CA2126452A1 - Adhesive composition and method - Google Patents
Adhesive composition and methodInfo
- Publication number
- CA2126452A1 CA2126452A1 CA002126452A CA2126452A CA2126452A1 CA 2126452 A1 CA2126452 A1 CA 2126452A1 CA 002126452 A CA002126452 A CA 002126452A CA 2126452 A CA2126452 A CA 2126452A CA 2126452 A1 CA2126452 A1 CA 2126452A1
- Authority
- CA
- Canada
- Prior art keywords
- amalgam
- composition
- intermediate layer
- carboxylic acid
- restorative material
- 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
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/70—Preparations for dentistry comprising inorganic additives
- A61K6/71—Fillers
Abstract
An adhesive composition comprising an ethylenically unsaturated phosphorylated compound, a carboxylic acid functional polymer, and a polymerization initiator, and optionally comprising a particulate metallic filler. 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
212~4~2 0~3/1Z758 PCT/US92/10399 AD~B8IVE CO~PO8~TION ~ND MB~OD
BACKG~OUN~ OF THE INYENTION
5 Technical Field This invention relates to adhesive compositions compris1ng a ~hosphorylated ~ompound. In another aspect, this in~ention relates to adhesive compositions comprising a carboxylic acid ~unctional polymer. This l0 invention also r~lates to methods o~ adhering a restorative materi~l to a substrate, and in another aspect to methods of adhering a dental rsstorati~e such as amalgam to hard tissue ~uch as dentin or enamel.
15 ~escription of the ~elated Art Dental amalgams and restorative composites are used extensively for intracoronal and extracoronal-restorations~ Amalgam, however, does not adhere to tooth structure and the dentist must prepare the tooth .
20 cavity with dovetails and various cu~out grooves that mechanically lock the amalgam into the ca~ity. Such preparation, however, results in excavation of more tooth structure than would otherwise be necessary if there was good adhesion between the tooth structure and 25 the amalgam. Moreover, leakage at the interface of the amalgam and cavity wall (known as "microleakage") 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 of the tooth, corrosion of the amalgam, and other attendant complications. An adhesive seal between amalgam and tooth structure could minimize and/or prevent microleakage and al}ow for a stronger 3s restoration due to excavation of less tooth material.
Products claiming to make amalgam adhesive to tooth structure are available. One such product is W093/l2758 2 ~ 2 6 4 5 PCT/US92/1039' sold in a kit under the trademark AMALGAMBONDT~ (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 similarly involve coating a ~pecific curable resin directly onto tooth structure to make amalgam adhere are available under the trademarks PANAVIATM Dental Adhesi~e ~Kuraray Company) and 10 SUPERBONDTM Adhesive (æun Medical Co., Ltd., Kyoto, Japan). These latter products also are dif~icult to employ, since there are a number of required preparatory steps ~or their application and curing.
Adhesive compositions that employ phosphorus-15 containing free-radically polymerizable compounds have been reported in the literature, see, e.g., ~.
Buonocore, W. Wile~an, and F. Brudevold, ~. ~ent. Res., 35, 846 ~1956), M. Buonocore and M. Quigley, J. Amer.
Dent. Assoc., ~, 807 (1958), M. Anbar and E. Farley, 20 J. Dent. Res~, 53, 879 ~lg74), E. Farley, ~. Jones, and M. Anbar, J. Dent. Res., 56, 1943 (1977),~U.S. Pat Nos.
3,882,600, 3,997,504, 4,222,780, 4,235,633, 4,259,075, 4,259,117, 4,368,043, 4,383,052, 4,499,251, 4,514,342,~
4,515,930, 4,537,940, 4,539,382, and 4,544,467, 25 European published patent application No. 0 058 483, and Japanese laid-open patent application (Kokai) Nos.
57-143~72 and 57-167364.
U.S. Pat.`No. 3,513,123 (Saffir) describes a curable epoxy composition that can be added to amalgam 30 in order to make the amalgam adhere to tooth structuré.
The curable epoxy composition contains a glycidyl ether type resin and a polyamine hardening agent.
U.S. Pat. No. 4,064,629 (Stoner) describes a method for applying amalgam restorations. The method 35 involves precoating the surfaces of a cavity within a carious tooth with a layer of an "adhesive-metal"
: ~ ;
, 2126~52 ~0~3/12758 PCT/US92/10399 lining composition. The metal o~ the lining composition is amalgamated by diffusion of the mercury ~rom the subsequently applied con~entional dental amalgam filling. The "adhesive-metal" lining 5 composition is said ~o improve corrosion re~istance of the dental amalgam ~illing and also to pr~mote bonding between the amalgam restoration and the cavity sur~aces.
U.S. Pat. No. 4,001,483 (Lee, Jr. et ~1.) 10 describes dental compositions ~or sealing margins between tooth structures and amalgam r~storations therein, the compositions c~ntaining ~a) an alkylene glycol dimethacrylate and/or its oligomer, ~b) a polymerization initia*or, ~c) a polymerization 15 accelerator and (d) a secondary monomer additive.
U.S. Pat. No. 3,574,943 ~Stark) describes a method of restoring a carious tooth whereby the ca~it~ is~
excavated, lined with a layer of a polysiloxane pressure sensitive adhesive polymer dissolved in a 20 fluorocarbon, and filled with amalgam. The polysiloxane layer iæ said to act as a barrier to leakage.
Further articles that describe bonding of amalgam~
to tooth structure by precoating the tooth with 25 adhesive resin include M. Staninec and N. Holt, Journal of Prosthetic~DentistrY ~1988), Vol. 59, pp. 397-402, A. Lacey and M. Staninec, Ouintessence International (1989), Vol. 20, pp. S21-524, Y. Aboush and C. Jenkins, Br. Dent. J. (1989), Vol. 166, pp. 255-2S7, Y. Aboush 30 and R.IElderton, Br. Dent. J. tl991), Vol. 170, pp.
219-222, and Y. Aboush and R. Elderton, Dent. Mater.
:, , (1991), Vol. 7, pp. 130-132. The last article involves ; adhesion to previously~hardened amalgam, whereas the other articles involve adhesion to fresh amalgam.
35 Also, A. ~en-~ ar, J. Am. Dent. Assoc. (1989) Vol. 119, pp. 725-728, describes a reduction in microleakage at the margins of amalgam restorations when "SCOTCHBOND"
: :
Wo~3/l~7s8 2126A52 PCT/US~2/103 Dual cure Dental ~dhesive resin (3M) is applied to cavity margins prior to application of amalgam, and M.
Mitrosky, Jr., ~uintessence I~ternational (1981) Vol.
9, pp. 871-874, descxibes the use o~ ethyl 5 cyanoacrylate as a bonding agent beneath amalgam and compo~ite restorati~es. H~ J. ~taehle et al., p~sGh.
Zahnartzt ~19B8) Yol. 43, pp. 952-957, describes the use of ~arious dental adhesives and varnishes to adhere amalgam to dentin.
Japanese Kokai 63-175085 describes an adhesive composition comprising an acid Punctional monomer, polymer, or copolymer, a ~inyl monomer in which the acid ~unctional component is ~olubl~, an organic peroxide, and an aromatic amine or sul~inate salt. The 15 composition is said to bond living tooth tissue to composites and amalgams.
French Patent 2,561,521 describes an intermediate adhesive composition for sealing dental cavities and chemically securing amalgams, compris~ng a metal powder 20 dispersed in an adhesi~e ~arni~h. The composition contains metal powdex, cellulosic varnish, ethyl acetate, amyl propionate, fluoride, and oil of pimento leaf.
Japanese Kokai 63-250310 describes dental adhesive 25 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, 30 alumina, gold, alloys, pqlymethyl methacrylate, polycarbonate, and the like.
SUMMARY OF_~HE INVENTION
This invention provides an adhesive composition, comprising:
, 2I26~5,~
~093/12758 PCT/US92/10399 (i) an ethylenically unsaturated phosphorylated compound;
(ii) a carboxylic acid functional polyme~ in an amount effective to increase adhesion of amalgam to 5 tooth structuxe when the composition is used as an intermediate layer between the amalgam and the tooth gtructure, compared to the adhes~on obtained using a like co~position absent the carboxylic acid ~unctional polymer; and (iii) a polymerization initiator in an amount su~ficient to effec~ cure o~ the composition. Such a compositlon of the invention optionally ~urther comprises a partl¢ulate metallic filler in an amount effective to increase adhesion of amalgam to tooth 15 structure when the composition is used as an intermediate layer between the amalgam and the tooth stru¢ture, compare~ to the adhesion obtained using a like composition absent the particulate metallic fille~.
This invention also provides an adhesive ~ composition, comprising:
:~ (i) an~ethylenically unsaturated phosphorylated compound :
(ii) a carboxylic acid functional polymer in an 25 amount of about 5 to about 200 parts by weight -based on 100 parts by weight of the phosphorylated compounds and ~ iii) a polymerization initiator in an amount sufficient to effect cure of the composition. These compositions optionally contain a particulate metallic 30 filler in an amount o about 50 to about 4000 parts ,by weight based on 100 parts by weight of the phosphorylated compound and the carboxylic acid : functional polymer. : ~
. This invention also provides a method o adhering 35 a restorative material to a substrate, comprising the steps of: ~
.
