EP2529643A1 - Oral care instrument including an oral care agent and a wear indicator - Google Patents
Oral care instrument including an oral care agent and a wear indicator Download PDFInfo
- Publication number
- EP2529643A1 EP2529643A1 EP12182542A EP12182542A EP2529643A1 EP 2529643 A1 EP2529643 A1 EP 2529643A1 EP 12182542 A EP12182542 A EP 12182542A EP 12182542 A EP12182542 A EP 12182542A EP 2529643 A1 EP2529643 A1 EP 2529643A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- oral care
- instrument
- head
- care agent
- agent
- 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.)
- Granted
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Classifications
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- A—HUMAN NECESSITIES
- A46—BRUSHWARE
- A46B—BRUSHES
- A46B11/00—Brushes with reservoir or other means for applying substances, e.g. paints, pastes, water
- A46B11/001—Brushes with reservoir or other means for applying substances, e.g. paints, pastes, water with integral reservoirs
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- A—HUMAN NECESSITIES
- A46—BRUSHWARE
- A46B—BRUSHES
- A46B11/00—Brushes with reservoir or other means for applying substances, e.g. paints, pastes, water
-
- A—HUMAN NECESSITIES
- A46—BRUSHWARE
- A46B—BRUSHES
- A46B11/00—Brushes with reservoir or other means for applying substances, e.g. paints, pastes, water
- A46B11/001—Brushes with reservoir or other means for applying substances, e.g. paints, pastes, water with integral reservoirs
- A46B11/0068—Brushes where the reservoir is specifically intended for solid substance that dissolves gradually
-
- A—HUMAN NECESSITIES
- A46—BRUSHWARE
- A46B—BRUSHES
- A46B15/00—Other brushes; Brushes with additional arrangements
- A46B15/0002—Arrangements for enhancing monitoring or controlling the brushing process
-
- A—HUMAN NECESSITIES
- A46—BRUSHWARE
- A46B—BRUSHES
- A46B15/00—Other brushes; Brushes with additional arrangements
- A46B15/0002—Arrangements for enhancing monitoring or controlling the brushing process
- A46B15/0004—Arrangements for enhancing monitoring or controlling the brushing process with a controlling means
- A46B15/001—Arrangements for enhancing monitoring or controlling the brushing process with a controlling means with means indicating the remaining useful life of brush
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- A—HUMAN NECESSITIES
- A46—BRUSHWARE
- A46B—BRUSHES
- A46B2200/00—Brushes characterized by their functions, uses or applications
- A46B2200/10—For human or animal care
- A46B2200/1066—Toothbrush for cleaning the teeth or dentures
Definitions
- the present invention relates to an oral care instrument with at least one oral care agent that can be delivered within the mouth of a user to provide the user with enhanced oral heath,
- the present invention also pertains to such an oral care instrument including a wear indicator that informs the user when the oral care agent has been depleted.
- Tooth decay and periodontal disease are typically caused by harmful bacteria within the mouth.
- the harmful bacteria mixes with proteins present in saliva, a film of plaque is formed on the teeth and soft tissue. If the plaque is not removed, it can attack the teeth and create cavities. Additionally, the plaque will attack the soft tissue within the mouth and cause gum disease, the leading cause of tooth loss in adults. As a result, decreasing the amount of harmful bacteria in the mouth has long been the target of persons working in the oral health care field.
- the most common way of minimizing the harmful bacteria within the mouth is brushing with a dentifrice that delivers at least one oral care agent into the mouth.
- Orally introduced liquids, including oral rinses, are also utilized to provide additional oral care beyond that achieved while brushing.
- Mouthwashes may also be used to deliver breath freshening agents within the mouth in an attempt to eliminate bad breath.
- An aspect of the present invention pertains to an oral care instrument that includes and delivers an oral care agent within the mouth of a user.
- the oral care instrument includes a head having at least a portion formed of a material that defines cavities. At least one oral care agent is provided in a plurality of the cavities and dispensed within the mouth of a user when the oral care agent(s) contact a fluid or chemical within the oral cavity.
- the oral care instrument includes a wear indicator for indicating the amount of oral care agent.
- an oral care device formed of a polymer that receives at least one oral care agent.
- the oral care agent(s) can be included in or on one or more surfaces of the oral care instrument for delivery into the oral cavity.
- the oral care agent(s) can be contained within cavities in one or more surfaces of a head.
- the oral care agent(s) can be formed into, or carried by, a thin slab subsequently bonded onto the toothbrush head; or applied onto the toothbrush head as a stable coating.
- the oral care agents can be released during one use, during multiple uses, or throughout the life of the instrument. Water, oral secretions and/or chemicals within the mouth can activate the oral care agents.
- Figure 1 is an isometric view of an oral care instrument according to aspects of the present invention.
- Figure 2 is a view of one surface of the instrument of Figure 1 ;
- Figure 3 illustrates a surface of the instrument of Figure 1 taken opposite Figure 2 ;
- Figure 4 is an enlarged portion 4-4 of the surface of the instrument of Figures 1-3 ;
- Figure 5 is a cross section of one embodiment of a cavity shown in Figure 4 ;
- Figure 6 is a cross section of one embodiment of a cavity shown in Figure 4 ;
- Figure 7 is a partial cross section of the instrument of Figure 2 ;
- Figure 8 is a partial cross section of an instrument according to an alternative embodiment of the present invention.
- Figure 9 illustrates an embodiment of the instrument of Figure 2 .
- Figure 10 is a perspective view of an alternative embodiment of an instrument according to the present invention.
- Figure 1 illustrates one embodiment of an oral care instrument 1 having an elongated handle 10 and a head 20 intended to be introduced into the mouth or oral cavity of a user.
- the oral care instrument 1 is not limited to a toothbrush as shown and described, but can have any shape or structure and perform any function that permits it to deliver oral care agents to the user, with non-limiting examples of other oral care instruments including tongue cleaners and portable brush, toothpick combinations.
- the instrument 1 can be used once and then discarded, or it can be used repeatedly over a period of time.
- the elongated handle 10 may be formed of many different shapes and with a variety of constructions that permit the oral care instrument 1 to be readily gripped and manipulated within the mouth of the user.
- the head 20 includes multiple surfaces that are exposed to fluids within the mouth during use.
- the head 20 includes a first surface 22 on a first side 23 and a second surface 24 on a second, opposite side 25. Sidewalls 26 extend between the surfaces 22, 24.
