AU714692B2 - Novel compositions for dental floss - Google Patents

Description

-1-

AUSTRALIA

PATENTS ACT 1990 COMPLETE SPECIFICATION FOR A STANDARD PATENT

ORIGINAL

0* cool PA N I es Name of Applicant: JOHNSON JOHNSON CONSUMER P-RODUCTS, INC.

Actual Inventors: Address of Service: Michael T. SCHIRALDI; John Charles SUBELKA; Ralph KORPMAN; Bruce C. JOHNSON; Atiye Erden TANVERDI and Ivor P. LEWIS BALDWIN SHELSTON WATERS MARGARET STREET SYDNEY NSW 2000 Invention Title: "NOVEL COMPOSITIONS FOR DENTAL FLOSS" Details of Original Application No. 20469/95 dated 2nd June 1995 The following statement is a full description of this invention, including the best method of performing it known to us:j la NOVEL COMPOSITIONS FOR DENTAL FLOSS This application is a further application in respect of an invention disclosed in Australian patent application AU 20469/95 (AU 694,983). AU 20469/95 is by this crossreference incorporated into the present specification.

BACKGROUND OF THE INVENTION i. Field of the Invention This invention relates to a novel composition for use '-in dental floss or tapes. More particularly, it relates to novel compositions containing a base polymer, a block copolymer and a nonmigrating compatibilizer or plasticizer that, in combination in a blend, result in a floss or dental tape having good breaking strength, tenacity, nick resistance and elongation properties. It also relates to a 15 novel extruded, flattened, monofilament tube structure useful in dental tapes and flosses, as well as a method for making such structure. It also relates to a flattened monofilament tube that is textured along the longitudinal axis as well as perpendicular to this axis.

ooooo 2. Prior Art The use of polymer compositions in dental flosses and tapes has been known previously. However, there have been S"continuous efforts to develop a floss which does not shred or fray upon use and which has sufficient tensile strength for use between the teeth.

For example, U.S. Patent No. 2,381,142 (Stonehill) describes a dental floss made from a strand or filament of synthetic fibers of an unplasticized vinyl resin such as a copolymer of vinyl chloride and vinyl acetate treated with wax. 2 U.S. Patent No. 3,359,344 (Fukushima) describes a method for manufacturing a spun fiber. According to Fukushima, a polymer selected from the group of polyethylene, polypropylene and polystyrene having a melting point lower than 170' C. is mixed with a second polymer selected from polyamides and polyesters having a melting point greater than 170' C. and an additional amount of the first polymer. The composition is blended and .:"extruded to form a fiber.

In U.S. Patent No. 3,639,505 (Hughes et there is described a method of improving the dyeability of polyolefin fibers and films. The method includes forming a polymer alloy containing a blend of 15 polyolefin, a minor amount of polyethylene terephthalate and from 0.2 to 5 parts per hundred parts of polymer of toluenesulfonamide compound.

U.S. Patent No. 3,800,812 (Jaffe) describes a dental floss made from a polyester elastomer, including Hytrel (available from DuPont). The elastomer is extruded into a hot and tacky tape, then cooled.

U.S. Patent-No. 3,900,549 (Yamane et al.) describes a method for preparing composite filaments composed of a polyethylene and a polyester. The method includes the steps of mixing a polyethylene having a melt indexof above 27 with a polyester having a specific inherent viscosity, the proportion of the polyethylene being 5 to 15% or 25 to 90% based on the total weight of the mixture, melt extruding the resulting mixture through a spinneret and then withdrawing the extruded filaments at a speed of above 2,500 meters per minute.

3 U.S. Patent No. 3,957,056 (Ferraro et al.) describes a dental floss containing aromatic polyamide fibers having at least 35% of the amide linkages attached directly to two aromatic rings.

U.S. Patent No. 4,552,603 (Harris, Jr. et al) describes heat bondable bicomponent fibers containing polyester and another thermoplastic polymer having a melting point which is at least 15% C. below that of polyester.

U.S. Patent No. 4,583,564 (Finkelstein et al.) describes a dental floss consisting of filaments containing a higher melting point core material and a lower melting point sheath material. The sheath material fibers are 15 fused by subjecting them to a temperature sufficient to S'.fuse them.