WO 93/1 Z758 2 1 2 6 ~ 5 2 PCI~/US92/1 039~r ~ 6 ~
(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 5 restorative material/substrate pair;
(iii) optionally curing the intermediat~ layer;
and (iv) adhering the other member o~ the restorative material/substrate pair to the first member 10 by way of the intermediate layer.
DET~I~ED DESCRIPTION OE T~ INVENTION
Materials suitable for use as the ethylenically 15 unsaturated phosphorylated compound in a composition of the invention include such materials known to those skilled in the art to be capable of bonding to hard tissue such as dentin, enamel, bone, or the like. This compound, sometime~ referred to herein as the 20 "phosphorus compoundn, i8 a monomer, oligomer, or polymer (or mixturs thereof), preferably suitable for use in the oral environment both in its unpolymerized and polymerized state.
Suitable phosphorus compounds comprise one or more 25 phosphorus atoms bonded through a carbon, nitrogen, oxygen, or sulfur atom, to a radical containing one or more ethylenically unsaturated groups. Preferred ethylenically unsaturated groups are ethenyl and 2-propenyl as found, respecti~ely, in acrylate and 30 methacrylate groups. ~è`or more of the phosphorus atoms can be~bonded~to one or more halogen atoms, active hydrogen atoms, or substituted or unsubstituted ~ hydrocarbyl groups (e.g., a~n alkyl, aryl, alkaryl, or ;~ aryalkyl groupj. ~A particular class of suitable 35 phosphorus compounds is~described in European Patent ~; Application No.~O 058 483 and U.S. Pat. No. 4,515,930.
These phosphorus compounds include those comprising an ~93/1275~ PCT/USg2/10399 . - 7 -organic ester of one or more acids of phosphorus, the organic radical of said ester con~aining at least one ethylenically unsaturated group, wherein said ester has ch}orine or bromine bonded directly to the phosphorus S (hereina~ter referred to as "halophosphorus acid esteræ"~. A pr~erred subclass o~ such halophosphorus acid esters includes halophosphorus acid esters of diglycidyl methacrylate of Bisphenol ~ Bis~GM~") prepared by r~acting Bis-GMA with a phosphorus acid.
10 Phosphorus acid halides (e.g., chlorides, bromides) that can be reacted with Bis-GM~ include POCl3, PCl3, PBr3, R'OP~O)Cl2, ~R'0)2P~O)Cl where ~' is a hydrocarbyl radical, pre~e~ably one derived ~rom remo~al o~ one or more hydroxyl groups from a hydr~xyl-containing 15 compound such as 2-hydro~yethyl methacrylate, ethylene glycol, polyethylene glycol, pentaerythritol, and the like, as would result from a reaction of the hydroxyl-containing compound and the phosphorus acid halide.
particularly pref~rr~d class of phosphoru~ compounds 20 includes chlorophosphorus acid esters o~ Bis-GMA.
An additional suitable class of phosphorus compounds includes the phosphorus acid esters described in U-S- Pat. Nos. 3,882,600, 3,997,504, 4,222~780, $
4,235,633, 4,259,075, 4,259,117, 4,368,043, 4,442,23g, 25 4t499,251, 4,514,342, 4,537,940, 4,539,382 and Japanese published pat~nt application (Koho) No, 85~17235.
Exemplary members of this class are the compounds 2-methacryloyloxyethyl phenyl phosphate and 10-methacryloyloxydecyl dihydrogen phosphate.
A further suitable class of phosphorus compounds includes the pyrophosphate ester derivatives described in U.S. Pat. Nos. 4,383,0S2 and 4,404,1SO and in Japanese Kokai 57-143372 and 57-167364.
A further suitable phosphorus compound is 35 glycerophosphate dimethacrylate, described in the '1'' ' ' ' ' ' ' ' 2l~64~æ
W~93/127s8 PCT/lJSg2/103~
abo~e-mentioned Buonocore, Wileman, and Brudevold publication.
Either a single phosphorus compound or a mixture of phosphorus compounds can be used. The phosphorus 5 compound can be prepared using methods known to those skilled in the art. It can also be obtained from existing commer¢ially a~ailable dental adhesives, such as I~SCOTCHBONDTUn Dual Cure D~ntal ~dhesive (3M), "ALL-BOND2TMI~ ~niversal ~ental Adhesive System tBisco, 10 Tnc.), "CLEARFILTM'I Photo ~ond Light-Cured Dental Bonding Agent ~Kuraray Co~, ~td.), 'IRESTOBOND 3TM~ Dual Dentin/Enamel Bonding Agent ~Lee Pharmaceuticals, see U.S. Pat. Nos. 4,524,527 and 4,521,550), "PRISMA
UNIVERSAL BOND3T~" Dentin/Enamel Bonding Agent tL. D.
15 Caulk Division of Dentsply International, Inc., see U.S. Pat. No. 4,814,423), "BOND~ITErM" Dental Adhesive (Sybron Corp.), nJohnson ~ Johnson" Dentin Bonding ~
Agent and "Johnson ~ JohnsonH ~ight-Curing Bonding Agent ~Johnson & Johnson Co.), "PALFIQUETM" Bonding 20 Agent ~Tokuyama Soda Co., Ltd.), "SHOFUTM" Bonding Base (Shofu, Inc.), and "SINTERBONDTM" Dental Adhesive ~Teledyne Getz).
The carboxylic acid functional polymer is preferably suitable for use in the mouth. Materials 25 suitable for use as the carboxylic acid functional polymer include those homopolymers and copolymers of unsaturated mono-, di-, or tricarboxylic acids known to those skilled in the art to be commonly used in glass ionomer cements. Representative materials are 30 described, for~èxample, in U.S. Pat. Nos. 3,655,605, 4,016,1~4, 4,089,830, 4,143,018, 4,342,677, 4,360,605, ` and 4,3~6,835,; and European Published Patent Application No.~88-312127.
Also suitable are those carboxylic acid functional 35 polymers prepared by th~ homopolymerization and ` copolymerizatio:n of unsaturated aliphatic carboxylic .
2I 26~ i2 ~vo93/~2758 P~T/USg2/10399 _ g _ acids, for example acrylic acid, 2-chloroacrylic acid, 3-chloroacrylic acid, 2-bromoacrylic acid, 3-bromoacrylic acid, methacrylic acid, itaconic acid, maleic acid, glutaconic acid, aconitic acid, citraconic 5 acid, mesaconic acid, fumaric acid, and tiglic acid.
~uitable monomers that can be copolymerized with the unsaturated aliphati~ carboxylic acid~ include unsaturated aliphatic compounds such as acrylamide, acrylonitrile, vinyl chloride, allyl chloride, ~inyl 10 acetate, and 2-hydroxyethyl me~hacrylate~ Ter- and higher polymers can also be used.
The carboxyIic acid ~unctional polymer can also contain ethylenically unsaturated groups such as ethenyl and 2-propenyl. Such materials can be prepared 15 by reacting a carboxylic acid Punctional polymer with an ethylenically unsaturated compound comprising at least one group capable of reacting with the carboxylic acid groups of the polymer. Suitable ~unctional groups include -OH, -NCO, -COCl, and -CH-CH2. Exemplary \ /
compounds include acryloyl chloride,--methacryloyl chloride, allyl isocyanate, 2-hydroxyethyl methacrylate, and 2-isocyanatoethyl methacrylate. A
25 particularly preferred carboxylic acid functional polymer is a~methacrylate-functional copolymer of itaconic acid and acrylic acid as disclosed in Example 11 of European Published Pat. Application No. 0 323 120.
In particular embodiments, the carboxylic acid functional polymer i8 present in an amount effective to increase the adhesion of amalgam to tooth structure : when the composition is used as an intermediate layer between the amalgam and the tooth structure, compared ; ~ 35 to the adhesion obtained~using a like composition absent the carboxylic:acid functional polymer. An effective amount of carboxylic acid functional polymer .
WO93/12758 2 ¦ ~ 6 4~ 2 PCT/US92/1039~
in these embodiments can be determined according to the method set forth in the EXA~PLES that follow~
I~ other embodiments, the carboxylic acid functional polymer is present in an amount o~ about 5 5 to a~out 200 parts by weight, preferably a~out 20 to ~bout ~00 parts by weight, based on 100 parts by weight o~ the phosphorylated compound.
A composition o~ khe inv~ntion also includes a polymerization initiator in an amount ~u~icient to 10 effect cure o~ the composition. Suitable polymerizakion initiators ~nclude autocure an~ light cure initiators such as those mentioned in columns 28 and 29 of U.S. Pat. No. 4,53g,332, chromophore-substituted halomethyl-s-triazines such as 15 those shown in U.S. Pat. No. 3,954,475, and chromophore-substituted halome~hyloxadiazoles such as those shown in U.S. Pat. No. 4,212,970.
The polymerization initiator is preferably pr~sent in an amount o~ about 0.01 to about 20 parts by weight, 20 more preferably about 0~1 to about 10 parts by weight based on 100 parts by weight of the phosphorylat~d compound and the carboxylic acid unctional polymer.
