WO1995013412A1 - Disposable toothbrush having mint flavored toothpaste composition bonded to bristles thereof - Google Patents

Disposable toothbrush having mint flavored toothpaste composition bonded to bristles thereof Download PDF

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Publication number
WO1995013412A1
WO1995013412A1 PCT/US1994/013208 US9413208W WO9513412A1 WO 1995013412 A1 WO1995013412 A1 WO 1995013412A1 US 9413208 W US9413208 W US 9413208W WO 9513412 A1 WO9513412 A1 WO 9513412A1
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WO
WIPO (PCT)
Prior art keywords
bristles
substrate
prepolymer
toothbrush
graft
Prior art date
Application number
PCT/US1994/013208
Other languages
French (fr)
Inventor
Mohan L. Sanduja
Kenneth Sugathan
Carl Horowitz
Lina Zilberman
Original Assignee
Gmz Holding Company
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Gmz Holding Company filed Critical Gmz Holding Company
Priority to CA002176003A priority Critical patent/CA2176003C/en
Priority to JP7514075A priority patent/JPH09505217A/en
Priority to KR1019960702434A priority patent/KR960705972A/en
Priority to AU11799/95A priority patent/AU1179995A/en
Priority to EP95902572A priority patent/EP0733133A4/en
Publication of WO1995013412A1 publication Critical patent/WO1995013412A1/en

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Classifications

    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • DTEXTILES; PAPER
    • D02YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02GCRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • AHUMAN NECESSITIES
    • A46BRUSHWARE
    • A46BBRUSHES
    • A46B11/00Brushes with reservoir or other means for applying substances, e.g. paints, pastes, water
    • A46B11/0003Brushes with reservoir or other means for applying substances, e.g. paints, pastes, water containing only one dose of substance, e.g. single-use toothbrushes
    • AHUMAN NECESSITIES
    • A46BRUSHWARE
    • A46DMANUFACTURE OF BRUSHES
    • A46D1/00Bristles; Selection of materials for bristles
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q11/00Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
    • AHUMAN NECESSITIES
    • A46BRUSHWARE
    • A46BBRUSHES
    • A46B2200/00Brushes characterized by their functions, uses or applications
    • A46B2200/10For human or animal care
    • A46B2200/1066Toothbrush for cleaning the teeth or dentures
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/57Compounds covalently linked to a(n inert) carrier molecule, e.g. conjugates, pro-fragrances

Definitions

  • disposable toothbrushes 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.
  • prior art disposable toothbrushes 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.
  • 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.
  • 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.
  • hospitals provide a toothbrush and a separate tube of toothpaste, the tube typically including sufficient toothpaste for a limited number of uses.
  • This 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.
  • the present invention is thus directed to a disposable toothbrush and toothpaste product obtained by a process which involves the chemical grafting and polymerization of selected monomers and prepolymers 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, thus forming an intimate covalent bond with the substrate. The 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.
  • normal mouth fluids i.e., water and saliva
  • 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.
  • graft initiators 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.
  • polypropylene this can be represented as follows :
  • (°) can represent either a free radical, anion or cation, depending on whether the G.I. removes a hydrogen and one electron, no electrons or two electrons, respectively.
  • CH 2 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.
  • the graft polymerization shown in steps (1) - (4) may be terminated by radical combination which may occur as : (CH 2 - CH) n - CH 2 - CH° + R-O c I I x x
  • reaction step (4) The foregoing reactions take place in the presence of a peroxide which concurrently regenerates the graft initiator forming a free radical as shown in reaction step (4) .
  • 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 a monomer mint prepolymer 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.
  • 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.
  • chemical grafting involves the use of monomers/prepolymers, a catalyst, and a graft initiator along with other excipients in the composition.
  • 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.
  • a peroxide catalyst preferably hydrogen peroxide
  • Other representative peroxides include peracetic acid and urea peroxide.
  • the amounts of the reactants employed is not a critical feature of the invention.
  • 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 0.2% by weight.
  • the amount of graft initiator ranges from about 0.00001% 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.
  • 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.
  • 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.
  • 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.
  • 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 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 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.
  • Example 2 The formulation in Example 2 was made exactly the 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.
  • 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.
  • 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.
  • the prime coat consists basically of the flavoring and the prepolymer
  • 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 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.
  • 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, 5 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) .

