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WO1993012759A1 - Adhesif a base d'eau pour amalgame - Google Patents

Adhesif a base d'eau pour amalgame Download PDF

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Publication number
WO1993012759A1
WO1993012759A1 PCT/US1992/010939 US9210939W WO9312759A1 WO 1993012759 A1 WO1993012759 A1 WO 1993012759A1 US 9210939 W US9210939 W US 9210939W WO 9312759 A1 WO9312759 A1 WO 9312759A1
Authority
WO
WIPO (PCT)
Prior art keywords
water
adhesive
acid
ethylenically
reducing agent
Prior art date
Application number
PCT/US1992/010939
Other languages
English (en)
Inventor
Sumita B. Mitra
Steven M. Aasen
Original Assignee
Minnesota Mining And Manufacturing Company
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 Minnesota Mining And Manufacturing Company filed Critical Minnesota Mining And Manufacturing Company
Priority to JP5511757A priority Critical patent/JPH07502531A/ja
Priority to BR9207009A priority patent/BR9207009A/pt
Priority to EP93901189A priority patent/EP0623017A1/fr
Publication of WO1993012759A1 publication Critical patent/WO1993012759A1/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

Definitions

  • This invention relates to dental adhesives, and especially amalgam adhesives.
  • An adhesive seal between amalgam and tooth structure could minimize and/or prevent microleakage and allow for a stronger
  • Products claiming to make amalgam adhesive to tooth structure are available.
  • One such product is sold in a kit under the trademark AMALGAMBONDTM (Parkell Co.).
  • This product is a liquid adhesive to be coated directly onto tooth structure.
  • the active ingredients in the adhesive include 4-META (4-methacryloxyethyl trimellitic anhydride) and TBB (tri-n butyl borane).
  • Other products which similarly involve coating a specific curable resin directly onto tooth structure to make amalgam adhere are available under the trademarks PANAVIATM Dental Adhesive (Kuraray Company) and
  • ethylenically unsaturated adhesive resin include M.
  • Adhesive resin (3M) is applied to cavity margins prior to application of amalgam, and M. Mitrosky, Jr.,
  • U.S. Pat. No. 3,513,123 (Saffir) describes a curable epoxy composition that can be added to amalgam in order to make the amalgam adhere to tooth structure.
  • the curable epoxy composition contains a glycidyl ether epoxy resin and a polyamine hardening agent.
  • U.S. Pat. No. 4,064,629 (Stoner) describes a method for applying amalgam restorations. The method involves precoating the surfaces of a cavity within a carious tooth with a layer of an "adhesive-metal" lining composition. The metal of the lining
  • composition is amalgamated by diffusion of the mercury from the subsequently applied conventional dental amalgam filling.
  • amalgamation-metal The "adhesive-metal" lining
  • composition is said to improve corrosion resistance of the dental amalgam filling and also to promote bonding between the amalgam restoration and the cavity
  • U.S. Pat. No. 4,001,483 (Lee, Jr. et al.) describes dental compositions for sealing margins between tooth structures and amalgam restorations therein, the compositions containing (a) an alkylene glycol dimethacrylate and/or its oligomer, (b) a polymerization initiator, (c) a polymerization
  • U.S. Pat. No. 3,574,943 (Stark) describes a method of restoring a carious tooth whereby the cavity is excavated, lined with a layer of a polysiloxane pressure sensitive adhesive polymer dissolved in a fluorocarbon, and filled with amalgam.
  • polysiloxane layer is said to act as a barrier to leakage.
  • Japanese Kokai 63-175085 describes an adhesive composition comprising an acid functional monomer, polymer, or copolymer, a vinyl monomer in which the acid functional component is soluble, an organic peroxide, and an aromatic amine or sulfinate salt.
  • the composition is said to bond living tooth tissue to composites and amalgams.
  • Japanese Kokai 63-250310 describes dental adhesive compositions containing (a) cellulose ether, (b) a vinyl monomer, (c) an organic peroxide, and (d) an aromatic amine or a sulfinate.
  • the composition is said to be applicable to a wide variety of restorative materials, including composite resins, amalgam, alumina, gold, alloys, polymethyl methacrylate, polycarbonate, and the like.
  • intermediate adhesive composition for sealing dental cavities and chemically securing amalgams, comprising a metal powder dispersed in an adhesive varnish.
  • the composition contains metal powder, cellulosic varnish, ethyl acetate, amyl propionate, fluoride, and oil of pimento leaf.
  • water-based cements are used in dentistry. These water-based cements may contain some of the same ingredients as water-based adhesives, but are
  • Examples include metal oxide cements such as those described in U.S. Pat. No. 3,655,605 and fluoroaluminosilicate glass cements (also known as "glass ionomer cements") such as those described in Example 6 of the '605 patent and in U.S. Pat. Nos.
  • a light-curable and apparently anhydrous cement is shown in European Pat. Application No. 0 391 619. It contains a number of ingredients, including benzoyl peroxide. Summary of the Invention
  • the present invention provides a water-based dental adhesive kit that can be used to adhere fresh (unhardened) amalgam to dentin.
  • the kit contains at least one adhesive having two "dark" curing modes, i.e., curing modes that will proceed in the absence of light.
  • the first curing mode employs an ionic reaction between acidic and inorganic filler components of the adhesive.
  • the second curing mode employs a redox- initiated free radical crosslinking reaction involving an ethylenically-unsaturated component of the adhesive.
