CA1306834C - Tampon applicators and compositions for making same - Google Patents
Tampon applicators and compositions for making sameInfo
- Publication number
- CA1306834C CA1306834C CA000566286A CA566286A CA1306834C CA 1306834 C CA1306834 C CA 1306834C CA 000566286 A CA000566286 A CA 000566286A CA 566286 A CA566286 A CA 566286A CA 1306834 C CA1306834 C CA 1306834C
- Authority
- CA
- Canada
- Prior art keywords
- tampon
- acid residues
- plasticizer
- present
- tampon applicator
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F13/00—Bandages or dressings; Absorbent pads
- A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
- A61F13/20—Tampons, e.g. catamenial tampons; Accessories therefor
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F13/00—Bandages or dressings; Absorbent pads
- A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
- A61F13/20—Tampons, e.g. catamenial tampons; Accessories therefor
- A61F13/26—Means for inserting tampons, i.e. applicators
Abstract
TAMPON APPLICATORS AND COMPOSITIONS FOR MAKING SAME
ABSTRACT
A biodegradable tampon applicator comprising a molded, flexible, polymeric hollow cylindrical body for enclosing a tampon therein and having a first open end through which said tampon is expelled and a second open end for receiving means for expelling said tampon. said body comprising a moldable poly 3-bydroxybutyric acid composition.
ABSTRACT
A biodegradable tampon applicator comprising a molded, flexible, polymeric hollow cylindrical body for enclosing a tampon therein and having a first open end through which said tampon is expelled and a second open end for receiving means for expelling said tampon. said body comprising a moldable poly 3-bydroxybutyric acid composition.
Description
130~ 4 TAMPON APPLICATORS AND COMPOSITIONS FOR MAKING SAME
Back~round of the Invention The pre6ent invention relate6 to tampon applicator6 and in particular to biodegradable tampon applicators focmed of poly 3-hydroxybutyric acid (PHB).
Tampon applicator6 are not suppo6ed to be di6po6ed of via the 6anitary and 6ewage 6y6tem~. However, it ig often the ca6e that they are. A popular material for tampon applicators i6 polyethylene which i6 a non-degradable pla6tic. Thu6 di~po6al of polyethylene tampon applicator6 will cause accumulation and clogging in 6anitary and sewage 6ystems, in particular in 6eptic tank system6.
Furthermore 6uch polyethylene applicator6 are not degraded in sewage treatment plant~ and are often pa66ed out into the environment to be wa6hed up on the 6hore6 of river6, lakes and oceans. Thus it is a problem of the art to provide tampon applicators which overcome or ameliorate the sanitary and environmental disadvantage6 of tho6e applicator6 commonly u6ed.
USP 2518486 6uggest6 the u6e of tampon applicator6 made of water-601uble polyvinyl alcohol. However, 6uch applicator6 have been found to become 6ticky on contact with damp 6urface6 and to become relatively un6table in humid condition6. USP 3882869 i6 al60 directed to the problem of di6po6al of tampon applicator6 and propo6e6 the u6e of a water soluble polymer compounded with filler material 6uch a6 clay, talc, wood, flour or fibre6. Such applicator6 are 6~id to have a lower tendency to adhere to moist human ti66ue. Neverthele66, they are ~till formed of water-601uble polyvinyl alcohol with the inherent di6advantage6 thereof. USP 3954104 di6clo~e6 a ,~
13~ 4 thermoplastic, water-dispersible, biodegradable composition which can for example be used to make a tampon applicator. The composition comprises hydroxycellulo6e which is biodegradable and water-601uble and starch as a biodegradabLe filler. Again these tampon applicators contain a water soluble material.
USP 4372311 seeks to solve this problem by providing disposable articles made from a water-soluble polymer, a surface of which articles being coated with a degradable water-insoluble polymer. The disposable articles include diapers, tampons, tampon applicators, sanitary napkins, bed liners and bandages. It is acknowledged that the utility of articles made from a water-soluble polymer is limited because even casual contact with moisture will cause the surface to become tacky or slippery thus interfering with the proper function of the article. Thus USP 4372311 proposes coating the water-soluble polymer with a water-insoluble polymer for protection. Poly ~-hydroxybutyrate is one of a number of degradable water-insoluble polymers which, it is stated, may be used as a coating. The coating may be applied for example by dipping, spraying or brushing.
Further attempts to solve the problem of providing disposable tampon applicators that are stable on storage have involved the study of paper or cardboard applicators. These are generally unsatisfactory because of poor durability in handling, packaging and u6e; they have a low crush resistance, poor bending strength and relatively poor frictional characteristics. Furthermore, they absorb relatively high quantities of moistu~e thereby enhancing the lack of durability.
13~ 4 Summary of The Invention A biodegradable tampon applicator is provided comprising a molded hollow cylindrical body of polymeric material for enclo6ing a tampon therein and having a first flexible open end through which said tampon is expelled and a second open end for receiving mean6, such as a plunger, for expelling the tampon.
In accordance with the teachings of this invention, tbe cylindrical body comprises a moldable poly 3-hydroxybutyric acid composition which preferably i6 a copolymer of 3-hydroxybutyric acid and 3-hydroxyvaleric acid residues. Preferably, the 3-hydroxyvaleric acid residues are present in the range of from about 5 to about 30 mol ~, based on the total moles of 3-hydroxybutyric and 3-hydroxyvaleric acid residues present. The composition is further modified by including a plasticizer. The proportion of the 3-hydroxyvaleric acid residue in the polymer and the plasticizer quantity are so chosen as to provide a moldable composition resulting in a flexible product. In particular the melt flow time, a6 hereinafter defined, is limited to not more than 20 minute6 and t~e final product is of such material that exhibits a modulus of elasticity of 0.2 to about 1.0 GPa.
Brief DescriPtion of the Drawinqs Figure 1 illu6trates a tampon applicator in longitudinal 6ide view; and Figure 2 illustrated the tampon applicator of Figure 1 in end view.
Detailed De6criPtion of the Invention The present invention provides tampon applicators that are biodegradable so that there is no blockage of sanitary and sewage systems. Furthermore there is significant benefit to the environment because of the biodegradability of the applicators. In addition the tampon applicator6 of the present invention are Qtable on storage, even in humid conditions, and exhibit the qualities and properties necessary for an applicator. In particular the applicators of the present invention are manufactured in one molding operation and are inexpensive and easy to make. The inherent disadvantages of a laminated or coated article are avoided.
