WO2002078646A1 - Compositions dentaires - Google Patents

Compositions dentaires Download PDF

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Publication number
WO2002078646A1
WO2002078646A1 PCT/US2001/046526 US0146526W WO02078646A1 WO 2002078646 A1 WO2002078646 A1 WO 2002078646A1 US 0146526 W US0146526 W US 0146526W WO 02078646 A1 WO02078646 A1 WO 02078646A1
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WIPO (PCT)
Prior art keywords
composition
methacrylate
acrylate
bioactive
calcium
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Application number
PCT/US2001/046526
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English (en)
Inventor
Weitao Jia
Shuhua Jin
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Pentron Corporation
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Publication of WO2002078646A1 publication Critical patent/WO2002078646A1/fr

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
    • A61L27/44—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
    • A61L27/446—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix with other specific inorganic fillers other than those covered by A61L27/443 or A61L27/46
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/50—Preparations specially adapted for dental root treatment
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/50—Preparations specially adapted for dental root treatment
    • A61K6/54—Filling; Sealing
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/70—Preparations for dentistry comprising inorganic additives
    • A61K6/71—Fillers
    • A61K6/74—Fillers comprising phosphorus-containing compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/70—Preparations for dentistry comprising inorganic additives
    • A61K6/71—Fillers
    • A61K6/77—Glass
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
    • A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
    • A61K6/887—Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
    • A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
    • A61K6/891—Compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L24/00—Surgical adhesives or cements; Adhesives for colostomy devices
    • A61L24/04—Surgical adhesives or cements; Adhesives for colostomy devices containing macromolecular materials
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
    • A61L27/44—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
    • A61L27/46—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix with phosphorus-containing inorganic fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/02—Homopolymers or copolymers of unsaturated alcohols
    • C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2430/00—Materials or treatment for tissue regeneration
    • A61L2430/12—Materials or treatment for tissue regeneration for dental implants or prostheses

Definitions

  • This invention relates to dental and medical compositions.
  • this invention relates to dental/medical compositions comprising degradable copolymers that are suitable for use as root canal sealants, root canal filling materials, dental restorative materials, implant materials, bone cements and pulp capping materials.
  • Endodontic therapy for a diseased or otherwise compromised tooth generally involves the dental practitioner accessing the root canal, debriding and disinfecting the root canal to clean and remove all ofthe soft tissue (the pulp) therein, and then enlarging the canal to remove irregularities or rough surfaces within the canal.
  • a pre-formed "cone” or “point” is then inserted into the canal, and the cone is laterally or vertically condensed into the canal so that the point ofthe cone terminates at the apex ofthe canal.
  • a commonly used cone material is gutta percha, which is a thermoplastic rubber.
  • U.S. Patent No. 4,449,938 discloses use of a two-component, room temperature setting organopolysiloxane compositions used for dental impression materials.
  • the most commonly used root canal sealants remain compositions comprising a mixture of zinc oxide with eugenol (ZOE), and mixtures comprising calcium hydroxide.
  • ZOE in particular is irritating to some patients, and has low adhesion to the walls ofthe root canal.
  • Root canal sealants should be non-toxic, non- irritating, radiopaque, and have no or minimal shrinkage. They should also set within a reasonable period of time.
  • Pulp capping compounds must be biologically compatible with tooth structure, and are preferably inert to moisture and to the pH conditions found in the mouth. Ideal preparations have low viscosity to facilitate insertion into the root canal, and even more preferably, are thixotropic. In the case of overflow of root canal sealant from the apex into the surrounding tissue or structure during a filling process, the overflowed excess should be desirably absorbed by the surrounding body tissue and cause tissue growth and recovery. h contrast to endodontic procedures, in certain other dental procedures the pulp ofthe tooth is left intact. Where the pulp is exposed, a "pulp capping" compound is required which will preserve the vitality ofthe pulp. Pulp capping compounds must also be non-toxic, and cannot result in any irritation to the pulp.
  • Ideal pulp capping compounds also allow for regrowth ofthe surrounding tissue and dentine.
