WO2009097152A1 - Acrylates multifonctionnels utilisés comme réticulants dans des adhésifs de liaison à auto-attaque dentaires et biomédicaux - Google Patents

Acrylates multifonctionnels utilisés comme réticulants dans des adhésifs de liaison à auto-attaque dentaires et biomédicaux Download PDF

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Publication number
WO2009097152A1
WO2009097152A1 PCT/US2009/000656 US2009000656W WO2009097152A1 WO 2009097152 A1 WO2009097152 A1 WO 2009097152A1 US 2009000656 W US2009000656 W US 2009000656W WO 2009097152 A1 WO2009097152 A1 WO 2009097152A1
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WO
WIPO (PCT)
Prior art keywords
bis
adhesive composition
propane
acrylate
methacrylate
Prior art date
Application number
PCT/US2009/000656
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English (en)
Inventor
James C. Ragain
David Charlton
Amer Tiba
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The United States Of America As Represented By The Secretary Of The Navy
General Dynamics Information Technology
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Application filed by The United States Of America As Represented By The Secretary Of The Navy, General Dynamics Information Technology filed Critical The United States Of America As Represented By The Secretary Of The Navy
Publication of WO2009097152A1 publication Critical patent/WO2009097152A1/fr

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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
    • A61K6/831—Preparations for artificial teeth, for filling teeth or for capping teeth comprising non-metallic elements or compounds thereof, e.g. carbon
    • A61K6/836—Glass
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/30—Compositions for temporarily or permanently fixing teeth or palates, e.g. primers for dental adhesives
    • 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

