CA2092176C - Combination for improved delivery of tobacco modifying agents - Google Patents

Abstract

Disclosed are articles, such as smoke filters, which contain fibers that have complex geometry in combination with tobacco modify-ing agents such as flavorants. The fibers are preferably made of polyester such as poly(eth-ylene terephthalate) and preferably are cap-able of spontaneously transporting water or n-decane on their surfaces. The articles of the invention result in improved delivery of the to-bacco modifying agent to the user.

Description

WO92/05713 PCI/US91tO7109 A ~R~N~ION FOR lCql:'m;Vhl~ DELI~tEP~Y O~
TOBACCO MODIFYING AGENTS
Field of the Invention This invention concerns certain f ibers in combination with tobacco modifying andior selective removal agents.
Back~round of the Invention Many types of tobacco modifying agents are known in the art to be added to smoking products to modify the tobacco smoke. For example, flavorants are added to 6moking products to enhance their taste and to compensate for variations in tobacco quality and blena.
Although flavorants are traditionally applied to the tobacco portion of the smoking product, this practice results in only a small fraction of the flavorant ever reaching the smoker. Most of a flavorant added to the tobacco is lost in the sidestream smoke produced during the static burn period of the smoking article or is removed by the smoke filter. The low flavorant delivery efficiencies associated with application on tobacco necessitates the use of relatively large quantities of flavorant to achieve the desired effect. Because many of these flavorants, such as menthol, for example, are expensive, inefficient utilization can add significantly to the cost of the smoking product. In addition, ~, flavorants applied to the tobacco are subjected to the high heat of combustion which can undesirably alter their organoleptic characteristics.
In response to these problems, there has been substantial effort to apply flavorants to the filter.
It was 6hown many years ago that smoke aerosols could tran6port signif icant quantities of relatively non-volatile materials from a structure of moderate surface WO 92/05713 PCr/US91/07109 .
2092176 ~
,~ , f ` -- 2 ---.
area, even though a gas at a comparable t~ Lur e is ineffective in this regard. Attempts at the practical implementation of this rhf~nl using celiulose acetate filters revealed, however, that although r aerosols transported flavorant very efficiently from freshly made filters, this advantage was lost as the flavoran~ diffused away from the surface and into the bulk of the f ilter f ibers .
Efforts to solve this problem by using polymers impermeable to the flavorants, such as polypropylene, eliminated the time d~rpn~nre of f lavorant delivery observed with cellulose acetate filters, but did not permit the development of a functional flavorant delivery system. The causes of this failure were, f irst, the f lavorant deIivery ef f iciencies f or these nonpermeable polymer systems were too low to be useful, and second, impermeable f ilter media had no af f inity f or -the flavorant which consequently diffused to the tobacco where it endured the same fate as flavorants applied 2 0 directly to the tobacco .
- In spite of years of concerted effort, neither the cigarette noF the filter material industry has developed an efficient general flavorant delivery system that does not absorb or loose the f lavorant over time .
Prior art of this area reflects a strong interest in technology for the efficient and consistent deliver of tobacco modifying agents, especially flavorants.
~owever, the abundant patented technologies f or flavorant delivery almost invariably employ one of the J
following four strategies:
l. A flavorant is contained by some physical means and is released either by mechanlcal destruction of the containment apparatus~ or by controlled leakage (see, f~r example, I~.S. Patents 3,219,041;

3~ 3,297,038,; 3,339,557; and 4,720,423~.
., . ,, ~-, -WO 92/05713 PCIIUS9110~109 . ~2as2l7~

2 . A f lavorant is adsorbed on a material whose surf ace has been customized so that the flavorant will be displaced by the moisture or heat in the smoke (see, for example, U.S. Patents 3,236,244;
3,280,823; and 4,662,384).
3 . A f lavorant is absorbed in a polymeric matrix and is then released by the plasticizing action of moisture or heat in the smoke ( see, f or example, U.S. Patents 4,662,384; 3,144,024; and 4,729,391).
A portion of the prior art in this area addresses the concept of modifying the fiber shape or filter geometry of current cellulose acetate f ilters to achieve improved flavorant containment or delivery (see, for example, U.S. Patents 4,180,536, 4,619,279; and 4,821,750).
4 . A f lavorant undergoes a chemical reaction with another compound to form a new _ulld that will regenerate the original flavorant upon thermal -sltion (see U.S. Patent 3,288,146).
Although there is substantial prior art, virtually every implementation of this art pQss~oesec limitations which render its commercial application impractical.
These limitations are largely def ined by the f lavorant delivery strategy employed and will, therefore, be so organized here.
Mechanical or physical f lavorant containment devices which are incorporated into the f ilter and ~LuLed prior to smoking are very complex and expensive to produce. They introduce signif icant variation into the performance of the smoking article because of inconsistencies in the pattern of their breakage, and they interfere with the normal function of the filter by altering smoke flow through the filter. They also increase the effort and complexity to the consumer who uses the product.

WO 92/05713 PCI/US91/0~l09 Ad60rbed flavorant6 which are incc,.~ulc.ted into the filter and released by the heat or moi6ture content o~
the 6moke are not efficiently delivered until enough of the 6moking article has been crn ' to allow adequate moi6ture and heat to reach the f ilter . A6 a con6equence, the flavorant i6 not available to augment smoke taste during the first few puff6, when it i6 generally acknowledged a6 being mo6t needed. In addition, ab60rbant6 mu6t be cu6tomized to achieve the desired release characteristics for each f lavorant and, therefore, are not useful for delivering naturally occurring f lavoring materials which consist of large numbers of independent chemical entities.
Absorbed flavorants which are dissolved in polymer matrice6 and relea6ed by the pla6ticizing action of moisture or heat in the 6moke are 6ubject to the 6ame limitation6 a6 ad60rbed flavorant6. In addition, ab60rbed flavorant6 are 6ubject to time ~ r-~n~l~nt 1066e6 in delivery efficiency becau6e of diffusion of the flavorant into the bulk of the fiber polymer. This limitation is especially evident when a conventional c~ 1ose acetate filter is used as the flavorant absorber .
Derivatized flavorants are almo6t always inappropriate for u6e in filter flavorant delivery sy6tem6 because relatively high temperatures are required for their release. Derivatized flavorants are, therefore, typically applied to the tobacco portion of the 6moking product, where the liberated flavorant .
produced during combustion is subject to chemical alteration and loss during the static burn period of the smoking article. The develûpment of derivatized flavorants is highly specific for each flavorant and, therefore, excludes naturally occurring~ flavoring -WO 92/05713 PCr~US91/07109 _ 5 _ 2~92~
materials which are ~-sefl of a large number of - ; nfl--r-~nflPnt chemical entities .
Although f lavorants are the most commonly used tobacco modifying agents, selective removal additives 5 can also serve as tobacco modifying agents. In contrast to flavorants, selective removal additives modify tobacco smoke by removing, rather than adding, certain c or classes of: .ul,ds. SelectiVe removal additives are applied to the filter and, therefore, like f lavorants, can be absorbed by the f ilter f ibers and lose their effectiveness. Here, too, significant vv~ -nts in the performance of selective removal additives could be achieved by OV~I~ in~ the limitations imposed by the substrate to which the additives are applied.
Such fibers capable of transporting hydrophilic or hydrophobic fluids will be referred to herein as "spontaneously transportable fibers" or, alternatively, "spontaneously wettable fibers". We have unexpectedly discovered that use of fibers of sufficiently complex geometry, especially spontAn~ollcly transportable fibers, in combination with tobacco modifying agents, such as flavorants, results in improved delivery of such agents.
We have also unexpectedly discovered that use of these fibers in combination with selective removal additives results in i ov~:d selective removal of unwanted materials such as phenol.
" ,C -ry of the Invention The present invention is directed to a combination comprising at least one fiber of sufficient geometry and at least one tobacco modifying agent.
The fiber useful in the present invention has at least one continuous groove oriented 2xia~ ly along the WO 92/05713 PCr/US91/07109 209217~ ~ --fiber wherein said fiber has a cross--section having a shape factor X that satisfies the following equation:
X 4r + (1r--2 ) D
wherein P is the perimeter of the f iber and r i8 the radius of the circumscribed circle circumscribing the f iber cross--section and D is the minor axis dimension across the fiber cros6--6ection.
In a preferred Pmho~ nt, the fiber u6eful in the present invention i6 capable of spontaneously transporting water on the surf ace thereof and ha6 at lea6t one continuous groove oriented axially along the fiber, and said fiber satisfies the following equation - (l--X cos a) < ~
wherein ~a i6 the advancing contact angle of water mea6ured on a flat film made from the same material as the fiber and having the same surface treatment, if any, X is a shape f actor of the f iber cross--section that satisfies the following equation X = 4r + (n--2)D
wherein Pw is the wetted perimeter of the ~iber and r is the radius of the circumscribed circle circumscribing the f iber cross--section and D i6 the minor axis dimension across the f iber cro66--6ection .
In another preferred ~ --nt, the fiber useful in the present invention is capable of spontaneously transporting n--decane on the surf ace thereof and has at least one continuous groove oriented axially along the fiber, and said fiber satisfies the following equation .

