CA2117347A1 - Metal filled adhesive composition and method - Google Patents
Metal filled adhesive composition and methodInfo
- Publication number
- CA2117347A1 CA2117347A1 CA002117347A CA2117347A CA2117347A1 CA 2117347 A1 CA2117347 A1 CA 2117347A1 CA 002117347 A CA002117347 A CA 002117347A CA 2117347 A CA2117347 A CA 2117347A CA 2117347 A1 CA2117347 A1 CA 2117347A1
- Authority
- CA
- Canada
- Prior art keywords
- composition
- amalgam
- ethylenically unsaturated
- metallic filler
- adhesive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
-
- 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
- A61K6/84—Preparations for artificial teeth, for filling teeth or for capping teeth comprising metals or alloys
- A61K6/847—Amalgams
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- Health & Medical Sciences (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Animal Behavior & Ethology (AREA)
- Epidemiology (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Plastic & Reconstructive Surgery (AREA)
- Dental Preparations (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
An adhesive composition comprising an ethylenically unsaturated compound, a particulate metallic filler, and a curing agent. Also disclosed is a method of adhering a restorative material such as amalgam to hard tissue such as dentin or enamel, involving the use of an adhesive composition of the invention as an intermediate layer between the restorative material and the hard tissue.
Description
C~21 1 7347 93~12757 PCr/US92/1~371 METAI, FILLED ~D~1~8IVE COMP08ITIO~ AND METHOD
BACKGROUND OF THE INVENTION
5 Technical Field This invention relates to adhesive compositions comprising an ethylenically unsaturated compound. In another aspect, this invention relates to adhesive compositions comprising a particulate metallic filler.
10 This invention also relates to methods of adhering a restorative material to a ~ubstrate, and in another aspect to methods of adhering a dental restorative such as amalgam to hard tissue such as dentin or enamel.
15 Descri~tion of the Related Art Dental amalgams and restorative co~posites are used extensively for intracoronal and exlracoronal restorations. Amalgam, however, does not adhere to tooth structure and the dentist must prepare the tooth 20 cavity with dovetails and various cutout groovss that mechanically loc~ the amalg~m into the cavit~y~ Such preparation, however, results in excavation of more tooth structure than would otherwise ~e necessary if there was good adhesion between the tooth structure and 25 the amalgam. Moreover, leakage at the interface of-the amalgam a~d cavity wall ~known as "micr~leakags") tends to occur. This microleakage allows penetration of bacteria, soluble salts, and saliva into any space between the amalgam and tooth structure. This can lead -30 to inflammation, pulp irritation, demineralization ofthe tooth, corrosion of the amalgam, and other at~endant complications. An adhesive seal between amalgam and toot~ structure could minimize and/or prevent microleakage and allow for a stronger 35 restoration due to excavation of less tooth material.
Products claiming to make amalgam adhesive to tooth struc~ure are available. One such product is sold in a kit under the trademark AMALGAM~ONDTM (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 5 trimellitic anhydride) and TBB (tri-n butyl borane).
Other products which sîmilarly involve coating a specific curable resin directly onto tooth structure to make amalgam adhere are available under the trademarks PANAVIAT~ Dental Adhesive (Kuraray Company) and 10 SUPERBONDTM Adhesive (Sun Nedical Co., Ltd., Kyoto, Japan). These latter products also are difficult to employ, since there are a number of required preparatory steps for their application and curing.
Articles that des~ribe bonding of amalgam to tooth 15 structure by precoating the tooth with ethylenically unsaturated adhesive resin include M. Staninec and M.
Holt, Journal of Prosthetic Dentistry (1988), Vol. 5~, pp. 397-402, A. Lacey and M. Staninec, Ouintessence International (1989), Vol. 20, pp. 521-524, Y. Aboush 20 and C. Jenkinæ, ~r. Dent. ~. (1989), Vol. 166, pp. 255-257, Y~ Aboush and R. Elderton, Br._Pent. J. ~1991), Vol. 170, pp. 219-222, and Y. Aboush and R. Elderton, ~ent. Mater. (1991), Vol. 7, pp. 130-132. The last article involves adhesion to previously hardened 25 amalgam, whereas the other articles involve adhesion- to fresh amalgam. Also, A. Ben-Amar, ~. Am. Dent. Assoc.
(1989) Vol. 119, pp. 725-728, de~cribes a reduction in microleakage at the margins of amalgam restorations when "SCOTCHBOND" ~ual Cure Dental Adhesive resin (3M) 30 is applied to cavity margins prior to application of amalgam, and M. Mitrosky~ Jr., Quintessence International (1981) Vol. 9, pp. 871-874, describes the use of ethyl cyanoacrylate as a bonding agent beneath amalgam and composite restoratives. H. J. Staehle et 35 al., Dtsch. Zahnartzt (1988) Vol. 43, pp. 952-g57, ~093/12757 PCT/US92/10371 describes the use of various dental adhesives and varnishes to adhere amalgam to dentin.
Adhesive compositions that employ phosphorus-containing free-radically polymerizable compounds have 5 been reported, see, e.g., ~. Buonocore, W. Wileman, and F. Brudevold, J. Dent. Res., 35, 846 (1956), M.
Buonocore and M~ Quigley, J. Amer. Dent. Assoc., 57, 807 (1958), M. Anbar and E. Farley, J. Dent. Res., 53, 879 (1974), E. Farley, R. Jones, and M. Anbar, J. Dent.
10 Res., 56, 1943 (1977), U.S. Pat Nos. 3,882,600, 3,997,504, 4,222,780, 4,235,~33, 4,259,075, 4,2S9,117, 4,368,043, 4,383,052, 4,499,251, 4,5~4,342, 4,~15,930, 4,537,940, 4,539,382, and 4,544,467, European published patent application No. 0 058 483, and Japanese 15 laid-open patent application (Kokai) Nos. 57-143372 and 57-167364.
U.S. Pat. No. 3,513,1~3 (Saffir) describes a curable epoxy composition that can be added to amalgam in order to make the amalgam adhere to tooth structure.
20 The curable epoxy composition contains a glycidyl ether type re~in and a polyamine hardening agent.
U.S. Pat. No. 4,064,62~ (Stoner) describes a .- method for applying amalgam restorations. The m~thod involves precoating the surfaces of a cavity within a 25 carious tooth with a layer of an l'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. ~he "adhesive-metal" lining 30 composition is said to improve corrosion resistance of the dental amalgam filling and also to promote bonding between the amalgam restoration and the cavity surfaces.
U.S. Pat. No. 4,001,483 (Lee, Jr. et al.) 35 describes dental compositions for sealing margins between tooth structures and amalgam restorations therein, the compositions containing (a) an alkylene (~A21 1 7347 W O 93/12757 PC~r/US92/1037 glycol dimethacrylate and/or its oligomer, (b) a polymerization initiator, (c) a polymerization accelerator and (d) a secondary monomer additive.
U.S. Pat. No. 3,574,943 (Stark) describes a method 5 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. The polysiloxane layer is said to act as a barrier to 10 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 lS peroxide, and an aromatic amine or sulfinate salt. The composition is said to bond living tooth tis ue to composites and amalgams.
French Patent 2,561,521 describes an intermediate adhesive composition for sealing dental cavities and 20 chemically securing amalgams, comprising a metal powder dispersed in an adhecive varniæh. The composition contains metal powder, cellulosic varnish, ethyl - acetate, a~yl propionate, fluoride, and oil of pimento lea~.
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 ~-omposition is said to be applicable to a wide variety of restorative 30 materials, including composite resins, amalgam, alumina, gold, alloys, polymethyl methacrylate, polycarbonate, and the like.
SUMMARY OF THE INVENTION
~ Thiæ invention provides an adhesive composition, ; comprising:
:
~093/12757 PCT/US9~/10371 -- S --(i) an ethylenically unsaturated compound;
(ii) a particulate metallic filler that does not interfere with the cure of the ethylenically unsaturated compound, in an amount effective to increase adhesion of amalgam to tooth structure when the composition is used as an intermediate layer between the amalgam and the tooth structure, compared to the adhesion o~tained using a like composition absent the particulate metallic filler; and (iii) a polymerization initiator in an amount sufficient to effect cure of the composition.