  • the adhesive optionally cures through a third curing mode, via photoinitiated free radical crosslinking of the ethylenically-unsaturated component.
  • the adhesive is water-based, and thus can be used under moist conditions such as are typically present in the mouth.
  • the adhesive is applied to tooth structure in one or more first coats followed by one or more subsequent or second coats.
  • Each coat employs both the ionic curing mode and the redox-initiated curing mode.
  • the initial coat or coats may optionally utilize a photoinitiated cure mode.
  • different adhesives can be employed for the first and subsequent coats.
  • the kit preferably contains only a single adhesive composition.
  • the adhesive for the first coat or coats (the "First Adhesive") comprises a water-containing,
  • ionically-hardenable, ethylenically-unsaturated dental adhesive comprising
  • the adhesive for the subsequent coat or coats comprises the above ingredients (a), (b), and optional photoinitiator as ingredient (c), (c), together with
  • the reducing agent and the oxidizing agent are capable of initiating gelation of a 10:10:1 (weight basis) water:acrylamide:methylene bis-acrylamide mixture.
  • the invention provides preferred adhesives in which the reducing agent or the oxidizing agent are contained in microcapsules.
  • the microcapsules improve shelf life and facilitate
  • both the First Adhesive and the Second Adhesive are formulated in two parts, although formulations employing three or more parts can be made up if desired.
  • the first part typically is a powder portion containing the acid- reactive filler.
  • the second part typically is a liquid portion containing the acidic polymer and water.
  • the liquid portion typically also contains one (but usually not both) of the water-soluble reducing agent and water-soluble oxidizing agent. If the reducing agent is present in the liquid portion of the Second Adhesive, then the oxidizing agent is typically present in the powder portion, and vice-versa.
  • oxidizing agent can be combined in the powder portion or in the liquid portion through the use of a
  • the invention is not limited to powder:liquid formulations.
  • one part anhydrous formulations containing filler, polymer, reducing agent and oxidizing agent can be prepared. These can be sold in dry form and prepared for use by adding water.
  • two part paste:paste formulations can be prepared by adding to the acid-reactive filler a suitable polymerizable liquid that does not react with that filler (e.g., 2-hydroxyethyl methacrylate, or "HEMA"), yielding a first paste.
  • a suitable polymerizable liquid that does not react with that filler e.g., 2-hydroxyethyl methacrylate, or "HEMA"
  • the acidic polymer described above is combined with a suitable filler that does not react with the acidic polymer (e.g., ground quartz), yielding a second paste.
  • the two pastes are prepared for use by stirring them together.
  • the combined pastes preferably have a sufficiently low filler loading and sufficiently low viscosity so that their mixture will be useful as a dental adhesive.
  • Both the First Adhesive and the Second Adhesive contain water.
  • the water can be present in the product as sold, or added by the dentist just prior to use.
  • the water can be distilled, deionized or plain tap water. Generally, deionized water is preferred. The amount of water should be sufficient to provide
  • water represents at least about 1%, more preferably about 3% to about 60%, and most preferably about 5% to about 40% of the total weight of
  • Both the First Adhesive and the Second Adhesive are ionically hardenable. By this is meant that they contain ingredients that, when combined, can react via an ionic reaction to produce a hardened mass. The ionic reaction occurs between acid groups on the polymer and acid-reactive groups on the filler.
  • Both the First Adhesive and the Second Adhesive are ethylenically-unsaturated. In other words, they contain at least one ethylenically-unsaturated moiety.
  • the ethylenically-unsaturated moiety can be present as a separate ingredient (for example, as an acrylate- or methacrylate-functional monomer) or it can, if desired, be present as a group on another ingredient such as the acidic polymer.
  • a wide variety of ethylenically- unsaturated moieties can be used. A useful list of suitable materials is shown at page 9, line 13 through page 13, last line of Australian Published Pat.
  • water-miscible or water-soluble acrylates and methacrylates such as 2-hydroxyethyl methacrylate, hydroxymethyl methacrylate, 2-hydroxypropyl
  • trimethacrylate ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, urethane
  • methacrylates acrylamide, methacrylamide, methylene bis-aerylamide or methacrylamide, and diacetone
  • acrylamide and methacrylamide are preferred. Mixtures of ethylenically-unsaturated moieties can be used if desired. Preferably, the ethylenically-unsaturated moieties are present as groups on the acidic polymer, as described in more detail below.
  • Both the First Adhesive and the Second Adhesive contain an acid-reactive filler.
  • the filler should be sufficiently finely-divided so that it can be
  • Preferred average particle diameters for the filler in both the First Adhesive and the Second Adhesive are about 0.2 to about 15
  • micrometers more preferably about 1 to 10 micrometers, as measured using, for example, a sedimentation
  • Suitable acid-reactive fillers include metal oxides, metal salts and glasses.
  • Preferred metal oxides include barium oxide, calcium oxide, magnesium oxide and zinc oxide.