U.S. Patent No. 4,609,710 (Iohara et al.) describes an undrawn polyester yarn and process for manufacturing such yarn. The main acid component of the yarn is an aromatic dicarboxylic acid.

U.S. Patent No. 4,986,288 (Kent et al.) describes dental floss and toothpicks which contain one or more coagulants to retard and stop bleeding during flossing.

U.S. Patent No. 4,996,056 (Blass) describes a dental floss or tape containing fluorocarbon polymer powder particles as a solid lubricant.

Despite the existence of such products as described heretofore, there still exists a need for dental floss and tape products having high breaking strength, high tenacity, nick resistance and suppleness which does not 4 fray or break easily when used. Furthermore, there is a need to have dental floss or tape which is gentle to gum tissue which can be manufactured at high speed and low cost.

It is, therefore, a preferred object of this invention to provide an extruded, flattened, monofilament tube with rounded edges suitable for use as a dental floss or tape.

It is another preferred object of this invention to provide a flattened, monofilament tube that is textured along the longitudinal axis as well as perpendicular to this axis.

It is another preferred object of this invention to 20 provide a polymer blend resulting in an acceptable dental floss or tape.

It is another preferred object of this invention to provide a dental floss or tape having high breaking o. strength, high tenacity, nick resistance and suppleness 25 which does not fray or break in use.

Another preferred object of this invention is to provide a method for making a polymer blend resulting in an excellent composition for use in dental flosses and tapes.

Another preferred object of this invention is to 30 provide a method of making polymer blend products in the form of a monofilament for use as a dental tape or floss.

Yet another preferred object of this invention is to provide low cost, high grade polymer compositions for use in dental flosses and tapes.

Additional preferred objects will become apparent throughout the ensuing description of the products and processes of this invention.

SUMMARY OF THE INVENTION According to a broad form of the present invention, there is provided a process for making a tubular dental hygiene device comprising: a) extruding a polymer blend into a small and thin tubing using an extrusion pump; b) orienting said polymer blend; c) annealing said polymer blend; and 5 d) collapsing said polymer blend.

Unless the context clearly requires otherwise, throughout the description and the claims, the words "comprise', 'comprising', and the like are to be construed in an inclusive sense as opposed to an exclusive or exhaustive sense; that is to say, in the sense of "including, but not limited to".

This invention also relates to novel compositions useful in making dental flosses and tapes. The compositions of this invention are extrudable and can be formed into a monofilament.

Dental flosses and tapes made with the novel 20 compositions of this invention may be formed into an o extruded, flattened, monofilament tube with rounded edges.

The unique monofilament shape provides rounded edges that will not cut or irritate gingiva tissue. The composition allows the monofilament to meet two primary concerns of the dental floss consumer: ease of passage between teeth and resistance to fraying. The composition provides a supple, slippery material that is capable of sliding and ,oo compressing as it moves between teeth. The individual fiber composing the novel monofilament structure and 30 composition does not break and is not perceived to fray as

S.

do ordinary dental flosses, which are composed of many fine monofilaments. It has been found that, upon preparation for use, the user generally stretches the floss or tape prior to insertion between the teeth. We have discovered that the flosses of this invention elongates and reduces its thickness such that it easily slides between the teeth.

The monofilaments of this invention can elongate at least about 30% of their original length and can reduce their thicknesses at least about 10%. 6 The flosses of this invention can be textured along the longitudinal axis as well as perpendicular to this axis.

This textured floss, which still slides easily between the teeth due to its unique composition, enhances the floss' effectiveness by exerting gentle pressure interstitially.

More particularly, the products of this invention relate to novel compositions containing a base polymer, such as 10 a polyolefins, modified polyamides, polyesters or *polyurethanes; block, or segmented, copolymers such as modified polyamides, polyesters or polyurethanes; and nonmigrating compatibilizer(s) or plasticizer(s) that in combination result in a polymer blend which can be 15 formed into a monofilament having good breaking strength, tenacity, nick resistance and elongation properties.

The products of this invention are considered, 20 generally, "polymer blends". Polymer blend technology involves the mixture of different polymers, and has been "necessitated by the increasing costs of synthesizing new polymer structures. It has been discovered that certain polymer blends, surprisingly, exhibit novel, unusual and unexpected properties different from the constituent polymers. The blending of polymers with careful control of the resulting blend's morphology by consideration of the rheological and thermodynamic properties of the individual components have led to new polymer blends of commercial interest.

