WO2006019801A1 - Dental compositions containing carbosilane monomers - Google Patents
Dental compositions containing carbosilane monomers Download PDFInfo
- Publication number
- WO2006019801A1 WO2006019801A1 PCT/US2005/024826 US2005024826W WO2006019801A1 WO 2006019801 A1 WO2006019801 A1 WO 2006019801A1 US 2005024826 W US2005024826 W US 2005024826W WO 2006019801 A1 WO2006019801 A1 WO 2006019801A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- carbosilane
- combinations
- meth
- dental composition
- Prior art date
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
- A61K6/896—Polyorganosilicon 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
- A61K6/884—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
- crystallizable it is meant that the material either alone or in the presence of other monomers displays a crystalline melting point at 20 0 C or above when measured by differential scanning calorimetry (DSC). The peak temperature of the observed endotherm is taken as the crystalline melting point.
- the crystalline phase includes multiple lattices in which the material assumes a conformation in which there is a highly ordered registry in adjacent chemical moieties of which the material is constructed.
- the packing arrangement (short order orientation) within the lattice is highly regular in both its chemical and geometric aspects.
- a crystallizable component may be in a "semicrystalline state" in that long segments of polymer chains appear in both amorphous and crystalline states or phases at 20 0 C or above.
- a “crystallizable” component encompasses semicrystalline materials.
- the present invention provides carbosilane monomers for use in (meth)acrylate- based dental compositions.
- the carbosilane monomers i.e., carbosilane-containing monomers
- arylene as used herein includes carbocyclic aromatic rings or ring systems.
- the carbosilane monomer is capable of polymerizing, and optionally crosslinking, due to preferred multi-functionality.
- a preferred carbosilane monomer is hardenable (e.g., polymerizable and/or crosslinkable), preferably by a free radical mechanism.
- Such carbosilane materials preferably include the following structural features: at least 2 Si-arylene bonds; at least 1 silicon atom; at least 1 (meth)acrylate moiety; and no Si-O bonds.
- the carbosilane monomer has a functionality greater than one, more preferably at least two.
- Ar is an arylene group having 6-14 carbon atoms in the ring system, optionally substituted by halogen, alkyl groups (preferably having 1-10 carbon atoms, and more preferably 1-6 carbon atoms), or alkoxy groups (preferably having 1-10 carbon atoms, and more preferably having 1-6 carbon atoms), or combinations thereof.
- each A is independently an aliphatic group having 1-6 carbon atoms, cycloaliphatic group having 1-6 carbon atoms, an aromatic group having 6-14 carbon atoms, or combinations thereof. More preferably, each A is independently an aliphatic group having 1-6 carbon atoms (and more preferably, 1-3 carbon atoms).
- each Q is independently an aliphatic group having 1-10 carbon atoms, cycloaliphatic group having 3-10 carbon atoms, aromatic group having 6-10 carbon atoms, or combinations of such groups, optionally including one or more O, Br, Cl, or Si atoms, or combinations thereof. More preferably, each Q is independently an (Cl-C3)alkylene, oxy(Cl -C3)alkylene group, or a (C3-C9)cycloaliphatic group.
- the carbosilane monomer can be formulated into dental composites that exhibit a total volumetric polymerization shrinkage of no greater than 2.0% (typically, a shrinkage of 1.4% to 2.0%), wherein the percentage is based on the volume of the composition prior to hardening, preferably while maintaining excellent physical properties.
- the total amount of the carbosilane monomer in the dental composition is at least 1 wt-%, more preferably, at least 3 wt-%, and most preferably, at least 5 wt-%, based on the total weight of the composition.
- the total amount of the carbosilane monomer is no greater than 60 wt-%, more preferably, no greater than 50 wt- %, and most preferably, no greater than 40 wt-%, based on the total weight of the composition.
- Scheme 1 outlines a general procedure for the preparation of a carbosilane- containing material.
- Scheme 1 is shown using a bis(dimethylsilyl)-arylene, substituents other than methyl can be used in the arylene disilane reactant.
- Scheme 1 is shown using a methacrylate functional olefin reactant, acrylates can be used as well as other ethylenically unsaturated compounds.
- one of the reactants includes a (meth)acrylate (i.e., acrylate or methacrylate) moiety.
- a multifunctional aromatic silane is reacted with a (meth)acrylate functional ethylenically unsaturated compound through a hydrosilation reaction, resulting in a monomeric product.
- platinum alkyne complexes such as those described in U.S. Pat. No. 4,603,215
- the reaction product of chloroplatinic acid with tetravinylcyclotetrasiloxanes in the presence of sodium bicarbonate in ethanol solution such as those described in U.S. Pat. No. 3,715,334.
