EP0967955A1 - Produit dentaire polymerisable a faible retrait - Google Patents

Produit dentaire polymerisable a faible retrait

Info

Publication number
EP0967955A1
EP0967955A1 EP98906494A EP98906494A EP0967955A1 EP 0967955 A1 EP0967955 A1 EP 0967955A1 EP 98906494 A EP98906494 A EP 98906494A EP 98906494 A EP98906494 A EP 98906494A EP 0967955 A1 EP0967955 A1 EP 0967955A1
Authority
EP
European Patent Office
Prior art keywords
low shrinking
group
composite
polymerizable
macromonomer
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.)
Withdrawn
Application number
EP98906494A
Other languages
German (de)
English (en)
Inventor
Joachim E. Klee
Uwe Walz
Dirk Holter
Armin Burgath
Holger Frey
Rolf Mulhaupt
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dentsply Sirona Inc
Original Assignee
Dentsply International 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 Dentsply International Inc filed Critical Dentsply International Inc
Publication of EP0967955A1 publication Critical patent/EP0967955A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • 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

Definitions

  • the present invention is directed toward a low shrinking polymerizable dental material. More particularly, the material includes a polymerizable resin and a polymerizable monomer. The material also includes a polymerization initiator and/or sensibilizer and a stabilizer and a filler component. The material has a volumetric polymerization shrinkage of less than 1.5 %, and it stiffens upon application of shear stress and /or pressure and does not relax within a predetermined working time, due to its rheopex rheologic behavior.
  • Dental filling materials mainly consist of polymerizable organic monomers and/ or polymers, polymerizable monomers, polymerization initiators, and fillers.
  • the main disadvantage using composites as dental filling materials is the relatively high shrinkage of organic monomers during polymerization.
  • the shrinkage causes the well known effect of contraction gaps and subsequent cracks.
  • Common dental composites show a volumetric shrinkage ( ⁇ V) of as much as 2.5 up to 4.0 % or more.
  • spiroorthoesters were synthesized which show only a small volumetric shrinkage or which expand during polymerization. However, most also show a volumetric shrinkage. Frequently, expansion was found when measuring the density of crystalline monomers, that their degree of polymerization is selectively low.
  • an object of the invention to provide a dental material useful, for example as a filling material or the like. It is another object of the invention to provide such a material having a respectively lower volumetric shrinkage after polymerization, as compared to those" materials heretofore known in the industry.
  • a low shrinking polymerizable dental material comprises a mixture of (I) at least one polymerizable resin; (ii) at least one polymerizable monomer; (iii) at least one polymerization initiator and/or sensibilizer and a stabilizer; and, (iv) at least one filler component in a content of 20 to 85 percent by weight.
  • the material has a volumetric polymerization shrinkage of less than about 1.5 %. The material stiffens upon application of shear stress and /or pressure and does not relax within a predetermined working time due to its rheopex rheologic behavior.
  • the polymerizable resin is for example, an epoxide-amine macromonomer, an epoxide-dicarboxylic acid macromonomer, an epoxide-diphenol macromonomer, an addition product of amines having at least two NH functions and acrylate methcrylates, a (meth)acryloyl terminated hyperbranched polyester, having at least an ethylenically unsaturated moiety, mixtures thereof and the like.
  • the polymerizable resin is a macromonomer or an addition product of amines having at least two NH functions and acrylate methcrylates having a molecular mass of from about 500 to about 5000 g/mol, mixtures thereof and the like.
  • the polymerizable resin can be a (meth)acryloyl terminated hyperbranched polymer having a molecular mass of from about 2000 to about 25000 g/mol.
  • the polymerizable monomer is for example, a mono- and polyfunctional acrylate or methacrylate, such as diethyleneglycol dimethacrylate, triethyleneglycol dimethacrylate, 3,(4),8,(9)-dimethacryloyloxymethyltricyclodecane, dioxolan bismeth- acrylate, vinyl-, vinylen- or vinyliden-, acrylic- or methacrylic substituted spiroorthoesters, spiroorthocarbonates or bicyloorthoesters, glycerin trimethacrylate, trimethylol propane triacrylate, furfurylmethacrylate in a content of 5 to 50 wt-% (weight percent), mixtures thereof and the like.
