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WO2003068174A1 - Amorce de gravure a l'eau forte et resine adhesive de scellement - Google Patents

Amorce de gravure a l'eau forte et resine adhesive de scellement Download PDF

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Publication number
WO2003068174A1
WO2003068174A1 PCT/US2002/004202 US0204202W WO03068174A1 WO 2003068174 A1 WO2003068174 A1 WO 2003068174A1 US 0204202 W US0204202 W US 0204202W WO 03068174 A1 WO03068174 A1 WO 03068174A1
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WO
WIPO (PCT)
Prior art keywords
composition
etching
self
primer
dental
Prior art date
Application number
PCT/US2002/004202
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English (en)
Inventor
Yantong J. Wang
Byoung I. Suh
Martin Hamer
Louis J. Sharp
Aleksandra Strukowska
Original Assignee
Bisco, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bisco, Inc. filed Critical Bisco, Inc.
Priority to AU2002248425A priority Critical patent/AU2002248425A1/en
Priority to PCT/US2002/004202 priority patent/WO2003068174A1/fr
Publication of WO2003068174A1 publication Critical patent/WO2003068174A1/fr

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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/30—Compositions for temporarily or permanently fixing teeth or palates, e.g. primers for dental adhesives

Definitions

  • the present invention relates generally to etchants, primers and adhesive bonding systems and methods. More specifically, the present invention relates to primer compositions that are self-etching, and to simplified adhesive bonding systems using such compositions.
  • the compositions and methods of the present invention enhance the bonding of dental adhesives, composites, and other dental prostheses to dentin, enamel and tooth tissue.
  • the dental restorative is applied to the dental substrate while it is still wet after rinsing with water to remove the etchant and/or primer solution.
  • some of these systems also employ at least two additional primer or adhesive enhancing or bonding compounds which must either (1) be applied separately and sequentially to the dental substrate, (2) must be mixed together by the dental professional in the office immediately before use on the patient to prevent premature polymerization of the components (for example see Bowen U.S. Patents Nos. 4,514,527; 4,551,550; 4,558,756, 4,659,751; 5,320,886; and 5,270,351; Suh U.S.
  • Patent 5,348,988; and Bunker U.S. Patent No. 4,544,467) Such multi-component/multi-step methods necessarily require the dental professional to perform an initial etching step followed by a separate rinsing step as well as a step of admixing of primers and/or primers and initiator while the patient waits in the chair, unnecessarily complicating the overall restorative process and increasing the treatment time for the patient.
  • Such systems generally require the use of an additional component, an adhesive bonding resin, applied as an additional step in the process in order to achieve such high bond strengths, further complicating the restorative process.
  • novel self-etching copolymerizable primer compositions comprising compounds having a polymerizable group or moiety and an acidic group or moiety that permits decalcification of tooth dentin and enamel without substantial interference with polymerization of the other group within self-cure and light-cure dental restorative systems.
  • SEMA sulfobenzoic anhydride- hydroxyethylmethacrylate
  • BA-HEMA sulfobenzoic anhydride- hydroxyethylmethacrylate
  • additional acid(s) optionally additional monomer(s)
  • solvent which can be used in conjunction or combination with an adhesive bonding resin component.
  • Preferred self-etching compositions include one or more of these compounds supplied in a single container or in two containers the contents of which are admixed before application to the dental surface.
  • Such novel self-etching primer compositions according to the present invention promote adhesion between a dental substrate such as dentin or enamel and a dental adhesive, and subsequently applied dental restorative materials, composites or other dental devices in direct and indirect dental techniques employing light-cure and self-cure polymerization protocols.
  • Methods according to the present invention include use of the foregoing novel compositions as a single step for etching and priming and imparting enhanced adhesion between dental substrates and dental adhesives without the need for separate rinsing steps or etching and priming steps.
  • compositions and methods according to the present invention provide for etching of tooth dentin and enamel substrates while providing consistently high bonding strengths between the substrate and adhesives, restoratives or devices.
  • compositions and methods according to the present invention allow light-curing or self-curing of these self-etching copolymerizable primer compositions with an applied dental adhesive and subsequent application of a self-cure, light-cure or dual-cure composite restorative compositions or other dental materials capable of bonding with the primer and adhesive.