This invention also provides an adhesive 15 composition, comprising:
(i) an ethylenically unsaturated compound;
(ii) a particulate metallic filler that dpes not interfere with the cure of the ethylenically unsaturated compound, in an amount of about 50 to about 4000 parts by weight based on 100 parts by weight of the ethylenically unsaturated compound;
and (iii) a polymerization initiator in an amount su~ficient to effect cure of the composition.
This invention also provides a method of adhering a restorative material to a substrata, comprising the steps o~:
(i~ combining the components of a composition of the invention as described above;
(ii) placing an intermediate layer of the composition from step (i) on one member of the restorative material/substrate pair;
(iii~ optionally ruring the intermediate layer; and (~Q21 1 7347 WO93/12757 PCT/US92/1037' (iv) adhering the other member of the restorative material/substrate pair to the first member by way of the in~ermediate layer.
DETAILED DESCRIPTION OF THE INVENTION
Materials suitable for use as the ethylenically unsaturated compound in a composition of the invention include such materials known to those skilled in the lO ar~ to be capable of bonding to hard tissue such as dentin, enamel, bone, or the like. This compound is a monomer, oligomer, or polymer (or mixture thereof), pref~rably suitable for use in the oral environment both in its unpolymerized and polymerized state. Both 15 phosphorylated and phosphorus-free ethylenically unsaturated compounds as well as mixtures thereof are suitable.
Suitable phosphorus-free ethylenically unsaturated compounds include ~ono- or poly- (e.g~, di-, tri- or 20 tetra-functional) acrylates and methacrylates such as ~ethyl acrylate, 2-hydroxyethyl acrylate, triethylene-glycol diacrylate, neopentylglycol diacrylate, hexamethyleneglycol diacrylate, trimethylolpropane triacrylate, pentaery~hri~ol tetraacrylate, 25 polyalkylene glycol ~ono- and di-acrylates, urethane-mono- or poly-functional acrylates, Bisphenol A
diacrylates, and the corresponding methacrylates of the above compound~, as well as acrylamides and methacrylamides r ~inyl compounds, styrene comp~unds, 30 and other olefinically unsaturated compounds suitable for use in the oral environment. UOS. Pat. NosO
4,499,251, 4,515,930, 4,537,940 and 4,539~382 contain an extensive list of such compounds.
Representative phosphorus-free ethylenically 35 unsaturated dental adhesives include "SCOTCHBOND 2TM"
Dental Adhesive ~3M), "CONCISET~" Enamel Bond (3M), ~93/127~7 PCT/US92/10371 "TENURETM" Solution Dentin Bonding System (Den-Mat Corp.), "G~UMATM" Bonding System (Columbus Dental Miles, Inc.) and "MIRAGE-BONDTM" Dentin-Enamel Bonding System (Chameleon Dental Products, Inc., see U.S. Pat. Nos.
5 4,514,527, 4,521,550, 4,588,756, and 4,659,751).
Suitable ethylenically unsaturated phosphorylated compounds comprise one or more phosphorus atoms bonded through a carbon, nitrogen, oxygen, or sulfur atom to a radical containing one or more ethylenically l0 unsaturated groups. Preferred ethylenically unsaturated groups are ethenyl and 2-propenyl as found, respectively, in acrylate and methacrylate groups. One or more of the phosphorus atoms can be bonded to one or more halogen atoms, active hydrogen atoms, or l5 substituted or unsubstituted hydrocarbyl groups (e.g., an al~yl, aryl, alkaryl, or aryalkyl group). A
particular~class of suitable phosphorylated compoundS
is de&cribed in European Patent Application No. 0 058 483 and U.S. Pat. No. 4,515,930. These phosphorylated 20 compounds include those comprising an organic ester of one or more acids of phosphorus, the organic radical of said ester containing a~ least one ethylenically unsaturated group, wherein aid ester has chlorine or bromine bonded directly to the phosphorus (hereinafter 25 nhalophosphorus acid estersn). A preferred subclass of such halophosphorus acid esters includes halophosphoru~
acid esters of diglycidyl methacrylatè of Bisphenol A
("Bis-GMA") prepared b~ reacting ~is-GMA with a pho~phorus acid halide. Phoæphorus acid halides (e.g., 30 chlorides, bromides) that can be reacted with Bis-GMA
include PQCl3, PCl3, PBr3, R'OP(O)Cl2, (R'O)2PtO)Cl where R' ic a hydrocarbyl radical, preferably one derived from remoYal of one or more hydroxyl groups from a hydroxyl-containing compound such as 2-hydroxyethyl 3~ methacrylate, ethylene glycol, polyethylene glycol, pentaerythritol, and the like, as would result from a WO93/127~7 PCr/VS92/l037 reaction of the hydroxyl-containing compound and the phosphorus acid halide. A particularly preferred class of phosphorylated compounds includes chlorophosphorus acid esters ~f Bis-GMA.
S An additional suitable class of phosphorylated compounds includes the pho~phorus acid esters described in U.S. Pat. Nos. 3,882,600, 3,997,S04, 4,222,780, 4,235,633, 4,259,07~, 4,~59,117, 4,368,043, 4,442,~39, 4,499,251, 4,S14,342, 4,537,940, 4,539,382 and Japanese 10 published patent application (Koho) No. 85~17235.
Exemplary members of this class are the compounds 2-methacrylQyloxyethyl phenyl phosphat~ and 10-methacryloyloxydecyl dihydrogen phosphate.
A further suitable class of phosphorylated 15 compounds includes the pyrophosphate ester derivatives described in U.S. Pat. Nos. 4,383,052 and 4,404,150 and in Japanese Kokai 57-143372 and 57-167364.
Glycerophosphate dimethacrylate, described in the above-mentioned Buonocore, Wileman, and Brudevold 20 publication ic also ~uitable.
Other dental adhesives suitable for use as the ethylenically unsaturated compound include those that contain phosphorylated compounds and/or acrylate- or methacrylate-functional polymers. In such dental 25 adhesives either a single phosphorylated compound or a mixture of phosphorylated compounds can be used.
Suitable dental adhesives include "SCOTCHBONDTM" Dual ~ure Dental Adhesive (3~), "ALL-BOND2T~" Universal Dental Adhesive System (Bisco, Inc.), "CLEARFILTM" Photo 30 Bond Light-Cured Dental Bonding Agent (Kuraray Co., Ltd.), "RESTOBOND 3TMIl Dual Dentin/Enamel Bonding Agent (Lee Pharmaceuticals, see U.~. Pat. Nos. ~,524,527 and 4,521,5503, "PRISM~ UNIVERSAL B~ND3TM" Dentin/Enamel Bonding Agent (L. D. Caulk Di~ision of Dentsply 35 International, Inc., see U.S. Pat. No. 4,814,423), "BONDLITETM" Dental Adhesive (Sybron Corp.), ~IJohnson &
C~21 1 7~47 `"O 93/12757 PC~r/US92110371 g Johnson" Dentin Bonding Agent and "Johnson & Johnson"
Light-Curing Bonding Agent (Johnson & Johnson Co.), "PALFIQUETM" Bonding Agent (Tokuyama Soda Co., Ltd.), "SHOFUTM" Bonding Base (Shofu, Inc.), and "SINTERBONDTM"
5 Dental Adhesive (Teledyne Getz).
In embodiments involving a mixture of ethylenically unsaturated compounds, suitable relative amounts of each compound can be easily selected by those skilled in the art.