The compositions of the invention preferably further compri~e a par~iculate metallic filler. The 25 filler can be a pure metàl such as those of Groups IVA, VA, VIA, VII~, 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 30 zinc, are also suitable.~ The particulate metallic filler preferably has an average particle size of about 1 micron to about 100 microns, more pre~erably 1 micron to about 50 microns.
In some ~mbodiments, the optional metallic filler 35 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 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 ~orth in the EXAMPLES that follow. In other embodlment~ the particulate metallic ~ller is present in an amount of ~0 to about 4000 parts by weight, preferably about ~Oo to about 3000 parts by weight based on 100 parts by weight of the phosphorylated compound and the carboxylic acid Punctional polymer.
Ethylenically unsaturated compounds ~other than the phosphorylated compound) can be incorporated in the compositions o~ the invention in appropriate amounts easily selected by those skilled in the art. Suitable compounds include mono- or poly- acrylates and methacrylates such as methyl acrylate, 2-hydroxyethyl acrylate, triethyleneglycol diacrylate, neopentylglycol diacrylate, hexamethyleneglycol dia¢rylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, polyalkylene glycol mono- and di-acrylates, urethane mono- or poly-functional acrylates, Bisphenol A diacrylates, and the corresponding methacrylates of the above compounds, as well as acrylamides and methacrylamides, vinyl compounds, styrene compounds, and other ole~inically unsaturated compounds suitable for use in the oral environment. U.S. Pat.~Nos. 4,499,251, 4,515,930, 4,S37,940 and 4,539,382 contain lists of such compounds. ~
Thç~compositions can also contain conventional adjuvants such as solvents, accelerators, inhibitors, stabilizers,~pigments, dyes,~viscosity modifiers, extendinq or reinforcing fillers, surface tension depressants, wetting aids, antioxidants, and other ingredients known t~those skilled in the art.
The compositions can be mixed like conventional dental materials according to methods well known to ; 4 5 2 WO93/12758 pcT/usg2/1o39s those skilled in the art. Ordinarily it is preferred to add the carboxylic acid funational polymer to the phosphorylated compound, foilowed by the addition o~
the polymerization initiator~ Some aarboxylic acid 5 functional pol~mers may be di~ficult to dissolve in or mix with the phosphorylated comp~und. ~n such cases a volatile, remo~able cosolvent ~uch as ethanol, methylene chloride, acetone, ethyl acetate, methyl ethyl ketone or tetrahydro~uran ~"T~F") can aid mixing.
lO The cosolvent can then be removed ~rom the dental material such as by vacuum and optional heating.
The compositions o~ the lnvention can be packaged according to methods well known to those skilled in the art. For example, when a redox type polymerization 15 initiator 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) a~phosphorylated compound, a 20 carboxylic acid functional polymer, and a reducing agent in one part and (b) a phosphorylated compound and an oxidant in the other; ~ii) two-part packages of ~a) a phoæphorylated compound and one element of a redox s pair, and (b) à carboxylic acid functional poly~er and 25 the other element of the redox pair; and (iii) two-part packages of ~a) a phosphorylated compound and an oxidant and ~b~ a~phosphorylated compound, a carboxylic acid functional polymer, and a reducing agent. In the case of an organic sulfinic acid (or salt 30 thereof)/amine~(or~ salt~thereof)/peroxide ternary system, it is also possible to use a three-part package form in which the sulfinic acid and the amine are packaged separately~. The optional particulate metallic - filler component can be~included in any or all parts of 35 the above-described package forms.
Where the polymerization initiator comprises a photoinitiator, the phosphorylatad compound and the VO93/12758 21 2 6 ~ ~ 2 PCT/~S92/10399 photoinitiator are preferably packaged sepaxately or in a container opaque to light~ With a thermal curing agent that initiates polymerization when it is brought into contact with the phosphorylated compound ~e.g., 5 tributylborane), the phosphorylated compound and the curing agent are packaged ~eparately. Such separately packaged components are mixed together shortly before use.
~ composltion o~ ~he invention can be used as an 10 intermedlate layer b~tween a substrate such as hard tissue (e.g., bone, enamel, or dentin), ceramic, porcelain, and the like, and a restorati~e material such as a pure metal or alloy, an amalgam, a ceramic composite, or a composite comprising an adhesive 15 polymer (or a mixture of polymers) and a particulate inorganic filler. A primer can be used, but good adhesion is obtained without the use o~ auxiliary primers, and the co~positions of the invention generally pro~ide better adhesion than is obtained 20 using the phosphorylated compound alone.
}n order to adhere a restorative material to a substrate, the components of a composition of the invention are first combined in appropriate amounts.
As discussed above, depending upon the particular type 25 of polymerization initiator used the components can be mixed prior to packaging or they can be packaged as two- or three-par~ systems and combined just prior to use. Onae the components are combined the resulting composition of the invention can be placed in the form 30 of a thin layér (e.g., by brushing) on either the substrate or on the restorative material. The layer can~then optionally be~cured by appropriate means (e.g., heat including`exposure to room temperature, visible light, ultraviolet light, or the like). The 35 other of the~restorative material/substrate pair can then be prepared (e.g., mixed~ if necessary and placed on the adhesive layer.
: :
W~93/l27s8z 12 6 45 2 PCT/US92/1039 For the reasons set forth above in connection with the Baakground of the Invention, it i~ desirable i~ an amalgam can be made to a~here well to kooth structure.
Accordingly, one use of the compositions o~ the 5 invention invol~es adhering dental amalgam to tooth structure in a prepared cavity.
It is prePT-rred to use ~ modi~i~d amalgam in order to optimize adh~sion to tooth structure. Such a modified amalgam can be produaed by admixing l0 particulate additive~ into conventional amalgam alloy powder~ The modi~ied amalgam is th~n prepared in a con~entional manner by tri~urating the modi~ied alloy powder with mercury in an amalgamator~
The preferred particulate additi~es are ~elected lS ~rom the ~ollowing groups: l) acrylate- or methacrylate-functional polymers, ~) metal salts of acrylates or methacrylates, 3) nonmetallic ~illers, ~) oxidizing agents, and S) reducing agents~ The ~articulate additives are applicable ~o the ~ull range 20 of conventional amalgam alloy powders and c~nventional weight ratios o~ mercury to amalgam alloy powder.
Representative acrylate- or methacrylate-functional polymers include poly(alkanoic acid) powder.
Representative metal salts of acrylates or 25 methacrylate include zinc dimethacrylate, zirconium dimethacrylat~, silver methacrylate, sodium methacrylate, and magne~ium methacrylate. Nonmetallic ~illers include both untreated organic fillers and surface-treated fillers. Representative nonmetallic 30 fillars~ also known as orgànic fillers, include blends of silane-treated OX-50TM pyrogenic silica (Degussa Company), tetraethyleneglycol dimethacrylate ("TEGDNA") (Rohm Tech Co.), and ~isphenol A diglycidylether dimethacrylate in a 60:17:17 weight ratio. Other 35 representative nonmetallic fillers include zirconia/silica filler either untreated or pretreated with gamma-methacryloxypropyl trimethoxysilane as 2l264s2 '~093/12758 ycT/usg2~1o39s described in U.S. Pat. No. 4,503,169. Preerred oxidizing agen~s include benzoyl peroxide. Preferred reducing agents include sodium benzenesulfinate Adhesion of amalgam to etched enamel was evaluated 5 as Pollows: Bovine teeth o~ similar age and appearance were partial~y embedded in circular acrylic disks such that the enamel was exposed. The exposed portion o~
each tooth was ground ~lat and parallel to the aarylic disc using Grade 120 silicon carbide paper-backed 10 abrasive mounted on a lapidary wheel~ Further grinding and polishing o~ the teeth was carried out by mounting Grade 320 sil~con carbide paper-backed abrasive on the lapidary wheel. During the grinding and polishing steps, the teeth were continuously rinsed with water.
15 The polished teeth wer~ stored in distilled water and used for testing within a hours after polishing.
The polished teeth were removed rom the water~and dried using a stream o~ compressed air. Phosphoric acid etching gel was applied to the enamel for 15 20 seconds, rinsed with water, and dried. The adhesive composition was applied to *he entire enamel surface with a brush and blown into a thin film with compressed air and cured for lO seconds with a VISI~UXSMZ dental cur~ng light (3M).
A mold made from a 2 mm thick TEFLONTN polytetra-fluoroethylene sheet with a 5 mm diameter circular hole through the sheet was clamped to each polished tooth so that the central axis of the hole in the mold was normal to the polished;tqoth surface. The hole in each 30 mold was filled with a prepared amalgam and allowed to stand for about l5 minutes at~room temperature, then stored in distilled ~water at 370C for 24 hours. The molds were then carefully~removed, leaving a molded 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 ., .
W~ g3/1Z75~12 6 ~S 2 PCT/US92/1039~
INSTRONTM testing apparatus with the polished tooth surface oriented parallel to the direction of pull. A
loop of orthodontic wir~ (O.44 mm diameter) was placed around the base of the amalgam button ad;acent to the 5 polished tooth sur~ace. The énds o~ the orthadontic wire were clamped in the pulling ~aw o~ the tensi~e testing apparatus, placing the bond in shear stress.