  • Preferred metal salts include salts of multivalent cations, for example aluminum acetate, aluminum chloride, calcium chloride, magnesium chloride, zinc chloride, aluminum nitrate, barium nitrate, calcium nitrate, magnesium nitrate, strontium nitrate and calcium fluoroborate.
  • Preferred glasses include borate glasses, phosphate glasses and
  • fluoroaluminosilicate glasses Fluoroaluminosilicate glasses are particularly preferred.
  • Suitable fillers are also available from a variety of commercial sources familiar to those skilled in the art. For example, suitable fillers can be obtained from a number of commercially available glass ionomer cements, such as "GC Fuji LC” adhesive and "Kerr XR" ionomer cement. Mixtures of fillers can be used if desired.
  • the filler can be subjected to a surface treatment.
  • Suitable surface treatments include acid washing, treatment with phosphates, treatment with chelating agents such as tartaric acid, treatment with a silane as described in Australian Published Pat. No. 46717/89, and treatment with a silanol solution.
  • the amount of filler should be sufficient to provide an adhesive having desirable mixing and
  • the filler preferably represents less than about 90%, more preferably about 25% to about 85%, and most preferably about 30% to about 75% by weight of the total weight (including water) of the unhardened adhesive components.
  • the acidic polymer need not be entirely water- soluble, but it should be at least sufficiently water- miscible so that it does not undergo substantial separation when combined with the liquid ingredients of the adhesives.
  • Suitable acidic polymers include those listed at column 2, line 62 through column 3, line 6 of U.S. Patent No. 4,209,434.
  • Preferred acidic polymers include homopolymers and copolymers of alkenoic acids such as acrylic acid, itaconic acid and maleic acid. Suitable polymers are also available from a wide variety of commercial sources, and many are found in currently-available glass ionomer cements.
  • the polymer should have a molecular weight sufficient to provide good storage, handling and mixing properties.
  • a preferred molecular weight is about 2000 to about 100,000 weight average molecular weight evaluated against a polystyrene standard using gel permeation
  • the acidic polymer contains one or more ethylenically-unsaturated groups. Suitable ethylenically-unsaturated acidic polymers are described in U.S. Pat. No. 4,872,936 and in European Pat.
  • the numbers of acid groups and ethylenically-unsaturated groups are adjusted to provide an appropriate balance of
  • the amount of acidic polymer in each adhesive should also be sufficient to provide a desired balance of physical properties.
  • a preferred acidic polymer amount is at least about 5%, more preferably about 10 to about 50%, and most preferably about 10 to about 30% of the total weight (including water) of the unhardened adhesive components.
  • the optional photoinitiator should be capable of promoting free radical crosslinking of the
  • ethylenically-unsaturated component on exposure to light of a suitable wavelength and intensity. It also preferably is sufficiently shelf-stable and free of undesirable coloration to permit its storage and use under typical dental conditions. Visible light
  • photoinitiators are preferred.
  • the photoinitiator preferably is water- soluble or water-miscible.
  • Photoinitiators bearing polar groups usually have a sufficient degree of water- solubility or water- miscibility.
  • the photoinitiator frequently can be used alone but typically it is used in combination with a suitable donor compound or a suitable accelerator (for example, amines, peroxides, phosphorus compounds, ketones and alpha-diketone compounds).
  • Preferred visible light-induced initiators include camphorquinone (which typically is combined with a suitable hydrogen donor such as an amine), diaryliodonium simple or metal complex salts,
  • chromophore-substituted halomethyl-s-triazines and halomethyl oxadiazoles are particularly preferred visible light-induced photoinitiators.
  • Particularly preferred visible light-induced photoinitiators include combinations of an alpha-diketone, e.g., camphorquinone, and a
  • diaryliodonium salt e.g., diphenyliodonium chloride, bromide, iodide or hexafluorophosphate, with or without additional hydrogen donors (such as sodium benzene sulfinate, amines and amine alcohols).
  • polymerization initiators include ketones such as benzyl and benzoin, and acyloins and acyloin ethers.
  • Preferred commercially available ultraviolet light- induced polymerization initiators include 2,2- dimethoxy-2-phenylacetophenone ("IRGACURE 651”) and benzoin methyl ether (2-methoxy-2-phenylacetophenone), both from Ciba-Geigy Corp.
  • the photoinitiator should be present in an amount sufficient to provide the desired rate of photopolymerization. This amount will be dependent in part on the light source, the thickness of the adhesive layer to be exposed to radiant energy, and the
  • the photoinitiator components for both the First Adhesive and the Second Adhesive will be present at a total weight of about 0.01 to about 5%, more preferably from about 0.1 to about 5%, based on the total weight (including water) of the unhardened adhesive components.
  • the photoinitiator can be
  • water-soluble reducing agent and water- soluble oxidizing agent are most conveniently discussed together. They should react with or otherwise
  • the reducing agent and oxidizing agent preferably are sufficiently shelf- stable and free of undesirable colorization to permit their storage and use under typical dental conditions. They should be sufficiently water-soluble to permit ready dissolution in (and discourage separation from) the other components of the Second Adhesive.