The compositions of the invention also comprise a particulate metallic filler that does not interfere with the cure of the ethylenically unsaturated compound. Particular suitable metallic fillers can be selected by those skilled in the art based on chemical 15 compatibility with the particular ethylenically unsaturated compound and the particular polymerization initiator present in the composition. Interference .
with the cure of the ethylenically unsaturated compound can also be determined empirically, e.g., by adding a 20 selected metallic filler to a mixture of ethylenically unsaturated compound and polymerization ini~iator, which mixture cures in a sa~isfactory manner absent the m¢tallic filler. When cure of the metal containing mixture is attempted, any interference with cure due to 25 the ~etallic filler will be readily ob ervable.
Depending on the identity of the ethylenically unsaturated compound and the polymerization initiator, the f iller can be a pure metal such as those of Groups IVA, VA, VIA, VIIA, VIII, IB, or IIB, aluminum, indium, 30 and thallium of Group IIIB, and tin and lead of Group IVB, or alloys thereof. Conventional dental amalgam alloy powders, typically mixtures of silver~ tin, copper, and zinc, are also suitable. The particulate metallic filler preferably has an average particle size 35 of about 1 micron to about lOQ microns, more preferably 1 micron to about 50 microns.
WO93/12757 PCT/US92/1037~
In some embodiments, the metallic filler is present in an amount effective to increase adhesion of amalgam to tooth structure when the composition is used as an intermediate layer between the tooth structure 5 and the amalgam, compared to the adhesion obtained using a like composition absent the metallic filler.
An effective amount in these embodiments can be determined according to the method set forth in the EXAMPLES that follow. In other embodiments the l0 particulate metallic filler is present in an amount of 50 to about 4000 parts by weight, preferably about 200 to about 3000 parts by weight based on lO0 par~s by weight of the ethylenically unsaturated compound.
A composition of the invention also includes a 15 polymerization initiator in an amount sufficient to effect cure of the composition. Suitable polymerization initiators include autocure and light~
~ure polymerization initiators such as those mentioned in columns 28 and 29 of U.S. Pat. No. 4,539,382, - 29 chromophore-substituted halomethyl-s-triazines such as those shown in U.S. Pat. No. 3,954,475, and~
chromophore-substituted halomethyl-oxadiazoles such as those shown in V.S. Pat. No. 4,212,970.
qhe polymerization initiator is preferably present 25 in an amount of about 0.0l to about 20 p~rt5 by weight, more pref~rably about 0.l to about l0 parts by weight, ~asQd on 100 part~ by weight of ethylenically unsaturated compound.
Other compounds (additional to the above-discussed 30 ethylenically unsaturated compound) can be incorporated in the compositions of the invention in appropriate amounts easily selected by those skilled in the art to provide desired propçrti~s. Suitable compounds include mono- or polyacrylates and methacrylates such as methyl 35 acrylate, 2-hydroxyethyl acrylate, triethyleneglycol diacrylate, neopentylglycol diacrylate, hexamethyl-eneglycol diacrylate, trimethylolpropane triacrylate, ' -, ~21 1 7347 '~'~ 93/12757 PC~r/US92/10371 11 -- !
pentaerythritol tetraacrylate, polyalkylene glycol mono- and di-acrylates, urethane mono- or polyfunctional acrylates, Bisphenol A diacrylates, and the corresponding methacrylates of the above compounds, 5 as well as acrylamides and methacrylamides, vinyl compounds, styrene compounds, and other olefinically unsaturated compounds suitable for use in the oral environment. U.S. Pat. Nos. 4,499,251, 4,515,930, 4,537,940 and 4,539,382 contain lists of such 10 compounds.
The compositions of the invention can also contain conventional adjuvants such as accelerators, inhibitors, stabilizers, pigments, dyes, viscosity modifiers, extending or reinforcing fillers, surface 15 tension depressants, wetting aids, antioxidants, and other ingredients known to those skilled in the art.
The compositions of the in~ention can be prepared by mixing and packaging the various components according to ~ethods well known to those skilled in the 20 art. For example, when a redox type curing agent is used, an appropriate package form keeps the~oxidant and : the reducing agent apart from each other in order to ensure storage stability of the composition. Examples of package forms include two-part packages of (a) an 25 ethylenically unsaturated compound, a metallic fil~er, and a reducing agent in one part and (b) an ethylenically unsaturated c~mpound and an oxidant in the other. In the ca~e of an organic sulfinic acid (or salt thereof)tamine (or salt thereof)/peroxide ternary 30 ~ystem, it is also possible to use a three-part package form in which the sul~inic acid and the amine are packaged separately.
Where the polymerization înitiator comprises a photoinitiator, an ethylenically unsaturated compound 35 and a photoinitiator are preferably packaged separately or in a container opaque to light. With a thermal initiator that initiates polymerization when it is :, CA21 1 73~
WO93/12757 PCT/US9~/1037 brought into contac~ with the ethylenically unsaturated compound (e.g., tributylborane), the ethylenically unsaturated compound and the initiator are packaged separately. Such separately packaged components are 5 mixed together shortly before use.
A composition of the invention can be used as an intermediate layer between a substrate such as hard r tissue (e.g., bone, enamel, or dentin~ or ceramic, and a restorative material such as a pure metal or alloy, lO an amalgam, a ceramic composite, or a composite comprising an adhesive polymer (or a mixture of polymers) and a particulate filler. A primer may be used, but good adhesion is obtained without the use of auxiliary primers. The compositions of the invention 15 generally provide better adhesion than is obtained using the ethylenically unsaturated compound alone.
In order to adhere a restorative material to a substrate, the components of a composition of the invention are first combined in appropriate amounts.
20 As discussed above, depending upon the particular type of curing agent used the components can be mixed prior to packaging or they can be packaged as two- or three-part systems and aombined just prior to use.
Once the components are combined the resulting 25 composition of the invention can be placed in the form of a thin layer (e.g., ~y brushing) on either the restorative material or on the substrate. The layer can then optionally be cured by appropriate means (e.g., heat including exposure to room temperature, 30 visible light, ultraviolet light, or the like). The other member of the restorative material/substrate pair can then be prepared (e.g., mixed) if necessary and placed on the adhesive layer.
For the reasons set forth above in connection with 35 the 8ackground of the Invention, it is desirable if an amalgam can be made to adhere well to tooth structure.
Accordingly, one use of the compositions of the :
" ~93/127~7 PCT/US92/10371 invention involves adhering dental amalgam to tooth structure in a prepared cavity.
It is preferred to ~se a modified amalgam in order to optimize adhesion to tooth structure. Such a 5 modified amalgam can be produced by admixing particulate additives into conventional amalgam alloy powder. The modified amalgam is then prepared in a conventional manner by triturating the modified alloy powder with mercùry in an amalgamator.
The preferred particulate additives are selected from the following groups: l) acrylate- or methacrylate-functional polymers, 2) metal salts of acrylates or methacrylates, 3) nonmetallic fillers, 4 oxidizing agents, and 5) reducing agents. The lS particulate additives are applicable to the full range of conventional ~malgam alloy powders and conventional weight ratios of mercury to amalgam alloy powderO
Representative acrylate- or methacrylate-functional polymers include poly(alkanoic acid) powder.
20 Representative metal salts of acrylates or methacrylates include zinc dimethacrylate, zirconium dimethacrylate, silver methacrylate, sodium - methacrylate, and magnesium methacrylate. Nonmetallic fillers include both untreated organic fillers and 25 surface-treated fillers. Representative nonmetallic fillers, also k~own as organic fillers, include b1ends of silane-treated OX-50TM pyrogenic silica ~Degussa Company~, tetraethyleneglycol dimethacrylate ("TEGDMA") (Rohm Tech Co.), and Bi~phen~l A diglycidylether 30 qimethacrylate in a 60:17:17 weight ratio. Other representative nonmetallic fillers include zirconia/silica filler ei~her untreated or pretreated with gamma-methacryloxypropyl trimethoxysilane as described in U.S. Pat. No. 4,503,169. Preferred 35 oxidizing agent~ include benzoyl peroxide. Preferred reducing agents include sodium benzenesulfinate.