The bond was stres~ed until it ~or the amalgam button) failed, using a crosshead speed o~ 2 mm/min.
The following are of~ered to aid in understanding of the present invention and are not to be construed as limiting the scope thereo~. Unless otherwise indicated, all parts and percentages are by weight.
15 EXAMPLES 1-7 and COMPARATIVE EXAMP~ES C-l thr~uah C-5 Using the procedure set forth above, the adhesive shear bond strength on etched enamel of several adhesive compositions was evaluated. ~he amalgam used was a two-spill capsule of DISPERSALLOYT~ amalgam.
20 Various amounts of an ethylenicaIly unsaturated phosphorylated compound ~SCOTCHBONDTM Dual Cure Dental Adhesive resin), a sodium benzene sulfinate polymerization initiator tSCOTCHBONDTM Dual Cure Dental~
Adhesive liquid), a carboxylic acid functional polymer ~VITREBONDrM polymer), and a particulate metallic iller (TYTINTM alloy~powd~r) were combined, mixed, and applied to the etched enamel. Set out below in TABLE I are the example num~ers, amounts of components and mean adhesive shear bond values for the samples tested.
.
, 2l264~2 '0 93/12758 - 17 - PCI'/~JS92/103gg ., ..~,,,~ _ ~ _ _ _ _ ~ ~ =C _ o o o ~ ~ o o o 'L~C';~ _ _ __ _ _ _ _ _ I ~ ~` ~ ~' ~7 m ~ o u~ o r~
a~ o o o ~ ai ~ o ~ ul 4n o ~
.............. _ _ _ _ . ~ _ _ _ __ _ ~o~ ~n m ~ o o u~ ~ u) u~l ~n u~ u~
. __ __ _ _ . __ _ _ _ _ ~ ~ l ~ .1 l l I l l o o o ~
3~! . _ _ _ _ __, _ _ _ _ ~3al ~ ~ fi ~ 6 fi~
~ u--~ _ ~____ __ _ _ _ ~c o ~V ~ I 3 3 ~ ~ o o 3 o o o o ~ ~ o ~ ~P~ _ _ _ __ . _ ~ 9 ~ vc~ __ _ - - - ~rk N O : O O O O O O O O O O C C ~ O
C o o ~ o o o o o o O O U ~ ~
l~c ------------~ --__ _--aaoz~`
J ~ a~ o t t o :: o o o o o t o ~a~ c cO o Se o _ _ o o o o o o O _ O G ~
Y C) U U .1 ~1 _ ------ U --_ C~ U O ,~
2l26~s2 W093/12758 - PCT/U$92/tO39 The results in TABLE I show that a composition containing an ethylenicall~ unsaturated phosphorylated compound, a carboxylic acid functianal polymer, and a curing agent results in a synergistic enhanc~ment of 5 adhesive shear bond strQngth of etched enamel to amalgam relative to any other two component combination of the three componen*s~ The results also show that the use o~ a particulate metallic ~iller further increases adhesion.
: .
' ' ~
:; :
BACKG~OUN~ OF THE INYENTION
5 Technical Field This invention relates to adhesive compositions compris1ng a ~hosphorylated ~ompound. In another aspect, this in~ention relates to adhesive compositions comprising a carboxylic acid ~unctional polymer. This l0 invention also r~lates to methods o~ adhering a restorative materi~l to a substrate, and in another aspect to methods of adhering a dental rsstorati~e such as amalgam to hard tissue ~uch as dentin or enamel.
15 ~escription of the ~elated Art Dental amalgams and restorative composites are used extensively for intracoronal and extracoronal-restorations~ Amalgam, however, does not adhere to tooth structure and the dentist must prepare the tooth .
20 cavity with dovetails and various cu~out grooves that mechanically lock the amalgam into the ca~ity. Such preparation, however, results in excavation of more tooth structure than would otherwise be necessary if there was good adhesion between the tooth structure and 25 the amalgam. Moreover, leakage at the interface of the amalgam and cavity wall (known as "microleakage") 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 of the tooth, corrosion of the amalgam, and other attendant complications. An adhesive seal between amalgam and tooth structure could minimize and/or prevent microleakage and al}ow for a stronger 3s restoration due to excavation of less tooth material.
Products claiming to make amalgam adhesive to tooth structure are available. One such product is W093/l2758 2 ~ 2 6 4 5 PCT/US92/1039' sold in a kit under the trademark AMALGAMBONDT~ (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 similarly involve coating a ~pecific curable resin directly onto tooth structure to make amalgam adhere are available under the trademarks PANAVIATM Dental Adhesi~e ~Kuraray Company) and 10 SUPERBONDTM Adhesive (æun Medical Co., Ltd., Kyoto, Japan). These latter products also are dif~icult to employ, since there are a number of required preparatory steps ~or their application and curing.
Adhesive compositions that employ phosphorus-15 containing free-radically polymerizable compounds have been reported in the literature, see, e.g., ~.
Buonocore, W. Wile~an, and F. Brudevold, ~. ~ent. Res., 35, 846 ~1956), M. Buonocore and M. Quigley, J. Amer.
Dent. Assoc., ~, 807 (1958), M. Anbar and E. Farley, 20 J. Dent. Res~, 53, 879 ~lg74), E. Farley, ~. Jones, and M. Anbar, J. Dent. Res., 56, 1943 (1977),~U.S. Pat Nos.
3,882,600, 3,997,504, 4,222,780, 4,235,633, 4,259,075, 4,259,117, 4,368,043, 4,383,052, 4,499,251, 4,514,342,~
4,515,930, 4,537,940, 4,539,382, and 4,544,467, 25 European published patent application No. 0 058 483, and Japanese laid-open patent application (Kokai) Nos.
57-143~72 and 57-167364.
U.S. Pat.`No. 3,513,123 (Saffir) describes a curable epoxy composition that can be added to amalgam 30 in order to make the amalgam adhere to tooth structuré.
The curable epoxy composition contains a glycidyl ether type resin and a polyamine hardening agent.
U.S. Pat. No. 4,064,629 (Stoner) describes a method for applying amalgam restorations. The method 35 involves precoating the surfaces of a cavity within a carious tooth with a layer of an "adhesive-metal"
: ~ ;
, 2126~52 ~0~3/12758 PCT/US92/10399 lining composition. The metal o~ the lining composition is amalgamated by diffusion of the mercury ~rom the subsequently applied con~entional dental amalgam filling. The "adhesive-metal" lining 5 composition is said ~o improve corrosion re~istance of the dental amalgam ~illing and also to pr~mote bonding between the amalgam restoration and the cavity sur~aces.
U.S. Pat. No. 4,001,483 (Lee, Jr. et ~1.) 10 describes dental compositions ~or sealing margins between tooth structures and amalgam r~storations therein, the compositions c~ntaining ~a) an alkylene glycol dimethacrylate and/or its oligomer, ~b) a polymerization initia*or, ~c) a polymerization 15 accelerator and (d) a secondary monomer additive.
U.S. Pat. No. 3,574,943 ~Stark) describes a method of restoring a carious tooth whereby the ca~it~ is~
excavated, lined with a layer of a polysiloxane pressure sensitive adhesive polymer dissolved in a 20 fluorocarbon, and filled with amalgam. The polysiloxane layer iæ said to act as a barrier to leakage.
Further articles that describe bonding of amalgam~
to tooth structure by precoating the tooth with 25 adhesive resin include M. Staninec and N. Holt, Journal of Prosthetic~DentistrY ~1988), Vol. 59, pp. 397-402, A. Lacey and M. Staninec, Ouintessence International (1989), Vol. 20, pp. S21-524, Y. Aboush and C. Jenkins, Br. Dent. J. (1989), Vol. 166, pp. 255-2S7, Y. Aboush 30 and R.IElderton, Br. Dent. J. tl991), Vol. 170, pp.
219-222, and Y. Aboush and R. Elderton, Dent. Mater.
:, , (1991), Vol. 7, pp. 130-132. The last article involves ; adhesion to previously~hardened amalgam, whereas the other articles involve adhesion to fresh amalgam.
35 Also, A. ~en-~ ar, J. Am. Dent. Assoc. (1989) Vol. 119, pp. 725-728, describes a reduction in microleakage at the margins of amalgam restorations when "SCOTCHBOND"
: :
Wo~3/l~7s8 2126A52 PCT/US~2/103 Dual cure Dental ~dhesive resin (3M) is applied to cavity margins prior to application of amalgam, and M.
Mitrosky, Jr., ~uintessence I~ternational (1981) Vol.
9, pp. 871-874, descxibes the use o~ ethyl 5 cyanoacrylate as a bonding agent beneath amalgam and compo~ite restorati~es. H~ J. ~taehle et al., p~sGh.
Zahnartzt ~19B8) Yol. 43, pp. 952-957, describes the use of ~arious dental adhesives and varnishes to adhere amalgam to dentin.
Japanese Kokai 63-175085 describes an adhesive composition comprising an acid Punctional monomer, polymer, or copolymer, a ~inyl monomer in which the acid ~unctional component is ~olubl~, an organic peroxide, and an aromatic amine or sul~inate salt. The 15 composition is said to bond living tooth tissue to composites and amalgams.