  • Certain of the preferred compositions and methods of the present invention exhibit high bond strengths even when packaged together in a single solution and stored over considerable periods of time, permitting formulation of the compositions well in advance of the time of their intended application.
  • the compositions can further comprise one or more antimicrobial agents.
  • Fig. 1 is a SEM (taken at lOOOx magnification) of the dentin surface of a human tooth after sanding with 320 grit paper before application of an etchant.
  • Fig. 2 is a SEM (taken at lOOOx magnification) of the dentin surface of a human tooth sanded as described in reference to Fig. 1 above and after application of a conventional 37% phosphoric acid etchant for 15 sec. and rinsing.
  • Fig. 3 is a SEM (taken at lOOOx magnification) of the dentin surface of a human tooth' sanded as described in reference to Fig. 1 above and after application of a self-etching copolymerizable primer composition with Primer B comprising 30 wt.% AMPS and 10 wt.%> Bis-MEP for 10 sec. with agitation and rinsing. >
  • Fig. 4 is a SEM (taken at lOOOx magnification) of the dentin surface of a human tooth sanded as described in reference to Fig. 1 above and after application of a self-etching copolymerizable primer composition with Primer B comprising 40 wt.% AMPS and 10 wt.% Bis-MEP for 10 sec. with agitation and rinsing.
  • Fig. 5 is a SEM (taken at lOOOx magnification) of the enamel surface of a human tooth sanded with 320 grit paper before application of an etchant.
  • Fig. 6 is a SEM (taken at lOOOx magnification) of the enamel surface of a human tooth sanded as described in reference to Fig. 5 above and after application of a conventional 37% phosphoric acid etchant for 15 sec. and rinsing.
  • Fig. 7 is a SEM (taken at lOOOx magnification) of the enamel surface of a human tooth sanded as described in reference to Fig. 5 above and after application of a self-etching copolymerizable primer composition with Primer B comprising 30 wt.% AMPS and 10 wt.% Bis-MEP for 10 sec. with agitation and rinsing.
  • Fig 8 is a SEM (taken at lOOOx magnification) of the enamel surface of a human tooth sanded as described in reference to Fig. 5 above and after application of a self-etching copolymerizable primer composition with Primer B comprising 40 wt.% AMPS and 10 wt.% Bis-MEP for 10 sec. with agitation and rinsing.
  • Fig. 9 is a SEM (taken at 2000x magnification) of the surface of uncut pumiced human tooth enamel before application of an etchant.
  • Fig. 10 is a SEM (taken at 2000x magnification) of the enamel surface of a human tooth pumiced as described in reference to Fig. 9 above and after application of a conventional 37% phosphoric acid etchant for 15 sec. and rinsing.
  • Fig. 11 is a SEM (taken at 2000x magnification) of the enamel surface of a human tooth pumiced as described in reference to Fig. 9 above and after application of a self-etching copolymerizable primer with Primer B composition comprising 30 wt.% AMPS and 10 wt.% Bis-MEP for 10 sec. with agitation and rinsing.
  • Fig. 12 is a SEM (taken at 2000x magnification) of the enamel surface of a human tooth pumiced as described in reference to Fig. 9 above and after application of a self-etching copolymerizable primer composition with Primer B comprising 38 wt.% AMPS and 10 wt.% ⁇ Bis-MEP for 10 sec. with agitation and rinsing.
  • Fig.13 is a SEM (taken at 2000x magnification) of the enamel surface of a human tooth pumiced as described in reference to Fig. 9 above and after application of a self-etching copolymerizable primer composition with Primer B comprising 40 wt.% AMPS and 10 wt.% Bis-MEP for 10 sec. with agitation and rinsing.
  • Fig. 14 is a SEM (taken at 2000x magnification) of the surface of cross burr cut human tooth enamel before application of an etchant.
  • Fig. 15 is a SEM (taken at 2000x magnification) of the enamel surface of a human tooth cut as described in reference to Fig. 14 above and after application of a conventional 37% phosphoric acid etchant for 15 sec. and rinsing.
  • Fig. 16 is a SEM (taken at 2000x magnification) of the enamel surface of a human tooth cut as described in reference to Fig. 14 above and after application of a self-etching copolymerizable primer composition with Primer B comprising 30 wt.% AMPS and 10 wt.% Bis-MEP for 10 sec. with agitation and rinsing.
  • Fig. 17 is a SEM (taken at 2000x magnification) of the enamel surface of a human tooth cut as described in reference to Fig. 14 above and after application of a self-etching copolymerizable primer composition with Primer B comprising 40 wt.% AMPS and 10 wt.% Bis-MEP for 10 sec. with agitation and rinsing.
  • SEMA polymerizable, hydrophilic, self-etching primer monomer sulfobenzoic anhydride-hydroxyethylmethacrylate
  • SBA-HEMA polymerizable, hydrophilic, self-etching primer monomer sulfobenzoic anhydride-hydroxyethylmethacrylate
  • SBA-HEMA polymerizable, hydrophilic, self-etching primer monomer sulfobenzoic anhydride-hydroxyethylmethacrylate
  • SBA-HEMA polymerizable, hydrophilic, self-etching primer monomer sulfobenzoic anhydride-hydroxyethylmethacrylate
  • 2-HEMA 2-hydroxyethyl methacrylate
  • the components (a), (b), (c) and (d) are selected so that upon mixing of the components, the substantial polymerization of the resin components (a) and (b) results upon contact of the mixture and a self-cure or activated light-cure polymerization initiator.
