CA1200530A - Process for steady state dispensing of volatile substance from particle into atmosphere and article therefor - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

Described is a process for dispensing at a constant rate, continuously or discontinuously for discrete periods of time, a volatile composition of matter from a container into the atmosphere surrounding said container which volatile composition of matter can be in the alternative, a perfume composition, a deodorant composition an air freshener composition, an insecticide composition, a herbicide composition, an odor masking composition, a pheromone composition, composition for the evaluation of olfactory functioning in humans, an animal repellent composition, or an insect repellent composition as well as a container for use in conjunction with said method which container is a hollow totally enclosed flexible, rigid or partially flexible-partially rigid structure comprising a thin shell totally enclosing an inner void, said thin shell having a base portion and an upper portion, said base portion having an inner surface:

(i) contained totally within said inner void of said thin shell and in place on said inner surface of said base portion, a volatile composition entrapped at least at the instant in time, 00 (t = 0) of commence-ment of the functional operation of said structure, in an entrapment material;

(ii) at least a finite section of said thin shell comprising a porous polymer (which may or may not contain a plurality of finite solid particles, e.g. "filler") said porous polymer having a porosity such that when said hollow totally enclosed structure is located in the ambient environment said volatile material molecules are either (a) adsorbed onto the inner surface of the microporous polymer section and desorbed fromthe microporous polymer from the outer surface of he shell at a substantially constant mass flow rate both of the individual volatile components and totally through such porous polymer section, or (b) transported through the porous polymer shell section by means of capillary action at a substantially constant mass flow rate totally both of the individual volatile components and flowing from said thin shell, the driving force of such molecular transport resulting from a difference in concentration of volatile substance between:

(x) the gas phase of the inner void of said shell; and (y) the space immediately adjacent the outer surface of said microporous polymer shell, the said container containing said film ceases to operate, discretely, when said container is placed in an outer air-tight container. The structure consisting of the two containers; the inner container containing the entrapped volatile substance and the outer container is also a part of our invention.

Basically, our invention involves the aforementioned function as enabled using a polymer shell or film or sheet, monolayer, bilayer or multilayer, (hereinafter referred to as a "membrane") that is defined by having (i) the property of either transporting water vapor at a rate of between about 100 up to 1000 g/m2/day at about 25°C and at about 50% relative humidity at about atmospheric pressure and/or having an air transport rate of 100-20,000 Gurley seconds (Gs); and (ii) a thickness in the range of from about 0.01 mils up to about 20 mils.

Description

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BACKGROUND OF THE INVEN~ION

Our inven-tion provides volatile substance-emittinq apparatus and methods for producing same and for using same wherein the volatile substance can be an air freshener, stan~ard aromati~ing materials, odor maskants, insecticides, insect repellants, animal repellants, herbicides, pheremones and the like. These volatile substances have previously been used with the following delivery systems:
aerosols;
gels;
paper;
felt;
large pore polymers;
powders;
candles; and wick-containing liquids.

With the exception of aerosols, the concentration and rate of release of volatile substance, e.g., perfume, into the atmosphere surrounding the container or emitting apparatus has been a function of the rate of evaporation of volatile material which, in turn, has been a function of the remaining concentration of volatile material in the container or emitting apparatus. Accordingly, the rate of mass transfer (e.g., diffusion in certain instances) of the volatile substance into the surrounding atmosphere has, in the prior art, been "first ~5 oxder", that is, a function of the concentration previously present, e.g.:
~c d- = kc Further~ore, with respect to the apparatus of the prior art there has been no practical way for ascertainment by the user as to whether or not the bulk of the volatile material has been depleted at a particular point in time. In all in-stances it is impossible to determine precisely when the volatile substance is no longer being discharged in an effective quantity andJor concentration per unit time into the atmosphere surrounding the container. In those situations where an aroma is being emit~ed, the actual aroma is usually relatively powerful during the emission notwithstanding the ~20~53~

rate of emission of active agent and said aroma retains its power even after its practical effect (e.g., air freshening) is deminimis.

Thus, in Japanese Patent J8-0036,515 assigned to Akane Soji K K, printings from which fra~rance is qraduallv emitted are indicated to be p~roduced by a process comprisin~
(1) preparing fragrance-emitting ink compositions by dispersing (a) fragrance-emitting bases prepared by mixing perfume solutions with thermoplastic resins at eleva-ted temperatures to homogenize the mixture, followed by cooling the mixture to separate fine particles of gelled resin in which the perfume is occluded in (b) a solution of film-forming material and (2) printing the base material with this fragrance-emitting in~ composition.

Scent-releasing polyurethane foams are shown to be prepared in German published Application 2,945,757 (assigned to the Tenneco Chemical, Inc.). In published Application

2,945,757, it is indicated that a ?olyurethane foam containing a particulatefiller and perfume is prepared by first mixinq the filler with the perfume and adding this mi~ture to a liquid polyol and finally mixing the thus-obtained composition with an organic polyisocyanate, water and a catalyst to produce the resulting foam. It is indicated that the resulting material is used as an air freshener, deodorant, perfume sachet and the like. It is further indicated that the foam releases the perfume at a limited and constant rate. The said published German Application corresponds to U.S. Patent 4,226,944 issued Oll October 7, 1980.

U.S. Patent 4,247,498 issued on January 27, 1981 discloses a method for preparing a homoaeneous microporous cellular polymer structure which evolves perfumes, insect repellants, odor masking agents and the like at a slow and steady rate.
The process of U.S. Patent 4,247,498 comprises (i) heating a mixture oE a polymer which may be an olefinic polymer, con-densation polymer, oxidation polymer or a blend thereof and a "compatible liq~lid" to a t~mperature and for a time sufficient ~q3il~s~

to form a homogeneous solution, (ii) forming at substantially the same time a plurality of liquid droplets of substantially the same size in a continuous liquid polymer phase by cooli.ng the solution, (iii) continuing cooling to solidify the polymer, (iv) then at least partially displating the "compatible liquid" with a perfume, an odor masking agent, an insect repellant or the like. It is indicated at column 15, line 30 of U.S. Patent 4,247,498 that the disclosed system may be used to create a "thin film of about 1 mil or less up to a relatively thick block of thickness of about 2-1/3 inches".

Japanese published Application J5-5081,655 assiqned to Kureha Chernical Industries KK discloses a slow release air aromatizing composition which comprises an aqueous solu-tion of water soluble high molecular weight substance of viscosity 500-30,000 cps such as polyvinyl acetate, carboxy-methyl cellulose, sodium al~inate, xanthan gum, etc.
admixed wi-th an oil soluble perfume or a water soluble perfume.

Nothing in the prior art, however, discloses the novel structure and process for preparing same of our invention wherein a commercially viable structure capable of dispensing at a steady state, at a visibly detectable rate either continuously or discontinuously for discrete periods of time, a volatile composition of matter such as a perfume, an air freshener, an air deodorant or the like,is created.

J 5~3 OBJECTS OF ~HE INV~TION

It is an object of our invention to provide a process for dispensing at a controllable, visibly detectable rate, continuously or discontinuouslv for discrete and controllable periods of time at steady state volatile compositions of matter from a container into the atmosphere surrounding such container.

It is a further object of our invention to provide an apparatus useful for performing the process for controllably dispensing at a visibly detectable rate, continuously or discontinuously for discrete periods of time, such volatile compositions of matter.

It is a further object of our invention -to provide â
process for dispensing at a visibly detectable rate, controllably, continuously or discontinuously for discrete periods of time, a perfume or air freshener or other volatile substance from a container into the atmosphere surrounding said container, so that when the effective volatile composition of matter is depleted, the fact of actual depletion as well as the rate of depletion is easily determinable by a person ~o who views the inner voi.d of t}le apparatus which is instrumental in carrying out the process.

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SUI~'L'`lAl~Y OF THE INVE~TION

Our invention defines a process for dis?ensing in a con-trollable manner at a visibly detectable rate, continuously or discontinuously for discrete periods of time, at steady state ("0 order"), a volatile composition of matter from a container into the atmosphere surrounding the container and apparatus necessary and useful for carrying out this process. The apparatus includes a hollow totally enclosed structure co~-prising a thin shell totally enclosin~ an inner void, the thin shell having a base portion and an upper Dortion, said base portion having an inner surface:

(i) at least a finite portion of the thin shell being transparent whereby that portion of the inner void which is located proximate to the base portion of the totally enclosed structure is visible from outside the -thin shell by a viewer in the presence of visible wavelengths of white light; and visible liaht;
(ii) contained totally with:in the inner void of the thin shell and in place on the inner surface of the base portion, a volatile composition temporarily entrapped in an entrapment material and totally entrapped in the entrapment material at least at the instant in time of commencement of the functional operation`of the structure (that is, when it is removed from an air-tight pac};age); and (iii) at least a finite section of the thin shell comprising a microporous ?ol~mer (preferably containing a plurality of finite solid particles) havinq a porosity such that when the hollow totally enclosed structure is located in an inert qas at a pressure less than or equal to about l atmosphere, the vola--tile material molecules (e.g., the perfume molecules or the air freshener ~olecules) are adsorbed onto the inner surface of the microporous polymer section and desorbed frorn the outer surface of the micro-porous polymer section at a constant linear veloci-ty and at constant total derivative of concentration of volatile substance within said thin shell with respect to time through the rnicroporous polymer section.

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- 8a -The volatile composition of another can be, in the al-ternative, a perfume composition, a deodoran-t composition, ar. air freshener composition, an insecticide composition, a herbicide composition, an odor masking composition, a pheremone composition, an animal repellant composition, or an insect repellant composition.
The base portion of the hollow totally enclosed structure is non-porous and transparent and the upper portion is a microporous polymeric membrane and is opaque at least at the instant in time of commellcement of the fullctional operation of said structure, said base portion being sealed to said upper portion. The upper portion preferably consists essentially of a polyolefin intimately admixed with a powder having an average particle diameter of from about 0.3 up to about 500 microns. The microporous polymer can be a microporous polymeric membrane consisting of a polyurethane foam containing a particulate filler having an average particle diameter of from about 0.3 up to about 500 microns, said polyurethane foam formed by reacting a liquid polyol with at ]east one organic polyisocyanate, water and at least one ca-talyst.
More specifically, the microporous polymer can be a

3-dimensional mi~croporous cellular polymer structure comprising a plurality oE substantially spherical microcells having an average diameter (C) of from 0.05 to 100 microns distributed substantially uniformly throughout the structure, adjacent cells being interconnected by pores smaller in diame-ter than the microcells, the pore size distribution expressed by (S) having a value in the range of from 0.01 to 30 microns, the Naperian base log ratio of the average cell diameter (C) to the average pore diameter (P) having a value in the range of from 0.2 to 2.4 and the Naperian base log ratio of the pore size distribution expressed by (S) to the average cell diameter (C) haviny a value in the range ~6)~S3~
- Sb -of from -1.4 -to 1.0, -the pores and the cells being void at the instant in time of commencement of the functional operation of said structure and the polymer being a synthetic the.remoplastic polymer which is a polymer or copolymer of an ethylenically unsaturated monomer, a condensation polymer, a polyphenylene oxide or a blend thereof.

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g B~IEF DESCRIP~ION OF THE DP~I~IN~,S

Figure 1 is a perspective view of a preferred e~bodiment of the hollow totally enclosed structure of our invention, with the material of fabrication being flexible polypro~ylene film.

Figure 2 is an elevation view of the hollow totally enclosed structure of Figure 1 shown in cross section with the structure fully loaded with temporarily-entrapped volatile substance;.

F'igure 3 is a partial cut-away plan view of the structure of Figure 1 with the structure fully loaded with vo]atile substance immediately prior to functional use thereof.

Figure 4 is a side view of the structure of Figure 1 shown in cross section with the volatile substance completely spent.

Figure 5 is a perspective view of a second preferred embodiment of the structure in accordance with our invention with a hollow cylillder fully loaded i~mediately prior to functional use thereof.

Figure 6 is an elevation view of the apparatus of Figure 1 shown in cross section fully loaded with volatile substance im~ediately prior to functional use thereof, the structure being located within an outer laraer air-tiaht structure, the apparatus containing the entrapped volatile substance not being in functional use.

Figure 7 is an elevation view of the cylindrical apparatus of Figure 5 shown in cross section, with the volatile sub-stance being fully loaded in said structure of Fiqure 5, the structure of Figure 5 contained in a larqer enclosing cylinder which is air-tight whereby the structure of Figure 5 is not in functional use.

Figure ~ is an elevation view of the apparatus of Figure 5 shown in cross section with the volatile substance previously contained in the cylindrical structure having been fully dep]eted.

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Figure 9 is an elevation view of another preferred embodiment of our invention, shown in cross section with the volatile substance contained in the structure of our invention being fully loaded in said structure immediately prior to use.

Figure 10 is an elevation view of the structure of Figure 9 shown in cross section with the entrapped volatile substance previously contained in said structure having been fully spent.

Figure 11 is a perspective view of a structure in accord-ance with our invention where multiple structures (as the individual structure of Figure 1) are connected to one-another at locations midway between the base portions of each of said structures and the upper portions of each of said structures and along at least portions of the circumferential sealed edges of each of said structures which are sealing the upper portion of each of said structures to the base portion of each of said structures.

Figure 1~ is an elevation view of the structure of Figure 11 shown in cross section with each of the individ~al structures of the inter-connected plurality of structures being fully loaded with volatile substance immediately Drior to functional use thereof.

Figure 13 is an elevation view of the apparatus of Figure 11 shown in cross section with each of the inter-connected structures of the structure of Figure 11 fully loaded with volatile substance prior to use, the plurality of inter-connected structures being contained in an air-tight sealed enclosure structure which has a volume greater than the volume of the plurality of inter-connected sealed structures.

Figure 14 is a plan view of the plurality of inter-connected structures of Figure 11.

Figure 15 is an elevation view of the structure of Figure 11 w~ich is actually a plurality of inter-connected structures (as the individual structure of Fisure 1)~ with each of the individual structures containing s?ent volatile sub-stances immediately subsequent to the last functional use of said structure.

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Figure 16 is a perspective cross-sectional view of the structure of Figure 11 rolled u~ and placed in an air-tiqht cylindrical outer-container when not being used.

Figure 17 is a perspective view of another preferred embodiment of our invention wherein a plurality of hollow totally enclosed structures are laterally and detachablv inter-connected and have a common midplane ~ith each of said structures being connected to at least two other of said structures at a location midway beiween the base portion of each of said structures and the upper portion of each of said structures and along at least a portion of the circumferential sealed edges of each of said structures sealing said upper portions to said base portions. In the embodiment as set forth in Figure 17~ the shape of the individual structures is "heart"-shaped rather than ellipsoidal in shape.

Figure 18 is a series of graphs of percent volatiles lost versus time comparing the functional use of structures as illustrated in Figure 1 containing temporarily-entrapped volatilizable substance tair freshener),not containing volatilizable substance (but replaced by ethanol, per se) and standard commercial air fresheners of the ~rior art as defined according to United States Letters Patent No.

4,014,501. The graphs are more particularly described in Examples I and II, infra.

2S Fiqure 19 is a comparative graph showing percent fraqrance loss versus time for a structure containing air freshener-containing volatilizable substance as set forth in Fiaure 1 versus the same volatilizable substance (air freshener con-tained in a gel) in the absence of said structure of our invention. (The graph is more particularly described in Example III, infra.) Figure 20 represents a graph of rate of fragrance loss versus time for the structure of Figure 1 for up to one month of use.

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Figure 21 represents an operational graph oF rate of fragrance loss versus ti3ne for a struc-ture as shown in Figure 6 wherein the structure of our invention is removed from an outer container for operation and then replaced in the outer container when not in use and the outer container is resealed when not in use. Figure 21 indicates three separate use (followed by storage) periods for the struc-ture of Figure 6.

Figure 22 represents a graph of rate of fraqrance loss versus time for the entire period of possible continuous use of the structure of Figure 1 assuminq that the structure of Figure 1 is not replaced at discrete ti.me intervals in an enclosed air-tight outer container.