French Patent 2,561,521 describes an intermediate adhesive composition for sealing dental cavities and chemically securing amalgams, compris~ng a metal powder 20 dispersed in an adhesi~e ~arni~h. The composition contains metal powdex, cellulosic varnish, ethyl acetate, amyl propionate, fluoride, and oil of pimento leaf.
Japanese Kokai 63-250310 describes dental adhesive 25 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, 30 alumina, gold, alloys, pqlymethyl methacrylate, polycarbonate, and the like.
SUMMARY OF_~HE INVENTION
This invention provides an adhesive composition, comprising:
, 2I26~5,~
~093/12758 PCT/US92/10399 (i) an ethylenically unsaturated phosphorylated compound;
(ii) a carboxylic acid functional polyme~ in an amount effective to increase adhesion of amalgam to 5 tooth structuxe when the composition is used as an intermediate layer between the amalgam and the tooth gtructure, compared to the adhes~on obtained using a like co~position absent the carboxylic acid ~unctional polymer; and (iii) a polymerization initiator in an amount su~ficient to effec~ cure o~ the composition. Such a compositlon of the invention optionally ~urther comprises a partl¢ulate metallic filler in an amount effective to increase adhesion of amalgam to tooth 15 structure when the composition is used as an intermediate layer between the amalgam and the tooth stru¢ture, compare~ to the adhesion obtained using a like composition absent the particulate metallic fille~.
This invention also provides an adhesive ~ composition, comprising:
:~ (i) an~ethylenically unsaturated phosphorylated compound :
(ii) a carboxylic acid functional polymer in an 25 amount of about 5 to about 200 parts by weight -based on 100 parts by weight of the phosphorylated compounds and ~ iii) a polymerization initiator in an amount sufficient to effect cure of the composition. These compositions optionally contain a particulate metallic 30 filler in an amount o about 50 to about 4000 parts ,by weight based on 100 parts by weight of the phosphorylated compound and the carboxylic acid : functional polymer. : ~
. This invention also provides a method o adhering 35 a restorative material to a substrate, comprising the steps of: ~
.
WO 93/1 Z758 2 1 2 6 ~ 5 2 PCI~/US92/1 039~r ~ 6 ~
(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 5 restorative material/substrate pair;
(iii) optionally curing the intermediat~ layer;
and (iv) adhering the other member o~ the restorative material/substrate pair to the first member 10 by way of the intermediate layer.
DET~I~ED DESCRIPTION OE T~ INVENTION
Materials suitable for use as the ethylenically 15 unsaturated phosphorylated compound in a composition of the invention include such materials known to those skilled in the art to be capable of bonding to hard tissue such as dentin, enamel, bone, or the like. This compound, sometime~ referred to herein as the 20 "phosphorus compoundn, i8 a monomer, oligomer, or polymer (or mixturs thereof), preferably suitable for use in the oral environment both in its unpolymerized and polymerized state.
Suitable phosphorus compounds comprise one or more 25 phosphorus atoms bonded through a carbon, nitrogen, oxygen, or sulfur atom, to a radical containing one or more ethylenically unsaturated groups. Preferred ethylenically unsaturated groups are ethenyl and 2-propenyl as found, respecti~ely, in acrylate and 30 methacrylate groups. ~è`or more of the phosphorus atoms can be~bonded~to one or more halogen atoms, active hydrogen atoms, or substituted or unsubstituted ~ hydrocarbyl groups (e.g., a~n alkyl, aryl, alkaryl, or ;~ aryalkyl groupj. ~A particular class of suitable 35 phosphorus compounds is~described in European Patent ~; Application No.~O 058 483 and U.S. Pat. No. 4,515,930.
These phosphorus compounds include those comprising an ~93/1275~ PCT/USg2/10399 . - 7 -organic ester of one or more acids of phosphorus, the organic radical of said ester con~aining at least one ethylenically unsaturated group, wherein said ester has ch}orine or bromine bonded directly to the phosphorus S (hereina~ter referred to as "halophosphorus acid esteræ"~. A pr~erred subclass o~ such halophosphorus acid esters includes halophosphorus acid esters of diglycidyl methacrylate of Bisphenol ~ Bis~GM~") prepared by r~acting Bis-GMA with a phosphorus acid.
10 Phosphorus acid halides (e.g., chlorides, bromides) that can be reacted with Bis-GM~ include POCl3, PCl3, PBr3, R'OP~O)Cl2, ~R'0)2P~O)Cl where ~' is a hydrocarbyl radical, pre~e~ably one derived ~rom remo~al o~ one or more hydroxyl groups from a hydr~xyl-containing 15 compound such as 2-hydro~yethyl methacrylate, ethylene glycol, polyethylene glycol, pentaerythritol, and the like, as would result from a reaction of the hydroxyl-containing compound and the phosphorus acid halide.
particularly pref~rr~d class of phosphoru~ compounds 20 includes chlorophosphorus acid esters o~ Bis-GMA.
An additional suitable class of phosphorus compounds includes the phosphorus acid esters described in U-S- Pat. Nos. 3,882,600, 3,997,504, 4,222~780, $
4,235,633, 4,259,075, 4,259,117, 4,368,043, 4,442,23g, 25 4t499,251, 4,514,342, 4,537,940, 4,539,382 and Japanese published pat~nt application (Koho) No, 85~17235.
Exemplary members of this class are the compounds 2-methacryloyloxyethyl phenyl phosphate and 10-methacryloyloxydecyl dihydrogen phosphate.
A further suitable class of phosphorus compounds includes the pyrophosphate ester derivatives described in U.S. Pat. Nos. 4,383,0S2 and 4,404,1SO and in Japanese Kokai 57-143372 and 57-167364.
A further suitable phosphorus compound is 35 glycerophosphate dimethacrylate, described in the '1'' ' ' ' ' ' ' ' 2l~64~æ
W~93/127s8 PCT/lJSg2/103~
abo~e-mentioned Buonocore, Wileman, and Brudevold publication.
Either a single phosphorus compound or a mixture of phosphorus compounds can be used. The phosphorus 5 compound can be prepared using methods known to those skilled in the art. It can also be obtained from existing commer¢ially a~ailable dental adhesives, such as I~SCOTCHBONDTUn Dual Cure D~ntal ~dhesive (3M), "ALL-BOND2TMI~ ~niversal ~ental Adhesive System tBisco, 10 Tnc.), "CLEARFILTM'I Photo ~ond Light-Cured Dental Bonding Agent ~Kuraray Co~, ~td.), 'IRESTOBOND 3TM~ Dual Dentin/Enamel Bonding Agent ~Lee Pharmaceuticals, see U.S. Pat. Nos. 4,524,527 and 4,521,550), "PRISMA
UNIVERSAL BOND3T~" Dentin/Enamel Bonding Agent tL. D.
15 Caulk Division of Dentsply International, Inc., see U.S. Pat. No. 4,814,423), "BOND~ITErM" Dental Adhesive (Sybron Corp.), nJohnson ~ Johnson" Dentin Bonding ~
Agent and "Johnson ~ JohnsonH ~ight-Curing Bonding Agent ~Johnson & Johnson Co.), "PALFIQUETM" Bonding 20 Agent ~Tokuyama Soda Co., Ltd.), "SHOFUTM" Bonding Base (Shofu, Inc.), and "SINTERBONDTM" Dental Adhesive ~Teledyne Getz).
The carboxylic acid functional polymer is preferably suitable for use in the mouth. Materials 25 suitable for use as the carboxylic acid functional polymer include those homopolymers and copolymers of unsaturated mono-, di-, or tricarboxylic acids known to those skilled in the art to be commonly used in glass ionomer cements. Representative materials are 30 described, for~èxample, in U.S. Pat. Nos. 3,655,605, 4,016,1~4, 4,089,830, 4,143,018, 4,342,677, 4,360,605, ` and 4,3~6,835,; and European Published Patent Application No.~88-312127.
Also suitable are those carboxylic acid functional 35 polymers prepared by th~ homopolymerization and ` copolymerizatio:n of unsaturated aliphatic carboxylic .
2I 26~ i2 ~vo93/~2758 P~T/USg2/10399 _ g _ acids, for example acrylic acid, 2-chloroacrylic acid, 3-chloroacrylic acid, 2-bromoacrylic acid, 3-bromoacrylic acid, methacrylic acid, itaconic acid, maleic acid, glutaconic acid, aconitic acid, citraconic 5 acid, mesaconic acid, fumaric acid, and tiglic acid.
~uitable monomers that can be copolymerized with the unsaturated aliphati~ carboxylic acid~ include unsaturated aliphatic compounds such as acrylamide, acrylonitrile, vinyl chloride, allyl chloride, ~inyl 10 acetate, and 2-hydroxyethyl me~hacrylate~ Ter- and higher polymers can also be used.