  • the reducing agent and oxidizing agent should be sufficiently soluble that at least 200 parts per million may be readily dissolved in water, and no undissolved material will be observed after the
  • the reducing agent and oxidizing agent should also be sufficiently soluble and present in an amount sufficient to permit an
  • the reducing agent and oxidizing agent preferably are sufficiently water-soluble and have sufficient reduction and oxidation potentials to initiate gelation of an aqueous crosslinkable
  • acrylamide solution This can be evaluated by adding 2 weight % each of the reducing agent and the oxidizing agent to an aqueous acrylamide:methylene bis-acrylamide solution (described below in Table la) and observing whether or not gelation occurs within 30 minutes.
  • Preferred reducing agents include ascorbic acid, cobalt (II) chloride, ferrous chloride, ferrous sulfate, hydrazine, hydroxylamine (depending upon the choice of oxidizing agent) oxalic acid, thiourea, and salts of a dithionite or sulfite anion.
  • Preferred oxidizing agents include cobalt (III) chloride, tert- butyl hydroperoxide, ferric chloride, hydroxylamine (depending upon the choice of reducing agent), perboric acid and its salts, and salts of a permanganate or persulfate anion. Hydrogen peroxide can also be used, although it may interfere with the optional
  • the amount of reducing agent and oxidizing agent should be sufficient to provide the desired degree of polymerization of the ethylenically- unsaturated component.
  • the preferred amount for each of the reducing agent and oxidizing agent is about 0.01 to about 10%, more preferably about 0.02 to about 5%, based on the total weight (including water) of the unhardened Second Adhesive components.
  • the reducing agent or the oxidizing agent can be microencapsulated. This will generally enhance shelf stability and permit packaging both the reducing agent and oxidizing agent together. For example, through appropriate selection of the encapsulant, both the oxidizing agent and reducing agent can be combined with the filler and kept in a storage-stable state. Likewise, through appropriate selection of a water-insoluble encapsulant, the
  • reducing agent and oxidizing agent can be combined with water and the acidic polymer and maintained in a storage-stable state.
  • water-soluble or water-insoluble encapsulants can be employed. However, water-insoluble encapsulants are preferred, as they generally provide better long term storage stability under moist or humid conditions. Although the use of a water-insoluble encapsulant may initially seem inappropriate in a water-based adhesive, it has been found that vigorous mechanical mixing generally will be sufficient to break apart the capsule walls and permit adequate release of the encapsulated reducing agent or oxidizing agent and subsequent hardening or cure of the Second Adhesive.
  • the encapsulant is a medically acceptable polymer and a good film former.
  • the glass transition temperature (T g ) of the encapsulant preferably is above room temperature.
  • encapsulants can be used, with cellulosic materials such as cellulose acetate, cellulose acetate butyrate, ethyl cellulose,
  • hydroxymethyl cellulose and hydroxyethyl cellulose being preferred.
  • Other encapsulants include
  • a suitable water- immiscible solvent such as methyl acetate, ethyl acetate or methylene chloride.
  • the reducing agent or oxidizing agent is dissolved in water.
  • the water solution can then be added to the solution of encapsulant and water-immiscible solvent. Stirring or other high speed shear techniques preferably are used to promote uniform microcapsule formation.
  • the capsule shells are formed around the aqueous solution droplets either by evaporation of the water-immiscible solvent or by the addition of a second water-immiscible solvent (e.g., n-hexane) that will precipitate the encapsulant.
  • a second water-immiscible solvent e.g., n-hexane
  • the capsules can then be removed by cooling and
  • the dry reducing agent or oxidizing agent is preferably suspended in a stirred solution of the encapsulant in a water- immiscible organic solvent. Vigorous stirring will promote uniform encapsulation of the reducing agent or oxidizing agent.
  • the capsules can be formed by
  • the First Adhesive or the Second Adhesive can optionally contain a chelating agent.
  • Preferred chelating agents include tartaric acid, ethylene diamine tetraacetic acid, citric acid, the salts of these acids, and the like.
  • the First Adhesive or the Second Adhesive can also optionally contain a metal or alloy powder to assist in adhering to the amalgam.
  • Preferred metal or alloy powders include metals of Group IVA, VA, VIA, VIIA, VIII, IB, and IIB, aluminum, indium, or thallium of Group IIIB, or tin or lead of Group IVB, or alloys thereof.
  • Conventional dental amalgam alloy powders typically mixtures of silver, tin, copper and zinc are also suitable.
  • Adhesive can contain adjuvants such as pigments, nonreactive fillers, inhibitors, accelerators,
  • viscosity modifiers such as surfactants, and other ingredients that will be apparent to those skilled in the art.
  • the First Adhesive and the Second Adhesive can be mixed and clinically applied using a variety of techniques. However, a preferred series of steps is as follows:
  • Etchants for use in step (a) above should promote formation of a strong long-lasting bond to dentin or enamel.
  • Suitable etchants include monomeric, oligomeric and polymeric organic and inorganic acids such as maleic acid, phosphoric acid, nitric acid, oxalic acid, citric acid, ethylenediamine tetraacetic acid (EDTA), methacrylic acid, polyacrylic acid, itaconic acid and mixtures thereof.
