Compositions and methods for controlled release of fragrance-bearing substances

Laundering compositions containing particulate olfactory polymers which provide for the controlled release of olfactory compositions such as perfumes, the particulate olfactory polymers comprising a water-soluble normally solid polymer, a water-insoluble normally solid polymer, and at least one olfactory composition which is in each polymer, one polymer being in the form of discrete entitles in a matrix of the other polymer, together with laundering articles such as packets containing such compositions; methods for laundering using such compositions; the particulate olfactory polymers; and methods for preparing the particulate olfactory polymers.

BACKGROUND OF THE INVENTION 
The present invention relates to methods for sequentially releasing 
olfactory compositions into the atmosphere under preselected conditions, 
and more particularly, it relates to methods for releasing fine chemicals 
such as perfumes during the course of a multi-stage operation, such as the 
laundering and drying of textiles, together with novel compositions 
adapted to such purposes and processes for preparing such compositions. 
The current state of the art for perfuming and/or deodorizing detergent 
compositions, fabric softener compositions, fabric softener articles and 
hair preparations generally involves mixing or emulsification of the 
perfume composition with a detergent, fabric softener, or other 
composition to be perfumed, or the surface application, as by spraying of 
the perfume composition onto a solid, without any means for effecting a 
controlled release of the perfume compositions over a period of time into 
the atmosphere around the article or composition containing the perfume. 
In instances where controlled release of the perfume is attempted, as with 
detergent compositions, the release of the perfume is too slow, and the 
resultant aroma is much too weak to be perceived, or the perfume 
composition is released too rapidly and is used up so that its effect is 
undesirably ephemeral. 
Shaped articles for controlling the release of a functional material are 
shown in Faucher et al U.S. Pat. Nos. 3,992,336 and 4,018,729 which 
describe the preparation of articles for conditioning hair by blending 
water-soluble polymers with water-insoluble polymers to form 
interpenetrating networks so that the water-soluble polymer can be 
extracted from the article when wet or when brought in contact with wet 
hair. 
Wise et al U.S. Pat. No. 4,657,693 shows a spray-dried granular detergent 
composition comprising a non-soap ionic detergent surfactant; an alkali 
metal tripolyphosphate detergent builder; and a mixture of a polyethylene 
glycol and a polyacrylate, the mixture having a polyethylene 
glycol:polyacrylate weight ratio of 1:10 to 10:1. This patent states that 
other ingredients commonly used in detergent compositions, such as 
bleaching agents, suds boosters, soil suspending agents, dyes, fillers, 
optical brighteners, germicides, enzymes, perfumes and water, can also be 
included. Buchanan U.S. Pat. No. 4,618,629 shows polyurethane foams 
containing a particulate resin carrying a fragrance which will be released 
over an extended period of time, but multi-phase perfume-containing 
polymer compositions are not disclosed. 
U.S Pat. No. 4,339,356 shows heavily perfumed particles prepared by 
emulsifying perfume in a water solution of water-soluble polymer and 
mixing with a hydratable material to provide a granular material which can 
be mixed into a detergent composition. U.S. Pat. No. 4,209,417 shows 
perfumed particles containing water-insoluble perfume and water-soluble 
polymer for use in detergent compositions. U.S. Pat. No. 4,668,434 shows 
compositions for the slow release of fragrances, repellants, and 
insecticides which compositions include a fragrance in a water-soluble 
polymer such as a vinyl copolymer. 
U.S. Pat. No. 3,576,760 shows fragrances entrapped in water-soluble 
hydroxyethyl acrylate or methacrylate polymers. U.S. Pat. No. 4,136,250 
shows water-insoluble gel of hydrophilic monoolefinic polymer or 
cross-linked copolymer for use as carriers. U.S. Pat. No. 4,548,764 shows 
e-caprolactone polymers used to release perfumes, pheromones, insect 
repellents, and animal repellents from solidified pellets made by 
extrusion. 
U.S. Pat. No. 2,577,921 shows a comb with water-soluble methyl cellulose 
containing hair-treating agent. U.S. Pat. No. 4,436,644 prepares phosphate 
particles which can absorb surfactant or liquids such as perfumes. U.S. 
Pat. No. 3,472,840 shows quaternary nitrogen-containing cellulose ethers 
useful as anti-static agents and substantive to substrates such as paper 
and coal dust. 
U.S. Pat. No. 4,471,717 provides animal litter of hydrophobic material 
which is granular material coated with hydrophobic substance and provided 
with top coating of non-water wettable material, which granular material 
can contain a distasteful organoleptic agent. U.S. Pat. No. 4,407,231 
shows animal litter with microcapsules filled with fragrance or deodorizer 
fixed to particles of absorbent material. U.S. Pat. No. 4,018,729 shows 
polyurethane foams with particulate resin carrying a fragrance, for air 
fresheners. 
U.S. Pat. No. 4,668,434 shows compositions for the slow release of 
fragrances, repellants, and insecticides which compositions include a 
fragrance in a water-soluble polymer such as a vinyl copolymer. U.S. Pat. 
No. 4,719,040 shows air freshener gels prepared from a premix of finely 
divided porous water-insoluble polymer and perfume with an aqueous 
gel-forming components comprising a gelling agent and water. European 
Patent Application No. 0 231 826 shows compressed tablets from which 
theophylline is released containing 43-50 percent theophylline, 10-20 
percent water insoluble polymer, and 5-15 percent acid insoluble polymer, 
so that the capsule swells and slowly erodes. Various carboxylic acid 
polymers are used as the acid-insoluble polymers. Japanese Application No. 
87-158724 shows placing unmelted plastic powders coated on the surface of 
melted plastic particles, which latter contain active ingredients such as 
perfumes. The particles are prepared by radio-frequency heating. 
THE INVENTION 
Briefly, the present invention provides methods for releasing olfactory 
compositions such as perfumes during the course of laundering and drying 
clothing and other textiles. The method comprises adding to the wash water 
in conjunction with the detergents and other ingredients the novel 
compositions of this invention in an appropriate package, releasing a 
portion of the perfume under the action of the wash water, optionally 
releasing another portion of the perfume during the rinse cycle, releasing 
a portion of the perfume during drying of the textiles, and optionally 
substantively depositing perfume on the textiles during the drying. 
The novel compositions include multiple phase polymer particles comprising 
a normally solid water-soluble polymer and a normally solid 
water-insoluble polymer, the solid polymers each containing an olfactory 
composition such as a perfume, the watersoluble and water-insoluble 
polymers being in the form of a matrix such that one of the polymers is 
dispersed in a matrix of the other polymer with an intercommunicating 
structure such that a substantial amount of each polymer can communicate 
with the exterior of the particle. Generally, these particles permit the 
penetration of a surrounding liquid into the particle. Thus, in some of 
the particulate olfactory polymers of this invention, the two polymers are 
physically associated with each other such that one is in the form of 
substantially discrete entities in a matrix of the other and having a pore 
structure such that a proportion of the water-soluble entities communicate 
with one another and at least some of the entities communicate with the 
exterior of the matrix. 
This invention also contemplates processes for the preparation of the novel 
particulate olfactory polymers. The processes broadly comprise 
incorporating an olfactory composition into a water-soluble polymer, 
incorporating the same or a different olfactory composition into a 
water-insoluble polymer, intermixing the two polymers under high shear to 
form the entity-containing matrix, and reducing the matrix containing the 
discrete entities into particles of the desired size. 