The carboxyIic acid ~unctional polymer can also contain ethylenically unsaturated groups such as ethenyl and 2-propenyl. Such materials can be prepared 15 by reacting a carboxylic acid Punctional polymer with an ethylenically unsaturated compound comprising at least one group capable of reacting with the carboxylic acid groups of the polymer. Suitable ~unctional groups include -OH, -NCO, -COCl, and -CH-CH2. Exemplary \ /
compounds include acryloyl chloride,--methacryloyl chloride, allyl isocyanate, 2-hydroxyethyl methacrylate, and 2-isocyanatoethyl methacrylate. A
25 particularly preferred carboxylic acid functional polymer is a~methacrylate-functional copolymer of itaconic acid and acrylic acid as disclosed in Example 11 of European Published Pat. Application No. 0 323 120.
In particular embodiments, the carboxylic acid functional polymer i8 present in an amount effective to increase the adhesion of amalgam to tooth structure : when the composition is used as an intermediate layer between the amalgam and the tooth structure, compared ; ~ 35 to the adhesion obtained~using a like composition absent the carboxylic:acid functional polymer. An effective amount of carboxylic acid functional polymer .
WO93/12758 2 ¦ ~ 6 4~ 2 PCT/US92/1039~
in these embodiments can be determined according to the method set forth in the EXA~PLES that follow~
I~ other embodiments, the carboxylic acid functional polymer is present in an amount o~ about 5 5 to a~out 200 parts by weight, preferably a~out 20 to ~bout ~00 parts by weight, based on 100 parts by weight o~ the phosphorylated compound.
A composition o~ khe inv~ntion also includes a polymerization initiator in an amount ~u~icient to 10 effect cure o~ the composition. Suitable polymerizakion initiators ~nclude autocure an~ light cure initiators such as those mentioned in columns 28 and 29 of U.S. Pat. No. 4,53g,332, chromophore-substituted halomethyl-s-triazines such as 15 those shown in U.S. Pat. No. 3,954,475, and chromophore-substituted halome~hyloxadiazoles such as those shown in U.S. Pat. No. 4,212,970.
The polymerization initiator is preferably pr~sent in an amount o~ about 0.01 to about 20 parts by weight, 20 more preferably about 0~1 to about 10 parts by weight based on 100 parts by weight of the phosphorylat~d compound and the carboxylic acid unctional polymer.
The compositions of the invention preferably further compri~e a par~iculate metallic filler. The 25 filler can be a pure metàl such as those of Groups IVA, VA, VIA, VII~, 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 30 zinc, are also suitable.~ The particulate metallic filler preferably has an average particle size of about 1 micron to about 100 microns, more pre~erably 1 micron to about 50 microns.
In some ~mbodiments, the optional metallic filler 35 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 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 ~orth in the EXAMPLES that follow. In other embodlment~ the particulate metallic ~ller is present in an amount of ~0 to about 4000 parts by weight, preferably about ~Oo to about 3000 parts by weight based on 100 parts by weight of the phosphorylated compound and the carboxylic acid Punctional polymer.
Ethylenically unsaturated compounds ~other than the phosphorylated compound) can be incorporated in the compositions o~ the invention in appropriate amounts easily selected by those skilled in the art. Suitable compounds include mono- or poly- acrylates and methacrylates such as methyl acrylate, 2-hydroxyethyl acrylate, triethyleneglycol diacrylate, neopentylglycol diacrylate, hexamethyleneglycol dia¢rylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, polyalkylene glycol mono- and di-acrylates, urethane mono- or poly-functional acrylates, Bisphenol A diacrylates, and the corresponding methacrylates of the above compounds, as well as acrylamides and methacrylamides, vinyl compounds, styrene compounds, and other ole~inically unsaturated compounds suitable for use in the oral environment. U.S. Pat.~Nos. 4,499,251, 4,515,930, 4,S37,940 and 4,539,382 contain lists of such compounds. ~
Thç~compositions can also contain conventional adjuvants such as solvents, accelerators, inhibitors, stabilizers,~pigments, dyes,~viscosity modifiers, extendinq or reinforcing fillers, surface tension depressants, wetting aids, antioxidants, and other ingredients known t~those skilled in the art.
The compositions can be mixed like conventional dental materials according to methods well known to ; 4 5 2 WO93/12758 pcT/usg2/1o39s those skilled in the art. Ordinarily it is preferred to add the carboxylic acid funational polymer to the phosphorylated compound, foilowed by the addition o~
the polymerization initiator~ Some aarboxylic acid 5 functional pol~mers may be di~ficult to dissolve in or mix with the phosphorylated comp~und. ~n such cases a volatile, remo~able cosolvent ~uch as ethanol, methylene chloride, acetone, ethyl acetate, methyl ethyl ketone or tetrahydro~uran ~"T~F") can aid mixing.
lO The cosolvent can then be removed ~rom the dental material such as by vacuum and optional heating.
The compositions o~ the lnvention can be packaged according to methods well known to those skilled in the art. For example, when a redox type polymerization 15 initiator 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) a~phosphorylated compound, a 20 carboxylic acid functional polymer, and a reducing agent in one part and (b) a phosphorylated compound and an oxidant in the other; ~ii) two-part packages of ~a) a phoæphorylated compound and one element of a redox s pair, and (b) à carboxylic acid functional poly~er and 25 the other element of the redox pair; and (iii) two-part packages of ~a) a phosphorylated compound and an oxidant and ~b~ a~phosphorylated compound, a carboxylic acid functional polymer, and a reducing agent. In the case of an organic sulfinic acid (or salt 30 thereof)/amine~(or~ salt~thereof)/peroxide ternary system, it is also possible to use a three-part package form in which the sulfinic acid and the amine are packaged separately~. The optional particulate metallic - filler component can be~included in any or all parts of 35 the above-described package forms.
Where the polymerization initiator comprises a photoinitiator, the phosphorylatad compound and the VO93/12758 21 2 6 ~ ~ 2 PCT/~S92/10399 photoinitiator are preferably packaged sepaxately or in a container opaque to light~ With a thermal curing agent that initiates polymerization when it is brought into contact with the phosphorylated compound ~e.g., 5 tributylborane), the phosphorylated compound and the curing agent are packaged ~eparately. Such separately packaged components are mixed together shortly before use.
~ composltion o~ ~he invention can be used as an 10 intermedlate layer b~tween a substrate such as hard tissue (e.g., bone, enamel, or dentin), ceramic, porcelain, and the like, and a restorati~e material such as a pure metal or alloy, an amalgam, a ceramic composite, or a composite comprising an adhesive 15 polymer (or a mixture of polymers) and a particulate inorganic filler. A primer can be used, but good adhesion is obtained without the use o~ auxiliary primers, and the co~positions of the invention generally pro~ide better adhesion than is obtained 20 using the phosphorylated compound alone.
}n order to adhere a restorative material to a substrate, the components of a composition of the invention are first combined in appropriate amounts.
As discussed above, depending upon the particular type 25 of polymerization initiator used the components can be mixed prior to packaging or they can be packaged as two- or three-par~ systems and combined just prior to use. Onae the components are combined the resulting composition of the invention can be placed in the form 30 of a thin layér (e.g., by brushing) on either the substrate or on the restorative material. The layer can~then optionally be~cured by appropriate means (e.g., heat including`exposure to room temperature, visible light, ultraviolet light, or the like). The 35 other of the~restorative material/substrate pair can then be prepared (e.g., mixed~ if necessary and placed on the adhesive layer.
: :
W~93/l27s8z 12 6 45 2 PCT/US92/1039 For the reasons set forth above in connection with the Baakground of the Invention, it i~ desirable i~ an amalgam can be made to a~here well to kooth structure.
Accordingly, one use of the compositions o~ the 5 invention invol~es adhering dental amalgam to tooth structure in a prepared cavity.
It is prePT-rred to use ~ modi~i~d amalgam in order to optimize adh~sion to tooth structure. Such a modified amalgam can be produaed by admixing l0 particulate additive~ into conventional amalgam alloy powder~ The modi~ied amalgam is th~n prepared in a con~entional manner by tri~urating the modi~ied alloy powder with mercury in an amalgamator~
The preferred particulate additi~es are ~elected lS ~rom the ~ollowing groups: l) acrylate- or methacrylate-functional polymers, ~) metal salts of acrylates or methacrylates, 3) nonmetallic ~illers, ~) oxidizing agents, and S) reducing agents~ The ~articulate additives are applicable ~o the ~ull range 20 of conventional amalgam alloy powders and c~nventional weight ratios o~ mercury to amalgam alloy powder.
Representative acrylate- or methacrylate-functional polymers include poly(alkanoic acid) powder.
