EP0753028A1 - Compositions de moulage capables de durcir sous l'effet de rayonnements - Google Patents

Compositions de moulage capables de durcir sous l'effet de rayonnements

Info

Publication number
EP0753028A1
EP0753028A1 EP95938945A EP95938945A EP0753028A1 EP 0753028 A1 EP0753028 A1 EP 0753028A1 EP 95938945 A EP95938945 A EP 95938945A EP 95938945 A EP95938945 A EP 95938945A EP 0753028 A1 EP0753028 A1 EP 0753028A1
Authority
EP
European Patent Office
Prior art keywords
range
weight
present
resin component
molding compositions
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Withdrawn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
EP95938945A
Other languages
German (de)
English (en)
Inventor
Duncan E. Waller
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.)
Kerr Corp
Original Assignee
Kerr Corp
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 Kerr Corp filed Critical Kerr Corp
Publication of EP0753028A1 publication Critical patent/EP0753028A1/fr
Withdrawn legal-status Critical Current

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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/067—Polyurethanes; Polyureas
    • 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
    • A61K6/893—Polyurethanes
    • H—ELECTRICITY
    • H04—ELECTRIC COMMUNICATION TECHNIQUE
    • H04R—LOUDSPEAKERS, MICROPHONES, GRAMOPHONE PICK-UPS OR LIKE ACOUSTIC ELECTROMECHANICAL TRANSDUCERS; DEAF-AID SETS; PUBLIC ADDRESS SYSTEMS
    • H04R25/00—Deaf-aid sets, i.e. electro-acoustic or electro-mechanical hearing aids; Electric tinnitus maskers providing an auditory perception
    • H04R25/65—Housing parts, e.g. shells, tips or moulds, or their manufacture
    • H04R25/652—Ear tips; Ear moulds
    • H—ELECTRICITY
    • H04—ELECTRIC COMMUNICATION TECHNIQUE
    • H04R—LOUDSPEAKERS, MICROPHONES, GRAMOPHONE PICK-UPS OR LIKE ACOUSTIC ELECTROMECHANICAL TRANSDUCERS; DEAF-AID SETS; PUBLIC ADDRESS SYSTEMS
    • H04R25/00—Deaf-aid sets, i.e. electro-acoustic or electro-mechanical hearing aids; Electric tinnitus maskers providing an auditory perception
    • H04R25/65—Housing parts, e.g. shells, tips or moulds, or their manufacture
    • H04R25/658—Manufacture of housing parts