  • Calcium hydroxide-based pulp capping compounds are therefore common, as described in U.S. Patent No. 3,047,400, and in U.S. Patent No. 4,240,832, which discloses use of condensates of alkyl salicylates with aldehydes reacted with calcium hydroxide or calcium oxide.
  • pulp capping materials which are biocompatible, non-toxic, and which have advantageous handling properties.
  • Bioative glass compositions have been proven effective in activating tissue and bone regrowth.
  • Commercially available materials marketed under BioGlass®, PeroGlasTM and NovaBoneTM trademarks available from USBiomaterials Corporation are supplied in the form of particulates. Although these products have been shown to activate growth of tissue, the applications for the products are limited due to the nature ofthe particulates. The particulates can only be used for certain applications, such as filling-type applications where no near-term stress or pressure is present.
  • U.S. Patent No. 6,051,247 to Hench et al. is directed to moldable bioactive compositions comprising a bioactive material in combination with a polysaccharide. The compositions are moldable, but do not cure to hardened form. Accordingly, the compositions are not useful as solid-forming materials that provide strength to the area of application. There remains a need to provide bioactive materials for dental and medical applications in compositions that can provide strength and integrity to the area of application.
  • compositions comprising degradable macromonomers having biodegradable segments selected from the group consisting of poly(lactide), poly(glycolide), and poly(caprolactone), together with terminal acrylate or methacrylate functionality, a curing composition, a filler composition comprising bioactive particles of bioactive glass, bioactive glass-ceramics, bioactive calcium phosphates, bioactive calcium apatites, or mixtures thereof, and optionally a co-polymerizable acrylate or methacrylate monomer.
  • Degradable macromonomers are manufactured by the polymerization of cyclic lactide, glycolide, or caprolactone in the presence of a compound having at least one active hydrogen and at least one acrylate or methacrylate functionality.
  • Preferred active hydrogen containing acrylate or methacrylate compounds comprise 2-hydroxyethyl methacrylate, hydroxypolyethyl methacrylate, phenoxy-2-hydroxypropyl methacrylate, and the like.
  • Preferred co- polymerizable acrylate or methacrylate monomers include diluent monomers such as 1,6- hexanediol dimethacrylate, triethylene glycol trimethacrylate, and 2-hydroxyethyl methacrylate.
  • Degradable macromonomers can also be manufactured by the esterification of hydroxyl-group(s) terminated macromonomers ofthe above-mentioned hydroxy acids with acrylic acid, methacrylic acid and their derivatives.
  • a degradable macromonomer means degradation by means of hydrolysis and/or biodegradation.
  • the bioactive particles in the filler composition are characterized by their ability to firmly attach to living tissues, to promote tissue growth and to bond chemically with bone. It has been shown that tissue bonds to bioactive glass due to formation of a Si-gel layer on the bioactive particles.
  • Bioactive particles can be made in the form of powder, granules, blocks and plates of different sizes and shapes.
  • the present compositions are expected to be biocompatible and biodegradable, which advantageously allows for tissue and bone regrowth.
  • the degradable macromonomer/bioactive filler compositions therefore find particular utility as root canal sealants, implant materials, bone cements and as pulp capping compositions.
  • the present compositions comprise degradable macromonomers having terminal acrylate or methacrylate groups, a curing agent, a filler comprising bioactive particles and optionally one or more co-polymerizable acrylate or methacrylate monomer.
  • the degradable macromonomer compositions may further comprise additional organic or inorganic fillers and a radiopacity-imparting agent.
  • Degradable macromonomers having terminal acrylate or methacrylate groups are obtained by the polymerization and copolymerization of lactide, glycolide or caprolactone in the presence of a compound having at least one active hydrogen, such as an amine or a hydroxyl group, and at least one acrylate or methacrylate functionality.
  • Such compounds include but are not limited to hydroxyalkyl acrylates and methacrylates wherein the alkyl group has from 1 to 12 carbons, such as 2-hydroxyethyl methacrylate (HEMA), 2- hydroxyethyl acrylate, diethylene glycol monomethacrylate, diethylene glycol monoacrylate, hydroxypropyl methacrylate, hydroxypropyl acrylate, tetraethyleneglycol monomethacrylate, terraethyleneglycol monoacrylate, pentaethyleneglycol monomethacrylate, pentaethyleneglycol monoacrylate, dipropyleneglycol monomethacrylate, dipropyleneglycol monoacrylate, hydroxy polyethyl methacrylates, phenoxyhydroxyphenyl methacrylate and the like.