The compositions of this invention generally have three constituent components: a base polymer, a block copolymer and a compatibilizer. The base polymer, which 7 is selected from the group of polyolefins, modified polyamides, polyesters or polyurethanes, provides strength and tenacity; it may also impart suppleness.

The segmented or block copolymer component assists in providing nick resistance and elasticity. In general, many polymer pairs are thermodynamically incompatible.

In order to facilitate intimate polymer blending, a polymeric compatibilizer should be introduced into the compositions of this invention. The compatibilizer acts 10 as a molecular bridge between the polymers, similar to S. the action of a surfactant in emulsifying oil and water systems. Thus, the nonmigrating compatibilizer assists in providing integrity to the composition. This, in turn, contributes to the suppleness of the compositions 15 and assists in melt processing and post-extrusion drawing of the monofilament tube by reducing melt viscosity and improving elongation characteristics.

The compositions of this invention are used in making S 20 flosses and tapes having excellent attributes. In use, .dental flosses and tapes must have a high breaking strength, high tenacity and a suitable denier and thickness. They should also have a softness or suppleness-such that they can easily be handled by the consumer. In practice, the dental floss or tape must not easily nick and break when the consumer encounters a sharp edge in flossing teeth and must not elongate, too readily. The polymer blends of this invention have all of these attributes. In addition, they are capable of being pigmented, readily processible on extruders using tubular die or spinneret die technology and may be waxed to accept flavors.

8 The products of this invention may be made by blending all the individual polymers in pellet or powder form in a dry mixer. They are then compounded on a twin screw compounding extruder and pelletized. Additionally, the individual polymer pellets may be gravity fed to a twin screw compounder to form the pellets of the compounded polymer blend. The compounded pellets are then extruded in a single screw extruder with a die head having an appropriate tubular or spinneret die. The extruded polymer is drawn down in a highly oriented form, annealed and calendered to achieve an appropriate thickness.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS r* Preferably, the base polymer is a high molecular-weight polymer having high tensile strength, suppleness and tenacity. The base polymer should be capable of contributing these properties to the final product such 20 that the resulting dental tape or floss has a tenacity (defined as strength per unit weight) of between about 2 about 6 g/denier and, more preferably between about and about 3.7 g/denier. Most preferably, the tenacity f the final product should be between about 2.8 and about 3.2 g/denier.

The base polymer of the compositions of this invention may include polyolefins, modified polyamides, polyesters or polyurethanes. Polyolefins having suitable strength for use in the products of this invention are, for example, polypropylene, Valtec HH-442H (available commercially from Himont U.S.A. Inc., of Wilmington, Delaware); modified polyolefins Profax KT-012P (or its equivalent, Himont Profax KT-025P) and Profax KS-031P 9 (available commercially from Himont U.S.A. Inc. of Wilmington, Delaware); Extrall 202.01 (available commercially from Exxon Corp). One or more polymers may be used in the base polymer constituent portion of the products of this invention.

The modified polyolefins useful in the products of this invention are preferably modified polypropylenes.

Preferably, they impart two advantageous properties to the compositions of this invention: tenacity of the resultant floss and suppleness. Together, these properties contribute to the "stretchability" of the floss.

15 Modified polyamides having suitable strength for use in the products of this invention are, for example, Pebax X1147 (available commercially from Atochem North America of Philadelphia, Pennsylvania).

20 Modified polyesters having strength suitable for use in the products of this invention are, for example, Hytrel G4778 (available commercially from Dupont Company of Wilmington, Delaware). Modified polyurethanes having strength-suitable for use in the products of this invention are, for example, Estane 58091 (available commercially from B.F. Goodrich Company of Brecksville, Ohio).

The block copolymer constituent of the compositions of this invention contribute to the tear strength and "nick" resistance of the floss compositions of this invention. Thus, the compositions of this invention will not tear when subjected to a small cut or nick.

Rather than permitting the tear to propagate along the 10 product, the compositions of this invention impede the propagation of nicks. Preferably, the block copolymer useful in the compositions of this invention are composed of a "hard" segment and a "soft" segment. The "hard" segments contribute to the strength of the polymer, while the "soft" segments increase its suppleness. The hard segments tend, generally, to be more compatible with each other than with the soft segments. In the composition, they tend to be attracted to each other and form clusters. These clusters tend to impede the propagation of nicks or cuts by standing in ~the path of a cut.