Abstract

A flavored toothpaste composition is bonded to the bristles of a disposable toothbrush by a process which involves the chemical grafting and polymerizing of selected monomers and prepolymers to the bristles via a free radical mechanism. This process locks in the flavor until the product can be utilized. When the toothpaste is brought into contact with an aqueous medium, such as saliva in the oral cavity, the toothpaste dissolves thereby releasing the desired flavor to the teeth and oral cavity.

Description

DISPOSABLE TOOTHBRUSH HAVING MINT FLAVORED TOOTHPASTE COMPOSITION BONDED TO BRISTLES THEREOF
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 chemical grafting and polymerization of selected monomers and prepolymers 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, thus forming an intimate covalent bond with the substrate. The 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.
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 :
CH3 CH3 CH3
G.I (1)
CH2_ -CH, C CH, C
1 I H H
CH3 CH3 CH3 (2) j I I CH2=CH CH2 — C° CH2 — C° CH2 C° X CH3 CH3 CH3 . I I
(3) CH2 C— CH, C — CH. -C
(CH2--CH)n- -H(CH2--CH)n H(CH2--CH)n--H
/ I \ 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 two 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 Applied to a Nylon, Polypropylene or Polyester 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) , CH3 0
■ II
H2C C CH2 PE C OH
I H
(polypropylene) [PP] or (polyester) [PE]
with the graft initiator to form a free radical which then reacts with a monomer/prepolymer 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+ S° + H+ + GI (1) nylon, PP graft free radical formation or PE initiator substrate
Figure imgf000009_0001
monomer initiation
S-CH2-CH° + (CH2-CH)n > S- (CH2-CH) _-CH2-CH° (3)
/ I / \
X X X X propagation
RiOH + GI+ R-.00 + H+ + GI (4)
Menthol
The graft polymerization shown in steps (1) - (4) may be terminated by radical combination which may occur as : (CH2 - CH)n - CH2 - CH° + R-Oc I I x x
-> S - (CH2-CH)n -CH2-CHOR! (5) x x
The foregoing reactions take place in the presence of a peroxide which concurrently regenerates the graft initiator forming a free radical as shown in reaction step (4) .
R2OOH + 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 a monomer mint prepolymer 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.
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 graft initiator system in 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 0.2% by weight. The amount of graft initiator ranges from about 0.00001% 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 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.
EXAMPLE 1
Composition 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 (solvent) 250.00
7. Acrylic acid, 0.1% in glycerol 0.10
(monomer)
8. GRAPHTOL GREEN 5884-2 (pigment) 0.10
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 (all 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.
EXAMPLE 2
Composition 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 585H-2 0.10
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
11. Spearmint oil 20.00
12. Hydrogen peroxide, 0.1% solution 0.01
The formulation in Example 2 was made exactly the 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.
EXAMPLE 3
Composition 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 0.10
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
11. Peppermint oil 20.00
12. Hydrogen peroxide, 0.1% solution 0.01
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.
EXAMPLE 4
Composition Parts byWeight
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 5854-2 0.10
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
11. Spearmint oil 20.00
12. Hydrogen peroxide, 0.1% solution 0.01
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 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.
EXAMPLE 5 Composition Parts by Weight Prime Application
1. Polyvinyl alcohol 523 8% solution in water 200.00
2. Peppermint (polarome) 30.00 Top 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 PYLA-Cert Green 0.20
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, 5 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.