Accordingly the present invention provides a tampon applicator comprising poly 3-hydroxybutyric acid.
Poly 3-hydroxybutyric acid is a thermoplastic polyester containing repeat units of the formula:
-CH(CH3)CH2C00-which is accumulated by many micro-organisms, in particular Alcaliqenes, Athiorhodium, Azotobacter, Bacillus, Nocardia, P6eudomonas, Rhizobium and SDirillum as an energy reserve material.
Poly 3-hydroxybutyric acid is conveniently prepared by cultivating ehe micro-organism in an aqueous medium on a suitable sub~trate, such as a carbohydrate or methanol, as an energy and carbon source. The substrate must, of course, be one that is assimilable by the micro-organism.
In order to promote the assimilation of the polymer, at least part of the cultivation is preferably conducted 3~ 3l~
under conditions wherein there is a limitation of a nutrient that is essential for growth of the micro-organism but which is not required for polymer accumulation. ~xamples of suitable proce6se~ are described in EP-A-15669, 46344 and USP 4336334 and 4433053.
The polymer can be extracted from the bacterial cells by a variety of techniques, often involving a solvent extraction step. Example~ of such processes are described in EP-A-15123.
Polymers containing both 3-hydroxybutyric acid units and other hydroxycarboxylic acid units, such as 3-hydroxyvaleric acid units can also be produced microbiologically. A microbiologically produced heteropolymer containing 3-hydroxybutyric acid and 3-hydroxyvaleric acid residues i~ described by Wallen et al. in "Environmental Science and Technology" 8 (1974) 576-9. In addition EP-A-52459 and 69497 and USP 4477654 describe that various copolymers, comprising poly 3-hydroxybutyric acid, can be produced. Cultivating on certain substrates varies the copolymer, for example propionic acid given rise to 3-hydroxyvaleric acid units in the copolymer.
Accordingly, in the present specification, the term "poly 3-hydroxybutyric acid", when mentioned in the context of the present invention, cover6 the homopolymer and copolymers wherein 3-hydroxybutyric acid units form at least 40 mol % and preferably at least 50 mol % of the polymer chain.
Poly 3-hydroxybutyric acid is non-toxic, compatible with living tissue without rejection or irritation and indeed ~3(,~
t~e degradation product, 3-hydroxybutyric acid, i8 a normal mammalian metabolite.
There ha~ been a number of disclosures on the processing S of poly 3-hydroxybutyric acid in order to form ~haped articles, for example USP 4360488, 4427614, 4477655 and 4537738. Poly 3-hydroxybutyric acid, in the present invention, can be processed in any convenient manner to form the tanpon applicator6.
Poly 3-hydroxybutyric acid homopolymer has a melting point of about 180C and the glass transition temperature (Tg) of the poly~er is about 0 to 5C. Poly 3-hydroxybutyric acid copoly~ers ~with poly 3-hydroxyvaleric acid) have lower melting-points and have a similar glass transition temperature. The melting-point will depend on the proportion of 3-hydroxyvalerate units, for example, material having about 25% of such units will have a melting-point of about 105C.
In order that a poly 3-hydroxybutyric acid polymer can be successfully injection molded or extruded, we have found it preferable that the melt-flow time is not more than about 20 minutes when assessed by the following procedure:
The polymer compocition (3.5 g) is charged to the barrel of a melt-flow grader (Davente~t, Welwyn, England) provided with a die having a circular orifice of 2 mm diameter and 8 mm land length. The barrel is maintained at a temperature of from 10C to about 20C above the melting-point of the highest melting polymer (e.g. 180 -190C for homopolymer). Polymer (3.5 g) is added and left for a 4 1/2 minute warm-up period; a 2.16 ~g load i~
applied to the piston which ha~ a weight of 0.16 Kg. The compo~ition ic extruded through the die and cut-off~ taken PPC 2~
13~34 at minute intervals. The cut-offs are weighed and weight vs ti~e is plotted (the test is performed in accordance with ASTM D 1238-73). Typical melt flow index (MFI) values are given in Table 1.
Various homopolymer and copolymer compositions can be used in the present invention with consideration given to both ease of handling and processability during manufacture and to the eventual end use of the applicator. The compositicn of the copolymer can be varied according to the teachings of the art. Thus variou6 copolymers are available for use and different copolymers give rise to different physical properties of the applicators and to various ease of processing. In a preferred aspect of this invention the poly 3-hydroxybutyric acid is a copolymer consisting of 3-hydroxybutyric acid and 3-hydroxyvaleric acid residues, the amount of 3-hydroxyvaleric acid residues being in the range 5 - 30 mol %. Such copolymers provide applicators with improved flexibility and improved toughness. Flexibility is an important characteristic in the use of the applicators and improved toughness enables the walls of the applicators to be thinner thus permitting said applicators to be lighter, improving the rate of biodegradation, enhancing cosmetic appearance and encouraging consumer acceptability. Preferably the proportion of 3-hydroxyvaleric acid residues in 10 - 20 mol %, for example about 15 mol %.
For ease of processing a polymer composition that molds well is preferred. In general the lower the proportion of 3-hydroxyvaleric acid residues the greater the ease of molding, that is the greater the degree of crystallinity leading to shorter cycle times and lower melt degradation. However, we have found that the lower the proportion of 3-hydroxyvaleric acid residues then the ~3~ 4 stif~er the polymer composition is. Accordingly it i6 usually necessary to include at least one plasticizer to provide a polymer composition havinq ~uitable properties, for example reduced modulus of elasticity or increased toughness. In general the lower the proportion of 3-hydroxyvaleric acid residues the greater the amount of plasticizer that is required. A preferred range for the modulus of elasticity of the polymer compo6itions for use in this invention is 0.2 - 1.0 GPa, in particular 0.3 -0.6 GPa and typically about 0.4 GPa. (giga Pascals) Suitably the total amount of plasticizer used can be up to 40 parts per hundred of polymer resin (phr), for example, 40 phr of plasticizer can be used with a copolymer containing 5 mol % of 3-hydroxyvaleric acid residues.
More conveniently, however, for a copolymer having 10 - 20 mol ~ of 3-hydroxyvaleric acid residues the preferred amount of plasticizer is in the range 10 - 30 phr for example about 20 phr. The amount of plasticizer used will also, of course, vary according to the specific plasticizer compound used. Suitable plasticizers include diacetin (Unichema ),dibenzoate (Lankroflex SP80; Lankro), triethyl phosphate, alkylarylphosphate (Santiciser 141;
Monsanto) iso-decyl diphenyl phosphate (Santiciser 148), butylbenzyl phthalate (Santiciser 160), neopentyl glycol (Benzoflex 8312; Velsicol Chemical Corporation), p-toluene sulphonamide (Santiciser 8) and dialkylalkyleneoxide glutarate (Plast~all 7050; C P Hall Ltd) and mixtures thereof. Preferred plasticizers are Santiciser 8 and Plasthall 7050 and mixtures thereof, in particular about a 50:50 mixture thereof.