The invention further provides a laundering composition having improved 
olfactory performance which comprises a detergent composition and a 
particulate olfactory polymer comprising a water-soluble normally solid 
polymer, a water-insoluble normally solid polymer, and at least one 
olfactory composition, a portion of the olfactory composition being 
incorporated in the water-soluble polymer and in the water-insoluble 
polymer, the water-soluble polymer and the water-insoluble polymer being 
physically associated with each other in such a manner that one is in the 
form of discrete entities in a matrix of the other. The particle size of 
the particulate olfactory polymers is controlled, as is the size of the 
discrete entities, to provide the desired properties for a particular end 
use, as described herein.

It will be understood from this description that the matrix or continuous 
phase of the perfumed particle can be water-soluble and the dispersed 
entities can be water-insoluble or the matrix can be water-insoluble and 
the dispersed entities can be water-soluble. In certain aspects of the 
invention, two types of particles can be produced for utilization in the 
same system; that is, one particulate olfactory polymer wherein the matrix 
is water-insoluble and the dispersed entities are water-soluble and 
another particulate olfactory polymer wherein the matrix is water-soluble 
and the dispersed entities are water-insoluble. 
The weight ratio of water-soluble polymer to water-insoluble polymer can be 
varied from about 5:95 to about 95:5. In certain preferred embodiments, 
the ratio of water-soluble to waterinsoluble polymer is from about 20:80 
to 80:20. Depending upon the ratio and the particular polymer or polymers 
used for the water-soluble polymer or for the water-insoluble polymer, the 
matrix will be one particular species and the dispersed entities will be 
the other particular species of polymers. 
As taught herein, the olfactory composition-containing polymer according to 
the present invention is in particulate form. The size of the particles 
can readily be varied to provide the desired function of the particulate 
olfactory polymer. Thus, the relative quantities of water-soluble and 
water-insoluble polymers can be varied to obtain the desired effect. In 
the use of the particulate olfactory polymers, for instance in a detergent 
composition, a greater quantity of water-soluble dispersed entities will 
release a greater quantity of the olfactory composition and accordingly 
fragrance impression during the wash and rinse cycles. 
It will be understood by those skilled in the art from the present 
disclosure, again alluding to compositions for various phases of a 
laundering operation, that the particle size and the relative ratio of 
water-soluble to water-insoluble polymer can be varied to release a lesser 
proportion of the olfactory composition during the wash cycle and a 
greater quantity during the rinse cycle. The quantity of olfactory 
composition released will depend upon the quantity of water-soluble 
material which dissolves during the wash cycle and that which dissolves 
during the rinse cycle. 
The particle size in certain embodiments of the invention is an important 
attribute of the particulate olfactory polymer. In general, taking the 
instance of a matrix of water-insoluble polymer, the greater the quantity 
of water-soluble discrete entities, the larger the particle size can be to 
provide the desired release of olfactory composition. Particle sizes of 
6000 micrometers and more can be used. In certain preferred embodiments, 
it is desirable at high levels of water-soluble discrete entities that the 
particle size not exceed about 3000 micrometers in average diameter. As 
the quantity of water-soluble discrete entities decreases, it is preferred 
that the overall particle size of the particulate olfactory polymer also 
be decreased. In general, in the practice of the invention with 
water-soluble discrete entities, the particle size can range from about 
200 to about 1000 micrometers in average diameter. 
When the water-soluble polymer is the matrix, the overall particle size of 
the particulate olfactory polymer again depends upon the use to be made of 
the particulate olfactory polymers, and can be varied widely. It has been 
found desirable that the particle size for particulate olfactory polymers 
with water-soluble polymer as the matrix be no larger than about 500 
micrometers. In certain desired embodiments, the average diameter ranges 
from about 100 to 400 micrometers. 
It will be understood from this description that the water-soluble polymer 
matrix can be formulated to dissolve more or less rapidly in an aqueous 
medium. Thus, such a particle can be formulated to dissolve relatively 
slowly, and thereby release olfactory composition relatively slowly, 
during the alkaline wash cycle, and then to dissolve more rapidly in the 
more pH-neutral rinse cycle. 
The particulate olfactory polymer particles in certain aspects of this 
invention can also include a functional chemical. This functional chemical 
can itself be a polymer. Whether or not the functional chemical is a 
polymer, olfactory composition can also be contained in the functional 
chemical. As an instance of such use, the functional chemical can be a 
cationic polymeric composition carrying an olfactory composition which 
will be substantive on the textile. In this manner, the particulate 
olfactory polymers of this invention will be able to impart the fragrance 
to the textiles during and then beyond the drying cycle. It will be 
apparent that this will have the beneficial effect, in the laundry art, of 
conferring a desirably pleasant fragrance on the dried textiles. It is 
apparent that this is very advantageous in providing further benefits to 
the consumer by imparting a sense of freshness and cleanness to the 
garments by means of the fragrance. 
The olfactory composition can also be included in the pores or interstices 
of the polymer matrix, as well as in the water-soluble and water-insoluble 
polymers. In other embodiments, the olfactory composition can be in the 
pores or interstices as well as in the water-soluble polymer, depending 
upon the nature of the constituents. 
The water-soluble polymers which are used in certain desired embodiments 
include: 
(i) a polymer resulting from the polymerization of 
(a) ethylene oxide and ethylene glycol; or 
(b) ethylene oxide, propylene oxide and ethylene glycol; 
(ii) polyvinyl pyrrolidone; 
(iii) water soluble cellulosics; 
(iv) polyvinyl alcohol; 
(v) polyvinyl methyl ether; 
(vi) water soluble polyamides (including polyacrylamides, e.g., cationic 
and anionic polyacrylamides such as Reten.RTM. 210 and Reten.RTM. 220 
manufactured by Hercules Inc., Wilmington, Del.); 
(vii) water soluble polyurethanes; 
(viii) polyethylene oxides; or 
(ix) polymers of acrylic acid and/or methacrylic acid; and/or methyl 
acrylate and/or ethylacrylate and/or methyl methacrylate and/or ethyl 
methacrylate; or mixtures of two or more of the foregoing. 
Thus, in certain embodiments, a polyethylene glycol having a weight average 
molecular weight of from about 4,000 up to about 20,000 can be utilized. 
Indeed, while polyethylene glycols are preferred in certain embodiments, 
other suitable water-soluble polymeric materials are the condensation 
products of C.sub.10 -C.sub.20 alcohols or C.sub.8 -C.sub.18 alkyl phenols 
with sufficient ethylene oxide, i.e., more than 50% by weight of the 
polymer, so that the resultant product (a) is soluble in water and (b) has 
a melting point of above about 35.degree. C. Preferred polymers contain at 
least about 70% ethylene oxide by weight and more preferred polymers 
contain at least about 80% ethylene oxide by weight. Polymers based on the 
addition of ethylene oxide and propylene oxide to propylene glycol, 
ethylene diamine and trimethylol propane are commercially available under 
the names Pluronics.RTM., Pluronic.RTM. R, Tetronics.RTM. and 
Pluradots.RTM. available from BASF Wyandotte Corporation, Wyandotte, Mich. 