Representative metal salts of acrylates or 25 methacrylate include zinc dimethacrylate, zirconium dimethacrylat~, silver methacrylate, sodium methacrylate, and magne~ium methacrylate. Nonmetallic ~illers include both untreated organic fillers and surface-treated fillers. Representative nonmetallic 30 fillars~ also known as orgànic fillers, include blends of silane-treated OX-50TM pyrogenic silica (Degussa Company), tetraethyleneglycol dimethacrylate ("TEGDNA") (Rohm Tech Co.), and ~isphenol A diglycidylether dimethacrylate in a 60:17:17 weight ratio. Other 35 representative nonmetallic fillers include zirconia/silica filler either untreated or pretreated with gamma-methacryloxypropyl trimethoxysilane as 2l264s2 '~093/12758 ycT/usg2~1o39s described in U.S. Pat. No. 4,503,169. Preerred oxidizing agen~s include benzoyl peroxide. Preferred reducing agents include sodium benzenesulfinate Adhesion of amalgam to etched enamel was evaluated 5 as Pollows: Bovine teeth o~ similar age and appearance were partial~y embedded in circular acrylic disks such that the enamel was exposed. The exposed portion o~
each tooth was ground ~lat and parallel to the aarylic disc using Grade 120 silicon carbide paper-backed 10 abrasive mounted on a lapidary wheel~ Further grinding and polishing o~ the teeth was carried out by mounting Grade 320 sil~con carbide paper-backed abrasive on the lapidary wheel. During the grinding and polishing steps, the teeth were continuously rinsed with water.
15 The polished teeth wer~ stored in distilled water and used for testing within a hours after polishing.
The polished teeth were removed rom the water~and dried using a stream o~ compressed air. Phosphoric acid etching gel was applied to the enamel for 15 20 seconds, rinsed with water, and dried. The adhesive composition was applied to *he entire enamel surface with a brush and blown into a thin film with compressed air and cured for lO seconds with a VISI~UXSMZ dental cur~ng light (3M).
A mold made from a 2 mm thick TEFLONTN polytetra-fluoroethylene sheet with a 5 mm diameter circular hole through the sheet was clamped to each polished tooth so that the central axis of the hole in the mold was normal to the polished;tqoth surface. The hole in each 30 mold was filled with a prepared amalgam and allowed to stand for about l5 minutes at~room temperature, then stored in distilled ~water at 370C for 24 hours. The molds were then carefully~removed, leaving a molded 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 ., .
W~ g3/1Z75~12 6 ~S 2 PCT/US92/1039~
INSTRONTM testing apparatus with the polished tooth surface oriented parallel to the direction of pull. A
loop of orthodontic wir~ (O.44 mm diameter) was placed around the base of the amalgam button ad;acent to the 5 polished tooth sur~ace. The énds o~ the orthadontic wire were clamped in the pulling ~aw o~ the tensi~e testing apparatus, placing the bond in shear stress.
The bond was stres~ed until it ~or the amalgam button) failed, using a crosshead speed o~ 2 mm/min.
The following are of~ered to aid in understanding of the present invention and are not to be construed as limiting the scope thereo~. Unless otherwise indicated, all parts and percentages are by weight.
15 EXAMPLES 1-7 and COMPARATIVE EXAMP~ES C-l thr~uah C-5 Using the procedure set forth above, the adhesive shear bond strength on etched enamel of several adhesive compositions was evaluated. ~he amalgam used was a two-spill capsule of DISPERSALLOYT~ amalgam.
20 Various amounts of an ethylenicaIly unsaturated phosphorylated compound ~SCOTCHBONDTM Dual Cure Dental Adhesive resin), a sodium benzene sulfinate polymerization initiator tSCOTCHBONDTM Dual Cure Dental~
Adhesive liquid), a carboxylic acid functional polymer ~VITREBONDrM polymer), and a particulate metallic iller (TYTINTM alloy~powd~r) were combined, mixed, and applied to the etched enamel. Set out below in TABLE I are the example num~ers, amounts of components and mean adhesive shear bond values for the samples tested.
.
, 2l264~2 '0 93/12758 - 17 - PCI'/~JS92/103gg ., ..~,,,~ _ ~ _ _ _ _ ~ ~ =C _ o o o ~ ~ o o o 'L~C';~ _ _ __ _ _ _ _ _ I ~ ~` ~ ~' ~7 m ~ o u~ o r~
a~ o o o ~ ai ~ o ~ ul 4n o ~
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. __ __ _ _ . __ _ _ _ _ ~ ~ l ~ .1 l l I l l o o o ~
3~! . _ _ _ _ __, _ _ _ _ ~3al ~ ~ fi ~ 6 fi~
~ u--~ _ ~____ __ _ _ _ ~c o ~V ~ I 3 3 ~ ~ o o 3 o o o o ~ ~ o ~ ~P~ _ _ _ __ . _ ~ 9 ~ vc~ __ _ - - - ~rk N O : O O O O O O O O O O C C ~ O
C o o ~ o o o o o o O O U ~ ~
l~c ------------~ --__ _--aaoz~`
J ~ a~ o t t o :: o o o o o t o ~a~ c cO o Se o _ _ o o o o o o O _ O G ~
Y C) U U .1 ~1 _ ------ U --_ C~ U O ,~
2l26~s2 W093/12758 - PCT/U$92/tO39 The results in TABLE I show that a composition containing an ethylenicall~ unsaturated phosphorylated compound, a carboxylic acid functianal polymer, and a curing agent results in a synergistic enhanc~ment of 5 adhesive shear bond strQngth of etched enamel to amalgam relative to any other two component combination of the three componen*s~ The results also show that the use o~ a particulate metallic ~iller further increases adhesion.
: .
' ' ~
:; :
Claims (8)
1. An adhesive composition, comprising:
(i) an ethylenically unsaturated phosphorylated compound;
(ii) a carboxylic acid functional polymer 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 obtained using a like composition absent the carboxylic acid functional polymer; and (iii) a curing agent in an amount sufficient to effect cure of the composition.
(i) an ethylenically unsaturated phosphorylated compound;
(ii) a carboxylic acid functional polymer 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 obtained using a like composition absent the carboxylic acid functional polymer; and (iii) a curing agent in an amount sufficient to effect cure of the composition.
2. A composition according to Claim 1, wherein the ethylenically unsaturated phosphorylated compound comprises a chlorophosphorus acid ester of Bis-GMA.
3. A composition according to Claim 1, wherein the carboxylic acid functional polymer is a methacrylate-functional copolymer of itaconic acid and acrylic acid.
4. A composition according to Claim 1, further comprising a particulate metallic filler 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 obtained using a like composition absent the particulate metallic filler.
5. A composition according to Claim 4, wherein the ethylenically unsaturated phosphorylated compound comprises a chlorophosphorus acid ester of Bis-GMA.
6. A composition according to Claim 4, wherein the carboxylic acid functional polymer. is a methacrylate-functional copolymer of itaconic acid and acrylic acid.
7. A method of adhering a restorative material to a substrate, comprising the steps of:
(i) combining the components of a composition according 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 material/substrate pair to the first member by way of the intermediate layer.
(i) combining the components of a composition according 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 material/substrate pair to the first member by way of the intermediate layer.
8. A method of adhering a restorative material to a substrate, comprising the steps of:
(i) combining the components of a composition according 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 material/substrate pair to the first member by way of the intermediate layer.