  • HEMA 2-hydroxyethyl methacrylate
  • 2- hydroxyethyl acrylate diethylene glycol monomethacrylate
  • diethylene glycol monoacrylate hydroxypropyl methacrylate
  • HEMA is preferred.
  • Degradable macromonomers having terminal acrylate or methacrylate groups can also be manufactured by the esterification of hydroxyl-group(s) terminated macromonomers ofthe above mentioned hydroxy acids with acrylic acid, methacrylic acid and their derivatives.
  • Lactide is the cyclic di er of lactic acid, and is available as both L-lactide ((3S)-cis- 3,6-dimethyl-l,4-dioxane-2,5-dione) and D,L-lactide (3,6-dimethyl-l,4-dioxane-2,5-dione).
  • HEMA poly(lactide-HEMA)
  • Another preferred degradable macromonomer is commercially available 2- (caprolactone)ethyl methacrylate (CLMA).
  • the optional co-polymerizable acrylate or methacrylate monomer is selected from those known for use as dental materials, and is typically present in amounts in the range from 0 % to 95% by weight ofthe total composition.
  • Multi-functional, diluent, i.e., low viscosity monomers are preferred. Such monomers provide crosslinking and allow the viscosity ofthe composition to be adjusted for easy delivery to the root canal, while maintaining advantageous physical properties ofthe polymerized product.
  • Exemplary diluent monomers include but are not limited to liquid dimethacrylate, trimethacrylate, or higher monomers, such as glycerol dimethacrylate, ethylene glycol dimethacrylate, tri(ethylene glycol) dimethacrylate (hereinafter TEGDMA), tetra(methylene glycol) dimethacrylate, trimethylolpropane trimethacrylate, 1,6-hexanediol dimethacrylate (hereinafter HDDMA), 2- hydroxyethyl acrylate and 1,3-butanediol dimethacrylate.
  • TEGDMA tri(ethylene glycol) dimethacrylate
  • HDDMA 1,6-hexanediol dimethacrylate
  • 2- hydroxyethyl acrylate and 1,3-butanediol dimethacrylate are characterized by relatively low molecular weight (e.g., 400 or less) and low viscosity.
  • Other monomers may be used in combination with the foregoing co-polymerizable monomers, including viscous methacrylate-based monomers such as 2,2'-bis [4-(2-hydroxy- 3-methacryloxypropoxy)phenyl] propane (hereinafter "Bis-GMA") as described in U.S. Patent No. 3,066,112 to Bowen, which is incorporated by reference herein, or non- hydroxylated resins such as urethane dimethacrylate (hereinafter "UDMA”), or alkylated hydroxyl-containing resins such as ethoxylated bisphenol A dimethacrylate (hereinafter
  • the filler composition comprises bioactive particles of a bioactive glass, bioactive glass-ceramics, bioactive calcium phosphates, e.g., tricalcium phosphate, bioactive calcium apatites, e.g., hydroxylapatite, or mixtures thereof.
  • bioactive glasses are typically silicon dioxide containing compositions capable of forming hydroxyapatite when exposed to physiological fluids. Examples of bioactive glasses include those taught in U.S. Patent Nos.
  • Typical bioactive glass compositions may comprise by weight about 40 to about 90 % SiO 2 , about 4 to about 45 % CaO, 0 to about 10 % Na 2 O, about 2 to aboutl ⁇ % P 2 O 5 , 0 to about 25 % CaF 2 , 0 to about 4 % B 2 O 3 , 0 to about 8 % 2 O and 0 to about 5 % MgO, as taught in the US Patent No. 6, 171 ,986, which is hereby incorporated by reference.
  • bioactive materials useful herein include BioGlass®, PeroGlasTM and NovaBoneTM materials, all available from USBiomaterials Corporation.