- Particularly preferred catalysts are the complexes prepared with chloroplatinic acid and certain unsaturated organosilicon compounds, such as those described in U.S. Pat.
- the catalyst should be present in an effective amount, i.e., an amount sufficient to catalyze the hydrosilation reaction. Satisfactory results may be obtained when the catalyst is present in an amount sufficient to provide as little as one part by weight of metal (e.g., platinum) per million parts by weight of the total composition. On the other hand, an amount of the catalyst sufficient to provide as high as 1 part to 10 parts by weight of metal (e.g., platinum) per 1,000 parts by weight of the total composition may also be used. In general, however, it is preferred to employ the catalyst in an amount sufficient to provide one to two hundred parts by weight of metal (e.g., platinum) per one million parts by weight of the total composition.
- metal e.g., platinum
- the secondary polymerizable components of the present invention can be part of a hardenable resin.
- These resins are generally thermosetting materials capable of being hardened to form a polymer network including, for example, acrylate-functional materials, methacrylate-functional materials, vinyl-functional materials, and mixtures thereof.
- the hardenable resin is made from one or more matrix-forming oligomers, monomers, polymers, or blends thereof.
- One class of hardenable resins includes materials having polymerizable components with free radically active functional groups. Examples of such materials include monomers having one or more ethylenically unsaturated groups, oligomers having one or more ethylenically unsaturated groups, polymers having one or more ethylenically unsaturated groups, and combinations thereof.
- Such free radically ethylenically unsaturated compounds include, for example, mono-, di- or poly-(meth)acrylates (i.e., acrylates and methacrylates) such as, methyl (meth)acrylate, ethyl acrylate, isopropyl methacrylate, n-hexyl acrylate, stearyl acrylate, allyl acrylate, glycerol triacrylate, ethyleneglycol diacrylate, diethyleneglycol diacrylate, triethyleneglycol dimethacrylate, 1,3-propanediol di(meth)acrylate, trimethylolpropane triacrylate, 1,2,4- butanetriol trimethacrylate, 1,4-cyclohexanediol diacrylate, pentaerythritol tetra(meth)acrylate, sorbitol hexacrylate, tetrahydrofurfuryl (meth)acrylate, bis[
- Especially preferred materials are saturated, linear, aliphatic polyester polyols that are modified (e.g., through primary hydroxyl end groups) to introduce polymerizable, unsaturated functional groups, e.g., polycaprolactone diol reacted with 2- isocyanatoethyl methacrylate, methacryloyl chloride, or methacrylic anhydride.
- Ketones e.g., monoketones or alpha diketones
- ketocoumarins aminoarylketones
- p-substituted aminostyryl ketone compounds are preferred sensitizers.
- particularly preferred visible light sensitizers include camphorquinone, glyoxal, biacetyl, 3,3,6,6 tetramethylcyclohexanedione, 3, 3,7,7-tetramethyl-1.2-cycloheptanedione, 3,3,8,8- tetramethyl-l,2-cyclooctanedione, 3,3,18,18-tetramethyl-l,2 cyclooctadecanedione, dipivaloyl, benzil, furil, hydroxybenzil, 2,3-butanedione, 2,3-pentanedione, 2,3- hexanedione, 3,4-hexanedione, 2,3-heptane
- Mono- and all-ketones can also be used as photoinitiators. Examples of such systems are described in U.S. Pat. No. 4,071,424 (Dart et al.).
- Cationic dyes useful as counterions can be cationic methine, polymethine, triarylmethine, indoline, thiazine, xanthene, oxazine or acridine dyes.
- Quaternary ammonium groups useful as counterions can be trimethylcetylammonium, cetylpyridinium, and tetramethylammonium.
- Other organophilic cations can include pyridinium, phosphonium, and sulfonium.
- Borate salt photoinitiators are described, for example, in U.S. Pat. Nos. 4,772,530 (Gottschalkea et al.), 4,954,414 (Adair et al.), 4,874,450 (Gottschalkea), 5,055,372 (Shanklin et al.), and 5,057,393 (Shanklin et al.).
- the initiator system is present in a total amount of no more than 10 wt-%, more preferably, no more than 5 wt-%, and most preferably, no more than 2.5 wt-%, based on the weight of the composition.
- Filler System is present in a total amount of no more than 10 wt-%, more preferably, no more than 5 wt-%, and most preferably, no more than 2.5 wt-%, based on the weight of the composition.