  • This invention relates to a biomaterial and more specifically a high molecular weight, multifunctional acrylate cross-linking composition that, when formulated with other compounds will self-etch and self-adhere to hard tissues, such as enamel, dentin, and bone.
  • Hard tissue typically means tissues that have become mineralized, or tissue having a firm intercellular substance, such as enamel, dentin, cartilage, and bone.
  • Bone and tooth structure such as enamel, dentin and cementum, have certain compositional and morphologic similarities.
  • enamel and dentin bone consists primarily of inorganic material, which is almost exclusively in the form of an apatite of calcium and phosphate that resembles hydroxylapatite, and a lesser amount of organic material, which is 90% collagen. Morphologic similarities also exist.
  • the Haversian Canals run parallel to the bone's surface, but Volkmann's Canals, which run from them meet the bone surface at a perpendicular angle.
  • the materials most commonly chosen as temporary fillings are zinc oxide-eugenol (ZOE) compounds, glass-ionomer materials, and resin-based dental materials. These filling materials are retained in teeth through mechanical retention and/or chemical bonding with the tooth structure.
  • ZOE zinc oxide-eugenol
  • Glass-ionomer dental filling materials can bond to tooth structure without the need of a separately applied bonding agent. In addition, glass-ionomer materials release fluoride, which strengthens the surface of the tooth.
  • a disadvantage of glass-ionomer dental filling materials is their relatively long setting time and concomitant sensitivity to moisture. Moisture exposure can result in premature disintegration of the glass-ionomer material and reduce bond strength. Furthermore, the chemical bond formed between glass-ionomers and tooth structure is relatively weak.
  • Resin-based filling materials can be bond to teeth using both mechanical and chemical retentions. Bonding of resin-based dental materials to tooth structure is currently achieved through a multi-step process. A dentin-enamel bonding agent must be applied to the tooth prior to placing the dental material. Applying this bonding agent often requires multiple steps and a significant amount of clinical time. Misapplication of the bonding material may also occur.
  • U.S. Pub. No. 2007/0155853 Al by Chen et al. is another one- component self-etching self-priming dental adhesive composition.
  • the formulation contains BisGMA (2,2-bis[4-(2-hydroxy-3-methacryloylpropoxy)-phenyl]-propane), DPPA (dipentaerythrytol pentaacrylate), GDM (glycerol dimethacrylate), GPDM (glycerol phosphate dimethacrylate), and PMGDM (pyromellitic glycerol dimethacrylate).
  • the formulation contains both water and an organic solvent such as acetone or ethanol. Additional clinical steps and resin materials are required to bond composite resins to dentin or enamel.
  • U.S. Pub. No. 2006/0069181 by Thalaker et al. presents a liquid self- etch adhesive that is composed of a carboxylic acid functional polymer and water.
  • This dental adhesive composition consists of two liquid components and contains no fluoride releasing agents or glass fillers. Additional clinical steps and resin materials are required to bond composite resins to dentin or enamel.
  • U.S. Pub. No. 2007/0248927 Al by Luchterhandt et al. is a self-adhesive composition based on polyacrylate, Kayamer, MH-P (Methacryloxyhexyl phosphate), MO-P (8-Methacryloxyoctyl phosphate), and MD-P (10-Methacryloxydecyl phosphate) polymerizable compounds. This formula is only photo-curable and requires additional priming step and curing equipment.
  • U.S. Pub. No. 2007/0203257 Al by Xuejun Qian describes a two-part paste/paste self-etch adhering dental composition based on UDMA (reaction product of 2-hydroxyethyl methacrylate with 2,4,4 -trimethylhexane diisocyanate), BisGMA, GDM-P (glyceryldimethacrylate phosphate), and GDM (glyceryidimethacrylate). It also contains a solvent, which may increase the oxidation rate of the formula. The formula does not contain any fluoride releasing agent. [0015] U.S. Pub. No. 2007/0203257 Al by Xuejun Qian, describes a two-part paste/paste self-etch adhering dental composition based on UDMA (reaction product of 2-hydroxyethyl methacrylate with 2,4,4 -trimethylhexane diisocyanate), BisGMA, GDM-P (glyceryldimethacrylate
  • the current invention aims to improve existing technology.
  • the inventive formulation has multiple advantages over the prior art. It is a self-etching material, which can be applied to tooth in a single step without the need of a primer.
  • the inventive formulation is also dual-curable, which means it can be photo-cured or chemically hardened. Chemical setting allows for curing in deep areas where light is not effective and eliminates the need of additional equipment in situations where such equipment are not readily available.
  • the inventive formula contains fluoride releasing materials and up to 75% of glass fillers in a combination of different particle sizes. The inclusion of fluoride releasing agent and high percentage of glass particles of varying sizes improve physical and mechanical properties of the final set material.