Definitions

  • the invention relates to molding compositions, and more particularly to radiation curable compositions for molding both rigid and flexible medical, orthodontic and other articles.
  • compositions which are biocompatible, permit safe and expeditious processing, accurate reproduction of intricate shapes, and can be custom pigmented as desired. Additionally, there are similar needs in the context of orthodontic appliances, and other moldable articles.
  • the compositions of the present invention as described fully hereinbelow, meet these requirements, provide significant advantages and have a wide variety of uses. Summary of the Invention
  • the present invention broadly encompasses pourable liquid compositions which are radiation curable to form rigid or flexible articles.
  • Uses of the compositions include medical devices, flexible or rigid prostheses, dental and orthodontic applications, model-making, and even industrial parts.
  • compositions of the present invention include as the primary component acrylic-functional polyurethane resin(s), diluent monomers to dilute the composition to the desired consistency, photosensitizers, synergistic reducing agents, lubricants, thickeners, reinforcing fillers and pigments, as needed for the particular application. These components are present in suitable proportions, as described in more detail hereinbelow, so as to achieve the desired results in terms of physical properties (i.e., strength, hardness, etc.).
  • compositions of the invention form a rigid polymeric material upon radiation curing.
  • compositions include the following components in the stated weight percentages:
  • Lubricant (Optional) 0-0.25%
  • the molding compositions form flexible polymeric material upon radiation curing. These embodiments contemplate the following compositions: Table 3
  • Lubricant (Optional) 1.0-3.0%
  • compositions of the present invention is a polyurethane resin having methacrylate or acrylate functionality, of the following general formula: s -O-C-N-R 4 -N-C-O-R 2 -O-R,-O-R 3 -O-C-N-R 5 -N-C-O-R 7 ,
  • R is an aromatic hydrocarbon (for rigid compositions) or an aliphatic hydrocarbon (for flexible compositions), or a combination aliphatic/aromatic to obtain intermediate properties.
  • R 2 and R 3 are aliphatic hydrocarbons of relatively short chain length (C 3 . 5 ) when rigidity is desired, and of relatively longer chain length (C 15 - 20 ) when maximum flexibility is desired.
  • the R, and R $ components in the diisocyanate units are preferably aliphatic hydrocarbons for flexible polymers and aromatic hydrocarbons for rigid polymers.
  • the I ⁇ and R 7 components are methacrylate or acrylate ester groups which provide the ethylenic unsaturation necessary for the resins to be polymerized, so as to form the desired molded shapes upon application of radiant energy.
  • the acrylic-functional resins of the type described above are combined with diluent monomers and other additives, including photosensitizers, synergistic reducing agents, lubricants, thickeners, reinforcing fillers and pigments to achieve the desired molding composition.
  • diluent monomers and other additives including photosensitizers, synergistic reducing agents, lubricants, thickeners, reinforcing fillers and pigments to achieve the desired molding composition.
  • the radiation curable compositions can be advantageously utilized to form rigid articles or flexible articles, depending upon the specific nature of the formulation.
  • the optional lubricant component is utilized in the composition when the molded form or part is to be in insertion/removal contact with the human body, particularly in contact with dry or hair-covered skin as in the case of a rigid or flexible hearing aid shell.
  • a photosensitizer or photoinitiator is used if the material is to be cured by radiant energy of wavelengths within the ultraviolet or visible regions of the spectrum.
  • the synergistic tertiary amine component is added to function as a reducing agent, which lowers the intensity and duration of the radiation exposure necessary for polymerization to occur and proceed to completion.
  • paniculate sub-micron sized thickeners typically surface treated for hydrophobicity, easier resin and monomer wetting, and increased physical properties of the resultant polymer.
  • Reinforcing fillers which are also optional, may be added to maximize the strength properties of the resulting material, particularly where rigidity is desired.
  • Such fillers are generally utilized in larger proportions when the resulting materials are to be used as "solid” forms or shapes, as opposed to hollow forms or shells with relatively thin walls.
  • suitable pigments of the soluble, insoluble and "Lake "-type are used to achieve the desired color in the final product, except in applications where the final product is to be colorless or "clear. " It is believed that the sub-micron sized thickeners serve to prevent the sedimentation of the pigments and reinforcing fillers.
  • composition which is unpigmented, is suitable for molding rigid articles, including orthodontic appliances, rigid prostheses, and hearing aid shells. Although the composition is unpigmented and thus cures to a clear material, pastels or other color additives could be included if desired.
  • the above composition can be molded to form an article of any desired shape, such as a molded orthodontic appliance.
  • an impression is taken of the appropriate area of the mouth with dental impression material, from which a positive model is then made utilizing low- expansion die stone.
  • the composition of the invention is then used to mold the orthodontic appliance by coating the model and curing with high intensity visible radiation in the 400-500 nanometer wavelength range, such as by using a commercial visible light-curing unit.