  • Suitable amalgams include “DISPERSALLOY” and “UNISON” amalgams (Johnson & Johnson Dental Products, Inc.), “TYTIN” and “CONTOUR” amalgams (Kerr Manufacturing Co.) and “VALIANT” amalgam (L. D. Caulk Division of Dentsply International, Inc.).
  • the adhesives will have particular utility in clinical amalgam applications where rapid cure,
  • the adhesives as described above may be provided together with the other components as used in the described process in the form of kits.
  • kits may comprise one or more
  • test solution was prepared by combining the ingredients set out below in Table la:
  • the glass was ball-milled to provide a pulverized frit with a surface area of 2.9 m 2 /g measured using the Brunauer, Emmet and Teller (BET) method, and labeled "Control Glass".
  • BET Brunauer, Emmet and Teller
  • the ascorbic acid-containing glass was labeled "Powder A” and the potassium persulfate-containing glass was labeled "Powder B". Equal weights of Powder A and Powder B were combined, and labeled "Powder C”.
  • Powder C and the liquid of Table lIb were hand-spatulated at a 1.4:1 powder:liquid ratio to provide an adhesive.
  • the adhesive was evaluated for shear bond strength using the procedure outlined below. The results are reported in Table III below.
  • Bovine teeth of similar age and appearance were partially embedded in circular acrylic disks.
  • the exposed portion of each tooth was ground flat and parallel to the acrylic disc using Grade 120 silicon carbide paper-backed abrasive mounted on a lapidary wheel, until the dentin or enamel was exposed. Further grinding and polishing of the teeth was carried out by mounting Grade 320 silicon carbide paper-backed
  • a Pretreatment of phosphoric acid etching gel was applied to the enamel or dentin for 15 to 30 seconds, rinsed with water and dried.
  • the adhesive composition of the invention was applied to the enamel or dentin surface with a spatula or ball applicator in either "One Coat” or "Two Coats".
  • a mold made from a 2 mm thick "TEFLON" polytetrafluoroethylene sheet with a gelatin sleeve having an inner area of 0.20 cm 2 was clamped to the uncured adhesive layer so that the central axis of the hole in the mold was normal to the polished tooth surface.
  • the hole in each mold was filled with triturated TYTIN amalgam and allowed to stand for 10-15 minutes at room temperature to allow the adhesive layer to autocure ("Autocured").
  • the molds were then stored in distilled water at 37°C for 24 hours.
  • the first coat was cured using a 20-30 second irradiation with a dental curing light ("VISILUX 2", 3M) ("Light-cured”).
  • a second coat of adhesive was applied atop the first coat, allowed to autocure and the mold filled with triturated amalgam.
  • the molds were allowed to stand at room temperature for 10-15 minutes and then stored in water as described in the One Coat method.
  • Adhesive strength was evaluated by mounting the acrylic disk in a holder clamped in the jaws of an "INSTRON" tensile testing apparatus with the polished tooth surface oriented parallel to the direction of pull. A loop of 0.44 mm diameter orthodontic wire was placed around the base of the amalgam button adjacent to the polished tooth surface. The ends of the orthodontic wire were clamped in the pulling jaw of the tensile testing apparatus, placing the bond in shear stress. The bond was stressed until it (or the amalgam button) failed, using a crosshead speed of 2 mm/min and an average of 5 or more samples.
  • microencapsulated potassium persulfate/CAB were prepared in PREPARATORY EXAMPLES 1 and 2.
  • the micronized CAB was obtained by comminuting CAB in a chopping mill.
  • Powders of Table V and liquids of Table VI were hand-spatulated at a 1.4:1 powder: liquid ratio, then tested for adhesion following the procedure of EXAMPLE 1, except that the dentin was not pretreated prior to application of the adhesive.
  • two coats of adhesive were applied. The first coat was light-cured for Run nos. 1 and 3, but allowed to autocure for Run nos. 2 and 4. The second coat was allowed to autocure in each of the runs.
  • the results are set out below in Table VIII, along with a brief identification of the applicable cure mechanism for each run.
  • compositions of Run nos. 2-4 exhibited no adhesion.
  • the Two Coat technique (Run no. 2) provided higher adhesion values than the One Coat method (Run no. 1).
  • EXAMPLE 3 was followed, except that amalgams other than DISPERSALLOY were used and adhesion to enamel instead of dentin was measured.
  • the shear adhesion values are set out below in Table X, along with the Pretreatment, the amalgam, and a brief identification of the
  • thermocycling did not adversely effect adhesion to either dentin or enamel and in Run no. 2 significantly increased adhesion.
  • Modified GC Powder was combined at a 1.4: powder: liquid ratio with the GC Fuji LC liquid supplied by the manufacturer.
  • EXAMPLE 1 In a first run, the procedure of EXAMPLE 1 was followed by a Pretreatment of the enamel with 37% phosphoric acid etchant gel. After rinsing and drying, a second Pretreatment consisting of a solution of 10 parts of the copolymer of EXAMPLE 2 (Table VI), 36 parts HEMA and 54 parts water was applied to the enamel and dried. AMALGAMBOND B liquid was applied to the pretreated enamel. Triturated DISPERSALLOY amalgam was condensed atop the AMALGAMBOND B liquid coat and the adhesion value obtained using the procedure of EXAMPLE 1 was 0.05 MPa.
  • AMALGAMBOND was applied according to the manufacturer's instructions to the pretreated enamel as detailed in the first run.
  • the adhesion value obtained was only 2.3 MPa.