(i) combining the components of a composition according 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 material/substrate pair to the first member by way of the intermediate layer.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/815171 | 1991-12-31 | ||
| US07/815,171 US5256447A (en) | 1991-12-31 | 1991-12-31 | Adhesive composition and method |
| PCT/US1992/010399 WO1993012758A1 (en) | 1991-12-31 | 1992-12-02 | Adhesive composition and method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2126452A1 true CA2126452A1 (en) | 1993-07-08 |
Family
ID=25217077
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002126452A Abandoned CA2126452A1 (en) | 1991-12-31 | 1992-12-02 | Adhesive composition and method |
Country Status (13)
| Country | Link |
|---|---|
| US (1) | US5256447A (en) |
| EP (1) | EP0623015B1 (en) |
| CN (1) | CN1073857A (en) |
| AU (1) | AU662794B2 (en) |
| BR (1) | BR9206998A (en) |
| CA (1) | CA2126452A1 (en) |
| DE (1) | DE69212502T2 (en) |
| DK (1) | DK0623015T3 (en) |
| ES (1) | ES2091588T3 (en) |
| IL (1) | IL104007A0 (en) |
| MX (1) | MX9207422A (en) |
| WO (1) | WO1993012758A1 (en) |
| ZA (1) | ZA9210057B (en) |
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| US5575644A (en) * | 1993-03-11 | 1996-11-19 | American Orthodontics | Orthodontic appliance |
| US6191190B1 (en) | 1993-04-19 | 2001-02-20 | Dentsply Research & Development Corp. | Method and composition for adhering to tooth structure |
| US6391940B1 (en) | 1993-04-19 | 2002-05-21 | Dentsply Research & Development Corp. | Method and composition for adhering to metal dental structure |
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| EP0767651B1 (en) * | 1994-06-30 | 2002-01-30 | Minnesota Mining And Manufacturing Company | Method for bonding amalgam to dental surfaces |
| SE9402528D0 (en) * | 1994-07-19 | 1994-07-19 | Astra Ab | Hard tissue stimulant with electricity |
| US6313191B1 (en) | 1994-08-22 | 2001-11-06 | Dentsply Gmbh | Method and composition for priming and adhering to tooth structure |
| US5645429A (en) * | 1994-08-22 | 1997-07-08 | Dentsply Research & Development Corp. | Method for adhering to tooth structure |
| DE69511822T2 (en) * | 1994-11-21 | 2000-05-25 | Tokuyama Corp | Dental mass and kit |
| US5925690A (en) * | 1995-11-20 | 1999-07-20 | Tokuyama Corproation | Dental primer composition and kit |
| US5866629A (en) * | 1995-12-05 | 1999-02-02 | The University Of Toronto Innovations Foundation | Dental and medical primer formulations containing tissue infiltrating agents |
| US6004390A (en) * | 1997-04-14 | 1999-12-21 | Dentsply Detrey Gmbh | Tooth surface treatment composition and methods |
| FR2767696A1 (en) * | 1997-09-01 | 1999-03-05 | Inst Nat Sante Rech Med | USE OF ANTI-OXIDIZING COMPOUNDS AND / OR CARRIERS OF THIOL GROUPS TO REDUCE THE TOXICITY OF BIOMATERIALS |
| US20050059753A1 (en) * | 1998-06-30 | 2005-03-17 | Junjie Sang | Method and composition for adhering to tooth structure |
| US6147137A (en) * | 1998-09-10 | 2000-11-14 | Jeneric/Pentron Incorporated | Dental primer and adhesive |
| DE19909069C2 (en) * | 1999-03-02 | 2001-08-30 | Hahn Schickard Ges | Micro valve arrangement |
| US6612769B2 (en) | 2000-12-13 | 2003-09-02 | Innovative Properties Company | Package and dispensing actuator for multiple-component compositions |
| US6756417B2 (en) * | 2002-03-13 | 2004-06-29 | Ultradent Products, Inc. | Dental bonding compositions for adhering amalgam restoratives to dental substrates |
| US6729879B2 (en) | 2002-03-13 | 2004-05-04 | Ultradent Products, Inc. | Dental bonding methods for adhering amalgam restoratives to dental substrates |
| JP4485117B2 (en) * | 2002-06-27 | 2010-06-16 | 日東電工株式会社 | Protective peeling film |
| US6773261B2 (en) * | 2002-06-28 | 2004-08-10 | 3M Innovative Properties Company | Processes for forming dental materials |
| US7134875B2 (en) * | 2002-06-28 | 2006-11-14 | 3M Innovative Properties Company | Processes for forming dental materials and device |
| US20040206932A1 (en) | 2002-12-30 | 2004-10-21 | Abuelyaman Ahmed S. | Compositions including polymerizable bisphosphonic acids and methods |
| EP1498098B1 (en) * | 2003-07-14 | 2006-05-03 | 3M Espe Ag | Adhesive composition with decreased polarity upon polymerization |
| EP1653913B1 (en) * | 2003-08-12 | 2012-05-23 | 3M Innovative Properties Company | Self-etching dental compositions and methods |
| US7030169B2 (en) * | 2003-09-26 | 2006-04-18 | 3M Innovative Properties Company | Arylsulfinate salts in initiator systems for polymeric reactions |
| US7026367B2 (en) * | 2003-09-26 | 2006-04-11 | 3M Innovative Properties Company | Photoiniators having triarylsulfonium and arylsulfinate ions |
| US7250452B2 (en) * | 2003-09-26 | 2007-07-31 | 3M Innovative Properties Company | Dental compositions and methods with arylsulfinate salts |
| US7064152B2 (en) * | 2003-09-26 | 2006-06-20 | 3M Innovative Properties Company | Arylsulfinate salts in photoinitiator systems for polymerization reactions |
| JP5214242B2 (en) | 2004-07-08 | 2013-06-19 | スリーエム イノベイティブ プロパティズ カンパニー | Dental methods, compositions, and kits containing acid-sensitive dyes |
| AU2005272808B8 (en) | 2004-08-11 | 2011-11-03 | 3M Deutschland Gmbh | Self-adhesive compositions including a plurality of acidic compounds |
| ATE439116T1 (en) * | 2004-09-24 | 2009-08-15 | 3M Espe Ag | DENTAL ADHESIVE COMPOSITION |
| US9943465B2 (en) | 2006-12-13 | 2018-04-17 | 3M Innovative Properties Company | Methods of using a dental composition having an acidic component and a photobleachable dye |
| HUE042067T2 (en) | 2015-02-02 | 2019-06-28 | Coloplast As | Ostomy device |
| PL3280368T3 (en) | 2015-04-10 | 2019-11-29 | Coloplast As | Ostomy device |
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| US3513123A (en) * | 1967-10-11 | 1970-05-19 | Dentsply Int Inc | Adhesive dental filling |
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| US3882600A (en) * | 1971-04-01 | 1975-05-13 | Richard W Plymale | Composition in method for treating teeth |
| US4001483A (en) * | 1974-10-22 | 1977-01-04 | Lee Jr Henry L | Dental sealant for amalgam restorations |
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| GB1569021A (en) * | 1976-03-17 | 1980-06-11 | Kuraray Co | Adhesive cementing agents containing partial phosphonic orphosphonic acid esters |
| JPS53134037A (en) * | 1977-04-27 | 1978-11-22 | Kuraray Co Ltd | Adhesive for human hard tissue with good adhesiveness |
| JPS6019723B2 (en) * | 1978-01-27 | 1985-05-17 | 而至歯科工業株式会社 | dental composition |
| JPS57106688A (en) * | 1980-12-20 | 1982-07-02 | Lion Corp | 1-methacryloxyethane-1,1-diphosphonic acid |
| CA1236844A (en) * | 1981-02-13 | 1988-05-17 | James E. Bunker | Dentin and enamel adhesives |
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| JPS57167364A (en) * | 1981-04-07 | 1982-10-15 | Sankin Kogyo Kk | Adhesive for hard tissue of human body |
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| JPS59135272A (en) * | 1983-01-21 | 1984-08-03 | Kuraray Co Ltd | Adhesive |
| JPS59137404A (en) * | 1983-01-27 | 1984-08-07 | Kuraray Co Ltd | Dental adhesive |
| US4544467A (en) * | 1983-06-28 | 1985-10-01 | Minnesota Mining And Manufacturing Company | Light-curable dentin and enamel adhesive |
| FR2561521B3 (en) * | 1984-03-23 | 1986-05-30 | Castel Alain | INTERMEDIATE PRODUCT FOR IMPROVING THE FIXATION OF DENTAL AMALGAMS |
| AU590671B2 (en) * | 1986-02-28 | 1989-11-09 | Minnesota Mining And Manufacturing Company | One-part visible light-curable dentin and enamel adhesive |
| JPS63175085A (en) * | 1987-01-14 | 1988-07-19 | Mitsubishi Rayon Co Ltd | Dental adhesive composition |
| JPS63250310A (en) * | 1987-04-03 | 1988-10-18 | Mitsubishi Rayon Co Ltd | Dental adhesive composition |
| DE3821578A1 (en) * | 1988-06-25 | 1989-12-28 | Bayer Ag | LIQUID FOR CONDITIONING TOOTH OR BONE SUBSTANCE |
| EP0423430B1 (en) * | 1989-10-19 | 1993-04-21 | Heraeus Kulzer GmbH | Dental adhesive |
| US5382284A (en) * | 1992-04-23 | 1995-01-17 | Mion International Corporation | Glass ionomer cement compositions and restorative methods |
-
1991
- 1991-12-31 US US07/815,171 patent/US5256447A/en not_active Expired - Lifetime
-
1992
- 1992-12-02 DE DE69212502T patent/DE69212502T2/en not_active Revoked
- 1992-12-02 WO PCT/US1992/010399 patent/WO1993012758A1/en not_active Application Discontinuation
- 1992-12-02 BR BR9206998A patent/BR9206998A/en not_active Application Discontinuation
- 1992-12-02 DK DK93900781.1T patent/DK0623015T3/en active
- 1992-12-02 ES ES93900781T patent/ES2091588T3/en not_active Expired - Lifetime
- 1992-12-02 EP EP93900781A patent/EP0623015B1/en not_active Revoked
- 1992-12-02 AU AU32344/93A patent/AU662794B2/en not_active Ceased
- 1992-12-02 CA CA002126452A patent/CA2126452A1/en not_active Abandoned
- 1992-12-07 IL IL104007A patent/IL104007A0/en unknown
- 1992-12-18 MX MX9207422A patent/MX9207422A/en unknown
- 1992-12-28 ZA ZA9210057A patent/ZA9210057B/en unknown
- 1992-12-30 CN CN92115104A patent/CN1073857A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| IL104007A0 (en) | 1993-05-13 |
| WO1993012758A1 (en) | 1993-07-08 |
| AU662794B2 (en) | 1995-09-14 |
| AU3234493A (en) | 1993-07-28 |
| MX9207422A (en) | 1993-12-01 |
| EP0623015B1 (en) | 1996-07-24 |
| BR9206998A (en) | 1995-12-05 |
| DE69212502T2 (en) | 1997-03-13 |
| ZA9210057B (en) | 1994-06-28 |
| DE69212502D1 (en) | 1996-08-29 |
| US5256447A (en) | 1993-10-26 |
| ES2091588T3 (en) | 1996-11-01 |
| EP0623015A1 (en) | 1994-11-09 |
| DK0623015T3 (en) | 1996-12-02 |
| CN1073857A (en) | 1993-07-07 |
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| Date | Code | Title | Description |
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| EEER | Examination request | ||
| FZDE | Discontinued |