  • inventive formula is a power and liquid combination format and contains no solvent, which may increase shelf-life and prevents premature setting.
  • An object of this invention is an acid-stable polymerizable composition with multi-functional acrylate cross-linkers suitable as a dental/biomedical self- adhesive bonding material.
  • Another object of the invention is a self-etching, acid-stable polymerizable composition with multifunctional acrylate cross-linkers, which provides good self-adherence without prior preparation of the hard tissue or the substrates.
  • An additional object of the invention is a self-etching, acid-stable polymerizable adhesive material, which contains chemical and/or light-activated free- radical initiators that allows the final material to set within a relatively short time, approximately 4-4.5 minutes at 37 0 C.
  • a further object of the invention is a fluoride-releasing composition that can be used as a self-etching, self-adhesive bonding agent between hard tissues (enamel, dentin, or bone) and dental and biomedical substrates.
  • Another object of this invention is a method of bonding dental and medical biomaterials via a molecular bridge formed from calcium reactive amines and acrylic or methacrylic ester monomers to hard tissues such as enamel, dentin, and bone.
  • This invention is directed to an adhesive composition that can be used in bonding dental and medical biomaterials to hard tissues via a molecular bridge formed from calcium reactive amines and acrylic or methacrylic ester monomers contained in the biomaterials and enamel, dentin, and bone.
  • the adhesive composition may be used as: (i) temporary dental restorative or dressing material, (ii) long-term dental restorative (filling) material through the incorporation of various inorganic filler materials, (iii) luting cement, for bonding fixed dental prosthetic devices, such as crowns and bridges, to dentin and enamel, or (iv) luting cement for bonding orthodontic brackets to enamel; (v) stint for stabilizing avulsed, inverted, or luxated teeth; (vi) bone cement, for bonding implant prostheses and skull implants to bone; (vii) liner or base under amalgam dental restorations.
  • This adhesive composition comprises of an acid-stable polymerizable compound with multi-functional acrylate cross-linkers and provides good self-etching and self-adherence without prior preparation of the hard tissue substrates, such as separate acid etching or priming steps.
  • the adhesive composition comprises a mixture of one or more polymerizable acrylic or methacrylate compounds, one or more hydrophilic acrylate or methacrylate compounds, one or more calcium reactive amines, one or more acrylic or methacrylic esters, one or more polymerization initiators, glass powder, fluoride-containing compounds, and other filter materials.
  • the esters functions both as an acrylic or methacrylate compound that polymerizes with the other a acrylic or methacrylate compounds and as a cross-linker, which forms a salt bridge with calcium in the dentin or enamel.
  • the preferred composition could vary slightly for different dental and biomedical applications. Considerations would include varying the formula to affect properties such as viscosity, flowability, working time, setting time, film thickness, and bond strength. Standard mechanical and material testing may be performed to assess these formulations for their designed application. In general, the laboratory tests that may be performed to measure the physical and mechanical properties of the inventive compound, which include compressive strength, DTS, flexural strength, shear bond strength, and film thickness. One of skill in the art will appropriate that the above material properties can be adjusted as appropriate for each dental/biomedical application.
  • the composition contains two components: a liquid component and a powder component.
  • the liquid component contains at least one polymerizable acrylic or methacrylate compound, and one or more hydrophilic acrylate or methacrylate compounds.
  • suitable hydrophilic acrylates are 2- hydroxyethyl acrylate and hydroxypropyl acrylate.
  • An example of a hydrophilic methacrylate compound is hydroxyethylmethacrylate (HEMA).
  • polymerizable acrylates are: ethyl acrylate, propyl acrylate, isopropyl acrylate, 2- hydroxyethyl acrylate, hydroxypropyl acrylate, tetrahydrofurfuryl acrylate, glycidyl acrylate, glycerol mono- and di-acrylate, ethyleneglycol diacrylate, polyethyleneglycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, mono-,di-, tri- acrylate, mono-, di-, tri-, and tetra-acrylates of pentacrythritol and dipentaerythritol, 1,3-butanediol diacrylate, 1 ,4-butanedioldiacrylate, 1,6-hexane diol diacrylate, 2,2'- bis[3(4-phenoxy)-2-hydroxypropane-l -acrylate,