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DETAILED DESCRIPTIO~ O~ ~HE I~IVENTION

The process of our invention comprises dispensing at a visibly detectable rate continuously (as illustrated in Figure 20) or discontinuously for discrete periods of time (as shown in Figure 21) at steady state a volatile composi-tion of matter 3 from a container, e.g., as represented by reference numeral 50n in Figure 1 into the atmosphere surrounding said container. The steps of this process are examplified using structure 500 as follows:

(a) entrap~ing a volatile composition of matter whi.ch may be a perfume composition, an air fresheninq composition, a deodorizing composition an animal repellant composition, an insect repellant com~osi-tion, an insecticide, a herbicide or a pheremone composition or the like in an entrapment agent whereby a temporarily entrap?ed volatile composition 3 is formed;
(b) providing a first thin shell section 4 composed of a thin polymeric shell having a curved surface and having an inner void portion, an inner surface and an outer surface and having a first sealable continuous circumferential edge and a first geometric configuration;
(c) placing the entrapped volatile composition 3 in the inner void portion of the first thi-~ shell section and onto the inner surface of the first thin shell section 4;
(d) providing a second thin shell section 2 having a second sealable circumferential edge and a shape and volume which are such that when said second . circumferential edge is placed in conforming adjacent edgewise contact with said first sealable circumfer-ential edge, a totally enclosed shell structure 500 is produced wi.th said entrapped volatile composition 3 being totally enclosed within said shell structure leaving a void 6 bet~Jeen sai.d second thin shell section 2 and said volatile substance 3;
(e) placing said second thin shell section 2 havinq a second sealable continuous circumferential edge which substantially conforms in shape to said first sealable circumferential edge onto said first thin :~2~53g3 shell section 4 whereby said ~irst sealable edge is in closely fitting sealable proximi~y with said second sealable edge at location l;
(~) sealing said first sealable edge to said second sealable edge at location 1 whereby the resultan~
shell structure enclosing said volatile composition 3 is air-tight except for mass transport of volatile substance through the polymer wall (by adsorption therefrom from void 6 and desorption therefrom into the surrounding atmosphere) with at least a finite section of preferably the second thin shell section being a microporous polymer having a porosity such that when the hollow totally enclosed structure, now sealed, 500, is located in an inert gas at a pressure of less than or e~ual to about 1 atmosphere, said volatile material molecules diffuse at a con-stant linear velocity and at a constant total derivative of concentration of volatile substance with respect to time throuqh said micronorous polymer section;
(g) optionally, at time intervals of non-use, or for storage purposes, placing the entire shell structure 500 into an outer container 7 which may or may not be transparent and sealing the opening of the outer container at 8 whereby the outer contai.ner 7 is air-ti~ht.

The outer container 7 prevents the escape of the volatile sub-stance from the entrapment medium into the atmosphere prior to the desired operation of the shel.l structure and during storage thereof. The outer container 7 has a volume greater than the shell structure which is the functional portion of the apparatus of our invention. The outer container may or may not be transparent or it may be ?artially transparent.

Examples of the aforesaid microporous polymer compositions of matter are as follows:

(a) ~icroporous polymers prepared, for example, according to Canadian Patents 1,021,916 or 1,039,911 and U.K.
Patent 1,414,785 manufactured by ~oninklijke Emballaae Industrie Van Leer B.V. of Amstelveen, ~2~ $3(~

The Netherlands, or example, disclosing a m.icroporous film containing talc having the following specifications:
Composition Polypropylene + filler Thickness 100 + micrometers Weight _ 9O g/m2 Ultimate tensile 30 MN/m2 (machine direction) strength 11 MN/m (transverse cirection) Elongation at break 180% (machine direction) 350% (transverse direction) Pore size 0.2 micrometers (max) Void volume .34 cm3/g (30~) Density - 900 kg/m Air flow 3 cm /cm2/min at 1 kg/cm2 Water flow 0.001 cm3/cm2/min at 1 kg/cm2 Air resistance (Gurley) 104 secs.

Water vapour trans- 150 g/m2/24 hrs at 23C
mission 50-~ rh Thermal stability 10 hrs at 130 C;
(b) Thin microporous films produced fxom Surlyn resin as described in Examples 362, 363, 364, 365 and 366 at columns 45 and 46 of United States Patent 4,247,498;
(c) A microporous polymer membrane produced according to Example 10 of U.S. Patent 4,226,944 which is a polyurethane resin containing a particulate filler except that the fragrance set forth therein is not initially (prior to functional use) contained in the microporous polymer shell, but is only initially (prior to functional use) contained in the porous retention entrapping sponge or gel 3 in Figure 2;
or 11 in Figure 5; or 19 in Figure 9;

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15.1 (c-bis) A microporous polymer prepared according to United States Patent 4,429,714, the abstract for which is set forth below:

UNIW* D16 01549 D/02*~S4239-714 Modi~fying pore size distribution of microporous sepn.
medium - by immobilising a pore blocking agent of known molecular size in the pores UNIV OF WA~HINGTON 15.11.78 US-960745 A96 JOl (16.12.80) B29d-27 15.11.78 as 960745 (6ppl302) The pore size distribution of a microporous sepn medium (I) is modified by filling its pores with a volatile liq. A controlled amt of the volatile liq is evaporated to lower the level of the liq within the pores to below the bulk surface of (I) and thereby form voids at the entrances to the pores.
A conc. soln of a pore blocking agen-t is applied to the bu]k suriace oE (I). The pore blocking acJent is insoluble in the volatile liq and capable of being insolubilised in its soln. Its molecular size distribution has a predetermined lower limit so that it only enters pores larger than that. Excess pore blocking agent is removed from the surface of (I) that which remains is insolubiulised to immobilise it in the pores.
The pore blocking agent obstructs the entrances to all pores larger than a certain size so that (I) has a sharp cut-off in the max molecular size it passes. (I) can be a polymeric membrane or chromatographic gel used to separate proteins, enzymes, viruses and immunological active fragments by ultrafiltration, dialysis, e]ec-trodialys;s, electrophoresis or gel perrneation or gel exclusion chromatography.

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(d) A membrane produced according to Japanese A~plication J5-5081,655 assigned to Kureha Chemical Industries KK
and published on June 19, 1980, containing a water soluble polyvinyl alcohol having a molecular weight of 12,000, intimately admixed with xanthan gum, the ratio of polyvinyl alcohol:xanthan gum being 6:4 (weight:weight);
(e) A cyclodextrin microporous film containing activated silicate as prepared according to Japanese published Application J5-5078,965 assisned to Kokando KK and published on June 14, 1980;
(f) A microporous polyurethane specifically as described in German Offenlegunysschrift 2,324,31~ published on November 29, 1973 and assigned to Teijin Cordlev Ltd. (abstracted in Chem. Abstracts Volume 81, 1974 at section 45~9u).

Insofar as the microporous film is concerned, it is preferred that a filler bè incorporated therein havina an average particle size of from about 0.3 Up to about 500 microns.
In the event that a filler is not contained, the pore size of the microporous polymer must be smaller than if a filler is contained by 3 or 4 orders.

Particulate or pulverulent fillers which are useful in the practice of this invention include, but are not limited to, clays, including both untreated clays and those which have been surface-treated in various ways well known in the art, ground limestone, talc, precipitated calcium carbonate, including surface-treated types, alumina, aluminium silicate, barytes, wollastonite or other calcium silicate, silica, zirconia, titanium dioxide, soap and synthetic detergents in solid form.

The synthetic detergent can be, for example, an alkylaryl sulphonate detergent, such as a sodium alkyl benzene sulphonate ox sodium alkyl naphthalene sulphonate. ~here the sulphonate used is an alk~l benzene sulphonate, the benzene ring of the sulphonate referably has only 1 allyl substituent and such substituent contains from 8 to 18 carbon atoms. Among such alkyl benzene sulphonates are sodium linear dodecylbenzene ~2~)~53~3 sulphonate, sodiu~ tridecylbenzene sulphonate and sodium nonylbenzene sulphonate. On the other hand, where the sul-phonate used is an alkyl naphthalene sulphonate, the naphthalene ring of the sulphonate preferably has 1 or 2 alkyl substituents and the total number of carbon atoms in the alkyl substituents is from 3 to 10. Among such sulphonates are sodium monoiso-propylnaphthalene sulphonate, sodium diisopropylnaphthalene sulphonate, sodium diamylnaphthalene sulphonate and sodium monocaprylnaphthalene sulphonate. The sulphonates in solid form are commercially available in 40~ to 90~ by weiaht active ; form, the rest being predominantly sodium sulphate. In practicing the present invention, it is preferable to use the 90~ active form, which is the highest available com~lercially, but other formscan also be used.

Useful clay fillers are described in U.S. Letters Patent 3,080,256 and are compositions which can be prepared by a procedure involving coating kaolin with a small amount ~for example, from 0.2% to 2~ by weight, based on the weight of the kaolin) of a polyamine, e.g. ethylene diamine, hexamethyl-ene diamine/ tetraethylene diamine, diethylene triamine, tetraethylene pentamine and guanidine.

Other useful clay fillers are describea in U.S. Letters Patent 3,151,993 and can be prepared by a procedure involving coating kaolinite particles with aluminum hydroxide precipitated in situ at a pH from 7.5 to 9. We prefer to use clay, limestone, soap, linear dodecylbenzene sodium sulphonate, combinations of clay and linear dodecylbenzene sodium sul-phonate, or combinations of clay and soap. Other particulate or pulverulent fillers can also be used. The only limitations are that the fillers should not adversely affect or react with the aromatizing substance or entrapping material entra~pinq the aromatizing substance used or absorb the aromatizina material to such a degree that release from the microporous polymer is unduly inhibited or entirely prevented. Although the particle size of the filler can be varied over a wide range, 0.3 microns up to 500 microns, extremely coarse particles are generally undesirable because they may detract from the aesthetic qualities of the finished microporous polymer.

The amount of filler can be varied over a wide range depending on the amount of volatilizing material to be released from entrapped volatilizable substance 3 and the viscosity of the aromatization material which is adsorbed onto and desorbed from the microporous polymer. We have found that filler levels in a range of from S to 100 parts by weight per 100 parts of polymer are generally satisfactory, although greater or less amounts can be used if desired.

Any type of aromatizing substance, e.g., air freshener, can be used in the practice of this invention provided that it does not react with any component of the microoorous polymer or polymer or other substance used ln fabricating the outer shell of the structure of our invention. Fragrances are usually c~mplex mixtures and no component of the desired fragrance should be reactive with any component of the microporous polymer or any other component which is used to fabricate the shell structure of our invention.

Insofar as the microporous film produced in accordance with United States Patent 4,247,498 is concerned, this microporous film is produced by heating a mixture of synthetic thermoplastic polymer which may be a polymer or a copolymer-of an ethylenically unsaturated monomer, condensation polymer, poly-phenylene oxide or a blend thereof and a compatible liquid to a temperature and for a time sufficient to form a homogeneous solution; allowing the solution to assume a desired shape (in this case, film or thin shell polymer) and cooling the solution to initiate liquid-li~uid phase separation and foxm at substantially the same time a plurality of liquid droplets of substantially the same size in the continuous liquid polymer phase, continuing the cooling to solidify the polymeric film and removing substantially all of the liquid resulting to form a polymer structure which is a three-dimensional microporous cellular structure comprising a plurality of substantially spherical microcells having an average diameter (C) from about 0.05 to about 100 microns ~more preferably 0.05 to 15 microns) distributed substantially uniformly throughout the structure, adjacent cells being interconnected by pores smaller in diameter than the microcells, the pore size distribution expressed by S having a value in the range of from 0.01 to 30 microns, the log ratio ~Naoerian base) of the average cell ~oa~s3~

diameter (C) to the average ?ore diameter (P) having a value in the range of from 0.2 to 2.~ and the log ratio (Naperian base) of the pore size distribution expressed by (S) to the average cell diameter (C) having a value in the range of from -1.4 up to 1.0, the pores and the cells being a void and the polymer being a synthetic thermoplastic polymer which is a polymer or copolymer of an ethylenically unsaturated monomer, a condensation polymer, a polyphenylene oxide or a blend thereof. Preferably, the polvmer phase and compatible liquid have intimately admixed therewith the aforedescribed filler in proportion ranges stated, supra.

When the structure of our invention is ready to be used in dispensing at a steady state, and at a visibly detectable rate continuously or discontinuously for discrete periods of time from container 500, the container 500 is removed from outer container 7 and maintained in an~ convenient area or 3-space. Figure 4 illustrates the container 500 in cross section after the entrapped volatile material is totally depleted as a result of the steady state mass transport of the volatile substance through microporous polYmer section of a portion of the container wall, e.g., preferably wall_2. The fully depleted substance is shown in Figure 4 as indicated in reference numeral 5.

If desired, as an additional embodiment of this invention, each of the shell structures of our invention may be inter-connected as shown in Figures 11, 12, 13, 14, 15, 16 and 17 as structures 504,505 and 506. Thus, a plurality of hollow totally enclosed structures, having upper portions 23A, 23B, 23C, 23D, 23E, 23F, 23G, 23H and 23J are laterally and _ _ _ _ _ detachably interconnected,having a co~mon midplane 22A, each of said structures being connected to at lease two other of said structures, for example in structure 504, at a location midway between the base portion of each of said structures and the upper portion of each of said structures, with the base portion and upper portion of three of said interconnected structures shown in Figure 12, to wit: the upper portions as 23C, 23D and 23J and the lower portionsshown as 29C, 29D and 29J.

:12~ 3(~

In constructing such a structure as structure 504 in Figures 11, 12, 13, 14, 15, 16 and 17, the upper polymeric portion containing upper portions 23A, 23B, 23C, 23D, 23E, 23F, 23G, 23H and 23J having a sealable circumferential edge 22A is sealed to a diametrically opposed lower portion con-taining such lower portions as 29C, 29D and 29J at sealable circurnferential edge 22B with sealable circumferential edges 22A and 22B being in closely fitting sealable proximity with one another whereby when they are sealed, an air-tight connection is produced with the only means of ingress and egress from the voids 27C, 27D and 27G for the volatile substances contained in _6C,_6D and 26J being through microporous polymer sections in upper shell portions 23C,_3D, 23J and the like, and/or lower portions 29C, 29D and 29J and the like.

When such a structure as structure 504 as illustrated in Figures 11, 12, 13, 14, and 15 are produced, they may be stored while not in use in a container such as container 24 as illustrated in cross section in Figure 13 or they may be rolled up and stored in container 505 as illustrated in Figure 16. Conveniently, the container 505 in Figure 16 is cylindrical in shape and has a closure which is in the form of a screw top which may be easily removed and replaced for the purposes of storing structure 504 while not in use. I~hen structure 504 is stored while not in use, the pressure within container 505 and without structure 504 and within structure 504 is equalized so that during storage no mass transfer from such entrapped volatile substance material as 26C, _6D and 26J takes place into the outer atmosphere.

~fter the structure 504 is removed from the outer container such as container 24 or container 505, it is then placed in an appropriately convenient place and the volatile substance is depleted from such substances as 26C, 26D and 26J until such point as the totally depleted substance is visible from without structure 504 and is shown to be depleted as illustrated in Figure 16 (asreference numerals 28C, 28D and 28J). Thusly, the void 27C~ 27D and 27J is fully visible l'rom outside the structure in the presence of the visible wavelengths of-light (e.g., white light) so that the depleted substance 28C, 28D
and 28J whether it be a gel or microencapsulated material or sponge material, is easily visible.

~Z(3~J~53~

Figure 17 illustrates a variation of structure 504 as structure 506 wherein the individual structures may be separated for individual use at 507, with the shape of the upper portion of each of the individual structures indicated as a "heart" shape at 50~.