  • the above composition but without the photoinitiator and synergistic reducing agent components, may be utilized and cured with microwave radiation or heat curing in the 100' -120 * C range. It will be appreciated that this composition may be used in the fabrication of a wide variety of medical, dental/orthodontic, industrial, etc. articles where accurate, intricate shapes are required in a rigid molded polymer material.
  • composition has been found to be suitable for the molding of rigid, hollow hearing aid shells.
  • This material can be pigmented to a desired flesh color to match white, African-American, or Asian skin tones.
  • the composition includes the following:
  • composition is curable by exposure to visible light radiation.
  • microwave radiation curing can be utilized.
  • Contemplated surface treatment is silanation (treatment with organofunctional silane) to convert the surface of the particles from hydrophilic to hydrophobic; this enables better wetting with the resin matrix and stronger bonding to the particles upon polymerization.
  • pigment changes may be made without departing from the physical properties of the composition to achieve desired coloration.
  • the above composition is suitable for the fabrication of solid or hollow molded articles for medical, dental, industrial, or hobby craft applications.
  • EXAMPLE 3 The following example is a specific formulation which has been found to be suitable for rigid hearing aid shells.
  • This component is custom synthesized by Caschem and is an adduct of polyester polyol(aliphatic), hexamethylene diisocyanate and hydroxypropyl methacrylate.
  • COMPONENT COMPONENT SOURCE/ WEIGHT COMPONENT COMPONENT SOURCE/ WEIGHT
  • Pigment blend Flesh pink 0.19%
  • EXAMPLE 4 The following is a flesh pigmented composition, specifically pigmented for matching Asian complexions believed to be suitable for molding flexible, hollow hearing aid shells, or other flexible articles.
  • a preferred resin is a polymethyl hexamethylene diisocyanatoethyl methacrylate.
  • the same composition may advantageously utilize an ultraviolet photoinitiator such as benzoin methyl ether, in place of the noted photoinitiator, to permit curing using high intensity ultraviolet radiation in the range of 320-400 nanometer wavelength, in a commercial ultraviolet light curing unit.
  • an ultraviolet photoinitiator such as benzoin methyl ether
  • EXAMPLE 5 An example of a preferred formulation which has been found to be suitable for molding flexible articles, such as flexible hearing aid shells is given below.
  • the custom synthesized resins such as Resin E and Resin F available from Kerr Dental Materials Center may be produced utilizing the following general procedure. X moles of medium molecular weight (350- 650) polyol are placed in a glass polymer kettle fitted with stirrer, thermometer and inlet port. Dropwise, through the inlet port, 2X moles of diisocyanate are added at a rate such that an exotherm temperature of 40 * C is never exceeded. The following reaction proceeds:
  • Step 2 OCN-R ⁇ N-C-O-R O-R O-Rj-O-C-N-Rj-NCO + 2 HO-CH 2 -CH 2 -0-C-CH - i n i i i n
  • a diluent monomer is also utilized and is selected for functionality and molecular weight, usually it is monofunctional when flexibility is desired, and poly functional when rigidity is desired in the final product.
  • the monomer may be methacry late-functional when the final material is intended for medical or dental applications, and of either acrylate or methacrylate-functionality for industrial applications when biocompatibility is not such an important issue.
  • Resin E is preferably an adduct of aliphatic polyester polyol, hexamethylene diisocyanate and hydroxymethyl methacrylate.
  • Resin F is preferably an adduct of aliphatic polyether polyol, hexamethylene diisocyanate and hydroxypropyl methacrylate.
  • a typical application for the moldable liquid compositions of the present invention is the formation of rigid or flexible hearing aid shells.
  • Compositions of the type disclosed hereinabove are suitable for producing such products according to the following procedure. Initially, a cotton plug is carefully placed in the ear canal to serve as a barrier to the inner ear. An impression of the outer ear is taken using a suitable dental impression material. A transparent mold is then made from this impression, using either pourable, unpigmented translucent dental impression material, or a suitable pourable reversible transparent Agar-Agar impression material. This mold is then filled in a filtered light environment with the desired composition of the present invention, covered with a cellophane, mylar or polyethylene film and an opaque metal or plastic disc.
  • This arrangement is then placed in a suitable visible light curing cabinet for 12-15 seconds, or for a sufficient time to allow a polymer shell of approximately one millimeter thickness to form around the exposed surfaces of the liquid. All unpolymerized liquid is allowed to drain out of the mold and the mold is then filled with a suitable air barrier liquid (such as aqueous 1,2,3-propane triol), to prevent air inhibition of the surface. The uncovered mold is returned to the visible light curing cabinet for a full cure of approximately two minutes duration. The air barrier liquid is then poured out of the mold, the mold is rinsed with water to remove any residual traces of air barrier liquid, and a cured shell is pried from the mold, using dry warm air. Thereafter, the shell is trimmed and fitted with a base plate carrying the necessary electronic/acoustical components for the hearing aid, and the two sections are affixed together. The above procedure permits the completion, after one visit, of a custom- fitted hearing aid device.
  • a suitable air barrier liquid such as aqueous 1,