- Preferred particulate filler is finely divided and has an average particle size (preferably, diameter) of less than 10 micrometers (i.e., microns).
- nanoscopic fillers are commonly used as viscosity and thixotropy modifiers. Due to their small size, high surface area, and associated hydrogen bonding, these materials are known to assemble into aggregated networks.
- Materials of this type (“nanoscopic" materials) have average primary particle sizes (i.e., the largest dimension, e.g., diameter, of unaggregated material) of no greater than 1000 nanometers (nm).
- the nanoscopic particulate material has an average primary particle size of at least 2 nanometers (nm), and preferably at least 7 nm.
- the nanoscopic particulate material has an average primary particle size of no greater than 50 nm, and more preferably no greater than 20 nm in size.
- the average surface area of such a filler is preferably at least 20 square meters per gram (m 2 /g), more preferably, at least 50 m 2 /g, and most preferably, at least 100 m 2 /g.
- Suitable fillers can be radiopaque, radiolucent, or nonradiopaque.
- Fillers as used in dental applications are typically ceramic in nature.
- suitable inorganic fillers are naturally occurring or synthetic materials such as quartz, nitrides (e.g., silicon nitride), glasses derived from, for example Ce, Sb, Sn, Zr, Sr, Ba, or Al, colloidal silica, feldspar, borosilicate glass, kaolin, talc, titania, and zinc glass, zirconia-silica fillers; and low Mohs hardness fillers such as those described in U.S. Pat. No. 4,695,251 (Randklev).
- the total amount of filler system is greater than 50 wt-%, more preferably, greater than 60 wt-%, and most preferably, greater than 70 wt-%, based on the total weight of the composition. If the filler system includes fibers, the fibers are present in an amount of less than 20 wt-%, based on the total weight of the composition. Preferably, the total amount of filler system is no more than 95 wt-%, and more preferably, no more than 80 wt-%, based on the total weight of the composition.
- the total amount of optional component is no more than 5.0 wt-%, more preferably, no more than about 2.5 wt-%, and most preferably, no more than 1.5 wt-%, based on the total weight of the composition.
- the above described carbosilane-containing monomer can be used as a component in dental compositions that are hardenable, preferably via radical polymerization of unsaturated groups, especially (meth)acrylate groups.
- Dental compositions of the present invention can be used, for example, as dental restoratives or prefabricated prosthetic devices. Examples of restoratives include dental composites and amalgams. Examples of prefabricated prosthetic devices include crowns, bridges, veneers, inlays, onlays, posts, pins, and the like.
- the compositions of the present invention can also be shaped (e.g., molded) into a variety of forms like three-dimensional shapes, preformed sheets, arch shaped trays, ropes, buttons, woven, or non-woven webs, and the like.
- the composition can be shaped (to form a first shape) in a variety of ways including, for example, extruding, injection molding, compression molding, thermoforming, vacuum forming, pressing, calendering, and web processing using rollers.
- a semi-finished shape is formed using a mold with a positive and negative impression.
- the shaped forms can be used, for example, as dental crowns, dental impression trays, and orthodontic appliances. Examples of orthodontic appliances include lingual retainers, space retainers, hooks, buttons, splints, and bases for orthodontic brackets.
- Compressive strength of a test sample was measured according to American National Standards Institute/American Standards Association (ANSI/ASA) specification No. 27 (1993).
- a sample was packed into a 4 millimeters (mm) (inside diameter) glass tube (and if necessary the sample was heated to accomplish the packing), and the tube was capped with silicone rubber plugs and compressed axially at approximately 0.28 megapascal (Mpa) for 5 minutes.
- the sample was then light cured for 90 seconds by exposure to two oppositely disposed VISILUX Model 2500 blue light guns (3M Co., St. Paul, MN) followed by irradiation for 180 seconds in a Dentacolor XS unit (Kulzer, Inc., Germany).
- Cured samples were cut with a diamond saw to form 8-mm long cylindrical plugs for measurement of compressive strength.
- the plugs were stored in distilled water at 37 0 C for 24 hours prior to testing. Measurements were carried out on an Instron tester (Instron 4505, Instron Corp., Canton, MA) with a 10 kilonewton (kN) load cell at a crosshead speed of 1 mm/minute. Five cylinders of cured samples were prepared and measured with the results reported in MPa as the average of the five measurements.
- Instron tester Instron 4505, Instron Corp., Canton, MA
- kN kilonewton
- the mixture was loaded onto a silica gel column and eluted with a mixture of ethyl acetate (30 vol%) in hexane (70 vol%).