- Oral care elements 30 can extend from either or both surfaces 22, 24 of the head 20, which elements 30 can include teeth cleaning elements 35, such as elongated bristles or elastomeric fingers, or soft tissue cleaning elements such as tongue cleaning members (not shown) extending from either surface 22, 24.
- a third example includes a head 20 having teeth cleaning elements 35 extending from the first surface 22 and tongue cleaning elements (not shown) extending from the second surface 24.
- oral care elements 30 disclosed herein are not limited to those discussed above. Instead, the term "oral care element” is generic and intended to include all types of elements that can be used within a mouth including different tooth and soft tissue cleaning members that are not mentioned above, gum massaging members and other forms of oral cleaning or massaging members.
- the head 20 also includes at least one oral care agent for introducing into the mouth to perform an intended function.
- the oral care agent(s) can be provided in cavities 50 (See Figure 4 ) formed or present in the head 20.
- the oral care agent(s) can also be included in or on a separate member 100 positioned on one or more of the surfaces 22, 24 or 26 of the head 20 (See Figure 2 ). This member 100 may be provided in place of, or in addition to, the cavities 50 within the head 20.
- the head 20 is generally formed of a material having a plurality of the externally exposed cavities 50 that are open to their respective outer surface 22, 24, 26.
- the entire head 20 can be formed of this material or the material can be applied over an inner core (not shown).
- the material used to form the head 20 can include any one of a wide variety of commercially available polymers, such as a thermoplastic polymer for example.
- the oral care instrument 1 is formed from a polypropylene, such that upon manufacture it is formed with internally extending cavities. Different thermoplastic polymers or polymers having different molecular weights typically have different melting and solidifying characteristics. Therefore, it is within the purview of a skilled artisan to select a polymer suitable for a given application.
- the oral care instrument 1 can be formed of polypropylene materials such as those available from M.A. Industries,
- the head 20 formed of a polypropylene material is manufactured using a sintering process.
- the head 20 can formed at the same time as the remaining portions of the oral care instrument 1 as a single, continuous member.
- the head 20 can be manufactured as a component that is assembled as part of the instrument 1, The head 20 can then be attached through a number of techniques including welding via ultrasonics, heat staking, laser, etc. or through mechanical methods that also permit the head 20 to be removed and discarded.
- the term "cavity” is intended to refer to an opening in the head 20, whether present in the head material itself or intentionally formed therein, that preferably does not extend all the way through the head.
- the term “exposed surface” relates to a surface that defines the shape of the head 20 and which generally defines the boundary between the head 20 and its environment.
- the externally exposed cavities 50 are capable of receiving and retaining one or more of the dispensable oral care agents.
- the cavities 50 can receive these agents in a powered form, a liquid form or both.
- the cavities 50 will receive and retain the oral care agent(s) until a predetermined amount has been received or the cavity is filled.
- the size and shape of these cavities 50 may be varied so they can include greater amounts of an oral care agent or an oral care agent with larger or different shaped molecules.
- the oral care instrument 1 can have cavities 50 that deliver oral care agent(s) into the mouth of a user at different rates. These rates can be controlled, for example, by the size of the exposed surface area of the respective cavity 50 and contained oral care agent in the outer surface 22, 24, 26 of the head, the shape of the cavities 50, the depth of the cavities 50 and/or the characteristics of the contained oral care agent(s).
- Adjacent cavities 50 can have different sizes in order to accommodate different amounts of oral care agent(s) or different molecular sized oral care agent(s).
- the oral care instrument 1 can have different oral care agent release characteristics that control when and how much of each oral care agent is delivered into the oral cavity.
- a larger thermoplastic granule size for the head 20 may preferably be selected and, where it is desired that the oral care agent(s) be dispensed more slowly, a smaller thermoplastic granule size may preferably be selected.
- Adjacent cavities 50 within the outer surfaces of the head 20 can carry the same or different oral care agents.
- the same void 50 can carry different oral care agents (A, B), either layered on top of each other ( Figure 5 ) for controlled release timing or adjacent to each other ( Figure 6 ) so they will react simultaneously when they come into contact with an activator.
- the active oral care agents can function as, for example, abrasives, mouth fresheners, tooth whiteners, vitamins, anti-bacterial/anti-microbial agents, plaque dispersants, de-sensitizing agents for the mouth and teeth, anti-cavity agents, and/or combinations of these functional agents to provide individual or combined, synergistic benefits.
- Oral care agents can also include flavorings, decorations, nutritional and body supplements such as calcium. The calcium could, for example, be provided in 1 mg single use dosages. The flavorings could be released to indicate that the oral care element 1 is functioning properly or to indicate that the instrument 1 is exhausted and ready to be disposed or recharged. Also, the oral care agents could eliminate particular enzymes from within the mouth of the user.
- the decorations applied by the oral care agents could temporarily add coloring, sparkle, glitter and/or indicia to the teeth of the user. Further, the lack of fluid within the mouth could trigger an oral care agent, such as stimulant for the salivary gland, provided within the cavities 50. The amount and rate of delivery for these agents will depend on the amount needed and the agent being applied.
- the oral care agents can be delivered to the cavities in a solid and/or liquid compound.
- the material of the oral care instrument 1 is immersed in a desired liquid so that the oral care agent(s) within the liquid can flow and remain within the cavities 50. As it dries, the oral care agent 20 becomes secure within the cavities 50. It is also possible to impregnate the cavities 50 of the portion of the head 20 with desired oral care agent(s) during production. It is also understood that a spent oral care instrument, i.e., one in which the oral care agent(s) has been depleted, may advantageously be recharged with an oral care agent by immersing it again in a liquid that carries the desired oral care agent(s).
- the cavities 50 can be replenished (recharged) on a regular basis, including daily for those instruments providing single dosages of at least one oral care agent.
- the head 20 may be advantageously used to dispense or release the oral care agent(s) within the mouth.
- the oral care agents will typically leach from their respective cavities 50 when they come into contact with fluids and/or chemicals within the mouth.
- active oral care agents that have been impregnated in the head material can be released into the mouth while brushing one's teeth.
- water and chemicals present in the mouth of a user will come into contact with the oral care agent(s) within the cavities 50 in the head 20. This will create a reaction in which the impregnated oral care agent(s) will leach out from the cavities 50 within the head 20.
- the use of different oral care agents in cavities 50 of the same head 20 has the capability of providing a synergistic benefit to the user. This can be especially useful when there are two beneficial oral care agent(s) which, in ideal circumstances, should be kept separated from each other until the desired time of use. In this manner the oral care instrument 1 can deliver multiple benefits to the user at one time.