  • SBA-HEMA The structure of SBA-HEMA is set out below.
  • the self-etching copolymerizable primer compositions according to the invention include a mixture of (a) at least about 0.5 to about 75 wt.% of one or more of the polymerizable self-etching copolymerizable monomer compound(s), more preferably from about 5 to about 70 wt.% and more preferably from about 10 to about 70 wt.% of such compound(s) suspended or dissolved in a suitable solvent.
  • the solvent can generally be any solvent that dissolves or suspends the self-etching primer monomer(s).
  • the solvent can comprise water, ethanol, acetone, or mixtures thereof.
  • the solvent can be mixtures of two or more solvents.
  • the solvent can be a mixture of water and ethanol, a mixture of water and acetone, a mixture of ethanol and acetone, or a mixture of water, ethanol, and acetone.
  • Preferred self-etching compositions according to the present invention include compositions in which AMPS, Bis-MEP and/or SEMA monomers are supplied in a first container suspended or dissolved in a suitable solvent. A second container containing colorant, dye or pH indicator, water and ethanol is also supplied. The contents of these two containers are admixed and the admixture is applied to the tooth structure.
  • Other preferred self-etching compositions include SBA-HEMA supplied in a one component system in a suitable solvent in a single container.
  • Presently preferred self-etching compositions include from about 5 to about 50 wt.% AMPS and from about 5 to about 40 wt.% Bis-MEP suspended and dissolved in a first solvent in a first container, and water, Thymol blue sodium salt and ethanol in a second container.
  • the containers comprising separate compartments of a two compartment delivery system such as "Dip 'N' Mix” made by Dentaco of Bad Homburg, Germany may be used for convenient mixing and dispensing by the dental practitioner.
  • self-etching copolymerizable compositions comprising an antimicrobial agent such .
  • BAC benzalkonium chloride
  • CHXG chlorhexidine gluconate
  • BAC in ranges from about 0.01 wt.% to about 0.5 wt.%
  • chlorhexidine gluconate in ranges from about 0.01 wt.% to about 0.5 wt.% may be added to the compositions.
  • AMPS AMPS 2404
  • Bis- MEP was obtained from Sigma- Aldrich Chemical Company (Milwaukee, WI).
  • SEMA was obtained from Polyscience, Inc. (Warrington, PA).
  • SBA-HEMA was made as disclosed below.
  • Presently preferred optional comonomers according to the present invention include 2-HEMA and other monomers such as hydroxypropyl methacrylate (HPMA) containing one or more functional hydroxy groups and reactive vinyl groups. Such comonomers may be employed to improve handling characteristics of the self-etching copolymerizable composition.
  • HPMA hydroxypropyl methacrylate
  • the comonomers are preferably present in the composition from about 0.5 wt.% to about 50 wt.%, more preferably from about 1 wt.% to about 30 wt.%, and presently most preferably from about 5 wt.% to about 25 wt.% of the total composition.
  • the preferred concentration of such comonomers depends in part on the particular self-etching copolymerizable monomers selected for use in the invention (AMPS, Bis-MEP, SEMA and/or SBA-HEMA, etc.) and solvent(s)' used in the composition.
  • the comonomers of the present invention are preferably intended to promote penetration of the self-etching copolymerizable primer composition into the openings created by abrading or decalcifying (etching) tooth dentin and/or enamel to assist in formation of strong adherence between the self- etching primer and adhesives and the dental substrate.
  • the self-etching comonomers of the present invention decalcify the uncut tooth dentin and enamel substrate and remove the smear layer present on cut dentin or enamel, opening microtubules in the dentin and spaces in the enamel. Those openings may be penetrated by the self-etching copolymerizable primer composition and the applied dental adhesive bonding composition and the primer and adhesive polymerized together upon contact with a supplied self-cure initiator or upon contact with a light cure initiator and activating light source.
  • Preferred methods of the present invention include initially applying a thin layer of the aforesaid preferred self-etching copolymerizable primer composition to tooth dentin and/or enamel substrates as one step of a dental restorative process.
  • the applied, self-etching primer composition is then preferably allowed to etch or decalcify uncut dentin or tooth enamel and remove the smear layer present on cut dentin or tooth enamel substrate, opening microtubules in the dentin and spaces in the enamel, and blot-dried.
  • a light-cure adhesive such as One Step® (OS) or One Step Plus® (OS+) from Bisco, Inc., or a light-cure and self-cure adhesive such as All Bond® 2 from Bisco, Inc.
  • OS One Step®
  • OS+ One Step Plus®
  • All Bond® 2 from Bisco, Inc.
  • a composite such as BIS-FIL® from Bisco, Inc. or other composite or other dental restorative resin, luting composite, or other component may then be applied to the self-etching primer and adhesive composition and preferably bonded to that layer by copolymerization through light-curing or self-curing according to the manufacturer's instructions.
