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WO1998013008A1 - Compositions et methodes a base d'oxydes metalliques - Google Patents

Compositions et methodes a base d'oxydes metalliques Download PDF

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Publication number
WO1998013008A1
WO1998013008A1 PCT/US1997/016325 US9716325W WO9813008A1 WO 1998013008 A1 WO1998013008 A1 WO 1998013008A1 US 9716325 W US9716325 W US 9716325W WO 9813008 A1 WO9813008 A1 WO 9813008A1
Authority
WO
WIPO (PCT)
Prior art keywords
nanoparticles
base
imidazole
metal oxide
tantalum
Prior art date
Application number
PCT/US1997/016325
Other languages
English (en)
Inventor
Stephen T. Wellinghoff
Original Assignee
Southwest Research Institute
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 Southwest Research Institute filed Critical Southwest Research Institute
Priority to JP51480298A priority Critical patent/JP2002515048A/ja
Priority to EP97941077A priority patent/EP0880349A4/fr
Publication of WO1998013008A1 publication Critical patent/WO1998013008A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • 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
    • A61K6/76—Fillers comprising silicon-containing compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
    • A61K6/802—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics
    • A61K6/824—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics comprising transition metal oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y5/00—Nanobiotechnology or nanomedicine, e.g. protein engineering or drug delivery