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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)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

Adhésif dentaire contenant de l'eau, une matière de remplissage réactive à l'acide, un polymère acide miscible dans l'eau, une fraction à insaturation éthylènique, un agent réducteur soluble dans l'eau, un agent d'oxydation soluble dans l'eau et, facultativement, une photoamorce. L'adhésif est durci de deux manières, par réaction ionique de la matière de remplissage-acide et par réaction de réticulation amorcée par oxydoréduction et, facultativement, par réticulation photoamorcée. L'adhésif peut être appliqué en une ou deux couches et est particulièrement conçu pour être utilisé au-dessous d'un amalgame.
PCT/US1992/010939 1991-12-31 1992-12-16 Adhesif a base d'eau pour amalgame WO1993012759A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP5511757A JPH07502531A (ja) 1991-12-31 1992-12-16 水ベースのアマルガム接着剤
BR9207009A BR9207009A (pt) 1991-12-31 1992-12-16 Composição de adesivo dental etilenicamente insaturado e processo e kit para aderir um metal ou restaurador contendo metal a um tecido duro e a uma superfície dura
EP93901189A EP0623017A1 (fr) 1991-12-31 1992-12-16 Adhesif a base d'eau pour amalgame

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US81569791A 1991-12-31 1991-12-31
US07/815,697 1991-12-31

Publications (1)

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WO1993012759A1 true WO1993012759A1 (fr) 1993-07-08

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PCT/US1992/010939 WO1993012759A1 (fr) 1991-12-31 1992-12-16 Adhesif a base d'eau pour amalgame