Landscapes

  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Public Health (AREA)
  • General Health & Medical Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Epidemiology (AREA)
  • Plastic & Reconstructive Surgery (AREA)
  • Dental Preparations (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne des compositions capables de durcir sous l'effet de rayonnements pour produire des articles moulés rigides ou flexibles, utilisables comme articles médicaux, orthodontiques et autres. La présente invention concerne d'une manière large les compositions liquides pouvant être déversées, capables de durcir sous l'effet de radiations pour former des articles rigides ou flexibles. Ces articles sont utiles en art dentaire ou en orthodontie, ou pour réaliser des dispositifs médicaux, des prothèses flexibles ou rigides, ou encore des modèles réduits ou même des pièces à usage industriel. Dans l'aspect le plus large de l'invention, les compositions contiennent en tant que composant primaire une ou plusieurs résines uréthane à fonctions acryliques, des monomères de dilution pour diluer la composition à la consistance souhaitée, des photosensibilisants, des agents réducteurs synergiques, des lubrifiants, des épaississants, des charges de renforcement et des pigments, en fonction des nécessités des différentes applications. Ces composants sont présents dans les proportions nécessaires pour avoir les propriétés physiques souhaitées (c'est-à-dire résistance, dureté, etc.).
EP95938945A 1994-11-04 1995-10-24 Compositions de moulage capables de durcir sous l'effet de rayonnements Withdrawn EP0753028A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US33427694A 1994-11-04 1994-11-04
PCT/US1995/013928 WO1996015179A2 (fr) 1994-11-04 1995-10-24 Compositions de moulage capables de durcir sous l'effet de rayonnements
US334276 1999-06-16

Publications (1)

Publication Number Publication Date
EP0753028A1 true EP0753028A1 (fr) 1997-01-15

Family

ID=23306450

Family Applications (1)

Application Number Title Priority Date Filing Date
EP95938945A Withdrawn EP0753028A1 (fr) 1994-11-04 1995-10-24 Compositions de moulage capables de durcir sous l'effet de rayonnements

Country Status (4)

Country Link
EP (1) EP0753028A1 (fr)
JP (1) JPH09504572A (fr)
DE (1) DE753028T1 (fr)
WO (1) WO1996015179A2 (fr)