  • the bioactive filler material undergoes chemical reactions at the interface between tissues and the polymerizable dental restorative material herein containing the bioactive filler material.
  • the degradation ofthe macromonomers described herein allows the reaction between the tissues and the bioactive filler material to occur.
  • the important aspect of this invention lies in the realization that the polymerizable macromonomers taught herein can be cured (as discussed below) to a sufficient hardness to support stress and strain from the forces generated during functions of the surrounding tissues, while simultaneously degrading to allow the bioactive material to interact with the surrounding tissues and regrow or repair the tissues that have been destroyed or damaged.
  • the bioactive filler has a particle size in the range of from about 0.5 micron to about 1000 microns, and preferably in the range of from about 1 micron to about 500 microns, and most preferably in the range of from about 2 microns to about 200 microns.
  • the filler may be present in an amount of about 5 to 90 percent by weight ofthe polymerizable dental composition, and preferably in an amount of about 10 to about 80 % by weight ofthe polymerizable dental composition, and most preferably in an amount of about 20 to about 70 % by weight ofthe polymerizable dental composition.
  • the filler composition may further comprise additional inorganic calcium-containing fillers that are not bioactive.
  • the inorganic calcium-containing fillers comprise at least about 5%, preferably at least about 25%, and most preferably at least about 50% by weight ofthe total composition, and no more than about 90% by weight ofthe composition.
  • Suitable inorganic calcium-containing fillers are particulate, having the same dimensions described above, and may be, for example, calcium hydroxide, calcium phosphates, tricalcium phosphate, calcium oxide, or mixtures comprising at least one ofthe foregoing inorganic calcium-containing compounds.
  • Other nonbioactive fillers known in the art may also be present.
  • inorganic and organic particulates and fibrous fillers known in the art, such as particulate poly(lactide), poly(glycolide), poly(lactide-c ⁇ -glycolide) or poly(methacrylate), or particulate or fibrous silica, silicate glass, quartz, barium silicate, strontium silicate, barium borosilicate, str
  • Particularly suitable fillers are those having a particle size from about 0.1 to about 5.0 microns, together with a fumed silica of 0.001 to about 0.07 microns and prepared by a series of milling steps comprising wet milling in an aqueous medium, surface etch milling and silanizing milling in a silane solution.
  • Some ofthe aforementioned inorganic filling materials are disclosed in commonly-assigned U.S. Patent Nos. 4,544,359 and No. 4,547,531 to Waknine, the pertinent portions of which are incorporated herein by reference.
  • radiopaque/high refractive index materials such as apatites
  • Suitable high refractive index filler materials include, but are not limited to, high refractive index silica glass fillers.
  • inert, non-toxic radiopaque materials such as barium sulfate and bismuth subcarbonate may be included.
  • the relative amounts of additional filler and radiopaque/high refractive index materials are readily determined by those of ordinary skill in the art, depending on the particular fillers used, the intended application, the desired final properties (e.g., hardness and radiopacity), and the like.
  • the acrylate- or methacrylate-terminated degradable macromonomer compositions further comprise a curing composition.
  • Suitable curing compositions for use with acrylate or methacrylate-based monomers are known in the art, and may be light cure, heat-cure, or a self cure system, or a combination thereof. Use of a dual-cure system and optional accelerators yields a composition that cures evenly and completely.
  • the light cure system is selected from known light-activated polymerization initiators, including but not being limited to benzil, benzoin, benzoin methyl ether, DL- camphorquinone (CQ) and benzil diketones. Either UN-activated cure or visible light- activated cure (approx. 230 to 750 nm) is acceptable.
  • the amount of photoinitiator is selected according to the curing rate desired. A minimally catalytically effective amount is generally about 0.01% by weight ofthe polymeric components, and will lead to a slower cure. Faster rates of cure are achieved with amounts of catalyst in the range from greater than about 0.01% to about 5 % by weight ofthe polymeric component.
  • the heat-cure initiator is selected from those known in the art such as benzoyl peroxide, lauroyl peroxide, dicumyl peroxide, l,r-azobis(cyclohexanecarbonitrile), or other free radical initiators.