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EP (1) EP0623017A1 (fr)
JP (1) JPH07502531A (fr)
CN (1) CN1075629A (fr)
AU (1) AU3326193A (fr)
BR (1) BR9207009A (fr)
CA (1) CA2117348A1 (fr)
IL (1) IL104203A (fr)
MX (1) MX9207575A (fr)
WO (1) WO1993012759A1 (fr)
ZA (1) ZA9210060B (fr)

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995022956A1 (fr) * 1994-02-28 1995-08-31 Minnesota Mining And Manufacturing Company Systeme de ciment ionomere de verre en formulation pate:pate, et procedes associes
WO1995022955A1 (fr) * 1994-02-28 1995-08-31 Minnesota Mining And Manufacturing Company Compositions dentaires a stabilite de couleur amelioree, contenant de l'acide ascorbique sous forme de complexe metallique
WO1998011862A1 (fr) * 1996-09-18 1998-03-26 MÜHLBAUER, Wolfgang, Carl, Friedrich Composition et procede de restauration dentaire
WO2002013768A3 (fr) * 2000-08-11 2002-06-06 Dentsply Int Inc Compositions dentaires contenant des bisacrylamides et utilisation correspondante
EP1222910A3 (fr) * 2001-01-15 2003-11-26 Ivoclar Vivadent AG Matériau dentaire contenant des amides polyfonctionnels
EP1413283A1 (fr) * 2000-08-11 2004-04-28 Dentspy International, Inc. Compositions dentaires contenant des bisacrylamides et utilisation correspondante
US6734223B2 (en) 2000-08-11 2004-05-11 Dentsply Detrey Gmbh Polyaminoester and their application in dental compositions
US6767936B2 (en) 2000-08-11 2004-07-27 Dentsply Detrey Gmbh Dental compositions comprising bisacrylamides and use thereof
US6953832B2 (en) 2001-01-15 2005-10-11 Ivoclar Vivadent Ag Dental materials based on polyfunctional amides
US8129444B2 (en) 2001-05-16 2012-03-06 3M Espe Ag Self-adhesive dental materials
US8263677B2 (en) 2009-09-08 2012-09-11 Creative Nail Design, Inc. Removable color gel basecoat for artificial nail coatings and methods therefore
US8492454B2 (en) 2009-10-05 2013-07-23 Creative Nail Design, Inc. Removable color layer for artificial nail coatings and methods therefore
US8541482B2 (en) 2009-10-05 2013-09-24 Creative Nail Design, Inc. Removable multilayer nail coating system and methods therefore
US8901199B2 (en) 2009-09-08 2014-12-02 Creative Nail Design, Inc. Compositions and methods for UV-curable cosmetic nail coatings
US9289358B2 (en) 2007-02-28 2016-03-22 Ultradent Products, Inc. Resin reinforced zinc polycarboxylate temporary cement compositions and related kits and methods
WO2020168201A1 (fr) * 2019-02-15 2020-08-20 Ohio State Innovation Foundation Compositions adhésives à composant unique
EP3166570B1 (fr) 2014-07-10 2022-04-20 3M Innovative Properties Company Composition dentaire auto-adhésive bi-composante, procédé de production et utilisation associée

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10228540A1 (de) * 2002-06-26 2004-01-22 Ivoclar Vivadent Ag Dentalmaterialien auf der Basis von Hydroxyalkylacrylamiden
CA2609169C (fr) * 2006-11-15 2011-01-18 Rohm And Haas Company Adhesifs pour elastomeres
JP2010280630A (ja) * 2009-06-05 2010-12-16 Gc Corp 歯科用プライマー及び歯科用接着材セット

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4064629A (en) * 1976-01-26 1977-12-27 The University Of Virginia Cavity liner for dental restorations
WO1988005651A1 (fr) * 1987-02-04 1988-08-11 Dental Composite Ltd. Revetement en ionomere vitreux radiopaque en deux pates a utiliser avec des composites dentaires selon la technique du sandwich
EP0323120A2 (fr) * 1987-12-30 1989-07-05 Minnesota Mining And Manufacturing Company Ciments ionomères durcissables par la lumière
EP0413174A2 (fr) * 1989-08-14 1991-02-20 Mitsubishi Rayon Co., Ltd. Composition d'adhésif dentaire
WO1992011837A1 (fr) * 1991-01-08 1992-07-23 Minnesota Mining And Manufacturing Company Composition adhesive a base d'amalgame
US5154762A (en) * 1991-05-31 1992-10-13 Minnesota Mining And Manufacturing Company Universal water-based medical and dental cement