Corresponding non-proprietary names of the first three tradename materials 
are Poloxamer, Meroxapol and Polyoxamine. 
Examples of water-soluble hydroxyalkyl carboxalkyl celluloses include 
hydroxyethyl carboxymethyl cellulose, hydroxyethyl carboxyethyl cellulose, 
hydroxymethyl carboxymethyl cellulose, hydroxypropyl carboxymethyl 
cellulose, hydroxypropyl carboxyethyl cellulose, hydroxypropyl 
carboxypropyl cellulose, hydroxybutyl carboxymethyl cellulose, and the 
like. Also useful are alkali metal salts of these hydroxyalkyl 
carboxyalkyl celluloses, particularly and preferably the sodium and 
potassium derivatives. 
Vinylpyrrolidone and methyl vinyl ether polymers can be used as 
water-soluble polymers in the practice of this invention, as can cationic 
acrylamide polymers, available from Hercules Corporation, Wilmington, 
Del., under the trade designations Reten.RTM. 210, 220, and 300. 
The normally solid water-soluble organic polymer components of the 
invention should be immiscible with (that is, capable of forming a 
separate solid phase in ) the water-insoluble polymer components. This 
facilitates formation of a network of pores in the matrix of the 
particulate olfactory polymer. 
The various water-soluble polymers shown in U.S. Pat. No. 4,018,729, such 
as cellulose ethers and quaternary nitrogen cellulose ehters, are useful 
in the practice of this invention. 
The water-insoluble thermoplastic polymers which can be used in certain 
desired embodiments of the practice of the invention include: 
(i) polyethylene; 
(ii) polypropylene; 
(iii) copolymers of ethylene and a higher alpha-olefin such as propylene of 
hexene-1; 
(iv) poly(epsilon-caprolactone); 
(v) polyvinyl chloride; 
(vi) polyesters resulting from the polymerization of (a) maleic anhydride 
and/or phthalic anhydride and/or terephthalic acid and (b) ethylene glycol 
and/or propylene glycol and/or ethylene oxide and/or 1,2-propylene oxide; 
(vii) copolymers of vinyl chloride and vinyl acetate; 
(viii) copolymers of vinyl chloride and ethylene and/or propylene; 
(ix) copolymers of vinyl acetate and ethylene and/or propylene and/or 
2-butene and/or 2methyl-1-propene; 
(x) thermoplastic polyurethanes derived from diisocyanates and polyols; 
(xi) polyamides; 
(xii) polyester polyamides; and 
(xiii) thermoplastic polyurethanes derived from diisocyanates and polyol 
polyesters. 
Other water-insoluble polymers useful in the practice of the invention are 
those described in U.S. Pat. No. 4,618,629. For example, a polyurethane 
produced by reacting toluene-2,4-diisocyanate with a glycol adipate ester 
having a hydroxyl number of approximately 60 and a molecular weight of 
from about 2,000 up to about 2,500 in the presence of N-ethyl morpholine 
can be used in the practice of this invention. 
Water-soluble polyamides shown in German Offenlegungschrift No. 3,615,514 
can be used. 
Examples of water-insoluble polyamides useful in practicing this invention 
are set forth in Japan Kokai No. 62/79808. Examples of water-insoluble 
polypropylene polymers useful in the present invention are in Japan Kokai 
No. 62/71502. 
Examples of polyesters useful in the present invention, such as 
poly(ethylene terephthalate) and mixtures of polypropylene and 
poly(ethylene terephthalate), are shown in Polymer Engineering Science, 
1987, Volume 27(9), pages 622-6. Polycarbonates and 
polycarbonate/acrylonitrile-butadiene-styrene blends which can be useful 
herein are set forth in Polymer Engineering Science, 1987, Volume 27(9), 
pages 632-9. 
Useful thermoplastic polyurethane elastomers comprising polyester polyols 
(obtained from polyols, polyacids or anhydrides and epsilon-caprolactone) 
and polyisocyanates, the polyesterpolyols of which are composed of 0-90 
mole percent polyesterpolyols (m.p. about 30.degree. C., molecular weight, 
1000-10,000) from polyhydric alcohols, 30-100% of which are C.sub.3 
-C.sub.10 branched diols, and 30-80% epsilon-caprolactone and 10-100 mole 
percent polyester polyols are shown in Japan Kokai No. 61/276814. Other 
water-insoluble polymers which can be used herein are thermoplastic 
polyurethane-type materials such as the thermoplastic 
polyester-polyurethane rubbers shown in Japan Kokai No. 62/53321. 
Other water-insoluble polyamides useful in the practice of this invention 
are set out in U.S. Pat. No. 4,670,522. 
Still other suitable water-insoluble thermoplastic polyurethane resins 
useful in the practice of this invention are mentioned in U.S. Pat. No. 
4,676,975. 
It is preferred in the practice of this invention to utilize a high-shear 
mixing device to disperse the separate entities of the one polymer through 
the matrix of the other polymer. In a batch process, a unit such as a 
Banbury mixer can be used. For continuous processing, it is preferred to 
use an extruder. 
In practicing the process of this invention to form the particulate 
olfactory polymers, single screw or double screw extruders can be 
utilized. Some of the extruders that can be used are shown at pages 
246-267 and 332-349 of the Modern Plastics Encyclopedia, 1982-1983. 
More particularly, examples of extruders which are desirable for carrying 
out the process of the invention include: 
1. The Krauss-Maffei twin screw extruder manufactured by the Krauss-Maffei 
Corporation/Extruder Division, 3629 West 30th St., Wichita, Kans. 67277; 
2. The CRT ("Counter-Rotating Tangential") Twin Screw Extruder manufactured 
by Welding Engineers, Inc., King of Prussia, Pa. 19406; 
3. The Leistritz Twin Screw Dispersion Compounder manufactured by the 
American Leistritz Extruder Corporation, 198 U.S. Route 206 South, 
Somerville, N.J. 08876; 
4. The ZSK Twin Screw Co-Rotating Extruder manufactured by the Werner & 
Pfleiderer Corporation, 663 East Crescent Ave Ramsey, N.J. 07446; 
5. The MPC/V Baker Perkins Twin Screw Extruder manufactured by the Baker 
Perkins Inc. Chemical Machinery Division, Saginaw, Mich. 48601; 
6. The Berstorff twin screw or foam extrusion equipment manufactured by 
Berstorff Corporation, P.O. Box 240357, 8200-A Arrowridge Blvd., 
Charlotte, N.C. 28224. 
FIG. 1A is a cross section of a perfumed particle comprising water-soluble 
polymer containing olfactory compositions in interconnected pores of a 
water-insoluble polymer matrix. 
Particle 200, representative of one embodiment of the particulate olfactory 
polymers of this invention, comprises matrix 201 of water-insoluble 
polymers such as polyethylene or copolymers of ethylene and vinyl acetate. 
Water-soluble polymer entities 202 and 202A are generally contained in 
matrix 201 and they are interconnected by pores 204 and 204A containing 
the water-soluble polymer. Referring to FIGS. 1B and 1C, when particle 200 
is immersed in water 206 in container 207, the water-soluble polymer 
located in pores 202 and 202A dissolves in water 206 as shown by arrows 
208, and olfactory composition (not separately shown) coming from 
water-soluble polymer 202 as well as, if desired, from water-insoluble 
polymer 201, emanates from the surface of water 209 as shown by arrows 
211. Of course, FIGS. 1A, 1B and 1C show the water-insoluble polymer being 
the matrix 201 and the water-soluble polymer being in the dispersed 
entities 202. 