- the solvent was evaporated to yield the product as a colorless oil (9.52 g) having a Molecular Weight (MW) of 603.06 and a viscosity of 3879 cP. Characterization of the oil by IH NMR and IR spectra was consistent with the m-PDN structure.
- the mixture was loaded onto a silica gel column and eluted with a mixture of ethyl acetate (20 vol%) in hexane (80 vol%).
- the solvent was evaporated to yield the product as a colorless oil (6.45 g) having a MW of 534.85 and a viscosity of 32 cP. Characterization of the oil by IH NMR and IR spectra was consistent with the p-PDE structure.
- Polymerizable compositions (Examples 6-32) were prepared according to the following general procedure.
- the photoinitiator/stabilizer components were initially dissolved in BisGMA and the resulting mixture combined with the other monomer components of the composition (BisEMA-6, UDMA, TEGDMA, and Carbosilane
- the concentrations of photoinitiator/stabilizer components used were CPQ (0.176 phr), EDMAB (1.55 phr), DPIHFP (0.517 phr), BHT (0.155 phr), and Benzotriazole (1.552 phr).
- the blended monomer components plus the filler component STZ were weighed into a MAX 20 plastic mixing cup having a screw cap (Flakteck, Landrum, SC) and then the closed cup heated in an oven at 85 0 C for 30 minutes.
- the cup was placed in a DAC 150 FV speed mixer (Flakteck) and spin mixing was carried out for 1 minute at 3000 rpm. The cup was then reheated for 30 minutes at 85°C followed by another minute of mixing at 3000 rpm to yield the final blended compositions.
- the amounts of components for each example are provided in Table 1.
- the weight of BisGMA in Table 1 includes the weight of the photoinitiator/stabilizer components.
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
Description
Claims
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT05771688T ATE447924T1 (en) | 2004-07-14 | 2005-07-13 | DENTAL COMPOSITIONS WITH CARBOSILANE MONOMERS |
CA002573716A CA2573716A1 (en) | 2004-07-14 | 2005-07-13 | Dental compositions containing carbosilane monomers |
US11/571,944 US7576144B2 (en) | 2004-07-14 | 2005-07-13 | Dental compositions containing carbosilane monomers |
EP05771688A EP1773281B1 (en) | 2004-07-14 | 2005-07-13 | Dental compositions containing carbosilane monomers |
AU2005275246A AU2005275246B2 (en) | 2004-07-14 | 2005-07-13 | Dental compositions containing carbosilane monomers |
JP2007521602A JP4819806B2 (en) | 2004-07-14 | 2005-07-13 | Dental composition containing carbosilane monomer |
DE602005017633T DE602005017633D1 (en) | 2004-07-14 | 2005-07-13 | DENTAL COMPOSITIONS WITH CARBOSILAN MONOMERS |
CN2005800238235A CN1997334B (en) | 2004-07-14 | 2005-07-13 | Dental compositions containing carbosilane monomers |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US58776204P | 2004-07-14 | 2004-07-14 | |
US60/587,762 | 2004-07-14 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2006019801A1 true WO2006019801A1 (en) | 2006-02-23 |
Family
ID=35124554
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2005/024826 WO2006019801A1 (en) | 2004-07-14 | 2005-07-13 | Dental compositions containing carbosilane monomers |
Country Status (9)
Country | Link |
---|---|
US (1) | US7576144B2 (en) |
EP (1) | EP1773281B1 (en) |
JP (1) | JP4819806B2 (en) |
CN (1) | CN1997334B (en) |
AT (1) | ATE447924T1 (en) |
AU (1) | AU2005275246B2 (en) |
CA (1) | CA2573716A1 (en) |
DE (1) | DE602005017633D1 (en) |
WO (1) | WO2006019801A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8084515B2 (en) | 2004-07-14 | 2011-12-27 | 3M Innovative Properties Company | Dental compositions containing carbosilane polymers |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA2573501A1 (en) * | 2004-07-14 | 2006-01-19 | 3M Espe Ag | Dental composition containing si-h functional carbosilane components |
AU2004321429A1 (en) * | 2004-07-14 | 2006-01-19 | 3M Espe Ag | Dental composition containing unsaturated carbosilane containing components |
JP6036703B2 (en) * | 2011-12-16 | 2016-11-30 | 株式会社スリーボンド | Curable resin composition |