Adhesion of amalgam to etched enamel was evaluated as follows: Bovine teeth of similar age and appearance were partially embedded in circular acrylic disks such that the enamel was exposed. The exposed portion of 5 each tooth was ground flat and parallel to the acrylic disc using Gr~de 120 silicon carbide paper-backed abrasive mounted on a lapidary wheel. Further grinding and polishing of the teeth was carried out by mounting Grade 320 silicon carbide paper-backed abrasive on the lO lapidary wheel. During the grinding and polishing steps, the teeth were continuously rinsed with water.
The polished teeth were stored in distilled water and used for testing within 2 hours after polishing.
The polished teeth were removed from the water and 15 dried using a stream of compressed air. Phosphoric acid etching gel was applied to the enamel for l~
~econds, rinsed with water, and dried. The adhesive~
composition was applied to the entire enamel ~urface with a brush and blown into a thin film with compressed 20 air and cured according to manufacturer's instructions.
A mold made from a 2 mm thick TEFLONTM ~olytetra-fluoroethylene sheet with a 5 mm diameter cir~ular hole - through the sheet was clamped to each polished tooth so ~hat the central ~xis of the hole in the mold was 25 normal to the poli~hed tooth surface. ~he hole in aach mold was filled with a prepared amalgam and allowed to stand for about l5 minutes at room temperature, then stored in distilled water at 37C for 24 hours. The molds were then carefully removed, leaving a molded 30 button of amalgam attached to each tooth.
Adhesive strength was evaluated by mounting the acrylic disk in a holder clamped in the jaws of an INSTRONTM tensile testing apparatus with the polished tooth surface orient~d parallel to the direction of 35 pull. A loop of orthodontic wire (O.44 mm diameter) was placed around the base of the amalgam button CA~ 34~
~"~93/127S7 PCT/US92~10371 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 5 amalgam button) failed, using a crosshead speed of 2 mm/min.
The following examples are offered to aid in understanding of the present invention and are not to be construed as limiting the scope thereof. Unless 10 otherwise indicated, all parts and percentages are by weight.
EXAMPLES l-l2 and CONPARATIVE EXANPLES C-l to C-6 Using the procedure set forth above, the adhesive 15 shear bond strength on etched enamel of several adhesive compositions was evaluated. The amalgam used was two-spill capsules of DISPERSALLOYl~ amalgam.
Commercially available adhesives were evaluated according to the manufacturer's instructions.
20 Compositions of this invention were prepared by preweighing the metal additive into a mixing well. One drop (approximately 0.03 g) of a phosphorylate~
ethylenically unsaturated compound (SCOTCHBONDTM Dual Cure Dental Adh~sive resin) and one drop (approximately 25 -0.02 g) of a poly~erization initiator ~SCOTCHBONDTM Dual Cure Dental Adhesive li~uid) were added to the metal additive.
Alternatively a composition comprising a ph~sphorus-free ethylenically unsaturated compound was 30 prepared ~y preweighing the metal additive into a mixing well and adding one drop each of: (i) a combination of a phosphorus-free ethylenically unsaturated compound and dihydroxyethyl-p-toluidine reducing agent (CONCISETM Enamel Bond A); and (ii) a 35 combination of a phosphorus-free ethylenically WO93~127~7 PCT/US92/103 unsaturated compound and benzoyl peroxide oxidizing agent (CONCISETM Enamel Bond B).
In each case the components were then mixed rapidly and applied with a brush to the etched enamel.
5 The applied adhesive was then cured according to manufacturer's instru~tions prior to placement of the amalgam.
Set out below in TABLE I are the example numbers, ethylenically unsaturated c~mpound, metallic filler, lO and mean adhesive shear bond values for the various compositions tested.
CA2~ 1 7347 '4) 93/127S7PCl/US92/10371 1~ tt~t~T tT
.~ a_. o ~ ' ~ ~ ~ r~ N Nll ~
~ 1~; _ _ _ _ . _ _ _ _ _ ~
4 ~ In It~ O IQ It~ O Itl 10 N O _ _ _ _ _ 4 ~
~ ~ m~ 0~Y
~ 11 ~ ~ ~ l l 3j jll 3 3~ e ~ Y
~ T
:~ L~
V D
The results in TABLE I illustrate that the exemplified compositions comprising a metallic filler and an ethylenically unsaturated compound provide improved shear adhesion to hard tissue and amalgam 5 relative to the unfilled ethylenically unsaturated compound. Several compositions of this invention provided mean shear adhesion values better than those obtained with commercially available hard tissue/amalgam adhesives. Also, it was observed in l0 Comparative Example C-6 that zinc interferes with the cure of the SCOTCHBOND~ Dual Cure Dental Adhesive resin when SCOTCHBOND~ Dual Cure Dental Adhesive liquid was used as the polymerization initiator.
EXAMPLES 13-14 and COMPARATIVE EXAMPLES C-7 to C-ll Using the procedure set forth above, the shear , adhesive bond strength on ~tched enamel of several adhesive compositions was evaluated. The amalgam used 20 was two-spill capsules of DISPERSALLOYTM amalgam (Johnson and Johnson) or a modified version.containing varying amounts of organic filler. Set out below in TABLE II are the example nu~bers, ethylenically unsaturated compound, metallic filler, amalgam, amalgam 25 additive, and maan shear adhesion values for the variou~ co~positions t~sted.
'~'') 93/12757 PCT/US92/10371 ~ -~T~
~ ~ U~ U~ O U~ U~ CD U~ C' Q ~i~ t5~
C~ I__ _ ~ ~ ~ 0~
~ ~ ~ _ l ~ l l ~ _ t ô O X
~ 3~ l l l l o l ~o ~ s a H_ __ _ ~ O 'a o E ~i ~ ~ l~i ~ a ~3 i ta H H H H H ca `' U~
~c~ ~ n a a a D ~ ~ a2 S
~_ _ _ - . ~ ~
O O _ . l l l . o ~: O
o~ ~ l l t l l ~ ~ ~ ~
_ _ __ __ I ~ ~ s ~ E~
e D U ~¢ m C~ ~ ~¢ lcc ~: ~a CO ~ ~ C i . _ _ _ ~_ _ ~ ~ ~ C O ~ ~
r~ c~ U ;~. U ~ E1 ~ ~ W ~
C~21 1 7347 W093/12757 PCT/US92/1037'~
The results in TABLE II show that the greatest mean ad~esive shear bond values are obtained for the combination of metal filled adhesive and powder modified amalgam.
BACKGROUND OF THE INVENTION
5 Technical Field This invention relates to adhesive compositions comprising an ethylenically unsaturated compound. In another aspect, this invention relates to adhesive compositions comprising a particulate metallic filler.
10 This invention also relates to methods of adhering a restorative material to a ~ubstrate, and in another aspect to methods of adhering a dental restorative such as amalgam to hard tissue such as dentin or enamel.
15 Descri~tion of the Related Art Dental amalgams and restorative co~posites are used extensively for intracoronal and exlracoronal restorations. Amalgam, however, does not adhere to tooth structure and the dentist must prepare the tooth 20 cavity with dovetails and various cutout groovss that mechanically loc~ the amalg~m into the cavit~y~ Such preparation, however, results in excavation of more tooth structure than would otherwise ~e necessary if there was good adhesion between the tooth structure and 25 the amalgam. Moreover, leakage at the interface of-the amalgam a~d cavity wall ~known as "micr~leakags") tends to occur. This microleakage allows penetration of bacteria, soluble salts, and saliva into any space between the amalgam and tooth structure. This can lead -30 to inflammation, pulp irritation, demineralization ofthe tooth, corrosion of the amalgam, and other at~endant complications. An adhesive seal between amalgam and toot~ structure could minimize and/or prevent microleakage and allow for a stronger 35 restoration due to excavation of less tooth material.
Products claiming to make amalgam adhesive to tooth struc~ure are available. One such product is sold in a kit under the trademark AMALGAM~ONDTM (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 5 trimellitic anhydride) and TBB (tri-n butyl borane).