Comparative operation of structure 500 with perfumed fragrance entrapped material or ethyl alcohol entrapped material at 3 with material 3 in prior art apparatus (e.g., that described in U.~. Patent 4,014,501) is set forth in Figure 18. The graphs shown by reference numerals 201 and 203 represent the o~eration of structure 500 (percent volatile sub~
stance loss versus time) without any perfume material contained within the entra~ped volatile substance 3 but only containing ethyl alcohol entrapped in ~el 3. The graphs shown by reference numerals202 and 204 (percent per~ume lost versus time) indicate the rate of release versus time using structure 500 when employing 2% fragrance in a gel indicated by reference numeral 3 with the microporous polymer in structure 500 for reference numerals 201, 202, 203 and 204 being that described in Canadian Patents 1,039,911 and 1,021,916 and U.K. Patent 1,414,785 whereby specially compounded poly-propylene film with talc is used, having the following specifications:
Composition Polypropylene + filler (talc~
Thickness 100 - micrometers Weight _ 90 g/m2 Ultimate tensile strength 30 MN/m2 (machine direction) 11 MN/m2 (transverse direction~
Elongation at break 1~0% (machine direction) 350~ (transverse direction) Pore size 0.2 ~micrometers (max) Void volume .34 cm3/g (30 Density - 900 kg/m Air flow 3 cm3 /cm2/min at 1 kg/cm2 Water flow 0.001 cm3/cm2/min at 1 kg/cm~
Air resistance (Gurley) 10 secs Water vapor transmission 150 g/m2/24 hrs at 23C 50% rh Thermal stability 10 hrs at 130C

as manufactured by Koninklijke Emballage Industrie Van Leer B.V. o~ Amstelveen, The Netherlands.

, ~ ' 53(3 In each of the graphs wherein perfurned material is used, it is apparent that for the major portion of the useful life of the structure, e.g., structure 500, the rate of mass transport of perfume substance, when in use, is "0" order, that is:
dc - k dt wherein k is a constant.

Discussion covering the preparation of the compositions of matter which constitute the fragranced gels and unfragranced gels whereby the graphs as represented by reference numerals 201, 202, 203, 204 and 205 of Figure 18 are prepared is set forth in Examples I and II, infra.

By the same token, in Figure 19, the graph indicated by reference numeral 302 indicates percent fragrance loss versus time for an air freshener gel containing 2~ by weight fragrance but not enclosed in a structure defined according to our invention. It will be noted that the diffusion of the air freshener is in accordance with ordinary diffusion laws and is not steady state, to wit:

~C, I~aoc,~ l~C"~ /~C~
_ = D~ J + ~ .2 J ~+ ~

On the other hand, the graph indicated by reference numeral 301 in Figure 19 is for the same air freshener gel 3 containing 2% by weight fragrance (as more particularly described in Example III) located in the thin shell structure of our invention as illustrated in Figures 1, 2 and 3. The depleted air freshener gel is shown by reference numeral 5 in Figure 4 (the depletion being at the end of a 55 day period as shown on the graph indicated by reference numberal 301 in Figure 19).

Figures 20 and 21 show, res~ectively, continuous and discrete usages of the shell structure as illustrated in ~igure 1. Figure 20 is a graph of dt versus time; wherein during the first five minutes of operation, the mass transfer rate is described as "unsteady state" until a "steady state"
condition is reached wherein ddt is a constant for at least one month (until de~letion as shown in Figures 4 and-8).

In Fig~lre 21, dt is a constant after the first five minutes of usa~e until the time tl-at the shell structure of our invention as shown in Figure 1 is placed into an outer contain-er as shown in any one of Figures 6, 7 or 16.

Fiyure 22 is a graph of dt versus time wherein the ~eriod ... ..
of from to to tl is a condition of "unsteady state" mass transport (usually no more than a few minutes) and the period from tl to t is a condition of "steady state" mass transport; a very long period of time, e.g., 55-75 days and even longer.

The "steady state" adsorption/desorption of volatile substance mass transport mechanism onto and from the mi.cro-porous polymer section of the shell structure of our invention may be set forth i.n the form of a mathematical model as taught by Adamson "Physical Chemistry of Surfaces" Second Edition, Interscience Publishers, 1967, as follows:
n2'(appare~t)=nO~N,7 rS~ = (n'/2)(AT2'--N:~) r2~ )tn2~/n~--Tl2'/n') rl'= (~/2)(N,- NaT)=TIo~N~

r2 = Tlo~ 2 /~-- = (~2 N~ A 2 )/~

1 + (A--l)Ars r2'=(n~/2) (K - I).N,AT2 1 + (~

A',N:/7-~N, = I/n'(K -- I) ~ (l/n~)Ars 2r2l = nS'--n~'(Ar2/N~) = n'(l~a'--N~'~r2/NI) 2r2~ = ~nlN~)(N2' -- N2) rl = r2~ N2 r~ = t~ N~ l)AT2]~

0 (K - I)NINJl1 + (K - 1)N~ ~ l)NIA~J(N~ + KNI) D = ~'N2/(ATI J~ h'~ )--N:

~(3~53~) wherein the -terms with the superscript "s" refer to components in the adsorbed layer and the terms with the superscript "1"
refer to terms in solution; the terms with the subscript "1"
refer to a "First" component and the terms with subscript "2"
refer to a "second" component; with "N" referring to mole fraction and "n" referring to number of moles and with ,~
being indicative of "surface excess"; "~" being indicative of equilibrium constant and representing the sum total of the moles on the adsorbed layer.

Another e~bodiment which is preferred for the practice of our invention involves the use of a rigid rather than flexible polymer in forming rigid cylindrical containers useful for the process of our invention as illustrated in Figures 5, 7, 8, 9 and 10~

The process of our invention for dispensing at a control-lable and visibly detectable rate, continuously or discontinu-ously, for discrete periods of time a volatile composition of matter from a cylindrical container 501 into the atmosphere surrounding the container in this particular e~bodiment comprises the steps of:
A. Entrapping the volatile composition of matter, e.g., perfume, in an entrapment agent (the entrapped material being indicated by reference numeral 11) whereby a temporarily entrapped volatile comPos,tion is formed;
B. Placing the entrapped volatile composition 11 within cylinder 501 (that is, a first thin shell section thereto). The top of the cylinder 101 and the bottom of the cylinder 102 may be fabricated from a trans-parent non-porous polymer (that is, a polymer which is not porous to the volatilizable substance) whereby the inner void of the cylinder can be viewed from the

5~3~

-~5-outside of the container so that one can easily ascertain when the entrapped volatile substance, 11 is depleted (as shown by reference numeral 16 in Figure 8), The side wall of the cylinder 12 may be fabricated from a microporous polymer such as that described in Canadian Patent 1,039,911 or United Kingdom Patent 1,~14,785 assigned to Koninklijke ~mballage Industrie Van Leer B.V. or can be produced of microporous polymers which are laminated such as that described in Israel Patent 52650 assigned to Koninklijke Emballage Industrie Van Leer B.V. wherein, for example, -the polymer is microporous and con:tains a talc filler.

When not in use, the cylinder 501 containing entrapped volati]e substance 11 is preferabl~ nlaced in an outer cylindrical container 502 as shown in Figure 7. The outer cylindrical container is referred to by reference numeral 502 in Figure 7. The outer cylindrical container has a removable cap _ which may be screwed at 103 into the lower portion 13_ _ of said outer container 502. ~Jhen the cylinder 15 is in use, the screw top 1~ is removed and the inner container 15 containing the entrapped volatile composition 11 may remain in place within the outer container 502 or may be removed to a more convenient location for use. Not all of the side wall 12 need be fabricated of microporous polymer. Indeed, merelv the upper third or the up~er quarter or the lower quarter of the side wall or even the top or the bottom of the cylindrical container may be fabricated from micro~orous polymer, the remainder of the container 15 shell being fabricated using a transparent substance which is rigid or flexible or using a silicate or quartz glass.

~other embodiment of the cy]indrical hollow structure which is illustrative of our invention is set forth in Figures 9 and 10 wherein the upper portion of the cylindrical structure 17 may be screwed into the lower portion of the structure 18 at screw threàds 20. Thus, structure 503 containing volatile substance 19 may be manufactured in a form which is reusable wllen the volatile substance 19 is depleted down to the remaining depleted gel (or other entrap~ent substance) 21 as indicated in Fisure 10. Con-veniently, lower portion 18 may be fabricated from a trans-parent substance such as transparent rigid polypropylene or glass and upper portion 17 may be fabricated from microporous polyurethane or polypropylene containing talc and may be perpetually opaque or opaque only when cylinder 503 is not in use. Thus, when volatile substance 19 is depleted down to depleted substance 21 (as illustrated in Figure 10), the upper portion 17 of cylinder 503 in Fiqures 9 and 10 may be temporarily removed and additional substance 19 may be added to the lower portion 18. Structure 503 in Fi~ures 9 and 10 may then be replaced into a larger cylinder to form a structure such as that illustrated in Figure 7, the purpose of which is for storage; until it is decided to reuse the structure 503.

The rate of mass transport of volatile substance from cylinder 501 or from cylinder 503 is over substantially the entire period of presence of volatile substance in entrapment composition, "steady state" or constant. Thus, altho~h the general mass transport equation is:

N ~ =--D,~
~y wherein NA is the molar rate of mass transport per unit area;
DAB is the "diffusivity" of A in B, a physical property of the volatile vapor and the adsorbing polymer, CA is the molar concentration of A in the void s~ace immediately within the shell; and y is the thickness of the adsorbing and desorbing polymer. For the purposes of our invention NA is a constant and is not a function of time during the operation of the hollow totally enclosed structure of our invention. Indeed, when operating in several directions, the equation for mass transport of volatile substance is:

~J ~( L~'- )~ ~ ( ~- )ZV~

wherein ~C{ is a constant.
a~

* * * * *

~Z(3li'530 The following examples serve to illustrate embodiments of our invention as it is now preferred to practice it with reference to using air freshener/perfume compositions in conjunction with the hollow totally enclosed structures of our invention as illustrated Figures 1, 5, and 9. It will be understood that these examples are illustrative and that the invention is to be restricted thereto only as defined in the appended claims.

EXAMPLE I

Into compartment 6, onto surface 4 of the structure 500 illustrated in Figures 1, 2 and 3 is placed a composition prepared as follows: 3.0 parts by weight of Carbopol ~ 940 (manufactured by the B.F. Goodrich Company) (see Note 1) is sifted into the vortex of rapidly stirring water (88.8 parts by weight) containing 0.2 parts by weight of methyl ~araben. The mixing is continued until a smooth clouay dispersion is formed.
2.0 parts by weight of a perfume co~position (see Note 2) is ~ added to the prepared slt~rry and the slurry is continued to be mixed until the perfume composition is dispersed. The slurry is then neutralized with 6.0 parts by weight of diisopropanol-amine (50% solution in water) using slow mixing to avoid the inclusion of air. The structure 500 is then sealed along the circumferential edges at location 1 as shown in Fi~ures 1, 2 and 3 and use of the structure resulting therefrom is shown in accordance with the graph referenced by reference numeral 202 in Fiqure 18. When instead of the perfume (Note 2), only _ ethyl alcohol is used as the volatilizable material, the operation of structure 500 is in accordance with the graph indicated by reference numeral 201 in Fi~ure 18. It will be noted that for periods of use, structure 500 operates at steady state very soon after (5 minutes) use is commenced.

* * * * *

Note 1: Carbopol ~ 940 is ~roduced by the B.F. Goodrich Chemical Company of 3135 Euclid Avenue, Cleveland, Ohio. It is identified as a carboxyvinyl ?olymer of hiqh molecular weight.
Note 2: The formulation of the fragrance is as follows:
IngredientsParts by Weight Para cresol ~lethyl jasmonate 100 Acetyl methyl anthranilate 20 Farnesol 4 -Cis-3-hexenyl benzoate 30 Nerolidol 30 Indol 15 Eugenol 20 Benzyl alcohol 40 53(~

Ingredients Parts by Weight Methyl linoleate 40 Jasmin lactone 20 Dihydromethyl jasmonate 10 Linalool 150 Benzyl acetate 400 Abietyl alcohol 150 Cis jasmone 150 * * * * *

, .
The evaporating surface in hollow structure 500 is 8 square inches; and the weight of entra?ped volatile substance 3 is 30 grams.

EXAMPLE II

3.0 parts by weight of Carbopol ~ 940 (manufactured by the ~.F. Goodrich Company) is sifted into the vortex of 44.4 parts rapidly stirring ethyl alcohol and 44.4 parts of distilled water. Mixing is continued until a smooth, cloudy dispersion is formed. 2.0 parts by weight of the perfume of Example I is then added to the prepared slurry and mixing is continued until the perfume is dispersed~ The slurry is then neutralized with 6.0 parts by weight of diisopropanolamine (50~ solution in water) using slow ~ixing to avoid inclusion of air. The resulting gel is then placed into cylinder 501 of Figure 5. The use of this air freshener cylinder is in accordance with the graph indicated by reference numeral 204 in Fiyure 18. ~ithout the use of the perfume composition of Example I, the cylindr,ical shell of Figure 5 operates in accordance with`the graph indicated by reference numeral 203 in Figure 18~ In both cases, the ~ercent volatiles lost during Example I (but using ethanol, instead), the cylindrical shell of Figure 5 operates in accordance with the graph indicated by reference numeral 2 in Figure 18. In both cases, the percent volatiles lost during operation of the cylinder 502 is in accordance with a steady state mass transport mechanism can be observed from the graphs 201, 202, 203 and 204 of Figure 18.

'53~

When the gel of this example is simply used in a commer-cial air freshener (in the air freshener of ~.S. Patent 4,014,501), the mass transport mechanism is "unsteady state"
in accordance with the graph indicated by reference numeral 205 in Figure 18.

EX~IPLE III

83.45 qrams of distilled water is heated to 85C. With rapid agitation on a propeller type mixer, Gelcarin ~ AFG-15 (carageenan prepared by the ~arine Colloids Corporation) is dispersed in the water. 3.50 grams of glycerine is slowly added to the carageenan dispersion. The mixture of glvcerine and carageenan is then reheated and combined with 2.0 parts by weight of the perfume composition of Example I and 8.00 parts by weight of Tween ~ 80 (a trademark of I.C.I. America) (see Note 3). 0.05 parts by weight of formaldehyde is then added to the resulting mixture slowly and the resulting material is then poured into the cylinder of Figure 9. It is material is then poured into lower portion 18 of cylinder 503 of Figure 9. The lower portion 18 of cylinder 503 is then sealed at 20 with upper portion 17 and placed in use.

The graph indicated by reference numeral 301 indicates the length of time of usefulness of the resulting cylinder;
a "steady state" mass transport mechanism for the use of cylinder 503 as an air freshening apparatus.

When the composition prepared above is used in accordance with a standard air freshener packa~e (per U.S. Patent 4,014,501),the rate of fragrance loss is shown in accordance with the graph indicated using reference numeral 302 in Fiaure 19 (an unsteady state mass transport mechanism rather than the steady state mass transport mechanism of graph 301 in Figure 19).

* * * * *

Note 3: Tween ~ 80 is a mixture of oleate esters of sorbitol and sorbitol anhydrides consisting predominantly of 12(3~530 the monoester condensed with approximately 20 moles of ethylene oxide in accordance with the formula:
MO(CH,CM,O~ (OCIl,Ct~",OM
o ct~--loCH~Ct1~rOH R
CH,--(OCH,CH,) O--C~CM,),u1=CH(c11~.CH, wherein w ~ x + y + z has an avera~e value of 20.

