI-18-A74*
Partition Size 216 mm x 267 mm Partition Gap l 9 mm Run Time 22 min.

20*Available from Coating Place, Inc.

The amoun~ of fatty alcohol coating applied to the so~tener particles is about 15% by weight of the total coated particle.
After the c02ting process is complete the particles are resized 25through 12 on 20 mesh and are then ready for use "as is" or for blending into detergent granules.

EXAMPLE l l Softener core particles prepared as in Example I are coated 30with ethyl cellulose based coating instead of fatty alcohol. The coating is applied by spraying a 10% solids solution in methanol of 9 parts ethyl cellulose and 1 part dibutyl sebacate. The coating is applied in an 18 Inch Wurster coater as described in Exam-ple 1. The ethyl cellulose used is Ethoce9~ Std. 4, (Dow Chemical 35Co., Midland, Michigan 48640) which has an Ubbelhhode viscosity ,~ .
. .

of 3.0 - 5.5, measured at 25C as a 5% solution in 80% toluene/20%
ethanol .
The following conditions are used to apply a solvent based coating:

Fluidizing Air 15.8 Cu.Mlmin. at 40.5C
Atomizing Air Volume 0.37 Cu.Mlmin.
Atomizing Air Rate 5624 g/sq.cm.
Inlet Air Temperature 38C - 43C
Outlet Air Temperature 30C - 32C
Pump Rate 0.2 Kg/min.
Nozzle Size CPI-18-A74*
Partition Size 216 mm x 267 mm Partition Gap 19 mm Run Time 120 min.

*Available from Coating Place, Inc.

The amount of ethyl celluloseldibutyl sebacate solids coated 20 onto the particles is about 5% by weight of the total coated particle weight. When the coatlng is completed, the softener particles are resized through 12 on 30 ~lesh U . S. Standard screens and are then ready for use "as is" or for blending into detergent granules.
EXAMPLE l l l A fabric softener core particle containing perfume capsules is prepared according to the following formula:
I ng redient Wt . %
Perfume 89.20 Gelatin 275 E~loom 8.80 Glutaraldehyde 1.12 Polyphosphate 0.88 Total100.00 The perfume capsules are prepared using a complex coacer-vation process as described in U.S. Pat. 3,697,437, supra.
Briefly, the process is as follows.
To a vessel equipped for stirring and heating, the following components are each prehea~ed to 52~C and combined: 1000 mls of deionized water, 1000 mls of a 10% by weight solution of gelatin in deionized water (Kind ~ Knox Type A gelatin, 275 Bloom) and 1000 mls of a water-insoluble perfume. The solution is then emulsified via agitation at 52C. The agitation speed is adjusted 10 such that the mean particle size of the droplets is between 100 and 200 microns.
When the system is stabilized, 200 mls of a 5% by weight polyphosphate (Calgon'~Conditioner 206, a polyphosphate having a minimum of 67% by weight P2O5 and an empirical formula of 15 Na16P24O43) preheated to 52C is added. At this point in the process the pH of the emulsion should be between S . 4 and S . 6.
The pH is then lowered to 4 . 3 using glacial acetic acid to initiate the coacervation reaction.
The solution is then cooled to ambient over a 2-3 hour 20 period with constant stirring. The solution is then cooled further to 5-1 0C before adding 50 mls of 25% glutaraldehyde solution to chemically harden the capsule wall. The glutaraldehyde is allowed to react for at least 4 hrs. while the solution temperature is slowly raised to ambient.
When the solution temperature returns to ambient, the reaction should be complete. Before filtering the solution to isolate the perfume capsules, 20 gms of Syloid~ (Syloid Silicas, ID/Aerogel ~'Grade 244, W. R. Grace) is added as a filtration aid.
The filter cake of capsules is then washed with deionized water.
30 The filter cake is then broken up and allowed to air dry, e.g., in trays, in a fluid bed, an air cGnveyor with heating.
Additional Syloid (20 gms) can be added to act as a drying and / or handl ing agent .

-~. '1 .