In another aspect the polymer composition can contain up to 5 phr of a nucleating agent to encourage * Trade-mark cry~tallization on molding. Suitable nucleating agents include talc, micronized mica, alumina, silica, boron nitride, calcium carbonate and calcium hydroxyapatite. Of these we have found boron nitride to be most ~atisfactory. ~ypically the amount of nucleating agent is in ~he range 0.3 - 3 phr, for example 0.5 - 2 phr and conveniently about 1 phr.
The polymer composition can contain variou6 other additives used in the polymer proce~sing art to aid handling and proces6ing, for example, molding aids ~uch as stearate salts and ester~. In addition, additives to improve the cosmetic appearance of the applicator can be included in the composition for example pigments and titanium dioxide. Such additives can be present in an amount sufficient to be effective, typically about 1 phr for pigments.
In another aspect the poly 3-hydroxybutyric acid polymer composition can further contain a biodegradable filler.
The filler has not significantly affect the characteristics of the polymer but enables the amount of poly 3-hydroxybutyric acid to be lowered thus resulting in economic savings. Suitable fillers include starch and hydroxyalkyl cellulose which do not significantly affect molding properties even when present in proportions of up to about 40 phr. Preferably any such filler is starch which is relatively inexpensive. In addition, the use of starch is advantageous as we have found that the rate of biodegradability of polymer composition is increased with increasing proportions of starch.
ExamPle 1 A polymer composition was prepared having the following ingredients:
Dhr poly 3-hydroxybutyric acid/poly 3-hydroxy-valeric acid copolymer (mol. wt about 750,000) having ~% 3-hydroxyvaleric acid units Santiciser 8 10 Plasthall 7050 10 15 ~oron nitride ~from Fluorochem Glossop, U.K.) 1.0 Titanium dioxide 1.0 This was molded using a Negri Bossi NB 90 (38 mm diameter screw) machine, having a cycle time of about 40 seconds, to provide tampon applicators each weighing about 1.9 g.
The machine ~as operated using barrel temperatures in the range of 120 - 180 C, and mold temperatures in the range of 30 - 70C, for example 40C.
Figure 1 shows a tampon applicator 1 having a hollow cylindrical body 2 about 55 mm in leng~h and about 15 mm in diameter. The body 2 has at one end thereof a shoulder 3 to whi~h i6 integrally molded a hollow cylindrical qrip portion 4 of about 0.75 mm wall thickne~s having annular ribs 5. At the other end of the body 2 are integrally molded four flexible petalfi 6. Each petal 6 is of approximate elliptical shape and has a maximum length of about 10 mm. The wall thickness is aproximately 0.7 mm in region 7 of the body 2 and is approximately 0.3 mm in the region of the petals 6.
In use a tampon (not shown) i8 inserted in the cylindrical body 2. A plunger (not shown), conveniently of a disposable material similar to that of the applicator, i~
5 pushed through hollow srip portion 4 to urge the tampon against the flexible petals 6 thereby opening them.
Continued pushing af the plunger re~ults in the successful expulsion of the tampon whereupon the applicator can be hygenically dispo6ed of. Conveniently qrip portion 4 is held by the thumb and middle finger while the index finger operate6 the plunger.
The biodegradability of the tampon applicators of the present invention was studied u&ing the following procedure. Anaerobic digester unitC composed of sealed glass bottles fitted with gas exhaust tubes whereby the gas expelled by the unit can be measured were prepared containing about 700 to 800 ml of anaerobic digested sludge to which fresh raw sewage had been added. Various tampon applicators according to the present invention were added and the units were sealed. Identical control units were also prepared without applicators. The gas produced was collected and measured daily and samples were remoYed periodically to determine the extent of actual solids degradation. The results for a number of applicators are given below:
Results All applicators were as described above in relation to the drawings; however, so~e were of thicker wall thicknes~
wherein the approximate wall thicknes&es of the grip, body and petals were 1.1 mm, 0.85 mm and 0.45 mm respectively.
SAMPLE DESCRIPTION DRY WEIGHT (~) lA Thin wall Composition of Example 1 1.93 lB Thin wall Composition of Example 1 1.945 2A Thick wall Composition of Example 1 2.31 ~B Thick wall Composition of Example l 2.30 3A Thick wall 2.49 (two samples) Composition of Example l 2.48 3B Thick wall 2.50 15(two samples) Composition (19% HV units) 2.50 havin~ Santiciser 8 5 phr Plasthall 7050 5 phr Tio2 1 phr Boron Nitride 1 phr PRODUCT RECOVERY (% Wei~ht Remainin~) Day SamDle lA 100 87 - 39 - 6 - O
In all cases the non-recovered residual material was totally soluble and not detected by gross examination of the sewage sludge.
~30~
TYPICAL MæLT FLOW INDE% (~FI) VALUES FOR VARIOUS S~MPLES
s TD
(doubling time) Sample MFI in minutes HV Units 6% 0.48 6.6 San~iciser 8 5 phr at 170C
Plasthall 7050 5 phr BN 1 phr TiO2 1 phr HV units 16~ 1.0 12 Santiciser 8 7 1/2 phr at 150C
Plasthall 7050 7 1/2 phr BN 1 phr TiO2 1 phr HV units 19% 0.~1 llol Santiciser 8 5 phr at 160C
Plasthall 7050 5 phr BN 1 phr ~i2 1 phr _ _ _
Back~round of the Invention The pre6ent invention relate6 to tampon applicator6 and in particular to biodegradable tampon applicators focmed of poly 3-hydroxybutyric acid (PHB).
Tampon applicator6 are not suppo6ed to be di6po6ed of via the 6anitary and 6ewage 6y6tem~. However, it ig often the ca6e that they are. A popular material for tampon applicators i6 polyethylene which i6 a non-degradable pla6tic. Thu6 di~po6al of polyethylene tampon applicator6 will cause accumulation and clogging in 6anitary and sewage 6ystems, in particular in 6eptic tank system6.