WO 92/05713 PCI /US9l/07109 ; 2Q92176 (1-X cos ~a) < ~
wherein ~a is the advancing contact angle of n--decane measured on a flat film made from the same material as the f iber and having the same 6urf ace treatment, if any, X is a shape f actor of the f iber cross--section that satisfies the following equation w X ~ 4r + (7r--2)D
wherein Pw is the wetted perimeter of the f iber and r is the radius of the circumscribed circle circumscribing the f iber cross--6ection and D is the minor axis dimension across the fiber cross--section .
For all of the f ibers useful in the present invention, it is preferred that X is greater than 1.2, more preferably greater than about 2.5, most preferably greater than about 4. Also, it is preferred that 2D is greater than 1, more preferred is where 2--D is between 1. 5 and 5 .
For the fibers that spontaneously transport water, 3 0 it is pref erred that the f iber of the invention satisf ies the f ormula:
12 10 ~ (1--X cos ~aj < --0 3~
wherein YLA is the surface tension of water in air in dynes~cm, p is the fiber density in grams~cc, and dpf is the denier (kg~m) of the single fiber.
The combination of the invention preferably comprises a plurality of the f ibers of the invention and at least one tobacco modifying agent wherein the WO 92/05713 PCr/US91/07109 l2~92i76 _ . . 8 --combination is in the form of a tobacco smoke filter in ubstantially cylindrical form.
~rief Descri~tion of thé Drawinc~s Figure 1 -- graph of percent delivery efficiency versus milligrams (mg) of triacetin per filter for a cigarette filter of the invention and for a conventional cigarette filter. The o symbols represent filters of the invention and the symbols represent filters made from fibers of round cross--section.
Figure 2A -- illustration of the behavior of a drop of a fluid which has just contacted a fiber that is spontaneously transportable at time = O. The arrows 1 ~hP] 1 ed "LFA" indicate the location of the liquid--fiber--air interface.
Figure 2B -- illustration of the behavior of a drop of a fluid on a fiber that is spontaneously transportable at time = t1 (tl >O). The arrows labelled "LFA" indicate the location of the liquid--f iber--air 2 O interf 2ce .
Figure 2C -- illustration of the behavior of a drop of a fluid on a fiber that is spontaneously transportable at time = t2 tt2 >tl). The arrows labelled "LFA" indicate the location of the liquid--fiber--air interface.
Figure 3 -- schematic representation of an orif ice of a spinneret useful for producing a spontaneously transportable f iber .
Figure 4 -- schematic representation of an orif ice of a spinneret useful for producing a spontaneously transportable f iber .
Figure 5 -- schematic representation of an orif ice of a spinneret useful for producing a spontaneously transportable f iber.
, WO 92/05713 PCr/US91/07109 -. .
` 2~217~
g _ , Figure 6 -- schematic L~:~uLesel~ation of an orifice of a spinneret useful for producing a spontaneously transportable f iber .
Figure 6B -- schematic representation of an orif ice of a spinneret useful for producing a spontaneously transportable f iber .
Figure 7 -- schematic representation of an orif ice of a spinneret having 2 repeating units, joined end to end, of the orifice as shown in Figure 3.
Figure 8 -- schematic representation of an orifice of a spinneret having 4 repeating units, joined end to end, of the orif ice as shown in Figure 3 .
Figure 9 -- photomicrograph of a poly (ethylene terephthalate) f iber cross--section made using a spinneret having an orif ice as illustrated in Figure 3 (specific dimensions of spinneret orifice described in Example 1 ) .
Figure 10 -- photomi~;L Ul ~L ~h of a polypropylene fiber cross--section made using a spinneret having an orifice as illustrated in Figure 3 (specific dimensions of spinneret orif ice described in Example 2 ) .
Figure 11 -- photomicrograph of a nylon 66 fiber cross--section made using a spinneret having an orif ice as illustrated in Figure 3 (specific dimensions of spinneret orifice described in Example 2).
Figure 12 -- 6chematic representation of a poly(ethylene terephthalate) fiber cross--section made using a spinneret having an orifice as illustrated in 0 Figure 4 (specific dimensions of spinneret orifice described in Example 8).
Figure 13 -- photûmicrograph of a poly(ethylene terephthalate) fiber cross--section made using a spinneret having an orifice as illustrated in Figure 5 (specific dimensions of spinneret orifice descrilbed in Example 9 ) .
_ _ _ WO 92/0~713 PCI/US91/07109 .
~- 1 0 Figure 14 -- photomicrograph of a poly(ethylene terephthalate) fiber cross--section made using a spinneret having an orifice as illustrated in Figure 7 (specific ~ of spinneret orifice described in Example lO).
Figure 15 -- photomicrograph of a poly (ethylene terephthalate~ f iber cross--section made using a spinneret having an orif ice as illustrated in Figure 8 (specific dimensions of spinneret orifice described in Example 11).
Figure 16 -- schematic representation of a f iber cross--section made using a spinneret having an orif ice as illustrated in Figure 3 (Example 1). Exemplified is a typical means of determining the shape f actor X .
Figure 17 -- photomiuLuyL-ph of a poly(ethylene terephthalate~ fiber cross--section made using a spinneret having an orif ice as illustrated in Figure 6 (specific_dimensions of spinneret oririce described in Example 12 ) .
Figure 17B -- schematic representation of a poly(ethylene terephthalate) fiber cross--section made using a spinneret having an orif ice as illustrated in Figure 6B (specific dimensions of spinneret orifice described in Example 13).
Figures 18 and 19 -- graphs showing the performance of the invention for maintaining a constant delivery efficiency for glycerol triacetate over extended pèriods of 6torage.
.v Detailed Descri~tion of the Invention The fibers useful in the present invention have a complex cross--section ,_ LLY that results in a surface area that allows far more efficient delivery of tobacco modifying agent to the user. These fiberS also allow for more efficient selective removal when selective WO 92/0~713 PCI/US91/07109 _' ., 20~7~
removal additives are applied to the fiber6 of the present invention. The fibers are preferably spontaneously transportable. For hydrophilic tobacco modifying agents, the fibers are preferably the preferred fibers that are capable of spontaneously tr~nsporting water on the surfaces thereof. Similarly, for hydrophobic tobacco modifying agents, the fibers are preferably the preferred fibers that are capable of spontaneously transporting n--decane on the surfaces thereof.
It iB not desired to be bound by any particular theory or ---hAnicm; however, it is believed that a spon~n~o11c1y wettable fiber, when contacted with an appropriate fluid tobacco modifying agent,~ transports said agent on the fiber surface thereby substantially or completely coating the fiber with the agent.- Also, it is believed that if a spontaneously wettable fiber is dipped or immersed in an appropriate f luid tobacco modifying agent and then removed from the fluid, said fiber retains a sufficient amount of said fluid which also results in a fiber substantially or completely coated with said agent. As used in this context, "an appropriate fluid tobacco modifying agent" is one which is capable of being spontaneously transported by the fiber in question. The coated fibers are optionally allowed to dry or substantially dry prior to use.
The three important variables fundamental to the liguid transport behavior are (a) surface tension of the liguid, (b) wettability or the contact angle of the solid with the liquid, and (c) the geometry of the solid surface. Typically, the wettability of a solid surface by a liguid can be characterized by the contact angle that the liquid surface (gas--liquid interface) makes with the solid surface (gas--solid surface). Typically, 3~ a drop of liquid placed on a solid surface makes a _ _ _ _ _, . _ . . ... .. _ . . .

WO 92/05713 PCr/US91/07109 '. .'" ' ~
12 - ~
contact angle, 0, with the solid surface. If this contact angle is less than 9O, then the solid is on~ red to be wet by the liquid. However, if the contact angle is greater than 90, 6uch as_with water on Teflon (trademark) surface, the solid is not wet by the llquid. Thus, it is desired to have a minimum contact angie for ~nhAnr-~d wetting, but definitely, it must be less than 90. However, the contact angle also depends on surface inh~ ,cneities (chemical and physical, such as r~ rhn~s), contamination, chemical~physical Lre~l L of the 601id surface, as well as the nature of the liquid surface and its contamination. Surface ~ree energy of the solid also influences the wetting behavior. The lower the surface energy of the solid, 15 the more difficult it is to wet the solid by liquids having high surface tension. Thus, for example, Teflon, which has low surface energy does not wet with water.
(Contact angle for Teflon--water system is 112 . ) However, it is possible to treat the surface of Teflon with a monomolecular film ~of protein, which signif icantly ~nhAnr~c the wetting behavior .~ Thus, it is possible to modify the surface energy of fiber - surfaces by al?propriate lubricants~finishes to enhance liquid transport. The contact angle of polyethylene terephthalate (PET), nylon 66, and polypropylene with water is 80, 71, and 108, respectively. Thus, nylon 66 is more wettable with water than PET. However, for polypropylene, the contact angle is >90~, and thus is nonwettable with water.
The second plO~er ~y of fl~nrl;~r Lal importance to the rh~n~ - of liquid transport is surface tension of the liquid.
The third property of fundamental importance to the rh~nl -n~ of liguid transport is the geometry of the solid surface. Although it is known that grooves .
~ . -- .

WO 92/057~3 PCr~US91/07109 ~92176 enhance f luid transport in general, it has been discovered that particular ~f tL les and arrangements of deep and narrow grooves on f ibers and treatments thereof can allow for the 6pontaneous surface transport of fluids in single fibers. Thus, preferred fibers for use herein are those with a combination of properties wherein an individual fiber is capable of spontaneously transporting water or n~ecane on its surf ace .
The particular geometry of the deep and narrow lo grooves can be important. For example, in grooves which have the f eature that the width of the groove at any depth is equal to or less than the width of the groove at the mouth of the groove, "bridging" of=the liquid ~cross the restriction is possible and thereby the effective wetted perimeter (Pw) is reduced. Of course, the f luid used to wet the f iber to determine the wetted perimeter is, accordingly, water in the case of f ibers which spontaneously transport water, and n-decane in the case of fibers which spontaneously transport n--decane.
In any case, it is preferred that Pw is substantially equal to the geometric perimeter.
The number of continuous grooves present in the fiber useful in the present invention is not critical as long as the required ge~ LLY is present. Typically there are at least 2 grooves present, and preferably less than 10.
"Spontaneously transportable" and derivative terms thereof refer to the behavior of a fluid in general and in particular a drop of f luid, such as water or n--decane, when it is brought into contact with a single fiber such that the drop spreads along the fiber. Such behavior is contrasted with the normal behavior of the drop which forms a static ellipsoidal shape with a unique contact angle at the intersection of the liquid ~nd the solid fiber. It is obvious that the formation _ . . . . _ . _ . .