- the oral care instrument 1 is also able to deliver the benefits of a dentifrice by impregnating the head material with the chemicals and abrasives found in toothpaste, for example. In such an embodiment, it would be possible to deliver some of the chemical and mechanical benefits of toothpaste solely through use of the toothbrush without toothpaste being applied to the cleaning elements of the toothbrush. At least one of the dispensed oral care agents could also operate as a catalyst or enhancer for the toothpaste or other agents introduced into the mouth. Also, with this oral care instrument 1, it may be possible to deliver the benefits of a chemical, such as chlorhexidine for example, in a more efficacious manner.
- a chemical such as chlorhexidine
- the delivery member 100 discussed above can provide or include, the oral care agents discussed above and also function as a wear indicator. This member 100 can be located at any position on the head 20 and can provide notice to the user when the oral care agent is depleted. In a non-limiting illustrative embodiment, the delivery member 100 is shown as a strip 102 on the second surface 24. The delivery member 100 can have any shape and be located on or in any surface(s) on the instrument 1 that can be viewed by the user. In addition to identifying when the instrument 1 needs to be discarded or recharged, the delivery member 100 can also include and deliver at least one of the above-discussed oral care agents within the oral cavity.
- the delivery member 100 is removable and one or more replacement strips 102 can be applied in its place, in series or in parallel, to perform the same function(s) as the delivery member 100.
- These replacement strips 102 can be applied after each use of the instrument 1 or after repeated uses.
- Single or multiple strips can also be applied on a head surface to deliver multiple individual benefits or benefits that arise from the combined presence of multiple different strip actives. Such strips could be sold separately and applied by a user as desired.
- the replacement strips 102 could be carried within a recess or compartment in the handle 10 of the instrument 1.
- Replacement/enhancement strips 102 that perform different functions within the mouth can also be provided.
- the replacement/enhancement strips 102 can be designed to freshen breath, activate salivary glands, and/or desensitize teeth, etc.
- these different functioning strips 102 can be applied to the instrument 1 in place of, or in addition to, the strips 102 that are regularly used on the head 20 to kill harmful bacteria within the mouth, for example.
- the delivery member 100 (and replacement strips 102, see Figure 2 ) includes a first layer 110 preferably of a water insoluble material, such as a resin, that can hold the oral care agent(s) being delivered within the mouth.
- the water insoluble material maintains the structure of the delivery member 100 as the oral care agent leaches out and is delivered to the oral cavity of the user.
- the layer 110 of material can include a portion of the head 20 or a material layer designed to incorporate the desired criteria of release rate and dosage that is securable to the head 20.
- the delivery member 100 can be secured on or within at least one surface of the head 20.
- the delivery member 100 could be secured within a groove 118 ( Figure 8 ) that extends along or around the head 20.
- a groove 118 could be about 1 to about 2 mm deep, relative to the outer surfaces of the head 20.
- a second layer 114 is positioned over the first layer 110.
- This layer may be made of any material or materials that may be chemically and/or mechanically altered. Chemical and/or mechanical alteration may be accomplished by, e.g., chemical reactions initiated by components of the saliva or water, including dissolution or enzyme conversion and/or abrasion of the layer against the surfaces of the oral cavity. This layer 114 can erode due to abrasion during use of the instrument 1 or it can be formed of a water-soluble material.
- the outer layer 114 includes a water-soluble polymer (preferably polyethylene oxide, polyethylene glycol, or polyvinyl alcohol for example).
- the second layer 114 can also include one or more oral care agents, such as an anti-microbial agent.
- the anti-microbial agent can be any of those discussed above, such as chlorhexidine.
- Non-limiting examples of anti-microbial agents that can be used in place of chlorhexidine digluconate include antibiotics such as actinobolin, chlortetracycline, tetracycline, streptomycin, kanamycin, neomycin, niddamycin, bacitracin, erythromycin, penicillin, rancemycin, gramicidin, saramycin, and polymyxin B; as well as antiplaque enzymes such as mucinases, pancreatin, fungal enzymes, protease-amylase, dextranase, moimnase, zendium, amyloglucosidase, and glucose oxidase.
- antibiotics such as actinobolin, chlortetracycline, tetracycline, streptomycin, kanamycin, neomycin, niddamycin, bacitracin, erythromycin, penicillin, rancemycin, gramicidin, sara
- phenolic compounds e.g., phenol, thymol, 2-phenylphenol, hexylresorcinol), and listerine (thymol, eucalyptol, menthol, methylsalicylate); bipyridines (e.g., octenidene); pyrimidines (e.g., hexetidine); halogens (e.g., iodine, iodophores, fluorides); quaternary ammonium salts (e.g., cetylpyridinium chloride, benzethonium chloride, domiphen bromide); oxygenating agents (e.g., peroxides; perborate); herbal extracts (e.g., sangnimarine); heavy metal salts (e.g., silver, mercury, zinc, copper, tin); and other bis-biguanidines besides chlorhexidine (e.g., alex
- the two layers 110, 114 can be produced either by conventional co-extrusion or co-injection molding techniques, from two different mixtures. Alternatively one layer can be extruded and then the other layer can be thermoformed/compression molded or laminated onto the extruded layer. Other methods of manufacture are also contemplated.
- the outer layer 114 dissolves and the oral care agent(s) leach out from the area exposed by the dissolved outer layer 114.
- the outer layer 114 dissolves away with repeated use, it not only exposes the oral care agent held in the resin, for example, but it also exposes indicia 120 that indicates the wear of the instrument 1, including when the oral care agent(s) within the instrument is depleted and needs to be replaced or recharged ( Figure 9 ).
- the indicia 120 can be a visible color that attracts the user's attention to the layer 110 and illustrates that the amount of effective life remaining in the instrument 1.
- the indicia 120 can be a message that tells the user when the oral care instrument 1 is depleted ( Figure 9 ).
- Other manners of communication are also contemplated.
- a hydrogel is applied over at least one surface of the instrument 1 and/or forms at least one layer of the delivery member 100.
- the hydrogel releases oral care agents and/or absorbs other agents, bacteria and/or chemicals within the mouth and on the instrument 1.
- the instrument 1 can include any number of containers or capsules 200 secured to a surface of the head 20 or included within the head 20.