Conversely, the water-soluble polymer can be the matrix and the 
water-insoluble polymer can be the dispersed entities as shown in FIGS. 
1D, 1E and 1F. In FIG. 1D particle 215 has water-soluble polymer 220 as 
the matrix and water-insoluble polymer 221 and 221A the dispersed 
entities. Edge 216 of particle 215 is shown. When particle 215 is immersed 
in water 226, shown in FIGS. 1E and 1F, water-soluble polymer 220 begins 
dissolving at surface 216 and loses a substantial amount of water-soluble 
polymer as shown by diminished edge 218. Meanwhile, the water-insoluble 
dispersed entity particles 221 leave polymer particle 215 and become 
independently immersed in water 226. Olfactory composition is released 
from water-soluble polymer 220 and, if desired, water-insoluble polymer 
221, as indicated by arrows 228A and 228B. The olfactory composition 
ultimately leaves the surface 230 of water 226, as shown by arrows 231. 
Particles 221 and 221A are contained in vessel 227, as shown in FIGS. 1E 
and 1F. 
Of course, both particles 200, having water-insoluble polymer 201 as the 
matrix and water-soluble polymer 202 as the dispersed entities, and 
particles 215, having water-soluble polymer 220 as the matrix and 
water-insoluble polymer 221 as the separate entities, can be used 
simultaneously with the same or different olfactory compositions as shown 
in FIG. 1G. 
Referring to FIG. 1G, polymeric particles 215, having as the matrix 
water-soluble polymer 220 containing water-insoluble dispersed entity 
polymers 221 and 221A, are immersed in water or other aqueous liquid 226, 
whereupon some olfactory composition leaves the liquid, as shown by arrow 
228A, going into the ambient environment 235 above the system. 
Simultaneously, water-insoluble continuous phase polymer particles 200 
having water-insoluble matrix 201, containing dispersed phase 
water-soluble polymer 202, partially dissolves, as shown by void 210. 
Water-soluble polymer 202 leaves the water-insoluble polymer matrix 
through pores 204 and proceeds into immersing water 226, as shown by 
arrows 208. Olfactory composition contained in water-soluble polymer 202 
leaves the system into ambient environment above aqueous liquid 226, as 
shown by arrows 235, in container 240. 
FIG. 2A is a schematic block flow diagram representing a screw extruder 
during the compounding of water-soluble resin with water-insoluble resin 
while simultaneously adding perfumery material into the hollow portion of 
the barrel of the extruder. 
FIG. 2B is a variation of the apparatus of FIG. 2A in schematic block flow 
diagram form depicting a screw extruder during the compounding of a 
water-insoluble thermoplastic resin with a water-soluble resin while 
simultaneously adding olfactory composition into the hollow portion of the 
barrel of the extruder. 
FIG. 2C is another variation of the apparatus of FIG. 2A showing in a block 
schematic flow diagram a screw extruder during the compounding of 
water-soluble resin, water-insoluble resin and olfactory composition, with 
one of the resins containing other additive(s). 
FIG. 2D is a block schematic flow diagram of another variation of the 
apparatus of FIG. 2A showing a screw extruder during the compounding of 
water-soluble resin, water-insoluble resin and another oil which has a 
functional use, e.g., in perfumery, insect repellency, or the like and, 
further, with one of the resins containing other additive(s). 
Thus, olfactory composition in tank 314 in apparatus 300 of FIG. 2A is fed 
into line 316 and thence into extruder 308 simultaneously with the feeding 
of water-insoluble polymer such as polyethylene from tank 302 through line 
304 and line 306 into extruder 308; and water-soluble polymer from tank 
310 through line 312 through line 306 into extruder 308. The extrudate is 
then cooled in cooling means 320 and, if desired, fed to particle size 
reducing means 324 through line 322. 
In another embodiment, referring to FIG. 2B, olfactory agent from tank 340 
is pumped through line 342 into extruder 338 simultaneously with the 
delivery to a hollow portion of extruder 338 further downstream of 
water-soluble polymer from tank 344 through line 346 into extruder 338. 
Upstream from the delivery point of the perfume into the extruder, 
water-insoluble polymer from tank 332 is fed through line 334 into 
extruder 338. The extruded strand passes through line 348 into cooling 
means 350 and, if desired, through line 352 to pelletizer 354 to produce 
pellets at 352. 
In an alternative embodiment, referring to FIG. 2C, polymer which already 
contains perfume in container 374 is passed through line 376; olfactory 
composition from tank 370 is passed through line 372; and water-insoluble 
polymer from tank 362 is passed through line 364 simultaneously into 
extruder 368. The strands issue from extruder 368 at 378 into a cooling 
system 380 and pelletizer 384 to be subsequently recovered as pellets from 
line 386. The resin feed from vessel 362 is upstream from the feeding of 
the olfactory composition from vessel 370, which, in turn, is upstream 
from the feeding of the perfumed polymers from container 374. 
In FIG. 2D, apparatus 390, water-insoluble polymer (which already contains 
perfume) from reservoir 392 is admixed in extruder 396 with additives from 
vessel 404. Simultaneously, Polyox.RTM. water-soluble polymer is passed 
from vessel 398 through line 402 into extruder 396 at a hollow portion 
thereof. Other desired additives, e.g., oil or solid or paste, such as a 
dog repellent located in vessel 404, are fed through line 406 into 
extruder 396. These other additives can include materials such as insect 
repellents, colorants, fabric softeners, anti-static agents, and the like. 
The extruded strands so formed are passed through line 408 into cooler 410 
and pelletizer 412, and are then recovered as pellets at 414. 
Generally, in certain preferred embodiments, double-screw extruders such as 
those aforesaid are used to mix the water-soluble and water-insoluble 
polymers, the olfactory composition or compositions, and any other 
polymers and additives. These extruders are well-known in the art. 
Such extruders comprise an inner shaft member to which an outer screw 
member is affixed coaxially. In a double-screw machine, there are two 
shafts, each of which drives an outer screw member. The screws are 
intermeshed so that they subject the material being extruded to high-shear 
conditions, which contribute to dispersing the polymer or polymers 
destined to be the discrete entities in the polymer which will form the 
matrix in the particulate olfactory polymers of this invention. 
These extruders also comprise an outer barrel member which encloses the 
screw or screws. Such extruders over their length can be fitted with 
different screws on the shaft and with different barrels surrounding the 
screws. Thus, over the length of the extruder various types and amounts of 
shear action can be used. The variation is carried out along the length of 
the extruder so that as various ingredients are initially introduced into 
the interior of the extruder, as the ingredients are initially mixed, and 
as the components become more highly mixed or dispersed, the mixing and 
shear action can be varied to obtain the particle size and amount of the 
polymer material to be the dispersed entities in the matrix. 
After the extrusion, the extrudate is usually cooled. This can be 
accomplished by suitable means such as belts, blowers, liquids, and the 
like. The cooled extrudate comprises a matrix with dispersed entities. 