WO 92/05713 PCr/US91/07109 of the ellipsoidal drop takes a very 6hort time but remains 6tationary thereafter. Figures 2A, 2B and 2C
illu6trate spontaneou6 f luid tran6port on a f iber 6urface. The key factor i6 the ~ L of the location of the air, liquid, solid interface with time. If such interface moves just after contact of the liquid with the fiber, then the fiber i8 spontaneously transportable; if such interf ace is stationary, the fiber is not spont;~nDol~cIy transportable. The 6pontaneously transportable phDn~ e~on is easily visible to the naked eye for large filaments (>20 denier (kg/m) per ~ilament (dpf) ) but a microscope may be nDcncsAry to view the fiber6 if they are less than 20 dpf. Colored fluids are more ea6ily seen but the spontaneously transportable rhPn~ --n is not rl~rDnrlDnt on the color.
It is possible to have sections of the circumference of the fiber on which the fluid moves faster than other SQctiOns. In such case the air, liquid, solid interface actually extends over a length of the fiber. Thus, such fibers are also spontaneously LLd~la~ Lable in that the air, liquid, solid interface is moving as opposed to stationary .
Spontaneous transportability is basically a surface p~D- -nnn; that is the movement of the f luid occurs on the surface of the fiber. However, it is possible and may in some cases be desirable to have the spontaneously tran6portable rhD- occur in conjunction with absorption of the f luid into the f iber . The behavior visible to the naked eye will depend on the relative ., rate of absorption v6. 6pontaneous transportability.
For example, if the relatiYe rate of absorption is large 6uch that most of the f luid i6 absorbed into the f iber, the liquid drop will fl; ~rpe~r with very little - .v~ - L
of the air, liquid, solid interface along the fiber 6urface wherea6 if the rate of absorption is small .. . _ _ _ .. . . _ _ _ _ _ _ _ _ _ _ _ _ WO 92/05713 PCll`/US91/07109 - 15 _ 2~ 92~7 ~
conpared to the rate of spontaneous transportability the observed behavior will be that of wlc.kins or transport, as exemplified in Figures 2A through 2C. In Figure 2A, a drop of aqueous fluid is just placed on the fiber (time = 0). In Figure 2B, a time interval has elapsed (time 5 tl) and the fluid starts to be 6pontaneously transported. In Figure 2C, a second time interval has passed (time = t2) and the fluid has been spontaneously tran6ported along the fiber surface further than at time = tl.
A preferred fiber useful in the present invention is capable of spontaneously transporting water on the surface thereof. Distilled water can be employed to test the spontaneous transportability phenomeno~;
however, it is of ten de6irable to incorporate a minor amount of a colorant into the water to better visualize the 6pontaneous transport of the water, so long as the water with colorant behaves substantially the same as pure water under test conditions. We have found aqueous Syltint Poly Red (trademark) from M; 11 ;k~n Chemicals to be a useful solution to test the spontaneous transportability ~h~n, -nnn. The Syltint Poly Red solution can be used undiluted or diluted significantly, e.g., up to about 50x with water. In addition to being capable of transporting water, such a fiber useful in the present invention is also capable of spontaneously transporting a multitude of other hydrophilic fluids such as aqueous f luids . Aqueous f luids are those f luids comprising about 50% or more water by weight, preferred '~ 30 is about 75~ or more water by weight, most preferred is about 90% or more water by weight. In addition to being able to transport aqueous fluids, such a fiber useful in the present invention is also capable of transporting an alcoholic fluid on its surface. Alcoholic fluids are WO 92/05713 - PCI`/US91/07109 ' ~ 209~176 -~16 -tbose fluids comprising greater than about 50% by weight of an alcoholic cu_~vu.,d of the f ormula R--O~ ~
wherein R is an aliphatic or aroDatic group containing up to 12 carbon atoms. It i6 preferred that R is an alkyl group of l to 6 carbon atoms, more preferred is l to 4 carbon atoms. Examples of alcohols include methanol, ethanol, n--propanol and iso--propanol.
Preferred alcoholic fluids comprise about 70% or more by weight of a suitable alcohol. Of course, it is also preferred that such a fiber is capable of spontaneously transporting hydrophilic tobacco modifylng agents.
Another class of preferred ~ibers useful in the present invention is capable of spontaneously transporting n--decane on the surface thereof. As~in the case of water as described hereinbefore, the n--decane can be colorized for better visualization. In addition to being capable of spontaneously transporting n--decane, such a f iber is also typically capable of spontaneously transporting other hydrophobic fluids such as cyclo--hexane, xylene or ~--pinene. Of course, it is also preferred that such a fiber is capable of spontaneously transporting hydrophobic tobacco modifying agents.
The fibers useful in the invention can be comprised of any material known in the art capable of having a cross--section of the desired y~ y. Preferred materials for use in the present invention are polyesters .
The preferred polyester materials useful in the present invention are polyesters or copolyesters that are well known in the art and can be prepared using standard techniques, such as, by polymerizing dicarboxylic acids or esters thereof and glycols. The dicarboxylic acid compounds used in the production of polyesters and copolyesters are well known to those Wo 92/0~713 PCT/USgl/07109 2~1~2176~

skilled in the art and illustratively include terephthalic acid, isophthalic acid, p,p'--diphenyl--dicarboxylic acid, p,p'--dicarboxydiphenyl ethane, p, p ~--d i carboxyd ipheny l hexane, p, p ~--d icarboxyd ipheny l ether, p,p'--dicaLLc,~y~llenoxy ethane, and the li~e, and the dialkylesters thereof that contain from 1 to about 5 carbon atoms in the alkyl groups thereof.
Suitable aliphatic glycols for the production of polyesters and copolyesters are the acyclic and alicyclic aliphatic glycols having from 2 to 10 carbon atoms, especially those represented by the general formula HOICH2)pOH, wherein p is an integer having a value of from 2 to about 10, such as ethylene glycol, trimethylene glycol, tetramethylene glycol, and pentamethylene glycol, decamethylene glycol, and the l ike .
Other known suitable aliphatic glycols include ~1,4--cycloh~Y~n~;r~thanol, 3--ethyl--1,5--pentanediol, 1, 4--xylylene, glycol, 2, 2, 4, 4--tetramethyl--1, 3--cyclo--butanediol, and the like. One can also have present a hydroxylcarboxyl c u.ld such as 4,--~,ydLuxybenzoic acid, 4--hydroxyethoxybenzoic acid, or any of the other hydroxylcarboxyl ~ ds known as useful to those skilled in the art. ~
It is also known that mixtures of the above dicarboxylic acid compounds or mixtures of the aliphatic glycols can be used and that a minor amount of the dicarboxylic acid component, generally up to about 10 mole percent, can be replaced by other acids or modifiers such as adipic acid, sebacic acid, or the esters thereof, or with modifiers that impart; LUV~d dyeability to the polymers.
The most preferred polyester for use in preparing the fiber useful in the invention is poly(ethylene terephthalate) (PET).
_ _ _ _ _ . . . .. . _ .. _ _ _ _ WO 92/05713 PCr/US91/07109 20g21~6 ~ -- 18 --Other materials that can be used to make the base fibers include polyamides such as a nylon, e.g., nylon 66 or nylon 6; polypropylene; polyethylene; and cDll--lose esters such as celllllo~e triacetate or cellulose diacetate.
A single f iber useful in the present invention preferably has a denier (kg~m) of between about 1 and about 1, 0 0 0, more pref erred is between about 5 and about 70 .
The fibers useful in the invention preferably have a surface treatment applied thereto. Such surface treatment may or may not be critical to obtain the desired spontaneous transportability IJLU~eL~y. The nature and criticality of such surface treatment for any given fiber can be determined by a skilled artisan through routine experimentation using techniques known in the art and~or disclosed herein . A pref erred surf ace treatment, when a hydrophilic tobacco modifying agent is contemplated, is a coating of a hydrophilic lubricant on the surface of the fiber. A preferred surface treatment, when a hydrophobic tobacco modifying agent is contemplated, is a coating of a hydrophobic lubricant on the surface of the fiber. Such coatings are typically uniformly applied at about a level of at least O . 05 weight percent, with about 0.1 to about 2 weight percent being preferred, based on the weight of the fiber.
Preferred hydrophilic lubricants include a potassium lauryl phosphate based lubricant comprising about 70 weight percent poly(ethylene glycol) 600 mono~aurate. A
preferred hydrophobic lubricant is mineral oii. Another surface treatment is to subject the fibers to oxygen plasma treatment, as taught in, for example, Plastics Fini~hin~t and Decoration, Chapter 4, Ed. Don Satas, Van Nostrand Reinho ld Company ( 19 8 6 ) .
.
, WO 9~/05713 PCr/US91/07109 2~217~
-- 19 --' Figures 3 through 8 illustrate spinneret orifices which will prepare fibers of a geometry suitable for use in the present invention.
In Figure 3, W is between 0 . 064 mi 11; ters (mm) and 0 .12 mm. X2 is 4W +lwi X4 is 2W + 0 . 5W; X6 is 6W +2ww; X8 is 6W +25ww; X10 is 7W +25W; X12 i5 9W +15Ww;
X is lOW +5W; X is llW +5W; X is 6W +5W; t1 is 30 _ 30; t~4 is 45 + 45; 6 is 30 _ 30; and t~8 is 450 + 45O
In Figure 4, W is between 0. 064 mm and 0 .12 mm;
X20 is 17W +25Ww; X22 is 3W + W; X24 is 4W _ 2W; X26 is 60W _4W; X28 is 17W _2W; X30 is 2W + 0.5W; X32 is 35 72W 15W; and ~10 is 45 _ 15- In addition, each 40 Leg B can vary in length from 0 to 26; and each 45 Leg A can vary in length from 0 to rX26 tan t90-t~lo) ~ 2 X2~1 =
In Figure 5, W is between 0. 064 mm and 0 .12 mm;
X34 is 2W + 0.5W; X36 is 58W 120W; X38 is 24W +26WW;
~12 is 20O +100; ~14 is 1 12; and n =
number of legs per 180 = 2 to 6.
In Figure 6, W is between 0.064 mm and 0.12 mm;
X42 is 6W +2Ww; X44 is llW + 5W; X46 is llW + 5W; X48 is 24W + lOW; X50 is 38W + 13W; X52 is 3W _3W; X54 is 80 6W +2W; X56 is llW + 5W; X58 is 7W + 5W; X60 is WO 92/05713 PCr/US91/07109 20~21~6 17W + 7W; X62 is 28W + llW; X64 is 24W + lOW; X66 is 17W + 7W; X 8 is 2W + 0.5W; Q16 is 45 --15; ~18 is 45 + 15; and 620 is i50 + 15.
In Figure 6B W is between 0 . 064 mm and 0.12 mm, X72 is 8W _2W' X74 is 8W _2W' X76 is 12W + 4W, X78 is 8W + 4W, X80 is 24W +~12W, X82 is 18W + 6W, X84 is 8W_2W X86 is 16W + 6W, X88 is 24W + 12W, X90 is 18W + 6W, X92 is 2W + 0.5W, 22 is 135 + 30 ~ ~24 is 90 + 3050, ~26 is 45 + 15, ~28 is 45 + 15~, ~30 is 45 + 15, ~32 is 45 + 15, ~34 is 45 + 15, ~36 is 45o + 15, and ~38 is 45 + 15-In Figure 7, the depicted spinneret orif ice contains two repeat units of the spinneret orif ice depicted in Figure 3, therefore, the same dimensions for Figure 3 apply to Figure 7. Li3cewise, in Figure 8, the depicted spinneret orifice contains four repeat units of the spinneret orif ice depicted in Figure 3, theref ore, the same dimension~ for Figure 3 applies to Figure 8.
Figure 16 illustrates the method for determining the shape factor, X, of the fiber cross--section. In Figure 16, r = 37.5 mm, Pw = 355.1 mm, D = 49.6 mm;
thus, for the fiber cross--section of Figure 16:
X = 355.1 = 1.72 4 x 37.5 + (7r -- 2) 49.6 "
The tobacco modifying agent useful in the present invention can be any such agent used in tobacco products and~or tobacco substitute products where delivery of such agent to the user is desirable. Such agents typically modify the taste and~or aroma of smoking ..