- Each capsule 200 can be formed of a biocompatible material and comprise at least one oral care agent, such as liquid and/or powder oral care agents. In certain instances, the agents provided in the capsules should not be mixed until within the mouth. These capsules 200 can burst under pressure or dissolve and release the oral care agent(s) into the oral cavity.
- a single container or capsule 250 having two or more chambers 252, 254 is secured to a surface of the instrument 1.
- a membrane 255 extends between the chambers 252, 254. Over time, the membrane 255 will dissolve or break. This failure of the membrane can be time dependent and/or as a result of use of the instrument 1 within the mouth. When the membrane 255 dissolves, breaks or otherwise wears away from an inner wall of the capsule 250, the materials in the chambers 252, 254 contact each other and cause a perceptible change that indicates that the oral care agent in the instrument 1 may be depleted.
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- Dental Tools And Instruments Or Auxiliary Dental Instruments (AREA)
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Abstract
Description
- The present invention relates to an oral care instrument with at least one oral care agent that can be delivered within the mouth of a user to provide the user with enhanced oral heath, The present invention also pertains to such an oral care instrument including a wear indicator that informs the user when the oral care agent has been depleted.
- People exhibit many forms of poor oral health including tooth decay, periodontal diseases and bad breath (halitosis). Tooth decay and periodontal disease are typically caused by harmful bacteria within the mouth. When the harmful bacteria mixes with proteins present in saliva, a film of plaque is formed on the teeth and soft tissue. If the plaque is not removed, it can attack the teeth and create cavities. Additionally, the plaque will attack the soft tissue within the mouth and cause gum disease, the leading cause of tooth loss in adults. As a result, decreasing the amount of harmful bacteria in the mouth has long been the target of persons working in the oral health care field.
- The most common way of minimizing the harmful bacteria within the mouth is brushing with a dentifrice that delivers at least one oral care agent into the mouth. Orally introduced liquids, including oral rinses, are also utilized to provide additional oral care beyond that achieved while brushing. Mouthwashes may also be used to deliver breath freshening agents within the mouth in an attempt to eliminate bad breath.
- Unfortunately, people do not always have the time to provide themselves with adequate oral care. For example, a busy person may not have the time or patience to brush thoroughly, floss and/or use an oral rinse. Alternatively, certain people may consider anything more than brushing their teeth to be unnecessary. For either reason, these people may leave a significant amount of harmful bacteria within their mouths after completing their oral care routines, which can begin to attack the teeth and gums.
- Additionally, even when all available and recommended products are used, they may not be as effective as they could be if delivered simultaneously. For example, using a dentifrice and an oral rinse at different times may diminish any synergistic effect that they could provide to the user when used simultaneously.
- An aspect of the present invention pertains to an oral care instrument that includes and delivers an oral care agent within the mouth of a user. The oral care instrument includes a head having at least a portion formed of a material that defines cavities. At least one oral care agent is provided in a plurality of the cavities and dispensed within the mouth of a user when the oral care agent(s) contact a fluid or chemical within the oral cavity. In another aspect of the present invention, the oral care instrument includes a wear indicator for indicating the amount of oral care agent.
- Another aspect of the present invention relates to an oral care device formed of a polymer that receives at least one oral care agent. The oral care agent(s) can be included in or on one or more surfaces of the oral care instrument for delivery into the oral cavity. The oral care agent(s) can be contained within cavities in one or more surfaces of a head. Alternatively, the oral care agent(s) can be formed into, or carried by, a thin slab subsequently bonded onto the toothbrush head; or applied onto the toothbrush head as a stable coating. The oral care agents can be released during one use, during multiple uses, or throughout the life of the instrument. Water, oral secretions and/or chemicals within the mouth can activate the oral care agents.
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Figure 1 is an isometric view of an oral care instrument according to aspects of the present invention; -
Figure 2 is a view of one surface of the instrument ofFigure 1 ; -
Figure 3 illustrates a surface of the instrument ofFigure 1 taken oppositeFigure 2 ; -
Figure 4 is an enlarged portion 4-4 of the surface of the instrument ofFigures 1-3 ; -
Figure 5 is a cross section of one embodiment of a cavity shown inFigure 4 ; -
Figure 6 is a cross section of one embodiment of a cavity shown inFigure 4 ; -
Figure 7 is a partial cross section of the instrument ofFigure 2 ; -
Figure 8 is a partial cross section of an instrument according to an alternative embodiment of the present invention; -
Figure 9 illustrates an embodiment of the instrument ofFigure 2 ; and -
Figure 10 is a perspective view of an alternative embodiment of an instrument according to the present invention. -
Figure 1 illustrates one embodiment of anoral care instrument 1 having anelongated handle 10 and ahead 20 intended to be introduced into the mouth or oral cavity of a user. Theoral care instrument 1 is not limited to a toothbrush as shown and described, but can have any shape or structure and perform any function that permits it to deliver oral care agents to the user, with non-limiting examples of other oral care instruments including tongue cleaners and portable brush, toothpick combinations. Theinstrument 1 can be used once and then discarded, or it can be used repeatedly over a period of time. Theelongated handle 10 may be formed of many different shapes and with a variety of constructions that permit theoral care instrument 1 to be readily gripped and manipulated within the mouth of the user. - The
head 20 includes multiple surfaces that are exposed to fluids within the mouth during use. In the embodiment illustrated inFigures 1-3 , thehead 20 includes afirst surface 22 on a first side 23 and asecond surface 24 on a second,opposite side 25.Sidewalls 26 extend between thesurfaces Oral care elements 30 can extend from either or bothsurfaces head 20, whichelements 30 can includeteeth cleaning elements 35, such as elongated bristles or elastomeric fingers, or soft tissue cleaning elements such as tongue cleaning members (not shown) extending from eithersurface head 20 havingteeth cleaning elements 35 extending from thefirst surface 22 and tongue cleaning elements (not shown) extending from thesecond surface 24. - The
oral care elements 30 disclosed herein are not limited to those discussed above. Instead, the term "oral care element" is generic and intended to include all types of elements that can be used within a mouth including different tooth and soft tissue cleaning members that are not mentioned above, gum massaging members and other forms of oral cleaning or massaging members. - Regardless of the number or position of the
oral care elements 30 provided on thehead 20, thehead 20 also includes at least one oral care agent for introducing into the mouth to perform an intended function. In an embodiment, the oral care agent(s) can be provided in cavities 50 (SeeFigure 4 ) formed or present in thehead 20. The oral care agent(s) can also be included in or on aseparate member 100 positioned on one or more of thesurfaces Figure 2 ). Thismember 100 may be provided in place of, or in addition to, thecavities 50 within thehead 20. - The