  • the amount of free-radical catalyst is selected according to the curing rate desired. A minimally catalytically effective amount is generally about 0.5% by weight of the polymeric components, and will lead to a slower cure. Faster rates of cure are achieved with amounts of catalyst in the range from above about 0.5% to about 6.0 % by weight ofthe polymeric component.
  • the heat-cure initiator is activated by the heat of reaction generated by the light-activated polymerization process.
  • compositions may be supplied to the practitioner pre-mixed, that is, as a single- component mixture ready for application to the site of restoration.
  • the composition is supplied in pre-packaged syringes, compules, or cartridges.
  • the compositions with a heat-cure initiator or the combination of heat and light cured initiators allow the material to be pre-cured and formed into a hardened block. Subsequent machining or CAD/CAM processing of the block to form a desired shape, such as the shape of an implant device, can then be performed.
  • the compositions having light cure and/or self- cure initiators allow the materials to be prepared and supplied to the practitioner for application at the site of restoration.
  • the compositions can be applied and cured either by light, or mixed, applied and self-cured. In this way, the compositions can be cured in situ, providing instant strength to the restoration.
  • Optional cure accelerators may further be included in the light curing composition.
  • Polymerization accelerators are the various organic tertiary amines well known in the art.
  • the tertiary amines are generally acrylate derivatives such as 2- (diethylamino)ethyl methacrylate (commonly known as "DEAEMA”) and 2- (dimethylamino)ethyl methacrylate, in amounts in the range from about 0.1 to about 1.0 percent by weight ofthe polymeric composition.
  • DEAEMA diethylaminoethyl methacrylate
  • 2- (dimethylamino)ethyl methacrylate in amounts in the range from about 0.1 to about 1.0 percent by weight ofthe polymeric composition.
  • the composition may be formulated with as a self-curing two-part system which is stored separately and mixed in equal amounts prior to use to initiate cure.
  • Self-cure systems comprise an initiator such as a peroxide in one part, and an accelerator such as a tertiary amine, generally tertiary aromatic amines such as ethyl 4- (dimethylamino)benzoate (commonly known as ⁇ DMAB”), 2-[4-(dimethylamino)phenyl] ethanol, N, N-dimethyl-p-toluidine (DMPT), bis(hydroxyethyl)-p-toluidine, and triethanolamine in a second part.
  • an initiator such as a peroxide in one part
  • an accelerator such as a tertiary amine, generally tertiary aromatic amines such as ethyl 4- (dimethylamino)benzoate (commonly known as ⁇ DMAB”), 2-[4-(di
  • Such accelerators are generally present in the range from about 0.5 to about 4.0 % by weight ofthe polymeric component.
  • Another self-curing system comprises thiourea or thiourea derivatives as the reductant and hydrogen peroxide as the oxidant, as described in U.S. Pat. No. 3,991,008.
  • Both parts generally comprise the degradable macromonomer, co-polymerizable acrylate or methacrylate monomer, and filler in various amounts, with the initiator, for example dibenzoyl peroxide (BPO), being stored in one part, and the accelerator, e.g., N,N-dihydroxyethyl-p-toluidine being stored in another part. Equal amounts of part A and Part B are mixed by the doctor or technician immediately prior to use.
  • BPO dibenzoyl peroxide
  • compositions may further comprise anti-oxidants, for example BHT (2,6-di-tert- butyl-4-methylphenol) or hydroquinone methyl ether in amounts in the range from about 0.1 to about 0.3% by weight ofthe polymerizable components; ultraviolet stabilizers to prevent discoloration, for example benzophenones such as 2-hydroxy-4-methoxybenzophenone, benzotriazoles, such as 2-(2'-hydroxy-5'-methylphenyl) benzotriazole, 2-(2-hydroxy-5-tert- octylphenyl) benzotriazole (available under the trade name UN-54 from American Cyanamid Company) and other derivatives thereof; fluorescent whitening agents such as 2,5-bis(5-tert- butyl-2-benzoxazole) thiophene (available under the trade name UN-OB); trace amounts of FDA and FDC approved dyes, for example iron oxides, yellow No. 5, yellow No. 6, and the like; and other additives known in the art.