DE102013008176A1 (en) | 2012-10-05 | 2014-04-10 | Voco Gmbh | Kit and method for the indirect chairside production of composite inlays |
JP6915405B2 (en) | 2017-06-29 | 2021-08-04 | 信越化学工業株式会社 | Poly (meth) acrylate and coating compositions and coating articles containing it |
US11945891B2 (en) * | 2017-09-20 | 2024-04-02 | Denka Company Limited | Speaker having an adhesive composition |
CN110357916B (en) * | 2019-07-23 | 2020-09-08 | 吉林奥来德光电材料股份有限公司 | Compound for packaging film, composition and film thereof, organic light-emitting device and packaging method |
CN110755270A (en) * | 2019-10-22 | 2020-02-07 | 华南理工大学 | Dental composite resin containing branched polysiloxane (methyl) acrylate |
CN112898330A (en) * | 2020-07-28 | 2021-06-04 | 吉林奥来德光电材料股份有限公司 | Compound for packaging organic light-emitting device and preparation method and application thereof |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001007444A1 (en) * | 1999-07-22 | 2001-02-01 | 3M Espe Ag | Hydrolyzable silanes and polymerizable silanes with low viscosity and use thereof |
Family Cites Families (76)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3220972A (en) * | 1962-07-02 | 1965-11-30 | Gen Electric | Organosilicon process using a chloroplatinic acid reaction product as the catalyst |
US3159601A (en) * | 1962-07-02 | 1964-12-01 | Gen Electric | Platinum-olefin complex catalyzed addition of hydrogen- and alkenyl-substituted siloxanes |
NL131800C (en) * | 1965-05-17 | |||
US3927116A (en) * | 1967-10-24 | 1975-12-16 | Union Carbide Corp | Bicyclo{8 2.2.1{9 {0 Hept-5(6)-yl compounds |
US3814730A (en) * | 1970-08-06 | 1974-06-04 | Gen Electric | Platinum complexes of unsaturated siloxanes and platinum containing organopolysiloxanes |
US3715334A (en) * | 1970-11-27 | 1973-02-06 | Gen Electric | Platinum-vinylsiloxanes |
US3775352A (en) * | 1971-03-22 | 1973-11-27 | Shell Oil Co | Metal-polymer matrices and their preparation |
US3775452A (en) * | 1971-04-28 | 1973-11-27 | Gen Electric | Platinum complexes of unsaturated siloxanes and platinum containing organopolysiloxanes |
GB1408265A (en) * | 1971-10-18 | 1975-10-01 | Ici Ltd | Photopolymerisable composition |
US3971754A (en) * | 1973-12-10 | 1976-07-27 | Pennwalt Corporation | X-ray opaque, enamel-matching dental filling composition |
US3933880A (en) * | 1974-12-02 | 1976-01-20 | Dow Corning Corporation | Method of preparing a platinum catalyst inhibitor |
US4288345A (en) * | 1980-02-06 | 1981-09-08 | General Electric Company | Platinum complex |
US4695251A (en) * | 1980-04-07 | 1987-09-22 | Minnesota Mining And Manufacturing Company | Orthodontic bracket adhesive and abrasive for removal thereof |
US4356296A (en) * | 1981-02-25 | 1982-10-26 | The United States Of America As Represented By The Secretary Of The Navy | Fluorinated diacrylic esters and polymers therefrom |
US4391590A (en) * | 1981-04-09 | 1983-07-05 | Dentsply Research & Development Corp. | Cartridge for viscous material |
US4421903A (en) * | 1982-02-26 | 1983-12-20 | General Electric Company | Platinum complex catalysts |
US4530879A (en) * | 1983-03-04 | 1985-07-23 | Minnesota Mining And Manufacturing Company | Radiation activated addition reaction |
US4510094A (en) * | 1983-12-06 | 1985-04-09 | Minnesota Mining And Manufacturing Company | Platinum complex |
US4600484A (en) * | 1983-12-06 | 1986-07-15 | Minnesota Mining And Manufacturing Company | Hydrosilation process using a (η5 -cyclopentadienyl)tri(σ-aliphatic) platinum complex as the catalyst |
US4503169A (en) * | 1984-04-19 | 1985-03-05 | Minnesota Mining And Manufacturing Company | Radiopaque, low visual opacity dental composites containing non-vitreous microparticles |
JPS60262303A (en) * | 1984-06-11 | 1985-12-25 | 株式会社東芝 | Ptc ceramic composition |
EP0194277A4 (en) | 1984-08-17 | 1987-02-03 | Mc Carry John D | Alkylsilane contact lens and polymer. |
US4603215A (en) * | 1984-08-20 | 1986-07-29 | Dow Corning Corporation | Platinum (O) alkyne complexes |
GR852068B (en) | 1984-08-30 | 1985-12-24 | Johnson & Johnson Dental Prod | |