  • a mono- and polyfunctional acrylate or methacrylate such as diethyleneglycol dimethacrylate, triethyleneglycol dimethacrylate, 3,(4),8,(9)-dimethacryloyloxymethyltricyclodecane
  • the polymerization initiator and/or sensibilizer is preferably, a photoinitiator, such as benzoinmethylether, benzilketal, camphor quinone, acylphos-phinoxides in a content of 0.1 to 3 wt-%, mixtures thereof and the like.
  • the polymerization initiator can be a redox initiator such as dibenzoylperoxide/aromatic or aliphatic tert. amine, tert. butyl peroxy benzoate/ascorbic acid/metal compound in a content of 0.1 to 3 wt-%, mixtures thereof and the like.
  • the filler includes inorganic compounds such as La 2 O 3 , ZrO 2 , BiPO 4 , CaWO 4 , BaWO 4 , SrF 2 , Bi 2 O 3 , porous glasses or organic fillers, such as polymer granulate or a combination of organic and/or inorganic fillers or reactive inorganic fillers, mixtures thereof and the like.
  • the fillers preferably have an average diameter of less than 10 ⁇ m.
  • a low shrinking polymerizable dental material preferably includes a mixture of (i) at least one polymerizable resin; (ii) at least one polymerizable monomer; (iii) at least one polymerization initiator and/or sensibilizer and a stabilizer; and, (iv) at least one filler in a content of about 20 to about 85 percent by weight.
  • low shrinking it is meant a material having a a volumetric polymerization shrinkage of less than about 1.5 %.
  • the present material stiffens upon the application of shear stress and /or pressure and does not relax within a predetermined working time of the material due to its rheopex rheologic behavior (the tendency to stiffen upon being so agitated).
  • the polymerizable resin is preferably an epoxide-amine macromonomer, an epoxide-dicarboxylic acid macromonomer, an epoxide-diphenol macromonomer, an addition product of amines having at least two NH functions and acrylate methacrylates, a (meth)acryloyl terminated hyperbranched polyester, having at least an ethylenically unsaturated moiety, mixtures thereof and the like.
  • the polymerizable resin is preferably a macromonomer having a molecular mass of about 500 to about 5000 g/mol or a (meth)acryloyl terminated hyperbranched polymer having a molecular mass of about 2000 to about 25000 g/mol, mixtures thereof and the like.
  • Useful polymerizable monomers include mono- and polyfunctional acrylates or methacrylates, such as diethyleneglycol dimethacrylate, triethyleneglycol" dimethacrylate, 3,(4),8,(9)-dimethacryloyloxymethyltricyclodecane, dioxolan bismethacrylate, vinyl-, vinylen- or vinyliden-, acrylic- or methacrylic substituted spiroorthoesters, spiroorthocarbonates or bicyloorthoesters, glycerin trimethacrylate, trimethylol propane triacrylate, furfurylmethacrylate in a content of about 5 to about ⁇ O wt-%, mixtures thereof and the like.
  • mono- and polyfunctional acrylates or methacrylates such as diethyleneglycol dimethacrylate, triethyleneglycol" dimethacrylate, 3,(4),8,(9)-dimethacryloyloxymethyltricyclodecane, dioxolan
  • the photoinitiator is preferably benzoinmethylether, benzilketal, camphor quinone/amine, or an acylphosphinoxide in a content of about 0.1 to about 3 wt-%, mixtures thereof and the like.
  • Useful redox initiators are dibenzoylperoxide/aromatic or aliphatic tert. amine, tert. butyl peroxy benzoate/ascorbic acid/metal compound in a content of about 0.1 to about 3 wt-%, mixtures thereof and the like.
  • the low shrinking dental material is preferably filled with inorganic compounds such as La 2 O 3 , ZrO 2 , BiPO 4f CaWO 4 , BaWO 4 , SrF 2 , Bi 2 O 3 , porous glasses or organic fillers, such as polymer granulate or a combination of organic and/or inorganic fillers or reactive inorganic fillers having a average diameter of less than about 10 ⁇ m, mixtures thereof and the like.
  • inorganic compounds such as La 2 O 3 , ZrO 2 , BiPO 4f CaWO 4 , BaWO 4 , SrF 2 , Bi 2 O 3
  • porous glasses or organic fillers such as polymer granulate or a combination of organic and/or inorganic fillers or reactive inorganic fillers having a average diameter of less than about 10 ⁇ m, mixtures thereof and the like.
  • a composite was prepared using a acetylated 2,2-Bis-[p-(2- hydroxy-3-methacryloyloxypropoxy)-phenyl]-propane, a modified macromonomer M- C11 using undecanoic acid, trimethylolpropane triacrylate, champhor quinone, DMABE, BHT and a Strontium-Alumo-Fluoro-Silicate glass.
  • a curing unit Densply De Trey