,--~2~53~) - 32 ~
SUPPLEMENTAR~ DISCLOSURE

It is a further object of our invention to provide a process for dispensing at an approximately constant rate, continuously or discontinuously for discrete and controllable periods of time volatile compositions of matter from a container into the atmosphere surrounding such container enabled by the use of a polymer shell or film or sheet, monolayer, bilayer or multilayer ("membrane") that is defined by (i) having the property of either transporting water vapor at a rate of between about 50 up to about 1000 g/m2/day at about 25C and at about 50~ relative humidity at about atmospheric pressure and/or having an air transport rate of 100-20,000 Gurley seconds (Gs);
and (ii) a thickness in the range of from about 0.01 mils up to about 20 mils.
Our invention utilizes a polymer shell or film or sheet, monolayer, bilayer or multilayer (thereinafter referred to as "membrane") that is defined by having (i) the property of either water vapor at a rate of between about 50 up to about 1000 g/m2/day at about 25C and at about 50% relative humidity at about atmospheric pressure and/or having an air transport 20 rate of 100-20,000 Gurley seconds tGs); and (ii) a thickness in the range of from about 0.01 mils up to about 20 mils, for enabling a process to take place for dispensing in a controllable manner at a constant rate, continuously or discontinuously for discrete periods of time at substantiallysteady state ("0 order") over an extended period of time a volatile composition of matter from a container into the environment surrounding the container. Our invention also defines an apparatus necessary and useful for carrying out this process. The apparatus includes a hollow totally enclosed structure comprising a thin shell totally enclosing an inner void, the thin shell having a base portion having an inner surface:

~-, :~2~ 3~

(i) contained totally within the inner void of the thin shell a volatile composition (which may optionally be temporarily entrapped in entrapment material and totally entrapped in the entrapment material at least at the instant in time of commencement of the functional operation of the structure --- that is, when it is removed from an air-tight package);
and (ii) at least a finite section of said thin shell compxising a porous polymer that is defined by (i) the property of either transporting water vapor at a rate of between about 50 up to about 1000 g/m2/day at about 25C
and at about 50~ relative humidity at about atmospheric pressure and/or having an air transport rate of 100-20,000 Gurley seconds (Gs); and (ii) a thickness in the range of from about 0.1 mils up to about 20 mils (e.g., a filled porous polymer containing embedded therein a plurality of finite solid particles) said porous polymer having a porosity such that when said hollow totally enclosed structure is located in an ambient envixonment said volatile material molecules are either (a) adsorbed onto the inner surface of the micro-porous polymer section and desorbed from the microporous polymer from the outer surface of the shell at a substantially constant mass flow rate both of the individual volatile 1353~

compo~ents and totally flowin~ through such porous polymer section, or (b) trans-ported through the porous polymer shell section by means of capillary action at a substantially constant mass flow rate both of the individual volatile components and totally flowing from said thin shell the driving force of such molecular transport resulting from a difference in concentration of volatile substance between:
(x) the gas phase of the inner void of said shell; and (y) the space immediately adjacent the outer surface of said microporous palymer shell section.
The microporous polymer shell section (also referred to herein as "lamina") useful in the practice of our invention has the following specifications:
(i) The property of transporting water vapor at a rate of between about 50 up to about 1000 g/m2/day at about 25C and at about 50% relative humidity at about atmospheric pressure;
(ii) Porosity range: 100-20,000 Gurley seconds;
(iii) Most preferred porosity range: 8,000-12,000 Gurley seconds;
(iv) Range of Temperature for Operation: -80 C
up to 150C;
(v) Most preferred temperature ranye of Operation:
0C - 60C; and (vi) A thickness in the range of from about 0.01 mils up to about 20 mils.

~2(3~S3~

Certain statements concerning operation of the microporous polymer film (~membrane~) of our invention are based upon information disclosed in the paper: ~PERMEATION
OF PURE GASES UNDER PRESSURE THROUGH ASSYMETRIC POROUS MEMB~ANES, MEMBRANE CHARACTERIZATION AND PREDICTION OF PERFORM~NCE", Rangarajan, et al, Ind. Eng. Chem. Proc. Des~ Dev., 198~, 23, 78-87.
The term "polymer" in this case is intended to include pol,vmers of varying molecular weights and degrees of branching, homopolymers, copolvmers, terpolymers and the like, including but no limited to substances such as polyolefins (e.g., polypropylene), polyamides (e.g., nylon 66), poly-fluorocarbons (e.g., TEFLON( )), polyesters, e.g. polyethylene terephthalate, polycarbonates, (e.g., LEXAN(R)), polyacrylates, (e.g., Lucite (R)) and blends of same in various molar ratios.
The term "membrane" is intended herein to define porous polymeric shells, films or sheets, monolayer, bilayer or multilayer which on functional operation of the structure of our invention-and thereafter, will have the ability to have transported therethrough volatile substances useful in the practice of our invention.

BRIEF DESCRIPTION OF THE DRAWINGS
Figure 22B represents a graph of rate of fragrance loss (dqt) versus time (resulting from a "burst effect") for the entire period of possible continuous use of the structure of Figure 1 assuming that the structure of Figure 1 is not replaced at discrete time intervals in an enclosed air-tight outer container.
Figure 22C represents graphs of fragrance loss versus time in the case of a "burst effect" ~B) and in the case of a "lag effect" (L).

~`

~z6:~S3~

Figure 23 represents a random section of a filled porous polymer lamina (12,000 Gurley second film) magnification of 500x, using a scanning electron microscope, which filled porous polymer lamina is useful in the practice of our invention.
Figure 24 represents a random section of a filled porous polymer lamina, (12,000 Gurley second film) magnification of 3500x, using a scanning electron microscope, which filled porous polymer lamina is useful in the practice of our invention.
Figure 25 is a plot of transport ra`tes (of water vapor) versus temperature through filled porous polypropylene films of the nature exemplified herein, infra.
Figure 26A is a series of graphs of time (elapsed hours~ vs.
grams water and fragrance lost from the article illustrated in Figure 5 using various temperatures of operation. The data points are set forth in Example V, infra.
Figure 26B is also a series of graphs of time (elapsed hours) vs. gram water and fragrance lGst from the article illustrated in Figure 5 using various temperatures of operation and working specifically with a fragrance identified as "278m"~ The method of obtaining such data is further specified in Example V, infra.
Figure 26C is a series of graphs of time (elapsed hours) vs.
grams water and fragrance lost from the article illustrated in Figure 5 using various temperatures of operation and particularly working with the fragrance ;n~ t~d at "394m" in Example V, infra.
Figure 27A sets forth graphs showing water transport through filled microporous polymeric membranes useful in the practice of our invention; and these graphs set forth mg. water lost per day vs. temperature in degrees Kelvin.

Figure 27B sets forth a graph showing water transport through filled microporous polymeric membranes useful in the practice of our invention; and this graph sets forth grams water lost per day per square meter vs. temperature in degrees Kelvin.

~'~

~z()U53V

Figure 28 is an Arrhenius Polot of the data set forth in Figure ~7A and sets forth the log (natural base) of transport rate vs. reciprocal temperature (degrees Kelvin ).
Figure ~9 is a perspective view of a cell used for determining the data as presented in the graphs of Figures 25, 26A, 26B, 26C, 2~A, 27B and 28.
Figure 30 is a side elevation view of the cell of Figure 29.
Figure 31 represents an "explosion" of the parts of the cell of Figure 29 and is indicative of how these parts are put together in order to enable the cell to be used to determine the data presented in the graphs of Figures 2~, 26A, ~6B, 26C, 27A, 27B and 28, inclusive.
~igure 32 is a cut-away side elevation view of the cell of Figure 29 looking in the direction of the arrows.
Figure 33 is a GLC profile of the frangrance material denoted as "278m" employed in Example VI at time, t=0 weeks.
~igure 34 is a GLC profile for perfume composition "278m'^
employed in Example VI at t=2 weeks.
Figure 35 is the GLC proile for perfume composition "278m"
employed in Example VI at t=3 weeks.
Figure 36 is the GLC profile for perfume composition "278m"
employed in Example VI at t-4 weeks.
Figure 37 is the GLC profile for perfume composition "894m"
employed in Example VI at t=0 weeks.
Figure 38 is the GLC profile for perfume composition "894m"
employed in Example VI at t=2 weeks.
Figure 39 is the GLC profile for per~ume composition ~894m"
employed in E~ample VI at t=3 weeks.
Figure 40 is the GLC profile or perfume composition "894m"
employed in Example VI at t=4 weeks.

Figure 41 is a dual graph for perfume composition "278m";
the graph indicate b~ reference numeral "401" showing weight lost over a period of time as measured in mg/cm2 and the line ,....
- -. ., "

~L20~?53(~
~ ", indicated by reference numeral U402~ indicating odor intensity vs. time (showing essentially no change in odor intensity) where odor intensity is on a scale of 0-30 odor intensity units.
Fi~ure 42 represents a series of graphs indicating mg/cm2 evaporated of fragrance through the membranes; a filled poly-propylene membrane (reference numeral ~411~) and non-filled polypropylene membrane (reference numeral "412~) and in addition, shows evaporation without the use of any membrane (reference numeral "410") as specifically set forth in detail in Example III, infra wherein the data points are set forth in tabular form.
Figure 43 is another series of graphs showing evaporation in mg/cm vs. time in days for fragrance which is a 2% mixture of fragrance in Carbopol gel as specifically exemplified in Example III. The graph indicated by reference "420" is a graph for evaporation without any interference from a membrane.
The graph indicated by reference numeral "421" is the graph showing rate of evaporation through a membrane which is filled polypropylene and is a membrane defined according to our invention. The graph indicate by reference numeral "422" is the graph for evaporation through a polypropylene membrane, not defined within the parameters of our invention.
The process of our invention comprises dispensing continuously (as illustrated in Figure 20) or discontinuously for discrete periods of time (as shown in Figure 2) at steady state, a volatile composition of matter 3 from a container, e.g. as represented by reference numeral 500" in Figure 1, into the atmosphere surrounding said container ~nabled by the use of a polymeric membrane that may be further defined by having (i) the property of either transporting water vapor at a rate of between about 50 up to about 1000 g/m2/day at about 25C and at about 50% relative humidity at about atmospheric pressure and/or having an air transport rate of 100-20,000 Gurley seconds (~s) and (ii) having a thic~ness in the range of from about 0.01 mils up to about 20 mils~
~~ 'i;' '`

3L;2 (~53~

A typical example of porous polymer composîtion of matter was described on page 15 of the Disclosure. Additional examples are those where the air resistance (Gurley) varies from about 8000 seconds up to about 12,000 seconds.
The microporous polymer membrane section useful in the practice of our invention has the following speci~ications:
(i) Water vapor transmission rate: from about 50 g/m2/day up to about 1000 9/m2/day at about 25 C and at about 50~ relative humidity at about atmospheric pressure;
(ii) Porosity range: 100-20,000 Gurley seconds;
(iii) Most preferred porosity range: 8,000-12,000 Gurley seconds;
(iv) Range of Temperature for Operation: from -80C up to + 150C;
(v) Most preferred temperat~lre range of operation:
0C up to 60C; and (vi) A thickness in the range of from about 0.01 mils up to about 20 mils.
The statements concerning operation of the microporous polymer membrane of our invention are based upon information disclosed in the paper: PERMEATION OF PURE GASES UNDER PRESSURE
THROUGH ASSYMETRIC POROUS MEMBRANES, MEMBRANE CHARACT~RIZATION
AND PREDICTION OF PERFORMANCE", Rangarajan, et al Ind.Eng.
Chem.Proc.Des.Dev., 1984, 23, 79-37.
Rangarajan, et al hypothesizes that one of the following five mechanisms are operative in working with the microporous polymeric membrane as used herein, to wit:

~`, 3~2(3~53~

(i) Molecular diffusion (following Fick's Law);
(ii) Capillary:
(a) Knudsen Flow;
(b) Slip Flow; and (c) Viscous Flow-(iii) Adsorption/Desorption.
We show herein that the probability of mechanism (i) contributing in any substantial manner to the operation of our invention is negligible.

~lthough a filler is not required insofar as the microporous polymeric membrane useful inour invention is concerned, it is now preferred that a filler be incorporated therein having an average particle size of from about 0.1 up to about 20 micro meters.

Particulate or pulverulent fillers which are useful in the practice of this invention include, but are not limited to, clays, including both untreated clays and those which have been surface-treated in various ways well known in the art, ground limestone, talc, precipitated calcium carbonate, including surface-treated t~pes, alumina, aluminium silicate, barytes, wollastonite or other calcium silicàte, silica, zirconia, titanium dioxide, and polymeric illers such as pulverized phenolic resins, polyamides, (e.g. nylon 56), polyfluorcarbons, (e.g. TEFLON(R)), polyesters, e.g., polyethylene terephthalate, polycarbonates, (e.g. LEXAN( )) polyacrylates, (e.g. LUCITE( )).
The only limitations are that the fillers should not adversely affect or react with the aromatizing or other functional volatile substance or any entrapping material which may be used in entrapping the aromatizing or other functional volatile substance, or absorb the aromatizing or ot~er functional volatile material to such a degree that release ~ro~ the microporous . ! ~, ~2~)~PS~
~ , polymer membrane is unduly inhibited or entirely prevented.
Although the particle size of the filler can be varied over a wide range, e.g., 0.1 micromemters up to 20 micromemters, extremely coarse particles are generally undesirable because they may detract from the physical functioning and mechanical operability of the membrane which is the key functioning member of the apparatus of our invention, as well the aesthetic qualities of the finished microporous polymeric membrane.
The amount of filler can be varied over a wide range depending on the amount of volatilizing material to be released from the entrapped volatilizable substance 3 and the vapor viscosity of the volatile vapor being transported (which is either transported by means of capillary action and/or is adsorbed onto and desorbed from the porous polymer). We have found that filler levels in a range of from 5 to 100 parts by weight per 100 parts of polymer are generally satisfactory, although greater or lesser amounts can be used if desired.
Indeed, it is not necessary to use any filler so long as the polymeric membrane has (i) the property of either transporting -- 20 water vapor at a rate of from about 50 g/m2/day up to about 1000 g/m2/day at about 25C and at about 50% relative humidity at about atmospheric pressure and/or having an air transport rate of 100-20,000 Gurley seconds ~Gs) and (ii) a thickness in the range of from about 0~01 mils up to about 20 mils.

., ~ .

;i3~

In each of the graphs wherein perfumed material is used, it is apparent that for the major portion of the useful life of the structure, e.g. structure 500, the rate of mass transport of perfume substance, when in use, is n o n order, that is:
dq = k wherein k is a constant and q is measure of the output of volatile substance for the outer surface of the outer polymeric membrane of the article of our invention.
Discussion covering the preparation of the compositions of matter which constitute the fragranced gels and unfragranced gels whereby the graphs as represented by reference numerals 201, 202, 203, 204 and 205 of Figure 18 are prepared is set forth in Examples I and II, infra.
By the same token, in Figure l9, the graph indicated by reference numeral "302" indicates percent fragrance loss versus time for a fragrancing gel containing 2%
by weight fragrance but not enclosed in a structure defined according to our invention. It will be noted that the diffusion of perfume compositions or other volatile substances as stated he~in~eeo~eis in accordance with the ordinary diffusion law and is not steady state, to wit:
dq ~ Constant Discussion covering the preparation o the compositions of matter which constitute the fragrances and fragranced gels whereby the graphs as represented by reference numbers "4107', "411" and "412" in Figure 42 and reference numerals "420", ~'421" and "422" in Figure 43 are prepared as set forth in ~xample III, infra.
The graph indicated by reference numeral "410"
in Figure 42 indicates mg/cm2 evaporated of fragrance s~

where the fragrance is not enclosed in a structure defined according to our invention. The graph indicated by reference numberal "411" in Figure 42 is for the same fragrance (indicated as "EGL-1433")(as more particularly described in Example III) located in the thin shell structure of our inventi~n as illustrated in Figures 1, 2, 3 and 5.
The graph indicated by reference numeral ~412" indicates percent fragrance loss (mg/cm2) vs. time for the same fragrance (EGL-1433) located in a thin shell structure wherein the membrane rather than being a membrane as defined for use with our invention ((i) having the property of either transporting vapor at a rate of between about 50 g/m2/day up to about 1000 g/m2/day at about 25C and at about 50~ relative humidity at about at atmospheric pressure and/or having an air transport rate of 100-20,000 Gurley seconds (Gs) and (ii) a thickness in the range of from about 0.01 mils up to about 20 mils) uses a poly-propylene membrane which has properties including a water transport property outside of the range of the properties of the membranes useful in our invention.
In Figure 43, the graph indicated by reference numeral "420" indicates fragrance loss (in mg/cm2 evaporated) vs. time for an air freshener gel containing 2~ by weight fragrance but not enclosed in a structure defined according to our invention.
The graph indicated by reference numeral "421"
is for the same fragrance gel containing 2% by weight fragrance (as more particularly described in Example III) located in the thin shell structure of our invention as illustrated in Figures 1, 2 and 3.