The fabric softener core particles are prepared according to the fol lowing formula:
I ngredient Wt . %
Dital lowdimethylammonium methylsulfate (DTDMAMS) 42.4 Sorbitan monostearate 21.3 Cetyl aicohol 21.3 Bentonite clay 12.0 Perfume 3.0 Total 100.0 The DTDMAMS is heated in a reaction vessel at 71C under vacuum (Ca. 710 mm Hg) for 4 hours to remove residual moisture and/or isopropanol. The cetyl alcohol and sorbitan monostearate 15 are then added, and the molten "triblend" is mixed for one hour at about 71C.
The triblend is transferred into a PVM 40 Ross mixer (Charles Ross ~ Sons Company, Hauppauge, New York 11788).
The temperature of the triblend is then raised to 79C - 85C
20 under vacuum (about 330-430 mm Hg). When the temperature has stabilized in this range, the Ross' anchor and disperser are turned on and the clay is added. The mixture is blended for 5 minutes and then sheared with the~Ross' colloid mixer for 20 minutes. The perfume capsules are then added and the mixture 25 is blended for 10 minutes with only the anchor on at its lowest speed. The softener composition is then poured into trays and cooled overnight at about 4C.
The solid softener core composition is then converted to particles by milling in a Fitzmil~ Model DA506 (The Fitzpatrick 30 Company, Elmhurst, Illinois 60126) a~ 4740 rpm's through a 4 mesh screen. The particles are then sized through 12 on 30 (U.S. Standard screens, 1.7 - 0.6 mm particle size).
The softener particles are then coated wi~h a 5% level of a blend of 90g~ Ethoce~910 and 10~6 Ethoce~ 45 (Dow Chemical Co., 35 Midland, Michigan 48640) . The Ethocel 10 has a Ubbelhhode ~b~

viscosity between 9-11 and the Ethocel 45 has a viscosity of 41-49, as measured as a 5~ solution in 80% toluene and 20%
ethanol .

EXAMPLE IV
A granular detergent/softener composition is prepared by mixing 4 parts of the coated softener particles of Example 1, l l or lll with 96 parts of the following granular detergent composition.

Ingredient Wt.%
Sodium C13 linear alkylbenzene sulfonate 16.5 Sodium Cl 4-C1 5 linear fatty alcohol sul fate 16 . 5 Sodium sulfate 23. 8 Sodium silicate 9.2 Polyethylene glycol 0, 9 Polyacryllc acid 1.3 Sodium tripolyphosphate13.7 Sodium carbonate 4. 8 Methyl cellulose 3.6 Optical brightener 1 . 3 Protease enzyme 1.6 Moisture and miscellaneous6.8 Total100 . 0 EXAMPLE V
A granuiar bleach/softener composition is prepared by mixing 30 4 parts of the coated softener particles of Example 1, ll or lll with 96 parts of the following granular bleach composition.

Ingredient Wt.%
Diperoxydodecanedioic acid 24. 0 Dodecanedioic acid 2 . 9 5Odium C1 3 linear alkylbenzene sulfonate 5 . 5 ~oric acid 27.7 Sod ium sul fate 39 . 7 Miscel laneous 0 . 2 Total100.0 EXAMPLE Vl .
A laundering article in the form of a multipouch sheet is prepared as follows.
The sheet is comprised of two sheets of P~eemay(~) 2420 spun-15 bonded polyester (DuPont, Wilminyton, Delaware). In between the sheets is a honeycomb web made from polyethylene. The web has a thickness of approximately 0. 04 inch ( 0.10 cm) and the cells of the web are diamond shaped, having a cross dimension of approximately 0.19 inch (0.48 cm) and a length dimension of 20 approximately 0.63 inch (1.60 cm). The three-layered structure has outer edge d~mensions of approximately 4 . 5 inches x 11 inches (11.4 cms x 27.9 cms). The structure is laminated together in a pattern so as to form six equal sized pouches, two pouches at each end containing about 14.7 grams each of the bleach/ethyl 25 cellulose coated softener composition of Example V and the four pouches in between containing about 15 . 5 grams each of the detergent/ethyl cellulose coated softener composition of Example lV.
The article is suitable for washing and softening laundry in 30 a process involving washing and rinsing the fabrics, followed by tumble drying in a heated clothes dryer, wherein the article remains with the laundry throuqhout the entire process.