  • BHT 2,
  • Medicaments may also be included in the compositions in an amount effective to prevent infection and/or inflammation, generally from about 1% to about 10% by weight of the total composition.
  • Suitable medicaments include but are not limited to pain relieving agents such as Novocaine (procaine hydrochloride), Benzocain (ethyl aminobenzoate), ascorbic acid, butacaine sulfonate, dibutacaine hydrochloride, anti-biotics such as sulfadiazine, procaine penicillin, aureomycin, streptomycin, terramycin, chloramphenicol, butabarbital, diethyl stilbestrol, and anti-inflammation agents such as p-aminosalicylic acid, aspirin, and the like.
  • pain relieving agents such as Novocaine (procaine hydrochloride), Benzocain (ethyl aminobenzoate), ascorbic acid, butacaine sulfonate, dibutacaine hydrochloride, anti-
  • a method of restoring a tooth comprises preparing a site on a tooth to be restored; and applying a composition comprising (a) at least one degradable macromonomer having terminal acrylate or methacrylate groups; (b) a curing composition; (c) a filler composition comprising bioactive particles; and (d) optionally one or more co- polymerizable acrylate or methacrylate monomers.
  • the site to be restored is a root canal.
  • Another preferred embodiment ofthe present invention is a method of repairing a bone comprising preparing a site to be restored in a portion of a bone; and applying a composition comprising (a) at least one degradable macromonomer having terminal acrylate or methacrylate groups; (b) a curing composition; (c) a filler composition comprising bioactive particles; and (d) optionally one or more co-polymerizable acrylate or methacrylate monomers.
  • the present invention is preferable to the currently available art for root canal sealants, implant materials, bone cements, and pulp capping compositions because the compositions ofthe present invention are expected to be non-toxic, biodegradable and biocompatible. These properties are ideal for tissue regrowth in the surrounding tissue and dentine when the compositions are used in pulp capping procedures or root canal procedures. Also, the present compositions have low shrinkage, which is required for use as root canal sealants.
  • the degradation of cured PLAMA/TEGDMA for varying quantities of PLAMA was studied in a buffer solution of pH 7 over time.
  • the curing of PLAMA/TEGDMA was performed in a light box for 2 minutes using a curing composition comprising 0.2% by weight CQ and 0.2% by weight DEAEMA.
  • PLAMA and TEGDMA were mixed to give various weight percents (based on the total resin composition) of PLAMA in accordance with Table 1 below.
  • the amount of TEGDMA or other suitable crosslinker/diluent resin can also be varied according to the viscosity and molecular weight ofthe PLAMA used.
  • the samples were prepared as 1 mm thick disks, weighed to determine the original weight, and immersed in pH 7 buffer and then stored at 37°C. The samples were removed from the solution monthly, oven-dried, and weighed to determine degradation, as reflected by weight loss. Weight loss is calculated by subtracting the dried weight from the original weight, and dividing that amount by the original weight. Results are shown in Table 1.
  • Self-curing formulations of 70/30 by weight PLAMA/TEGDMA compositions comprising organic and/or inorganic fillers were studied, using a two-part formulation.
  • the inorganic fillers are BaSO 4 and tricalcium phosphate (TCP).
  • TCP tricalcium phosphate
  • An exemplary formula is shown in Table 3. When equal parts ofthe base and catalyst formulation are mixed, this formula has a viscosity suitable for root canal sealants and for pulp capping.
  • Example 3 above was tested for degradation using the method of Example 1. Results are shown in Table 4.
  • Example 6 Degradation of Example 5.
  • Example 5 was tested for degradation using the method of Example 1. Results are shown in Table 6.
  • the monomers used in this formulation are 70/30 PLAMA/TEGMA.
  • Example 9 Physical Properties of Dual Curable Paste-Paste Two-Part Compositions.
  • Paste-paste formulations containing Bioglass filler were evaluated for flexural strength and weight loss.
  • the following Table 8 shows base and catalyst components for two-part compositions.
