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WO1998036729A1 - Produit dentaire polymerisable a faible retrait - Google Patents

Produit dentaire polymerisable a faible retrait Download PDF

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Publication number
WO1998036729A1
WO1998036729A1 PCT/US1998/003032 US9803032W WO9836729A1 WO 1998036729 A1 WO1998036729 A1 WO 1998036729A1 US 9803032 W US9803032 W US 9803032W WO 9836729 A1 WO9836729 A1 WO 9836729A1
Authority
WO
WIPO (PCT)
Prior art keywords
low shrinking
group
composite
polymerizable
macromonomer
Prior art date
Application number
PCT/US1998/003032
Other languages
English (en)
Inventor
Joachim E. Klee
Uwe Walz
Dirk Holter
Armin Burgath
Holger Frey
Rolf Mulhaupt
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.
Priority to EP98906494A priority Critical patent/EP0967955A1/fr
Priority to AU61705/98A priority patent/AU6170598A/en
Priority to BR9807449-0A priority patent/BR9807449A/pt
Priority to JP53678498A priority patent/JP2001509179A/ja
Publication of WO1998036729A1 publication Critical patent/WO1998036729A1/fr

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.
PCT/US1998/003032 1997-02-21 1998-02-18 Produit dentaire polymerisable a faible retrait WO1998036729A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP98906494A EP0967955A1 (fr) 1997-02-21 1998-02-18 Produit dentaire polymerisable a faible retrait
AU61705/98A AU6170598A (en) 1997-02-21 1998-02-18 Low shrinking polymerizable dental material
BR9807449-0A BR9807449A (pt) 1997-02-21 1998-02-18 Material dental polimerizável de baixa contração.
JP53678498A JP2001509179A (ja) 1997-02-21 1998-02-18 収縮の少ない重合可能な歯科材料

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US3881297P 1997-02-21 1997-02-21
US96095597A 1997-10-30 1997-10-30
US08/960,955 1997-10-30
US60/038,812 1997-10-30

Publications (1)

Publication Number Publication Date
WO1998036729A1 true WO1998036729A1 (fr) 1998-08-27

Family

ID=26715556

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1998/003032 WO1998036729A1 (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)

Cited By (10)

* 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
US6306927B1 (en) 1999-04-12 2001-10-23 Dentsply Detrey Gmbh Dental composite restorative material and method of restoring a tooth
US6359090B1 (en) 1998-06-09 2002-03-19 Kerr Corporation Polymerizable dispersant
WO2002062901A1 (fr) * 2001-02-06 2002-08-15 Pekka Vallittu Composites et compositions polymères pour applications dentaires et médicales
WO2003015720A1 (fr) * 2001-08-15 2003-02-27 3M Innovative Properties Company Structures autoportantes durcissables et procedes
US6855197B2 (en) 2003-02-13 2005-02-15 National Taiwan University Tooth cavity restoration with nanocomposite of epoxy resin and nanoparticles
US7001932B2 (en) 1999-04-12 2006-02-21 Dentsply Detrey Gmbh Dental composite restorative material and method of restoring a tooth
US7354969B2 (en) 2001-02-06 2008-04-08 Stick Tech Oy Dental and medical polymer composites and compositions
US9114080B2 (en) 2011-02-17 2015-08-25 Tokuyama Dental Corporation Curable composition for dentistry
EP4389105A1 (fr) 2022-12-20 2024-06-26 Dentsply DeTrey GmbH Composition dentaire comprenant un médiateur de retrait de polymérisation

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
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
WO2014061467A1 (fr) 2012-10-16 2014-04-24 株式会社ダイセル Composition liquide
EP3052481B1 (fr) * 2013-10-03 2020-04-08 DENTSPLY SIRONA Inc. Utiliation de radicaux stables polymérisables pour réduire la contrainte de retrait de compositions dentaires
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

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EP0438629A2 (fr) * 1990-01-24 1991-07-31 Heraeus Kulzer GmbH Mélange polymérisable et sa préparation
EP0571983A2 (fr) * 1992-05-29 1993-12-01 Dentsply Gmbh Composés macromonomériques terminés en alpha, oméga avec méthacrylate
EP0678533A2 (fr) * 1994-04-22 1995-10-25 DENTSPLY GmbH Procédé et composition pour la préparation d'un produit dentaire polymérique
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WO1996019179A1 (fr) * 1994-12-19 1996-06-27 Dentsply International Inc. Composes et compositions de polymerisation
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Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6359090B1 (en) 1998-06-09 2002-03-19 Kerr Corporation Polymerizable dispersant
US6384106B1 (en) 1998-06-09 2002-05-07 Kerr Corporation Dental restorative composite
US6395803B1 (en) 1998-06-09 2002-05-28 Kerr Corporation Dental restorative composite
US6127450A (en) * 1998-06-09 2000-10-03 Kerr Corporation Dental restorative composite
US7001932B2 (en) 1999-04-12 2006-02-21 Dentsply Detrey Gmbh Dental composite restorative material and method of restoring a tooth
US6306927B1 (en) 1999-04-12 2001-10-23 Dentsply Detrey Gmbh Dental composite restorative material and method of restoring a tooth
US7354969B2 (en) 2001-02-06 2008-04-08 Stick Tech Oy Dental and medical polymer composites and compositions
KR100893126B1 (ko) * 2001-02-06 2009-04-10 스틱 테크 오와이 치과용 및 의료용 폴리머 복합체들 및 조성물들
CN100393813C (zh) * 2001-02-06 2008-06-11 佩卡·瓦利突 牙用和医用聚合物复合材料和组合物
AU2002231823B2 (en) * 2001-02-06 2006-02-23 Lippo Lassila Dental and medical polymer composites and compositions
WO2002062901A1 (fr) * 2001-02-06 2002-08-15 Pekka Vallittu Composites et compositions polymères pour applications dentaires et médicales
WO2003015720A1 (fr) * 2001-08-15 2003-02-27 3M Innovative Properties Company Structures autoportantes durcissables et procedes
CN100415198C (zh) * 2001-08-15 2008-09-03 3M创新有限公司 可硬化的自支撑结构和方法
US7674850B2 (en) 2001-08-15 2010-03-09 3M Innovative Properties Company Hardenable self-supporting structures and methods
US7816423B2 (en) 2001-08-15 2010-10-19 3M Innovative Properties Company Hardenable self-supporting structures and methods
EP2275077A3 (fr) * 2001-08-15 2014-07-16 3M Innovative Properties Co. Structures autoportantes durcissables et procédés
EP2272485A3 (fr) * 2001-08-15 2014-07-16 3M Innovative Properties Co. Structures autoportantes durcissables et procedes
US6855197B2 (en) 2003-02-13 2005-02-15 National Taiwan University Tooth cavity restoration with nanocomposite of epoxy resin and nanoparticles
US9114080B2 (en) 2011-02-17 2015-08-25 Tokuyama Dental Corporation Curable composition for dentistry
EP4389105A1 (fr) 2022-12-20 2024-06-26 Dentsply DeTrey GmbH Composition dentaire comprenant un médiateur de retrait de polymérisation
WO2024132860A1 (fr) 2022-12-20 2024-06-27 Dentsply Detrey Gmbh Composition dentaire comprenant un médiateur de retrait de polymérisation

Also Published As

Publication number Publication date
BR9807449A (pt) 2000-04-25
AU6170598A (en) 1998-09-09
EP0967955A1 (fr) 2000-01-05
JP2001509179A (ja) 2001-07-10

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