~0~530 The graph indicated by reference numeral ~422"
in Figure 43 is for the same fragrance gel containing 2~ by weight fragrance (as more particularly described in Example III) located in a thin shell structure of our invention as indicated in Figures 1, 2 and 3 wherein the membrane of the structure of our invention is replaced by a polypropylene membrane having an infinite resistance (as being essentially non-porous).
Figure 22B is a graph of ddq versus time (resulting from a "time burst" effect after a buildup of fragrance within the totally enclosed structure of our invention) wherein the period of from to to tl is a condition of "unsteady state" mass transport (usually no more than a few minutes) and the period from tl to t2 is a condition of "steady state" mass transport; a very long period of time, e.g., 55-75 days and even longer.
Figure 22C shows graphs of fragrance loss versus time in the case of a "burst effect" (graph "B") and in the case of a "lag effect" (graph "L"). Reference: Robinson "Sustained And Controlled Release Drug Delivery Systems"
published by Marcel Dekker Inc. (1978), pages 258 and 259.

V5;~0 !!
" - 45 -Figures 23 and 24 set forth scanning electron microscope photographs of porous polymer film filled with CaCO3 filler.
~igure 23 is a photograph showing 500x magnification. Figure 24 is a photograph showing 3500x magnification.

In Figure 25, (which is a plot of transport rate of water vapor versus temperature in degrees centigrade), the graph indicated by reference numeral "250" is a graph of transport rate ~ersus temperature for film having a porosi~y of, nominally, 8000 Gurley seconds.

The graph indicated by reference numeral "251" is a graph o~ transport rate versus temperature for water loss from a silanized 8000 Gurley second film (the silanization being carried out by treatment with a trimethylchlorosilane silanizing agent).

~he graph indicated by reference numeral "253" in ~igure 25 is a graph of transport rate versus temperature in degrees centigrade for rate of water loss from a nominally 12,000 Gurley second filled polypropylene film.

The graph indicated by reference numeral "252" in Figure 25 sho~s transport rate versus temperature in degrees centigrade for rate of water loss from a silanized nominally 12,000 Gurley second film.

;' The graph indicated by reference numeral "254" is a graph ' of transport rate versus temperature in degrees centi~rade , for rate of water loss from an untreated non-porous non-filled polypropylene film.

.....
,~i~'.
~ ~L

s~

., Both treated and untreated films as depicted in the graphs in Figure 25 were placed into diffusion cells as illustrated in ~igures 29-3~, inclusive which were loaded with distilled water.
The cells were then placed in a constant temperature/humidity , oven at 25C and 63.5% relative humidity. These conditions . I provided for a nominal water vapor differential of 10 Torr between ~he inside and the outside of the cells. After ~wo days, the temperature was adjusted to 35C and the relative humidity to 79~ providing $he same nominal 10 Torr water ~apor pressure differential.

The graph indicated by reference numeral "253'l in Figure 25 is a graph of transport rate ~ersus temperature in degrees centigrade for rate of water loss from a nominally 12,000 Gurley second filled polypropylene film.

The graph indicated by reference numeral ~254" is a ~ra-h of transport rate versus temperature in degrees ~enti~rade for rate of ~ater 105s from a non-porous, non-filled polypro~i~er.e film.

The films as depicted in the ~raphs in Figure 25 ~:ere r,la-ed into diffusion cells as illustrated in Figures 28-31 which ~ere loaded ;ith dis~illed water. The cells ~ere then placed in a ccnctant temperature/humidity oven at 25C and 63.5~ relati-e hur.,idity. These conditions provided for a no~inal ~a!er ~-aror di'ferential of 10 Torr between the inside and the outside o' the cells. After t~o da~s, the temperature has adjusted to 3;C and the relative hur..idity to 79~ providing the sar.e no-.inal 10 Torr ~ater vapor pressure differential.

3 5 3 ~

Figure 29 is a perspective view oE the diffusion cell which was used in order to obtain the data set forth in Examples III, IV, V and VI, infra. Figure 31 is an exploded view of the cell of Figure 29. Membrane 290 is placed in gland 291 and gland 291 is placed into sealed cap 293 causing the membrane 290 and the gland 291 to be firmly in place and threaded into the sealed cap 293 using lock nut 292. The sealed cap 293 previously has the liquid or gel substance the properties of which are being measured, located ~ithin it for the purpose of testing the porosity of membrane 290.
During the testing, volatile substance passes through me~brane 290 into the surrounding atmosphere at 294 as shownin Figures 30 and 32. Sealed cap 293 is shown to be screwed in place using lock nut 292 holding membrane 290 on gland 291 in Figures 30 and 32.
The details concerning Figures 26A, 26B, 26C, 27A, 27B 28 and 41 are set forth in Examples V and VI, infra.
Thus, the physical rationale or "mechanism" for operation of our invention may be (i) "a steady state"
adsorption/desorption mechanism or ~ii) by means of capillary action; or (iii) a combination of adsorption/desorption and capillary action. The adsorption/desorption mechanism would be operable, for example, as a result of the critical surface tension of the filler phase being greater than the critical surface tension of the volatile composition existing in the liquid state in the device o~ our inventionO

. . ,~,, ~i ' `, ~Z0~53~) ., EX~MPLE III~A) Into a group ~ three jars incicated as (i), ~ii) o'.C
each ha~ing an opening havin~ an area of of 15.48 c~2, a ~.~ir~.
o~ 4.2 cm, an ~pening diameter of 4.4 cm and an internal dia,meter of 4.8 cm (total volume: 72.5 cc) is placed 5~00 r~
; (5 grams) of the f~llowing ~erfume CQmDosition.

Inoredients Parts ~v h'eioht Citrus oil distilled .......................... 275 Dipentene...................................... 150 ~he ~,ixture of compounds avin~ the structures:
1~`~' uod R~S - - - - - - - - .. 130 ~re?ared aecording to r~ . S . Letters Patent 4,330,416 issued on ';ay 18, l9S2 tthe s~ecification for which is incorporated by reference herein) Geraniol........................................ 50 Tetrahydro ;luguol.............................. 50 ~emon oil....................................... 5Q
Grapefruit oil.................................. 50 Geranonitrile................................... 25 n-Octanal...........~........................... 20 n-Nonanal.................................. ..... 20 n-Decanal.................................. ..... 10 Citronellol....................O................ lO
~-(4-Per.tenoyl)-3,3-dimethv~
cyclohexane 1............................ .... 25 Beta pinene................................. ..... 5 n-Nonanol................................... .... 20 Cis-3-hexenyl formate..~.................................. , 5 Cis-3-hexenol.......... O... ~............................... 10 ~ethyl jasmonate.. O.....O................................. 2S
Dihydro methyl jasmonate..........O........................ 20 12~3~DS30 ~ 49 Jar ~i) i5 left open and the eva~OratiGn of th~- a!,-~.c-fra~rance for~ulation is measured on a dail~ ba~is.

; Jar (ii) is co~ered in a tight fitting manner wit~. a , me.~.~rane ha~in~ the followins specifications:

S ' Composition ~o~ypropylene ~ CaC03 filler Thickness 100 micrometers ~'eis~t 90 q/m Ultimate tensile ~trength 30 M~`/r2 (ma~hine dire_tio) 11 M`;/m2 (~ran~v~rse dire~ti~
Elongation at break iBo~ (machine direction) ~50~ (transverse direction) ~ore size O02 micrometers (ræx) Void volu~ 0.34 cm /g (30~) De~sity 900 kg/m Air flow 3 cm3 /cm /rin at 1 k-/cm ~ater flow O.OGl cm3/c~2/r~in at ; kS/c-2 Air resista~ce (Gurley) a ,ooo seconds h'ater vapor transmission 1~0 5~F.. ~24 hrs at 23C a. 5J~
re ative humidity Ther~.al sta~ility lD hrs at 13DCC

Jar (iii) is covered in a ~i~ht fittinc ~anner with a pol~rrop~lene film of 1 mîl thickness. In each of the jars the rate of e~aporation of the fragrance is measured on a daily basis. The weight .oss occurs at constant ter.~erature, 22C and constant relative humidity, SO~ relative hu-.idit~-.

Ta~le I set forth below shows weight loss as a function of ti~e and w~ight loss per square cen~i~e~er as ~ function of time for each of jars (i), lii) ~nd (iii).

, . . .

;: -TA BI,E
JAR (i~ Jt\n ~ JM (iii~
n~ of pc~rf~ne ~,~g/cm2 of ~rflme mg o~ ~rf~ mg/an of ~r~ mg of ~rh~r~ ~/sn2 of r~erf~
Daysc~ ion lost c~ ition lori~ ~nTy~.s~tion lo~t c~ition kr.t ~or~ition lc~st c~ositinn lr7~t 130 12 . 3 80 5 20 1 . 3 2 4~0 - 150 . - 5~ -3 G30 45.0 23~ 15 8~ 5.

6 1070 69. 0 31~ 24 120 8.

7 1330 - 43t~ - 140 9 185~ 119.0 56r) 36 20~J 13.Q
~0 15 2310 1~9.0 ~8~ 57 31~ 20.
31 2660 172.0 145~ 94 600 39.0 36 2740 177.0 156~ 1~0 680 44.0 o The series of graphs set forth in ~i~ure 42 lndicates ~raphically the results set forth in Table I,~u~ra.
Thus~ the graph indicated by reference numeral "410" is the qra~h for the rate of fraqrance comnosition evaporation from Jar (i). ~he graph indicated by reference num~ral "411" is the ~ranh for the rate o evaporation of fragrance eompvsition from Jar ~ii). The ~raph ~ndicated by reference numeral "412"
on Fiqure 42 is ~he graph for the rate oF evaporation o~ fraqrance com~osition from Jar (iii).

.. . . . . . . . . . ... . . ..

` ! lZOt~530 'i EX~iPLE III(B) i' Three jars are provided, Jar (iv), Jar (v) and Jar (vi) having dimensions identical to those of Example III(A). To i;each of the jars, 20 grams of a perfumed gel is added which 1 is prepared as follows:
1, ~
i~ n3 .o Parts by weight of Carbopol ~ 940 (manufac~ured by the B. F. Goodrich Company) (see Note 1 of Example I) is sifted into the vortex of rapidly stirring water (88.8 parts by weight~ containing 0.2 parts by weight of methyl paraben at a temperature of 220C. The mixing is continued until a smooth cloudy dispersion is formed. 2.0 Parts by weight of the perfume composition of Example III(A) is added to the prepared ~lurry and the slurry is continued to be mixed until the perfume composition is dispersed. The slurry is neutralized with 6.0 parts of weight o diethylpropenol~amine (50%
solution in water) using 510w mixing to avoid the in-clusion of air."

Jar (iv) is permitted to rer.ain open ~hile measure-er. s for ~eisht loss of gel are made on a daily basis.

Jar (v) is tightly co~ered with a me~brane hauing the sa...e specifications as the me.~rane used to co-er Jar lii) in Example III(A) and the weight loss is measured on a dail~
basis.

Jar (vi) is covered with a polypropylene film hat~in~ a t~,ickness of 1 mil and the weight loss of the gel is meas~red on a daily basis.

~. .

,i ~20~53~
.

~ able Il, below sets forth weight 1oss as m~a~ured in m~,~c~2 for each of Jars (iv), (v) and (vi):

T,.BL~ I I
;
Da~-s J~R (iv)JAR (v) J~R (vi) ~ ,7 2 (mg/cm )(m~/cm~) ~ms/cm ) 1 13~ 28 0.7 3 555 113 2.0 6 lOD7 219 ` 2.0 ~ 1201 349 3.g 15 12~7 57~ ~.5 31 1210 lQ83 9.0 36 1209 1154 9.7 Figure 43 is a ~ranhical representation of the results se~ forth in Ta7~1e II, supra. The ~ra~h indicated b~ refererce n~-eral "420" is the gra?h for the open jar, Jar (i~7) (.-,'c ' VS7. time). The graph indicated by reference numeral "~21" is the sraph for the weight loss of gel from Jar (~ he c~
incicated b,~ reference nu~eral "422" is the ~ra-h for t..e we~ght loss of gel fro~ Jar (~i) a5 a function of tir,e.
!

~2~ 530 ji - 53 - !
., il EXA'lPLE IV (A) The following experimental design was established through j an evolutionary process in order to determine the permeability ,j of water vapor through filled polypropylene film as exemplified 5 ¦ I on Page 21l supra.
I
Cell Design Stainless steel 316 diffusion cells as illustrated in ~isuxes 28-31, inclusive the details for which are set forth, s~pra, were specially designed to measure the transPort of s~all a~ount of ~ater vapor throu~h a film sample under controlled experimental conditions. Commercially a~aila~le ~ittinss ~nut, plug and glands) were modified to acco~mo~ate ~ater or a volatile substance in one side of the gland and a film specimen between the two glands. ' IIo Materials A. Films: A film designated as having a nominal air transport rate of 12,000 Gurley seconds (Gs) was e~?lo~ed. Six sa-ples, each measuring 6" x 6", were cut from the center of a 10" ~ide stock sample. From each ~f these test samples, a sam?le ap?rQximately 2.0 cm in diameter was used for the permea~io~ ', experi~ents and a s~ple of a?proximately 5" diameter was used for air per~eation measurements. Approxi~ately 0.5 g of ~ater were used in each o~ ~he test ~ells.

1 B. Silylation procedure: Trimethylsilyl chloride (20 gms) 25 ~ was placed in a 200 ml beaker and placed in a glass desicator.
Three of the 6" x 6" test samples were suspended inside of the desicator and the desicatDr was closed tightly and placed in a 45C oven overnight. The beaker was then removed from the desicator after it returned to ambient emperature. The desicator was then evacuated at approximately 20 mm/Hg for a p~riod of 4~5 hours to remove residual volatilesO The films were then used for the experimen~al procedure.

C. Water: Approximately O.S g of water were used in each of the test cells.

; !

Il ~2~53~ 1 !' III. Environmental Conditions A. Oven: A Blue "~" controlled tem~erature and hu~idity ove~ was used for all experimental conditions. Theter~erature and hu~.idity conditions were controlled by t~e dry and wet bulb thermome~ers located inside of the test chamber.
B. Conditions. The following conditions were use2 in the experiments:
Temperature ~C) 25 30 35 40 45 50 55 Relative Humidity (%) 50 63 72 78.5 83.5 89 90 These conditions established a relative water vapor press~re difference of 15.85 mb between the inside and outside ~f the cell.

C. Ter..perature conditions: The following se~.uenc~s of te.,?eratures (C) were employed to randomize the sam~le treG~D...
a-.~ re~uce ~ossible systematic error:
(A~ 25 - 45 - 30 - 40 - 55 - 35 - 25 - 35 C
(B~ 35 - 50 - 30 - 45 - 25 - 35 - 40 - 25 - 30C

IV. Sam~le heiching The cells were placed in the oven at the selected te-per2ture condition so that the film was in the "up" position as irdica.
in Fig~res 30 and 31. After the sar,ples were e~uilibrated for at least 10-12 hours, ~he sarples were weighed using a ~le~tler -163 electronic balance interfaced to the Disital E~uip~er.t Corporation (ISalnard, r~assachusetts) VAX ~ 11/7B0 computer. The samples were then replaced in the oven and were reweighed after approximately 12 hours to ~iv~ the transport rate for each condition. ~ive re?licates were run and ~arm~les ~ere re-tested at 25, 30 and 35C ~o monitor reproducibili~.

,~

il ~2q)~s3~

jl - 55 -V. Da~a ~andlinq A11 data were entered directly into the Va~: 11/7B0 c~~.,.,ut~r u~ing s~ecified sof~are in ordcr to faci1itate t},~- c~lc~-;~ion of weight-loss, the plotting of graphs, and the ~.2,.ipU-lation ~or com?utational purposes~

; VI. Experimental Details ~ xperiment using ~000 ~s and 12,000 Gs films, regular and silylated, ~t 25C ~50~ R.H.), 35~C (71~ R.H.) and 4;C (83~ R.~.).