  • the volumetric shrinkage under shear stress is measured using a machine of the Zahnklinik of Zurich (Zurich machine). Using this machine the composite material is put between a glass plate and a metal plate. Then, the material is polymerized photochemically and the change of the high of the material is registered by using a photodiode or other detector.
  • the Archimedes method for estimation of the shrinkage is based on the measurement of the weight of the unpolymerized and of the polymerized material on air and in water. From these values the densities are calculated. The densities of the unpolymerized and of the polymerized material are used for calculating the shrinkage.
  • a composite was prepared using 8.2296 g of the polymerizable resin of Example 1 , 19.3496 g of 2,2-Bis-[p-(2-hydroxy-3-methacryloyloxypropoxy)-phenyl]- propane (Bis-GMA), 0.0965 g champhor quinone, 0.0956 g N.N-dimethyl-p-amino benzoic acid ethyl ester (DMABE), 0.0278 g 2.6-di-tert.butyl-p-cresol (BHT) and 72.2000 g of a Strontium-Alumo-Fluoro-Silicate glass.
  • the composite was polymerized by irradiation with visible light during 40 seconds.
  • a composite was prepared using 8.3166 g of the polymerizable resin of example 2, 19.2629 g of Bis-GMA, 0.0965 g champhor quinone, 0.0956 g DMABE, 0.0275 BHT and 72.2000 g of a Strontium-Alumo-Fluoro-Silicate glass. Using a curing unit (Dentsply De Trey) the composite was polymerized by irradiation with visible light during 40 seconds.
  • a curing unit Densply De Trey
  • a composite was prepared using 13.0938 g of the modified Bis-GMA-C2 of example 3, 13.0938 g of the modified macromonomer M-C11 of example 3, 1.390 of trimethylolpropane triacrylate, 0.0973 g champhor quinone, 0.0973 g DMABE, 0.0278 g BHT and 72.2000 g of a Strontium-Alumo-Fluoro-Silicate glass. Using a curing unit (Dentsply De Trey) the composite was polymerized by irradiation with visible light during 40 seconds.
  • a curing unit Densply De Trey
  • HHG2-OH (corresponds to 0.5 mol OH-groups assuming complete conversion)
  • Bis-MPA 67.07 g
  • p-toluenesulfonic acid was mixed in a three necked flask equipped with a nitrogen inlet, a drying tube and a stirrer. Subsequently the flask was placed in a oil bath previously heated to 140 °C and the mixture was stirred at this temperature for 2 hours under a stream of nitrogen. Afterwards the nitrogen stream was turned off and the mixture dried for two hours in vacuum at 140 °C, yielding HHG3-OH. Synthesis of a hyperbranched polyester of the 4th generation (HHG4-OH)
  • HHG3-OH (corresponds to 0.25 mol OH-groups assuming complete conversion)
  • 33.53 g of Bis-MPA and 0.168 g of p-toluenesulfonic acid were mixed in a three necked flask equipped with a nitrogen inlet, a drying tube and a stirrer. Subsequently the flask was placed in a oil bath previously heated to 140 °C and the mixture was stirred at this temperature for 2 hours under a stream of nitrogen. Afterwards the nitrogen stream was turned off and the mixture dried for two hours in vacuum at 140 °C, yielding HHG4-OH.
  • HHG4-OH (corresponds to 0.494 mol OH-groups assuming complete conversion)
  • 66.25 g of Bis-MPA and 0.331 g of p-toluenesulfonic acid were mixed in a three necked flask equipped with a nitrogen inlet, a drying tube and a stirrer. Subsequently the flask was placed in a oil bath previously heated to 140 °C and the mixture was stirred at this temperature for 2 hours under a stream of nitrogen. Afterwards the nitrogen stream was turned off and the mixture dried for two hours in vacuum at 140 °C, yielding HHG5-OH.
  • a composite was prepared using 20.7919 g of the polymerizable resin of example 4, 4.6375 g of triethylenglycoldimethacrylate, 0.0975 g champhor quinone, 0.0976 g N,N-dimethyl-p-amino benzoic acid ethyl ester, 0.0257 g di-tert. butyl-p- hydroxy toluene and 74.3500 g of a Strontium-Alumo-Fluoro-Silicate glass. Using a curing unit (Dentsply De Trey) the composite was polymerized by irradiation with visible light during 40 seconds.
  • a curing unit Densply De Trey
  • ⁇ V (Z.) Measurement of the volumetric shrinkage at the Zurich-machine ⁇ V (A.) - Measurement of the volumetric shrinkage according Archimedes ⁇ V (calc.) - Shrinkage calculated from shrinkage of the resin
  • a composite comprising 25 % (w/w) of a resin composed of Bis-GMA and TGDMA (70/30), 75 % (w/w) of a glass filler and BHT, camphor quinone and DEABE shows a volumetric shrinkage of 3.05 % when measured using the Archimedes method.
  • a shrinkage in the same range of 3.35 ⁇ 0.07 is found if the material was stored for one minute (without of pressure). Under pressure a shrinkage of approximately 1 % is found using both methods.