Preferably, the segmented or block copolymer is a 15 modified polyamide, polyester or polyurethane. Modified polyamides that contribute significantly to nick or cut resistance are, for example, Pebax 5533 (available commercially from Atochem North America of Philadelphia, Pennsylvania). Modified polyesters that contribute 20 significantly to nick or cut resistance are, for oo example, Hytrel 4056 (available commercially from Dupont Company of Wilmington, Delaware). Modified polyurethanes I. that contribute significantly to nick or cut resistance are, for-example, Estane 58137 (available commercially from B.F. Goodrich of Brecksville, Ohio).

The compatibilizer portion of the compositions of this invention assist in maintaining the integrity of the compositions. They interact with both the base polymer and the block copolymer in order to "glue" them together in the blend. This activity contributes to reducing the melt viscosity, which in turn improves processing and aids in elongation, thus maintaining the blend's suppleness at room temperature.

11 Preferably, the compatibilizer or plasticizer component is a nonmigrating polymer. Of course, those of ordinary skill in the art will be aware that the appropriate compatibilizer for each composition according to this invention will be different, depending upon the polymers which constitute the remainder of the composition. So long as the compatibilizer contains substituent groups which are compatible with both the base polymer and the block copolymer, the compatibilizer will be an appropriate choice for use in the compositions of this invention. Nonmigrating plasticizers that contribute significantly to suppleness, reduce melt viscosity and improve drawing characteristics of the extruded monofilament are, for example, Elvaloy HP441 (available 15 commercially from Dupont Company of Wilmington, Delaware), a terpolymer of ethylene, carbon monoxide and butyl acrylate; Polybond 1002 (available commercially from BP Chemicals of Hackettstown, New Jersey), a propylene polymer having acrylic acid end groups; or 20 Orevac 9314 (available commercially from Atochem North America of Philadelphia, Pennsylvania), a propylene copolymer also having acrylic acid end groups.

The preferred compatibilizer for a composition containing a polyolefin base polymer and a polyester block copolymer is a terpolymer of n-butylacrylate, carbon monoxide and ethylene. This polymer has a very high molecular weight (about 400,000), with a low melting point (about 65 0 The amount of n-butyl acrylate present as a free monomer is about 10% maximum.

The boiling point of n-butyl acrylate is about 145-6 0

C.

During processing, when temperatures of 2200C are seen, any remaining free monomer is volatilized and removed from the melt. The thermal stability measured on the 12 floss ribbon also indicates that the polymers are stable up to about 275-300 0

C.

Preferably, the compositions of this invention contain as their base polymer one or more polyolefins. The preferable block copolymer is a modified polyester.

Preferably, the compatibilizer is n-butyl acrylate, ethylene, carbon monoxide terpolymer. Most preferably, the composition of this invention should contain Himont Profax KT-012P polyolefin (or its equivalent, Himont Profax KT-025P), Himont Profax KS-031P polyolefin, DuPont Hytrel 4056 polyester block copolymer and DuPont Elvaloy HP 441 n-butyl acrylate, ethylene carbon monoxide terpolymer.

Of course, the ranges of concentrations of the base polymer, block copolymer and compatibilizer will vary depending upon the constituent polymers. For example, a preferred range of base polymer when the base polymer is S. 20 polyolefin is between about 30 and about 50 weight percent of the composition. In such a polyolefin-based composition, a preferred range of polyester block copolymer is between about 30 and 50 weight percent of the composition. The preferred range of compatibilizer is between about 2.5 and about 7.5 weight percent of the composition. In other systems, such as a polyamide system, the preferred ranges are as follows:between about 5 and about 15 weight percent of the base polymers, between about 10 and about 70 weight percent of the block polyamide, and between about 3 and about weight percent of the compatibilizer.

Most polymer blends are intimate mixtures of the individual polymers. The term "intimate" refers to the 13 domain or size of the individual polymers. If improperly processed, the domain size may be on the order of tens to hundreds of microns, and may be visible to low power light magnification. Such a polymer blend tends to have inferior properties. The more intimate the mixture, the better its physical properties. The polymer blends of this invention are preferably made using techniques which result in homogeneous materials on a micro-scale. Preferably, the blends of this invention are compounded using a twin-screw compounding .extruder. The use of a twin-screw extruder results in high shear mixing in localized areas. Preferably, a Werner Pfleiderer ZSK 30 or ZSK 58 twin-screw compounding extruder may be used, or an American Leistritz 40 or 34 may be used. Other twin-screw compounding extruders known to those of ordinary skill in the art may also be used to compound the compositions of this invention. Other acceptable methods of compounding the compositions of this invention include batch mixers using Banbury Mills, Brabender Plasticorders or the like.