Claims

CLAIMS What is claimed is:
1. A toothbrush and flavored toothpaste combination comprising:
(a) a plurality of bristles;
(b) a polymer chemically bonded to the bristles; and
(c) a flavoring chemically bonded to said polymer.
2. The combination of claim 1, wherein the bristles contain in their molecular structure active hydrogens capable of undergoing abstraction for graft polymerization at vacated hydrogen sites.
3. The combination of claim 2, wherein the bristles are selected from the group consisting of nylon, polypropylene and polyester bristles.
4. The combination of claim 1, wherein the polymer is chemically grafted to said bristles.
5. The combination of claim 3, wherein the polymer is chemically grafted to said bristles.
6. The combination of claim 4, wherein the polymer is selected from the group consisting of monomers and prepolymers having one or more carboxyl and hydroxyl groups.
7. The combination of claim 6, wherein the monomers and prepolymers are acrylic acid, polyacrylic acid and polyvinyl alcohol.
8. The combination of claim 1, wherein the chemical bond is a covalent bond.
9. The combination of claim 5, wherein the chemical bond is a covalent bond.
10. The combination of claim 6, further comprising a graft initiator in the form of metal ions for abstracting active hydrogens and transforming the abstracted sites into free radical sites to which the monomer/prepolymer attaches, the result being a covalent bond of the monomer/prepolymer to the bristles.
11. A method of bonding a flavored toothpaste composition to a substrate, comprising:
(a) providing a toothbrush having bristles comprising said substrate;
(b) activating the substrate with a graft initiator;
(c) bonding a monomer/prepolymer to the activated substrate;
(d) polymerizing the monomer/prepolymer to form a graft polymer chain;
(e) chemically bonding a flavoring to the polymer chain, (b) through (e) being performed in the presence of a catalyst; and
(f) drying the toothbrush containing the flavored toothpaste composition to complete the graft polymerization whereby the flavoring is preserved until the toothbrush and flavored toothpaste composition is utilized.
12. The method of claim 11, wherein said (a) comprises providing a toothbrush having bristles containing in their molecular structure active hydrogens capable of undergoing abstraction for graft polymerization at vacated hydrogen sites.
13. The method of claim 11, wherein said
(a) comprises providing a toothbrush having nylon, polypropylene or polyester bristles.
14. The method of claim 11, wherein said
(b) comprises activating the substrate with a graft initiator in the form of metal ions for abstracting active hydrogens and transforming the abstracted sites into free radical sites to which the monomer/prepolymer attaches, the result being a covalent bond of the monomer/prepolymer to the toothbrush bristles.
15. The method of claim 14, wherein said (b) comprises activating the substrate with a graft initiator in the form of ferrous ions.
16. The method of claim 11, wherein (b) further comprises reduction of the graft initiator and oxidation of the substrate to transform the substrate into a free radical.
17. The method of claim 11, wherein (c) further comprises grafting the monomer/prepolymer to the activated substrate to form a graft polymer radical on the substrate.
18. The method of claim 11, wherein (d) further comprises growing polymer chains on the substrate.
19. The method of claim 11, wherein (e) further comprises:
(i) forming a menthol radical; and (ii) combining the menthol radical with the activated graft polymer substrate formed in (d) , the result being a covalent bonding of the flavoring to the surface of the toothbrush bristles.
20. The method of claim 11, further comprising the step of curing the toothbrush containing the flavored toothpaste composition at a temperature of about 212°F to about 300°F for about 1 to 2 minutes.
21. The method of claim 11, wherein said (e) comprises chemically bonding a flavoring to the polymer chain in the presence of a peroxide catalyst.
22. The method of claim 21, wherein said (e) comprises chemically bonding a flavoring to the polymer chain in the presence of hydrogen peroxide.
23. The method of claim 11, wherein said (c) comprises bonding acrylic acid and polyacrylic acid to the activated substrate.
24. A method of bonding a flavored toothpaste composition to a substrate, the substrate being the bristles of a toothbrush, comprising the steps of :
(a) applying a prime coat to the bristles of the toothbrush, the prime coat including a flavoring and a prepolymer;
(b) curing the prime coat;
(c) applying a top coat over the prime coat, the top coat including a monomer, a catalyst, a graft initiator, and auxiliary excipients; and
(d) curing the top coat.
25. The method of claim 24, wherein said step (a) comprises:
(i) activating the substrate with the graft initiator;
(ii) bonding the prepolymer to the activated substrate; and
(iii) chemically bonding the flavoring to the prepolymer, (i) through (iii) being performed in the presence of a catalyst.
26. The method of claim 24, wherein said step (c) comprises applying a top coat including a graft initiator in the form of metal ions for abstracting active hydrogens and transforming the abstracted sites into free radical sites to which the monomer/prepolymer attaches, the result being a covalent bond of the monomer/prepolymer to the toothbrush bristles.
27. The method of claim 26, wherein said step (c) comprises applying a top coat including a graft initiator in the form of ferrous ions.
28. The method of claim 25, wherein (i) further comprises reduction of the graft initiator and oxidation of the bristles to transform the bristles into a free radical .
29. The method of claim 25, wherein (ii) further comprises grafting the prepolymer to the activated substrate to form a graft prepolymer radical on the substrate.