This extrudate is then comminuted to provide the finished particles by 
means known in the art. 
In addition to the use of a single extruder, it will be apparent from this 
description that a series of extruders can be used to form extrudate. 
Thus, a functional composition with or without olfactory composition can 
also be added. It can be desirable not to mix this functional composition 
into the bulk as thoroughly as the dispersed entities are mixed. A 
functional composition is herein understood to mean a polymer or other 
material which will provide a desired function to the particles. Thus, a 
cationic polymer can be added to provide substantivity of the fragrance on 
dried textiles when the particulate olfactory polymers of this invention 
are used in laundering compositions. 
The extrusion and subsequent comminution enable the facile control of the 
size of the dispersed entities and the overall size of the particulate 
olfactory polymers. This in turn provides control over the ultimate 
properties of the particulate olfactory polymers, as taught herein. 
Apparatus suitable for use in the practice of this invention is shown in 
more detail in FIG. 2E. 
FIG. 2E is an elevation, partly in section, of apparatus 100 showing the 
practice of a preferred aspect of the invention. It comprises screw 
extruder 118 for compounding of water-insoluble resin with water-soluble 
resin while simultaneously adding olfactory composition into the hollow 
portion of the barrel of the extruder and incorporates the pelletizing 
apparatus used in pelletizing the extruded product of the extrusion 
operation. 
Motor 115 drives extruder screws 118 in barrel 116, the extruder being 
operated at temperatures in the range of about 150.degree. to about 
250.degree. C. At the beginning of the barrel resin from hopper 112 (e.g., 
water-insoluble resin such as polyethylene) together with additives, such 
as opacifiers, processing aids, colors, cationic and/or nonionic fabric 
softeners, anti-static agents, pearlescent agents and densifiers, and 
water-soluble resin (e.g., Polyox.RTM.) from hopper 113, together with any 
desired additives, such as cationic or nonionic fabric softening or 
anti-static agents, is conducted via addition hopper 114 into extruder 
102. Simultaneously, when the operation reaches "steady state", an 
olfactory composition, such as a perfume, is added to the extruder one, 
two or more of barrel segments 3-8 of the twin-screw extruder at locations 
118a, 118b, 118c and 118d by means of gear pump 123 from tank 117. From 
line 119, optionally, gaseous or liquid blowing agents, e.g., nitrogen, 
carbon dioxide, and the like can be added simultaneously with the addition 
of the olfactory composition. 
The feed rate range of the resin is about 80-300 pounds per hour. The feed 
rate range of the perfumant is between one and 70 percent of the feed rate 
range of the resin. If desired, the blowing agent rate range is such that 
the pressure of the gas or the pressure over the perfumant being fed into 
the extruder is between about 50 and about 1000 psig. Cooling means 140 
comprises passing extrudate 141 onto belt 145 being cooled from the side 
opposite to that of the extrudate using water spray 146 coming from 
nozzles 144, from manifold 143 which, in turn, is fed by line 142. 
One of the outstanding uses of the particulate olfactory polymers of the 
present invention is in particulate detergent compositions and washing 
systems. The detergent compositions and washing systems are normally 
solid. In other words, they are generally in the form of solid particles 
and are not liquids. In one embodiment of a method according to the 
invention, the particulate olfactory polymer is incorporated into a 
laundry dose system, that is, a pouch or envelope of nonwoven material 
which contains detergent and fabric softening ingredients. In another 
embodiment of the invention, the pouch can contain a detergent composition 
containing a bleach and a fabric softener. 
In embodiments like the foregoing, the package of bleach, detergent 
composition, and softener is placed in the washing machine with the 
clothing to be cleaned and it remains with the clothes to the end of the 
dry cycle, at which time it is removed from the cleaned and dried clothing 
and discarded. In embodiments described herein, the olfactory agent is 
substantive on the clothes, and provides the dried clothing with a 
pleasant scent for a time following the dry cycle. 
The detergent compositions with improved olfactory properties are prepared 
with ingredients which include those already well-known in the art. 
Generally, the detergent compositions contemplated herein are granular or 
particulate, as those produced by spray-drying. Such detergent 
compositions generally include a natural or synthetic surface active 
agent; a builder; and adjuvant ingredients to improve the washing or 
detergent properties, reduce corrosion, reduce pollution, improve the 
whiteness of the composition, improve the brightness of the textiles being 
washed, and/or to provide color and other desired appearance 
characteristics or improvements to the detergent composition. 
Thus, detergent compositions involved by this invention can include anionic 
soap and non-soap surfactants, including alkali metal soaps and 
alkylammonium soaps of natural and/or synthetic higher fatty acids having 
from about eight to 24 carbon atoms, alkali metal salts of organic 
sulfuric reaction products having an alkyl radical containing from about 
eight to 22 carbon atoms, esterified fatty acid products, succinamates, 
anionic phosphate surfactants such as alkyl phosphate esters; nonionic 
synthetic detergents such as those produced by the condensation of 
alkylene oxide groups with an organic hydrophobic compound which can be 
aliphatic or alkyl aromatic, amine oxide derivatives, phosphine oxide 
derivatives, and sulfoxide derivatives; ampholytic synthetic detergents 
such as derivatives of aliphatic or aliphatic derivatives of heterocyclic 
secondary and tertiary amines with various sulfo, carboxy, sulfato, 
phosphato, or phosphono groups; and zwitterionic surfactants such as 
derivatives of aliphatic quaternary ammonium and phosphonium or tertiary 
sulfonium groups in which the cationic function can be in a heterocyclic 
ring and wherein a substituent contains a water-solubilizing group such as 
a carboxy, sulfo, sulfato, phosphato, or phosphono group, all as described 
in more detail in U.S. Pat. Nos. 3,664,961 and 4,180,485. 
The so-called builders can be water-soluble inorganic builders such as 
carbonates, borates, phosphates, polyphosphates, bicarbonates, and 
silicates; organic builders such as alkaline sequestrant builder salts 
like amino carboxylates, nitriloacetates or carboxylates, phosphonates, 
citrates, or various organic acid salts well-known in the art. The 
detergent compositions can also contain coagglomerants and other materials 
some of which are briefly mentioned above to improve, change, or modify 
appearance and other cleaning and non-cleaning functions of the 
composition. 
Other ingredients used in detergent compositions can of course be used in 
the particulate olfactory polymer-containing detergent compositions of the 
present invention. Thus, the compositions can contain bleaching agents, 
bleach activators, suds boosters or suds suppressors, anti-tarnish and 
anti-corrosion agents, soil-suspending agents, soil release agents, dyes, 
fillers, optical brighteners, germicides, pH adjusting agents, non-builder 
sources of alkali, hydrotropes, enzymes, stabilizing agents for enzymes, 
and the like. 
In some embodiments of the invention, the detergent composition can contain 
a bleaching agent, for example, an oxidizing agent including percompounds 
such as a perborate or the like. It will be recognized that such bleaching 
agents can rapidly modify or destroy the olfactory composition or agent in 
the total detergent composition, and one of the outstanding attributes of 
the presently described invention is the ability to protect the olfactory 
agents from untoward effects of the other detergent composition 
ingredients, such as bleaches. 