.Preferably, the flattened, tubular dental floss is produced by extruding a unique polymer blend into a small and thin tubing and subsequently oriented (or "drawn"), annealed, collapsed ("flattened") and wound on a spool. A double walled product, with high tensile strength and tear, or "nick" resistance is formed. The round edges of the flattened tube eliminate the cause for gum irritation.

The initial diameter and wall thickness of the "asextruded" tube are functions of the inside and outside diameter of the female and male tubing die components.

14 An appropriate tubular die useful in extruding flosses has the dimensions of about 0.212 inches (outer diameter) for the male portion and about 0.222 inches (inner diameter) for the female portion. Other dimensions may be used, in accordance with the teachings in the art, however, the aforementioned dimensions are preferred. When a spinneret die is used, hollow filaments are extruded by the suitable arrangement and design of orifices such that the polymer melt fuses below the spinneret before entering the water quenching bath. Preferably, a "C"-shaped spinneret die is used, through which the polymer melt is extruded. As the polymer melt flows through the spinneret die and proceeds toward the cooling bath, the polymer located on the ends of the fuse together and form a hollow tube. The preferable dimensions for the "C"-shaped spinneret die are about 0.1000 inches (outer diameter) and about 0.0896 inches (inner diameter), with an allowance of about 0.0200 inches between the "ends" of 20 the Of course, other dimensions may be utilized in accordance with the teachings in the art. In both methods of forming the hollow tube or filament, gas or air can be injected into the tube in the melt stage to help control the wall thickness.

The polymer blend is extruded through a series of zones, each subjecting the extruded material to a progrespively higher temperature through four temperature zones. For example, the first zone has a temperature of about 350 0 F, the second zone, about 420 0 F, the third, about 440 0 F, at which point the blend material melts and the fourth, about 470 0 F, at the die head. The extruded tube is then quenched in a quench bath at a temperature of about 75 to about 80 0 F. The resulting fiber is pulled 15 through a series of five Godet rolls at about 20 rpms.

The fiber is then pulled through a water bath at about 205 0 F during stretching. Heating the fiber quickly during stretching reduces the formation of fibrils. The fiber is then stretched in the hot water bath over a length of six feet to a second series of Godet rolls at about 145 rpms. The fiber is then annealed by pulling it through an annealing oven at 205 0 F to stabilize the structure and prevent shrinking. The maximum draw ratio of the process is about 7.25:1. The annealing process is performed through a third series of Godet rolls at a speed of about 140 rpms with the overall draw ratio being about 7:1. Other draw ratios may be used, :depending on the polymer blend composition. Other ratios used were: 7.0:1.0 maximum and 6.5:1.0 overall; 6.75:1.00 maximum and 6.25:1.00 overall. The filament is then calendered, flattened and wound up onto spools for subsequent waxing and made into bobbins for consumer use.

Preferably, the dimensions of the flattened, tubular monofilament are between about 2 and about 4.5 mils in thickness and, the width between about 0.025 to about 0.070 in-ches when the denier is in the range of about 700 to about 900. Most preferably, the monofilament is about 2.5 mils to about 3 mils in thickness at this denier. When higher deniers are used, from.about 1200 to about 1300, the preferred thickness is between about 2 mils and about 4.5 mils, but the width should preferably be between about 50 mils and about 80 mils.

When the denier range is in the range of between about 600 and about 900, the preferred thickness should be between about 2 mils and about 4.5 mils and the width should be between about 25 and about 35 mils. This 16 enables us to make ribbons or tapes with a broad range of widths suitable for use in dental hygiene.

Referring to Figure 1, there is illustrated a method of making flosses and dental tapes of this invention.

Polymer blend pellets are fed into a dryer/feed hopper, through which the resin travels to an extruder, The polymer is extruded through a die head, 30, forming a monofilament, and is then deposited into a water quench bath, 40. Water quench bath 40 should be kept at a temperature relatively lower than the temperature of the polymer resin as it exits the extruder 20. For example, water quench bath 40 may be kept at about 70 0

F.