  • compositions of the invention may be used in Class I, II or III, IV, or V direct restorations and in indirect restorations such as inlays, onlays, crowns and luting techniques wherever maximum strength and convenience is desired.
  • direct restorations and in indirect restorations such as inlays, onlays, crowns and luting techniques wherever maximum strength and convenience is desired.
  • indirect restorations such as inlays, onlays, crowns and luting techniques wherever maximum strength and convenience is desired.
  • Step a Extracted human teeth were embedded in resin discs, abraded on the facial surface with a model trimmer, and subsequently abraded with wet 600 or 320 grit SiC paper to create a flat and smooth dentin substrate for bonding. Step b-1 or b-2 was then followed as described below depending on the selected monomer. (Step b-1). SBA-HEMA as self-etching monomer
  • the 600 grit paper was used in this case. 2-3 coats of the chosen self-etching primer composition were applied by brush to the dentin to achieve a uniform layer. -. The dentin surfaces were then allowed to etch for up to 15 seconds by allowing to set on the surface of the dentin or optionally with agitation with the brush. Adhesive was then applied according to step c, below. (Step b-2 . AMPS. SEMA and Bis-MEP as self-etching primer monomerCs
  • the 320 grit paper was used in this case.
  • a drop of the solution containing the self- etching copolymerizable monomer(s) was dispensed into a mixing well after shaking the solution to evenly disperse the primer monomer for monomer(s) supplied in one component systems.
  • a bottle containing Primer B (if the self-etching primer system is two component system) was shaken for 5 sec to bring the slurry to a homogenous state.
  • a drop of Primer A was added to a mixing well and then a drop of Primer B was dispensed into the same well. The components mixed on contact (solution turns violet).
  • the prepared dentin surface was dried with an air syringe for about 3 seconds to remove visible moisture.
  • a sponge pellet or brush was dipped in the well containing the single primer or mixed Primers A and B.
  • One or two coats of the single component solution or of the mixture, an amount sufficient to cover the surface, were applied with 10 seconds agitation.
  • the excess primer was blot dried with a fresh sponge pellet.
  • Adhesive was then applied according to step c, below. (Step c )
  • the etched and primed surface was treated with 2 coats of an adhesive One-
  • Step® (OS), One-Step® Plus (OS+), All Bond® 2 (AB2) or other commercial adhesives identified in the following Tables.
  • the adhesive was air dried, and light cured (LC) or self cured (SC) according to the individual manufacturer's instructions.
  • a #5 gel cap (bonding area 0.1684 cm 2 ) or #9 gel cap (bonding area 0.04757 cm 2 ) was filled with BIS-FIL or the indicated light cure (LC) or self cure (SC) (BIS-FIL2B) composite or cement and placed on the prepared dentin surface.
  • the shear bond strength test to enamel was determined by the above procedure with the exception that the embedded teeth were ground and sanded to expose a layer of enamel surface Uncut Enamel
  • the shear bond strength test to uncut enamel was determined by the above procedure with the following modifications-the teeth were embedded shallow in the acrylic in such way that a desired enamel surface was already exposed.
  • the enamel surface was pumiced with a pumice slurry for 5-10 seconds.
  • the primer mixture was then applied directly to such prepared surface according to the procedure above.
  • Example 1 Preparation and Testing of Single Component Self-Etching Copolymerizable Composition Using SBA-HEMA. AMPS .
  • SEMA and Bis-MEP on both dentin and cut enamel in LC mode
  • SBA-HEMA monomer synthesis The SBA-HEMA monomer was prepared according to the following method. Two moles of sulfobenzoic anhydride (SB A) was weighed into a flask to which was added 2.4 moles of 2-hydroxyethylmethacrylate (HEMA) along with 15 grams of triethylamine. The mixture was stirred and heated at 70-80 °C for one hour, during which time a clear solution resulted. At this time, the infrared spectrum of the product revealed the disappearance of the anhydride absorption bands.
  • SB A sulfobenzoic anhydride
  • HEMA 2-hydroxyethylmethacrylate
  • SA-HEMA monomer synthesis This monomer was prepared according to the procedure used to prepare SBA-HEMA set out above, but the starting anhydride for SA-HEMA is succinic anhydride (SA). Two moles of SA and 2.4 moles of HEMA were used for the synthesis of SA- HEMA monomer according to the SBA-HEMA procedure.
  • SA succinic anhydride
  • SC self cure
  • LC light cure
  • NA not available
  • N/A not applicable
  • SSBS standard shear bond strength test results
  • USBS Ultradent shear bond strength results
  • SBS shear bond strength.
  • Primer A Two component systems comprising a first Primer A solution containing a pH indicator, water and ethanol and a second Primer B solution containing self etching copolymerizable monomer compounds were prepared according to the following general methods, Primer A:
