|Veröffentlichungsdatum||8. Jan. 2002|
|Eingetragen||10. Nov. 1994|
|Prioritätsdatum||10. Nov. 1993|
|Auch veröffentlicht unter||CA2176003A1, CN1139962A, EP0733133A1, EP0733133A4, WO1995013412A1|
|Veröffentlichungsnummer||CA 2176003, CA 2176003 C, CA 2176003C, CA-C-2176003, CA2176003 C, CA2176003C, PCT/1994/13208, PCT/US/1994/013208, PCT/US/1994/13208, PCT/US/94/013208, PCT/US/94/13208, PCT/US1994/013208, PCT/US1994/13208, PCT/US1994013208, PCT/US199413208, PCT/US94/013208, PCT/US94/13208, PCT/US94013208, PCT/US9413208|
|Erfinder||Mohan L. Sanduja, Kenneth Sugathan, Carl Horowitz, Lina Zilberman|
|Antragsteller||Mohan L. Sanduja, Kenneth Sugathan, Carl Horowitz, Lina Zilberman, Zaken, Steven, Golden, Robert, Gmz Holding Company|
|Zitat exportieren||BiBTeX, EndNote, RefMan|
|Klassifizierungen (24), Juristische Ereignisse (2)|
|Externe Links: CIPO, Espacenet|
,WO 95/13412 PCT/US94/13208 DISPOSABLE TOOTHBRUSH HAVING MINT FLAVORED
TOOTHPASTE COMPOSITION BONDED TO
BACKGROUND OF THE INVENTION
To accommodate the busy and often harried traveler, disposable toothbrushes have been designed that can be used away from home, for example on a trip, or that can be offered for single use in establishments receiving the public, such as hotels and restaurants. These disposable toothbrushes have eliminated the need for a separate tube of toothpaste by incorporating in or on the brush a sufficient dose of a flavored toothpaste for brushing the teeth, the flavor being added to encourage oral hygiene practices. Many such prior art disposable toothbrushes are complex and/or expensive, as where a mechanism is included for distributing the toothpaste onto the bristles just prior to use. In other prior art disposable toothbrushes, the toothpaste is preapplied to the bristles, but such toothbrushes have proved unstable, in that the flavoring dissipates after a relatively short period of time, which is impractical as commercial considerations require a reasonable shelf life. As a result, prior art disposable toothbrushes have, for the most part, not proved commercially successful, primarily because no known prior art disposable toothbrush has satisfied the multiple criteria of a preapplied toothpaste thereby eliminating the need for a distribution mechanism, a reasonable shelf life, and a low manufacturing cost. Regarding manufacturing costs, it is well known that service establishments, such as hotels, will not provide to their patrons disposable items which exceed a preestablished cost.
Hospitals, of course, also provide toothbrushes to their patients. Typically, hospitals provide a toothbrush and a separate tube of toothpaste, the tube typically including sufficient toothpaste for a limited number of uses. This, however, poses two problems. First, there is a risk of transmission of infectious disease, as when a patient places his/her toothbrush on a sink, etc. Secondly, in the case of a patient having use of only one arm, as is sometimes the case when patients are treated intravenously, it is difficult for the patient to manipulate the toothpaste onto the bristles of the toothbrush.
For the foregoing reasons, there is a need for an individually wrapped, inexpensive disposable toothbrush having a toothpaste composition distributed over the bristles of the toothbrush and in which the flavoring does not dissipate over a reasonable shelf life.
OBJECTS AND SUMMARY OF THE INVENTION
It is therefore an object of the present invention to provide a flavored toothpaste composition bonded to a toothbrush, wherein the flavor is stabilized and long-lasting.
It is a further object of the invention to provide a disposable toothbrush which is coated with an amount of toothpaste sufficient for a single tooth brushing operation such that the toothbrush may be disposed of after initial use.
It is another object of the invention to provide a method of manufacture of a disposable toothbrush and toothpaste product with a long-lasting, stabilized flavor.