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4064629A (en) * 1976-01-26 1977-12-27 The University Of Virginia Cavity liner for dental restorations
WO1988005651A1 (fr) * 1987-02-04 1988-08-11 Dental Composite Ltd. Revetement en ionomere vitreux radiopaque en deux pates a utiliser avec des composites dentaires selon la technique du sandwich
EP0323120A2 (fr) * 1987-12-30 1989-07-05 Minnesota Mining And Manufacturing Company Ciments ionomères durcissables par la lumière
EP0413174A2 (fr) * 1989-08-14 1991-02-20 Mitsubishi Rayon Co., Ltd. Composition d'adhésif dentaire
WO1992011837A1 (fr) * 1991-01-08 1992-07-23 Minnesota Mining And Manufacturing Company Composition adhesive a base d'amalgame
US5154762A (en) * 1991-05-31 1992-10-13 Minnesota Mining And Manufacturing Company Universal water-based medical and dental cement

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995022956A1 (fr) * 1994-02-28 1995-08-31 Minnesota Mining And Manufacturing Company Systeme de ciment ionomere de verre en formulation pate:pate, et procedes associes
WO1995022955A1 (fr) * 1994-02-28 1995-08-31 Minnesota Mining And Manufacturing Company Compositions dentaires a stabilite de couleur amelioree, contenant de l'acide ascorbique sous forme de complexe metallique
WO1998011862A1 (fr) * 1996-09-18 1998-03-26 MÜHLBAUER, Wolfgang, Carl, Friedrich Composition et procede de restauration dentaire
US6734223B2 (en) 2000-08-11 2004-05-11 Dentsply Detrey Gmbh Polyaminoester and their application in dental compositions
EP1413283A1 (fr) * 2000-08-11 2004-04-28 Dentspy International, Inc. Compositions dentaires contenant des bisacrylamides et utilisation correspondante
US6767936B2 (en) 2000-08-11 2004-07-27 Dentsply Detrey Gmbh Dental compositions comprising bisacrylamides and use thereof
WO2002013768A3 (fr) * 2000-08-11 2002-06-06 Dentsply Int Inc Compositions dentaires contenant des bisacrylamides et utilisation correspondante
EP1222910A3 (fr) * 2001-01-15 2003-11-26 Ivoclar Vivadent AG Matériau dentaire contenant des amides polyfonctionnels
US6953832B2 (en) 2001-01-15 2005-10-11 Ivoclar Vivadent Ag Dental materials based on polyfunctional amides
US8129444B2 (en) 2001-05-16 2012-03-06 3M Espe Ag Self-adhesive dental materials
US9289358B2 (en) 2007-02-28 2016-03-22 Ultradent Products, Inc. Resin reinforced zinc polycarboxylate temporary cement compositions and related kits and methods
US10369085B2 (en) 2007-02-28 2019-08-06 Ultradent Products, Inc. Resin reinforced zinc polycarboxylate temporary cement compositions and related kits
US9907732B2 (en) 2007-02-28 2018-03-06 Ultradent Products, Inc. Resin reinforced zinc polycarboxylate temporary cement compositions and related kits and methods
US8263677B2 (en) 2009-09-08 2012-09-11 Creative Nail Design, Inc. Removable color gel basecoat for artificial nail coatings and methods therefore
US8901199B2 (en) 2009-09-08 2014-12-02 Creative Nail Design, Inc. Compositions and methods for UV-curable cosmetic nail coatings
US9717672B2 (en) 2009-09-08 2017-08-01 Creative Nail Design, Inc. Compositions and methods for UV-curable cosmetic nail coatings
US8541482B2 (en) 2009-10-05 2013-09-24 Creative Nail Design, Inc. Removable multilayer nail coating system and methods therefore
US8492454B2 (en) 2009-10-05 2013-07-23 Creative Nail Design, Inc. Removable color layer for artificial nail coatings and methods therefore
EP3166570B1 (fr) 2014-07-10 2022-04-20 3M Innovative Properties Company Composition dentaire auto-adhésive bi-composante, procédé de production et utilisation associée
WO2020168201A1 (fr) * 2019-02-15 2020-08-20 Ohio State Innovation Foundation Compositions adhésives à composant unique

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JPH07502531A (ja) 1995-03-16
CN1075629A (zh) 1993-09-01
BR9207009A (pt) 1995-12-05
AU3326193A (en) 1993-07-28
IL104203A (en) 1995-10-31
ZA9210060B (en) 1994-06-28
IL104203A0 (en) 1993-05-13
CA2117348A1 (fr) 1993-07-08
EP0623017A1 (fr) 1994-11-09
MX9207575A (es) 1993-10-01

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