:'After travelling through water quench bath 40, the 15 monofilament is drawn through Godet A, 50, which causes the monofilament to elongate. Godet A, 50, should run at a speed of about between 10 and 50 revolutions per minute (RPM). More preferably, Godet A should run at a speed of between about 20 RPMS. The monofilament is then 20 drawn through a hot water bath, 60. Hot water bath should be kept at about 150 to about 210 Most preferably, it should be kept at about 205 0 F. After passing through hot water bath 60, the monofilament is drawn through another set of Godet rolls, Godet B, for further extension. Godet B, 70, should run at a speed of between about 130 and about 200 RPM. The speed differential between Godet A, 50, and Godet B, passing the monofilament through hot water bath assists in elongating the monofilament without breaking it or causing nicks or tears in the filament. From Godet B, 70, the monofilament is routed through annealing oven 1, 80, which is held at about 250OF and then through annealing oven 2, 90, which is held at about 205 0 F. This portion of the process assists in 17 stabilizing the compositions of the invention, strengthening the monofilament. The monofilament is then routed through Godet C, 100, which is run at between about 125 and about 140 RPM. Preferably, the monofilament is flattened through calender 110 and then wound around a spool at rewind station 120.

The following examples serve to illustrate the compositions and methods of this invention, however, it should be understand that the compositions and methods of this invention are not limited to the illustrated embodiments.

Example 1 2550 grams of Extrall 202.01 from Exxon Corporation, a thermoplastic polyolefin believed to be polypropylene modified in a reactor process with a thermoplastic rubber, 300 grams of Hytrel 4056 available from the 20 E.I. dupont de Nemours Corporation of Wilmington, Delaware, a block copolymer consisting of polybutylene terephthalate and polyether glycols, and 150 grams of Elvaloy HP441 from the Dupont Corporation, a terpolymer 9. made from ethylene, butylacrylate and carbon monoxide monomers, were tumble-blended in a vee blender. The composition was compounded and pelletized on a Werner Pfleiderer ZSK-30 twin screw compounding extruder and subsequently extruded into a monofilament in a Killion (1/4 inch) single screw extruder with a tubular die head. The extruded polymer was drawn down, annealed and calendered. The resulting polymer monofilament had reasonable physical properties. Denier, thickness, width, maximum force to break and maximum elongation and tenacity are shown in Table 1. Denier was determined by 18 measuring a length of floss and multiplying to assess the weight of the floss per 9000 meters of filament.

Thickness was determiend by using a micrometer. Width was measured using a shadowgraph. Breaking strength and percent elongation were determined using the procedures set forth in ASTM D2256, with the samples tested under TAPPI conditions 73 0 F and 60% relative humidity).

Examples 2-6 and 8-35 were similarly tested. The results are set forth in Table I.

Examples 2 and 3 Polymers were blended, pelletized, extruded and drawn down as described in Example 1. The components and 15 respective percentages are shown in Table 2.

Table 2 99° Example 2 Example 3 20 Extrall 202.01 80 Hytrel 4056 10 Elvaloy HP441 10 Examples 4, 5 and 6 To test the significance of the amount of block copolymer (Hytrel 4056) had on nick resistance, polymers having varying amounts of block copolymer were blended, pelletized, extruded and drawn (as in Example the compositions are shown in Table 3.

Table 3 Example 4 Example 5 Example 6 19 Extrall 202.01 Hytrel 4056 Elvaloy HP441 Exa Dles-7 and a Monofilaments were made in accordance with the procedure described in Example 1. The compositions of Examples 7 and 8 contained Ampacet 11343 from the Ampacet Company, a white pigmented (Ti02) polypropylene concentrate, and' are shown in table 4.

o* 0 904 9. 6 *0 to Extrall 202.01 Hytrel 4056 Elvaloy HP441.