It is still another object of the invention to provide a disposable toothbrush and toothpaste product that can be produced at low cost .
It is yet another object of the invention to provide a disposable toothbrush that is both safe and convenient to use, e.g., in a hospital setting.
The present invention is thus directed to a disposable toothbrush and toothpaste product obtained by a process which involves the polymerization of selected monomers and prepolymers and the chemical grafting of the resulting polymer to the bristles of the toothbrush. More particularly, the process of the present invention comprises the steps of contacting the bristles of the toothbrush (in general hereinafter being referred to as "the substrate") with a composition containing a ferrous salt as the graft initiator, a monomer/prepolymer, and a catalyst which activates polymerization by the ferrous ion, whereby the ferrous ions are reduced by the substrate with free radicals being formed as a result on the substrate.
The monomer/prepolymer attaches itself to these free radical sites, and the resulting polymer forms an intimate covalent bond with the substrate. The S a toothbrush containing the toothpaste composition is then dried to complete the graft bonding of the toothpaste to the substrate.
The strength of the resulting bond can be adjusted so that the flavored toothpaste is immediately activated when brought into contact with normal mouth fluids, i.e., water and saliva, and is released by the scrubbing action of the bristles against the teeth, imparting a desirable flavor to the teeth and mouth of the user thereof.
In one aspect, the present invention provides a toothbrush and toothpaste combination comprising: (a) a plurality of polymeric bristles;
and (b) a toothpaste composition comprising a polymer covalently bonded to the surface of the bristles.
In another aspect, the present invention provides a toothbrush and toothpaste combination comprising: (a) a plurality of polymeric bristles;
and (b) a toothpaste composition comprising a polymer graft polymerized to the surface of the bristles.
In yet another aspect, the present invention provides a toothbrush comprising a plurality of bristles having a toothpaste composition graft polymerized to the bristle surfaces forming a coating thereon.
In yet another aspect, the present invention provides a toothbrush and toothpaste combination comprising: (a) a plurality of polymeric bristles; and (b) a toothpaste composition comprising a polymer covalently bonded to the surface of the bristles, the covalent bond being the result of graft polymerization involving a grafting solution comprising: (i) at least one acrylic or vinyl monomer or prepolymer selected from the group consisting of acrylic acid, polyacrylic acid and polyvinyl alcohol, methacrylic acid, ethyl acrylate, 21~~0~~
- 4a -ethyl methacrylate, isobutylmethacrylate and methyl acrylate, and ranging from about 0 . 0001 o to about 2 by weight of the composition, (ii) a graft initiator ranging from about O.OOOOlo to about O.Olo by weight of the composition, and (iii) a peroxide catalyst ranging from about O.OOlo to about to of weight of the composition.
In yet another aspect, the present invention provides a toothbrush and toothpaste combination comprising: (a) a plurality of polymeric bristles; and (b) a toothpaste composition comprising a polymer graft polymerized to the surface of the bristles, the graft polymerization involving the use of a grafting solution comprising:
(i) at least one acrylic or vinyl monomer or prepolymer selected from the group consisting of acrylic acid, polyacrylic acid and polyvinyl alcohol, methacrylic acid, ethyl acrylate, ethyl methacrylate, isobutylmethacrylate and methyl acrylate, and ranging from about 0 . 0001 o to about 2 0 by weight of the composition, (ii) a graft initiator ranging from about 0 . 00001 % to about 0 . O1 % by weight of the composition, and (iii) a peroxide catalyst ranging from about 0.0010 to about to of weight of the composition.
a DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Mechanism of Chemical Grafting A. As Applied to Natural and Polymeric Substrates Chemical grafting involves activation of a substrate. Once the substrate has been activated, chains of monomers linked by carbon-carbon bonds grow on the substrate, bonding to the substrate without damaging any of the existing positive characteristics of the materials involved. Many materials, both naturally occurring and synthetic, possess active hydrogens which are more reactive than the "bulk hydrogens," the tertiary hydrogen in polypropylene for example.