Landscapes

  • Health & Medical Sciences (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Plastic & Reconstructive 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

Cette invention se rapporte à un produit dentaire polymérisable à faible retrait, composé d'un mélange d'une résine polymérisable, d'un monomère polymérisable, d'un initiateur de polymérisation et/ou d'un agent de sensibilisation et d'une charge représentant environ 20 à environ 85 % du mélange. Le retrait volumétrique au cours de la polymérisation est inférieur à environ 1,5 % du volume en raison du comportement rhéopexique dudit produit.
EP98906494A 1997-02-21 1998-02-18 Produit dentaire polymerisable a faible retrait Withdrawn EP0967955A1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US960955 1992-10-14
US3881297P 1997-02-21 1997-02-21
US38812P 1997-02-21
US96095597A 1997-10-30 1997-10-30
PCT/US1998/003032 WO1998036729A1 (fr) 1997-02-21 1998-02-18 Produit dentaire polymerisable a faible retrait

Publications (1)

Publication Number Publication Date
EP0967955A1 true EP0967955A1 (fr) 2000-01-05

Family

ID=26715556

Family Applications (1)

Application Number Title Priority Date Filing Date
EP98906494A Withdrawn EP0967955A1 (fr) 1997-02-21 1998-02-18 Produit dentaire polymerisable a faible retrait

Country Status (5)

Country Link
EP (1) EP0967955A1 (fr)
JP (1) JP2001509179A (fr)
AU (1) AU6170598A (fr)
BR (1) BR9807449A (fr)
WO (1) WO1998036729A1 (fr)

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6127450A (en) * 1998-06-09 2000-10-03 Kerr Corporation Dental restorative composite
US6359090B1 (en) 1998-06-09 2002-03-19 Kerr Corporation Polymerizable dispersant
JP4212777B2 (ja) 1999-04-12 2009-01-21 デンツプライ インターナショナル インコーポレーテッド 歯科用複合体修復材料および歯を修復する方法
US7001932B2 (en) 1999-04-12 2006-02-21 Dentsply Detrey Gmbh Dental composite restorative material and method of restoring a tooth
FI20010222A0 (fi) 2001-02-06 2001-02-06 Yli Urpo Antti Lääketieteellisesti hammashoidolliset polymeerikomposiitit ja -koostumukset
CA2437622C (fr) * 2001-02-06 2011-05-31 Pekka Vallittu Composites et compositions polymeres pour applications dentaires et medicales
EP1416902B1 (fr) 2001-08-15 2014-09-24 3M Innovative Properties Company Structures autoportantes durcissables et procedes
TWI236374B (en) 2003-02-13 2005-07-21 Univ Nat Taiwan Light curable epoxy nano composite for dental restorative material
DE102007034457A1 (de) * 2007-07-20 2009-01-22 Heraeus Kulzer Gmbh Dentalkomposite mit niedriger Schrumpfspannung und hoher Biegefestigkeit
JP2010126569A (ja) * 2008-11-26 2010-06-10 Hakuto Co Ltd 感光性樹脂組成物
US9114080B2 (en) 2011-02-17 2015-08-25 Tokuyama Dental Corporation Curable composition for dentistry
JP5804807B2 (ja) * 2011-07-07 2015-11-04 株式会社トクヤマデンタル 歯科用充填修復材
US20150329754A1 (en) 2012-10-16 2015-11-19 Daicel Corporation Liquid composition
US9931280B2 (en) * 2013-10-03 2018-04-03 Dentsply Sirona Inc. Dental composite compositions for reduced shrinkage stress
JP6501214B2 (ja) * 2014-11-04 2019-04-17 国立大学法人 東京医科歯科大学 歯科用硬化性組成物
EP4389105A1 (fr) 2022-12-20 2024-06-26 Dentsply DeTrey GmbH Composition dentaire comprenant un médiateur de retrait de polymérisation