Other products which sîmilarly involve coating a specific curable resin directly onto tooth structure to make amalgam adhere are available under the trademarks PANAVIAT~ Dental Adhesive (Kuraray Company) and 10 SUPERBONDTM Adhesive (Sun Nedical Co., Ltd., Kyoto, Japan). These latter products also are difficult to employ, since there are a number of required preparatory steps for their application and curing.
Articles that des~ribe bonding of amalgam to tooth 15 structure by precoating the tooth with ethylenically unsaturated adhesive resin include M. Staninec and M.
Holt, Journal of Prosthetic Dentistry (1988), Vol. 5~, pp. 397-402, A. Lacey and M. Staninec, Ouintessence International (1989), Vol. 20, pp. 521-524, Y. Aboush 20 and C. Jenkinæ, ~r. Dent. ~. (1989), Vol. 166, pp. 255-257, Y~ Aboush and R. Elderton, Br._Pent. J. ~1991), Vol. 170, pp. 219-222, and Y. Aboush and R. Elderton, ~ent. Mater. (1991), Vol. 7, pp. 130-132. The last article involves adhesion to previously hardened 25 amalgam, whereas the other articles involve adhesion- to fresh amalgam. Also, A. Ben-Amar, ~. Am. Dent. Assoc.
(1989) Vol. 119, pp. 725-728, de~cribes a reduction in microleakage at the margins of amalgam restorations when "SCOTCHBOND" ~ual Cure Dental Adhesive resin (3M) 30 is applied to cavity margins prior to application of amalgam, and M. Mitrosky~ Jr., Quintessence International (1981) Vol. 9, pp. 871-874, describes the use of ethyl cyanoacrylate as a bonding agent beneath amalgam and composite restoratives. H. J. Staehle et 35 al., Dtsch. Zahnartzt (1988) Vol. 43, pp. 952-g57, ~093/12757 PCT/US92/10371 describes the use of various dental adhesives and varnishes to adhere amalgam to dentin.
Adhesive compositions that employ phosphorus-containing free-radically polymerizable compounds have 5 been reported, see, e.g., ~. Buonocore, W. Wileman, and F. Brudevold, J. Dent. Res., 35, 846 (1956), M.
Buonocore and M~ Quigley, J. Amer. Dent. Assoc., 57, 807 (1958), M. Anbar and E. Farley, J. Dent. Res., 53, 879 (1974), E. Farley, R. Jones, and M. Anbar, J. Dent.
10 Res., 56, 1943 (1977), U.S. Pat Nos. 3,882,600, 3,997,504, 4,222,780, 4,235,~33, 4,259,075, 4,2S9,117, 4,368,043, 4,383,052, 4,499,251, 4,5~4,342, 4,~15,930, 4,537,940, 4,539,382, and 4,544,467, European published patent application No. 0 058 483, and Japanese 15 laid-open patent application (Kokai) Nos. 57-143372 and 57-167364.
U.S. Pat. No. 3,513,1~3 (Saffir) describes a curable epoxy composition that can be added to amalgam in order to make the amalgam adhere to tooth structure.
20 The curable epoxy composition contains a glycidyl ether type re~in and a polyamine hardening agent.
U.S. Pat. No. 4,064,62~ (Stoner) describes a .- method for applying amalgam restorations. The m~thod involves precoating the surfaces of a cavity within a 25 carious tooth with a layer of an l'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. ~he "adhesive-metal" lining 30 composition is said to improve corrosion resistance of the dental amalgam filling and also to promote bonding between the amalgam restoration and the cavity surfaces.
U.S. Pat. No. 4,001,483 (Lee, Jr. et al.) 35 describes dental compositions for sealing margins between tooth structures and amalgam restorations therein, the compositions containing (a) an alkylene (~A21 1 7347 W O 93/12757 PC~r/US92/1037 glycol dimethacrylate and/or its oligomer, (b) a polymerization initiator, (c) a polymerization accelerator and (d) a secondary monomer additive.
U.S. Pat. No. 3,574,943 (Stark) describes a method 5 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. The polysiloxane layer is said to act as a barrier to 10 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 lS peroxide, and an aromatic amine or sulfinate salt. The composition is said to bond living tooth tis ue to composites and amalgams.
French Patent 2,561,521 describes an intermediate adhesive composition for sealing dental cavities and 20 chemically securing amalgams, comprising a metal powder dispersed in an adhecive varniæh. The composition contains metal powder, cellulosic varnish, ethyl - acetate, a~yl propionate, fluoride, and oil of pimento lea~.
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 ~-omposition is said to be applicable to a wide variety of restorative 30 materials, including composite resins, amalgam, alumina, gold, alloys, polymethyl methacrylate, polycarbonate, and the like.
SUMMARY OF THE INVENTION
~ Thiæ invention provides an adhesive composition, ; comprising:
:
~093/12757 PCT/US9~/10371 -- S --(i) an ethylenically unsaturated compound;
(ii) a particulate metallic filler that does not interfere with the cure of the ethylenically unsaturated compound, in an amount effective to increase adhesion of amalgam to tooth structure when the composition is used as an intermediate layer between the amalgam and the tooth structure, compared to the adhesion o~tained using a like composition absent the particulate metallic filler; and (iii) a polymerization initiator in an amount sufficient to effect cure of the composition.
This invention also provides an adhesive 15 composition, comprising:
(i) an ethylenically unsaturated compound;
(ii) a particulate metallic filler that dpes not interfere with the cure of the ethylenically unsaturated compound, in an amount of about 50 to about 4000 parts by weight based on 100 parts by weight of the ethylenically unsaturated compound;
and (iii) a polymerization initiator in an amount su~ficient to effect cure of the composition.
This invention also provides a method of adhering a restorative material to a substrata, comprising the steps o~:
(i~ combining the components of a composition of the invention as described above;
(ii) placing an intermediate layer of the composition from step (i) on one member of the restorative material/substrate pair;
(iii~ optionally ruring the intermediate layer; and (~Q21 1 7347 WO93/12757 PCT/US92/1037' (iv) adhering the other member of the restorative material/substrate pair to the first member by way of the in~ermediate layer.
DETAILED DESCRIPTION OF THE INVENTION
Materials suitable for use as the ethylenically unsaturated compound in a composition of the invention include such materials known to those skilled in the lO ar~ to be capable of bonding to hard tissue such as dentin, enamel, bone, or the like. This compound is a monomer, oligomer, or polymer (or mixture thereof), pref~rably suitable for use in the oral environment both in its unpolymerized and polymerized state. Both 15 phosphorylated and phosphorus-free ethylenically unsaturated compounds as well as mixtures thereof are suitable.
Suitable phosphorus-free ethylenically unsaturated compounds include ~ono- or poly- (e.g~, di-, tri- or 20 tetra-functional) acrylates and methacrylates such as ~ethyl acrylate, 2-hydroxyethyl acrylate, triethylene-glycol diacrylate, neopentylglycol diacrylate, hexamethyleneglycol diacrylate, trimethylolpropane triacrylate, pentaery~hri~ol tetraacrylate, 25 polyalkylene glycol ~ono- and di-acrylates, urethane-mono- or poly-functional acrylates, Bisphenol A
diacrylates, and the corresponding methacrylates of the above compound~, as well as acrylamides and methacrylamides r ~inyl compounds, styrene comp~unds, 30 and other olefinically unsaturated compounds suitable for use in the oral environment. UOS. Pat. NosO
4,499,251, 4,515,930, 4,537,940 and 4,539~382 contain an extensive list of such compounds.
Representative phosphorus-free ethylenically 35 unsaturated dental adhesives include "SCOTCHBOND 2TM"
Dental Adhesive ~3M), "CONCISET~" Enamel Bond (3M), ~93/127~7 PCT/US92/10371 "TENURETM" Solution Dentin Bonding System (Den-Mat Corp.), "G~UMATM" Bonding System (Columbus Dental Miles, Inc.) and "MIRAGE-BONDTM" Dentin-Enamel Bonding System (Chameleon Dental Products, Inc., see U.S. Pat. Nos.