Thus, graft initiators (G.I.) have the capacity of removing these active hydrogens and concomitantly initiating the growth of polymer chains at the site from where the active hydrogen was removed. In the case of polypropylene, this can be represented as follows:
I I G.I. (1) CHz- C CHZ C CHZ C ---------i H H H
( 2 ) I CHZ=CH
CHZ - C ° - CH2 - C ° - CH2 C ° X
t i i ( 3 ) CHZ - C CHZ C CHz C
f t 1 X X X
In this illustration, (°) can represent either a free radical, anion or cation, depending on whether the G.I. removes a hydrogen and one electron, no electrons or twc electrons, respectively. CH2=CHx represents a unit of vinyl monomer where "x" governs the property or properties obtained. In many instances a mixture of monomers is employed and often more than one property can be altered in one processing step. These polymer chains, whose length can be controlled, are strongly attached to the substrate. The linkage between the graft polymer and the substrate is covalent in nature, and therefore, the graft polymer cannot be leached from the substrate. In essence, chemical grafting is a matter of growing polymer chains on the backbone chain of a substrate. The graft polymer chains are formed from vinyl monomers or monomers containing appropriate functionality, e.g., groups such as hydroxyl, carboxyl, epoxy, amide, amine, anhydride.
B. Chemical Grafting as Apt~lied to a Nvlon Polvnropvlene or Polvester Substrate of a Toothbrush In the case of a nylon, polypropylene or polyester substrate, such as a toothbrush bristle, the chemical grafting is carried out via the abstraction of the hydrogen atom from the -CONH- group (nylon), ~~~~~~3 n I
(polypropylene) (PP] or (polyester) [PE]
with the graft initiator to form a free radical which then reacts with a graft polymer solution, by which graft polymerization commences.
The sequence of reaction steps involved in the chemical attachment of the monomer/prepolymer onto the toothbrush substrate is believed to take place as follows:
S-H + GI' -------j S° + H' + GI (1) nylon, PP graft free radical formation or PE initiator substrate S ° + CHZ = CH - - - - -j S - CHZ - CH ° ( 2 ) x x monomer initiation S-CH2-CH° + (CH2-CH)n _____j S_([~2-CH)n-CHZ-CH° (3) l ~ I \
X X X X
propagation R10H + GI' -----j R10° + H' + GI (4) Menthol The graft polymerization shown in steps (1) - (4) may be terminated by radical combination which may occur as:
_g_ S - ( CHz - CH ) n - CHz - CH ° + R10 °
x x ---------j~ S - (CH2-CH) n -CH2-CHORl (5) X X
The foregoing reactions take place in the presence of a peroxide catalyst which concurrently regenerates the graft initiator forming a free radical as shown in reaction step (6).
RZOOH + GI -----~ R20° + OH' + GI' (6) peroxide Reaction (1) provides a radical site on an exemplary substrate (S-H) by the reduction of the graft initiator and oxidation of the substrate to transform the substrate into a free radical.
Reaction (2) illustrates the grafting of an exemplary monomer to the activated substrate (S°) at the free radical site to form a graft polymer radical on the substrate. This is followed by propagation in reaction (3). Reaction (4) illustrates the formation of a menthol radical, e.g., from a peppermint compound. Reaction (5) illustrates chain termination via combination of the menthol radical with the activated substrate graft polymer formed in step ( 3 ) , the end result being the chemical attachment of the mint flavor to the surface of the toothbrush bristles. Reaction (6) illustrates the regeneration of the graft initiator ion by the presence of peroxide in the monomer solution.
Method of Preparation of the Mint-Flavored Toothpaste Formulation The present invention is directed to a polymeric toothpaste composition that is chemically grafted to the bristles of a toothbrush to form a strong adhesion to the bristles over an extended period of time. As previously stated, chemical grafting involves the use of monomers/prepolymers, a catalyst, and a graft initiator along with other excipients in the composition. Thus, the polymeric toothpaste composition of the present invention requires the use of monomers/prepolymers, a graft initiator and catalyst, and may also include other excipients such as fillers, surfactants, buffers, pigments and flavoring.