head 20 is generally formed of a material having a plurality of the externally exposedcavities 50 that are open to their respectiveouter surface entire head 20 can be formed of this material or the material can be applied over an inner core (not shown). The material used to form thehead 20 can include any one of a wide variety of commercially available polymers, such as a thermoplastic polymer for example. In an embodiment, theoral care instrument 1 is formed from a polypropylene, such that upon manufacture it is formed with internally extending cavities. Different thermoplastic polymers or polymers having different molecular weights typically have different melting and solidifying characteristics. Therefore, it is within the purview of a skilled artisan to select a polymer suitable for a given application. Theoral care instrument 1 can be formed of polypropylene materials such as those available from M.A. Industries, In an embodiment, thehead 20 formed of a polypropylene material is manufactured using a sintering process. Thehead 20 can formed at the same time as the remaining portions of theoral care instrument 1 as a single, continuous member. Alternatively, thehead 20 can be manufactured as a component that is assembled as part of theinstrument 1, Thehead 20 can then be attached through a number of techniques including welding via ultrasonics, heat staking, laser, etc. or through mechanical methods that also permit thehead 20 to be removed and discarded. - As used herein, the term "cavity" is intended to refer to an opening in the
head 20, whether present in the head material itself or intentionally formed therein, that preferably does not extend all the way through the head. As used herein, the term "exposed surface" relates to a surface that defines the shape of thehead 20 and which generally defines the boundary between thehead 20 and its environment. The externally exposedcavities 50 are capable of receiving and retaining one or more of the dispensable oral care agents. Thecavities 50 can receive these agents in a powered form, a liquid form or both. In an embodiment, thecavities 50 will receive and retain the oral care agent(s) until a predetermined amount has been received or the cavity is filled. The size and shape of thesecavities 50 may be varied so they can include greater amounts of an oral care agent or an oral care agent with larger or different shaped molecules. - It is understood that a wide variety of material specifications (such as polymer type, polymer size, granule size distribution, the type of oral care agent used, oral care agent particle size distribution and ratio of porous polymer to oral care agent) and also a wide variety of manufacturing/processing parameters (such as temperature and pressure) may be used to provide an
instrument 1 having various advantageous characteristics including cavity sizing, shape and spacing. For example, theoral care instrument 1 can havecavities 50 that deliver oral care agent(s) into the mouth of a user at different rates. These rates can be controlled, for example, by the size of the exposed surface area of therespective cavity 50 and contained oral care agent in theouter surface cavities 50, the depth of thecavities 50 and/or the characteristics of the contained oral care agent(s). -
Adjacent cavities 50 can have different sizes in order to accommodate different amounts of oral care agent(s) or different molecular sized oral care agent(s). As a result, theoral care instrument 1 can have different oral care agent release characteristics that control when and how much of each oral care agent is delivered into the oral cavity. For example, in an embodiment in which it is desired that the oral care agent(s) be released relatively quickly from theoral care instrument 1, a larger thermoplastic granule size for thehead 20 may preferably be selected and, where it is desired that the oral care agent(s) be dispensed more slowly, a smaller thermoplastic granule size may preferably be selected. -
Adjacent cavities 50 within the outer surfaces of thehead 20 can carry the same or different oral care agents. Similarly, thesame void 50 can carry different oral care agents (A, B), either layered on top of each other (Figure 5 ) for controlled release timing or adjacent to each other (Figure 6 ) so they will react simultaneously when they come into contact with an activator. - The active oral care agents can function as, for example, abrasives, mouth fresheners, tooth whiteners, vitamins, anti-bacterial/anti-microbial agents, plaque dispersants, de-sensitizing agents for the mouth and teeth, anti-cavity agents, and/or combinations of these functional agents to provide individual or combined, synergistic benefits. Oral care agents can also include flavorings, decorations, nutritional and body supplements such as calcium. The calcium could, for example, be provided in 1 mg single use dosages. The flavorings could be released to indicate that the
oral care element 1 is functioning properly or to indicate that theinstrument 1 is exhausted and ready to be disposed or recharged. Also, the oral care agents could eliminate particular enzymes from within the mouth of the user. The decorations applied by the oral care agents could temporarily add coloring, sparkle, glitter and/or indicia to the teeth of the user. Further, the lack of fluid within the mouth could trigger an oral care agent, such as stimulant for the salivary gland, provided within thecavities 50. The amount and rate of delivery for these agents will depend on the amount needed and the agent being applied. - During the production of the
oral care instruments 1, the oral care agents can be delivered to the cavities in a solid and/or liquid compound. In one embodiment, the material of theoral care instrument 1 is immersed in a desired liquid so that the oral care agent(s) within the liquid can flow and remain within thecavities 50. As it dries, theoral care agent 20 becomes secure within thecavities 50. It is also possible to impregnate thecavities 50 of the portion of thehead 20 with desired oral care agent(s) during production. It is also understood that a spent oral care instrument, i.e., one in which the oral care agent(s) has been depleted, may advantageously be recharged with an oral care agent by immersing it again in a liquid that carries the desired oral care agent(s). Thecavities 50 can be replenished (recharged) on a regular basis, including daily for those instruments providing single dosages of at least one oral care agent. - Once the
cavities 50 receive their intended oral care agent(s), thehead 20 may be advantageously used to dispense or release the oral care agent(s) within the mouth. The oral care agents will typically leach from theirrespective cavities 50 when they come into contact with fluids and/or chemicals within the mouth. According to an aspect of the present invention, active oral care agents that have been impregnated in the head material, for example, can be released into the mouth while brushing one's teeth. During the tooth brushing process water and chemicals present in the mouth of a user will come into contact with the oral care agent(s) within thecavities 50 in thehead 20. This will create a reaction in which the impregnated oral care agent(s) will leach out from thecavities 50 within thehead 20. Additionally, the use of different oral care agents incavities 50 of thesame head 20 has the capability of providing a synergistic benefit to the user. This can be especially useful when there are two beneficial oral care agent(s) which, in ideal circumstances, should be kept separated from each other until the desired time of use. In this manner theoral care instrument 1 can deliver multiple benefits to the user at one time. - The
oral care instrument 1 is also able to deliver the benefits of a dentifrice by impregnating the head material with the chemicals and abrasives found in toothpaste, for example. In such an embodiment, it would be possible to deliver some of the chemical and mechanical benefits of toothpaste solely through use of the toothbrush without toothpaste being applied to the cleaning elements of the toothbrush. At least one of the dispensed oral care agents could also operate as a catalyst or enhancer for the toothpaste or other agents introduced into the mouth. Also, with thisoral care instrument 1, it may be possible to deliver the benefits of a chemical, such as chlorhexidine for example, in a more efficacious manner. - The