Definitions

  • the instant invention relates to compositions primarily suitable for dental and medical restoration: i.e.. dental fillings or dental and bone adhesive, and to the method of their use for such purposes and methods of manufacture.
  • bis-GMA bisglycidylmethylmethacrylate polymer
  • U.S. Patent No. 4,659,751 discusses the use of a variety of acids and other materials in order to treat the surface of teeth, such as enamel and dentin. to activate the surfaces for improved adhesion to polymers, but no disclosure or suggestion is made therein of the use of the GMA or bis-GMA.
  • Nematic liquid crystals which can be photopoiymerized at high temperature, i.e.. 90°C. within seconds with very low polymerization shrinkage to densely crosslinked networks of reaction extent greater than 95% by the usual free radical methods.
  • T e low polymerization shrinkage for such compounds originates from the high packing efficiency that already exists in the nematic state, thus minimizing the entropy reduction that occurs during polymerization.
  • polymerization at lower temperatures, such as room temperature results in undesirable intervening smetic and crystalline phases making them unsuitable as photopolymerized medical and dental restoratives.
  • the present invention comprises novel transparent or translucent acrylate (or methacrylate) based matrix-metal oxide compositions, metal oxide nanoparticles with surface complexes, mixed particles formed by such nanoparticles with larger monosized silica particles to improve mechanical strength, and photopolymerizable room temperature nematics that have high strength and hardness with essentially zero shrinkage.
  • the invention also comprises the methods hereinafter set forth for making such tantalum oxide-silica microparticles. for making composites having reduced particle surface acidity, and the method of dental and bone restoration using the noted composites.
  • Tantalum is particularly desired for dental and medical uses since it will provide X-ray opaque materials necessary for subsequent review of the treated site; i.e., tooth or bone, by dentists and doctors.
  • These tantalum nanoparticles are prepared as set forth in U.S. Patent No. 5,372,796 by ester exchange of tantalum oxide with an acid such as formic acid.
  • a polymerizable, biocompatible, heterocyclic base that can complex the acid sites on the surface of the tantalum oxide nanoparticles is admixed therewith.
  • alkene terminated imidiazoles and phosphates for this purpose with specific examples being 1 -vinyl imidazole (VIM) and the phosphonated acrylic ester, PHEMA, formed by reacting diethylchlorophosphate with hydroxyethyl methacrylate (HEMA) in the presence of triethylamine in ether.
  • VAM 1 -vinyl imidazole
  • PHEMA phosphonated acrylic ester
  • the matrix monomers there are used photopolymerizable. acrylate based monomers, particularly those useful in dental applications. Particularly preferred are the
  • n is a C 6 to C 12 substituted or unsubstituted alkyl group
  • R, and R are H or a methyl group
  • R 2 is a bulky group (a group of providing steric hindrance), such as a tertiary butyl group and the like.
  • This large group size "mismatch" between the central aromatic group and the two surrounding aromatic groups is required to achieve in the final product a nematic state at room temperature while suppressing crystallinity at the same temperature.
  • the methacrylic derivates of the above diacrylates are also suitable. Also, as discussed below, bis-GMA and other bis-GMA and other bis-glycidylacrylate and methacrylate compounds can be included in the matrix.
  • the method of making metal oxide clusters set forth in U.S. Patent 5,372,796 permits growth of tantalum oxide particles of 1-2 nm in diameter. Assuming perfect bonding between the particle and matrix, a decrease in particle size at a given volume fraction of particles will increase the elastic constraint on the deforming matrix molecules and lead to an increase in modulus. However, as the particle size approaches molecular dimensions, the very closely spaced crosslinking points of high functionality within the matrix will substantially quench any large scale molecular motions. It is these motions which are important for energy dissipation and fracture toughness.
  • the Ta-nanoparticles are combined with relatively large, preformed silica particles has the advantage of increasing particle size and reducing X-ray opacity.
  • Monosized silica particles in the 10-20 nm diameter range are commercially available, but some are only stable as individual non- interacting particles at basic pH, where coagulation of the tantalum oxide nanoparticles will occur.
  • Silica particles of 12 nm that are stable at acidic pH are available with a 13% aluminum oxide coating.
  • Organic phosphate triesters are known to be strong complexing agents for many metal ions with the potential to extract metal ions into hydrophobic phases, in order to take advantage of this complexing potential, the Ta j O j -SiO-, composite is reacted with PHEMA. While PHEMA is a liquid at room temperature and is insoluble in water, it can be made soluble in water by the addition of a small quantity of methanol.
  • the strategy is to utilize the diethylphosphate terminus to bind to the nanoparticle surface and use the methacrylate end to copolymerize and couple the nanoparticles into the matrix resin.
  • liquid crystalline materials such as C10(H,H,H) melted above room temperature (ca85°C) dilution of C10(H.H,H) with 50wt%bisGMA generated a mobile liquid crystalline phase at room temperature (28°C). This mobile liquid crystal phase converted to an isotropic phase at 63°C.
  • bis-GMA can be included as part of the matrix
  • other C, to C 12 acrylates and methacrylates can be used, such as bis-glycidylmethylacrylate. bis-glycidylethylacrylate. bis-glycidylethylmethacrylate. 2-hydroxyethylmethacrylate. mixtures thereof, and the like.
  • the amount of nanoparticles added to the matrix can vary widely. Amounts of up to
  • 40 wt. % of nanoparticles for 100 wt. % of nanoparticles and matrix can be utilized. At amounts above about 40 wt. % the admixture becomes pasty. Obviously, the amount of loading is in the range necessary to give the desired final product and thus can be determined for such particular nanoparticle and matrix used by routine experimentation. In using the transparent or translucent nanoparticle-matrix composition, it need only be applied to the surface to be treated and photopolymerized.
  • the liquid or pasty composition is placed on the tooth by a dentist or dental technician and ultra-violet light used to effect the polymerization (cure) into a high strength, hard, transparent, X-ray opaque coating, or filling, with essentially zero shrinkage.
  • essentially zero shrinkage is most important for fillings.
  • the transparency or translucency is an important characteristic, because it permits deeper photocure in thicker layers of the restorative composition, thus avoiding the multiple applications of opaque photocured restoratives presently used.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Nanotechnology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Epidemiology (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Animal Behavior & Ethology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Biotechnology (AREA)
  • Medical Informatics (AREA)
  • General Engineering & Computer Science (AREA)
  • Molecular Biology (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Biophysics (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • Polymers & Plastics (AREA)
  • Plastic & Reconstructive Surgery (AREA)
  • Dispersion Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Composite Materials (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Dental Preparations (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne des nanoparticules d'oxydes métalliques et d'oxydes métalliques/de silice dont les surfaces forment des complexes avec une base hétérocyclique polymérisable et biocompatible. On obtient des compositions polymérisables en chargeant lesdites nanoparticules dans des matrices monomères à base d'acrylates; ces compositions sont ensuite photopolymérisées pour former des solides opaques aux rayons X ou transparents ou translucides. L'invention concerne des méthodes permettant de créer lesdites compositions et lesdits complexes à base de nanoparticules et d'utiliser ces compositions comme matériaux de restauration médicaux ou dentaires.
PCT/US1997/016325 1996-09-27 1997-09-17 Compositions et methodes a base d'oxydes metalliques WO1998013008A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP51480298A JP2002515048A (ja) 1996-09-27 1997-09-17 金属酸化物組成物及び方法
EP97941077A EP0880349A4 (fr) 1996-09-27 1997-09-17 Compositions et methodes a base d'oxydes metalliques

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US72174296A 1996-09-27 1996-09-27
US08/721,742 1996-09-27

Publications (1)

Publication Number Publication Date
WO1998013008A1 true WO1998013008A1 (fr) 1998-04-02

Family

ID=24899131

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1997/016325 WO1998013008A1 (fr) 1996-09-27 1997-09-17 Compositions et methodes a base d'oxydes metalliques

Country Status (4)

Country Link
EP (1) EP0880349A4 (fr)
JP (1) JP2002515048A (fr)
CA (1) CA2229923A1 (fr)
WO (1) WO1998013008A1 (fr)