In Pigure 25 (which is a plot of transport rate of water vapor versus temperature and degrees centigrade) the graph indicated by reference numeral '`250" is a graph of transport rate versus temperature for 8,000 Gurley second film which is not treated (silylated).

lS The graph indicated by reference numeral "251" is a graph of transport rate versus temperature for water loss from a silanized 8,000 Gurley second film for the three temperatures, 25C, 35C and 45C.

The graph indicated by reference numeral "253" in ~igure 25 is a graph of transport rate versus temperature in degrees centigrade for rate of water loss from a nominally 12,000 Gurley second filled polypropylene film at temperatures of 25C, 35C and 45DC.

The graph indicated by reference numeral ~252" in ~igure 25 shows transport rate versus temperature in degrees centigrade for rate of water loss from a silani~ed nominally 12,000 Gurley second film at 25C, 35C and 45C~

The results of this study are:

(i) Diffusion of water through a filled polypropylene matrix (membrane defined according to the properties set forth on page 21, supra) does not contribute significantly to the mechanism of the total ~ransport through said film;

S3~ 1, (ii) A "high" activation energy process (such as viscous capillary flow~ appears to contribute significantly to the transport of water through the filled poly-propylene films especially above 40~C; and (iii) A "low" activation energy process (such as sorption-i driven surface flow) appears to contribute signifi-cantly to the transport of water through the filled i polypropylene films especially below 40C.

.

53~3 "
' - 57 -EXP~IPLE IV(B) . .

~he following Table III ~h~h~s ~he air resistance ratin~
of 15 films measured in Gurley seconds and the minimu~ an~
; maximum water ~ransport rates that were ~bserved at 25~C a-.
'~ a~ 50~ relative humidity. The measure~ents were carried o~t using cells and pr~cedures substantially as described in ExamFle IV(A~, supra.

h~.~R T.~:C.~ A~ 25C
~nimum Water ~;~ ~ Wate~
Fi1~ o. tir Resistance Transpoxt Rate Transport Rate ~C~ ley seconds) (g~m2/day)(g~m2/day) 1 1600 370 ~83 6 4003 375 4~1

8 4300 413 677

9 540~ 143 ~1 600~ 140 34~

14 1020~ 222 317 1~3~S3(3 EX~MPLE V
"

J~.._~lALS

'I~ A. TE~T PR~D~CT5: Eigh~ samples o~ the articl~s as '1, illustrated in Figure 5.
5 , B. ~ECT C~ ERS: The ~est char.~ers were construc~ed ~rom white polypropylene canisters of 5 gallon li~ id volume which has been fitted with an air-tic~t lid.
The lid had a 2 inch evaluation hole cut in t~e ~
~.hich ~s fitted with a cork stopper. ~nci~idual sc~ s were placed in the cha~ers approxir.iately 1 hour ~rior ,. to e~aluation to permi equilibration.
C. J~'DGES: A panel of 23 individuals trair,ed and ckille~
in the practice of ma~nitude esti~.,ation ~ere e.~-,lv~e_ as odor intensity judaes. The jud~es ~ro~ide~ r2~ io-scaled assess~ents of the percei~ed odcr in~ensit.~.
D. CO~ROL S~:r'LES: The follo~ina control sa~ les were ir,corporated into the ex~erimertal design:
1. 100 g Unfragranced ~el, fully exposed fro.. a petri plate, the gel being prepared in accordance ~ith the process of Exa~rle III(B).
2. 100 g ~racranced Gel ("894~."), full~ ex,oce~
from a petri plate (prepared accor~inq to t~e procedure of Exa~.~?le III~B).
E. S~`~PLE E~PO~ E: Du~licate sa~les ~ere schedl_le~ ~or ar.~ient roo~ ex~osure based upon a cor.ver~in~ cr-le~ic~
design so that sa...rles re~resenLing 0, 2, 3, an~ 4 ~e;~
of exposure ~ere a~ailable at the date of t~,e ser.~or.
~est~
~T~O~S
~11 exposed samples were submitted in the blind ~o the par.el , of jud~es after 1 hour in the test ~ha~bers. ~ total of 22 s~les ~ere evaluated in the test. All ~es~ ~a.?les were ra~ ed upon sub~ission ~o ~he judges and re-rando~,ized peri~ically t~,roughout the evaluation period.

The magnitude estimation sensory data ~reference: Warren, C.B., Paper No. 3 "De~elopment Of Fragrances With Functional Properties By Quanti~at,i~e Measurement Of Sensory And Physical Parametexs"; Moskowi~z and Warren "Odor ~uality And Chemical Structure", American Chem.icals Society Symposium Series , 148 (American Chemical Society - Washington, D. C., 1981) was normalized by the method of 'no standards". Standard errors - ; of the measurements were calculated to detenmine he significance of the perceived test sample intensities.

" ~ 5~

A`;.~L~ICAL DA~A
The cu~lative weisht-l~ss ~-as ~taine~ during the e~c~re peri~d f~r each ~f the test samples (excluding the cor,trc~s a~ the 2ero-time sa~ples). The peri~dic weio'r,inas w~re c~
~n~ rep~rted as Cumulative Weight-l~ss vs. time and this i5 s~o~n in ~igures 26A, 26B and 26C.
; R~S~LTS
The su~r,arized sensory testing results are prese..te~ f~r fra~rance "894m" in Table IV, infra. The nor~alized prc~u^t ~eig~t-loss data for "8g4m" are incorporated int~
~he last t~o columns of this Table ~IV) and repGrted gra?hically in Figures 26A, 2SB and 26C.
~ he graph indicated by reference numeral "260" is the grarh sho~ing grams loss ~f gel vs. time for four wee~s of ex~sure of gel containing frasrance "2?Br.".

~ he graph in~icated by reference numeral "2~2" is the graph sh~wins the mean weight loss after 4 ~eeks of ex.posure for the gel containing fragrance "~94m".

The graph indicated by reference numeral "264" is the craDh showins ~he ~ean weight l~ss rate for gel co~air.lnc frasrance "2~8~" after 3 ~eeks.

~ he sraph indicated by reference nu~,eral "263" is ~-.e gra~ shohing the mean weight loss of a gel containing fragra~ce "894m" a~ter 3 weeks.

~he graph indicated by reference numeral "265" is the srap~ shc,~ing the mean weight l~ss of a fra~ra~ced gel cc-.~air fra~rance "278~" after 2 weeks exposure.

The graph indicated by reference numeral "261" is t~e graph of the mean weight lcss of a gel containing frasrance "894."
after 2 weeks exposure~

Graphs 260, ~64 and 265 are sh~wn separately on Fi~ure 2~.

Gr~phs 261, 262 and 263 of ~igure ~6A are sh~n s~2rate!~
in ~igure 26C.

53~3 DISC~SSION

The results of the sens~ry experiments suggest that there is a critical equilibration point sometime between "zero" and 2 weeks. This is reflected in the intensity decay between these ~wo evaluation points in this experiment.
The product containing fragrance "894m" did not ~how any significant perceived odor intensity decay over the period of 2 thru 4 weeks of exposure.

SU~ ~RY

10 , The results of this study indicate that the product fragranced with "894m" quickly equili~rates to what is perceived as a "steady-state" fragrance delivery rate over a 4 week period.

3(~

EX~1~E Vl AIR FRESY.r~;lR P~ODUCTS

~ERI~LS
Air fresheners ~roduced accordin~ to Example V an~ used in said Ex2.,~1e V were then utilized for this example.
GLC anal~sis ~as performed on dual 50 meter fused silica ca?illar~ colu~,ns containing OV-l or Carbohax 20~ licuid p.~aae_.

.~_,:~ODS
Aliquots of the test sarples were prepared for a~al~sis by Flacing 5 sra~s of sa~?le, in a shaker jar with 25 ~ls Or food grade ethanol and shaking on a wrist-action sha~er fcr a?proximately 24 hours until no additional rolor could be re.
frc~ the gelatinous residue. The ethanol solution was quantitatively decanted and the gelatinous resi~ue was washe~
with an additional l0 ~1 of food grade ethanol. The extr~-t and wash were co~bined, d ~ ted volumetrically to 50 ml a~d fil,ered usi~g a Milipore filter.

RE C7~ S
GLC analvsis of the isolates confirme~ that the pr~file o~
the isolate was consistent hith that of the original fra~ra.~ce oil.
The results of the internal standard GLC anal~-ses are pre-sented (a) for fragrance 278m on Carbo~ax 20~ in Figures 33 ~0 weeks), 34 (2 weeks), 35 t3 wee};s) and 36 (4 weeks~ ar.d (b) for 894m on Carbo~ax, 20,1 in Fi~ure 37 (0 weeks), 38 (2 weeks), 39 ~3 weeks) and 40 (4 weeks).
Fisure 4l sets forth a dual graph of weigh~ loss ~s. time for 27~m las shohn by the graph indicated by reference numeral "401")and for odor intensity on a scale of 0 to 30 units as shown hy ~he graph indicated by reference numeral "402".
;

DISCUSSION

~he iso'ates were subjected ~o internal standard capillary GLC to confirm sensory evaluations. In comparing the GLC
results across the 4 week period, it is obvious that there is no apparent disproportionation of the fragrance over the 4 week exposure.

~., i ~2~?53~

TABLE IV

. QUA~iTITA~IVE OF ODOR "EVALUATION OF '.
! PRAGRANCE" "894m" BY MAGNITUDE ESTI~ATION

, Fragrance: "894m"
No. of Panelists: 23 '.

,~ mg~.
Exposure ~an b Std. Average Std. a Fra~. Loss , 5ample Indent. Time Intensity Errora Intensity Error Nom, /Ave~ ;

Con4ro1 ~ray~lced Gel 0 hrs. ~0.3 1.05 77.5 1.05 78.89 ~.04 Ze-o ~ime16 hrs. 53.1 1.13 52.6 1.10 52.87 1.0~

2 l~e~s 319 43.0 1.07 ~6.4 4~.9 1.10 43.94 1.06 6~.7 ~7.6 3 ~}s ~82 51.1 1.05 54.2 41.1 1.12 45.83 1.06 55.~ 55.0 4 We~s fi46 36.1 1.09 59.5 ` S7.0 1.05 45.36 1.05 65.~ 62.6 ~ Ge~etric means are calculated for all intensities. 5t~dard erro~s sho~ld be read as 1. ~ ~ error, e.g., 1.13=13~ relative errcr.
A l-cdel~e odor Lntensity has a Yalue of 30 on ~his scale.
I' i ., O

11 1 '.

..~

Claims

The embodiments of the invention in which an exclusive property of privilege is claimed, are defined as follows:

Claim 1: A hollow totally enclosed structure comprising a thin shell totally enclosing an inner void, said thin shell having a base portion and an upper portion, said base portion having an inner surface:
(i) at least a finite portion of said thin shell being transparent whereby that portion of said inner void which is located proximate to the base portion of said totally enclosed structure is visible from without said thin shell, in the presence of visible wavelengths of light (ii) contained totally within the said inner void of said thin shell and in place on said inner surface of said base portion, a volatile composition temporarily entrapped and totally entrapped at least at the instant in time of commencement of functional operation of said structure, in an entrapment material, said volatile composition being selected from the group consisting of perfume compositions, herbicide compositions, insecticide compositions, animal repellent compositions, air freshener compositions, pheremone compositions, odor maskant compositions, deodorant compositions and insect repellent compositions;

(iii) at least a finite section of said thin shell com-prising a microporous polymer having a porosity such that when said hollow totally enclosed structure is located in an inert gas at a pressure of less than or equal to about 1 atmosphere, said volatile material molecule are transported at a constant linear velocity and at a constant total derivative of concentration of volatile substance with respect to time onto the inner surface of said microporous polymer section via an adsorption mechanism and from the outer surface of said microporous polymer section to the surrounding atmosphere via a desorption mechanism.

Claim 2: The hollow totally enclosed structure of Claim 1 wherein said base portion is non-porous and trans-parent and said upper portion is a microporous polymeric membrane and is opaque at least at the instant in time of commencement of the functional operation of said structure, said base portion being sealed to said upper portion.

Claim 3: The hollow totally enclosed structure of Claim 2 wherein said upper portion consists of a microporous polymeric membrane which consists essentially of a polyolefin intimately admixed with a power having an average particle diameter of from about 0.3 up to about 500 microns.

Claim 4: The hollow totally enclosed structure of Claim 1 wherein the microporous polymer is a microporous polymeric membrane consisting of a polyurethane foam containing a particulate filler having an average particle diameter of from about 0.3 up to about 500 microns, said polyurethane foam formed by reacting a liquid polyol with at least one organic polyisocyanate, water and at least one catalyst.

Claim 5: The hollow totally enclosed structure of Claim 1 wherein said microporous polymer is a 3-dimentional microporous cellular polymer structure comprising a plurality of substantially spherical microcells having an average diameter (C) of from 0.05 to 100 microns distributed substantially uniformly throughout the structure, adjacent cells being interconnected by pores smaller in diameter than the microcells, the pore size distribution expressed by (S) having a value in the range of from 0.01 to 30 microns, the Naperian base log ratio of the average cell diameter (C) to the average pore diameter (P) having a value in the range of from 0.2 to 2.4 and the Naperian base log ratio of the pore size distribution expressed by (S) to the average cell diameter (C) having a value in the range of from -1.4 to 1.0, the pores and the cells being void at the instant in time of commencement of the functional operation of said structure and the polymer being a synthetic thermoplastic polymer which is a polymer or copolymer of an ethylenically unsaturated monomer, a condensation polymer, a polyphenylene oxide or a blend thereof.

Claim 6: The hollow totally enclosed structure of Claim 1 which is in the shape of a cylinder, the ends of the cylinder being translucent and non-porpus and the side of said cylinder being opaque at least at the instant in time of commencement of the functional operation of said structure, said side consisting of a microporous polymeric structure.

Claim 7: The hollow totally enclosed structure of Claim 3 wherein the thickness of the microporous polymer is about 100 millimicrons; the pore size is approximately 0.2 millimicrons; the void volume of the polypropylene is approximately 34 cubic centimeters per gram and the density is approximately 900 kilograms per cubic meter.

Claim 8: A structure comprising (a) a first hollow totally enclosed structure defined according to Claim 1 and enclosing said first structure, (b) a second air-tight totally enclosed structure, said first totally enclosed structure having a volume less than said second air-tight totally enclosed structure, said first totally enclosed structure being of such dimensions that it is (i) enclosable within said second air-tight totally enclosed hollow structure, and (ii) the internal volume of said second air-tight totally enclosed hollow structure is greater than the external volume of said first hollow totally enclosed structure.

Claim 9: A structure defined according to Claim 1 wherein (i) said base portion comprises a first thin polymer shell having a curved surface and an inner void portion and an inner surface and an outer surface and a first sealable continuous circumferential edge; (ii) said upper portion comprises a second thin shell section having a second sealable continuous circumferential edge which substantially conforms in shape to said first sealable circumferential edge and (iii) said base portion is sealed by means of a continuous seal at the said first circumferential edge thereof to said upper portion at the said second circumferential edge thereof.

Claim 10: A structure defined according to Claim 2 wherein (i) said base portion comprises a first thin polymer shell having a curved surface and an inner void portion and an inner surface and an outer surface and a first sealable continuous circumferential edge, (ii) said upper portion comprises a second thin shell section having a second sealable continuous circumferential edge which substantially conforms in shape to said first sealable circumferential edge and (iii) said base portion is sealed by means of a continuous seal at the said first circumferential edge thereof to said upper portion at the said second circumferential edge thereof.

Claim 11: A structure defined according to Claim 3 wherein (i) said base portion comprises a first thin polymer shell having a curved surface and an inner void portion and an inner surface and an outer surface and a first sealable continuous circumferential edge; (ii) said upper portion comprises a second thin shell section having a second sealable continuous circumferential edge which substantially conforms in shape to said first sealable circumferential edge and (iii) said base portion is sealed by means of a continuous seal at the said first circumferential edge thereof to said upper portion at the said second circumferential edge thereof.