WO9~/05713 PCl`~US9~J~7~09 ~921 7~

product6. Thus, the tobacco modifying agent can be a flavorant or other aromatic material including both naturally occurring and synthetic materials regardless of their hydrophobic or hydrophilic nature. Examples of such tobacco modifying agents include flavorants, 6ynergistic flavor Pnh~nr~rs, physiological coolants and other mouth or throat stimulants, with f lavorants being pref erred .
Examples of f lavorants include tobacco note flavorants comprising naturally occurring materials such as aqueous (hydrophilic) tobacco extracts (as discloced in U. S . Patent 3, 316, 919 incorporated herein by reference in its entirety) and aromatics (as disclose~:l in U. S . Patent 3, 424 ,171 incorporated herein by reference in its entirety), and synthetic materials which augment the minty, camphoraceous, spicy, peppery, fruity, flowery, woody, green, or other tobacco flavor and aroma notes. Other flavorants contemplated for use in the invention include naturally occurring or synthetic flavorants which introduce flavor notes that are not normally indigenous to tobacco such as the following which have been demonstrated to be useful on filters by U.S. Patent 3,144,024 (incorporated herein by reference in its entirety), wine, rum, coumarin, honey, vanilla, juniper, molasses, maple syrup, chocolate, menthol, and sugars. In addition, vanillin, licorice, anethole, anise, cocoa, cocoa and chocolate by products, sugars, humectants, eugenol, clove oil, triacetin, and other generally accepted cellulose acetate flavorant 3 0 f ilter additives .
Examples of synergistic flavor ~nh;~nr-~rs include smoothers such as glutamates and nucleotides as disclosed in U.S. Patent 3,397,700 (incorporated herein by reference in its entirety) and 2 cyclohexylcyclohexanone as disclosed in U. 5 . Patent~

WO 92/0~713 PCI/US91J07109 , .
~217~

.. ; .
3,342,186 (incorporated herein by reference in its entirety) .
r 1P~ of naturally occurring physiological coolants include mint oils, menthol, camphor and 5 camphoraceous ~
- Examples of synthetic physiological coolants include synthetic menthol and menthol derivatives (the ~:atter exemplif ied by menthol monoester disclo6ed in U.S. Patent 3,111,127 (incorporated herein by reference in its entirety), menthol acetals di6closed in U. S .
Patent 3,126,012 (incoL~v~i~ted herein by reference in its entirety), menthol ethers dlsclosed in U. S. Patent 3,128,772 (incorporated herein by reference in its entirety), menthol esters disclosed in U. S . Patent -15 3,136,319 (incorporated herein by reference in its entirety), synthetic camphor and camphvraceous compounds such as cycloh~ Pnnn~c and cyclnh~Y In~nPc disclosed in U.S. Patent 3,380,456 (incorporated herein by reference in its entirety), and synthetic coolants as disclosed in U.K. Patents 1,351,761 and 1,351,762 and U.S. Patents 4,296,255 and 4,230,688.
Examples of other mouth or throat stimulating include either natural or synthetic compounds such as nicotine, and its dérivatives, including, for example, nicotine complexes and salts disclosed in U. S.
Patent 3,109,436 (incvl~v,~ted herein by reference in its entirety).
A feature of the invention is the spontaneously wettable character of the pref erred f ibers used f or the . 30 tobacco modifying agent delivery substrate and~or the selective removal additive substrate. Although not - desired to be bound by any particular theory or r~-h~n;~:~, it is believed that the ability of spontaneously wettable fibers to transport and spread fluids on fibers having high surface areas which are not .
_ _ _ _ _ _ _ _ _ _ _ _ _ .