30. The method of claim 25, wherein (iii) further comprises:
(a) forming a menthol radical; and
(b) combining the menthol radical with the activated graft prepolymer substrate formed in (ii) , the result being a covalent bonding of the flavoring to the surface of the toothbrush bristles.
31. The method of claim 24, wherein the application of the top coat comprises:
(i) grafting a monomer to the activated substrate; and
(ii) polymerizing the monomer to form a graft polymer chain, (i) and (ii) being performed in the presence of a catalyst.
32. The method of claim 24, wherein step (b) is conducted at a temperature of about 200°F for about four to five minutes.
33. The method of claim 24, wherein step (d) is conducted at a temperature of about 300°F for about two minutes.
34. The method of claim 24, wherein said step (c) comprises applying a top coat including a peroxide catalyst.
35. The method of claim 34, wherein said step (c) comprises applying a top coat including a hydrogen peroxide catalyst.
36. The method of claim 31, wherein (i) and (ii) are performed in the presence of a peroxide catalyst.
37. The method of claim 36, wherein (i) and (ii) are performed in the presence of a hydrogen peroxide catalyst.
38. The method of claim 24, wherein said step (a) comprises applying a prime coat including a polyvinyl alcohol prepolymer and wherein said step (c) comprises applying a top coat including an acrylic acid monomer.
39. The method of claim 24 wherein the top coat also includes a pigment.
40. The method of claim 26 wherein the top coat also includes a pigment.
41. The method of claim 27 wherein the top coat also includes a pigment.
42. A method of bonding a flavored toothpaste composition to a substrate, the substrate being the bristles of a toothbrush, comprising the steps of :
(a) applying a single coat of the toothpaste composition to the bristles of the toothbrush, the single coat including a monomer/prepolymer, a catalyst, a graft initiator, flavoring and other auxiliary excipients; and
(b) air drying the toothbrush containing the flavored toothpaste composition.
43. The method of claim 42, wherein the single coat further comprises a pigment.
44. The method of claim 42, wherein said step (a) comprises:
(i) activating the substrate with the graft initiator;
(ii) bonding the monomer/prepolymer to the activated substrate;
(iii) polymerizing the monomer/prepolymer to form a graft polymer chain; and
(iv) chemically bonding the flavoring to the polymer chain, (i) through (iv) being performed in the presence of the catalyst.
45. The method of claim 42, wherein said step (a) comprises applying a single coat including a graft initiator in the form of metal ions for abstracting active hydrogens and transforming the abstracted sites into free radical sites to which the monomer/prepolymer attaches, the result being a covalent bond of the monomer/prepolymer to the toothbrush bristles.
46. The method of claim 45, wherein said step (a) comprises applying a single coat including a graft initiator in the form of ferrous ions.
47. The method of claim 45, wherein the single coat also includes a pigment.
48. The method of claim 46, wherein the single coat also includes a pigment.
49. The method of claim 44, wherein (i) further comprises reduction of the graft initiator and oxidation of the bristles to transform the bristles into a free radical.
50. The method of claim 44, wherein (ii) further comprises grafting the prepolymer to the activated substrate to form a graft prepolymer radical on the substrate.
51. The method of claim 44, wherein (iii) further comprises growing polymer chains on the substrate.
52. The method of claim 44, wherein (iv) further comprises:
(a) forming a menthol radical; and
(b) combining the menthol radical with the activated graft prepolymer substrate formed in (ii) , the result being a covalent bonding of the flavoring to the surface of the toothbrush bristles.
53. The method of claim 42, wherein step
(b) is conducted at room temperature for about 30 to 40 minutes.
54. The method of claim 42, further comprising the optional step (c) of curing the toothbrush containing the flavored toothpaste composition.
55. The method of claim 54, wherein step
(c) is conducted at a temperature of about 212°F to 300°F for about one to two minutes.
56. The method of claim 42, wherein said step (a) comprises applying a single coat including a peroxide catalyst.
57. The method of claim 56 wherein said step (a) comprises applying a single coat including a hydrogen peroxide catalyst.
58. The method of claim 44, wherein (i) through (iv) are performed in the presence of a peroxide catalyst.
59. The method of claim 58, wherein (i) through (iv) are performed in the presence of a hydrogen peroxide catalyst.
60. The method of claim 42, wherein said step (a) comprises applying a single coat including an acrylic acid monomer and a polyacrylic acid prepolymer.
PCT/US1994/013208 1993-11-10 1994-11-10 Disposable toothbrush having mint flavored toothpaste composition bonded to bristles thereof WO1995013412A1 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
CA002176003A CA2176003C (en) 1993-11-10 1994-11-10 Disposable toothbrush having mint flavored toothpaste composition bonded to bristles thereof
JP7514075A JPH09505217A (en) 1993-11-10 1994-11-10 Disposable toothbrush with mint flavoring toothpaste composition bound to bristles
KR1019960702434A KR960705972A (en) 1993-11-10 1994-11-10 DISPOSABLE TOOTHBRUSH HAVING MINT FLAVORED TOOTHPASTE COMPOSITION BONDED TO BRISTLES THEREOF
AU11799/95A AU1179995A (en) 1993-11-10 1994-11-10 Disposable toothbrush having mint flavored toothpaste composition bonded to bristles thereof
EP95902572A EP0733133A4 (en) 1993-11-10 1994-11-10 Disposable toothbrush having mint flavored toothpaste composition bonded to bristles thereof