  • Polymerizable methacrylate compounds may be: methacrylates, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, tetrahydrofurfuryl methacrylate, glycidyl methacrylate, the diglycidyl methacrylate of bis-phenol A (2,2-Bis[4-(2-hydroxy-3- methacryloxypropoxy)phenyl]propane) (BisGMA), glycerol mono-and di-methacrylate, ethyleneglycol dimethacrylate, polyethyleneglycol dimethacrylate, triethylene glycol dimethacrylate (TEGDMA), neopentylglycol dimethacrylate, trimethylol propane trimethacrylate, mono-, di-, tri-, and tetra-methacrylates of pentacrythritol and dipentaerythritol, 1,3-butanediol dimethacrylate
  • the liquid component also contains an amine that is capable of forming a salt bridge between the calcium ions in the dentin and acrylic or methacrylic esters.
  • An example of a methacrylate ester is Bis[2-(methacryloyloxy)ethyl]phosphate (BisMEP).
  • the preferred amines include but are not limited to aromatic amines such as 4-(dimethylamino) benzoic acid (DMABA) and ethyl 4-dimethylaminobenzoate (EDMAB). The selection of the appropriate amine is critical.
  • the amine used in the preferred embodiment is stable in an acidic environment.
  • aromatic amines such as DMABA and EDMAB, have been experimentally determined to be effective at permitting adherence of the polymerizable acrylate to dentin, others, such as 2, 2'-(p-tolylimino) diethanol (P-TID) is not effective.
  • the liquid component of the inventive formulation contains one or more acrylic ester or methacrylic ester.
  • the esters function as an ester and as an acrylic or methacrylate compound and form a cross-link between the polymerizable acrylic or methacrylate compounds.
  • dipentaerthritol pentaacrylate esters (SR 399 LV) are used as this cross-linker.
  • SR 399 LV is stable in an acid-polymerizable formula that contains an acid such as Bis[2-(methacryloyloxy)ethyl]phosphate (BisMEP) and an amine base such as ethyl-4-dimethylaminobenzoate (EDMAB).
  • SR 399 LV is easily blended and co-polymerized with other methacrylates, such as 2,2-Bis[4-(2-hydroxy-3- methacryloxypropoxy)phenyl]propane (BisGMA), hydroxyethylmethacrylate (HEMA) and triethyleneglycol dimethacrylate (TEGDMA), in the polymerizable formula.
  • BisGMA 2,2-Bis[4-(2-hydroxy-3- methacryloxypropoxy)phenyl]propane
  • HEMA hydroxyethylmethacrylate
  • TEGDMA triethyleneglycol dimethacrylate
  • the powder component of the inventive composition contains many filler materials, which include glass powder of various particles sizes and one or more fluoride releasing agents.
  • the glass particles not only improve the physical and mechanical properties of the composition but also serve as the base for the acid-base reaction.
  • the powder component may also contain other filler materials such as Barium, Aerosil 200, Pigments, Silica, Alumina, Aluminum Fluoride, Calcium Fluoride, Sodium Fluoride, Aluminum Phosphate, Calcium, Strontium, Zinc, Sodium, Potassium, Lanthanum, Alumino-silicates, other metal oxides, metal fluorides and metal phosphates
  • the adhesive composition also uses at least one initiator to permit photo or chemical initiation of curing, which could be incorporated into either the liquid component or the powder component.
  • the formulation may, additionally, contain a co- initiator to accelerate the curing process.
  • a light- curing initiator camphorquinone (CQ) and a self-curing initiator (BPO) are used.
  • a curing inhibitor, such as BHT may also be included in the adhesive composition in order to have a more controlled setting time.
  • the inventive formulation also contemplates that other chemicals, with similar characteristics, can be used.
  • other chemicals in place of BisMEP, 4 methacryloxyethyltrimellitic anhydride, biphenyldimethacrylate, ethylene glycol methacrylate phosphate or other esters of methacrylate can be used.
  • other photo-initiators or chemical initiators, other than CQ can be used, such as diphenyl(2,4,6-trimethylbenzoyl) phosphine oxide.
  • DMABA other amines could be substituted, such as ethyl 4-dimethylaminobezoate (EDMAB).
  • EDMAB ethyl 4-dimethylaminobezoate
  • urethanedimethacrylate can be substituted for BisGMA.
  • Other dimethacrylate or multimethacrylate diluents can be used instead of TEGDMA, such as trimethylpropane trimethacrylate.
  • inventive adhesive composition may be used for many dental and medical applications, for illustrative purposes, the following examples shows the inventive adhesive material being used as a dental restoration materials and as luting cement.
  • a preferred formulation of the invention composition for use as a dental restorative and luting cement includes the following in the liquid and powder
  • the powder and liquid were mixed in a powder: liquid ratio of 3 : 1 by weight. Mixing requires thorough incorporation and blending of the separate powder and liquid components. After mixing, the paste sets (hardens) by way of an acid/base reaction and a free-radical polymerization reaction in 4 to 4.5 minutes at 37 °C.