WO 9t/05713 PCIIU59t/07109 2~9~17~

n~ S~ rily penetrated by the modifying agent is responsible for the high delivery efficiencies and high peL~;en~dge of selective removal of unwanted 6ubstrates achieved by the combination of the invention. The invention is, therefore, not limited to a specific polymer or fiber ~L~a, ~, 6uch as fiber finish, or to ~ particular form of final fiber assemblage. Tobacco modifying agent delivery articles and~or selective removal additive delivery articles might, therefore, be made from fibers in any suitable form, including but not limited to, webs, continuous tows, and cut staple.
Also, webs can be powder, calendar or binder f iber bonded, and staple can be loose or as a sliver.
Although thei preferred implementation of the invention is a filter--like article employed either alone or in a multi--component conf iguration such as in a combination with a conventional cellulose acetate f ilter plug in a dual filter arrangement, the physical form of the tobacco delivery article and~or selective removal delivery article is not thus limited. In addition, the invention is not limited in its uses to cigarettes and is likewi6e applicable to all smoking products including pipes, and even novel and as yet unconceived of aerosol sources. Thus, the combination of the present invention is preferably in the form of a tobacco smoke filter or material useful for the preparation thereof. Cigarette filters are especially preferred. Accordingly, the present invention is also directed to a tobacco smoke f ilter comprising the combination of the invention wherein said filter is in substantially cylindrical form - having a length of about 5 to about 40 millimeters (mm), preferably about 10 to about 30 mm, and a diameter of about 15 to about 30 mm, preferably about 22 to about 2 mm. In a preferred, dual filter arrangement, the WO 92/0i713 PCr/US91/07109 ` 20~21~6 24 -portion of the dual filter comprising the combination of the invention is pref erably about 6 to about 15 mm .
The combination of the invention is useful for the e~ficient and uniform delivery of tobacco modifying agents. The combination of the invention is also usefu for efficient and uniform selective removal of unwanted substances such as phenol or nicotine. The direct economic value of the invention results from cost savings achieved through reductions in the quantity of expensive agents, ~cpec~lly flavorants and selective removal additives, that are needed to achieve a desired organoleptic Qffect. Other benefits of the invention include increased shelf life, improved con6istency of product taste which results from more constant delivery of the tobacco modifying agent over time, and improved efficiency of selective removal of unwanted substances.
To prepare the combination of the invention, the tobacco modifying agent(s) and~or selective removal additive of choice is applied, typically as a fluid, to an assemblage of fibers contemplated herein, especially spontaneously wettable f ibers . Such assemblage can be, for example, a nonwoven web or continuous tow, which is then preferably made into a rod--like or cylindrical article using f ilter making technology that is well known to one skilled in the art. After application of the tobacco modifying agent (s) and~or selective removal additive to the fibers, the combination is optionally dried by conventional pLocedu~s, for example, air drying or oven drying, especially to remove excess r solvent, if present. The rod--like article can be subdivided into segments of an appropriate length which are attached to an aerosol source such as the tobacco column of a conventional cigarette either alone or in conjunction with a conventional filter element, e.g., cellulose acetate filter, on the mouth and so as to give _ _ _ _ _ _ _ , - 25 -2~g2~
the appearance of a conventional cigarette f ilter . The resulting;, U~IG L in fiavorant delivery performance achieved by the invention is exemplified in Figures 1, 17 and 18 for the implementations described in Examples 14 and 15 hereof. The resulting improvement in 6elective delivery performance is described in Example 16 hereof.
Figure 1 contrasts the delivery of the commonly used smoking article flavorant triacetin (glycerol tri--acetate) from identical fiber assemblages consisting of spontaneously wettable and non--spontaneously wettable (round) fibers of comparable filament denier. The f igure clearly demonstrates the substantial f lavorant delivery advantage achieved by the spontaneously wettable f iber assemblage .
Figure 18 contrasts the delivery of the commonly used smoking article $1avorant triacetin (glycerol triacetate) from equal pressure drop fiber assemblages consisting of spontaneously wettable and conventional cellulose acetate fibers. This figure shows that the flavorant delivery advantage achieved by the spontaneously wettable $iber assemblage is even greater when compared to the performance of conventional cP11l~1Ose acetate fibers. FurthP -L~t Figure 19 shows that the delivery efficiency of the spontaneously wettable polyester fiber web filter segments for glycerol triacetate is relatively constant over extended periods of storage, whereas the delivery efficiency of the conventional cellulose acetate f ilter decreases significantly.
For certain tobacco modifying agents, such as volatile flavorants, it may be desirable to apply such agents in a solution of a nonvolatile sûlvent in which the agent is highly soluble. An example of this implementation is to prepare a solution of menthol in a WO 92/05713 PCr/US9l/07tO9 ~ .
2o92l~ 6 sufficiently nonvolatile solvent such as triacetin, polyethyrene glycol, or mineral oil. The flavorant, applied as a solution to the fiber ~sP~nhlage, will remain on the AcE~ lAge dissolved in the solvent but will still be spread uniformly over the fibers in a way that results in its high delivery efficiency.
The amount of tobacco modifying agent in the combination of the invention (as well as A~leDmhl AgeS
made therefrom such as cigarette filters) will vary dDrDn~lin~ on, among other things, the nature of the particular fibers, the chemical nature and potency of the particular tobacco modifying agent, and the desired type of delivery of the agént. However, a typical amount of tobacco modifying agent is about O . 001 to about 100 percent, ba6ed on the weight of the f ibers.
If the tobacco modifying agent is present as a solid free of solvent, a preferred amount of agent is about 0.1 to about 50%, based on the weight of the fibers. If the tobacco modifying agent is present as a liquid, a preferred amount of agent is about 0.1 to about 109~, based on the weight of the f iber .
Regarding total delivery o~ tobacco modifying agent, the combination of the invention in a single component cigarette filter form preferably results in at least a 10% i uv~ - t, more preferably at least a 30%
uv, ~, in delivery of such agent to the user as compared to a control filter using fibers of round cross--section .
The selective removal additives useful in the present invention are specific rhD~nic~ c or mixtures of o~n~c that are applied to f ilter fibers to enhance the removal of certain ~ ,ul.ds or classes of s _ -c from cigarette smoke. Selective removal additives may be fluids or solids. If solids are used, they are frequently applied to the filter medium as a WO 92/0~713 PC~IUS91/011û9 2~92~76 , solution in an appropriate solYent or as a suspension in an ~JL V,~ iate f luid medium .
Examples of fluid selective removal additives which t are useful for removal of phenols include polyols and their esters such as diethyl citrate, glycerol triacetate, triethylene glycol diacetate, poly(ethylene glycol) 400 or 600, and triethylene glycol.
Examples of fluid selective removal additives which are useful for removal of nicotine are glycerin and distilled monoglycerides derived from edible fats and glycerine, such as Myverol (trademark) and Myvatem (trademark) sold by Eastman Chemical Company, a division of Eastman Kodak Company, T~n~qpr~rt, TN.
Examples of solid selective removal additives that can be applied as solutions or suspensions in the appropriate fluid include salcomine, which is useful for selectively removing nitrogen oxides, zinc oxide, which is useful for selectively removing hydrogen cyanide, polyethyl~nr~;~;ne, which is useful for selectively removing aldehydes. Other generally useful additives include activated carbon, ion exchange resins, zeolites, waxes or starches.
The following examples are to illustrate the invention but should not be interpreted as a limitation 2 5 thereon .
,TCXAMP,T .l;~.C
ExAMPLE 1 (Fiber Preparation) Poly(ethylene terephthalate) (PET) polymer of 0.6 I.V. was used in this example. I.V. is the inherent viscosity as measured at 25C at a polymer concentration of O . 50 g~loO milliliters (mL) in a suitable solvent such as a mixture of 60% phenol and 40% tetra-chloro-3 5 ethane by weight . The polymer was dried to a moisture . . , _ . _ _ _ _ _ ; = ' ~.
~ ~ .
. .
~og21~6 - 28 -level of <0 . 003 weight percent in a Patterson Conaf orm dryer at 1206C for a period of 8 hours. The polymer was exl_~uded at 283C through an Egan extruder 1.5--inch (38.1 mm) diameter with a length to diameter ratio of 28:1. The fiber wa6 extruded through an eight orifice spinneret wherein each orif ice is as shown in Figure 3 wherein W is 0. 084 mm X2 is 4W X4 is 2W X6 is 6W X8 is 6W X10 is 7W X12 i8 9W X14 is lOW X16 is llW X18 iB 6W ~2 i6 0, 04 is 45 66 is 30 and ~8 is 45.
The polymer tll~uuyll~u~ was about 7 pounds (lb)~hour (3.18 kg~hour). The air quench system has a cross--flow conf iguration . The quench air velocity at the top of the screen was an average of 294 feet (ft)~minute (89.61 m/minute) . At a distance of about 7 inches ( 177 . 8 mm) from the top of the screen the average velocity of the guench air was about 285 ft/minute (86.87 m~minute) and at a distance of about i4 inches (355. 60 mm) from the top of the screen the average quench air velocity was about 279 ft~minute (85. 04 m/minute) . At about 21 inches (533.40 mm) ~rom the top of the air screen the average air velocity was about 340 ft/minute (103 . 63 m/minute). The rest of the screen was blocked.
Spinning lubricant was applied via ceramic kiss rolls.
The lubricant has a general composition as follows: it is a potassium lauryl phosphate (PLP) based lubricant having poly(ethylene glycol) 600 monolaurate (70% by weight) and polyoxyethylene (5) potassium lauryl phosphate (30% by weight). An emulsion of the above lubricant with water (90%) was used as the spinning lubricant. The lubricant level on the fiber samples was about 1.5%. Fibers of 20 dpf (denier per filament in kg/m) were wound at 3 000 meters per minute = (MPM) on a Barmag SW4SL winder. A photomicrograph of a cross--section of this fiber is shown in Figure 9 (150x magnification). The single fiber was tested for .. ,,,.,.. .. ,, .. ~._ _ .. ,.. .. ,.,, ... , , , _ ___ WO92/057t3 PCI/US91/07109 spontaneous surf ace transportation of an aqueous solution which was aqueous Syltint Poly Red (obtained from Mi 11 ;k~n Chemicals) which is 80 weight % water and r 20 weight ~ red colorant. The single fiber of 20 dpf (kg~m per filament) spontaneously surface transported the above aqueous solution. The following denier (kg~m) per filament PET fiber6 were also made at different speeds as shown in Table 1 below:
Tilhl e 1 Denier (kg~m) per Spin Speed Fi l ~--nt rMP~l Winder 3, 000 Barmag 1,500 Leesona l, 000 Leesona 120 500 Leesona 240 225 ~ Leesona 4 0 0 15 0 Leesona All the single fibers of above PET fiber with the denier (kg~m) per filament of 20, 40, 60, 120, 240, and 400 spontaneously surface transported the aqueous solution of Syltint Poly Red liquid. The value of the "X"
parameter (as defined hereinbefore) for these fibers was about 1.7. PET film of 0.02 inch (0.51 mm) thickness was _ .~ssion molded from the same polymer as that used f or making the above f iber . Contact angle of distilled water on the above film was measured in air with a contact angle goniometer. The contact angle was 71.7. Another sample of the same film as above was sprayed with the same lubricant as used for making the fiber in this example at about 1.59c level. The contact angle of distilled water on the PET film sprayed with 3~ the lubricant was about 7 0 . Thu~, the factor WO 92/05713 PCr/US91/07109 (1--X cos 0) in this case i6 (1--1.7(cos 7)) =--0.69, which i5 less than zero.
I;Y~ pT,F 2 (Fiber Preparation) Polyhexamethylene ~l;rAm;fl~ (nylon 66) was obtained from Du Pont [ Zytel (trademark) 42 ] . The polymer was t:XL- uded at 279C. A spinneret as shown in Figure 3 was used to form 46 denier (kg~n~) per filament fiber at 255 meter6~minute speed. The specif ic dimension6 of the spinneret orifices were the same a6 described in Example 1 except that ~2 wa6 30 instead of 0. The g~ nch; n~ conditions were the same as those f or obtaining PET fiber a6 in Example 1. A photomicrograph of the fiber cro66--6ection i6 6hown in Figure 11 (lSOx magnif ication) . The lubricant level on the f iber wa6 about 1. 8% by weight . The 6ame lubricant a6 u6ed in the PET fiber wa6 u6ed (Example 1). Thi6 nylon 66 fiber 6pontaneou61y tran6ported the agueou6 Syltint Poly Red 601ution on the fiber surface. The value of the "X"
parameter for this fiber was about 1.9. Nylon 66 film of 0. 02 inch (0. 51 mm) thickness wa6 compre66ion molded from the 6ame polymer a6 that u6ed for making the fiber of Example 2. Contact angle of di6tilled water on the above f ilm was measured in air with a contact angle goniometer. The contact angle was 64 . Another 6ample of the 6ame f ilm a6 above wa6 sprayed with the 6ame lubricant as used for making the fiber in this example at about the 1. 8% level . The contact angle of distilled water on the nylon 66 film sprayed with the lubricant wa6 about 2. Thu6, the factor (1--X cos ~) in this case i6 (1--l.9(c06 2)) = --0.9, which i6 le66 than 2ero.

WO 92/057t3 PCrJOS91/D7109 2~176 ,, F~AMPLE 3 tFiber Preparation) Polypropylene polymer was obtained from Shell Company (Grade 5C14). It was extruded at 279C. A
spinneret as shown in Figure 3 was used to f orm 51 denier (kg~m) per filament fiber at 2,000 MPM speed.
The specific diDensions of the 6pinneret orifices were the same as in Example 2 . The gl~pnr~h; n~ conditions were the same as those f or obtaining PET f iber . A
photomi.:, vy~clph of the fiber cross--section is shown in Figure 10 t375x magnification). The lubricant level on the f iber was 2 . 6% . The same lubricant as used in PET
fiber was used (Example 1). The polypropylene fiber spontaneously transported the aqueous Syltint Poly Red solution on the fiber surface. This spontaneously transportable phPr rm along the fiber surface was also observed for a 10 denier (kg~m) per filament, single polypropylene fiber. The value of the "X"
parameter f or this f iber was about 2 . 2 . Polypropylene film of 0.02 inch (0.51 mm) thickness was: ~ssion molded from the same polymer as that used for making the above fiber of Example 3. Contact angle of aistilled water on the above f ilm was measured in air with a contact angle goniometer. The contact angle was about 110. Another sample of the same film as above was sprayed with the same lubricant as used for making the fiber in this example at about the 2 . 6% level. The contact angle of distilled water on the polypropylene film sprayed with the lubricant was 12. Thus, the factor (1--X cos 0) in this case is --1.1, which is less 3 0 than zero .
F~AMPT.~ 4 (Fiber Preparation) Cellulose acetate (Eastman Grade CA 398--30, Class I) was blended with PEG 400 polymer and small quantities of antioxidant and thermal stabilizer. The WO92/05713 ~ PCI~US91/07109 r 2~2i7 blend was melt exL- uded at 270C. A 6pinneret as shown in Figure 3 was used to form 115 denier ~kg~m) per fllament fiber at 540 meters~minute speed. The specific in~C of the spinneret orifices were the same as in Example 2. No forced quench air was used. The lubricant level on the fiber was 1.6%. The same lubricant as used in the PET fibers (Example 1) was used. The celiulose acetate fiber spontaneously transported the aqueous Syltint Poly Red solution on the fiber surface. The yalue of the "X" parameter fQr this f iber was about 1. 8 ~
E~AMPLE 5 (Comparative) PET f iber of Example 1 was made without any spinning lubricant at 20 denier (kg~m) per filament. A
single f iber did not spontaneously transport the aqueous Syltint Poly Red solution along the fiber surface.
FXAMPL~ 6 (Comparative) PET fiber of circular cross--section was made. The denier (kg~m) per filament of the fiber was 20. It had about 1. 5% of the lubricant used in Example 1. A single f iber did not spontaneously transport the aqueous Syltint Poly Red solution along the f iber surf ace .
.
~XAMPLE 7 (Fiber Preparation) Poly(ethylene terephthalate) (PET) fiber of Example 5 (without any spinning lubricant) was treated with oxygen plasma for 30 seconds. Model "Plasmod"
3 0 oxygen plasma equipment was used . Exciter power is provided by the RF generator operating at 13.56 MHz frequency. The plasma treatment was conducted at a constant level of 50~ watts power. The oxygen plasma treated f iber spontaneously transported the aqueous Syltint Poly Red solution along the fiber. This fiber ~ .
_ 2~2176 was tested again after washing five times and after 3 days and the spontaneously transportable behavior with the above aqueous solution was still observed. In order to cletermino the reduction in contact angle after the plasma treatment, a PET f ilm of the same material as that of the fiber was subjected to the oxygen plasma treatment under the same conditions as those used for the f iber sample . The average contact angle of the oxygen plasma treated f ilm with distilled water in air was observed to be 26 as measured by a contact angle goniometer . The corroSpQn~l; n~ contact angle f or the control PET film (not exposed to the oxygen plasma) was 70. The significant reduction in contact angle upon subjecting the untreated PET fiber to the oxygen plasma treatment renders it to be spontaneously surf ace transportable for aqueous solutions.
~MPL~ 8 ~Fiber Preparation) Poly (ethylene terephthalate) (PET) polymer of 0 . 6 IV was used in this example. It was extruded through a spinneret having eight orif ices as shown in Figure 4 wherein W is 0. 084 mm, X20 is 17N, X22 is 3W, X2~ is 4W, X26 is 60W, X28 is 17W, X30 is 2W, X32 i5 72W, ~lO is 45, Leg 8 is 30W, and Leg A i5 26W. The rest of the prococcin~ conditions were the same as those described in Example l. A lO0 denier (kg~m) per filament fiber was spun at 600 MPM. A sketch of the cros6--section of the f iber is shown in Figure 12 . The lubricant level on the f iber was about 1% . The same lu~ricant as used in Example l was used. The above fiber spontaneously transported the aqueous Syltint Poly Red solution along the fiber surface. The value of the "X" parameter for this f iber was l . 5 .