  • the base and catalysts set forth in Table 8 were mixed in ratios of 1 : 1 by volume, which was performed by using a dual-barrel cartridge with an auto-mixing tip. The base and catalyst were preloaded into each side of a dual-barrel cartridge, such as that used for Cement-It ® Universal C & B luting cement cartridge, available from Pentron Corporation. As shown in Table 8, Base 1 contains Bioglass and Catalyst 1 contains PLAMA. Base 1 was mixed with Catalyst 1 as the preferred composition. Base 1 was also mixed with Catalyst 2. Base 2 was mixed with Catalyst 1 and Base 2 was mixed with Catalyst 2.
  • Powder-liquid formulations containing PLAMA and Bioglass filler were evaluated for flexural strength and weight loss.
  • the following Table 10 shows liquid and powder compositions for the two-part compositions.
  • the bioactive glass used herein has particle sizes of less than about 200 ⁇ ms and an approximate composition of about 45% SiO 2 , about 24.5% Na 2 O, about 24.5% CaO and about 6% P 2 O 5 by weight as taught in U.S. Patent No. 4,171,544, which is hereby incorporated by reference.
  • the liquid and powders were mixed in ratios of about 1 : 1 by weight on a glass pad with a dental spatula.
  • the mixtures were then self-cured in about five minutes and flexural strengths were measured under dry conditions and after the samples were immersed in water for 24 hours and 168 hours. Weight loss was measured at the end ofthe 168 hour period.
  • Table 11 lists the flexural strength and weight loss ofthe two-component compositions.

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  • Health & Medical Sciences (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Chemical & Material Sciences (AREA)
  • Epidemiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Inorganic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Composite Materials (AREA)
  • Materials Engineering (AREA)
  • Dermatology (AREA)
  • Transplantation (AREA)
  • Plastic & Reconstructive Surgery (AREA)
  • Surgery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Dental Preparations (AREA)

Abstract

L'invention porte sur des compositions durcissables comprenant des macromonomères dégradables possédant une ou plusieurs fonctionnalités terminales acrylate ou méthacrylate, une composition de durcissement, une composition de charge comprenant des particules bioactives de verre bioactif, des céramiques de verre bioactif, des phosphates de calcium, des apatites de calcium ou des mélanges de ceux-ci et éventuellement un ou plusieurs comonomères polymérisables acrylate ou méthacrylate. Les macromonomères dégradables sont fabriqués à partir de monomères cycliques dont les composés ont une fonctionnalité acrylate ou méthacrylate. Selon leur utilisation, les compositions macromonomères dégradables comprennent également une ou plusieurs charges organiques ou inorganiques comprenant un composé à base de calcium et/ou un agent conférant une radio-opacité. Les compositions sont notamment appropriées pour les résines de scellement des canaux des racines, les implants, les ciments osseux et les matériaux de coiffage de la pulpe.
PCT/US2001/046526 2000-12-05 2001-12-05 Compositions dentaires WO2002078646A1 (fr)

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Cited By (9)

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WO2004037214A1 (fr) * 2002-10-24 2004-05-06 Pentron Clinical Technologies, Llc Materiau d'obturation dentaire
WO2006008499A1 (fr) * 2004-07-16 2006-01-26 Drfp Holdings Limited Adhésifs dentaires/chirurgicaux incluant des particules pouvant être mises en forme
EP1621179A1 (fr) * 2004-07-30 2006-02-01 DENTSPLY DETREY GmbH Composition polymérisable durcissable par laser pour la protection d'un tissu dur
WO2007036782A1 (fr) * 2005-09-27 2007-04-05 Council Of Scientific And Industrial Research Macromere de lactide oligomere fonde sur un copolymere et processus de preparation de celui-ci