Families Citing this family (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SG55351A1 (en) * 1996-07-17 1998-12-21 Asahi Chemical Ind Photosensitive resin composition for photocast-molding
DE19825984C1 (de) * 1998-06-10 2000-03-16 Fraunhofer Ges Forschung Verfahren zur Herstellung thermotroper Gießharzsysteme und seine Verwendung
US6304663B1 (en) * 1998-09-25 2001-10-16 Beltone Netherlands B.V. Otoplastic for a hearing aid
US6107436A (en) * 1998-10-05 2000-08-22 3M Innovative Properties Company Polyfunctional polymer
US6350823B1 (en) 1998-10-05 2002-02-26 3M Innovative Properties Company Pavement marking composition
DE19848886C2 (de) * 1998-10-23 2000-11-16 Heraeus Kulzer Gmbh & Co Kg Lichtpolymerisierbares Einkomponenten-Dentalmaterial
DE19961341C2 (de) 1999-12-17 2003-09-11 3M Espe Ag Verbesserte Dentalmaterialien
ITRM20010024U1 (it) * 2001-02-14 2002-08-14 D A P Dental Advanced Products Resina poliuretanica per modelli odontotecnici di precisione.
DE10258361B4 (de) * 2002-12-12 2007-04-05 Dreve Otoplastik Gmbh Verwendung eines Werkstoffes für Lärm-, Schwimmschutzteile, Otoplastiken und zur Fixierung von Ventings sowie Verfahren zur Herstellung solcher Teile
DE602005020289D1 (de) 2005-09-13 2010-05-12 Coltene Whaledent Ag Verfahren zum Abdrucknehmen
US20070116311A1 (en) * 2005-11-16 2007-05-24 Henkel Corporation High strength curable compositions for the solid freeform fabrication of hearing aids
EP1801140A1 (fr) * 2005-12-22 2007-06-27 Mnemoscience GmbH Macro diacrylate
EP3658602A4 (fr) * 2017-07-25 2021-04-14 3M Innovative Properties Company Compositions photopolymérisables comprenant un composant uréthane et un diluant réactif, articles et procédés
EP3681434A4 (fr) 2017-09-11 2021-04-07 3M Innovative Properties Company Compositions durcissables par rayonnement et articles composites fabriqués à l'aide d'un procédé de fabrication additive
US11904031B2 (en) 2017-11-22 2024-02-20 3M Innovative Properties Company Orthodontic articles comprising polymerized composition comprising at least two free-radical initiators
WO2019104072A1 (fr) * 2017-11-22 2019-05-31 3M Innovative Properties Company Articles orthodontiques comprenant une composition polymérisable par voie radicalaire durcie contenant un polymère ou une macromolécule ayant un groupe photo-initiateur
WO2019104079A1 (fr) * 2017-11-22 2019-05-31 3M Innovative Properties Company Articles orthodontiques comprenant une composition polymérisée contenant au moins deux initiateurs radicalaires
WO2019103855A1 (fr) * 2017-11-22 2019-05-31 3M Innovative Properties Company Compositions photopolymérisables comprenant un composant uréthane et un diluant réactif monofonctionnel, articles et procédés
EP3806774A4 (fr) * 2018-06-29 2022-07-06 3M Innovative Properties Company Articles orthodontiques préparés à l'aide d'un polycarbonate diol, et leurs procédés de fabrication
EP3752123A1 (fr) 2018-06-29 2020-12-23 3M Innovative Properties Company Compositions photopolymérisables comprenant un polymère de méthacrylate de polyuréthane préparé à l'aide d'un polycarbonate diol, articles, et procédés
EP3813763A1 (fr) * 2018-06-29 2021-05-05 3M Innovative Properties Company Articles orthodontiques comprenant une composition polymérisable par polymérisation radicalaire et durcie, offrant une résistance améliorée dans un environnement aqueux
CN113015511A (zh) * 2018-11-19 2021-06-22 3M创新有限公司 包含聚酯氨基甲酸酯(甲基)丙烯酸酯聚合物和单官能(甲基)丙烯酸酯单体的正畸制品、方法和可聚合组合物

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US4554336A (en) * 1983-10-28 1985-11-19 Sybron Corporation Urethane modified orthodontic adhesive
DE3610683A1 (de) * 1986-03-29 1987-10-01 Wolfgang Heynold Polymerisierbare masse fuer die herstellung weichbleibender formteile von insbesondere zahnprothesen
JPS63130611A (ja) * 1986-11-21 1988-06-02 Nippon Kayaku Co Ltd ポリウレタン（メタ）アクリレ−ト混合物，樹脂組成物及びコ−テイング剤
EP0498592A3 (en) * 1991-02-06 1993-03-31 Imperial Chemical Industries Plc Coloured hearing aid shell

Non-Patent Citations (1)

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Also Published As

Publication number Publication date
WO1996015179A3 (fr) 1996-10-10
JPH09504572A (ja) 1997-05-06
DE753028T1 (de) 1997-04-30
WO1996015179A2 (fr) 1996-05-23

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