Ampacet 11343 Table 4 Example 7 72.5 20.0 Example 8 70.0 20.0 Examples 9 and io Monofilaments were made as described in Example 1. The compositions, which contain Polybond 1002 from BP Chemicals Company, a plasticizer a polypropylene grafted with acrylic acid, are set forth in Table Table Extrall 202.01 Hytrel 4056 Polybond 1002 Ampacet 11343 Exampl1e 9 72.5 20.0 2.5 5.0 Exampl1e 70.0 20.0 Examio1es 11 and 12 Monofilaments were made as described in Example 1 having 20 the compositions, which contain Hytrel G4778, a block copolymer consisting of polybutylene phthalate and polyetherglycols, are shown in Table 6.

Table 6 Extrall 202.01 Hytrel G4778 Elvaloy HP441 10 Ampacet 11343 Examples 13, 14 and Example 11 72.5 20.0 2.5 5.0 Example 12 70.0 20.0

S

a.

S.

S

S.

S.

S. Modified polyolef in base polymers were evaluated. These polymers, Himont KS-021P, KS-03lP, KS-052P and KS-063P are ethylene propylene polymers. KT-012P is a terpolymer which also contains ethylene and propylene.

The compositions are shown in Tables 7-12.

Table 7 EXample 13 Example 14 Example Himont KS-021P Himont KS-031P Himont KS-052-P Hytrel 4056 Elvaloy HP44.1 Ampacet 11343 Himont KS-031P Hytrel 4056 Elvaloy HP441 Ampacet 11343 Table a Example 16 Example 17 65 25 5 5 21 Himonit KS-063P Himont KS-031P Hytrel 4056 Elvaloy HP441 Aiupacet 11343 Table 9 Example is Example 1i9 Example 20 ZXa%121_2 25 35 49 50 35 21 15 20 20 5 5 5 5 5 5 a a a a a. a a a a.

a a.

a. a a a a.

22 Himont KT-012P Himont KS-031P Hytrel 4056 Elvaloy HP441 Ainpacet 11343 Table lo EXample 22 EXaMple 23 25 35 50 35 is 20 5 5 5 5 a a a a.

a.

a a.

a.

a.

a. a .a Table 11 10 Example 25 Example 26 Example 27 Examiple 28 Himont KT-012P 45 20 45 -Himont KS-031P 20 45 10 Hytrel 4056 25 25 35 Elvaloy HP441 5 5 5 Ainpacet 11343 5 5 5 Himont KT-012P 20 Himont KS-031P Hytrel 4056 Elvaloy HP441 Ampacet 11343 Table 12 Example 29 Example 20 45 25 5 5 -Examples 31. and 32 A plasticizer, Elvaloy 742, was used in the compoqitions of Examples 31, 32, 33, 34 and 35. Elvaloy 742 contains ethylene, vinyl acetate and carbon monoxide. The compositions were made in accordance with the procedure set forth in Example 1. The compositions of Examples 31 and 32 are set forth in Table 13. The compositions of Examples 33, 34 and 35 are set forth in Table 14. The polymer blends of Examples 33, 34 and 35 were tumbled-blended in a vee-blender.

23 The compositions were compounded and pelletized on an American Leistritz ASE-50 twin screw compounding extruder and subsequently extruded into a monofilmanet tube in a David- Standard (1-1/4 inch single screw) extruder with a spinneret "C"-shaped die. The extruded polymer was quenched, drawn down, annealed and calendered. The resulting polymer monofilments had good physical properties (See Table

I).

Himont KT-012P Himont KS-031P Hytrel HTR-6108 Elvaloy 742 15 Ampacet 11343 Himont KT-012P Himont KS-031P Hytrel 4056 Elvaloy HP441 Ampacet 11343 Table 13 Example 31 20 35 35 5 5 Example 32 Table 14 Example 33 Example 34 ExamDle 45 35 10 45 45 5 5 5 5 The floss of Example 33, in its relaxed state, had a thickness of..0.0030 inches. The floss was prepared for use by wrapping the ends around two fingers prior to insertion in the mouth. The floss was subjected to a slight tension and measurement of the thickness taken. The floss, when under slight tension, measured 0.0026 inches in thickness, a reduction of about 13%. In contrast, in most traditional monofilament flosses such as expandable Teflon, the elongation of the monofilament under such tension is about 3without any measurable reduction in thickness.

24 Example 36 Monofilaments were made as described in Example 33, 34 and the composition shown in table 15 contained Pebax 5533 and X1147, both modified polyamides, and Orevac 9314, a compatibilizer (all available commercially from Atochem North America of Philadelphia) and Unitane OR 450, Titanium Dioxide.