delivery member 100 discussed above can provide or include, the oral care agents discussed above and also function as a wear indicator. Thismember 100 can be located at any position on thehead 20 and can provide notice to the user when the oral care agent is depleted. In a non-limiting illustrative embodiment, thedelivery member 100 is shown as astrip 102 on thesecond surface 24. Thedelivery member 100 can have any shape and be located on or in any surface(s) on theinstrument 1 that can be viewed by the user. In addition to identifying when theinstrument 1 needs to be discarded or recharged, thedelivery member 100 can also include and deliver at least one of the above-discussed oral care agents within the oral cavity. - In an embodiment, the
delivery member 100 is removable and one or more replacement strips 102 can be applied in its place, in series or in parallel, to perform the same function(s) as thedelivery member 100. These replacement strips 102 can be applied after each use of theinstrument 1 or after repeated uses. Single or multiple strips can also be applied on a head surface to deliver multiple individual benefits or benefits that arise from the combined presence of multiple different strip actives. Such strips could be sold separately and applied by a user as desired. For the user's convenience, the replacement strips 102 could be carried within a recess or compartment in thehandle 10 of theinstrument 1. - Replacement/enhancement strips 102 that perform different functions within the mouth can also be provided. For example, the replacement/enhancement strips 102 can be designed to freshen breath, activate salivary glands, and/or desensitize teeth, etc. In such embodiments, these different functioning strips 102 can be applied to the
instrument 1 in place of, or in addition to, thestrips 102 that are regularly used on thehead 20 to kill harmful bacteria within the mouth, for example. - As illustrated in the embodiment of
Figure 7 , the delivery member 100 (and replacement strips 102, seeFigure 2 ) includes afirst layer 110 preferably of a water insoluble material, such as a resin, that can hold the oral care agent(s) being delivered within the mouth. The water insoluble material maintains the structure of thedelivery member 100 as the oral care agent leaches out and is delivered to the oral cavity of the user. Thelayer 110 of material can include a portion of thehead 20 or a material layer designed to incorporate the desired criteria of release rate and dosage that is securable to thehead 20. Thedelivery member 100 can be secured on or within at least one surface of thehead 20. For example, thedelivery member 100 could be secured within a groove 118 (Figure 8 ) that extends along or around thehead 20. Such agroove 118 could be about 1 to about 2 mm deep, relative to the outer surfaces of thehead 20. - A
second layer 114 is positioned over thefirst layer 110. This layer may be made of any material or materials that may be chemically and/or mechanically altered. Chemical and/or mechanical alteration may be accomplished by, e.g., chemical reactions initiated by components of the saliva or water, including dissolution or enzyme conversion and/or abrasion of the layer against the surfaces of the oral cavity. Thislayer 114 can erode due to abrasion during use of theinstrument 1 or it can be formed of a water-soluble material. In an embodiment, theouter layer 114 includes a water-soluble polymer (preferably polyethylene oxide, polyethylene glycol, or polyvinyl alcohol for example). However, any known, non-toxic polymer, copolymer or combinations of the same providing a controllable water solubility to the layer can be used. The solubility of the polymer used in theouter layer 114 should be low enough that it dissolves out slowly, over a period of many uses. Thesecond layer 114 can also include one or more oral care agents, such as an anti-microbial agent. The anti-microbial agent can be any of those discussed above, such as chlorhexidine. - Non-limiting examples of anti-microbial agents that can be used in place of chlorhexidine digluconate include antibiotics such as actinobolin, chlortetracycline, tetracycline, streptomycin, kanamycin, neomycin, niddamycin, bacitracin, erythromycin, penicillin, rancemycin, gramicidin, saramycin, and polymyxin B; as well as antiplaque enzymes such as mucinases, pancreatin, fungal enzymes, protease-amylase, dextranase, moimnase, zendium, amyloglucosidase, and glucose oxidase. Other conventional antimicrobials that can be used include phenolic compounds (e.g., phenol, thymol, 2-phenylphenol, hexylresorcinol), and listerine (thymol, eucalyptol, menthol, methylsalicylate); bipyridines (e.g., octenidene); pyrimidines (e.g., hexetidine); halogens (e.g., iodine, iodophores, fluorides); quaternary ammonium salts (e.g., cetylpyridinium chloride, benzethonium chloride, domiphen bromide); oxygenating agents (e.g., peroxides; perborate); herbal extracts (e.g., sangnimarine); heavy metal salts (e.g., silver, mercury, zinc, copper, tin); and other bis-biguanidines besides chlorhexidine (e.g., alexidine). Of course, other chlorhexidine salts like the diacetate and dihydrochloride can be used in place of chlorhexidine digluconate.
- The two
layers - As the
delivery member 100 comes into contact with water, saliva or a chemical in the mouth, theouter layer 114 dissolves and the oral care agent(s) leach out from the area exposed by the dissolvedouter layer 114. As theouter layer 114 dissolves away with repeated use, it not only exposes the oral care agent held in the resin, for example, but it also exposesindicia 120 that indicates the wear of theinstrument 1, including when the oral care agent(s) within the instrument is depleted and needs to be replaced or recharged (Figure 9 ). Theindicia 120 can be a visible color that attracts the user's attention to thelayer 110 and illustrates that the amount of effective life remaining in theinstrument 1. Alternatively, theindicia 120 can be a message that tells the user when theoral care instrument 1 is depleted (Figure 9 ). Other manners of communication are also contemplated. - In an alternative embodiment, a hydrogel is applied over at least one surface of the
instrument 1 and/or forms at least one layer of thedelivery member 100. In this embodiment, the hydrogel releases oral care agents and/or absorbs other agents, bacteria and/or chemicals within the mouth and on theinstrument 1. - In an alternative embodiment illustrated in
Figure 10 , theinstrument 1 can include any number of containers orcapsules 200 secured to a surface of thehead 20 or included within thehead 20. Eachcapsule 200 can be formed of a biocompatible material and comprise at least one oral care agent, such as liquid and/or powder oral care agents. In certain instances, the agents provided in the capsules should not be mixed until within the mouth. Thesecapsules 200 can burst under pressure or dissolve and release the oral care agent(s) into the oral cavity. - In another embodiment, a single container or
capsule 250 having two ormore chambers instrument 1. In this embodiment, amembrane 255 extends between thechambers membrane 255 will dissolve or break. This failure of the membrane can be time dependent and/or as a result of use of theinstrument 1 within the mouth. When themembrane 255 dissolves, breaks or otherwise wears away from an inner wall of thecapsule 250, the materials in thechambers instrument 1 may be depleted. - As described above, a wide variety of molding techniques may be used in accordance with the oral care instrument, and a wide variety of material specifications and parameters may be used to provide instruments having a variety of desired characteristics. While the shapes of various preferred inventive articles are described above, it is readily understood that a wide variety of alternate shapes and sizes are contemplated by the invention. Preferably, shapes and sizes are selected such that fluid contact with the porous portion of the oral care instrument is optimized. Further, those skilled in the art will appreciate that there are numerous variations and permutations of the above described systems and techniques. It is to be understood that other embodiments may be utilized and structural and functional modifications may be made without departing from the scope of the present invention.