Furthermore 6uch polyethylene applicator6 are not degraded in sewage treatment plant~ and are often pa66ed out into the environment to be wa6hed up on the 6hore6 of river6, lakes and oceans. Thus it is a problem of the art to provide tampon applicators which overcome or ameliorate the sanitary and environmental disadvantage6 of tho6e applicator6 commonly u6ed.
USP 2518486 6uggest6 the u6e of tampon applicator6 made of water-601uble polyvinyl alcohol. However, 6uch applicator6 have been found to become 6ticky on contact with damp 6urface6 and to become relatively un6table in humid condition6. USP 3882869 i6 al60 directed to the problem of di6po6al of tampon applicator6 and propo6e6 the u6e of a water soluble polymer compounded with filler material 6uch a6 clay, talc, wood, flour or fibre6. Such applicator6 are 6~id to have a lower tendency to adhere to moist human ti66ue. Neverthele66, they are ~till formed of water-601uble polyvinyl alcohol with the inherent di6advantage6 thereof. USP 3954104 di6clo~e6 a ,~
13~ 4 thermoplastic, water-dispersible, biodegradable composition which can for example be used to make a tampon applicator. The composition comprises hydroxycellulo6e which is biodegradable and water-601uble and starch as a biodegradabLe filler. Again these tampon applicators contain a water soluble material.
USP 4372311 seeks to solve this problem by providing disposable articles made from a water-soluble polymer, a surface of which articles being coated with a degradable water-insoluble polymer. The disposable articles include diapers, tampons, tampon applicators, sanitary napkins, bed liners and bandages. It is acknowledged that the utility of articles made from a water-soluble polymer is limited because even casual contact with moisture will cause the surface to become tacky or slippery thus interfering with the proper function of the article. Thus USP 4372311 proposes coating the water-soluble polymer with a water-insoluble polymer for protection. Poly ~-hydroxybutyrate is one of a number of degradable water-insoluble polymers which, it is stated, may be used as a coating. The coating may be applied for example by dipping, spraying or brushing.
Further attempts to solve the problem of providing disposable tampon applicators that are stable on storage have involved the study of paper or cardboard applicators. These are generally unsatisfactory because of poor durability in handling, packaging and u6e; they have a low crush resistance, poor bending strength and relatively poor frictional characteristics. Furthermore, they absorb relatively high quantities of moistu~e thereby enhancing the lack of durability.
13~ 4 Summary of The Invention A biodegradable tampon applicator is provided comprising a molded hollow cylindrical body of polymeric material for enclo6ing a tampon therein and having a first flexible open end through which said tampon is expelled and a second open end for receiving mean6, such as a plunger, for expelling the tampon.
In accordance with the teachings of this invention, tbe cylindrical body comprises a moldable poly 3-hydroxybutyric acid composition which preferably i6 a copolymer of 3-hydroxybutyric acid and 3-hydroxyvaleric acid residues. Preferably, the 3-hydroxyvaleric acid residues are present in the range of from about 5 to about 30 mol ~, based on the total moles of 3-hydroxybutyric and 3-hydroxyvaleric acid residues present. The composition is further modified by including a plasticizer. The proportion of the 3-hydroxyvaleric acid residue in the polymer and the plasticizer quantity are so chosen as to provide a moldable composition resulting in a flexible product. In particular the melt flow time, a6 hereinafter defined, is limited to not more than 20 minute6 and t~e final product is of such material that exhibits a modulus of elasticity of 0.2 to about 1.0 GPa.
Brief DescriPtion of the Drawinqs Figure 1 illu6trates a tampon applicator in longitudinal 6ide view; and Figure 2 illustrated the tampon applicator of Figure 1 in end view.
Detailed De6criPtion of the Invention The present invention provides tampon applicators that are biodegradable so that there is no blockage of sanitary and sewage systems. Furthermore there is significant benefit to the environment because of the biodegradability of the applicators. In addition the tampon applicator6 of the present invention are Qtable on storage, even in humid conditions, and exhibit the qualities and properties necessary for an applicator. In particular the applicators of the present invention are manufactured in one molding operation and are inexpensive and easy to make. The inherent disadvantages of a laminated or coated article are avoided.
Accordingly the present invention provides a tampon applicator comprising poly 3-hydroxybutyric acid.
Poly 3-hydroxybutyric acid is a thermoplastic polyester containing repeat units of the formula:
-CH(CH3)CH2C00-which is accumulated by many micro-organisms, in particular Alcaliqenes, Athiorhodium, Azotobacter, Bacillus, Nocardia, P6eudomonas, Rhizobium and SDirillum as an energy reserve material.
Poly 3-hydroxybutyric acid is conveniently prepared by cultivating ehe micro-organism in an aqueous medium on a suitable sub~trate, such as a carbohydrate or methanol, as an energy and carbon source. The substrate must, of course, be one that is assimilable by the micro-organism.
In order to promote the assimilation of the polymer, at least part of the cultivation is preferably conducted 3~ 3l~
under conditions wherein there is a limitation of a nutrient that is essential for growth of the micro-organism but which is not required for polymer accumulation. ~xamples of suitable proce6se~ are described in EP-A-15669, 46344 and USP 4336334 and 4433053.
The polymer can be extracted from the bacterial cells by a variety of techniques, often involving a solvent extraction step. Example~ of such processes are described in EP-A-15123.
Polymers containing both 3-hydroxybutyric acid units and other hydroxycarboxylic acid units, such as 3-hydroxyvaleric acid units can also be produced microbiologically. A microbiologically produced heteropolymer containing 3-hydroxybutyric acid and 3-hydroxyvaleric acid residues i~ described by Wallen et al. in "Environmental Science and Technology" 8 (1974) 576-9. In addition EP-A-52459 and 69497 and USP 4477654 describe that various copolymers, comprising poly 3-hydroxybutyric acid, can be produced. Cultivating on certain substrates varies the copolymer, for example propionic acid given rise to 3-hydroxyvaleric acid units in the copolymer.
Accordingly, in the present specification, the term "poly 3-hydroxybutyric acid", when mentioned in the context of the present invention, cover6 the homopolymer and copolymers wherein 3-hydroxybutyric acid units form at least 40 mol % and preferably at least 50 mol % of the polymer chain.
Poly 3-hydroxybutyric acid is non-toxic, compatible with living tissue without rejection or irritation and indeed ~3(,~
t~e degradation product, 3-hydroxybutyric acid, i8 a normal mammalian metabolite.