WO 92/05713 PCI`/US91/07109 --2092~ 34_ ~= -l~n~MPT.T;~ 9 (Fiber Preparation) Poly (ethylene terephthalate) polymer of 0 . 6 IV was used in this example. It was extruded through a spinneret having eight orif ice6 as shown in Figure 5 wherein W is 0.10 mm X34 is 2W X36 is 58W X38 is 24W
~12 is 20 ~14 is 28 and n is 6. The rest of the extruding and spinning conditions were the same as those described in Example 1. A photomicrograph of the f iber cross--section is shown in Figure 13 (585x magnifi--cation). A 20 denier (kg~m) per filament fiber was spun at 3000 MPM. The lubricant level on the fiber was about 1.7%. The same lubricant as used in Example 1 was used.
The above f iber spontaneously transported the aqueous Syltint Poly Red solution along the f iber surf ace . The value of the "X parameter f or this f iber was about 2 . 4 .
F~AMPLr 10 (Fiber Preparation) Poly (ethylene terephthalate) (PET) polymer of about 0. 6 IV was used in this example. The polymer was extruded through a spinneret having four orifices as shown in Figure 7 wherein the dimensions of the orifices are repeats of the dimensions described in Example 2.
The rest of the processing conditions were the same as those described in Example 1 unless otherwise stated. A
200 denier (kg~m) per filament fiber was spun at 600 MPM. The polymer Llllouyll~u~ was about 7 lbs~hr (3 .18 kg~hr) . An optical photomicrograph of the f iber is shown in Figure 14 (150x magnification). The lubricant level on the fiber was 2.0%. The same lubricant as used in Example 1 was used. The above fiber spontaneously transported the aqueous Syltint Poly Red solution along the fiber surface. The value of the "X parameter f or this f iber was about 2 . 2 .

WO 92/05713 PCI`~US91~07109 .~
2~2176 ~XAMPT F 11 (Fiber Preparation) Poly (ethylene terephthalate) (PET) polymer of O . 6 IV was used in this example. The polymer was extruded through a spinneret having two orif ices as shown in Figure 8 wherein the dimen6ions of the orif ices are repeats of the dimensions described in Example 2. The rest of the proces6ing conditions were the same as those described in Example 1. A 364 denier (kg~m) per filament fiber was spun at 600 MPM. The cross--section of the fiber is shown in Figure 15 (150X magnification).
The lubricant level on the fiber was about 2.7%. The same lubricant as used in Example 1 was used. The above f iber spontaneously transported the aqueous Syltint Poly Red solution along the fiber surface. The value of the "X" parameter for this fiber was 2.1.
~AMPLF 12 ~Fiber Preparation) Poly(ethylene terephthalate) (PET) polymer of 0.6 IV was used in this example. It was extruded through a spinneret having eight orifices as shown in Figure 6 wherein W is 0.10 mm X42 is 6W, X44 is llW X46 is llW
X48 is 24N~ Xso is 38W, Xs2 is 3W, X54 is 6W, X56 is llW, X58 is 7W, X60 is 17W, X62 is 28W, X64 is 24W, X66 is 17W, X68 is 2W, 16 is 45, G18 is 45, and ~20 is 45. The rest of the processing conditions were the 6ame as tho6e de6cribed in Example 1. A 100 denier (kg~m) per filament fiber was spun at 600 MPM. The cros6--6ection of the f iber is shown in Figure 17 . The lubricant level on the f iber was about 1% . The 6ame 3 0 lubricant a6 u6ed in Example 1 was used . The above - fiber spontaneously transported the aqueous Syltint Poly Red solution along the fiber surface. The value of the X parameter for this fiber was 1.3.

WO92/0~713 PCI/USgl/07109 2Q~21~
13 (Fiber Preparation) PET polymer of 0. 6 I.V. is used in this example.
It is extruded through a spinneret having 8 orif ices as shown in Figure 6B wherein W is 0.10 mm, X72 i8 8W, X74 i5 8W, X76 is 12W, X78 is 8W, X80 is 24W, X82 is 18W, X84 is 8W, X86 is 16W, X88 is 24W, XgO is 18W, X92 is 2W, 22 is 135, 24 is 90, ~26 is 45, ~28 is 45, ~30 is 45, 632 is 45, 034 is 45, 36 is 45O and 638 is 45. A 20 denier (kgxm) per filament fiber is spun at lo 3, ooo m~min. The rest of the prorc~c~:i n~ conditions are the same as those used in Example 1. The lubricant level on the f iber is about 1% . The cross--section of the f iber is shown in Figure 17B . This f iber spontaneously transports the aqueous Syltint Poly Red solution along the fiber surface. The "X" value for this f iber is about 2 .1.
LF 14 (Example of the Invention) Spontaneously wettable polyester fibers were melt spun from polyethylene terephthalate polymer according to the methods described in Example 1. The value of the X parameter (as defined hereinbefore) for these fibers was about 1.8. A yarn of these fibers was then drafted to 5 . 5 denier (kg~m) per f ilament, heat set at about 180C, crimped to about 7 or 8 crimps per inch (25.4 mm), and cut into 2--inch (50.8 mm) long staple fibers.
The resulting staple f ibexs were carded and bonded with about 15 weight % Eastobond (trademark) FA--252 polyester adhesive in powder form into a nonwoven web with a density of about 19 grams per square yard (22.71 grams~square meter) . Round cross section f iber webs to be used as controls were made by an identical process except that the f ibers were melt spun through spinnerets with round holes.

WO 92/0~713 PCl/US91/07tO9 2~921~
The resulting round and spontaneously wettable polye6ter fiber webs were slit lengthwise into pieces approximately 12 inches (304.80 mm) wide which were then cut into 24--inch (609_ 60 mm) long sections. The resulting 12--inch (304.80 mm) wide by 24--inch (609.60 mm) long web sections weighed approximately 4 grams each. Glycerol triacetate, also referred to as triacetin flavorant, either in its pure form or as a 10, 20, or 50 weight % solution in ethanol, was applied in roughly equal quantities to both round and spontaneously wettable fiber web sections using an aerosol sprayer.
The web sections were air dried overnight to remove the residual ethanol.
The dried web sections were pulled lengthwise into drinking straws which were about 23 mm in circumference and each straw was cut into 21--mm long segments. The 21--mm long round fiber web filled straw segments contained about 150 mg of web and had an average pressure drop of about 28 mm of water when measured at a flow rate of 17.5 cc~sec. of air. The 21--mm long spontaneously wettable fiber web filled straw segments also contained about 150 mg of web but had an average pressure drop of about 55 mm of water when measured at a f low rate of 17 . 5 cc~sec . of air . Each 21--mm segment contained between 2 and 18 mgs of glycerol triacetate depending upon the application rate.
The 21--mm long web filled straw segments were then attached to 63--mm long blended tobacco columns that had been cut of f a popular king--sized domestic cigarette 3 o brand, and the resulting cigarettes were smoked according to CORESTA Standard Method No. 10 enti~led "Machine Smoking of Cigarettes and Determination of Crude and Dry Smoke c~n~pn~atel~ Experimental cigarettes were smoked in groups such that one glasS
fiber filter pad was used to collect the smoke WO 92/0~713 PCr/US91/0710g ~ .i 2~9217~

con~Pn~:ate from five cigarettes. Each glas6 fiber f iiter pad was then extracted with 15 ml o~ isopropanol containing 0 . 4 mg~ml hPY~d~Pc~np as an internal standard .
The glycerol triacetate present in the isopropanol extract of the cnn~lPn~ate from each glass fiber pad was then quantitatively detPrm; nPd by capillary gas chromatography .
The performance of the invention for delivering glycerol triacetate is reported in Figure 1. The reported delivery efficiency is defined as the percentage of the f lavorant present on the f iber web filled straw segment before smoking that was delivered to the glass fiber filter pad by smoking the experimental cigarettes. The term "4SW" represents fibers capable of spontaneously transporting water on the surfaces thereof.
; XAMP~,F lS (Example of the Invention) Spontaneously wettable polyester fibers were melt spun from polyethylene terephthalate polymer according to the methods described in Example 1. The value of the X parameter (as defined hereinbefore) for these fibers was about 1. 7 . A yarn of these f ibers was then draf ted to 10.3 denier (kg~m) per filament, heat set at about 180 degrees centigrade, crimped to about 7 or 8 crimps per inch (2S.4 mm), lubricated with poly(ethylene) 600 monolaurate lubricant, and cut into 2 inch (50.8 mm) long staple fibers. The spontaneously wettable staple fibers were blended with about 20 weight % Kodel (trademark) 410 amorphous polyester binder fiber, carded and thermally bonded into a nu.l u vt:., web with a density of about 35 grams per square yard (41.53 grams~square meter). The resulting web was then slit into sections 9.4 inches (238.76 mm) wide and wound onto rolls about 1000 linear yards (914.40 meters) long.
-WO 92/05713 PCr/US9l/07109 ~ ~92176 , Rolls o~ spontaneously wettable polyester fiber web were processed into filter rods in the following manner.
An Eastman Niniature filter tow processing unit was used to unwind the web from the roll, to quantitatively apply glycerol triacetate to the web at each of the two target application rates, and to control the rate of delivery of the web to the next step of the process. A Molins PM--2 f ilter rod making machine was then used to f old the web into rod shaped cylinders which were wrapped with Ecusta 646 plugwrap. The resulting filter rods were cut into 21 mm long segments which were 24.5 mm in circumference, contained about 178 mg of nonwoven web, and had an average ~L~S::~UL~ drop of about 27 mm of water when measured at a f low rate of 17 . 5 cc~sec of air .
DPPPr~ n~ on the rate of application, each filter segment contained either 2 . ~ mg or 5 . 6 mg of glycerol triacetate which, when expressed a6 a percentage of the total filter weight, COLLe~y~ ded to levels of 1.3 and 2 . 8 weight percent respectively .
As a comparison, flavored control filters were made in the conventional manner from 3 . 3 denier (kg/m) per filament, 39,000 total denier (kg~), Y cross section, Estron (trademark) fiolution spun cellulose acetate filter tow. The 21 mm long filter segments were 24.5 r~n in circumference, contained 120 mg of filter tow, and had an average ~L~S~UL~: drop of about 65 mm of water when measured at a f low rate of 17 . 5 cc~sec of air .
Each filter segment contained 10. 3 mg of glycerol triacetate which, when expressed as percentage of the total filter weight, corresponded to a leYel of 7.0 weight percent.
~he spontaneously wettable polyester fiber web filter segments were then placed in sealed glass jars and stored for intervals consisting of 10, 18, 28, 39, 52, 66, and 82 days. At the end of each storage _ . .. _ _ .. ... . . ..