  • the liquid and powder components may be mixed and applied to the tooth structure immediately in one step and simply wait for the restorative to set. Alternatively, the liquid and powder components may be mixed and placed onto the tooth in an incremental fashion. For example, mixing a small amount of power and liquid components in the same 3:1 ratio by weight and apply the paste to the tooth surface. Once the layer of paste hardens, a subsequent coat of adhesive may be mixed and applied to the tooth. This incremental build-up of adhesive materials allows the tooth to be restored its physiological shape.
  • Example 1 Properties of the adhesive composition as dental restorative materials
  • the preferred inventive formulation is tested in the lab as a dental restorative material. Laboratory tests shows that the incorporation of the multifunctional acrylate cross-linking compound dramatically enhanced the physical and mechanical properties of the final set in the prototype dental material. When using this formula as a bonding agent, the clinical pre-treatment techniques of acid etching and priming the tooth structure are not necessary. The material was tested against other classes of dental materials commonly used as temporary fillings. Those materials were FUJI IXTM GP fast (GC America, IL), KETAC-MOLARTM (3MTM ESPE, MN), and IRM (Dentsply Caulk, DE).
  • the tests used were hardness (Knoop), compressive strength, diametral tensile strength (DTS), fiexural strength, and dentin shear bond strength. Table 1 below provides the results of those tests. Table 1. Physical property tests of inventive formulation as applied to a dental dressing.
  • inventive formulation proved to have properties that were comparable or better than those of the materials tested. Placement of the inventive formulation on teeth requires minimal surface preparation and fewer steps for application, such as acid etching, priming, or use of bonding agents, resulting in less clinical time.
  • inventive formulation releases fluoride. Table 2 presents the results of fluoride-release tests. Table 2. Cumulative fluoride release after 385 hours.
  • the inventive formulation may also be used as luting cement, for bonding fixed dental prosthetic devices, such as inlays, onlays, laminate veneers, bridges and crowns (including porcelain and porcelain fused to metal restorations), to dentin and enamel.
  • fixed dental prosthetic devices such as inlays, onlays, laminate veneers, bridges and crowns (including porcelain and porcelain fused to metal restorations), to dentin and enamel.
  • Example 2 Properties as Luting Cement for Bonding Ceramic Dental Prosthetic Devices
  • Ceramic blocks provided by the manufacturers were used without mechanical modification. All ceramic surfaces were treated using porcelain etching gel (Pulpdent Co. Watertown, MA) and silanated following the manufacturers' instructions.
  • a #4 gelatin capsule (Torpac, Inc., Fairfield, NJ ) was half-filled with a resin composite (P60, 3MTM ESPE, St. Paul, MN) and light activated for 40 seconds using a curing light (Spectrum 800, Dentsply/Caulk, Milford, DE). The remainder of the capsule was filled with the dental luting cement being tested, placed against the ceramic test surface, and stabilized with finger pressure. Excess material was removed from the base of the capsule, and the luting cement was allowed to set at room temperature (23 ⁇ I 0 C) for 10 minutes. The specimens were stored in 37 ⁇ 1°C
  • Example 3 Properties as Luting Cement for bonding Fixed Metal Dental Prosthetic Devices
  • SBS shear bond strengths
  • Metal alloy specimens (approximately 8mm long, 8mm wide and 4mm thick) were fabricated per manufacturers' instructions using the lost wax technique. The metal specimens were mounted in autopolymerizing acrylic resin using cylindrical polytetrafluoroethylene molds with the test surface of the specimens flush with the surface of the acrylic. The test surfaces were sandblasted. Table 5. Luting cements and metal alloys used in this study.
  • a #4 gelatin capsule (Torpac, Inc., Fairfield, NJ ) was half-filled with a resin composite (P60, 3MTM/ESPE Corporation, St. Paul, MN) and light activated for 20 seconds using a curing light (Spectrum 800, Dentsply/Caulk, Milford, DE). The remainder of the capsule was filled with the dental luting cement being tested, placed against the metal test surface, and stabilized with finger pressure. Excess material was removed from around the base of the capsule, and the luting cement was allowed to set at room temperature (23 ⁇ 1°C) for 10 minutes. The specimens were stored in 37 ⁇ 1°C deionized water for 24 hours before testing.
  • inventive formulation may also be used as a luting cement for bonding orthodontic brackets to enamel.
  • Example 8 Inventive formulation used as a luting cement for bonding orthodontic brackets to enamel.
  • SBS shear bond strengths
  • Table 7 (Table 7) was designated as an experimental group with ten specimens in each group.
  • inventive composition may be used in many other dental or biomedical applications, such as stint for stabilizing avulsed, inverted, or luxated teeth, or as bone cement, for bonding implant prostheses and skull implants to bone, or liner and base under amalgam dental restorations.