  • compositions according to the present invention were also investigated as follows: 0.5 wt.% of BAC or CHXG antimicrobial agent was added to the Primer A solutions of the two component self etching system of Example 2 wherein the second component of the both systems comprises 38-40wt.% AMPS and 10% Bis-MEP. The shear bond strength of these compositions was evaluated according to the SBBS methods described above.
  • Example 3 Testing Two Component Self-Etching Copolymerizable Composition Using AMPS and Bis-MEP on Cut Enamel in LC Mode
  • the SBS of 38 wt.% AMPS/10 wt.% Bis-MEP on uncut enamel was also evaluated. The following results were observed.
  • Example 5 Testing AMPS/Bis-MEP (38/10wt% ⁇ SE Bond and Prompt L-Pop on dentin and enamel in LC and SC modes
  • compositions using the AMPS/Bis-MEP Primer B self-etching primers in one container and a separate Primer A component including water and ethanol in another container according to the present invention exhibited good stability, when stored at room temperature for many months and at elevated temperature (37 °C) for at least four months, they still provided good bond strengths after admixture and application.
  • the self-etching copolymerizable compositions according to the present invention also yielded excellent bonding results for all the substrates tested.
  • self-etching copolymerizable primers of the present invention provide etching of both cut and uncut dentin and enamel surfaces to a degree comparable to that of conventional acid etchants.
  • the self-etching primers of the present invention also etch cut enamel to a degree comparable to that provided by conventional acid etchant (compare with Figs. 14 burr cut enamel) and conventional acid etched burr cut enamel (Fig. 15).
  • compositions and methods according to the present invention simplify the overall restorative process while providing high bond strengths and stable, storable compositions or components.
  • Simplification and significant time savings are realized through formulation of applicants' self-etching copolymerizable primer component(s) - well in advance of use of such component(s) in compositions on the patient.
  • Such advance formulation can be undertaken by the manufacturer at the plant due to the considerable shelf life of applicant's components.
  • compositions and methods can be realized by formulating applicants' compositions in one or two component parts and in placing those parts into kits containing one or two separate containers, the contents of which could be admixed by the dental professional in his or her office.
  • the advantages of simplification and expeditious patient treatment could be realized by the manufacturer supplying the one or two container formulations in amounts whereby their admixture can be conducted in amounts sufficient to treat two or more restorations on a given patient. Treatment time can be minimized because such use of such compositions does not require a separate rinsing step or the application of a separate bonding resin before application of the dental adhesive required by other commercial products.
  • a third component comprising a dental adhesive could also be supplied in the kit.
  • components according to the present invention are both “self-etching” and “shelf-stable”, i.e., they exhibit high bond strengths over at least about four months storage at elevated temperatures, which is expected to translate into even longer stability at room temperature.
  • Such enhanced stability permits pre-formulation of the self-etching copolymerizable components of applicants' compositions and their use in applicants' claimed methods.
  • Compositions and methods of the present invention may also be used in indirect procedures, such as the seating of inlays, onlays and crowns in which self curing catalysts may be a necessity, as well as direct restorations involving light curing or self curing, permitting the dental professional to choose the best curing procedure for the clinical picture.
  • compositions according to the present invention also lessen or eliminate polymerization inhibition exemplified by poor bond strength found in commercial self-etch systems seeking to employ self-cure protocols.
  • Compositions and methods of the present invention are also contemplated wherein only one or two coatings are necessary to apply the composition to the tooth enamel and/or dentin substrate and adequately etch, prime and impart improved adhesion to such substrates, saving further patient time and professional time and effort.
  • Formulations of other stable self etching primer and adhesive bonding compositions according to the present invention will also be apparent to those skilled in the art in view of applicants' disclosure of their presently preferred compositions and presently preferred methods.
  • applicants' preferred solvents may include combinations of various concentrations of other well-known solvents which are appropriate for the monomers and acids of the present invention, such as water and other volatile solvents, together with or possibly in place of some or all of applicants' presently preferred ethanol, water, and/or acetone solvents.