WO 92/05713 PCr/US91/07109 2~g2~ 40 -interval, the filters were attached to 63 mm long blended tobacco columns that had been cut of f of a popular King sized domestic cigarette brand and the resulting cigarettes were smoked acccording to CORESTA
Standard Method No. 10 entitled "Machine Smoking of Cigarettes and Determination of Crude and Dry Smoke ~nn~ ncate~l. The cellulose acetate control filters were stored for intervals of 3, 7, 14, 21, 28, 42, 56, and 84 days prior to smoking.
Both eYperimental and control cigarettes were smoked in groups such that one glass f iber f ilter pad was used to collect the smoke con~l~n~te from 4 cigarettes. Each glass fiber filter pad was then extracted with 15 ml of isopropanol containing 0 . 4 mg~ml h~Y~qeC;~ne as an internal standard. The glycerol triacetate present in the extract of the cnnrl~nc~te from each glass f iber pad was then quantitatively determined by capillary gas chromatography.
Figure 18 reports the perf ormance of the invention for achieving consistantly higher delivery efficiencies of glycerol triacetate than the control cellulose acetate filters. The delivery efficiency reported in Figure 18 is def ined as the percentage of the glycerol triacetate present on the f ilter segment bef ore smoking that was dèlivered to the glass f iber pad by smoking the experimental and control cigarettes. Figure 2 shows that the delivery efficiency of the spontaneously wettable polyester fiber web filter segments for glycerol triacetate was 2 to 3 times greater than the delivery efficiency of the conventional cellulose acetate filter segments initially and 3 to 4 times greater by the end of the experiment. These higher delivery efficiencies permit significant reductions in the amount of flavorant that must be used to achieve a desired delivery.
_ _ . . _ . . . _ . . . _ .

WO 92/0~713 PCr/US9~07109 ~09217f~ ~-Figure l9 reports the perf ormance of the invention for maintaining a constant deliYery efficiency of glycerol triacetate over extended periods of storage.
The delivery efficiency change reported in Figure 3 is defined as the percentage change in deliYery efficiency relative to the delivery efficiency anticipated from a freshly made filter. Figure 19 shows that the delivery efficiencies of the two spontaneously wettable polyester fiber web filter segments for glycerol triacetate are virtually in~r~n~t of storage t~ime and, therefore, show little change, whereas the conventional cellulose ~cetate filter segments loose almost half of their already lower dellvery ef f iciency during the time spanned by this experiment. - =
F~AMPLF 16 (Example of the Invention) Spontaneously wettable polyester f ibers were melt spun from polyethylene terephthalate polymer according to the methods described in Example 1. The value of the X parameter (as defined hereinbefore) for these fibers was about 1.8. A yarn of these fibers was then drafted to 5.5 denier (kg~m) per filament, heat set at about 180 degrees centigrade, crimped to about 7 or 8 crimps per inch (25.4 mm), and cut into 2 inch (50.8 mm) long staple fibers. The resulting staple fibers were carded and bonded with about 15 weight % Eastobond FA--252 polyester adhesive powder into a nonwoven web with a density of about 19 grams per square yard (22 . 71 grams~square meter) . Round cross section f iber webs to be used as controls were made by an identical process except that the f ibers were melt spun through spinnerets with round holes.
The resulting round and spontaneously wettable polyester fiber webs were slit lengthwise to widths of 35 15 and 12 inches (381.Oo and 304.80 mm), respectively.

The round webs were slit to a wider width in order to better match the pressure drops of the resulting filters. Selective removal additives consisting of either glycerol triacetate or poly(ethylene glycol) 600 were applied to each web at a level of 7 weight percent using an aerosol sprayer. Glycerol triacetate was applied to the webs in pure form but, because of its higher viscosity, poly(ethylene glycol) 600 was applied as a 10% aqueous solution. The poly(ethylene glycol) 600 treated webs were dried in an oven at 60 degrees centigrade for 1 hour after spraying to remove excess water. All of the treated webs were allowed to air dry overnight to remove residual volatiles.
The dried web sections were pulled lengthwise into drinking straws which were about 23 mm in circumference and each straw was cut into several 21 mm long segments.
Filters were made in this manner to achieve a target pressure drop of about 70 mm of water when measured at a flow rate of 17.5 cc/sec of air. Because of differences in the relative abilities of the round and 4SW fiber webs to generate pressure drop, filters made from these two types of web contained different quantities of coated substrate. To achieve the target pressure drop, 21 mm long filters required about 210 mg of coated round fiber PET web and about 160 mg of coated 4SW fiber web.
As an additional comparison, straw filters were also made from a 3.3 denier (kg/m) per filament, 39,000 total denier, Y cress section, Estron solution spun cellulose acetate filter tow that had been treated with either glycerol triacetate or poly(ethylene glycol) 600.
The resulting 21 mm long filter tips were 23 mm in circumference, contained about 130 mg of treated cellulose acetate filter tow, and had an average pressure drop of about 75 mm of water when measured at a flow rate of 17.5 cc/sec of air. Each filter segment WO 92/05713 PCr~US91~07109 . .~
20~2~7~

contained between 8 and 9 mg of either glycerol triacetate or poly (ethylene glycol) 600 which, L-~sced as percentage, ccLLe~ ds to an application level of 7 . 0 weight percent.
The 21 mm long treated straw filters were attached to 63 mm long blended tobacco columns that had been cut off of a popular King sized domestic cigarette brand and the resulting cigarettes were smoked acccording to CORESTA Standard Nethod No. l0 entitled "Machine Smoking of Cigarettes and Determination of Crude and Dry Smoke ~,n~PnRate". Experimental cigarettes of a given type were smoked in groups such that one glass f iber f ilter pad was used to collect the smoke cQn~lPncate from 5 cigarettes. The selective removal efficiency of the filters was then detP~m;nP~l by measuring the amount of phenol present in the glass fiber filter pads and the freshly smoked cigarette f ilters .
In order to measure the phenol present, the glass f iber f ilter pads and cigarette f ilters were both 6eparately extracted with diethyl ether and the resulting extracts were concentrated, purif ied, and quantitately measured using gas chromatography. The percentage of selective phenol removal reported herein is defined as l00 times the amount of phenol on the cigarette filters divided by the sum of the amount of phenol on the cigarette f ilters and the amount of phenol on the glass fiber filter pad.
The perf ormance of the invention f or the selective removal of phenol from cigarette smoke is reported in Table l. In all cases, the application of selective removal additives such as glycerol triacetate and poly (ethylene glycol~ 600 to 4SW PET fiber web produced filters with higher selective removal efficiencies for phenol than were obtained when round PET f iber web or Estron filter tow were used as filter substrates. This WO 92/05713 PC~r/US91/07109 ~,.
2~19~17~ 44-superior phenol removal efficiency was obtained even though the 4SW PET fiber web filters had consistantly lower },resDu-~ drops than the filters made from either round PET fiber web or Estron filter tow and lower S welg _: ~ n ~i er~ m~de f r_ rou~d l~T f iber web .

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WO 92/û5713 PCI /US91/07109 ., --20~21~6 _ 46 -The invention has been described in detail with particular reference to the preferrred ~"~ho~ ts thereof, but it will be understood that variations and modifications can be effected within the spirit and 5 scope of the invention. All of the U. S . patents cited herein are hereby incorporated herein by ref erence in their entirety.

Claims (71)

- 47 - We Claim:

1. A combination comprising:
(A) at least one fiber having at least one continuous groove oriented axially along said fiber which is capable of spontaneously transporting n-decane on the surface thereof wherein said fiber satisfies the equation (1-X cos .theta.a) < 0, wherein .theta.a is the advancing contact angle of n-decane measured on a flat film made from the same material as the fiber and having the same surface treatment, if any, X is a shape factor of the fiber cross-section that satisfies the following equation X = wherein P is the perimeter of the fiber and r is the radius of the circumscribed circle circumscribing the fiber cross-section and D
is the minor axis dimension across the fiber cross-section, and (B) at least one tobacco modifying agent applied to said fiber.

2. The combination of Claim 1 wherein for the fiber of component (A), 2? is greater than 1.

3. The combination of Claim 1 wherein for the fiber of component (A) 2? is between 1.5 and 5.

4. The combination of Claim 1 wherein for the fiber of component (A) X is greater than 1.2.

5. The combination of Claim 1 wherein for the fiber of component (A) X is greater than 2.5.

6. The combination of Claim 1 wherein for the fiber of component (A) X is greater than 4.

7. The combination of Claim 1 wherein the fiber of component (A) has a single fiber denier (kg/m) of between 1 and 1,000.

8. The combination of Claim 1 wherein the fiber of component (A) has a single fiber denier (kg/m) of between 5 and 70.

9. The combination of Claim 3 wherein the fiber of component (A) has a single fiber denier (kg/m) of between 5 and 70.

10. The combination of Claim 1 wherein the fiber of component (A) is comprised of a material selected from the group consisting of a polyester, polypropylene, polyethylene, a cellulose ester, and a nylon.

11. The combination of Claim 1 having a plurality of the fiber of component (A) in the form of webs, continuous tows, and cut staple.