The monomers and prepolymers are vinyl monomers and acrylic and vinyl prepolymers which chemically bond to the bristles via a free radical system. The monomers and prepolymers are preferably acrylic monomers having one or more hydroxyl and carboxyl groups. Some of the monomers and prepolymers of this type are the following:
polyvinyl alcohol, acrylic acid, polyacrylic acid, methacrylic acid, ethyl acrylate, ethyl methacrylate, isobutylmethacrylate, and methyl acrylate. Also, mixtures of two or more monomers can be used. Polyvinyl alcohol, acrylic acid and polyacrylic acid are preferred.
The formulation is prepared by taking the ingredients in the order as indicated in the examples or any other convenient order.
Ferrous ions are preferred as graft initiators for the , grafting of desired monomers/prepolymers onto the bristles, but other metal ions such as Ag' ions could also be used or any other metal ion which is safe for mouth application.
The presence of a small amount of a peroxide catalyst, preferably hydrogen peroxide, helps to regenerate the gra't initiator system in A
, ~~~6 the process which in turn provides free radicals for further chain graft polymerization. Other representative peroxides include peracetic acid and urea peroxide.
The amounts of the reactants employed is not a critical feature of the invention. For obvious economical reasons, the amounts of monomer/prepolymer, graft initiator and catalyst employed in the system will be the minimum amounts necessary to .complete the reaction as previously described herein. The amounts of monomer and prepolymer employed will normally range from about 0.0001% to about 2% by weight of the composition, though the preferred concentration ranges from about 0.0001% to about 0.2o by weight. The amount of graft initiator ranges from about O.OOOOlo to about 0.01% by weight, preferably from about 0.00001% to about 0.001%. The amount of peroxide catalyst employed will normally range from about 0.001% to about 1% by weight, preferably from about 0.001% to about 0.5%.
Suitable materials for use as flavors~are those which allow the user to detect a strong, noticeable flavor while permitting maintenance of an acceptable product appearance. The flavors may be of natural or synthetic origin. Such flavors include peppermint, spearmint, wintergreen, cinnamon, and the like; fruit flavors such as cherry, strawberry, lime, and the like. Preferred flavors for use in toothpaste include peppermint and spearmint.
Examples of auxiliary excipients utilized in the present invention include fillers, surfactants, buffers and. pigments.
The formulation described herein has several advantages. First, it eliminates the need for a complex and expensive article that is intended to be used only once. Second, it eliminates, when traveling, the need for packing both a toothbrush and a tube of toothpaste. And finally, the intimate bond that is formed when the toothpaste is applied to the bristles locks in the freshness and flavor for a long period of time.
In the preferred embodiment of the invention, the bristles of the toothbrush are dipped into a toothpaste that contains monomers, prepolymers, graft initiator ions, peroxide ions and other excipients of the composition. The coated samples are then air dried at room temperature for approximately 30 to 40 minutes, whereby the hydroxyl and carboxyl groups from the monomers/prepolymers in the toothpaste polymerize to form a strong adhesion to the bristles of the toothbrush.
Where the toothpaste is applied to the bristles as a single coat, the formulation consists basically of the monomer/prepolymer, catalyst, graft initiator, pigment, flavoring and other auxiliary excipients. The desired amounts of each filler, namely calcium carbonate, sodium hydrogen carbonate, sodium lauryl sulfate, potassium tripolyphosphate and sodium fluoride are combined in a container and mixed until a homogeneous mixture is obtained.
Likewise the desired amounts of the monomer/prepolymer, graft initiator and pigment are combined in a container and stirred until the solution is uniform. The mixture of fillers is then added in small increments with continuous stirring to the uniform solution. The polyacrylic acid is X176~~~
then added, followed by the mint flavored compound, and the contents are blended to a smooth paste . The hydrogen peroxide is finally added and the paste is mixed again until uniform. The prepared reactive formulation may then be applied to the toothbrush by dipping the toothbrush into the toothpaste and then, if necessary, the product may be exposed to air drying for 30 to 40 minutes to complete the graft bonding. If desired, the drying process may be accelerated by subjecting the product to heat, e.g., at a temperature of about 212°F to 300°F for 1 to 2 minutes.