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  • Health & Medical Sciences (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Epidemiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Dental Preparations (AREA)

Abstract

La présente invention a trait à des compositions d'amorce de gravure à l'eau forte copolymérisable comprenant des composés comportant des groupes à insaturation ethylénique et des groupes acides, et éventuellement des comonomères et des solvants appropriés. De telles compositions sont utilisées conjointement avec des résines de scellement pour la réalisation de systèmes dentaires à un ou plusieurs composants aptes au mordançage ou à la décalcification de la dentine ou de l'émail dentaire sans nécessiter une étape de rinçage distincte. L'invention a trait également à l'utilisation de telles compositions selon la présente invention comportant l'application pour l'amorçage et la réalisation d'un adhérence améliorée entre les amorces, les résines de scellement et les substrats dentaires tels que la dentine ou l'émail taillé ou non taillé, et ultérieurement des composites dentaires, des éléments de dentisterie restaurative ou autres éléments dentaires.
PCT/US2002/004202 2002-02-14 2002-02-14 Amorce de gravure a l'eau forte et resine adhesive de scellement WO2003068174A1 (fr)

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Application Number Priority Date Filing Date Title
AU2002248425A AU2002248425A1 (en) 2002-02-14 2002-02-14 Self-etching primer and adhesive bonding resin
PCT/US2002/004202 WO2003068174A1 (fr) 2002-02-14 2002-02-14 Amorce de gravure a l'eau forte et resine adhesive de scellement