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4001978C2 (de) * 1990-01-24 1994-10-27 Heraeus Kulzer Gmbh Polymerisierbare Mischung und ihre Verwendung
DE4217761A1 (de) * 1992-05-29 1993-12-02 Univ Schiller Jena â,þ-methacrylatterminierte Epoxid-Carbonsäure-Macromonomere
CA2146816A1 (fr) * 1994-04-22 1995-10-23 Joachim E. Klee Methode et composition pour la preparation d'un produit polymerique dentaire
DE4443702A1 (de) * 1994-12-08 1996-06-13 Ivoclar Ag Feinkörnige unter Druck oder Scherbeanspruchung fließfähige polymerisierbare Zusammensetzungen
EP0799016B1 (fr) * 1994-12-19 2002-12-04 Dentsply International, Inc. Composes et compositions de polymerisation
DE19525031A1 (de) * 1995-07-10 1997-01-16 Heraeus Kulzer Gmbh Derivate aromatischer Carbonsäuren, aromatische Carbonsäureanhydride und Hydroxy(meth)acrylaten sowie Adhäsive, enthaltend diese Verbindungen
DE19525033A1 (de) * 1995-07-10 1997-01-16 Heraeus Kulzer Gmbh Polymerisierbare aromatische Carbonsäuren und Carbonsäureanhydride mit cyclischen Carbonatgruppen, sowie Adhäsive enthaltend diese Verbindungen

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9836729A1 *

Also Published As

Publication number Publication date
WO1998036729A1 (fr) 1998-08-27
BR9807449A (pt) 2000-04-25
AU6170598A (en) 1998-09-09
JP2001509179A (ja) 2001-07-10

Similar Documents

Publication Publication Date Title
US20030125412A1 (en) Low shrinking polymerizable dental material
US5026902A (en) Dental compsition of perfluoroalkyl group-containing (meth-)acrylate esters
JP2880455B2 (ja) 液晶モノマーベースの歯科用材料
WO1998036729A1 (fr) Produit dentaire polymerisable a faible retrait
US5886064A (en) Fine-grained polymerizable compositions flowable under pressure or shear stress
EP0861230B1 (fr) Composes a base de (meth)acrylates a cristaux liquides, compositions et procede d'utilisation
EP0323521B1 (fr) Composition polymerisable
CA2150438C (fr) Materiaux dentaires radio-opaques
JPH0791172B2 (ja) 歯科材料を調製するための硬化性モノマー混合物
PT90853B (pt) Processo para a preperacao de materiais para uso dental a base de (met) acrilatos polimericos de ligacao cruzada
JPH09176151A (ja) 環式カーボネート基を含むウレタン（メタ）アクリレート
US6057460A (en) Polymerizable hybrid monomers
EP1879544B1 (fr) Matieres et composites dentaires faits de ces matieres
US6369164B1 (en) Polymerizable compounds and compositions
EP0799016B1 (fr) Composes et compositions de polymerisation
EP0798286B1 (fr) Dérivés multifonctionnels du vinylcyclopropane
EP0943601B1 (fr) (Méth)-acrylates du vinylcyclopropane ainsi que leur utilisation
AU9724701A (en) Low shrinking polymerizable dental material
JP4813731B2 (ja) 光安定性のある歯科用組成物

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19990819

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): CH DE ES FR GB IT LI

RIN1 Information on inventor provided before grant (corrected)

Inventor name: MULHAUPT, ROLF

Inventor name: FREY, HOLGER

Inventor name: BURGATH, ARMIN

Inventor name: HOLTER, DIRK

Inventor name: WALZ, UWE

Inventor name: KLEE, JOACHIM, E.

17Q First examination report despatched

Effective date: 20031031

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20050203