There ha~ been a number of disclosures on the processing S of poly 3-hydroxybutyric acid in order to form ~haped articles, for example USP 4360488, 4427614, 4477655 and 4537738. Poly 3-hydroxybutyric acid, in the present invention, can be processed in any convenient manner to form the tanpon applicator6.
Poly 3-hydroxybutyric acid homopolymer has a melting point of about 180C and the glass transition temperature (Tg) of the poly~er is about 0 to 5C. Poly 3-hydroxybutyric acid copoly~ers ~with poly 3-hydroxyvaleric acid) have lower melting-points and have a similar glass transition temperature. The melting-point will depend on the proportion of 3-hydroxyvalerate units, for example, material having about 25% of such units will have a melting-point of about 105C.
In order that a poly 3-hydroxybutyric acid polymer can be successfully injection molded or extruded, we have found it preferable that the melt-flow time is not more than about 20 minutes when assessed by the following procedure:
The polymer compocition (3.5 g) is charged to the barrel of a melt-flow grader (Davente~t, Welwyn, England) provided with a die having a circular orifice of 2 mm diameter and 8 mm land length. The barrel is maintained at a temperature of from 10C to about 20C above the melting-point of the highest melting polymer (e.g. 180 -190C for homopolymer). Polymer (3.5 g) is added and left for a 4 1/2 minute warm-up period; a 2.16 ~g load i~
applied to the piston which ha~ a weight of 0.16 Kg. The compo~ition ic extruded through the die and cut-off~ taken PPC 2~
13~34 at minute intervals. The cut-offs are weighed and weight vs ti~e is plotted (the test is performed in accordance with ASTM D 1238-73). Typical melt flow index (MFI) values are given in Table 1.
Various homopolymer and copolymer compositions can be used in the present invention with consideration given to both ease of handling and processability during manufacture and to the eventual end use of the applicator. The compositicn of the copolymer can be varied according to the teachings of the art. Thus variou6 copolymers are available for use and different copolymers give rise to different physical properties of the applicators and to various ease of processing. In a preferred aspect of this invention the poly 3-hydroxybutyric acid is a copolymer consisting of 3-hydroxybutyric acid and 3-hydroxyvaleric acid residues, the amount of 3-hydroxyvaleric acid residues being in the range 5 - 30 mol %. Such copolymers provide applicators with improved flexibility and improved toughness. Flexibility is an important characteristic in the use of the applicators and improved toughness enables the walls of the applicators to be thinner thus permitting said applicators to be lighter, improving the rate of biodegradation, enhancing cosmetic appearance and encouraging consumer acceptability. Preferably the proportion of 3-hydroxyvaleric acid residues in 10 - 20 mol %, for example about 15 mol %.
For ease of processing a polymer composition that molds well is preferred. In general the lower the proportion of 3-hydroxyvaleric acid residues the greater the ease of molding, that is the greater the degree of crystallinity leading to shorter cycle times and lower melt degradation. However, we have found that the lower the proportion of 3-hydroxyvaleric acid residues then the ~3~ 4 stif~er the polymer composition is. Accordingly it i6 usually necessary to include at least one plasticizer to provide a polymer composition havinq ~uitable properties, for example reduced modulus of elasticity or increased toughness. In general the lower the proportion of 3-hydroxyvaleric acid residues the greater the amount of plasticizer that is required. A preferred range for the modulus of elasticity of the polymer compo6itions for use in this invention is 0.2 - 1.0 GPa, in particular 0.3 -0.6 GPa and typically about 0.4 GPa. (giga Pascals) Suitably the total amount of plasticizer used can be up to 40 parts per hundred of polymer resin (phr), for example, 40 phr of plasticizer can be used with a copolymer containing 5 mol % of 3-hydroxyvaleric acid residues.
More conveniently, however, for a copolymer having 10 - 20 mol ~ of 3-hydroxyvaleric acid residues the preferred amount of plasticizer is in the range 10 - 30 phr for example about 20 phr. The amount of plasticizer used will also, of course, vary according to the specific plasticizer compound used. Suitable plasticizers include diacetin (Unichema ),dibenzoate (Lankroflex SP80; Lankro), triethyl phosphate, alkylarylphosphate (Santiciser 141;
Monsanto) iso-decyl diphenyl phosphate (Santiciser 148), butylbenzyl phthalate (Santiciser 160), neopentyl glycol (Benzoflex 8312; Velsicol Chemical Corporation), p-toluene sulphonamide (Santiciser 8) and dialkylalkyleneoxide glutarate (Plast~all 7050; C P Hall Ltd) and mixtures thereof. Preferred plasticizers are Santiciser 8 and Plasthall 7050 and mixtures thereof, in particular about a 50:50 mixture thereof.
In another aspect the polymer composition can contain up to 5 phr of a nucleating agent to encourage * Trade-mark cry~tallization on molding. Suitable nucleating agents include talc, micronized mica, alumina, silica, boron nitride, calcium carbonate and calcium hydroxyapatite. Of these we have found boron nitride to be most ~atisfactory. ~ypically the amount of nucleating agent is in ~he range 0.3 - 3 phr, for example 0.5 - 2 phr and conveniently about 1 phr.
The polymer composition can contain variou6 other additives used in the polymer proce~sing art to aid handling and proces6ing, for example, molding aids ~uch as stearate salts and ester~. In addition, additives to improve the cosmetic appearance of the applicator can be included in the composition for example pigments and titanium dioxide. Such additives can be present in an amount sufficient to be effective, typically about 1 phr for pigments.
In another aspect the poly 3-hydroxybutyric acid polymer composition can further contain a biodegradable filler.
The filler has not significantly affect the characteristics of the polymer but enables the amount of poly 3-hydroxybutyric acid to be lowered thus resulting in economic savings. Suitable fillers include starch and hydroxyalkyl cellulose which do not significantly affect molding properties even when present in proportions of up to about 40 phr. Preferably any such filler is starch which is relatively inexpensive. In addition, the use of starch is advantageous as we have found that the rate of biodegradability of polymer composition is increased with increasing proportions of starch.
ExamPle 1 A polymer composition was prepared having the following ingredients:
Dhr poly 3-hydroxybutyric acid/poly 3-hydroxy-valeric acid copolymer (mol. wt about 750,000) having ~% 3-hydroxyvaleric acid units Santiciser 8 10 Plasthall 7050 10 15 ~oron nitride ~from Fluorochem Glossop, U.K.) 1.0 Titanium dioxide 1.0 This was molded using a Negri Bossi NB 90 (38 mm diameter screw) machine, having a cycle time of about 40 seconds, to provide tampon applicators each weighing about 1.9 g.