s~

EXAMPLE Vl I
This example is the same as Example Vl, except that ( 1 ) the softener and detergent levels are, respectively, 2. 2 parts and 97.8 parts, (2) the softener and bleach levels are, respectively, S 2.6 parts and 97.4 parts and ~3) the multipouched sheet is comprised of a top sheet of a latex bonded, wet laid polyester/-wood pulp substrate (James River 5227, James River Corp., ~ireenville, South Carolina) and an embossed sheet of Reemay(~3) 2420, a spunbonded polyester (Dupont, Wilmington, Delaware).
10 The two sheets are laminated together with an outer edge dimen-sion of approximaely 4.5 inches x lt inches (11.4 x 27.9 cms) and with a pattern so as to form six equal sized pouches. The two pouches at each end are filled with about 14.7 grams of the bleach/ethyl cellulose coated softener composition of Example V
15 and the four pouches in between are filled with about 15. 5 grams of the detergent/ethylcellulose coated softener composition of Example IV.
When a dusty detergent powder is used in a pouched sheet, as set forth above, the porous substrates may not be ab le to 20 contain the dust adequately. One solution to this problem is to spray the inside of the detergent pouches with a wetting agent selected from suitable, relatively nonvolatile, organic liquids like water, surfactant solutions, propylene or ethylene glycol, light oils, liquid polyethylene glycols, nonionic surfactants, etc., 25 capable of forming and maintaining a tacky surface on the detergent powder particles. Said liquid should not be capable of forming, by itself, a barrier of any type between the substrate and the detergent composition. The portion of the substrate that defines the pouch that contains the detergent powder is sprayed 30 with an effective amount, typically from about 0.01 gram to about 0.2 gram per square inch, preferably from about 0.04 gram to about 0.1 gram per square inch, of said wetting agent. The detergent powder is added to the detergent pouch before the wetting agent evaporates or otherwise disappears. The tacky 35 detergent powder then obstructs, at least partially, the pores of the substrate, and thus minimizes the escape of the very fine detergent powder particles (dust). The porous substrate in this Example is coated with approximately 0.06 gram per square inch of organic liquid (propylene glycol) and, before it dries, the 5 detergent powder is added to the sheet, The finished article is suitable ~r washing and softening laundry in a process involving washing and rinsing the fabrics, followed by tumble drying in a heated clothes dryer, wherein the article remains with the laundry throughout the entire process.
~JIIAT l~ CL~IMLD IS:

Claims (11)

1. A through-the-wash detergent and fabric softening composition comprising:
(A) from about 1% to about 50% of detersive surfactant;
(B) from about 15% to about 60% of detergency builder;
(C) from about 0.5% to about 10% of detergent-compatible, dryer activated fabric softener composition in particulate form, the said particles comprising:
(a) an inner core of fabric softener composition consisting essentially of at least about 10% of a cationic fabric softener, the said softener composition having a melting point of from about 50°C to about 80°C and the remainder of said inner core being materials which can be applied to fabrics along with said cationic fabric softener in a laundry dryer;
(b) a coating surrounding said core, said coating being a substantially water-insoluble material having a melting point above about 35°C, and a penetration value of about 0.6 mm or less as measured by ASTM Test D-1321, modified by using a 100 gram weight, said water-insoluble material being selected from the group consisting of: cellulose ethers, cellulose esters, and mixtures thereof;
the said coating comprising from about 3% to about 30% of said particle, the said inner core comprising from about 97% to about 70% of said particle, and the said particles having a size of from about 5 to about 1,000 microns.

2. The particulate composition of Claim 1 wherein the cationic softener in the inner core (a) is of the formula [R1R2R3R4N]+Y-wherein one or two of the R1, R2, R3 and R4 groups is an organic radical containing a group selected from C12-C22 aliphatic radicals having from 10 to 16 carbon atoms in the alkyl chain and alkylbenzyl radicals having from 10 to 16 carbon atoms in the alkyl chain, the remaining groups being selected from C1-C4 alkyl, C2-C4 hydroxyalkyl, and cyclic structures in which the nitrogen atom in the formula forms part of a ring, and wherein Y- is an anionic radical, and wherein the cationic softener comprises from about 10% to about 50% of the softener composition of the inner core (a), and wherein the coating (b) comprises from about 3% to about 15% of said particle.

3. The particulate composition of Claim 2 wherein the coating (b) has a melting point above 50°C.

4. The particulate composition of Claim 3 wherein the cationic softener is ditallowdimethylammonium methylsulfate.

5. The particulate composition of Claim 4 wherein the coating material comprises ethyl cellulose.

6. The composition of Claim 5 wherein the ethyl cellulose is plasticized with dibutyl sebacate.

7. The composition of Claim 1 wherein said inner core (a) additionally comprises microcapsules of fabric conditioning compositions that comprise materials that are not cationic fabric softeners.

8. The composition of claim 7 wherein said fabric conditioning compositions comprise at least one perfume material.

9. The composition of Claim 8 wherein said perfume is encapsulated in a cross-linked gelatin.

10. The composition of Claim 1 wherein said detersive surfactant (A) is present at a level of from about 10% to about 25%; said detergency builder (B) is present at a level of from about 20% to about 45%; and said fabric softener composition in particulate form (C) is present at a level that will give from about 1% to about 5% of quaternary ammonium fabric softener in said detergent composition.

11. The composition of Claim 10 wherein the coating material comprises ethyl cellulose.