5 4,514,527, 4,521,550, 4,588,756, and 4,659,751).
Suitable ethylenically unsaturated phosphorylated compounds comprise one or more phosphorus atoms bonded through a carbon, nitrogen, oxygen, or sulfur atom to a radical containing one or more ethylenically l0 unsaturated groups. Preferred ethylenically unsaturated groups are ethenyl and 2-propenyl as found, respectively, in acrylate and methacrylate groups. One or more of the phosphorus atoms can be bonded to one or more halogen atoms, active hydrogen atoms, or l5 substituted or unsubstituted hydrocarbyl groups (e.g., an al~yl, aryl, alkaryl, or aryalkyl group). A
particular~class of suitable phosphorylated compoundS
is de&cribed in European Patent Application No. 0 058 483 and U.S. Pat. No. 4,515,930. These phosphorylated 20 compounds include those comprising an organic ester of one or more acids of phosphorus, the organic radical of said ester containing a~ least one ethylenically unsaturated group, wherein aid ester has chlorine or bromine bonded directly to the phosphorus (hereinafter 25 nhalophosphorus acid estersn). A preferred subclass of such halophosphorus acid esters includes halophosphoru~
acid esters of diglycidyl methacrylatè of Bisphenol A
("Bis-GMA") prepared b~ reacting ~is-GMA with a pho~phorus acid halide. Phoæphorus acid halides (e.g., 30 chlorides, bromides) that can be reacted with Bis-GMA
include PQCl3, PCl3, PBr3, R'OP(O)Cl2, (R'O)2PtO)Cl where R' ic a hydrocarbyl radical, preferably one derived from remoYal of one or more hydroxyl groups from a hydroxyl-containing compound such as 2-hydroxyethyl 3~ methacrylate, ethylene glycol, polyethylene glycol, pentaerythritol, and the like, as would result from a WO93/127~7 PCr/VS92/l037 reaction of the hydroxyl-containing compound and the phosphorus acid halide. A particularly preferred class of phosphorylated compounds includes chlorophosphorus acid esters ~f Bis-GMA.
S An additional suitable class of phosphorylated compounds includes the pho~phorus acid esters described in U.S. Pat. Nos. 3,882,600, 3,997,S04, 4,222,780, 4,235,633, 4,259,07~, 4,~59,117, 4,368,043, 4,442,~39, 4,499,251, 4,S14,342, 4,537,940, 4,539,382 and Japanese 10 published patent application (Koho) No. 85~17235.
Exemplary members of this class are the compounds 2-methacrylQyloxyethyl phenyl phosphat~ and 10-methacryloyloxydecyl dihydrogen phosphate.
A further suitable class of phosphorylated 15 compounds includes the pyrophosphate ester derivatives described in U.S. Pat. Nos. 4,383,052 and 4,404,150 and in Japanese Kokai 57-143372 and 57-167364.
Glycerophosphate dimethacrylate, described in the above-mentioned Buonocore, Wileman, and Brudevold 20 publication ic also ~uitable.
Other dental adhesives suitable for use as the ethylenically unsaturated compound include those that contain phosphorylated compounds and/or acrylate- or methacrylate-functional polymers. In such dental 25 adhesives either a single phosphorylated compound or a mixture of phosphorylated compounds can be used.
Suitable dental adhesives include "SCOTCHBONDTM" Dual ~ure Dental Adhesive (3~), "ALL-BOND2T~" Universal Dental Adhesive System (Bisco, Inc.), "CLEARFILTM" Photo 30 Bond Light-Cured Dental Bonding Agent (Kuraray Co., Ltd.), "RESTOBOND 3TMIl Dual Dentin/Enamel Bonding Agent (Lee Pharmaceuticals, see U.~. Pat. Nos. ~,524,527 and 4,521,5503, "PRISM~ UNIVERSAL B~ND3TM" Dentin/Enamel Bonding Agent (L. D. Caulk Di~ision of Dentsply 35 International, Inc., see U.S. Pat. No. 4,814,423), "BONDLITETM" Dental Adhesive (Sybron Corp.), ~IJohnson &
C~21 1 7~47 `"O 93/12757 PC~r/US92110371 g Johnson" Dentin Bonding Agent and "Johnson & Johnson"
Light-Curing Bonding Agent (Johnson & Johnson Co.), "PALFIQUETM" Bonding Agent (Tokuyama Soda Co., Ltd.), "SHOFUTM" Bonding Base (Shofu, Inc.), and "SINTERBONDTM"
5 Dental Adhesive (Teledyne Getz).
In embodiments involving a mixture of ethylenically unsaturated compounds, suitable relative amounts of each compound can be easily selected by those skilled in the art.
The compositions of the invention also comprise a particulate metallic filler that does not interfere with the cure of the ethylenically unsaturated compound. Particular suitable metallic fillers can be selected by those skilled in the art based on chemical 15 compatibility with the particular ethylenically unsaturated compound and the particular polymerization initiator present in the composition. Interference .
with the cure of the ethylenically unsaturated compound can also be determined empirically, e.g., by adding a 20 selected metallic filler to a mixture of ethylenically unsaturated compound and polymerization ini~iator, which mixture cures in a sa~isfactory manner absent the m¢tallic filler. When cure of the metal containing mixture is attempted, any interference with cure due to 25 the ~etallic filler will be readily ob ervable.
Depending on the identity of the ethylenically unsaturated compound and the polymerization initiator, the f iller can be a pure metal such as those of Groups IVA, VA, VIA, VIIA, VIII, IB, or IIB, aluminum, indium, 30 and thallium of Group IIIB, and tin and lead of Group IVB, or alloys thereof. Conventional dental amalgam alloy powders, typically mixtures of silver~ tin, copper, and zinc, are also suitable. The particulate metallic filler preferably has an average particle size 35 of about 1 micron to about lOQ microns, more preferably 1 micron to about 50 microns.
WO93/12757 PCT/US92/1037~
In some embodiments, the metallic filler is present in an amount effective to increase adhesion of amalgam to tooth structure when the composition is used as an intermediate layer between the tooth structure 5 and the amalgam, compared to the adhesion obtained using a like composition absent the metallic filler.
An effective amount in these embodiments can be determined according to the method set forth in the EXAMPLES that follow. In other embodiments the l0 particulate metallic filler is present in an amount of 50 to about 4000 parts by weight, preferably about 200 to about 3000 parts by weight based on lO0 par~s by weight of the ethylenically unsaturated compound.
A composition of the invention also includes a 15 polymerization initiator in an amount sufficient to effect cure of the composition. Suitable polymerization initiators include autocure and light~
~ure polymerization initiators such as those mentioned in columns 28 and 29 of U.S. Pat. No. 4,539,382, - 29 chromophore-substituted halomethyl-s-triazines such as those shown in U.S. Pat. No. 3,954,475, and~
chromophore-substituted halomethyl-oxadiazoles such as those shown in V.S. Pat. No. 4,212,970.
qhe polymerization initiator is preferably present 25 in an amount of about 0.0l to about 20 p~rt5 by weight, more pref~rably about 0.l to about l0 parts by weight, ~asQd on 100 part~ by weight of ethylenically unsaturated compound.
Other compounds (additional to the above-discussed 30 ethylenically unsaturated compound) can be incorporated in the compositions of the invention in appropriate amounts easily selected by those skilled in the art to provide desired propçrti~s. Suitable compounds include mono- or polyacrylates and methacrylates such as methyl 35 acrylate, 2-hydroxyethyl acrylate, triethyleneglycol diacrylate, neopentylglycol diacrylate, hexamethyl-eneglycol diacrylate, trimethylolpropane triacrylate, ' -, ~21 1 7347 '~'~ 93/12757 PC~r/US92/10371 11 -- !
pentaerythritol tetraacrylate, polyalkylene glycol mono- and di-acrylates, urethane mono- or polyfunctional acrylates, Bisphenol A diacrylates, and the corresponding methacrylates of the above compounds, 5 as well as acrylamides and methacrylamides, vinyl compounds, styrene compounds, and other olefinically unsaturated compounds suitable for use in the oral environment. U.S. Pat. Nos. 4,499,251, 4,515,930, 4,537,940 and 4,539,382 contain lists of such 10 compounds.