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004073660A1 (fr) * 2003-02-14 2004-09-02 Bisco, Inc. Couche primaire auto-décapante et résine adhésive de fixation
EP1421927A4 (fr) * 2001-07-09 2004-10-20 Univ School Nihon Juridic Per Agent dentaire de decapage a mordancage spontane
US7632098B2 (en) 2003-08-12 2009-12-15 3M Innovative Properties Company Self-adhesive dental compositions and methods
US8404144B2 (en) 2002-12-30 2013-03-26 3M Innovative Properties Company Compositions including polymerizable bisphosphonic acids and methods
US8465284B2 (en) 2004-07-08 2013-06-18 3M Innovative Properties Company Dental methods, compositions, and kits including acid-sensitive dyes
US8722760B2 (en) 2004-08-11 2014-05-13 3M Innovative Properties Company Self-adhesive compositions including a plurality of acidic compounds
US9943465B2 (en) 2006-12-13 2018-04-17 3M Innovative Properties Company Methods of using a dental composition having an acidic component and a photobleachable dye

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4640936A (en) * 1984-04-14 1987-02-03 Kulzer & Co. Gmbh Photopolymerizable phosphate-containing adhesion promoting dental composition
US5264513A (en) * 1990-02-15 1993-11-23 Kabushiki Kaisha Shofu Primer composition
EP0705590A1 (fr) * 1994-10-07 1996-04-10 Kuraray Co., Ltd. Composition adhésive à activité antimicrobienne pour utilisation dentaire
US5834532A (en) * 1993-08-02 1998-11-10 Sun Medical Co., Ltd. Primer composition and curable composition
US5925690A (en) * 1995-11-20 1999-07-20 Tokuyama Corproation Dental primer composition and kit
US6245872B1 (en) * 1998-02-17 2001-06-12 Espe Dental Ag Adhesive securing of dental filling materials
US20020019456A1 (en) * 2000-05-11 2002-02-14 Weitao Jia Self-etching primer and method of use therefor

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4640936A (en) * 1984-04-14 1987-02-03 Kulzer & Co. Gmbh Photopolymerizable phosphate-containing adhesion promoting dental composition
US5264513A (en) * 1990-02-15 1993-11-23 Kabushiki Kaisha Shofu Primer composition
US5834532A (en) * 1993-08-02 1998-11-10 Sun Medical Co., Ltd. Primer composition and curable composition
EP0705590A1 (fr) * 1994-10-07 1996-04-10 Kuraray Co., Ltd. Composition adhésive à activité antimicrobienne pour utilisation dentaire
US5925690A (en) * 1995-11-20 1999-07-20 Tokuyama Corproation Dental primer composition and kit
US6245872B1 (en) * 1998-02-17 2001-06-12 Espe Dental Ag Adhesive securing of dental filling materials
US20020019456A1 (en) * 2000-05-11 2002-02-14 Weitao Jia Self-etching primer and method of use therefor

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1421927A4 (fr) * 2001-07-09 2004-10-20 Univ School Nihon Juridic Per Agent dentaire de decapage a mordancage spontane
US7614879B2 (en) 2001-07-09 2009-11-10 Nihon University, School Juridical Person Dental self-etching primer
US8404144B2 (en) 2002-12-30 2013-03-26 3M Innovative Properties Company Compositions including polymerizable bisphosphonic acids and methods
WO2004073660A1 (fr) * 2003-02-14 2004-09-02 Bisco, Inc. Couche primaire auto-décapante et résine adhésive de fixation
US7632098B2 (en) 2003-08-12 2009-12-15 3M Innovative Properties Company Self-adhesive dental compositions and methods
US8029286B2 (en) 2003-08-12 2011-10-04 3M Innovative Properties Company Self-etching dental compositions and methods
US8465284B2 (en) 2004-07-08 2013-06-18 3M Innovative Properties Company Dental methods, compositions, and kits including acid-sensitive dyes
US8722760B2 (en) 2004-08-11 2014-05-13 3M Innovative Properties Company Self-adhesive compositions including a plurality of acidic compounds
US9943465B2 (en) 2006-12-13 2018-04-17 3M Innovative Properties Company Methods of using a dental composition having an acidic component and a photobleachable dye

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