Table Pebax 5533 80.0 Pebax X1147 7.2 Orevac 9314 10.8 .Unitane OR 450 Examples 37 and 38 Tables 16 and 17 show compositions made in accordance with the procedure set forth in Examples 33, 34 and 35 containing 20 Pebax 6333, a modified polyamide (available commercially from Atochem North America of Philadelphia) as the base polymer in the compositions of this invention.

S.

Table 16 Pebax 6333 80.0 Orevac 9314 18.0 Unitane OR 450 25 Pebax 5533 80.0 Pebax X1147 7.2 Orevac 18211 10.8 Unitane OR 450 Example 39 Table 18 show compositions made in accordance with the procedure set forth in Examples 33, 34 and 35 containing Himont KT-025P, a proprietary terpolymer which is commercially from the Himont Co. of Wilmington, Delaware, *15 Hytrel 4056, Elvaloy HP441 and pigment.

Table 18 Himont KT-025P 45.0 Hytrel 4056 45.0 Elvaloy HP441 *Pigment 26 Tabe 61 EXAMPLE

DENIER

THICKNESS

WIDTH BREAK 4AXINWI TENACITy 99 999 949.

.4 9 9 999 *999 9~ 9. 4 9.

9 9 99 9 9 9.

99 .9 *99* 9 49 9 .9 S. 99 .9

NUMBER

1 1269 2 1129 3 1190 10 4 1136 5 1143 6 1168 7 (NO DATA 8 1382 9 1915 10 2415 11 1439 12 1058 13 1000 20 14 950 15 900 16 960 17 950 18 96co 19 940 960 21 940 22 960 23 1000 24 960 950 26 960 27 950 28 960 (INCH) (INCH)

STRENGTH

0.0039 0.0684 6.63 0.0039 0.0560 6.42 0.0043 0.0555 7.00 .0.0047 0.0484 6.30 0.0032 0.0671 6.50 0.0042 0.0521 6.08 FOR EXAMPLE available] 0.0079 0.0390 7.46 0.0086 0.0518 9.87 0.0086 0.0510 9.87 0.0086 0.0417 8.77 0.0073 0.0358 5.83 <5.00 <5.00 <5.00 <5.00 <5.50 <5.00 <5.00 <5.00 <5.00 <5.00 6.00 5.80 <5.50 <5.50 5.50 5.50

ELONG

21.8 18.*5 19.4 31.9 32.3 50.7 46.1 56.0 56.0 60.1 35.5 %6 9/D 2.37 2.58 2.67 2.51 2.58 2.36 2.45 2.34 1.86 2.77 2.50 27 Table I continued...

EXAMPLE DENIER

NUMBER

29 930 970 31 960 32 950 33 970 34 938 35 970

THICKNESS

(INCH)

WIDTH BREAK MAXIMUM TENACITY (INCH) STRENGTH ELONG q/D <5.50 5.50 <5.00 5.50 4.

4. 4 0*4 4 4 9444 4 9.

9 4 @44 4 4.

49 44 94 4 4 4 ~44.

*4 49 9 "*4 4 4.99 449444 44 4 .9 44 4.

4* 0. 0370 0. 0380 0. 0350 0. 0450 0.0500 0. 0510 7.13 6.15 5.11 41.7 62. 1 53. 6 3 .34 2.98 2.*39

Claims (5)

1. A process for making a tubular dental hygiene device comprising: a) extruding a polymer blend into a small and thin tubing using an extrusion pump; b) orienting said polymer blend; c) annealing said polymer blend; and d) collapsing said polymer blend.

2. A process according to claim 1 wherein, during said extrusion step, the extrusion pump is rhythmically pulsed, thereby producing a textured tubing.

3. A process according to claim 1 or 2 wherein said polymer blend is extruded into a cooling bath having a temperature of between about 75°F and about 80 0 F. 15

4. A process according to any one of claims 1 to 3 wherein after said extrusion step, said polymer blend is heated and pulled through Godet rolls.

5. A process for making a tubular dental hygiene device, substantially as herein described with reference .eFiure 1 or any one of the accompanying Examples. DATED this 28th Day of October, 1998 JOHNSON JOHNSON CONSUMER PRODUCTS, INC. 104 Attorney: RUTH M. CLARKSON S*Fellow Institute of Patent Attorneys of A a of SHELSTON WATERS