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999017716A3 (fr) * 1997-10-03 1999-09-10 Dentsply Int Inc Produits dentaires comprenant une charge de l'ordre de grandeur du nanometre
US6410765B1 (en) 1993-04-13 2002-06-25 Southwest Research Institute Methods of making functionalized nanoparticles
US6417244B1 (en) 1993-04-13 2002-07-09 Southwest Research Institute Metal oxide compositions and methods
WO2002059553A2 (fr) 2001-01-23 2002-08-01 Southwest Research Institute Nouveaux procedes et melanges destines a reguler la rheologie et la temperature de transition de cristaux liquides
WO2002062702A1 (fr) * 2000-11-14 2002-08-15 Beijing University Of Chemical Technology Procede de fabrication de silice
US6696585B1 (en) 1993-04-13 2004-02-24 Southwest Research Institute Functionalized nanoparticles
JP2004536033A (ja) * 2001-01-23 2004-12-02 サウスウェスト リサーチ インスティテュート 新規メソゲン
US6899948B2 (en) 1999-10-28 2005-05-31 3M Innovative Properties Company Dental materials with nano-sized silica particles
US7037583B2 (en) 1999-05-19 2006-05-02 Southwest Research Institute Functionalized zirconium oxide particles
US7094358B2 (en) 2001-03-07 2006-08-22 The University Of Texas System Ultra-low shrinkage composite resins based on blended nematic liquid crystal monomers
US7094360B2 (en) 2001-07-09 2006-08-22 Southwest Research Institute Resin blends and methods for making same
DE102005019600A1 (de) * 2005-04-27 2006-11-09 Ivoclar Vivadent Ag Oberflächenmodifizierte Füllstoffe
DE102006045628A1 (de) * 2006-09-27 2008-04-03 Ivoclar Vivadent Ag Röntgenopaques Dentaladhäsiv
US7393882B2 (en) 2002-01-31 2008-07-01 3M Innovative Properties Company Dental pastes, dental articles, and methods
EP2080503A1 (fr) 2008-01-18 2009-07-22 Ivoclar Vivadent AG Matériaux dentaires dotés d'agents de remplissage à surface fonctionnalisée
US9308616B2 (en) 2013-01-21 2016-04-12 Innovative Finishes LLC Refurbished component, electronic device including the same, and method of refurbishing a component of an electronic device

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1454911A1 (fr) * 2003-03-07 2004-09-08 DENTSPLY DETREY GmbH Dérivés polymérisables d'esters d'acide phosphorique et composition dentaire les contenant
US7947125B1 (en) * 2009-10-30 2011-05-24 Canon Kabushiki Kaisha Fine particle dispersion liquid containing tantalum oxide fine particles, tantalum oxide fine particle-resin composite, and method of producing fine particle dispersion liquid

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5064877A (en) * 1988-07-18 1991-11-12 Fraunhofer-Gesellschaft Zur Forderung Der Angewandten Forschung E.V. Process for fixing inorganic species in an organic matrix
US5231156A (en) * 1986-10-03 1993-07-27 Ppg Industries, Inc. Organic/inorganic hybrid polymers
US5316855A (en) * 1990-07-13 1994-05-31 Virginia Tech Intellectual Properties, Inc. High abrasion resistance coating materials from organic/inorganic hybrid materials produced by the sol-gel method
US5337129A (en) * 1993-10-27 1994-08-09 Xerox Corporation Intermediate transfer component coatings of ceramer and grafted ceramer

Family Cites Families (4)

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EP0242278A3 (fr) * 1986-04-11 1989-06-14 The Board Of Trustees Of The University Of Illinois Polymères présentant des propriétés électriques et magnétiques
DE4133621A1 (de) * 1991-10-10 1993-04-22 Inst Neue Mat Gemein Gmbh Nanoskalige teilchen enthaltende kompositmaterialien, verfahren zu deren herstellung und deren verwendung fuer optische elemente
US5372796A (en) * 1993-04-13 1994-12-13 Southwest Research Institute Metal oxide-polymer composites
JP3513888B2 (ja) * 1993-08-16 2004-03-31 大日本インキ化学工業株式会社 液晶表示素子及びその製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5231156A (en) * 1986-10-03 1993-07-27 Ppg Industries, Inc. Organic/inorganic hybrid polymers
US5064877A (en) * 1988-07-18 1991-11-12 Fraunhofer-Gesellschaft Zur Forderung Der Angewandten Forschung E.V. Process for fixing inorganic species in an organic matrix
US5316855A (en) * 1990-07-13 1994-05-31 Virginia Tech Intellectual Properties, Inc. High abrasion resistance coating materials from organic/inorganic hybrid materials produced by the sol-gel method
US5337129A (en) * 1993-10-27 1994-08-09 Xerox Corporation Intermediate transfer component coatings of ceramer and grafted ceramer