The machine ~as operated using barrel temperatures in the range of 120 - 180 C, and mold temperatures in the range of 30 - 70C, for example 40C.
Figure 1 shows a tampon applicator 1 having a hollow cylindrical body 2 about 55 mm in leng~h and about 15 mm in diameter. The body 2 has at one end thereof a shoulder 3 to whi~h i6 integrally molded a hollow cylindrical qrip portion 4 of about 0.75 mm wall thickne~s having annular ribs 5. At the other end of the body 2 are integrally molded four flexible petalfi 6. Each petal 6 is of approximate elliptical shape and has a maximum length of about 10 mm. The wall thickness is aproximately 0.7 mm in region 7 of the body 2 and is approximately 0.3 mm in the region of the petals 6.
In use a tampon (not shown) i8 inserted in the cylindrical body 2. A plunger (not shown), conveniently of a disposable material similar to that of the applicator, i~
5 pushed through hollow srip portion 4 to urge the tampon against the flexible petals 6 thereby opening them.
Continued pushing af the plunger re~ults in the successful expulsion of the tampon whereupon the applicator can be hygenically dispo6ed of. Conveniently qrip portion 4 is held by the thumb and middle finger while the index finger operate6 the plunger.
The biodegradability of the tampon applicators of the present invention was studied u&ing the following procedure. Anaerobic digester unitC composed of sealed glass bottles fitted with gas exhaust tubes whereby the gas expelled by the unit can be measured were prepared containing about 700 to 800 ml of anaerobic digested sludge to which fresh raw sewage had been added. Various tampon applicators according to the present invention were added and the units were sealed. Identical control units were also prepared without applicators. The gas produced was collected and measured daily and samples were remoYed periodically to determine the extent of actual solids degradation. The results for a number of applicators are given below:
Results All applicators were as described above in relation to the drawings; however, so~e were of thicker wall thicknes~
wherein the approximate wall thicknes&es of the grip, body and petals were 1.1 mm, 0.85 mm and 0.45 mm respectively.
SAMPLE DESCRIPTION DRY WEIGHT (~) lA Thin wall Composition of Example 1 1.93 lB Thin wall Composition of Example 1 1.945 2A Thick wall Composition of Example 1 2.31 ~B Thick wall Composition of Example l 2.30 3A Thick wall 2.49 (two samples) Composition of Example l 2.48 3B Thick wall 2.50 15(two samples) Composition (19% HV units) 2.50 havin~ Santiciser 8 5 phr Plasthall 7050 5 phr Tio2 1 phr Boron Nitride 1 phr PRODUCT RECOVERY (% Wei~ht Remainin~) Day SamDle lA 100 87 - 39 - 6 - O
In all cases the non-recovered residual material was totally soluble and not detected by gross examination of the sewage sludge.
~30~
TYPICAL MæLT FLOW INDE% (~FI) VALUES FOR VARIOUS S~MPLES
s TD
(doubling time) Sample MFI in minutes HV Units 6% 0.48 6.6 San~iciser 8 5 phr at 170C
Plasthall 7050 5 phr BN 1 phr TiO2 1 phr HV units 16~ 1.0 12 Santiciser 8 7 1/2 phr at 150C
Plasthall 7050 7 1/2 phr BN 1 phr TiO2 1 phr HV units 19% 0.~1 llol Santiciser 8 5 phr at 160C
Plasthall 7050 5 phr BN 1 phr ~i2 1 phr _ _ _
Claims (24)
1. A biodegradable tampon applicator comprising a molded, hollow cylindrical body of polymeric material for enclosing a tampon therein and having a first flexible open end through which said tampon is expelled and a second open end for receiving means for expelling said tampon, said body comprising a moldable poly 3-hydroxybutyric acid composition.
2. The tampon applicator of claim 1 wherein said poly
3-hydroxybutyric acid is a copolymer comprising 3-hydroxybutyric acid and 3-hydroxyvaleric acid residues.
3. The tampon applicator of claim 2 wherein said 3-hydroxyvaleric acid residues are present in the range of from about 5 to about 30 mol %, based on the total moles of 3-hydroxybutyric and 3-hydroxyvaleric acid residues present.
3. The tampon applicator of claim 2 wherein said 3-hydroxyvaleric acid residues are present in the range of from about 5 to about 30 mol %, based on the total moles of 3-hydroxybutyric and 3-hydroxyvaleric acid residues present.
4. The tampon of claim 3 wherein said 3-hydroxyvaleric acid residues are present in the range of from about 10 to about 30 mol %, based on the total moles of 3-hydroxybutyric and 3-hydroxyvaleric acid residues present.
5. The tampon applicator of claim 1 wherein said body further comprises a plasticizer in an amount sufficient to impart the material of said body with a modulus of elasticity of from about 0.2 to about 1.0 GPa.
6. The tampon applicator of claim 5 wherein said plasticing is in an amount sufficient to impart the material of said body with a modulus of elasticity of from about 0.3 to about 0.6 GPa.
7 The tampon applicator of claim 5 wherein said plasticizer is present in an amount of less than 40 parts per hundred parts (by weight) of polymer.
8. The tampon applicator of claim 7 wherein said plasticizer is present in an amount of from 10 to about 30 parts per hundred parts by weight of polymer
9. The tampon applicator of claim 5 wherein said plasticizer is selected from the group consisting of diacetin, dibenzoate, triethyl phosphate, alkylaryl phosphate, iso-decyl diphenyl phosphate, butylbenzyl phthalate, neopentyl glycol, p-toluene sulphonamide, dialkylalkyleneoxide glutarate and mixtures thereof.
10. The tampon applicator of claim 9 wherein said plasticizer comprises a mixture of p-toluene sulphonamide and dialkylalkyleneoxide glutarate.
11. The tampon applicator of claim 1 including a nucleating agent.
12. The tampon applicator of claim 1 including a biodegradable filler.
13. The tampon applicator of any one of claims 1-12 having a tampon enclosed therein.
14. A method for making a tampon applicator comprising the steps of providing a composition comprising a copolymer of 3-hydroxybutyric acid and 3-hydroxyvaleric acid residues and a plasticizer, the mol % of said 3-hydroxyvaleric acid residues and the quantity of plasticizer being selected to result in said composition having a melt flow of not more than 20 minutes and, when molded, to result in a material having a modulus of elasticity of 0.2 to 1.0 GPa; and molding said composition into the hollow cylindrical body
15. The method of claim 14 wherein said material has a modulus of elasticity ranging from about 0.3 to about 0.6 GPa.
16. The method of claim 14 wherein said 3-hydroxybutyric acid residues are present in the range of from about 5 to about 30 moles %, based on the total moles of 3-hydroxybutyric and 3-hydroxyvaleric acid residues present.