US4642126A (en) | 1985-02-11 | 1987-02-10 | Norton Company | Coated abrasives with rapidly curable adhesives and controllable curvature |
DE3516257A1 (en) | 1985-05-07 | 1986-11-13 | Bayer Ag, 5090 Leverkusen | (METH) ACRYLIC ACID ESTERS AND THEIR USE |
DE3516256A1 (en) * | 1985-05-07 | 1986-11-13 | Bayer Ag, 5090 Leverkusen | (METH) ACRYLIC ACID ESTERS AND THEIR USE |
US4652274A (en) * | 1985-08-07 | 1987-03-24 | Minnesota Mining And Manufacturing Company | Coated abrasive product having radiation curable binder |
US4772530A (en) * | 1986-05-06 | 1988-09-20 | The Mead Corporation | Photosensitive materials containing ionic dye compounds as initiators |
US4705765A (en) * | 1985-12-19 | 1987-11-10 | General Electric Company | Hydrosilylation catalyst, method for making and use |
DE3609038A1 (en) * | 1986-03-18 | 1987-09-24 | Espe Stiftung | ROENTGENOPAKE POLYMERIZABLE DENTAL MATERIALS |
US4706765A (en) * | 1986-08-11 | 1987-11-17 | Four E Inc. | Drill bit assembly |
US4874450A (en) * | 1987-01-29 | 1989-10-17 | The Mead Corporation | Laminating transparent or translucent materials using ionic dye-counter ion complexes |
CA1323949C (en) * | 1987-04-02 | 1993-11-02 | Michael C. Palazzotto | Ternary photoinitiator system for addition polymerization |
US4771530A (en) * | 1987-04-08 | 1988-09-20 | General Atomics | Application of inwardly directed prestressing pressure to concrete members |
US4788268A (en) * | 1987-05-05 | 1988-11-29 | Hughes Aircraft Company | Method for preparation of epoxysilicone compounds and allyl-terminated silicone compounds |
US5145886A (en) * | 1988-05-19 | 1992-09-08 | Minnesota Mining And Manufacturing Company | Radiation activated hydrosilation reaction |
US4954414A (en) * | 1988-11-08 | 1990-09-04 | The Mead Corporation | Photosensitive composition containing a transition metal coordination complex cation and a borate anion and photosensitive materials employing the same |
DE3841617C1 (en) | 1988-12-10 | 1990-05-10 | Th. Goldschmidt Ag, 4300 Essen, De | |
US5026902A (en) * | 1988-12-10 | 1991-06-25 | Th. Goldschmidt AG & GDF Gesellschaft fur Dentale Forschung u. Innovationen GmbH | Dental compsition of perfluoroalkyl group-containing (meth-)acrylate esters |
US5076844A (en) * | 1988-12-10 | 1991-12-31 | Goldschmidt AG & GDF Gesellschaft fur Dentale Forschung u. Innovationen GmbH | Perfluoroalkyl group-containing (meth-)acrylate esters, their synthesis and use in dental technology |
US5057393A (en) * | 1989-07-10 | 1991-10-15 | The Mead Corporation | Dye branched-alkyl borate photoinitiators |
DE4011044A1 (en) | 1990-04-05 | 1991-10-10 | Fraunhofer Ges Forschung | SILANES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE FOR THE PRODUCTION OF POLYMERISATS AND POLYCONDENSATES |
US5055372A (en) * | 1990-04-23 | 1991-10-08 | The Mead Corporation | Photohardenable composition containing borate salts and ketone initiators |
US6046250A (en) * | 1990-12-13 | 2000-04-04 | 3M Innovative Properties Company | Hydrosilation reaction utilizing a free radical photoinitiator |
US6376569B1 (en) * | 1990-12-13 | 2002-04-23 | 3M Innovative Properties Company | Hydrosilation reaction utilizing a (cyclopentadiene)(sigma-aliphatic) platinum complex and a free radical photoinitiator |
US5165890A (en) * | 1991-01-07 | 1992-11-24 | Centrix, Inc. | Dosing dental cartridge |
US5346980A (en) * | 1992-04-14 | 1994-09-13 | Minnesota Mining And Manufacturing Company | Crosslinkable silarylene-siloxane copolymers |
US5322440A (en) * | 1992-10-20 | 1994-06-21 | Kerr Manufacturing Company | Dental syringe tip |
DE69427275T2 (en) | 1993-12-28 | 2001-10-25 | Kanegafuchi Chemical Ind | Silicon containing polymer, method of manufacture and monomer |
DE19648283A1 (en) * | 1996-11-21 | 1998-05-28 | Thera Ges Fuer Patente | Polymerizable compositions based on epoxides |
US6653375B2 (en) * | 1998-01-28 | 2003-11-25 | Ivoclar Ag | Urethane di(meth)acrylate derivatives of 1,3-bis(1-isocyanato-1-methylethyl)benzene |