Claim 12: The structure claimed according to Claim 1 wherein the driving force of the molecular mass transfer of the volatile substance from within the hollow totally enclosed structure to the atmosphere surrounding said structure on operation thereof results from (a) a difference in the pressure between the gas phase of the inner void of said shell and the gas phase-containinq 3-space immediately adjacent the outer surface of said microporous polymer shell section and (b) the steady state desorption of the liquid phase of the volatile substance present in the microporous polymer into the gas phase-containing 3-space immediately adjacent the outer surface of said microporous polymer sheet section and (c) the steady state absorption of the liquid phase of volatile substance present in a microporous polymer from the gas phase within the inner void of said shell onto the inner surface of said microporous polymer sheet substance.

Claim 13: A plurality of hollow totally enclosed structures laterally and detachably interconnected having a common midplane, each of said structures being defined indi-vidually according to Claim 9, each of said structures con-nected to at least one other of said structures (i) at a location midway between the base portion of each of said structures and the upper portion of each of said structures and (ii) along at least a portion of the circumferential sealed edge of each of said individual structures sealing said upper portion to said base portion of each of said individual hollow totally enclosed structures.

Claim 14: A plurality of hollow totally enclosed structures laterally and detachably interconnected having a common midplane, each of said structures being defined indi-vidually according to Claim 10, each of said structures con-nected to at least one other of said structures (i) at a location midway between the base portion of each of said structures and the upper portion of each of said structures and (ii) along at least a portion of the circumferential sealed edge of each of said individual structures sealing said upper portion to said base portion of each of said individual hollow totally enclosed structures.

Claim 15: A plurality of hollow totally enclosed structures laterally and detachably interconnected having a common midplane, each of said structures being defined indi-vidually according to Claim 11, each of said structures con-nected to at least one other of said structures (i) at a location midway between the base portion of each of said structures and the upper portion of each of said structures and (ii) along at least a portion of the circumferential sealed edge of each of said individual structures sealing said upper portion to said base portion of each of said individual hollow totally enclosed structures.

Claim 16: A process for controllably dispensing at a visibly detectable rate continuously or discontinuously for discrete periods of time a volatile composition of matter from a container into the atmosphere surrounding said container which process comprises the steps of:

(a) entrapping the volatile composition of matter in an entrapment agent whereby a temporarily entrapped volatile composition is formed;

(b) providing a first thin shell section composed of a thin polymer shell having a curved surface and having an inner void portion, an inner surface and an outer surface and having a first continuous sealable circumferential outer edge and a first geometric configuration;

(c) placing the entrapped volatile composition in the inner void portion of said first thin shell section and onto the inner surface of said first thin shell section, said volatile composition being selected from the group consisting of perfume compositions, herbicide compositions, insecticide compositions, animal repellent compositions, air freshener compositions, pheremone compositions, odor maskant compositions, deodorant compositions and insect repellent compositions;

(d) providing a second thin shell section having a second sealable circumferential edge and having a shape and volume which are such that when said second shell is placed in conforming adjacent edge-wise contact with said first shell, a totally enclosed shell structure is produced with said entrapped volatile composition being totally enclosed within said shell section;

(e) placing said second thin shell section having said second sealable circumferential continuous edge which substantially conforms in shape to said first sealable circumferential edge onto said first thin shell section whereby said first sealable edge is in closely fitting sealable proximity with said second circumferential edge; and (f) sealing said first sealable edge to said second sealable edge whereby the resulting shell structure enclosing said entrapped volatile composition is totally enclosed and substantially air-tight with the exception of ingress and egress of volatile composition molecules controllably and at a constant velocity through the polymer wall during functional operation of the resulting shell structure;

at least a finite section of said first thin shell section or said second thin shell section comprising a microporous polymer having a porosity such that when said hollow totally enclosed structure thus formed is located in an inert gas at a pressure of less than or equal to about 1 atmosphere, said volatile material molecules are transported at a constant linear velocity and at a total derivative of concentration of volatile substance with respect to time onto the inner surface of said microporous polymer section via an adsorption mechanism and from the outer surface of said microporous polymer section via a desorption mechanism.

Claim 17: The process of Claim 16 wherein the first thin shell section is composed of a non-porous and transparent polymer and said second thin shell section is a microporous polymeric membrane and is opaque at least at the instant in time of commencement of the functional operation of said structure, said microporous polymer membrane containing solid particles having an average particle diameter of from about 0.3 up to about 500 microns.

Claim 18: The process of Claim 16 comprising the additional step (g) of placing the resulting shell structure when not in use into an outer all-enclosing container which outer container is non-porous and is composed of a material which prevents the volatile material molecules from being transported or diffusing therethrough, the dimensions of the outer container being such that the volume of said outer contain-er and the shape of said outer container are such that the outer container totally encloses the inner container, said outer container having a sealable entrance therein whereby the shell structure defined according to Claim 16 may be placed into and removed from said outer container and whereby said outer container may be sealed in an air-tight manner after the placing of said shell structure of Claim 16 into said outer container.

Claim 19: The process of Claim 16 wherein the volatile composition of matter entrapped in the entrapment agent is placed in a plurality of hollow totally enclosed structures which are laterally and detachably interconnected having a common midplane as defined according to Claim 13.

Claim 20: The hollow totally enclosed structure of Claim ]. which is in the shape of a cylinder, the ends of the cylinder being microporous and the side of said cylinder being non-porous to said volatilizable composition of matter, at least a finite portion of the side of said cylinder being translucent.

CLAIMS SUPPORTED BY THE SUPPLEMENTARY DISCLOSURE

Claim 21: A hollow totally enclosed structure capable of the release into the space surrounding said structure at a sub-stantially constant rate of at least one material selected from the group consisting of: perfume compositions, herbicide compositions, insecticide compositions, animal repellent compositions, air freshener compositions, pheromone compositions, odor maskant compositions, deodorant compositions, insect repellent compositions and compositions for the evaluation of olfactory functioning in humans; said structure comprising a thin shell totally enclosing an inner void with at least a first finite section of said thin shell consisting of a porous membrane having (i) the property of either transporting water vapor at a rate of from about 50 g/m2/day up to about 1000 g/m2/day at about 25°C and at about 50% relative humidity at about atmospheric pressure and/or having an air transport rate of 100-20,000 Gurley seconds (Gs) and (ii) a thickness in the range of from about 0.01 mils up to about 20 mils; the remaining second section of said thin shell having a porosity equal to or less than the porosity of said first finite section.

Claim 22: The hollow totally enclosed structure of Claim 21 which is capable of controllable functional operation for the controlled release into the space surrounding said structure of at lease one consumable material selected from the group consisting of perfume compositions, herbicide compositions, insecticide compositions, animal repellent compositions, air freshener compositions, pheromone compositions, odor maskant compositions, deodorant compositions, insect repellent compositions and compositions for the evaluation of olfactory functioning in humans comprising a thin shell totally enclosing an inner void, said thin shell having an inner surface and an outer surface, the inner surface thereof being the boundary of said inner void, said thin shell having a base portion and an upper portion, said base portion having an inner surface:

(a) contained totally within the inner voi of said thin shell and in place on said inner surface of said base portion, a volatile composition existing in the liquid state at ambient conditions temporaily entrapped and totally entrapped in an entrapment material at least at the instant in time of commencement of functional operation of said structure, said volatile composition being selected from the group consisting of perfume compositions, herbicide compositions, insecticide compositions, animal repellent compositions, air freshener compositions, pheromone compositions, odor maskant compositions, deodorant compositions, insect repellent compositions and compositions for the evaluation of olfactory functioning in humans;
and (b) at least a finite section of said thin shell consisting of a porous polymer membrane section having an inner surface and an outer surface, and having (i) the properties of transporting water vapor at a rate of from about 50 g/m2/day up to about 1000 g/m2/day at about 25°C at about 50% relative humidity at about atmospheric pressure and having an air transport rate of 100-20,000 Gurley seconds (Gs) and (ii) a thickness in the range of from about 0.01 mils up to about 20 mils, said porous polymer membrane section having a porosity such that when said hollow totally enclosed structure is located in the ambient environment at a point in time substantially immediately or subsequent to the commencement of functional operation of said structure and thereafter in a controllable time release manner, said volatile material molecules are transported at a constant mass flow rate both of the individual volatile components and totally through said poroas section.

Claim 23: The hollow totally enclosed structure of Claim 3 wherein the thickness of the microporous polymers is about 100 microns; the pore size is approximately 0.2 microns; the void volume of the microporous polymers is approximately 34 cubic centimeters per gram and the density is approximately 900 kilograms per cubic meter.

Claim 24: The hollow totally enclosed structure of Claim 1 wherein the thickness of the microporous polymer film is about 100 micrometers; the pore size is approximately 0.1 micrometers; the void volume of the polypropylene is approximately 34 cubic centimeters per 100 grams and the density is approximately 900 kilograms per cubic meter.

Claim 25: A structure defined according to Claim 21 wherein (i) said base portion comprises a first thin polymer shell having a curved surface and an inner void portion and an inner surface and an outer surface and a first sealable continuous circumferential edge; (ii) said upper portion comprises a second thin shell section having a second sealable continuous circumferential edge which substantially conforms in shape to said first sealable circumferential edge and (iii) said base portion is sealed by means of a continuous seal at the said first circumferential edge thereof to said upper portion at the said second circumferential edge thereof.

Claim 26: A plurality of hollow totally enclosed structures laterally and detachably interconnected having a common midplane, each of said structures being defined indi-vidually according to Claim 24 , each of said structures con-nected to at least one other of said structures (i) at a location midway between the base portion of each of said structures and the upper portion of each of said structures and (ii) along at least a portion of the circumferential sealed edge of each of said individual structures sealing said upper portion to said base portion of each of said individual hollow totally enclosed structures.

Claim 27: A process for controllably dispensing continuously or discontinuously for discrete periods of time a volatile composition of matter from a container into the atmosphere surrounding said container which process comprises the steps of:

(a) entrapping the volatile composition of matter in an entrapment agent whereby a temporarily entrapped volatile composition is formed;

(b) providing a first thin shell section composed of a thin polymer shell having a curved surface and having an inner void portion, an inner surface and an outer surface and having a first continuous sealable circumferential outer edge and a first geometric configuration;

(c) placing the entrapped volatile composition in the inner void portion of said first thin shell section and onto the inner surface of said first thin shell section, said volatile composition being elected from the group consisting of perfume compositions, herbicide compositions, insecticide compositions, animal repellant compositions, air freshener compositions, pheromone compositions, odor maskant compositions, deodorant compositions and compositions for the evaluation of olfactory functioning in humans;

(d) providing a second thin shell section having a second sealable circumferential edge and having a shape and volume which are such that when said second shell is placed in conforming adjacent edge-wise contact with said first shell, a totally enclosed shell structure is produced with said entrapped volatile composition being totally enclosed within said shell section;

(e) placing said second thin shell section having said second sealable circumferential continuous edge which substantially conforms in shape to said first sealable circumferential edge onto said first thin shell section whereby said first sealable edge is in closely fitting sealable proximity with said second circumferential edge; and (f) sealing said first sealable edge to said second sealable edge whereby the resulting shell structure enclosing said entrapped volatile composition is totally, at least a finite section of said first thin shell section or said second thin shell section comprising a microporous polymer having a porosity such that when said hollow totally enclosed structure thus formed is located in the ambient environment said volatile material molecules are transported at a constant mass flow rate both of the individual volatile components and totally through said microporous polymer section.

Claim 28: The process of Claim 27 wherein the first thin shell section is composed of a non-porous and transparent polymer and said second thin shell section is a microporous polymeric membrane and is opaque at least at the instant in time of commencement of the functional operation of said structure, said microporous polymer membrane containing solid particles having an average particle diameter of from about 0.1 up to about 20 micrometers.

Claim 29: The process of Claim 27 wherein the volatile composition of matter entrapped in the entrapment agent is placed in a plurality of hollow totally enclosed structures which are laterally and detachably interconnected having a common midplane.

Claim 30: A hollow totally enclosed structure capable of controllable functional operation for the controlled release into the space surrounding said structure of at least one consumable material selected from the group consisting of perfume compositions, herbicide compositions, insecticide compositions, animal repellent compositions, air freshener compositions, pheromone compositions, odor maskant compositions, deodorant compositions, insect repellent compositions, and compositions for the evaluation of olfactory functioning in humans comprising a thin shell totally enclosing an inner void, said thin shell having an inner surface and an outer surface, the inner surface thereof being the boundary of said inner void, said thin shell having a base portion and an upper portion, said base portion having an inner surface:

(a) contained totally within the inner void of said thin shell and in place on said inner surface of said base portion, a volatile composition existing in the liquid state at ambient conditions temporarily entrapped and totally entrapped in an entrapment material at least at the instant in time of commencement of functional operation of said structure, said volatile composition being selected from the group consisting of perfume compositions, herbicide compositions, insecticide compositions, animal repellent compositions, air freshener compositions, pheremone compositions, odor maskant compositions, deodorant compositions, insect repellent compositions and compositions for the evaluation of olfactory functioning in humans.

(b) at least a finite section of said thin shell consisting of a porous polymer shell section having an inner surface and an outer surface, and having (i) the property of transporting water vapor at a rate of between about 50 g/m2/day up to about 1000 g/m2/day at about 25°C and about 50% relative humidity at about atmospheric pressure and having an air transport rate of 100-20,000 Gurley seconds (Gs) and (ii) a thickness in the range of from about 0.01mils up to about 20 mils; and (c) a non-porous containment means removably encclosing said filled porous polymer section and located outwardly from the said outer surface of said filled porous polymer shell section, the removal of said non-porous containment means causing the commencement of functional operation of said structure and the presence of said non-porous containment means preventing said functional operation when said non-porous containment means encloses said filled porous polymer section on its outer surface.

said microporous polymer shell section having a porosity such that when said hollow totally enclosed structure is located in the ambient environment at a point in time substantially immediately or subsequent to the commencement of functional operation of said structure and thereafter in a controllable time release manner, said volatile material molecules are transported at a substantially constant mass flow rate both of the individual volatile components and totally through said microporous polymer shell section.

Claim 31: A process for providing an environment with a consumable material selected from the group consisting of perfume compositions, herbicide compositions, insecticide compositions, animal repellent compositions, air freshener compositions, pheremone compositions, odor maskant compositions, deodorant composition, insect repellent composition, compositions for the evaluation of olfactory functioning in humans comprising the steps of:

(i) placing the hollow totally enclosed structure of Claim 30 in said environment;

(ii) removing the non-porous containment means enclosing said filled porous polymeric section from the said filled porous polymeric section; and (iii) permitting the resulting system to equilibrate.

Claim 32: The hollow totally enclosed structure of Claim30 wherein the thickness of the microporous polymer film is about 100 micrometers; the pore size is approximately 0.1 micro-meters; the void volume of the polypropylene is approximately 34 cubic centimeters per 100 grams and the density is approxi-mately 900 kilograms per cubic meter.

Claim 33: A structure comprising (a) a first hollow totally enclosed structure defined according to Claim 30 and enclosing said first structure, (b) a second air-tight totally enclosed structure, said first totally enclosed structure having a volume less than said second air-tight totally enclosed structure, said first totally enclosed structure being of such dimensions that it is (i) enclosed within said second air-tight totally enclosed hollow structure, and (ii) the internal volume of said second air-tight totally enclosed hollow structure is greater than the external volume of said first hollow totally enclosed structure.

Claim 34: A structure defined according to Claim 30 wherein (i) said base portion comprises a first thin polymer shell having a curved surface and an inner void portion and an inner surface and an outer surface and a first sealable continuous circumferential edge; (ii) said upper portion comprises a second thin shell section having a second sealable continuous circumferential edge which substantially conforms in shape to said first sealable circumferential edge and (iii) said base portion is sealed by means of a continuous seal at the said first circumferential edge thereof to said upper portion at the said second circumferential edge thereof.