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  • Health & Medical Sciences (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Epidemiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Plastic & Reconstructive Surgery (AREA)
  • Dental Preparations (AREA)

Abstract

Cette invention porte sur un adhésif utilisé pour la liaison de biomatériaux dentaires et médicaux à des tissus durs par un pont moléculaire formé à partir d'amines réagissant avec le calcium et de monomères esters acryliques ou méthacryliques à des tissus durs tels que l'émail, la dentine et l'os. Cette formulation consiste en un composé polymérisable stable vis-à-vis des acides avec des réticulants acrylates multifonctionnels. Cette formule fournit une bonne auto-adhérence sans préparation préalable des substrats du tissu dur. La formulation peut contenir des amorceurs de radicaux libres activés par voie chimique et/ou par la lumière.
PCT/US2009/000656 2008-01-31 2009-02-02 Acrylates multifonctionnels utilisés comme réticulants dans des adhésifs de liaison à auto-attaque dentaires et biomédicaux WO2009097152A1 (fr)

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US2504508P 2008-01-31 2008-01-31
US61/025,045 2008-01-31

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102639157A (zh) * 2009-11-06 2012-08-15 引健特株式会社 糊膏-粉末双聚合物基骨水泥和用于注射该骨水泥的设备
WO2015108487A1 (fr) 2014-01-14 2015-07-23 Nanyang Technological University Compositions bioadhésives électroactives
US10005936B2 (en) 2012-11-23 2018-06-26 Nanyang Technological University Photoactive bioadhesive compositions

Citations (6)

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Publication number Priority date Publication date Assignee Title
US20030180691A1 (en) * 2002-02-07 2003-09-25 Martin Hamer Difunctional IDBM and related compounds as novel dentin bonding agents
US20040039078A1 (en) * 2002-08-21 2004-02-26 Suh Byoung I. Non-volatile dental compositions containing multifunctional acrylate compounds and lacking an oxygen-inhibited layer
US20050028705A1 (en) * 2003-08-08 2005-02-10 Wagh Arun S. Method and product for phosphosilicate slurry for use in dentistry and related bone cements
US20060189728A1 (en) * 2005-02-21 2006-08-24 Kerr Corporation Acid-tolerant dental composition
US20070049656A1 (en) * 2005-09-01 2007-03-01 Pentron Clinical Technologies, Inc Dental resin composition, method of manufacture, and method of use thereof
US20070197683A1 (en) * 2006-02-23 2007-08-23 Pentron Clinical Technologies, Inc Self etch all purpose dental compositions, method of manufacture, and method of use thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030180691A1 (en) * 2002-02-07 2003-09-25 Martin Hamer Difunctional IDBM and related compounds as novel dentin bonding agents
US20040039078A1 (en) * 2002-08-21 2004-02-26 Suh Byoung I. Non-volatile dental compositions containing multifunctional acrylate compounds and lacking an oxygen-inhibited layer
US20050028705A1 (en) * 2003-08-08 2005-02-10 Wagh Arun S. Method and product for phosphosilicate slurry for use in dentistry and related bone cements
US20060189728A1 (en) * 2005-02-21 2006-08-24 Kerr Corporation Acid-tolerant dental composition
US20070049656A1 (en) * 2005-09-01 2007-03-01 Pentron Clinical Technologies, Inc Dental resin composition, method of manufacture, and method of use thereof
US20070197683A1 (en) * 2006-02-23 2007-08-23 Pentron Clinical Technologies, Inc Self etch all purpose dental compositions, method of manufacture, and method of use thereof

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102639157A (zh) * 2009-11-06 2012-08-15 引健特株式会社 糊膏-粉末双聚合物基骨水泥和用于注射该骨水泥的设备
CN102639157B (zh) * 2009-11-06 2014-08-13 引健特株式会社 糊膏-粉末双聚合物基骨水泥
US10016526B2 (en) 2009-11-06 2018-07-10 Injecta Inc. Paste-powder dual polymer-based bone cement and injection apparatus for same
US10005936B2 (en) 2012-11-23 2018-06-26 Nanyang Technological University Photoactive bioadhesive compositions
WO2015108487A1 (fr) 2014-01-14 2015-07-23 Nanyang Technological University Compositions bioadhésives électroactives
US11357884B2 (en) 2014-01-14 2022-06-14 Nanyang Technological University Electroactive bioadhesive compositions
US11964071B2 (en) 2014-01-14 2024-04-23 Nanyang Technological University Electroactive bioadhesive compositions

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