DE19860361A1 (en) * | 1998-12-24 | 2000-06-29 | Espe Dental Ag | Crosslinkable monomers based on cyclosiloxane, their preparation and their use in polymerizable compositions |
DE19860364C2 (en) | 1998-12-24 | 2001-12-13 | 3M Espe Ag | Polymerizable dental materials based on siloxane compounds capable of curing, their use and manufacture |
US6730156B1 (en) | 1999-10-28 | 2004-05-04 | 3M Innovative Properties Company | Clustered particle dental fillers |
US6387981B1 (en) * | 1999-10-28 | 2002-05-14 | 3M Innovative Properties Company | Radiopaque dental materials with nano-sized particles |
US6572693B1 (en) * | 1999-10-28 | 2003-06-03 | 3M Innovative Properties Company | Aesthetic dental materials |
EP1586294B2 (en) | 1999-10-28 | 2016-02-17 | 3M Innovative Properties Company | Nano-sized silica particles in a dry powder form |
DE10001228B4 (en) * | 2000-01-13 | 2007-01-04 | 3M Espe Ag | Polymerizable preparations based on silicon-containing epoxides |
DE60029015T2 (en) * | 2000-04-03 | 2007-06-28 | 3M Innovative Properties Co., Saint Paul | DENTAL MATERIALS WITH EXTENDED PROCESSING TIME, KITS AND METHOD |
DE10026432A1 (en) | 2000-05-29 | 2002-02-14 | 3M Espe Ag | Prepolymer (meth) acrylates with polycyclic or aromatic segments |
FR2809728B1 (en) | 2000-05-30 | 2003-02-28 | Merial Sas | USEFUL PROCESS FOR TRANSFORMING THE CARBONYL FUNCTION TO THE 4 "POSITION OF THE CLADINOSE PATTERN FROM A MACROLIDE AZA TO AN AMINATED DERIVATIVE |
US6562953B2 (en) * | 2000-05-30 | 2003-05-13 | Merial | Process which is useful for converting the carbonyl function in position 4″ of the cladinose unit of an aza-macrolide into an amine derivative |
WO2001095862A1 (en) | 2000-06-13 | 2001-12-20 | Dentsply International Inc. | Low shrinking polymerizable dental material |
AU6426901A (en) | 2000-06-14 | 2001-12-24 | Pure Green Co Ltd | Oily cosmetics |
DE10107985C1 (en) | 2001-02-19 | 2002-04-18 | 3M Espe Ag | Polymerizable formulation used for coating and/or bonding substrates or as dental formulation, contains organosilicon compound with aliphatic and cycloaliphatic epoxide groups, filler and initiator, inhibitor and/or accelerator |
JP4748938B2 (en) * | 2002-01-31 | 2011-08-17 | スリーエム イノベイティブ プロパティズ カンパニー | Dental paste, dental article, and method |
US20040209990A1 (en) * | 2003-04-15 | 2004-10-21 | Uwe Walz | Low shrinking polymerizable dental material |
US8425926B2 (en) * | 2003-07-16 | 2013-04-23 | Yongxing Qiu | Antimicrobial medical devices |
US7156911B2 (en) * | 2004-05-17 | 2007-01-02 | 3M Innovative Properties Company | Dental compositions containing nanofillers and related methods |
US7649029B2 (en) * | 2004-05-17 | 2010-01-19 | 3M Innovative Properties Company | Dental compositions containing nanozirconia fillers |
US7090721B2 (en) * | 2004-05-17 | 2006-08-15 | 3M Innovative Properties Company | Use of nanoparticles to adjust refractive index of dental compositions |
CN101060827A (en) * | 2004-07-14 | 2007-10-24 | 3M埃斯佩股份公司 | Dental composition containing an epoxy functional carbosilane compound |
AU2004321429A1 (en) * | 2004-07-14 | 2006-01-19 | 3M Espe Ag | Dental composition containing unsaturated carbosilane containing components |
AU2004321434A1 (en) * | 2004-07-14 | 2006-01-19 | 3M Espe Ag | Dental composition containing unsaturated carbosilane containing components |
DE602005015333D1 (en) * | 2004-07-14 | 2009-08-20 | 3M Innovative Properties Co | DENTAL COMPOSITIONS WITH CARBOSILAN POLYMERS |
-
2005
- 2005-07-13 AU AU2005275246A patent/AU2005275246B2/en not_active Ceased
- 2005-07-13 WO PCT/US2005/024826 patent/WO2006019801A1/en active Application Filing
- 2005-07-13 AT AT05771688T patent/ATE447924T1/en not_active IP Right Cessation
- 2005-07-13 US US11/571,944 patent/US7576144B2/en not_active Expired - Fee Related
- 2005-07-13 EP EP05771688A patent/EP1773281B1/en not_active Not-in-force
- 2005-07-13 DE DE602005017633T patent/DE602005017633D1/en active Active
- 2005-07-13 JP JP2007521602A patent/JP4819806B2/en not_active Expired - Fee Related
- 2005-07-13 CN CN2005800238235A patent/CN1997334B/en not_active Expired - Fee Related