Claim 35: A plurality of hollow totally enclosed structures laterally and detachably interconnected having a common midplane, each of said structures being defined indi-vidually according to Claim 34, each of said structures con-nected to at least one other of said structures (i) at a location midway between the base portion of each of said structures and the upper portion of each of said of structures and (ii) along at least a portion of the circumferential sealed edge of each of said individual structures sealing said upper portion to said base portion of each of said individual hollow totally enclosed structures.

Claim 36: The process of Claim 27 comprising the additional step (g) of placing the resulting shell structure when not in use into an outer all-enclosing container which outer container is non-porous and is composed of material which prevents the volatile material molecules from being transported or therethrough, the dimensions of the outer container being such that the volume of said outer contain-er and the shape of said outer container are such that the outer container totally encloses the inner container, said outer container having a sealable entrance therein whereby the shell structure defined according to Claim 27 may be placed into and removed from said outer container and whereby said outer container may be sealed in an air-tight manner after the placing of said shell structure of Claim 27 into said outer container.

Claim 37: A hollow totally enclosed structure capable of controllable functional operation for the controlled release into the environment surrounding said structure of at least one consumable material selected from the group consisting of perfume compositions, herbicide compositions, insecticide compositions, pheromone compositions, odor maskant compositions, deodorant compositions, insect repellent compositions, and compositions for evaluation of olfactory functioning in humans comprising a thin shell totally enclosing an inner void, said thin shell having an inner surface and an outer surface, the inner surface thereof being the boundary of said inner void, said thin shell having a base portion and an upper portion, said base portion having an inner surface:

(a) contained totally within the inner void of said thin hell and in place on said inner surface of said base portion, a volatile composition existing in the liquid state at ambient conditions temporarily entrapped and totally entrapped in an entrapment material at least at the instant in time of commencement of functional operation of said structure, said volatile composition being selected from the group consisting of perfume compositions, herbicide compositions, insecticide compositions, animal repellent compositions, air freshener compositions, pheromone compositions, odor maskant compositions, deodorant compositions, insect repellent compositions and compositions for the evaluation of olfactory functioning in humans;

(b) at least a finite section of said thin shell consisting of a filled porous polymer shell section having an inner surface and an outer surface, said porous thin shell section consisting essentially of (i) a porous polymer lamina and (ii) in random admixture with said polymer lamina a filler dispersed in the pores of said polymer lamina, said filler being in the solid phase, the filler being in a phase separate from the polymer phase of the polymeric lamina; and (c) a non-porous containment means removably enclosing said filled porous polymer section and located outwardly from the said outer surface of said filled porous polymer shell section, the removal of said non-porous containment means causing the commencement of functional operation of said structure and the presence of said non-porous containment means preventing said functional operation when said non-porous containment means encloses said filled porous polymer section on its outer surface said filled porous polymer shell section having a porosity such that when said hollow totally enclosed structure is located in the ambient environment at a point in time sub-stantially immediately or subsequent to the commencement of functional operation of said structure and thereafter in a controllable time release manner, said volatile material molecules are transported at a constant mass flow rate both of the individual volatile components and totally through said microporous polymer shell section.

Claim 38: A process for providing a space with a consumable material selected from the group consisting of perfume compositions, herbicide compositions, insecticide compositions, animal repellent compositions, air freshener compositions, pheromone compositions, odor maskant compositions, deodorant compositions, insect repellent compositions, and compositions for the evaluation of olfactory functioning in humans comprising the step of ;

(i) placing the hollow totally enclosed structure of Claim 37 in said space;

(ii) removing the non-porous containment means enclosing said filled porous polymeric section of the said filled porous polymeric section; and (iii) permitting the resulting system to equilibrate.

Claim 39: The hollow totally enclosed structure of Claim 37 wherein the thickness of the microporous polymer is about 100 micrometers; the pore size is approximately 0.1 micrometers; the void volume of the polypropylene is approximatley 34 cubic centimeters per 100 grams and the density is approximately 900 kilograms per cubic meter.

Claim 40: A structure comprising (a) a first hollow totally enclosed structure defined according to Claim 37 and enclosing said first structure, (b) a second air-tight totally enclosed structure, said first totally enclosed structure having a volume less than said second air-tight totally enclosed structure, said first totally enclosed structure being of such dimensions that it is (i) enclosable within said second air tight totally enclosed hollow structure, and (ii) the internal volume of said second air-tight totally enclosed hollow structure is greater than the external volume of said first hollow totally enclosed structure.

Claim 41: A structure defined according to Claim 37 wherein (i) said base portion comprises a first thin polymer shell having a curved surface and an inner void portion and an inner surface and an outer surface and a first sealable continuous circumferential edge; (ii) said upper portion comprises a second thin shell section having a second sealable continuous circumferential edge which substantially conforms in shape to said first sealable circum-ferential edge and (iii) said base portion is sealed by means of a continuous seal at the said first circumferential edge thereof to said upper portion at the said second circumferential edge thereof.

Claim 42: A plurality of hollow totally enclosed structures laterally and detachably interconnected having a common midplane, each of said structures being defined individually according to Claim 41, each of said structures connected to at least one other of said structures (i) at a location midway between the base portion of each of said structures and the upper portion of each of said structures and (ii) along at least a portion of the circumferential sealed edge of each of said individual structures sealing said upper portion to said base porition of each of said individual hollow totally enclosed structures.

Claim 43: The structure defined according to Claim 21 wherein the porous membrane has the property of transporting water vapor at a rate of from about 50 g/m2/day up to about 1000 g/m2/day at about 25°C and at about 50% relative humidity at about atmospheric pressure.

Claim 44: The structure of Claim21 wherein the porous membrane has the property of having an air transport rate of 100-20,000 Gurley seconds.

Claim 45: A hollow totally enclosed structure capable of the release into the space surrounding said structure at a substantially constant rate of at least one material selected from the group consisting of perfume compositions, herbicide compositions, insecticide compositions, animal repellent compositions, air freshener compositions, pheromone compositions, odor maskant compositions, dodorant compositions, insect repellent compositions and compositions for the evaluation of olfactory functioning in humans; said structure comprising a thin shell totally enclosing an inner void with at lease a first finite section of said thin shell consisting of a porous membrane having (i) the property of either transporting water vapor at a rate of between about 50 up to about 1000 g/m2/day at about 25°C
and at about 50% relative humidity at about atmospheric pressure and/or having an air transport rate of 100-20,000 Gurley seconds;
and (ii) a thickness in the range of from about 0.01 mils up to about 20 mils, the remaining said second section of said thin shell having a porosity equal to or less than the porosity of said first finite section, said porous polymer shell section having a porosity such that when said hollow totally enclosed structure is located in the ambient environment at a pressure of less than or equal to about one atmosphere at a point in time substantially immediately or subsequent to the commencement of functional operation of said structure and thereafter in a controllable time release manner and at a constant rate, said volatile material molecules are transported at a constant mass flow rate both of the individual volatile components and totally, either:

(i) onto the inner surface of said porous polymer shell section via an adsorption mechanism and from the outer surface of said porous polymer shell section to the atmosphere surrounding said structure via a desorption mechanism; and/or (ii) through said porous polymer shell section by means of capillary action.

Claim 46: A hollow totally enclosed structure capable of controllable functional operation for the controlled release into the environment surrounding said structure of at least one consumable material selected from the group consisting of perfume compositions, herbicide compositions, insecticide compositions, animal repellent compositions, air freshener compositions, pheromone compositions, odor maskant compositions, deodorant compositions, insect repellent compositions and compositions for the evaluation of olfactory functioning in humans, comprising a thin shell totally enclosing an inner void, said thin shell having an inner surface and an outer surface, the inner surface thereof being the boundry of said inner void, said thin shell having a base portion and an upper portion, said base portion having an inner surface:

(a) contained totally within the inner void of said thin shell and in place on said inner surface of said base portion, a volatile composition existing in the liquid state at ambient conditions temporarily entrapped and totally entrapped in an entrapment material at least at the instant in time of commencement of functional operation of said structure, said volatile composition being selected from the group consisting of perfume compositions, herbicide compositions, insecticide compositions, animal repellent compositions, air freshener compositions, pheromone compositions, odor maskant compositions, deodorant compositions, insect repellent compositions and compositions for the evaluation of olfactory functions in humans;

(b) at least a finite section of said thin shell consisting of a filled porous polymer shell section having an inner surface and an outer surface, said porous thin shell section consisting essentially of (i) a porous polymer lamina and (ii) in randon admixture-with said polymer lamina a filler dispersed in the pores of said polymer lamina, said filler being in the solid phase, the filler being in a phase separate from the polymer phase of the polymeric lamina; and (c) a non-porous containment means removably enclosing said filled porous polymer section and located outwardly from the said outer surface of said filled porous polymer shell section, the removal of said non-porous containment means causing the commencement of functional operation of said structure and the presence of said non-porous containment means preventing said functional operation when said non-porous containment means encloses said filled porous polymer section on its outer surface said filled porous polymer shell section having a porosity such that when said hollow totally enclosed structure is located in the ambient environment at a pressure of less than or equal to about one atmosphere at a point in time substantially immediately or subsequent to the commencement of functional operation of said structure and thereafter in a controllable time release manner, said volatile material molecules are transported at a substantially constant mass flow rate, both of the individual volatile components and totally, either:

(i) onto the inner surface of said filled porous polymer shell section via an adsorption mechanism and from the outer surface of said filled porous polymer shell section to the atmosphere surrounding said structure via a desorption mechanism, the said adsorption mechanism and the said desorption mechanism being operable as a result of the critical surface tension said filler phase being greater than the critical surface tension of said volatile composition existing in the liquid state; and/or (ii) through said filled porous polymer shell section by means of capillary action.

Claim 47: A process for providing a environment with a consumable material selected from the group consisting of perfume compositions, herbicide compositions, insecticide compositions, animal repellent compositions, air freshener compositions, pheremone compositions, odor maskant compositions, deodorant compositions, insect repellent compositions, compositions for the evaluation of olfactory functions in humans comprising the steps of:

(i) placing the hollow totally enclosed structure of Claim 45 in said three-space;

(ii) removing the non-porous containment means enclosing said filled porous polymeric section from the said filled porous polymeric section; and (iii) permitting the resulting system to equilibrate.

Claim 48: The hollow totally enclosed structure of Claim 46 wherein said filled porous polymer shell section has a porosity such that when said hollow totally enclosed structure is located in an inert gas at a pressure of less than or equal to about one atmosphere at a point in time substantially immediately and subsequent to the commencement of functional operation of said structure and thereafter in a controllable time release manner, said volatile material molecules are transported at a substantially constant mass flow rate, both of the individual volatile components and totally onto the inner surface of said filled porous polymer shell section via an adsorption mechanism and from the outer surface of said filled porous polymer shell section to the atmosphere surrounding said structure via a desorption mechanism, the said adsorption mechanism and the said desorption mechanism being operable as a result of the critical surface tension of said filler phase being greater than the critical surface tension of said volatile composition existing in the liquid state.

Claim 49: The hollow totally enclosed structure of Claim 45 wherein the thickness of the microporous polymer is about 100 micrometers; the pore size is approximately 0.1 micrometers; the void volume of the polypropylene is approximately 34 cubic centimeters per gram and the density is approximately 900 kilograms per cubic meter.

Claim 50: A structure comprising (a) a first hollow totally enclosed structure defined according to Claim 45 and enclosing said first structure, (b) a second air-tight totally enclosed structure, said first totally enclosed structure having a volume less than said second air-tight totally enclosed structure said first totally enclosed structure being of such dimensions that it is (i) enclosable within said second air-tight totally enclosed hollow structure, and (ii) the internal volume of said second air-tight totally enclosed hollow structure is greater than the external volume of said first hollow totally enclosed structure.

Claim, 51: A structure defined according to Claim 45 wherein (i) said base portion comprises a first thin polymer shell having a curved surface and an inner void portion and an inner surface and an outer surface and a first sealable continuous circumferential edge; (ii) said upper portion comprises a second thin shell section having a second sealable continuous circumferential edge which substantially conforms an shape to said first sealable circumferential edge and (iii) said base portion is sealed by means of a continuous seal at the said first circumferential edge thereof to said upper portion at the said second circumferential edge thereof.

Claim 52: A plurality of hollow totally enclosed structures laterally and detachably interconnected having a common midplane, each of said structures being defined indi-vidually according to Claim 50, each of said structures con-nected to at least one other of said structures (i) at a location midway between the base portion of each of said structures and the upper portion of each of said structures and (ii) along at least a portion of the circumferential sealed edge of each of said individual structures sealing said upper portion to said base portion of each of said individual hollow totally enclosed structures.

Claim 53: A process for controllably dispensing continuously or discontinuously for discrete periods of time a volatile composition of matter from a container into the environment surrounding said container which process comprises the steps of:

(a) entrapping the volatile composition of matter in an entrapment agent whereby a temporarily entrapped volatile composition is formed;

(b) providing a first thin shell section composed of a thin polymer shell having a curved surface and having an inner void portion, an inner surface and an outer surface and having a first continuous sealable circumferential outer edge and a first geometric configuration:

(c) placing the entrapped volatile composition in the inner void portion of said first thin shell section and onto the inner surface of said first thin shell section, said volatile composition being selected from the group consisting of perfume compositions, herbicide compositions, insecticide compositions, animal repellant compositions, air freshener compositions, pheremone compositions, odor maskant compositions, deodorant compositions for the evaluation of olfactory functions in humans and insect repellent compositions;

(d) providing a second thin shell section having a second sealable circumferential edge and having a shape and volume which are such that when said second shell is placed in conforming adjacent edge-wise contact with said first shell, a totally enclosed shell structure is produced with said entrapped volatile composition being totally enclosed within said shell section;

(e) placing said second thin shell section having said second sealable circumferential continuous edge which substantially conforms in shape to said first sealable circumferential edge onto said first thin shell section whereby said first sealable edge is in closely fitting sealable proximity with said second circumferential edge; and (f) sealing said first sealable edge to said second sealable edge whereby the resulting shell structure enclosing said entrapped volatile composition is totally enclosed and substantialllly air-tight with the exception of ingress and egress of volatile composition molecules controllably and at a constant velocity through the polymer wall during functional operation of the resulting shell structure;

at least a finite section of said first thin shell section or said second thin shell section comprising a microporous polymer having a porosity such that when said hollow totally enclosed structure thus formed is located in the ambient environment at a pressure of less than or equal to about one atmosphere, said volatile material molecules are transported at a substantially constant mass flow rate, both of the individual volatile components and totally, onto the inner surface of said microporous polymer section via an adsorption mechanism and from the outer surface of said microporous polymer section via a desorption mechanism.

Claim 54 : The process of Claim 53 wherein the first thin shell section is composed of a non-porous and transparent polymer and said second thin shell section is a microporous polymeric membrane and is opaque at least at the instant in time of commencement of the functional operation of said structure, said microporous polymer membrane containing solid particles having an average particle diameter of from, about 0.1 up to about 20 micrometers.

Claim 55: The process of Claim 53 comprising the additional step (g) of placing the resulting shell structure when not in use into an outer all-enclosing container which outer container is non-porous and is composed of a material which prevents the volatile material molecules from being transported or diffusing therethrough, the dimensions of the outer container being such that the volume of said outer contain-er and the shape of said outer container are such that the outer container totally encloses the inner container, said outer container having a sealable entrance therein whereby the shell structure defined according to Claim 53 may be placed into and removed from, said outer container and whereby said outer container may be sealed in an air-tight manner after the placing of said shell structure of Claim 53 into said outer container.

Claim 56 : The process of Claim 53 wherein the volatile composition of matter entrapped in the entrapment agent is placed in a plurality of hollow totally enclosed structures which are laterally and detachably interconnected having a common midplane.

Claim 57: The structure of Claim 45 wherein the porous membrane has the property transporting water vapor at a rate of from about 50 g/m2/day up to about 1000 g/m2/day at about 25°C and at about 50% relative humidity at about atmospheric pressure.

Claim 58: The structure of Claim 45 wherein the porous membrane has the property of having an air transport rate of 100-20,000 Gurley seconds.

Claim 59: The structure of Claim 45 wherein the porous membrand has the property of having an air transport rate of 8,000-12,000 Gurley seconds.