The following examples illustrate formulations which may be used in the invention.
Composition ~ WeiQht ' Parts 1. Calcium carbonate 500.00 2. Sodium hydrogen carbonate 20.00 3. Sodium lauryl sulfate 15.00 4. Potassium tripolyphosphate 2.50 5. Sodium fluoride 1.00 6. Glycerol (solvent) 250.00 7. Acrylic acid, 0.1% in glycerol 0.10 (monomer) 8. GRAPHTOL GREEN 5884-2 (a phthalo- 0.10 cyanine CI pigment Green #7) 9. Ferrous ammonium sulfate, 0.01 0.1% solution (Items 6, 7, 8 and 9 are blended together as a premix.) 10. Polyacrylic acid, 1% solution 0.10 (prepolymer) 11. Peppermint oil 20.00 12. Hydrogen peroxide, 0.1% solution 0.01 Ingredients 1 - 5 (a11 solids) were blended together until a uniform mix was obtained. This mixture was then poured with continuous stirring to the glycerol premix of ingredients 6 - 9 and the resulting blend mixed again to a uniform paste. The polyacrylic acid was then added, followed by the peppermint oil, and the paste blended until smooth. Hydrogen peroxide was added and the paste was mixed again, the resulting paste being ready for use.
The bristle part of the toothbrush was dipped directly into the toothpaste and lifted up.
The amount of paste on the brush was adjusted by controlling the depth the bristles sink into the paste. The paste was then air dried.
Composition by Weight Parts 1. Calcium carbonate 500.00 2. Sodium hydrogen carbonate 20.00 3. Sodium lauryl sulfate 15.00 4. Potassium tripolyphosphate 2.50 5. Sodium fluoride 1.00 6. Glycerol 250.00 7. Acrylic acid, 0.1% in glycerol 0.10 8. GRAPHTOL GREEN 585H-2 (a phthalo- 0.10 cyanine CI pigment Gzeen #~) 9. Ferrous ammonium sulfate, 0.01 O.I% solution (Items 6, 7, and are blended together as a premix .
) 10.Polyacrylic acid, 1%~solution , 0.10 11.Spearmint oil 20.00 12.Hydrogen peroxide, 0.1% solution 0.01 The formulation in Example 2 was made exactly the A
same as in Example 1, the only difference being that spearmint oil was substituted for the peppermint oil. The paste was applied to the brush also by the same method.
Combosition Parts by Weight 1. Calcium carbonate 500.00 2. Sodium hydrogen carbonate 20.00 3. Sodium lauryl sulfate 15.00 4. Potassium tripolyphosphate 2.50 5. Sodium fluoride 1.00 6. Glycerol 250.00 7. Acrylic acid, 0.1% in glycerol 0.10 8. GRAPHTOL GREEN 5884-2 (a phthalo-0.10 cyanine CI pigment Green #7) 9. Ferrous ammonium sulfate, 0.01 0.1% solution (Items 6, 7, 8 and 9 are blended together as a premix.) 10. Polyacrylic acid, to solution 0.10 11. Peppermint oil 20.00 12. Hydrogen peroxide, 0.1% solution0.01 13. Deionized water 80.90 Example 3 was made exactly as Example 1 but after the first 12 ingredients were blended, water was slowly added with continuous mixing, the resulting mix blended to a smooth consistency. The bristles were dipped into the formulation and allowed to dry.
Composition Parts by Weight 1. Calcium carbonate 500.00 2. Sodium hydrogen carbonate 20.00 . ;.
~! ~x 3. Sodium lauryl sulfate 15.00 4. Potassium tripolyphosphate 2.50 5. Sodium fluoride 1.00 6. Glycerol 250.00 7. Acrylic acid, O.lo in glycerol 0.10 8. GRAPHTOL GREEN 5854-2 (a phthalo-0.10 cyanine CI pigment Green #7) 9. Ferrous ammonium sulfate, 0.01 0.1% solution (Items together as 6, a 7, and are blended premix .