- 2005-07-13 CA CA002573716A patent/CA2573716A1/en not_active Abandoned
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001007444A1 (en) * | 1999-07-22 | 2001-02-01 | 3M Espe Ag | Hydrolyzable silanes and polymerizable silanes with low viscosity and use thereof |
US6852822B1 (en) * | 1999-07-22 | 2005-02-08 | 3M Espe Ag | Hydrolyzable silanes and polymerizable silanes with low viscosity and use thereof |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8084515B2 (en) | 2004-07-14 | 2011-12-27 | 3M Innovative Properties Company | Dental compositions containing carbosilane polymers |
Also Published As
Publication number | Publication date |
---|---|
US20070276059A1 (en) | 2007-11-29 |
JP2008506698A (en) | 2008-03-06 |
DE602005017633D1 (en) | 2009-12-24 |
CN1997334B (en) | 2012-03-21 |
JP4819806B2 (en) | 2011-11-24 |
AU2005275246A1 (en) | 2006-02-23 |
CA2573716A1 (en) | 2006-02-23 |
CN1997334A (en) | 2007-07-11 |
US7576144B2 (en) | 2009-08-18 |
EP1773281B1 (en) | 2009-11-11 |
ATE447924T1 (en) | 2009-11-15 |
EP1773281A1 (en) | 2007-04-18 |
AU2005275246B2 (en) | 2011-10-06 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1773281B1 (en) | Dental compositions containing carbosilane monomers | |
CN102985052B (en) | Dental composition, assembly box set and application thereof | |
US7816423B2 (en) | Hardenable self-supporting structures and methods | |
EP1781724B1 (en) | Dental compositions containing carbosilane polymers | |
CN102196799B (en) | Dental composition comprising biphenyl di(meth)acrylate monomer | |
CN102209708B (en) | Dental composition comprising biphenyl di(meth)acrylate monomer comprising urethane moieties | |
CN103370041A (en) | Dental compositions comprising ethylenically unsaturated addition-fragmentation agent | |
WO2009006282A2 (en) | Dental composition containing a polyfunctional (meth)acrylate comprising urethane, urea or amide groups, method of production and use thereof | |
AU2002331604A1 (en) | Hardenable self-supporting structures and methods | |
EP2042486A1 (en) | Methacrylate Based Monomers containing a Urethane Linkage, Process for Production and Use thereof | |
CN106029045A (en) | Dental composition and use thereof | |
US20230414458A1 (en) | Multi-part dental composition having staged viscosity prior to hardening | |
KR20070032381A (en) | Dental Compositions Containing Carbosilane Polymers | |
KR20070032380A (en) | Dental Compositions Containing Carbosilane Monomers |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KM KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NG NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SM SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LT LU LV MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWE | Wipo information: entry into national phase |
Ref document number: 2573716 Country of ref document: CA |
|
WWE | Wipo information: entry into national phase |
Ref document number: 200580023823.5 Country of ref document: CN Ref document number: 2007521602 Country of ref document: JP |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2005275246 Country of ref document: AU |
|
WWW | Wipo information: withdrawn in national office |
Country of ref document: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2005771688 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref document number: 2005275246 Country of ref document: AU Date of ref document: 20050713 Kind code of ref document: A |
|
WWP | Wipo information: published in national office |
Ref document number: 2005275246 Country of ref document: AU |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1020077003445 Country of ref document: KR |
|
WWP | Wipo information: published in national office |
Ref document number: 1020077003445 Country of ref document: KR |
|
WWP | Wipo information: published in national office |
Ref document number: 2005771688 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 11571944 Country of ref document: US |
|
WWP | Wipo information: published in national office |
Ref document number: 11571944 Country of ref document: US |