The fabric softeners are those conventionally utilized in the preparation 
of cleaning and washing agents. These softeners are generally cationic or 
nonionic products which impart softness effect. A review of fabric 
softener types and functionality is given in the three-part series "Fabric 
Softeners" by B. Milwidsky in Household and Personal Products Industry, 
September, October, and November 1987, Vol. 24, Nos. 9-11. 
As taught above, the particulate olfactory polymers provided herein can be 
used in a pouch which contains detergent, detergent including bleaching 
agent, or detergent-containing fabric softener. In some aspects, the 
unitized dose detergent compositions can be used with non-woven sheets 
provided with pockets or protuberances. Some of these pouches in the sheet 
contain detergent, some can contain bleach, and some can contain softener. 
An advantage of the particulate olfactory polymers according to the 
present invention is that they can be placed in the unitized dose package, 
either with the several ingredients or in one or more of the pouches of 
woven sheets of multiple-action packages. The polymers act to protect the 
olfactory composition, such as a fragrance, from the untoward action of 
the bleach, whether the detergent be in a unitized dose or in a 
conventional box or carton. 
Customarily, if a perfume is present in a detergent composition, it is 
totally released with the detergent in the wash cycle and its 
substantivity on cloth will depend, to a large extent, on its ability to 
withstand the actions and components of the complete laundry cycle. An 
outstanding feature of the particulate olfactory polymers according to the 
present invention is that the olfactory agent is not only protected from 
inimical components of the detergent compositions, but also the action of 
the olfactory agent is extended through the wash cycle, the rinse cycle, 
and the drying cycle. This is due to the unique combination of 
water-soluble and water-insoluble components of the particulate olfactory 
polymer and the physical combination of these two components in the 
particulate olfactory polymer. 
As noted above, the particulate olfactory polymers of this invention have 
the capabilty in one embodiment of permitting the water-soluble polymer to 
dissolve and thereby release the olfactory agent. This then provides a 
pleasant scent during the wash cycle. By controlling the solubility of the 
water-soluble component of the particulate olfactory polymer, as by 
formulating it to be more or less soluble at various pH levels, some of 
the dissolution can take place during the rinse cycle as well. The 
dissolution of the water-soluble portion or component creates a greater 
pore volume. Indeed, when the water-soluble component comes out of the 
particulate olfactory polymer in the wash cycle, its solubility increases 
the exposed surface area of the residual polymer matrix and facilitates 
additional fragrance release in the dryer cycle. Thus, the olfactory 
composition provides a scent throughout the use of the detergent 
composition. 
By balancing the perfume quantity, there will be some scent in the box and 
to the detergent composition itself, there will be a pleasant scent during 
the wash and rinse cycles, and there will be a pleasant scent during the 
drying, all achieved with a unitized dose form of the detergent 
composition containing the particulate olfactory polymer. Fragrance 
substantivity on the dried textiles can even be achieved through the use 
of a functional component, that is, fabric-softening or anti-static agent, 
contained in the particulate olfactory polymer. Moreover, throughout the 
laundering or cleaning cycle with the particulate olfactory polymer, the 
olfactory composition is protected from the deleterious effects of the 
various components of the unitized dose detergent composition and 
associated materials as taught above. 
For use with detergent compositions, the relative quantity of the 
water-soluble polymer component desirably rages from ten to 85 percent of 
the total particulate olfactory polymer. If there is too little 
water-soluble component, there is insufficient permeability of the 
particulate olfactory polymer by the aqueous liquid, whereas if the 
water-soluble component comprises more than about 85 percent, the 
particulate olfactory polymer will usually disintegrate too rapidly during 
the wash and rinse cycles. 
The particulate olfactory polymer of the present invention is of course 
capable of wider usage, as will be apparent to those skilled in the art 
from the present description. Thus, hair fragrance is put in material 
substantive on the hair to have the olfactory composition release later. 
In order to achieve the precise action for a particular product, it is 
possible to put more or less olfactory composition in the water-soluble or 
the water-insoluble component of the particulate olfactory polymer. Thus, 
in certain embodiments of the invention, it is desirable to have from 20 
to 80 percent of the total olfactory composition in the water-soluble 
component, and the remainder in the water-insoluble component. 
It has been found that when there is less than 20 percent of the olfactory 
composition in the water-soluble component, not enough fragrance is 
released in the wash or rinse cycles of the laundry process to impart the 
desired pleasant aroma. Conversely, when there is more than 80 percent of 
the olfactory composition in the water-soluble component, there is too 
little of the olfactory composition remaining in the water-insoluble 
component for imparting a pleasant aroma in the drying cycle. 
Generally, for purposes of the present invention, it has been found 
desirable to have the particulate olfactory polymers comprise from about 
0.5 to about three percent of the detergent composition. At levels below 
this, it is difficult to create the intensity of desired aroma in the 
ambient space around the washer, and greater amounts than three percent 
tend to be too intense. In certain embodiments, it is preferred to have 
from one to two percent of the particulate olfactory polymer in a 
detergent composition. 
The quantity of the olfactory composition in the total particulate 
olfactory polymer is desirably from about one to about 40 percent. In 
certain preferred embodiments, the quantity of olfactory composition is 
preferably from about 10 to about 30 percent of the particulate olfactory 
polymer. In certain preferred embodiments, 20 percent gives good results. 
It will be understood from the present description that olfactory 
compositions can include perfumes and perfume compositions which generally 
impart a desirable aroma to articles and to the ambient atmosphere 
surrounding the articles. They can also include olfactory compositions 
such as pheromones, insect and animal attractants, and insect and animal 
repellants. In general, such olfactory materials are known and have been 
described in the art. 
The properties of the polymers can also be selected for the particular end 
use to which the particulate olfactory polymers are to be put. Thus, for 
instance, the water-soluble polymer used can be one which is more or less 
soluble in alkaline solutions. 
The olfactory composition is present in both the water-soluble and the 
water-insoluble polymers. It is incorporated in the polymers by mixing, 
and it will be understood that the olfactory composition can be dispersed, 
dissolved, or otherwise distributed in each polymer. This provides another 
tool in controlling the release of the olfactory composition during the 
use of the material. 
All parts, percentages, proportions and ratios herein are by weight unless 
otherwise stated. 
The following Examples are given to illustrate embodiments of the invention 
as it is presently preferred to practice it. It will be understood that 
these Examples are illustrative, and the invention is not to be considered 
as restricted thereto except as indicated in the appended claims. 
In the following Examples, various terms are used to describe the 
materials. "LDPE" is low-density polyethylene, a water-insoluble polymer, 
with a density below 0.94, and more particularly a density of about 0.92. 
"EVA" is a copolymer of ethylene and vinyl acetate, a water-insoluble 
thermoplastic polymer. "POLYOX" is a trademark for a polyethylene oxide 
polyether made by the Specialty Chemicals & Plastics Division of Union 
Carbide Corporation, Danbury, Conn. and having the structure 
EQU H--(O--CH.sub.2 CH.sub.2).sub.n --O--CH.sub.2 CH.sub.2 --OH 
wherein n is the degree of polymerization, and the molecular weight of the 
polymer ranges from about 100,000 to 5,000,000, depending on the viscosity 
grade of the resin. Polyox resins are water-soluble resins. 