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US15059993A 1993-11-10 1993-11-10
US08/150,599 1993-11-10

Publications (1)

Publication Number Publication Date
WO1995013412A1 true WO1995013412A1 (en) 1995-05-18

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JP (1) JPH09505217A (en)
KR (1) KR960705972A (en)
CN (1) CN1139962A (en)
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CA (1) CA2176003C (en)
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WO (1) WO1995013412A1 (en)

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CN102551897A (en) * 2010-12-27 2012-07-11 吴铭远 Disposal handheld dental device
KR101415267B1 (en) * 2012-11-27 2014-07-04 기순종 Disposable tooth brush with toorh powder manufacture device
CN105726407B (en) * 2016-03-28 2018-06-01 两面针(江苏)实业有限公司 A kind of preparation method for combination of brushing teeth

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3302230A (en) * 1964-10-30 1967-02-07 Poppelmann Ake Toothbrush
US3378870A (en) * 1967-03-22 1968-04-23 Matsunaga Kenji Toothbrush

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3302230A (en) * 1964-10-30 1967-02-07 Poppelmann Ake Toothbrush
US3378870A (en) * 1967-03-22 1968-04-23 Matsunaga Kenji Toothbrush

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0733133A4 *

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CA2176003C (en) 2002-01-08
EP0733133A4 (en) 1999-06-30
AU1179995A (en) 1995-05-29
JPH09505217A (en) 1997-05-27
IL111595A (en) 1999-11-30
KR960705972A (en) 1996-11-08
IL111595A0 (en) 1994-11-10
CN1139962A (en) 1997-01-08
EP0733133A1 (en) 1996-09-25
CA2176003A1 (en) 1995-05-18

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