WO2007036783A1 (fr) * 2005-09-27 2007-04-05 Council Of Scientific And Industrial Research Copolymere sensible au ph de faible poids moleculaire du processus de preparation de celui-ci
CN1331809C (zh) * 2005-11-17 2007-08-15 哈尔滨工业大学 适合口腔cad/cam系统的可切削复合氧化锆陶瓷及其制备方法
US7275933B2 (en) 2000-08-11 2007-10-02 Pentron Clinical Technologies, Llc Method of manufacturing dental restorations
US9492360B2 (en) 2001-10-24 2016-11-15 Pentron Clinical Technologies, Llc Endodontic post and obturator
US10940097B2 (en) 2018-10-18 2021-03-09 Imam Abdulrahman Bin Faisal University Resin composite and restoration containing bioactive glass fillers

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WO1998020839A1 (fr) * 1996-11-13 1998-05-22 Merck Patent Gmbh Produits de polymerisation pouvant etre resorbes biologiquement, constitues de systemes de liants durcissables par rayonnement
US6051247A (en) * 1996-05-30 2000-04-18 University Of Florida Research Foundation, Inc. Moldable bioactive compositions
WO2001012129A1 (fr) * 1999-08-13 2001-02-22 Jeneric/Pentron Incorporated Compositions dentaires comprenant des polymeres biodegradables

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US4732943A (en) * 1985-04-24 1988-03-22 Commonwealth Scientific And Industrial Research Organization Dental restorative material
WO1996019179A1 (fr) * 1994-12-19 1996-06-27 Dentsply International Inc. Composes et compositions de polymerisation
US6051247A (en) * 1996-05-30 2000-04-18 University Of Florida Research Foundation, Inc. Moldable bioactive compositions
WO1998020839A1 (fr) * 1996-11-13 1998-05-22 Merck Patent Gmbh Produits de polymerisation pouvant etre resorbes biologiquement, constitues de systemes de liants durcissables par rayonnement
WO2001012129A1 (fr) * 1999-08-13 2001-02-22 Jeneric/Pentron Incorporated Compositions dentaires comprenant des polymeres biodegradables

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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7275933B2 (en) 2000-08-11 2007-10-02 Pentron Clinical Technologies, Llc Method of manufacturing dental restorations
US9492360B2 (en) 2001-10-24 2016-11-15 Pentron Clinical Technologies, Llc Endodontic post and obturator
JP4657102B2 (ja) * 2002-10-24 2011-03-23 ペントロン クリニカル テクノロジーズ リミテッド ライアビリティ カンパニー 歯科充填材
JP2006507361A (ja) * 2002-10-24 2006-03-02 ペントロン クリニカル テクノロジーズ リミテッド ライアビリティ カンパニー 歯科充填材
WO2004037214A1 (fr) * 2002-10-24 2004-05-06 Pentron Clinical Technologies, Llc Materiau d'obturation dentaire
WO2006008499A1 (fr) * 2004-07-16 2006-01-26 Drfp Holdings Limited Adhésifs dentaires/chirurgicaux incluant des particules pouvant être mises en forme
AU2005263945B2 (en) * 2004-07-16 2008-08-21 Drfp Holdings Limited Dental/surgical sealants including shapeable particles
JP2008508223A (ja) * 2004-07-30 2008-03-21 デンツプライ デトレイ ゲー．エム．ベー．ハー． レーザー硬化性重合性歯科組成物
WO2006010631A1 (fr) * 2004-07-30 2006-02-02 Dentsply De Trey Gmbh Composition dentaire polymerisable par laser
US8853321B2 (en) 2004-07-30 2014-10-07 Dentsply International Inc. Laser curable polymerisable composition for the protection of hard tissue
EP1621179A1 (fr) * 2004-07-30 2006-02-01 DENTSPLY DETREY GmbH Composition polymérisable durcissable par laser pour la protection d'un tissu dur
WO2007036783A1 (fr) * 2005-09-27 2007-04-05 Council Of Scientific And Industrial Research Copolymere sensible au ph de faible poids moleculaire du processus de preparation de celui-ci
WO2007036782A1 (fr) * 2005-09-27 2007-04-05 Council Of Scientific And Industrial Research Macromere de lactide oligomere fonde sur un copolymere et processus de preparation de celui-ci
CN1331809C (zh) * 2005-11-17 2007-08-15 哈尔滨工业大学 适合口腔cad/cam系统的可切削复合氧化锆陶瓷及其制备方法
US10940097B2 (en) 2018-10-18 2021-03-09 Imam Abdulrahman Bin Faisal University Resin composite and restoration containing bioactive glass fillers

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