"PLURONIC" is a trademark for polyol polyethers marketed by BASF 
Corporation, Wyandotte, Mich., with the structure 
##STR1## 
and having a molecular weight ranging from about 4700 to about 14,000, 
with a, b, and c being integers from one to nine and (a+c)/b being from 
2.5 to 6.0. 
EXAMPLE I 
A. Preparation of Particulate Olfactory Polymers 
______________________________________ 
Composition (percent) 
A B C 
______________________________________ 
Perfume oil 20 20 20 
LDPE 50 50 30 
Polyox WSR3154 
-- 30 50 
EVA 30 -- -- 
______________________________________ 
In wide-mouth pint jars, 60 gram batches containing the appropriate amounts 
of the above components are mixed together. Then a Haake mixer is used to 
mix the components of each composition together in a melt. The mixtures 
are then removed from the Haake machine and allowed to cool. Using liquid 
nitrogen and a grinding mill set at 2 mm, the resins are ground 
cryogenically. Size separation is carried out by sieving the compositions 
through US Standard sieves #18, #45 and #70, and each fraction is 
collected and labeled. 
B. Volatile Levels of Initial Particulate Polymers 
The volatile level of each composition is determined by weighing (to the 
nearest 0.0001 g) 1-2 grams of each resin (in duplicate) into an aluminum 
weighing dish and drying the samples in a vacuum oven at 180.degree. C. 
for 18 hours. Table I lists the percent of volatiles of each particulate 
polymer (-18, +45 mesh) prepared in A, with volatility assumed to be due 
solely to the fragrance oil (20% oil content). 
TABLE I 
______________________________________ 
PERCENT VOLATILES OF COMPOSITIONS A, B, C 
SAMPLE VOLATILES 
______________________________________ 
POLYMER A (1) 18.35% 
POLYMER A (2) 18.29% 
AVERAGE 18.32% 
POLYMER B (1) 17.69% 
POLYMER B (2) 17.48% 
AVERAGE 17.58% 
POLYMER C (1) 18.42% 
POLYMER C (2) 18.38% 
AVERAGE 18.41% 
______________________________________ 
C. Laundry Use 
1. Preparation of Detergent Packet 
Using a non-woven sheet formed into a pouch, 30 g of non-fragranced 
detergent is mixed with 1.5 grams of particulate olfactory polymer (-18, 
+45 mesh) and added into the pouch, which is then sealed to prevent loss 
of particles. Three pouches are prepared for each of Compositions A, B, 
and C. 
2. Laundry Evaluation 
a. Wash cycle: Five cotton towels and five cotton wash cloths are placed in 
a conventional household top-loading washing machine and washed with a 
unitized packet containing one of particulate olfactory Compositions A, B, 
or C. Each packet and respective component contained in the pouch is 
weighed to 0.0001 g prior to introduction into the washing machine. The 
water level is set at low (30 liters) and the wash cycle to 10 minutes 
using hot water (55.degree. C.). The packet and fabric are removed after 
the wash/spin cycle and placed in the dryer for a 40-minute drying cycle. 
b. Rinse cycle: The same procedure as in 2a is repeated, except the packet 
is removed from the machine upon completion of the total hot wash/warm 
rinse cycle (rinse for 5 minutes at 35.degree. C.). Again the packet is 
placed into the dryer for a 40-minute drying cycle with the cloth. 
c. Dryer cycle: Another test is run in which the laundry load is subjected 
to the wash/rinse cycle and a pouch containing only 1.5 grams of polymer 
is added solely to the dryer cycle. Weight loss in this test is due 
strictly to volatilization of the fragrance composition from the polymer. 
3. Weight Loss from the Laundry Cycle 
a. Upon completion of the drying cycle, each packet is reweighed for 
residual solid level. Residual fragrance levels and fragrance release 
levels in the corresponding laundry process are readily calculated based 
on the weight loss. 
TABLE II 
__________________________________________________________________________ 
FRAGRANCE RELEASE IN THE LAUNDRY CYCLE 
INITIAL 
RESIDUAL 
% SOLIDS 
% VOLATILES 
WT (g) 
WT (g) REMAINING 
LOST* 
__________________________________________________________________________ 
POLYMER A (W) 
1.5007 
1.3810 92.0 39.9 
POLYMER A (R) 
1.5094 
1.3849 91.8 41.2 
POLYMER A (D) 
1.5034 
1.4508 96.5 18.4 
POLYMER B (W) 
1.5080 
0.8432 55.9 90.9 
POLYMER B (R) 
1.5143 
0.8439 55.7 91.3 
POLYMER B (D) 
1.5208 
1.4682 96.5 19.7 
POLYMER C (W) 
1.5243 
0.8063 52.9 67.9 
POLYMER C (R) 
1.5579 
0.5315 34.1 94.9 
POLYMER C (D) 
1.5563 
1.5154 97.4 14.3 
__________________________________________________________________________ 
(W) = Wash cycle/dry cycle 
(R) = Wash cycle/rinse cycle/dry cycle 
(D) = Dry cycle only 
*% Volatiles Lost = percent loss of volatiles and/or solubles. 
It will be understood that in the wash or wash/rinse cycle tests, weight 
loss can be due to Polyox solubility and/or fragrance release. Therefore 
the percentage volatiles lost is the ratio (.times.100) of the total 
weight loss to the fraction of polymer that is water soluble and volatile. 
In the dry cycle test, the percentage of volatiles lost is the ratio of 
weight loss to the fraction of polymer that is volatile (perfume oil 
content from Table I). 
b. Determination of percent volatiles remaining in each polymer upon 
completion of the laundry process: 
All solids recovered from the packet are subjected to vacuum drying at 
150.degree. C. for 18 hours. In this test, the remaining volatiles are 
driven off from the polymer resins and indicate the level of fragrance 
release in the particular laundry process. The percent volatiles remaining 
is the percent remaining in the recovered polymer. The percent fragrance 
released is the percent of fragrance or volatiles released into the 
appropriate laundry process, that is, 100 percent less the remaining 
volatiles in the particulate olfactory polymer recovered from the pouch. 
TABLE III 
______________________________________ 
FRAGRANCE REMAINING IN POLYMER AS 
DETERMINED FROM VACUUM OVEN WEIGHT LOSS 
% % FRA- % 
VOLATILES GRANCE POLYMER 
SAMPLE REMAINING RELEASE RELEASE 
______________________________________ 
POLYMER A (W) 
62.9 37.1 -- 
POLYMER A (R) 
63.4 36.6 -- 
POLYMER A (D) 
82.2 17.8 -- 
POLYMER B (W) 
16.5 83.5 95.1 
POLYMER B (R) 
16.1 83.9 95.5 
POLYMER B (D) 
84.5 15.5 2.5 
POLYMER C (W) 
38.9 61.1 70.3 
POLYMER C (R) 
13.9 86.1 98.1 
POLYMER C (D) 
87.3 12.7 0.6 
______________________________________ 
It will be appreciated from the foregoing that the addition of Polyox to 
water-insoluble polymer has a tremendous impact on fragrance release in 
the laundry process. As indicated by the data in Table III, only 36 to 37 
percent of the fragrance is released from the water-insoluble portion of 
the particulate olfactory polymer A (LDPE/EVA) when subjected to a 
wash/dry or a wash/rinse/dry cycle. Replacing the 30 percent EVA with 30 
percent water-soluble polymer (Polymer B) results in an 83 to 84 percent 
fragrance release, with the amount released in the wash/dry cycle being 
the same as the wash/rinse/dry cycle. 