12. The combination of Claim 1 wherein said tobacco modifying agent is a hydrophobic or hydrophilic material.

13. The combination of Claim 1 wherein said tobacco modifying agent is a flavorant, a synergistic flavor enhancer, a physiological coolant or at least one mouth or throat stimulant.

14. The combination of Claim 1 wherein said tobacco modifying agent is a flavorant.

15. The combination of Claim 1 wherein said tobacco modifying agent is an aqueous tobacco extract, aromatic tobacco extract, rum, coumarin, honey, vanilla, wine, juniper, molasses, maple syrup, chocolate, menthol, sugars, vanillin, licorice, anethole, anise, cocoa, cocoa and chocolate by products, sugars, humectants, eugenol, clove oil, triacetin, glutamates, nucleotides, 2-cyclohexyl-cyclohexanone, mint oil, menthol, camphor, camphoraceous compounds, menthol derivatives, or nicotine or its derivatives.

16. The combination of Claim 1 wherein the amount of component (B) is 0.001 to 100 percent based on the weight of component (A).

17. The combination of Claim 1 further comprising (C), a selective removal additive.

18. The combination of Claim 17 wherein said selective removal additive is a liquid.

19. The combination of Claim 18 wherein said liquid comprises polyols, ester of polyols, or combinations thereof.

20. The combination of Claim 19 wherein polyols and esters of polyols comprise diethyl citrate, glycerol triacetate, triethylene glycol diacetate, poly(ethylene glycol) 400 or 600, triethylene glycol, glycerin, distilled monoglycerides derived from edible fats and glycerin.

21. The combination of Claim 17 wherein said selective removal additive is a solid.

22. The combination of Claim 21 wherein said solid comprises salcomine, zinc oxide, polyethyleneimine, activated carbon, ion exchange resins, zeolites, waxes or starches.

23. A combination comprising:
(A) at least one fiber having at least one continuous groove which is capable of spontaneously transporting water on the surface thereof wherein said fiber satisfies the equation (1-X cos .theta.a) < 0, wherein .theta.a is the advancing contact angle of water measured on a flat film made from the same material as the fiber and having the same surface treatment, if any, X is a shape factor of the fiber cross-section that satisfies the following equation X = wherein Pw is the wetted perimeter of the fiber and r is the radius of the circumscribed circle circumscribing the fiber cross-section and D is the minor axis dimension across the fiber cross-section, and (B) at least one tobacco modifying agent.

24. The combination of Claim 23 wherein for the fiber of component (A), 2? is greater than 1.

25. The combination of Claim 23 wherein for the fiber of component (A) 2? is between 1.5 and 5.

26. The combination of Claim 23 wherein the fiber of component (A) satisfies the equation .gamma.LA (1-X cos .theta.a) - 0.3, wherein .gamma.LA is the surface tension of water in air in dynes/cm, ? is the fiber density in grams/cc, and dpf is the denier in kg/m of the single fiber.

27. The combination of Claim 23 wherein for the fiber of component (A) X is greater than 1.2.

28. The combination of Claim 23 wherein for the fiber of component (A) X is greater than 2.5.

29. The combination of Claim 23 wherein for the fiber of component (A) X is greater than 4.

30. The combination of Claim 23 wherein the fiber of component (A) has a single fiber denier (kg/m) of between 1 and 1,000.

31. The combination of Claim 23 wherein the fiber of component (A) has a single fiber denier (kg/m) of between 5 and 70.

32. The combination of Claim 23 wherein the fiber of component (A) has a single fiber denier (kg/m) of between 5 and 70.

33. The combination of Claim 23 wherein the fiber of component (A) is comprised of a material selected from the group consisting of a polyester, polypropylene, polyethylene, a cellulose ester, and a nylon.

34. The combination of Claim 23 wherein said fiber of component (A) is comprised of a polyester having coated thereon a layer of a hydrophilic lubricant.

35. The combination of Claim 34 wherein said polyester is poly(ethylene terephthalate) and said hydrophilic lubricant is a potassium lauryl phosphate based lubricant comprising 70 weight percent poly (ethylene glycol) 600 monolaurate which is uniformly applied at a level of at least 0.05%
by weight of the total fiber.

36. The combination of Claim 23 wherein for said fiber of component (A) the width of each groove in the fiber cross-section at any depth in the groove is equal to or less than the width of the groove at its mouth.

37. The combination of Claim 23 having a plurality of the fiber of component (A) in the form of webs, continuous tows, and cut staple.

38. The combination of Claim 23 wherein said tobacco modifying agent is a hydrophilic material.

39. The combination of Claim 38 wherein said tobacco modifying agent is a flavorant.

40. The combination of Claim 23 wherein the amount of component (B) is 0.001 to 100 percent based on the weight of component (A).

41. A combination comprising:
(A) at least one fiber having at least one continuous groove which is capable of spontaneously transporting n-decane on the surface thereof wherein said fiber satisfies the equation (1-X cos .theta.a) < 0, wherein .theta.a is the advancing contact angle of n-decane measured on a flat film made from the same material as the fiber and having the same surface treatment, if any, X is a shape factor of the fiber cross-section that satisfies the following equation X = wherein Pw is the wetted perimeter of the fiber and r is the radius of the circumscribed circle circumscribing the fiber cross-section and D is the minor axis dimension across the fiber cross-section, and (B) at least one tobacco modifying agent.

42. The combination of Claim 41 wherein for the fiber of component (A), 2? is greater than 1.

43. The combination of Claim 41 wherein for the fiber of component (A) 2? is between 1.5 and 5.

44. The combination of Claim 41 wherein for the fiber of component (A) X is greater than 1.2.

45. The combination of Claim 41 wherein for the fiber of component (A) X is greater than 2.5.

46. The combination of Claim 41 wherein for the fiber of component (A) X is greater than 4.

47. The combination of Claim 41 wherein the fiber of component (A) has a single fiber denier (kg/m) of between 1 and 1,000.

48. The combination of Claim 41 wherein the fiber of component (A) has a single fiber denier (kg/m) of between 5 and 70.

49. The combination of Claim 43 wherein the fiber of component (A) has a single fiber denier (kg/m) of between 5 and 70.

50. The combination of Claim 41 wherein the fiber of component (A) is comprised of a material selected from the group consisting of a polyester, polypropylene, polyethylene, a cellulose ester, and a nylon.

51. The combination of Claim 41 wherein said fiber of component (A) is comprised of a polyester having coated thereon a layer of a hydrophobic lubricant.

52. The combination of Claim 51 wherein said polyester is poly (ethylene terephthalate) and said hydrophobic lubricant is mineral oil which is uniformly applied at a level of at least 0.05% by weight of the total fiber.

53. The combination of Claim 41 having a plurality of the fiber of component (A) in the form of webs, continuous tows, and cut staple.

54. The combination of Claim 41 wherein said tobacco modifying agent is a hydrophobic material.

55. The combination of Claim 54 wherein said tobacco modifying agent is a flavorant.

56. The combination of Claim 41 wherein the amount of component (B) is 0. 001 to 100 percent based on the weight of component (A).

57. A tobacco smoke filter comprising a combination comprising:
(A) a plurality of fibers wherein each fiber of said plurality has at least one continuous groove wherein said fiber has a cross-section having a shape factor X that satisfies the following equation X = wherein P is the perimeter of the fiber and r is the radius of the circumscribed circle circumscribing the fiber cross-section and D
is the minor axis dimension across the fiber cross-section, and (B) at least one tobacco modifying agent.

58. The tobacco smoke filter of Claim 57 in substantially cylindrical form having a length of 5 to 40 mm and a diameter of 15 to 30 mm.

59. The tobacco smoke filter of Claim 57 in substantially cylindrical form having a length of 10 to 30 mm and a diameter of 22 to 25 mm.

60. The tobacco smoke filter of Claim 57 which is a cigarette filter.

61. The tobacco smoke filter of Claim 57 which is a multicomponent configuration.

62. The tobacco smoke filter of Claim 57 which is in a dual configuration with a conventional cellulose acetate filter component.

63. A cigarette comprising the tobacco smoke filter of Claim 57.

64. A tobacco smoke filter comprising a combination comprising:
(A) a plurality of fibers wherein each fiber of said plurality has at least one continuous groove which is capable of spontaneously transporting water on the surface thereof wherein said fiber satisfies the equation (1-X cos .theta.a) < 0, wherein .theta.a is the advancing contact angle of water measured on a flat film made from the same material as the fiber and having the same surface treatment, if any, X is a shape factor of the fiber cross-section that satisfies the following equation X = wherein Pw is the wetted perimeter of the fiber and r is the radius of the circumscribed circle circumscribing the fiber cross-section and D is the minor axis dimension across the fiber cross-section, and (B) at least one tobacco modifying agent.

65. The tobacco smoke filter of Claim 64 in substantially cylindrical form having a length of 5 to 40 mm and a diameter of 15 to 30 mm.

66. The tobacco smoke filter of Claim 64 in substantially cylindrical form having a length of 10 to 30 mm and a diameter of 22 to 25 mm.

67. The tobacco smoke filter of Claim 64 which is a cigarette filter.

68. The tobacco smoke filter of Claim 64 which is a multicomponent configuration.

69. The tobacco smoke filter of Claim 64 which is in a dual configuration with a conventional cellulose acetate filter component.

70. A cigarette comprising the tobacco smoke filter of Claim 64.
71. A tobacco smoke filter comprising a combination comprising:

(A) a plurality of fibers wherein each fiber of said plurality has at least one continuous groove which is capable of spontaneously transporting n-decane on the surface thereof wherein said fiber satisfies the equation (1-X cos .theta.a) < 0, wherein .theta.a is the advancing contact angle of n-decane measured on a flat film made from the same material as the fiber and having the same surface treatment, if any, X is a shape factor of the fiber cross-section that satisfies the following equation X = wherein Pw is the wetted perimeter of the fiber and r is the radius of the circumscribed circle circumscribing the fiber cross-section and D is the minor axis dimension across the fiber cross-section, and (B) at least one tobacco modifying agent.
72. The tobacco smoke filter of Claim 71 in substantially cylindrical form having a length of 5 to 40 mm and a diameter of 15 to 30 mm.
73. The tobacco smoke filter of Claim 71 in substantially cylindrical form having a length of 10 to 30 mm and a diameter of 22 to 25 mm.
74. The tobacco smoke filter of Claim 71 which is a cigarette filter.

75. The tobacco smoke filter of Claim 71 which is a multicomponent configuration.
76. The tobacco smoke filter of Claim 71 which is in a dual configuration with a conventional cellulose acetate filter component.
77. A cigarette comprising the tobacco smoke filter of

Claim 71.