Claims (15)
- An oral care instrument comprising:at least one oral care agent; anda wear indicator.
- The oral care instrument of claim 1, wherein the wear indicator visually communicates the existence of the at least one oral care agent.
- The oral care instrument of claim 1, wherein said wear indicator includes a first layer and a second layer, the second layer having a portion that becomes exposed, and wherein one of said layers comprises the at least one oral care agent.
- The oral care instrument of claim 3, wherein said second layer includes a material having cavities that comprise said at least one oral care agent;
optionally wherein said material also forms at least a portion of a head of said oral care instrument. - The oral care instrument of claim 3, wherein said second layer is removably secured to a portion of a head of said oral care instrument;
optionally wherein said second layer is secured within a recessed portion of said head. - The oral care instrument of claim 1, wherein said wear indicator comprises a plurality of different materials that, when in contact, indicate that the at least one oral care agent is depleted;
optionally further comprising a first layer that acts as a barrier between the plurality of different materials that wears away to allow the plurality of different materials to contact. - The oral care instrument of claim 1, further comprising a rupturable element on at least one surface of the oral care instrument, said rupturable element comprising the least one oral care agent.
- The oral care instrument of claim 1, further comprising a head having a plurality externally open cavities that comprise the at least one oral care agent.
- The oral care instrument of claim 8, wherein a first of said cavities comprises a first oral care agent and a second of said cavities comprises a second oral care agent, said first oral care agent being different from said second oral care agent;
optionally wherein said first oral care agent is dispensed at a first rate and said second oral care agent is dispensed at a second rate that is different from said first rate. - The oral care instrument of claim 8, wherein at least one of said cavities comprises a first oral care agent arranged relative to a second oral care agent such that said first oral care agent is proximate an outer surface of said head relative to said second oral care agent;
or wherein at least one of said cavities comprises a first oral care agent and a second oral care agent such that both said first and second oral care agents are substantially simultaneously exposed to an outer surface of said head. - The oral care instrument of claim 1, further comprising a head having a plurality of cavities, and wherein said cavities include additional oral care agents that are dispensed at different rates.
- The oral care instrument of claim 1, comprising:a head, at least a portion of said head including the at least one oral care agent.
- The oral care instrument of claim 12, wherein said wear indicator comprises a first layer and a second layer that is chemically or mechanically altered to expose said first layer
- The oral care instrument of claim 13, wherein said first layer indicates when the oral care instrument should be discarded or recharged with additional oral care agents;
or wherein at least one of said layers includes an oral care agent;
or wherein said first layer is secured to the head. - The oral care instrument of claim 12, wherein said at least one oral care agent is provided in a removable member secured to the head.
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Application Number | Priority Date | Filing Date | Title |
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US71155705P | 2005-08-26 | 2005-08-26 | |
EP06789969.0A EP1924169B1 (en) | 2005-08-26 | 2006-08-24 | Oral care instrument including an oral care agent |
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Application Number | Title | Priority Date | Filing Date |
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EP06789969.0 Division | 2006-08-24 | ||
EP06789969.0A Division EP1924169B1 (en) | 2005-08-26 | 2006-08-24 | Oral care instrument including an oral care agent |
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EP2529643A1 true EP2529643A1 (en) | 2012-12-05 |
EP2529643B1 EP2529643B1 (en) | 2016-11-30 |
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Application Number | Title | Priority Date | Filing Date |
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EP06789969.0A Active EP1924169B1 (en) | 2005-08-26 | 2006-08-24 | Oral care instrument including an oral care agent |
EP12182542.6A Not-in-force EP2529643B1 (en) | 2005-08-26 | 2006-08-24 | Oral care instrument including an oral care agent and a wear indicator |
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Application Number | Title | Priority Date | Filing Date |
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EP06789969.0A Active EP1924169B1 (en) | 2005-08-26 | 2006-08-24 | Oral care instrument including an oral care agent |
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EP (2) | EP1924169B1 (en) |
KR (1) | KR100979832B1 (en) |
CN (1) | CN101299944B (en) |
AU (2) | AU2006283081B2 (en) |
BR (1) | BRPI0615130A2 (en) |
CA (3) | CA2742129C (en) |
ES (1) | ES2441041T3 (en) |
HK (1) | HK1115038A1 (en) |
MX (2) | MX344589B (en) |
MY (1) | MY146561A (en) |
RU (3) | RU2376917C1 (en) |
TW (1) | TWI412340B (en) |
WO (1) | WO2007025012A1 (en) |