The compositions of the invention can also contain conventional adjuvants such as accelerators, inhibitors, stabilizers, pigments, dyes, viscosity modifiers, extending or reinforcing fillers, surface 15 tension depressants, wetting aids, antioxidants, and other ingredients known to those skilled in the art.
The compositions of the in~ention can be prepared by mixing and packaging the various components according to ~ethods well known to those skilled in the 20 art. For example, when a redox type curing agent is used, an appropriate package form keeps the~oxidant and : the reducing agent apart from each other in order to ensure storage stability of the composition. Examples of package forms include two-part packages of (a) an 25 ethylenically unsaturated compound, a metallic fil~er, and a reducing agent in one part and (b) an ethylenically unsaturated c~mpound and an oxidant in the other. In the ca~e of an organic sulfinic acid (or salt thereof)tamine (or salt thereof)/peroxide ternary 30 ~ystem, it is also possible to use a three-part package form in which the sul~inic acid and the amine are packaged separately.
Where the polymerization înitiator comprises a photoinitiator, an ethylenically unsaturated compound 35 and a photoinitiator are preferably packaged separately or in a container opaque to light. With a thermal initiator that initiates polymerization when it is :, CA21 1 73~
WO93/12757 PCT/US9~/1037 brought into contac~ with the ethylenically unsaturated compound (e.g., tributylborane), the ethylenically unsaturated compound and the initiator are packaged separately. Such separately packaged components are 5 mixed together shortly before use.
A composition of the invention can be used as an intermediate layer between a substrate such as hard r tissue (e.g., bone, enamel, or dentin~ or ceramic, and a restorative material such as a pure metal or alloy, lO an amalgam, a ceramic composite, or a composite comprising an adhesive polymer (or a mixture of polymers) and a particulate filler. A primer may be used, but good adhesion is obtained without the use of auxiliary primers. The compositions of the invention 15 generally provide better adhesion than is obtained using the ethylenically unsaturated compound alone.
In order to adhere a restorative material to a substrate, the components of a composition of the invention are first combined in appropriate amounts.
20 As discussed above, depending upon the particular type of curing agent used the components can be mixed prior to packaging or they can be packaged as two- or three-part systems and aombined just prior to use.
Once the components are combined the resulting 25 composition of the invention can be placed in the form of a thin layer (e.g., ~y brushing) on either the restorative material or on the substrate. The layer can then optionally be cured by appropriate means (e.g., heat including exposure to room temperature, 30 visible light, ultraviolet light, or the like). The other member of the restorative material/substrate pair can then be prepared (e.g., mixed) if necessary and placed on the adhesive layer.
For the reasons set forth above in connection with 35 the 8ackground of the Invention, it is desirable if an amalgam can be made to adhere well to tooth structure.
Accordingly, one use of the compositions of the :
" ~93/127~7 PCT/US92/10371 invention involves adhering dental amalgam to tooth structure in a prepared cavity.
It is preferred to ~se a modified amalgam in order to optimize adhesion to tooth structure. Such a 5 modified amalgam can be produced by admixing particulate additives into conventional amalgam alloy powder. The modified amalgam is then prepared in a conventional manner by triturating the modified alloy powder with mercùry in an amalgamator.
The preferred particulate additives are selected from the following groups: l) acrylate- or methacrylate-functional polymers, 2) metal salts of acrylates or methacrylates, 3) nonmetallic fillers, 4 oxidizing agents, and 5) reducing agents. The lS particulate additives are applicable to the full range of conventional ~malgam alloy powders and conventional weight ratios of mercury to amalgam alloy powderO
Representative acrylate- or methacrylate-functional polymers include poly(alkanoic acid) powder.
20 Representative metal salts of acrylates or methacrylates include zinc dimethacrylate, zirconium dimethacrylate, silver methacrylate, sodium - methacrylate, and magnesium methacrylate. Nonmetallic fillers include both untreated organic fillers and 25 surface-treated fillers. Representative nonmetallic fillers, also k~own as organic fillers, include b1ends of silane-treated OX-50TM pyrogenic silica ~Degussa Company~, tetraethyleneglycol dimethacrylate ("TEGDMA") (Rohm Tech Co.), and Bi~phen~l A diglycidylether 30 qimethacrylate in a 60:17:17 weight ratio. Other representative nonmetallic fillers include zirconia/silica filler ei~her untreated or pretreated with gamma-methacryloxypropyl trimethoxysilane as described in U.S. Pat. No. 4,503,169. Preferred 35 oxidizing agent~ include benzoyl peroxide. Preferred reducing agents include sodium benzenesulfinate.
Adhesion of amalgam to etched enamel was evaluated as follows: Bovine teeth of similar age and appearance were partially embedded in circular acrylic disks such that the enamel was exposed. The exposed portion of 5 each tooth was ground flat and parallel to the acrylic disc using Gr~de 120 silicon carbide paper-backed abrasive mounted on a lapidary wheel. Further grinding and polishing of the teeth was carried out by mounting Grade 320 silicon carbide paper-backed abrasive on the lO lapidary wheel. During the grinding and polishing steps, the teeth were continuously rinsed with water.
The polished teeth were stored in distilled water and used for testing within 2 hours after polishing.
The polished teeth were removed from the water and 15 dried using a stream of compressed air. Phosphoric acid etching gel was applied to the enamel for l~
~econds, rinsed with water, and dried. The adhesive~
composition was applied to the entire enamel ~urface with a brush and blown into a thin film with compressed 20 air and cured according to manufacturer's instructions.
A mold made from a 2 mm thick TEFLONTM ~olytetra-fluoroethylene sheet with a 5 mm diameter cir~ular hole - through the sheet was clamped to each polished tooth so ~hat the central ~xis of the hole in the mold was 25 normal to the poli~hed tooth surface. ~he hole in aach mold was filled with a prepared amalgam and allowed to stand for about l5 minutes at room temperature, then stored in distilled water at 37C for 24 hours. The molds were then carefully removed, leaving a molded 30 button of amalgam attached to each tooth.
Adhesive strength was evaluated by mounting the acrylic disk in a holder clamped in the jaws of an INSTRONTM tensile testing apparatus with the polished tooth surface orient~d parallel to the direction of 35 pull. A loop of orthodontic wire (O.44 mm diameter) was placed around the base of the amalgam button CA~ 34~
~"~93/127S7 PCT/US92~10371 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 5 amalgam button) failed, using a crosshead speed of 2 mm/min.
The following examples are offered to aid in understanding of the present invention and are not to be construed as limiting the scope thereof. Unless 10 otherwise indicated, all parts and percentages are by weight.
EXAMPLES l-l2 and CONPARATIVE EXANPLES C-l to C-6 Using the procedure set forth above, the adhesive 15 shear bond strength on etched enamel of several adhesive compositions was evaluated. The amalgam used was two-spill capsules of DISPERSALLOYl~ amalgam.
Commercially available adhesives were evaluated according to the manufacturer's instructions.
20 Compositions of this invention were prepared by preweighing the metal additive into a mixing well. One drop (approximately 0.03 g) of a phosphorylate~
ethylenically unsaturated compound (SCOTCHBONDTM Dual Cure Dental Adh~sive resin) and one drop (approximately 25 -0.02 g) of a poly~erization initiator ~SCOTCHBONDTM Dual Cure Dental Adhesive li~uid) were added to the metal additive.
Alternatively a composition comprising a ph~sphorus-free ethylenically unsaturated compound was 30 prepared ~y preweighing the metal additive into a mixing well and adding one drop each of: (i) a combination of a phosphorus-free ethylenically unsaturated compound and dihydroxyethyl-p-toluidine reducing agent (CONCISETM Enamel Bond A); and (ii) a 35 combination of a phosphorus-free ethylenically WO93~127~7 PCT/US92/103 unsaturated compound and benzoyl peroxide oxidizing agent (CONCISETM Enamel Bond B).