Non-Patent Citations (1)

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Title
See also references of EP0880349A4 *

Cited By (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6696585B1 (en) 1993-04-13 2004-02-24 Southwest Research Institute Functionalized nanoparticles
US6410765B1 (en) 1993-04-13 2002-06-25 Southwest Research Institute Methods of making functionalized nanoparticles
US6417244B1 (en) 1993-04-13 2002-07-09 Southwest Research Institute Metal oxide compositions and methods
US6743936B1 (en) 1993-04-13 2004-06-01 Southwest Research Insittute Composites made using functionalized nanoparticles
US6695617B1 (en) 1993-04-13 2004-02-24 Southwest Research Institute Methods of dental repair using functionalized nanoparticles
WO1999017716A3 (fr) * 1997-10-03 1999-09-10 Dentsply Int Inc Produits dentaires comprenant une charge de l'ordre de grandeur du nanometre
US7037583B2 (en) 1999-05-19 2006-05-02 Southwest Research Institute Functionalized zirconium oxide particles
US6899948B2 (en) 1999-10-28 2005-05-31 3M Innovative Properties Company Dental materials with nano-sized silica particles
US6827916B2 (en) 2000-11-14 2004-12-07 Beijing University Of Chemical Technology Method of making silica
WO2002062702A1 (fr) * 2000-11-14 2002-08-15 Beijing University Of Chemical Technology Procede de fabrication de silice
EP1572716A4 (fr) * 2001-01-23 2005-09-14 Southwest Res Inst Procedes de synthese de cristaux liquides
JP2004536033A (ja) * 2001-01-23 2004-12-02 サウスウェスト リサーチ インスティテュート 新規メソゲン
EP1572716A2 (fr) * 2001-01-23 2005-09-14 Southwest Research Institute Procedes de synthese de cristaux liquides
WO2002059553A2 (fr) 2001-01-23 2002-08-01 Southwest Research Institute Nouveaux procedes et melanges destines a reguler la rheologie et la temperature de transition de cristaux liquides
EP1366133B1 (fr) * 2001-01-23 2010-03-24 Southwest Research Institute Nouveaux procedes et melanges destines a reguler la rheologie et la temperature de transition de cristaux liquides
EP1366133A2 (fr) * 2001-01-23 2003-12-03 Southwest Research Institute Nouveaux procedes et melanges destines a reguler la rheologie et la temperature de transition de cristaux liquides
US7108801B2 (en) 2001-01-23 2006-09-19 Southwest Reasearch Institute Methods and blends for controlling rheology and transition temperature of liquid crystals
US7238831B2 (en) * 2001-01-23 2007-07-03 Southwest Research Institute Mesogens
US7135589B2 (en) 2001-03-07 2006-11-14 Board Of Regents, The University Of Texas System Bridged monomers
US7094358B2 (en) 2001-03-07 2006-08-22 The University Of Texas System Ultra-low shrinkage composite resins based on blended nematic liquid crystal monomers
US7098359B2 (en) 2001-07-09 2006-08-29 Southwest Research Institute Mesogens and methods for their synthesis and use
US7094360B2 (en) 2001-07-09 2006-08-22 Southwest Research Institute Resin blends and methods for making same
US7393882B2 (en) 2002-01-31 2008-07-01 3M Innovative Properties Company Dental pastes, dental articles, and methods
DE102005019600A1 (de) * 2005-04-27 2006-11-09 Ivoclar Vivadent Ag Oberflächenmodifizierte Füllstoffe
EP2277496A1 (fr) 2005-04-27 2011-01-26 Ivoclar Vivadent AG Matériau dentaire contenant une charge à surface modifiée
US8367748B2 (en) 2005-04-27 2013-02-05 Ivoclar Vivadent Ag Surface-modified fillers
DE102006045628A1 (de) * 2006-09-27 2008-04-03 Ivoclar Vivadent Ag Röntgenopaques Dentaladhäsiv
EP2080503A1 (fr) 2008-01-18 2009-07-22 Ivoclar Vivadent AG Matériaux dentaires dotés d'agents de remplissage à surface fonctionnalisée
US9308616B2 (en) 2013-01-21 2016-04-12 Innovative Finishes LLC Refurbished component, electronic device including the same, and method of refurbishing a component of an electronic device

Also Published As

Publication number Publication date
JP2002515048A (ja) 2002-05-21
EP0880349A4 (fr) 2005-04-13
CA2229923A1 (fr) 1998-03-27
EP0880349A1 (fr) 1998-12-02

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