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DE102007061607A1 (en) | 2007-12-18 | 2009-06-25 | Carl Freudenberg Kg | cleaner |
MX370239B (en) * | 2008-05-06 | 2019-12-06 | Colgate Palmolive Co | Implement having a reaction and delivery system. |
MY159356A (en) * | 2008-06-04 | 2016-12-30 | Colgate Palmolive Co | Oral care implement with cavitation system |
US8202230B2 (en) * | 2009-08-20 | 2012-06-19 | Colgate-Palmolive Company | Oral care implement having a liquid collection system |
CN102665483B (en) * | 2009-09-16 | 2015-08-12 | 高露洁-棕榄公司 | Oral care systems, external member and method |
WO2011140346A1 (en) * | 2010-05-07 | 2011-11-10 | The Gillette Company | Toothbrush |
WO2019104288A1 (en) | 2017-11-27 | 2019-05-31 | Colgate-Palmolive Company | Oral care implement |
EP3886994A1 (en) | 2018-11-27 | 2021-10-06 | Colgate-Palmolive Company | Oral care implement having a release component |
US11607033B2 (en) | 2019-01-22 | 2023-03-21 | Colgate-Palmolive Company | Whitening system |
US11051606B2 (en) * | 2019-06-28 | 2021-07-06 | Colgate-Palmolive Company | Oral care implement and method of assembling the same |
CN115251562A (en) * | 2022-08-19 | 2022-11-01 | 好来化工(中山)有限公司 | Tooth brush |
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US5340581A (en) * | 1991-08-23 | 1994-08-23 | Gillette Canada, Inc. | Sustained-release matrices for dental application |
WO2004021914A2 (en) * | 2002-09-05 | 2004-03-18 | Colgate-Palmolive Company | Disposable toothbrush |
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US5061106A (en) * | 1988-03-08 | 1991-10-29 | Colgate-Palmolive Company | Toothbrush with slow release of disinfectant and antibacterial agents and method of manufacturing the same |
WO1990008488A1 (en) * | 1989-01-26 | 1990-08-09 | Inroel, Comunidad De Bienes | Tooth-brush |
CN1046272A (en) * | 1989-04-15 | 1990-10-24 | 株式会社三木 | Toothbrush |
EP0600004B1 (en) * | 1991-08-23 | 1998-12-02 | The Gillette Company | Sustained-release martrices for dental application |
IT1261302B (en) * | 1992-02-07 | 1996-05-14 | TOOTHBRUSH | |
US6085379A (en) * | 1998-11-16 | 2000-07-11 | Stafford; Bryan Wynn | Mouthbrush adapted for use with liquid cleanser paste |
US6331088B2 (en) * | 1999-09-16 | 2001-12-18 | Zena Elizabeth Owens | Toothbrush with multiple pumping systems |
DE10212701B4 (en) * | 2002-03-21 | 2015-05-13 | Geka Gmbh | Bristle, method and device for its manufacture, and bristles |
AU2002249575A1 (en) * | 2002-04-11 | 2003-10-20 | Chafflose Corporation | Tooth brush |
-
2006
- 2006-08-24 ES ES06789969.0T patent/ES2441041T3/en active Active
- 2006-08-24 AU AU2006283081A patent/AU2006283081B2/en not_active Ceased
- 2006-08-24 KR KR1020087007320A patent/KR100979832B1/en not_active IP Right Cessation
- 2006-08-24 RU RU2008111502/12A patent/RU2376917C1/en not_active IP Right Cessation
- 2006-08-24 CA CA 2742129 patent/CA2742129C/en not_active Expired - Fee Related
- 2006-08-24 CN CN200680040423XA patent/CN101299944B/en not_active Expired - Fee Related
- 2006-08-24 RU RU2009133035/12A patent/RU2517554C2/en not_active IP Right Cessation
- 2006-08-24 RU RU2013156598/12A patent/RU2567680C2/en not_active IP Right Cessation
- 2006-08-24 EP EP06789969.0A patent/EP1924169B1/en active Active
- 2006-08-24 BR BRPI0615130-2A patent/BRPI0615130A2/en not_active IP Right Cessation
- 2006-08-24 CA CA2620057A patent/CA2620057C/en not_active Expired - Fee Related
- 2006-08-24 MX MX2012004500A patent/MX344589B/en unknown
- 2006-08-24 EP EP12182542.6A patent/EP2529643B1/en not_active Not-in-force
- 2006-08-24 WO PCT/US2006/033021 patent/WO2007025012A1/en active Application Filing
- 2006-08-24 MY MYPI20080332A patent/MY146561A/en unknown
- 2006-08-24 MX MX2008002465A patent/MX2008002465A/en active IP Right Grant
- 2006-08-24 CA CA2854080A patent/CA2854080A1/en not_active Abandoned
- 2006-08-25 TW TW095131227A patent/TWI412340B/en not_active IP Right Cessation
-
2008
- 2008-09-23 HK HK08110534.4A patent/HK1115038A1/en not_active IP Right Cessation
-
2010
- 2010-10-13 AU AU2010231393A patent/AU2010231393B2/en not_active Ceased
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US3491396A (en) * | 1966-01-12 | 1970-01-27 | Joseph M Eannarino | Toothbrush |
US5340581A (en) * | 1991-08-23 | 1994-08-23 | Gillette Canada, Inc. | Sustained-release matrices for dental application |
WO2004021914A2 (en) * | 2002-09-05 | 2004-03-18 | Colgate-Palmolive Company | Disposable toothbrush |
Also Published As
Publication number | Publication date |
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RU2567680C2 (en) | 2015-11-10 |
RU2009133035A (en) | 2011-03-10 |
CA2620057C (en) | 2011-08-23 |
AU2010231393B2 (en) | 2013-02-07 |
KR20080041718A (en) | 2008-05-13 |
AU2006283081B2 (en) | 2010-07-15 |
AU2010231393A1 (en) | 2010-11-04 |
TWI412340B (en) | 2013-10-21 |
MY146561A (en) | 2012-08-30 |
CN101299944B (en) | 2010-09-01 |
MX344589B (en) | 2016-12-20 |
AU2006283081A1 (en) | 2007-03-01 |
ES2441041T3 (en) | 2014-01-31 |
KR100979832B1 (en) | 2010-09-02 |
CA2854080A1 (en) | 2007-03-01 |
MX2008002465A (en) | 2008-04-07 |
TW200727819A (en) | 2007-08-01 |
CA2742129C (en) | 2015-03-31 |
CA2620057A1 (en) | 2007-03-01 |
HK1115038A1 (en) | 2008-11-21 |
CN101299944A (en) | 2008-11-05 |
CA2742129A1 (en) | 2007-03-01 |
RU2008111502A (en) | 2009-10-10 |
RU2376917C1 (en) | 2009-12-27 |
EP1924169B1 (en) | 2013-10-23 |
BRPI0615130A2 (en) | 2013-01-01 |
RU2013156598A (en) | 2015-04-10 |
RU2517554C2 (en) | 2014-05-27 |
EP1924169A1 (en) | 2008-05-28 |
WO2007025012A1 (en) | 2007-03-01 |
EP2529643B1 (en) | 2016-11-30 |
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