17. The method of claim 16, wherein said 3-hydroxybutyric acid residues are present in the range of from about 10 to about 30 mol %, based on the total moles of 3-hydroxybutyric and 3-hydroxyvaleric acid residues present.
18. The method of claim 14, wherein said plasticizers present in an amount of less than 40 parts per hundred parts (by weight) of polymer.
19. The method of claim 18 wherein said plasticizer is present in an amount of from about 10 to about 30 parts per hundred parts by weight of polymer.
20. The method of claim 14 wherein said plasticizer is selected from the group consisting of diacetin, dibenzoate, triethyl phosphate, alkylarylphosphate, iso-decyl diphenyl phosphate, butylbenzyl phthalate, neopentyl glycol, p-toluene sulphonamide, dialkylalkyleneoxide glutarate, and mixtures thereof.
21. The method of claim 20 wherein the plasticizer comprises a mixture of p-toluene sulphonamide and dialkylalkyleneoxide glutarate.
22. The method of claim 14 including a nucleating agent.
23. The method of claim 14 including a biodegradable filler.
24. A method according to any one of claims 14-23 comprising the further step of inserting a tampon into said hollow cylindrical body.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US48,338 | 1987-05-11 | ||
| US07/048,338 US4900299A (en) | 1987-05-11 | 1987-05-11 | Biodegradable tampon application comprising poly(3-hydroxybutyric acid) |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1306834C true CA1306834C (en) | 1992-09-01 |
Family
ID=21954035
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000566286A Expired - Lifetime CA1306834C (en) | 1987-05-11 | 1988-05-09 | Tampon applicators and compositions for making same |
Country Status (19)
| Country | Link |
|---|---|
| US (1) | US4900299A (en) |
| EP (1) | EP0291024B1 (en) |
| JP (1) | JP2703558B2 (en) |
| KR (1) | KR970007093B1 (en) |
| AR (1) | AR241682A1 (en) |
| AT (1) | ATE102001T1 (en) |
| AU (1) | AU620805B2 (en) |
| BR (1) | BR8802273A (en) |
| CA (1) | CA1306834C (en) |
| DE (1) | DE3888014T2 (en) |
| ES (1) | ES2061549T3 (en) |
| GR (1) | GR1000095B (en) |
| IE (1) | IE62839B1 (en) |
| MY (1) | MY102822A (en) |
| NZ (1) | NZ224439A (en) |
| PH (1) | PH27307A (en) |
| PT (1) | PT87455B (en) |
| ZA (1) | ZA883306B (en) |
| ZW (1) | ZW5688A1 (en) |
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| US5334520A (en) * | 1990-05-25 | 1994-08-02 | Center For Innovative Technology | Production of poly-beta-hydroxybutyrate in transformed escherichia coli |
| US5002526A (en) * | 1989-12-22 | 1991-03-26 | Kimberly-Clark Corporation | Tampon applicator |
| GB9012975D0 (en) * | 1990-06-11 | 1990-08-01 | Ici Plc | Hydroxyalkanoate polymer composition |
| GB9016345D0 (en) * | 1990-07-25 | 1990-09-12 | Ici Plc | Polymer blends |
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| US5300358A (en) * | 1992-11-24 | 1994-04-05 | E. I. Du Pont De Nemours And Co. | Degradable absorbant structures |
| EP0606050A1 (en) * | 1993-01-05 | 1994-07-13 | Bruno Plüss | Tampon with tube |
| GR1002998B (en) * | 1993-03-04 | 1998-10-27 | Mcneil-Ppc Inc. | Improved injection molded product and method. |
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| US5437628A (en) * | 1993-11-10 | 1995-08-01 | Kimberly-Clark Corporation | Curved tampon applicator having an improved fingergrip |
| US5690884A (en) * | 1995-05-04 | 1997-11-25 | Kimberly-Clark Worldwide, Inc. | Method of injection molding a thin walled article |
| US5954683A (en) * | 1996-04-15 | 1999-09-21 | Playtex Products, Inc. | Composition and coating for a disposable tampon applicator and method of increasing applicator flexibility |
| US6203515B1 (en) | 1997-01-28 | 2001-03-20 | Playtex Products, Inc. | Infrared treated tampon applicators |
| US5782794A (en) * | 1997-01-28 | 1998-07-21 | Playtex Products, Inc. | Infrared treated tampon applicators |
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| US7455999B2 (en) * | 1998-01-22 | 2008-11-25 | Metabolix, Inc. | Transgenic systems for the manufacture of poly (3-hydroxy-butyrate-co-3-hydroxyhexanoate) |
| IL126111A0 (en) * | 1998-09-07 | 1999-05-09 | Medivice Systems Ltd | Tampon applicator |
| US6368442B1 (en) | 1999-06-25 | 2002-04-09 | Mcneil-Ppc, Inc. | Method of making applicators having improved finger grip features |
| JP3797835B2 (en) * | 1999-11-19 | 2006-07-19 | ユニ・チャーム株式会社 | Tampon applicator |
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| WO2002085983A1 (en) * | 2001-04-20 | 2002-10-31 | E.I. Du Pont De Nemours And Company | Processing of polyhydroxyalkanoates using a nucleant and a plasticizer |
| US8756791B2 (en) * | 2001-10-17 | 2014-06-24 | Eveready Battery Company, Inc. | Tampon applicator |
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| US7727208B2 (en) | 2002-09-12 | 2010-06-01 | Playtex Products, Inc. | Ergonomic tampon applicator |
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| US7098292B2 (en) * | 2003-05-08 | 2006-08-29 | The Procter & Gamble Company | Molded or extruded articles comprising polyhydroxyalkanoate copolymer and an environmentally degradable thermoplastic polymer |
| US6706942B1 (en) * | 2003-05-08 | 2004-03-16 | The Procter & Gamble Company | Molded or extruded articles comprising polyhydroxyalkanoate copolymer compositions having short annealing cycle times |