) 10.Polyacrylic acid, 1% solution 0.10 11.Spearmint oil 20.00 12.Hydrogen peroxide, 0.1% solution0.01 13.Deionized water 80.90 Example 4 was made the same way as Example 3 except for the substitution of spearmint oil for peppermint oil. The bristles were dipped into the paste and were ready for packing when dry.
Where the toothpaste is applied to the bristles in two coats, the prime coat consists basically of the flavoring and the prepolymer, whereas the top coat consists of the monomer, catalyst, graft initiator, pigment and other auxiliary excipients. The desired amount of flavor is mixed with.the prepolymer and applied to the bristles by dipping, then curing at 200°F for 4-5 minutes. The desired amounts of each filler, namely calcium carbonate, sodium hydrogen carbonate, sodium lauryl sulfate and potassium tripolyphosphate are combined in a container and mixed until a uniform mix is obtained. A solution of the pigment is prepared, added to the uniform mix, and mixed until ~~s~~
a uniform blend is obtained. The desired amounts of the monomer, graft initiator and catalyst are then added to the blend and the contents are mixed well.
The prepared formulation may then be applied as a top coat over the prime coat by dipping the already flavor-treated toothbrush into the top coat and curing at 300°F for 2 minutes.
The following example illustrates a formulation which may be used in the invention.
Composition Parts by Weiaht Prime ADDlication 1. Polyvinyl alcohol 523 8% solution in water 200.00 2. Peppermint (polarome) 30.00 Ton Application 3. Calcium carbonate 1000.00 4. Sodium hydrogen carbonate 50.00 5. Sodium lauryl sulfate 34.00 6. Potassium tripolyphosphate 5.00 7. Deionized water 162.00 8. Mx 439 PLYACERT GREEN (a mixture 0.20 of FD&C Blue #1 and FD&C Yellow #5) 9. Glycerol 500.00 10. Acrylic acid, 0.1% in glycerol 0.20 11. Ferrous ammonium sulfate, 0.02 0.1% solution 12. Hydrogen peroxide, 0.1% solution 0.02 Ingredient 1 was prepared by adding small increments of polyvinyl alcohol to deionized water with continuous stirring until all particles were wetted out. The solution was heated to 185°F - 205°F (85°C
- 96°C~ for 30 minutes and then allowed to cool to room temperature. The peppermint was then added to this solution, mixed and applied as a prime coat to the bristles by dipping. The product was then cured at 200°F for 4-5 minutes. Next, ingredients 3, 4, and 6 were blended together until a uniform mix was obtained (Part A). Ingredients 7 and 8 were mixed well, ingredient 9 was added, and the contents mixed again (Part B) . Part B was then mixed into Part A until a uniform blend was obtained (Part C).
Ingredients 10, 11 and 12 were then added to Part C
and mixed well for 1-2 minutes. The formulation thus prepared was ready to use as a top coat over the prime coat containing the flavor. This top coat was applied to the already treated bristles by dipping. The product was then cured at 300°F for 2 minutes.
It should be understood that the preferred embodiments and examples described are for illustrative purposes only and are not to be construed as limiting the scope of the present invention which is properly delineated only in the appended claims.
|Internationale Klassifikation||A61K8/00, A46B15/00, C08L51/00, A46D1/00, C08L67/00, A46D1/04, A46B11/00, C11B9/00, A61K8/91, A61K8/02, A61Q11/00, A61K8/97, C08L77/00, C08F291/00|
|Unternehmensklassifikation||A61K8/02, A61K2800/57, A46D1/00, A46B2200/1066, A46B11/0003, A61Q11/00|
|Europäische Klassifikation||A61K8/02, A46D1/00, A46B11/00A, A61Q11/00|
|1. Juni 1998||EEER||Examination request|
|10. Nov. 2011||MKLA||Lapsed|