In particulate olfactory polymer B, it appears that all the water-soluble 
polymer dissolves in the wash cycle since a further rinse does not alter 
fragrance release or Polyox dissolution. However, changing the ratio of 
LDPE/Polyox/perfume from 50:30:20 (particulate olfactory polymer B) to 
30:50:20 (particulate olfactory polymer C) does alter polymer solubility 
in the wash and wash/rinse cycles as well as the release of fragrance. 
As further shown in the data for particulate olfactory polymer C in Table 
III, 70 percent of the polymer is dissolved in the wash cycle with 61 
percent of the fragrance released in the wash/dry cycle. Subjecting the 
same particulate olfactory polymer to a wash and rinse cycle increases 
polymer solution to 95 percent and correspondingly increases fragrance 
release in the wash/rinse/dry cycle to 86 percent. Thus, the effectiveness 
of the particulate olfactory polymer to release fragrance in a laundry 
process is significantly influenced by not only the substitution of a 
water-soluble polymer for water-insoluble polymer in the matrix, but also 
by the ratio of water-soluble to water-insoluble polymer in the matrix. 
EXAMPLE II 
Particulate polymer compositions are prepared with a high-shear Banbury 
mixer system according to the following formulas: 
______________________________________ 
Composition (parts by weight) 
Ingredient A B C 
______________________________________ 
Perfume oil 20 20 20 
LDPE 50 60 20 
EA 30 -- -- 
POLYOX WSR-3154 
-- 20 60 
______________________________________ 
The particulate olfactory polymer compositions of this Example are prepared 
in the manner taught in Example I and a powder having a nominal particle 
size of 250 microns is collected for each sample. 
The particulate olfactory polymers are then admixed with an unperfumed 
heavy duty built granular detergent composition at a weight ratio of 
particulate olfactory polymer to detergent of 1:50. The resulting 
detergent with olfactory polymer particles is placed in a non-woven pouch 
of the type used in Example I. The packets are made up to contain 
sufficient detergent so that the concentration of the detergent powder is 
0.1 weight percent in a Launder-O-Meter washing machine. 
The detergent packets are used in the Launder-O-Meter to wash textile 
fabrics according to a specified method for 40 minutes with hot 
(54.degree. C.) water. After the washing is completed, the packets are 
recovered and the remaining powder is dried in a dessicator for 72 hours. 
This powder is then examined with a scanning electron microscope, and the 
micrographs so obtained are shown in FIGS. 3-8. 
FIG. 3 is a scanning electron photomicrograph (100.times.magnification) of 
a portion of particulate olfactory polymer D containing all 
water-insoluble polymer (LDPE/EVA) in its original form prior to exposure 
to the Launder-O-Meter process. 
FIG. 4 is a scanning electron photomicrograph of particulate olfactory 
polymer D as in FIG. 3 after the Launder-O-Meter wash cycle. 
FIG. 5 is a scanning electron photomicrograph of particulate olfactory 
polymer E of the invention containing 60% water-insoluble polymer (LDPE) 
and 20% water-soluble polymer (Polyox) in its original form prior to 
exposure to the Launder-O-Meter process. 
FIG. 6 is a scanning electron photomicrograph of particulate olfactory 
polymer E as in FIG. 5 after the Launder-O-Meter wash cycle. 
FIG. 7 is a scanning electron photomicrograph of particulate olfactory 
polymer F of the invention containing 20% water-insoluble polymer (LDPE) 
and 60% water-soluble polymer (Polyox) in its original form prior to 
exposure to the Launder-O-Meter process. 
FIG. 8 is a scanning electron photomicrograph of olfactory polymer F as in 
FIG. 7 after the Launder-O-Meter wash cycle. 
The scanning electron micrographs of olfactory polymers D, E and F 
recovered after washing compared to the same olfactory polymers in their 
original state show that although substantially no structural change 
occurs in the water-insoluble polymer matrix (polymer D, FIGS. 3 and 4), 
particulate olfactory polymers E and F of this invention containing the 
water-soluble polymer (Polyox) do indeed change, showing much more 
porosity after the water wash than before (FIGS. 5 and 6 and FIGS. 7 and 
8). This further illustrates, as did Example I, that the water-soluble 
polymer component of the particulate matrix dissolves out, leaving behind 
the water-insoluble (LDPE) skeleton as shown in FIGS. 1A, 1B and 1C. 
While the foregoing description relates to pouches made from nonwoven 
fabrics, it will be apparent from this disclosure that the pouches or 
envelopes for the particulate olfactory polymer can be made of a variety 
of materials, such as synthetic or natural woven textiles, plastic film 
and formed plastic containers having various of the detergent and/or 
bleaching and/or fabric-softening and/or antistatic ingredients in 
different portions of the container. The envelope, pouch, or other 
container is closed so as to retain therein any solid particles of the 
particulate olfactory polymer, or of products therefrom. In any event, the 
container for the particles permits the ingress and egress of liquids so 
that the soluble components of the composition can be released from the 
interior of the container. 
The particulate olfactory polymer particles can also contain other 
functional materials as set forth above. These functional materials can 
comprise separate entities. When extrusion is used to prepare the 
particulate olfactory polymers according to this invention, the functional 
chemical can even be used as a core partially or entirely surrounded by 
the matrix. 
The size of the discrete entities herein can be varied over a range which 
will depend upon the use of the particulate olfactory polymer, the 
specific water-soluble and water-insoluble polymers used, the intended 
rate of release of the olfactory composition, the nature of the use 
environment of the particulate olfactory polymer, and the like. The size 
of the discrete entities in the practice of this invention is smaller than 
the effective diameter of the particulate olfactory polymer, and it has 
been found desirable in some embodiments of the invention that the sizes 
of the discrete entities be from about 50 to about 1000 micrometers. 
It will be understood that the particulate olfactory polymers of this 
invention can be used with a variety of olfactory compositions. An 
olfactory composition is one containing a perfume or other ingredient 
which acts through the atmosphere to provide a physiological or sensory 
effect as generally described herein. The olfactory composition can also 
contain various solid or liquid vehicles, preservatives, coloring agents 
and other adjuvants which augment or protect the ingredients. 
The particulate olfactory polymers of the present invention have been most 
particularly described for use in laundering compositions, but from this 
disclosure it will be apparent to those skilled in the art that the 
particulate olfactory polymers are susceptible of a wide variety of uses 
to provide for the controlled release of olfactory compositions. Thus, the 
particulate olfactory polymers can be used in other detergent and cleaning 
compositons such as dishwasher detergents and shampoos, hair conditioning 
and other cosmetic and personal care compositions, in agricultural 
products for the release of olfactory materials such as pheromones, in 
other cleaning or household compositions such as toilet bowl deodorizers 
which are placed in the water reservoir, as well as in numerous other 
products which benefit from the controlled release of olfactory 
compositions. 
It will be understood from the foregoing that for uses such as toilet bowl 
deodorizers, larger particle sizes can be prepared to effect a gradual 
release of the olfactory composition. Thus, particle sizes up to about 50 
mm can be used. Of course, in this instance, the water-soluble polymer 
will be prepared to form a network thereof in the water-insoluble matrix.