| US7798986B2 (en) * | 2003-06-20 | 2010-09-21 | Playtex Products, Inc. | Tampon applicator barrels having gripping structures and methods of forming |
| AU2004253945B2 (en) * | 2003-06-26 | 2009-02-19 | Playtex Products, Inc. | A coating composition and articles coated therewith |
| CA2558484C (en) | 2004-03-08 | 2012-03-06 | Playtex Products, Inc. | Tampon applicator and method for making same |
| US7928180B2 (en) * | 2005-06-30 | 2011-04-19 | Mitsui Chemicals, Inc. | Biodegradable polymer, production method thereof, molded product thereof, and use thereof |
| US8680192B2 (en) * | 2008-07-29 | 2014-03-25 | Polyone Corporation | Crystallized thermoplastic polyhydroxyalkanoate compounds |
| US9320656B2 (en) | 2013-11-27 | 2016-04-26 | Kimberly-Clark Worldwide, Inc. | Water-dispersible thermoplastic injection molded composition |
| US9456931B2 (en) | 2013-11-27 | 2016-10-04 | Kimberly-Clark Worldwide, Inc. | Thermoplastic and water-dispersible injection moldable materials and articles |
| US9339580B2 (en) | 2013-11-27 | 2016-05-17 | Kimberly-Clark Worldwide, Inc. | Flushable tampon applicator |
| US10821033B2 (en) * | 2016-05-26 | 2020-11-03 | Edgewell Personal Care Brands, Llc | Composition for thin walled molded parts |
| US11278456B2 (en) | 2020-07-21 | 2022-03-22 | Lacey Janell Lund | Tampon insertion device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US3724462A (en) * | 1971-11-01 | 1973-04-03 | Kimberly Clark Co | Water-dispersible insertion devices for tampons and the like |
| US3921333A (en) * | 1972-07-28 | 1975-11-25 | Union Carbide Corp | Transplanter containers made from biodegradable-environmentally degradable blends |
| US3830236A (en) * | 1973-02-28 | 1974-08-20 | Kimberly Clark Co | Applicator tube for inserting hygienic media |
| US3954104A (en) * | 1974-11-27 | 1976-05-04 | Personal Products Company | Water-dispersible, biodegradable compositions and containers and the like made therefrom |
| US4286341A (en) * | 1979-04-16 | 1981-09-01 | Iowa State University Research Foundation, Inc. | Vascular prosthesis and method of making the same |
| US4503098A (en) * | 1980-09-12 | 1985-03-05 | Union Carbide Corporation | Disposable articles coated with degradable water insoluble polymers |
| US4372311A (en) * | 1980-09-12 | 1983-02-08 | Union Carbide Corporation | Disposable articles coated with degradable water insoluble polymers |
| DE3168826D1 (en) * | 1980-11-18 | 1985-03-21 | Ici Plc | Polymer blends |
| DE3121364A1 (en) * | 1981-05-29 | 1982-12-16 | Henkel KGaA, 4000 Düsseldorf | "APPLICATOR FOR THE HYGIENIC INSERTION OF A TAMPON" |
| US4477654A (en) * | 1981-07-07 | 1984-10-16 | Imperial Chemical Industries Plc | 3-Hydroxybutyrate polymers |
| DE3376485D1 (en) * | 1982-04-05 | 1988-06-09 | Ici Plc | Process for producing a shaped article of beta-hydroxybutyrate polymer |
| US4650459A (en) * | 1985-10-21 | 1987-03-17 | Kimberly-Clark Corporation | Convolutely wound paper tampon tube |
-
1987
- 1987-05-11 US US07/048,338 patent/US4900299A/en not_active Expired - Lifetime
-
1988
- 1988-04-29 NZ NZ224439A patent/NZ224439A/en unknown
- 1988-05-09 AU AU15814/88A patent/AU620805B2/en not_active Expired
- 1988-05-09 KR KR1019880005350A patent/KR970007093B1/en not_active IP Right Cessation
- 1988-05-09 CA CA000566286A patent/CA1306834C/en not_active Expired - Lifetime
- 1988-05-10 ES ES88107526T patent/ES2061549T3/en not_active Expired - Lifetime
- 1988-05-10 MY MYPI88000492A patent/MY102822A/en unknown
- 1988-05-10 GR GR880100301A patent/GR1000095B/en not_active IP Right Cessation
- 1988-05-10 EP EP88107526A patent/EP0291024B1/en not_active Expired - Lifetime
- 1988-05-10 BR BR8802273A patent/BR8802273A/en not_active IP Right Cessation
- 1988-05-10 AR AR88310810A patent/AR241682A1/en active
- 1988-05-10 ZW ZW56/88A patent/ZW5688A1/en unknown
- 1988-05-10 DE DE3888014T patent/DE3888014T2/en not_active Expired - Lifetime
- 1988-05-10 ZA ZA883306A patent/ZA883306B/en unknown
- 1988-05-10 IE IE141288A patent/IE62839B1/en not_active IP Right Cessation
- 1988-05-10 AT AT88107526T patent/ATE102001T1/en not_active IP Right Cessation
- 1988-05-10 JP JP63111718A patent/JP2703558B2/en not_active Expired - Lifetime
- 1988-05-11 PH PH36914A patent/PH27307A/en unknown
- 1988-05-11 PT PT87455A patent/PT87455B/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| EP0291024B1 (en) | 1994-03-02 |
| GR880100301A (en) | 1989-02-23 |
| AU620805B2 (en) | 1992-02-27 |
| ATE102001T1 (en) | 1994-03-15 |
| ZW5688A1 (en) | 1989-11-22 |
| GR1000095B (en) | 1991-03-15 |
| PT87455B (en) | 1992-08-31 |
| ES2061549T3 (en) | 1994-12-16 |
| DE3888014T2 (en) | 1994-10-06 |
| PH27307A (en) | 1993-05-28 |
| AU1581488A (en) | 1988-11-17 |
| EP0291024A2 (en) | 1988-11-17 |
| JPS63302845A (en) | 1988-12-09 |
| IE881412L (en) | 1988-11-11 |
| NZ224439A (en) | 1989-12-21 |
| JP2703558B2 (en) | 1998-01-26 |
| KR880013789A (en) | 1988-12-21 |
| BR8802273A (en) | 1988-12-06 |
| ZA883306B (en) | 1990-01-31 |
| IE62839B1 (en) | 1995-03-08 |
| DE3888014D1 (en) | 1994-04-07 |
| PT87455A (en) | 1989-05-31 |
| EP0291024A3 (en) | 1990-05-30 |
| AR241682A1 (en) | 1992-11-30 |
| KR970007093B1 (en) | 1997-05-02 |
| MY102822A (en) | 1992-11-30 |
| US4900299A (en) | 1990-02-13 |
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