In each case the components were then mixed rapidly and applied with a brush to the etched enamel.
5 The applied adhesive was then cured according to manufacturer's instru~tions prior to placement of the amalgam.
Set out below in TABLE I are the example numbers, ethylenically unsaturated c~mpound, metallic filler, lO and mean adhesive shear bond values for the various compositions tested.
CA2~ 1 7347 '4) 93/127S7PCl/US92/10371 1~ tt~t~T tT
.~ a_. o ~ ' ~ ~ ~ r~ N Nll ~
~ 1~; _ _ _ _ . _ _ _ _ _ ~
4 ~ In It~ O IQ It~ O Itl 10 N O _ _ _ _ _ 4 ~
~ ~ m~ 0~Y
~ 11 ~ ~ ~ l l 3j jll 3 3~ e ~ Y
~ T
:~ L~
V D
The results in TABLE I illustrate that the exemplified compositions comprising a metallic filler and an ethylenically unsaturated compound provide improved shear adhesion to hard tissue and amalgam 5 relative to the unfilled ethylenically unsaturated compound. Several compositions of this invention provided mean shear adhesion values better than those obtained with commercially available hard tissue/amalgam adhesives. Also, it was observed in l0 Comparative Example C-6 that zinc interferes with the cure of the SCOTCHBOND~ Dual Cure Dental Adhesive resin when SCOTCHBOND~ Dual Cure Dental Adhesive liquid was used as the polymerization initiator.
EXAMPLES 13-14 and COMPARATIVE EXAMPLES C-7 to C-ll Using the procedure set forth above, the shear , adhesive bond strength on ~tched enamel of several adhesive compositions was evaluated. The amalgam used 20 was two-spill capsules of DISPERSALLOYTM amalgam (Johnson and Johnson) or a modified version.containing varying amounts of organic filler. Set out below in TABLE II are the example nu~bers, ethylenically unsaturated compound, metallic filler, amalgam, amalgam 25 additive, and maan shear adhesion values for the variou~ co~positions t~sted.
'~'') 93/12757 PCT/US92/10371 ~ -~T~
~ ~ U~ U~ O U~ U~ CD U~ C' Q ~i~ t5~
C~ I__ _ ~ ~ ~ 0~
~ ~ ~ _ l ~ l l ~ _ t ô O X
~ 3~ l l l l o l ~o ~ s a H_ __ _ ~ O 'a o E ~i ~ ~ l~i ~ a ~3 i ta H H H H H ca `' U~
~c~ ~ n a a a D ~ ~ a2 S
~_ _ _ - . ~ ~
O O _ . l l l . o ~: O
o~ ~ l l t l l ~ ~ ~ ~
_ _ __ __ I ~ ~ s ~ E~
e D U ~¢ m C~ ~ ~¢ lcc ~: ~a CO ~ ~ C i . _ _ _ ~_ _ ~ ~ ~ C O ~ ~
r~ c~ U ;~. U ~ E1 ~ ~ W ~
C~21 1 7347 W093/12757 PCT/US92/1037'~
The results in TABLE II show that the greatest mean ad~esive shear bond values are obtained for the combination of metal filled adhesive and powder modified amalgam.
Claims (7)
Our Ref: E 833 PCT
1. An adhesive composition, comprising:
(i) an ethylenically unsaturated phosphorylated com-pound;
(ii) a particulate metallic filler that does not in-terfere with the cure of the ethylenically un-saturated phosphorylated compound, in an amount effective to increase adhesion of amalgam to tooth structure when the composition is used as an intermediate layer between the amalgam and the tooth structure, compared to the adhesion ob-tained using a like composition absent the parti-culate metallic filler; and (iii) a curing agent in an amount sufficient to effect cure of the composition.
(i) an ethylenically unsaturated phosphorylated com-pound;
(ii) a particulate metallic filler that does not in-terfere with the cure of the ethylenically un-saturated phosphorylated compound, in an amount effective to increase adhesion of amalgam to tooth structure when the composition is used as an intermediate layer between the amalgam and the tooth structure, compared to the adhesion ob-tained using a like composition absent the parti-culate metallic filler; and (iii) a curing agent in an amount sufficient to effect cure of the composition.
2. A composition according to Claim 1, wherein the phos-phorylated compound comprises a chlorophosphorus acid ester of Bis-GMA.
3. A composition according to Claim 1, which additionally comprises an ethylenically unsaturated phosphorous-free compound.
4. A composition according to Claim 1, wherein the parti-culate metallic filler has an average particle size of about 1 micron to about 100 microns.
5. A composition according to Claim 1, wherein the parti-culate metallic filler has an average particle size of about 1 micron to about 50 microns.
6. A composition according to Claim 1, wherein the parti-culate metallic filler is a dental amalgam alloy pow-der.
7. A method of adhering a restorative material to a sub-strate, comprising the steps of:
(i) combining the components of a composition accord-ing to Claim 1;
(ii) placing an intermediate layer of the composition from step (i) on one member of the restorative material/substrate pair;
(iii) optionally curing the intermediate layer; and (iv) adhering the other member of the restorative ma-terial/substrate pair to the first member by way of the intermediate layer.
(i) combining the components of a composition accord-ing to Claim 1;
(ii) placing an intermediate layer of the composition from step (i) on one member of the restorative material/substrate pair;
(iii) optionally curing the intermediate layer; and (iv) adhering the other member of the restorative ma-terial/substrate pair to the first member by way of the intermediate layer.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US81517291A | 1991-12-31 | 1991-12-31 | |
| US07/815172 | 1991-12-31 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2117347A1 true CA2117347A1 (en) | 1993-07-08 |
Family
ID=25217081
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002117347A Abandoned CA2117347A1 (en) | 1991-12-31 | 1992-12-02 | Metal filled adhesive composition and method |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0623016A1 (en) |
| CN (1) | CN1073961A (en) |
| AU (1) | AU3233493A (en) |
| BR (1) | BR9207010A (en) |
| CA (1) | CA2117347A1 (en) |
| IL (1) | IL104008A0 (en) |
| MX (1) | MX9207423A (en) |
| WO (1) | WO1993012757A1 (en) |
| ZA (1) | ZA9210019B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SE9402528D0 (en) * | 1994-07-19 | 1994-07-19 | Astra Ab | Hard tissue stimulant with electricity |
Family Cites Families (3)
| 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 |
| JPS59137404A (en) * | 1983-01-27 | 1984-08-07 | Kuraray Co Ltd | Dental adhesive |
| US5662886A (en) * | 1991-01-08 | 1997-09-02 | Minnesota Mining And Manufacturing Company | Adhesive amalgam system |
-
1992
- 1992-12-02 BR BR9207010A patent/BR9207010A/en not_active Application Discontinuation
- 1992-12-02 CA CA002117347A patent/CA2117347A1/en not_active Abandoned
- 1992-12-02 WO PCT/US1992/010371 patent/WO1993012757A1/en not_active Application Discontinuation
- 1992-12-02 EP EP93900802A patent/EP0623016A1/en not_active Withdrawn
- 1992-12-02 AU AU32334/93A patent/AU3233493A/en not_active Abandoned
- 1992-12-07 IL IL104008A patent/IL104008A0/en unknown
- 1992-12-18 MX MX9207423A patent/MX9207423A/en unknown
- 1992-12-23 ZA ZA9210019A patent/ZA9210019B/en unknown
- 1992-12-30 CN CN92111811A patent/CN1073961A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| BR9207010A (en) | 1995-12-05 |
| WO1993012757A1 (en) | 1993-07-08 |
| AU3233493A (en) | 1993-07-28 |
| IL104008A0 (en) | 1993-05-13 |
| CN1073961A (en) | 1993-07-07 |
| EP0623016A1 (en) | 1994-11-09 |
| MX9207423A (en) | 1993-06-01 |
| ZA9210019B (en) | 1994-06-23 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |