Dental composition and method

O P I c

Office de la propriété INTELLECTUELLE DU CANADA

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C I P O

Canadian Intellectual Property Office

Ottawa Hull ΚΙΛ 0C9 (21) (Al) (22) (43)

2,118,959

1994/03/14

1994/10/20 (51) INTL.CL. A61K-006/087 (19) (ca) APPLICATION FOR CANADIAN PATENT (12) (54) Dental Composition and Method (72) Lu, Kewang - U.S.A. ;

Huang, Chin-Teh - U.S.A. ; Hammesfahr, Paul - U.S.A. ;

(71) Dentsply International Inc. - U.S.A.

(30) (US) 08/049,221 1993/04/19 (57) 20 Claims

5,090,7/38

Notice

This application is as filed and may therefore contain an incomplete specification.

1Φ1

Industrie Canada Industry Canada

3488

Canada

DENTAL COMPOSITION AND METHOD

ABSTRACT OF THE INVENTION

The invention provides dental cement compositions and methods of using them for binding hard tooth material, metal and ceramic. The cement compositions include polymerizable acid reactive ethylenically unsaturated monomers, and a source of cations reactive therewith, to further crosslink the resulting polymer. The cements have superior adhesion to tooth without separately acid etching dentin or enamel. Compositions of are useful as dental luting cements, liners, bases and restoratives.

B:\1709.A

2118359

PATENT CASE 1709

DENTAL COMPOSITION AND METHOD

The invention relates to dental cernent compositions and methods of use thereof to bind hard tooth material, metal and ceramic. The invention provides cement compositions including polymerizable acid reactive ethylenically unsaturated monomers, and a source of cations reactive therewith, to provide further crosslinking in the resulting polymer. The invention provides cements with superior adhesion to dentin, enamel and dentin without the need for separate steps of acid etching dental enamel to adhere to enamel, cement, and superstructure. Compositions of the invention are useful as dental luting cements, liners, bases and restoratives. The compositions of the invention are hydrolytically stable. The heterogeneous multi-phase dental cements disclosed herein include liquid and solids, and show improved mechanical strength. They provide advantages, for example, improved bond strength to tooth and are less sensitive the effects of moisture during the setting reaction.

Prior art zinc oxide/phosphoric acid combinations, known as zinc phosphate cements, are not adhesive to metals, enamel or dentin. Zinc oxic)e and polyacrylic

<img file="CA2118959A1_D0002.tif" />

acid combinations are known as zinc polycarboxylate cements. They are relatively weak and soluble. Glass ionomers are described by A. Wilson in U.S. Patents 5,079,277 and 4,758,612. Prior art glass ionomer compositions are combinations of a polyalkenoic acid polymer such as polyacrylic acid and an elutable glass which provides a source of cations to react with the polyacrylic acid. Prior art glass ionomers are brittle and weak in high stress applications and set poorly in the presence of moisture unless protected from water. Prior art pit and fissure materials include polymerizable hydrophobic resins with essentially no adhesion to tooth. They are adhered by infiltrating micromechanical undercuts produced by acid etching. They harden in-situ to protect the tooth from colonization by bacteria in order to reduce caries, but because they are difficult to use they are not universally employed to achieve this valuable result. They require the tooth be cleaned, acid etched, washed, dried and isolated by rubber dam to maintain dryness, to avoid contamination by saliva, and achieve suitable results. The procedure is thus uncomfortable for the patient and laborious for the dentist. The present invention provides pit and fissure sealant compositions which are applied to tooth without a separate acid etching step.

Olivier in U.S. Patent 3,234,181 discloses meltfabricable end-capped aromatic polyimides.

Lonerini in U.S. Patent 3,407,176 discloses polyamide-acids and polymide from a mixture of dianhydrides.

Gall in U.S. Patent 3,422,061 discloses coalesceable polyimide powders from a polycarboxylic aromatic dianhydride and phenylene diamine.

Angelo in U.S. Patent 3,424,718 discloses copolymers of aromatic tetracarboxylic acids with at least two organic diamines.

Rogers in U.S. Patent 3,959,350 discloses meltfusible linear polyimide of 2,2-bis(3,4dicarboxyphenyl)-hexafluoropropane dianhydride .

Madsen in U.S. Patent 4,322,207 discloses dental cleaning slurry.

Beede et al in U.S. Patent 4,324,591 discloses modifying agents for ion-leachable cement compositions.

Gibbs in U.S. Patent 4,336,175 discloses polymide precursor solutions.

Schmitt et al in U.S. Patent 4,372,836 disclose light curable acrylic dental composition with calcium fluoride pigment.

Smyth in U.S. Patent 4,401,773 discloses highly reactive ion-leachable glass.

r

<img file="CA2118959A1_D0003.tif" />

Denyer et al in U.S. Patent 4,457,818 discloses dental compositions from urethane acrylate, diacrylate monomer, camphorquinone and dimethylaminoethy1 methacrylate .

Ratcliffe et al in U.S. Patent 4,459,193 discloses dental compositions containing camphorquinone and organic peroxide as catalyst.

Denton, Jr. et al in U.S. Patent 4,492,777 discloses heat treated barium or strontium glass.

Bowen in U.S. Patent 4,514,527 discloses method for obtaining strong adhesive bonding of composites to dentin enamel and other substrates.

Bowen in U.S. Patent 4,521,550 discloses method for obtaining strong adhesive bonding of composites to dentin, enamel and other substrates.

Martin in U.S. Patent 4,525,256 discloses photopolymerizable composition including catalyst comprising diketone plus 4-(Ν,Ν-Dimethylamino)benzoic acid or ester thereof.

Bowen in U.S. Patent 4,588,756 discloses multistep method for obtaining strong adhesive bonding of composites to dentin, enamel and other substrates.

Ratcliffe et al in U.S. Patent 4,602,076 discloses photopolymerizable compositions.

Peters in U.S. Patent 4,612,361 discloses poly(etherimides) and compositions containing the same.

Blackwell et al in U.S. Patent 4,657,941 discloses biologically compatible adhesive containing a phosphorus adhesion promoter and a sulfinic accelerator.

Bowen in U.S. Patent 4,659,751 discloses simplified method for obtained strong adhesive bonding of composites to dentin, enamel and other substrates.

Gallagher et al in U.S. Patent 4,680,373 discloses process for the production of a random copolymer containing repeating polyimide units and repeating polyetherimide units.

Aasen et al in U.S. Patent 4,719,149 discloses method for priming hard tissue.

Berdahl et al in U.S. Patent 4,794,157 discloses polyetherimide copolymers, and method for making.

Engelbrecht et al in U.S. Patent 4,806,381 discloses polymerizable compounds containing acid and acid derivatives, mixtures containing the same, and use thereof.

Blackwell et al in U.S. Patent 4,816,495 discloses biologically compatible adhesive visible light curable compositions.

Calla et al in U.S. Patent 4,864,015 discloses method for making thianthrene dianhydride and polyiinides obtained therefrom.

Engelbrecht in U.S. Patent 4,872,936 teaches dental cement mixtures containing polymerizable unsat5 urated monomers and/or oligomers and/or prepolymers containing acid groups and/or their reactive acidderivative groups.

Aasen et al in U.S. Patent 4,880,660 discloses method for priming hard tissue.

Kawaguchi et al in U.S. Patent 4,918,136 discloses adhesive composition.

Ibsen et al in U.S. Patent 4,964,911 discloses adhesive bonding of acrylic resins, especially in dentistry.

Huang et al in U.S. Patent 4,966,934 discloses biological compatible adhesive containing a phosphorous adhesion promoter and accelerator.

Hirasawa et al in U.S. Patent 4,985,198 discloses tooth-adhesive compounds.

Okada et al in U.S. Patent 5,055,497 discloses curable resinous composition.

Akahane et al in U.S. Patent 5,063,257 discloses dental glass ionomer cement compositions.

Wilson et al in U.S. Patent 5 079,277 discloses poly-vinylphosphonic acid and metal oxide or cermet or glass ionomer cement.

Mitra in U.S. Patent 5,130,347 discloses photocurable ionomer cement systems.

Mitra et al in U.S. Patent 5,154,762 discloses universal water-based medical and dental cement.

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Ohno et al in U.S. Patent 5,171,763 discloses curable composition.

Rambosek in Canadian Patent 873,935 discloses lithium aluminum silicate, polymer dental filling compositions.

Rossi in Canadian Patent 934,085 discloses dental restorative material of improved polishability.

Spoor in Canadian Patent 968,741 discloses production of coatings by curing with ionizing radiation.

Knight in Canadian Patent 969,299 discloses resins prepared from vinyl-ended polyurethane prepolymers.

Waller in Canadian Patent 983,190 discloses photopolymerizable acrylic dental products.

Lee et al in Canadian Patent 1,018,294 discloses dental filling package.

O'Sullivan in Canadian Patent 1,020,687 discloses urethane-acrylate dental filling composition.

Rockett et al in Canadian Patent 1,028,441 discloses three package dental restoration system.

Lorenz in Canadian Patent 1,117,242 discloses coating composition comprising N-vinyl-2-Pyrrolidone and an oligomer.

Osborn in Canadian Patent 1,131,388 discloses radiation curable urethane compositions.

Davies et al in Canadian Patent 1,136,796 discloses potopolymerizable compositions.

<img file="CA2118959A1_D0004.tif" />

//: ///////

Skudelny et al in Canadian Patent 1,154,895 discloses flowable mixture and use of synthetic calcium silicate.

Schaefer in Canadian Patent 1,159,984 discloses dental material having a plastics material base.

Munk in Canadian Patent 1,164,124 discloses pourable solid mixture.

Chevreux et al in Canadian Patent 1,176,787 discloses photosetting adhesive composition.

Gruber et al in Canadian Patent 1,179,094 discloses radiation curable coating composition comprising an oligomer and a copolymerizable ultra-violet absorber.

Morgan in Canadian Patent 1,194,637 discloses UV and thermally curable, thermoplastic-containing compositions .

Ratcliffe et al in Canadian Patent 1,198,847 discloses dental Compositions.

Szycher et al in Canadian Patent 1,200,647 discloses actinic radiation cured polyurethane acrylic copolymer.

Temin et al in Canadian Patent 1,213,699 discloses dental restorative composition.

Moran in Canadian Patent 1,216,982 discloses cure to elastomers composition

Ibsen et al in Canadian Patent 1,243,796 discloses dental composite and porcelain repair.

Ibsen in Canadian Patent 1,244,177 discloses methacrylate functional resin dental composite and porcelain repair compositions.

Ying in Canadian Patent 1,259,149 discloses dental restorative composition containing monofunctional monomer .

Randklev in Canadian Patent 1,261,992 discloses orthodontic bracket adhesive compositions.

Waknine in Canadian Patent 1,262,791 discloses a two component (Paste-Paste) self curing dental restorative .

Dougherty et al in Canadian Patent 1,262,981 discloses methods for posterior dental restoration employing light curable packable compositions.

Waknine in Canadian Patent 1,269,790 discloses dental restorative material.

Heid et al in Canadian Patent Application

2,009,471 discloses Hybrid plastic filling material.

Ibsen et al in Canadian Patent Application

2,011,438 discloses light-curable ionomer dental cement.

Rhelnberger et al in Canadian Patent Application 2,038,695 discloses polymerizable dental materials.

W·

211895S

Rheinberger et al in Canadian Patent Application 2,051,333 discloses polymerizable dental material.

Billington in European Patent Application 0 241

277 discloses glasses and poly(carboxylic acid) cement compositions containing them.

Billington in European Patent Application 0 244

959 discloses glass/poly(carboxylic acid) cement compositions .

Montgomery in European Patent Application 0 325

038 discloses surface priming composition for proteinaceous substrates, method of making and using same.

Kawaguchi et al in European Patent Application 0 335 645 discloses adhesive composition.

Griffin et al in European Patent Application 0 470 446 Al discloses High glass transition temperature mixed polyimides and composites formed therefrom.

Masuhara in U.K. Patent Application 2 000 789 A discloses curable composition.

Hirasawa in U.K. Patent Application 2 156 347 A discloses (Meth) acrylic acid ester compounds boundable to tooth substrates.

Akahane et al U.K. Patent Application 2 202 221 discloses glass powders for dental glass ionomer cements.

U.S. Patent 4,588,756 relates to aromatic based compositions employed in dentistry as a component in a ·$&amp; A J;

·&gt;&lt;··'· 10 dental adhesive system requiring multiple pretreatment steps including application of an acid.

Engelbrecht in U.S. Patent 4,872,936 broadly teaches dental cement mixtures containing polymerizable unsaturated monomers and/or oligomers and/or prepolymers containing acid groups and/or their reactive acidderivative groups.

Mitra in U.S. Patent 5,130,347 discloses a photocurable ionomer cement having a photocurable amid monomer.

Mitra in U.S. Patent 5,154,762 discloses water soluble reducing and oxidizing agents.

It is an object of the invention to provide a cement composition which reduces the steps and time required to adhere metal or ceramic to tooth structure.

It is an object of the invention is to provide new dental compositions useful as filling materials, cavity liners and bases, cements, and pit and fissure sealants .

It is an object to provide an adhesive cement composition for adhesion between tooth structure and/or bone and polymeric composites.

It is an object is to provide dental restorative/cement compositions that are relatively inexpensive and easy to manufacture.

<img file="CA2118959A1_D0005.tif" />

It is an object of the invention to provide dental cements which are adhesive to tooth structure, and ceramics and metals.

It is an object of the invention to provide dental cement compositions useful as luting cements, pit and fissure sealants, filling and other restorative materials which are adhesive to tooth structure.

It is an object of the invention to provide compositions comprised of polymerizable partial esters of aromatic dianhydrides, and a source of cations capable of reacting with residual acid groups thereupon to further harden and/or crosslink the polymerized acid functional aromatic esters.

Work time as used herein means the time between mixing the components of a polymerizable composition and the time at which the composition is very viscous but pliable and not yet firm.

Set time as used herein means the time between mixing the components of a polymerizable composition and the time at which the composition becomes firm, stiff and nonpliable.

As used herein The MAX Lite means THE MAX™, a resin curing unit for light-polymerizable dental materials sold by Dentsply International Inc. through its L.D. Caulk Division.

<img file="CA2118959A1_D0006.tif" />

Throughout this disclosure unless otherwise specified amounts of each component of a composition are in percent by weight.

DETAILED DESCRIPTION OF THE INVENTION

Compositions of the invention provide superior adhesion to dentin, enamel and bone. In a preferred embodiment cement compositions of this invention are used without a separate step of etching the surfaces to be joined. The adhesive dental materials provided by this invention include restorative materials especially cavity bases and liners, luting cements, pit and fissure sealants and filling materials.

The dental materials of the invention include novel polymerizable partial esters of aromatic dianhydrides and a source of cations capable of reacting with residual acid groups to further harden and/or crosslink the resulting polymerized acid functional aromatic ester polymers.

Dental compositions of the invention include polymerizable unsaturated substituted aromatic compounds containing at least one acid moiety. These aromatic compounds are within the scope of the general formula (I):

ο

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or

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^R6

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wherein Ri and R2 each independently is a polymerizable unsaturated moiety having from 2 to 13 carbon atoms,

R3, R4, R5, and R5 each independently is hydrogen, halogen, alkyl having from 1 to 10 carbon atoms or halogenated alkyl of from 1 to 10 carbon atoms,

R9, ^R10» ^Rll, ^r12/ ^r13 and ^r14 each independently is hydrogen, alkyl having from 1 to 10 carbon atoms or aryl having from 6 to 10 carbon atoms.

Zi and Z2 each independently is a moiety including an acid group or a reactive acid derivative, a ,m and n each independently is 0 or 1, b and p each independently is an integer from 1 to 10.

<td colspan="2"> In accordance</td><td colspan="2"> with a preferred embodiment of the</td>

<td> invention</td><td> and R2</td><td> each</td><td> independently is:</td>

<td> 0 I I</td><td> 0 I 1</td><td></td><td></td>

<td> 1 1 - C - Ft, - 0</td><td> 11 - C -</td><td> C = 1</td><td></td>

<td></td><td></td><td>^R8</td><td></td>

wherein R7 a divalent carbon containing radical and

Rg is hydrogen,halogen or alkyl having from 1 to carbon atoms.

In a preferred embodiment of the invention compounds are provided within the scope of general formula I wherein n and rn are zero, X is oxygen, sulfonyl or ditrifluoromethyl ; Zj and Z2 are - COO(M) wherein M is hydrogen or an alkali metal, alkalineearth metal, amine or amine salt; and Rj and R2 are

CH,

II I

- C - 0 - CH CH , - 0 - C - C = CH

II 0

I·.'.

BY?'

Most preferably compounds within the scope of general formula I are those wherein X is oxygen, and M is hydrogen, Li, Na or K. Appropriate polymerizable unsaturated groups Ri and R2 independently are alkenyl, alkenoxy, cycloalkenyl, arylalkenyl, and alkenaryl moieties; with vinyl, and styryl moieties being preferred, and acryl and methacryl moieties that constitute the polymerizable groups of many monomers in dental materials being especially preferred.

Exemplary Κχ and R₂(meth)acrylate moieties include :

CH₂ o - c

CH = CH ;

O - CB, (- 0 - CH

CH,

II I

CHj - 0 - C - C = CH₂;

^CH2 -&gt; n °

CH, ; and (0 - CH ₂

-’n ⁰ CH, ii r* c - c

CH, ¹⁰ - ^CF2 ^CF2 ’’η

C = CH, where n preferably is an integer from 1 to 10. Preferably Rj and R₂ are (meth)acryloyloxyethyl moieties.

Preferred compounds within the scope of formula I include diesters which are the adducts of 4,4'oxydiphthalic anhydride, 2,2-bis(3,4-dicarboxylphenyl) hexafluoropropane anhydride, 4,4 *-sulfonyldiphthalic anhydride, respectively with 2-hydroxyethyl methacrylate. In a preferred embodiment at least two aromatic rings of a compound with the scope of formula I are joined through at least one saturated carbon, oxygen or sulfonyl.

Aromatic dianhydrides preferred for making compounds within the scope of general formula I react to form partial esters and carboxylic acid functionality. Dianhydrides having at least two aromatic rings are more preferred. Most preferably at least two aromatic rings are joined as shown in formula I to provide disruption of conjugation between the aromatic rings. It has been found that such compositions are less sensitive to light induced changes in color, and are therefore preferred when esthetic considerations are of importance. Most preferred examples are 4,4 'oxydiphthalic anhydride and 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride.

<img file="CA2118959A1_D0010.tif" />

Dental cernent compositions in accordance with a preferred embodiment of the invention include an acid functional polymerizable organic ester within the scope of general formula I, water, cation elutable glass filler, and a polymerization catalyst system. Optionally, additional polymerizable monomers and/or prepolymers are included.

A composition in accordance with a preferred embodiment of the invention provides polymerizable monomer having at least one acid radical or reactive acid derivative, and a source of cations reactive with the acid moiety, and a catalyst system. Preferably the catalyst system promotes free radical polymerization and preferably includes visible light curing and/or a redox catalyst system. Preferably the composition includes liguid diluents, and/or filler adjuvants. Diluent preferably co-polymerizes with the polymerizable monomer within the scope of general formula I. Alternatively the diluent is nonreactive with the polymerizable monomer. Water for example is a nonreactive diluent. Suitable polymerizable co-monomers are disclosed in U.S. Patent 4,657,941 particularly at column 3 line 5 through column 5 line 59 and U.S. 4,514,342 both of which are incorporated herein by reference. The filler adjuvants are preferably reactive, for example by providing a source of cations

O' · ' -V

<img file="CA2118959A1_D0011.tif" />

which are reactive with the acid moiety of the polymerizable monomer. Nonreactive filler is preferably included in compositions in accordance with a preferred embodiment of the invention. Optionally, fillers have surface treatments to improve compatibility and strength of the resulting composition. Exemplary fillers include silica, silicates, alumina, aluminates, calcium fluoride, strontium fluoride, glasses including fluorine glasses, ceramics and minerals including mica, zeolites, ceramics, calcium apatites and organic polymers and those disclosed in U.S. Patents 4,758,612 and 5,079,277.

In accordance with a preferred embodiment a liquid and a powder are mixed to form a dental cement composition. The liquid includes polymerizable monomer within the scope of formula I, and the powder includes a source of cations reactive with the polymerizable monomer. The liquid preferably Includes diluent. The powder composition preferably includes a free radical polymerization catalyst system, and a glass powder which provides a source of cations and filler adjuvants.

A preferred composition of the invention includes a monomer compound within the scope of general formula I, at least one finely divided reactive filler which provides a source of cations reactive with the acids or acid derivative of the monomer compound and curing agent. A dental luting cement composition in accordance with the invention includes a compound of general formula I, catalysts, initiators, accelerators, filler, adjuvants, source of cations, water, and diluent. Dental cements and dental filling compositions in accordance with a preferred embodiment of the invention include monomer compounds within the scope of general formula I.

The compounds within the scope of general formula I have at least two different functional substituent groups, one of which is capable of addition polymerization and the other of which is carboxyl or other acid or reactive acid derivative. Most preferably these compounds include at least one polymerizable group and one or more acid or reactive acid derivative groups. Preferred compounds within the scope of general formula I are derived from the reaction of 4,4'-oxydiphthalic anhydride or 2,2-bis(3,4-dicarboxylphenyl)hexafluorpropane dianhydrides with a hydroxyl or polyhydric compound to form esters and partial esters thereof.

The new compounds of the invention are capable of being polymerized to form linear or crosslinked polymers which contain multiple acid groups or reactive acid derivative groups that may be further reacted with cations, especially those of valence 2 or greater to form poly-salts relatively insoluble in water. Because the compounds are monomers of relatively low molecular weight with a high density of both ethylenic unsaturation and carboxylic reactive acid derivative sites, excellent curing with superior integrity occurs. The cations may be supplied by ingredients or components of the given formulation or they may be supplied from a solution of cations supplied from a second component of the formulation, or they may be supplied from the substrate against which the formulation is polymerized especially the tooth in the preferred dental compositions where this provides strong bond in the preferred applications. In such a case the carboxyl ions, other acid ions or reactive acid derivative ions may be chelated with surface cations of the substrate to provide an adhesive bond. In a preferred dental composition not only is this substrate bonding available but bonding with an ion contributing inorganic filler aids in binding the entirety together. It will be understood that the term reactive acid derivative ions as used here includes the water compatible salts, and others of cations, especially the monovalent species of cations, for example the lithium, sodium, ammonium and potassium salts, which are displaced by cations of greater valency by metathesis. However, the carboxyl group itself is most preferred over other acid moieties or the reactive acid derivative ions. Especially appropriate acid moieties are all those that can react with oxidic, mineral, ceramic, vitreous, or metallic fillers.

<td> Examples</td><td> of these</td><td> other</td><td> acid</td><td> moieties</td><td> include:</td>

<td> 0</td><td> 0</td><td></td><td> 0</td><td></td><td> 0</td>

<td> 11</td><td> 11</td><td></td><td> 11</td><td></td><td> I 1</td>

<td> - P - OH,</td><td> P - OR,</td><td> 0</td><td> P</td><td> OH, and</td><td> 0 - P - OR,</td>

<td> OH</td><td> OH</td><td></td><td> OH</td><td></td><td> OH</td>

of phosphorus acids wherein R is alkyl, aryl, or vinyl; the moieties -SO₂H, SO₃H, or -O-SO3H of sulfuric acids; the moieties:

<td> - B - OH. I OH</td><td> B 1 OH</td><td> - OR, - 0</td><td> B - OH. and - O 1 OH</td><td> B 1 OH</td><td> OR,</td>

<td> of boron</td><td colspan="2"> acids wherein</td><td> R is alkyl, aryl</td><td> , or</td><td> vinyl and</td>

<td> cationic</td><td> acid</td><td> moieties</td><td> including ”NR₂H+</td><td colspan="2"> wherein R is H</td>

or alkyl. The reactive acid derivatives can be substituted with acid halides, with acid anhydrides, and with acid amides, nitriles, and esters that readily hydrolyze into acid, such as can enter into ionexchange, neutralization, salt formation, or chelation reactions with the reactive filler. Preferred acid or reactive acid derivatives are carboxylate, phosphate, phosphonate, sulfonate, or borate acid moieties and/or of their reactive derivatives.

The compositions of the invention are formulated as one, two or more components, visible light curable, self cure, and/or dual cure product or combinations of these. The composition of a preferred embodiment of the invention includes polymerizable carboxylic acid monomer, an optional filler and/or diluent, a cationic elutable glass or other source of polyvalent cations, and a polymerization catalyst system. The polymerizable carboxylic acid monomers are chosen to provide a suitable balance of hydrophobic and hydrophilic moieties in order to provide a balanced set of properties including adhesion to metal, ceramics and tooth. They are essentially non-volatile and provide cement compositions that are prompt setting and not critically affected by moisture during hardening within the oral cavity; strength at least as great as zinc phosphate cement in a particular embodiment intended for permanent cementation; and provide the ability to be used on hydrated surfaces such as found on and in teeth; and in a preferred embodiment do not require the separate steps of acid etching and adhesive priming to achieve adhesion to tooth structure.

For a better understanding of the characteristics and method of producing the preferred ethylenically

21189

ί) tj unsaturated carboxylic acid monomer compounds of the present invention the preparation of a preferred series of the compounds of the invention is carried out as follows :

In the presence of acid, base or other suitable catalyst one mole 4,4' oxydiphthalic anhydride is reacted with two moles of a compound of the general formula R-OH, wherein R is a polymerizable unsaturated moiety having from 2-13 carbon atoms. This yields a liquid product which is believed to be a mixture of isomer monomers of general formulas II-IV:

<img file="CA2118959A1_D0012.tif" />

II

<img file="CA2118959A1_D0013.tif" />

OR

OH

III and

<img file="CA2118959A1_D0014.tif" />

OR

OH

IV

As discussed reacting one mole in detail in Example 3 below by of oxydiphthalic anhydride with two moles of methacryloyloxyethy1 alcohol also known as hydroxyethyl methacrylate (HEMA) in the presence H2SO4 a liquid product is formed which is believed be a mixture of isomer monomers V-VII:

2of to

<img file="CA2118959A1_D0015.tif" />

Monomer compounds within the scope of general formula I are reactive esters which have at least one unreacted carboxylic acid group and one polymerizable group in the monomer. The number of reacted or unreacted carboxylic acid groups in the monomer is controlled by varying the reaction conditions and molar ratio of reactants. The monomer compounds of the invention polymerize by addition polymerization through the ethylenically unsaturated group. Curing agents, catalysts, initiators and/or accelerators, are used to expedite and control the polymerization. A peroxide initiator, for example benzoyl peroxide, and/or heat are useful to initiate the reaction. Accelerators enhance the reaction so that it may proceed more expeditiously at room temperature. Accelerators preferably include reducing agents such as amines or sulfinates, and/or transition metal ions. Ultraviolet and/or visible light are used with initiators and accelerators to initiate and accelerate the polymerization. Visible light curing is preferred for curing the compositions of the invention in the mouth. For preformed objects, or those cured outside the body, other forms of radiation, for example ultraviolet ionizing radiation is preferred for curing the compositions of the invention.

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In accordance with the method of the invention invivo polymerization does not harm the patient within whom polymerization of monomer compound within the scope of general formula I occurs. The polymerization catalyst system, for example a peroxide and an amine, is preferably formulated as two parts. Polymerization is delayed until both parts are combined and react to polymerize the monomer. Alternatively a single part composition is induced to polymerize by the application of heat or light. To initiate by irradiation with ultraviolet or visible light the initiator, for example a benzophenone or camphorquinone is preferably combined within a single, premixed, ready to use shelf-stable composition. A preferred embodiment of the composition of the invention includes a polymerization catalyst system having a light sensitive polymerization initiator such as camphorquinone, a reducing agent such as ethyl 4-diraethylaminobenzoate (EDAB) and an oxidizing agent such as benzoyl peroxide. Redox polymerization systems known to the art are preferably used to polymerize the composition of the invention. Preferred redox polymerization catalyst systems for use in accordance with the invention include, a peroxide and tributyl boron and/or a transition metal salt. Redox polymerization catalysts and catalyst systems are those disclosed in U.S. Patent 4,657,941 at column 7 line 10 through column 8 line 27 incorporated herein by reference. A particular polymerization method and system may be preferred depending on the application requirements of the material. Whatever the mode of polymerization, or cure of the composition including the monomers, an important characteristic of the polymers which form are that they are capable of further reaction with di- or polyvalent cations to crosslink the product. The compounds and compositions of the invention are adapted to form or include resin which exhibit adhesion between the resin and a cation containing surface, metal, metal oxide, tooth, and/or bone against which they are polymerized.

Fillers which are especially suited for use in compositions of the invention are inorganic glasses such as are used in glass ionomer cements. Exemplary of such fillers are those of U.S. Patent 4,814,362 which is incorporated herein by reference in its entirety. Preferred fillers are glasses formed from or including, barium, calcium, strontium, lanthanum, tantalum, and/or tungsten silicates and aluminates and/or aluminosilicates, silica, including submicron silica, quartz, and/or ceramics for example, calcium hydroxy apatite. In a preferred embodiment of the invention reactive cations, especially those of calcium, strontium and aluminum, and anions especially fluoride ions; are eluted from the fillers. The fillers used in the invention preferably are reduced in particle size and are preferably silanated before they are incorporated into such compositions. Preferred levels of filler are from about 20% to about 85% based on the total weight of the cement composition, with from about 40% to about 85% being more preferable and about 50-80% being most preferred. If a more finely particulated filler is used, amounts of filler may be decreased due to the relative increase in surface area which attends the smaller sizes of particles. Preferred particle size distributions are from 0.02 to 50 microns, more preferably 0.1 to 10 microns, and most preferably 1 to 6 microns.

In a preferred embodiment sources of cations, for example salts of di- and polyvalent cations such as SrF2 are preferably used to crosslink the products of the invention. In another preferred embodiment compositions of the invention include solvents, plasticizers, pigments, anti-microbials and therapeutics which may be time released from the composition, and oxidation inhibitors such as butylated hydroxytoluene. In addition to compounds within the scope of general formula I compositions in accordance with the invention preferably include polymerizable unsaturated diluent monomers and/or oligomers and/or prepolymers that do not contain any acid groups and/or salts thereof an^3/or reactive readily hydrolyzing acid-derivative groups thereof. One such preferred monomer is hydroxyalkyl methacrylates. Compositions of the invention may also preferably include compounds having acid groups and/or their salts and/or their reactive readily hydrolyzing derivative groups but do not contain any groups that are unsaturated and polymerizable, such as multi-basic acids or their reactive, readily hydrolyzing derivatives. Especially preferred multibasic acids are hydroxy acids such as tartaric or citric acid, but also preferred are polyacids such as polycarboxylie, polyphosphoric, polyphosphonic, or polysulfonic acids.

Compounds that have chelating groups but do not contain carboxylic acid groups or readily hydrolyzing acid-derivative groups are preferably included in composition in accordance with the invention, for example vanillates, syringates, and salicylates. Nonreactive diluents are also desirable to more completely and quickly wet substrates. Suitable diluents are ethanol, acetone, water, and less viscous reactive monomers.

Mixing the compositions of the present invention may be achieved using standard compounding techniques. For example, liquids, photoinitiator(s), and accelerator (s) are blended first, and fillers are added incrementally thereafter. When blending light sensitive compositions, however, a photosafe room illumination, i.e., one that does not contain substantial amounts of wavelengths of electromagnetic radiation that would activate the photoinitiating system is used to avoid initiating polymerization of the composition prematurely.

CEMENTS

The compounds of the present invention also have medical applications such as in self adhesive bone cements. However, they are most preferred to use in dental treatment by application to a tooth or a number of teeth in vivo, in the mouth of a live patient by a dentist or dental practitioner.

The application of the compositions of the invention is preferably as a dental cement applied to tooth. The dental cement compositions of the invention preferably include a compound within the scope of general formula I, a source of cations, and other ingredients, such as curing catalysts, initiators, accelerators, diluents and/or adjuvants. The composition is applied as a cement using conventional techniques and preferably cured with application of visible light in a conventional manner. Cements in accordance with the invention are self adhesive to dentin and enamel. These cements are used in bonding dentin to structures, for example, to bond a ceramic inlay to a prepared cavity of a tooth. Inlays preferably are polymers, or ceramics which are cast or built-up from porcelain frits and fired. Alternatively, inlays are machined from metal such as titanium or gold or preformed polymeric composite or homogeneous monolithic polymer compositions, for example by CAD-CAM procedures. In accordance with a preferred embodiment of the invention metal or ceramic superstructures for crowns, and bridges and/or ortho~dontic appliances are bonded to teeth using cement compositions of the invention. Such cement compositions join metal or ceramic to tooth by application of the cement composition by bringing them into contact until the cement hardens.

A preferred composition of the invention includes a two-part system. One part includes a curing agent. The two parts are spatuled to form a cement prior to placement on tooth. The placement is by standard technique(s). Preferably the cement includes a visible light and/or a self-curing redox polymerization initiator system. In a preferred embodiment of the invention luting cement compositions have low viscosity and film thicknesses less than about 25 pm to bond close fitting appliances to prepared teeth. In one embodi33

<img file="CA2118959A1_D0016.tif" />

21189 ment luting cement compositions of the present invention may be prepared of such high viscosity and consistency that they form adhesive glue lines of thicknesses up to several hundred microns to lute less close fitting restorations, for example inlays prepared using present state-of-the-art CAD-CAM devices. Compositions of the invention are mechanically strong, abrasion resistant, and are esthetically suitable and serve as the sole structural element to retain inlay, crowns and bridges or other appliances to tooth structure.

FILLING COMPOSITIONS

A preferred dental treatment in accordance with the invention is the application of dental filling compositions which include a curing agent and at least one compound within the scope of general formula I. Preferably the dental filling composition includes finely divided reactive filler that can react ionically with the acids or acid derivatives of the monomer. Preferably the composition is applied to a tooth as a filling material using conventional techniques as a one-component material and is cured with application of visible light in conventional manner.

<img file="CA2118959A1_D0017.tif" />

PIT AND FISSURE SEALANTS

In a preferred embodiment of the invention a one or two component pit and fissure sealant which includes at least one compound within the scope of general formula I is applied to anatomic defects and/or the exterior of teeth. The sealant limits the ability of caries-forming bacteria to colonize the pits, fissures and other surfaces of the teeth. Pit and fissure sealant compositions in accordance with the invention are an especially valuable means of reducing caries by filling and eliminating enamel defects. The pit and fissure sealants of the invention are preferably applied without prior acid etching or the use of rubber dam to teeth. In one embodiment fluoride eluting compounds and glasses are preferably included in compositions of the invention. Fluoride is eluted to reduce the incidence of caries in tooth substance adjacent the compositions of the invention.

In accordance with the method of the invention cement and restorative compositions include at least one polymerizable acid reactive ethylenically unsaturated compound within the scope of general formula I. Such compositions are applied to tooth without prior etching of the tooth.

Method for measurement of compressive strength using

International Standard Organization(ISO) 9917:1991(E) at pages 5-7 Dental water-based cements

For each material to be tested, cylinders 4 mm diameter and 6 mm long were prepared by filling the mixed material into teflon molds and light curing from each end for 4 0 seconds using The MAX Lite. The cylinders were removed from the molds and stored in water at 37°C for 24 hours prior to testing. The force needed to load the specimens to breaking point was measured using a universal testing machine operating at a crosshead speed of 1 mm/min.

Method of transverse flexural strength using

International Standard Organization(ISO)4049:1988(E) at pages 6-8 Resin-based filling materials

The uncured material was filled into a split

Teflon® mold with internal dimensions 25 mm x 2 mm x 2 mm. The exposed faces were then covered with polyester foil and clamped between transparent plastic blocks. The material was light cured for a total of 120 seconds by moving a dental curing light evenly backwards and forwards along the mold with the wand of the light in contact with the plastic blocks. After curing, the hardened specimens were stored in water at 37°C for 24 hours. Before being tested, any remaining flash along ^847::^448448^3384/ ///-4::-://:4::3348-:::4//3- /:: /:4:4: .&gt;: //,.::2. 3./8:: ,:434888:4:.8-*4 .-:4 :-2:'-2:W :4:/2848/|423/'3^:ί844·,4'/

<img file="CA2118959A1_D0018.tif" />

<img file="CA2118959A1_D0019.tif" />

<img file="CA2118959A1_D0020.tif" />

the edges of the specimens was carefully removed and the exact dimensions of each specimen measured. The specimens were then tested in three point bending mode using a universal testing machine set to a crosshead speed of 1 mm/min, with the sample resting on supports 20 mm apart and being loaded at the mid point. The transverse bending strength was calculated from the standard formula in Megapascals (MPa).

Method for measurement of diametral tensile strength

Modified procedures of ADA Specification No. 9 and No. 27 were utilized for all materials tested. Split teflon molds with internal dimensions of 3 mm + 0.1 mm high and 6 mm + 0.1 mm diameter were used. Mylar film was placed at the bottom of the mold. After the mixed material was conveyed into the mold in excess, a second piece of mylar film was placed on top of the mold and pressed with a metal plate to squeeze out excess material. The plate was then removed with the mylar still in place on top of the material and each side was cured for one minute using The MAX Lite. After being stored in 37°C water for 24 hours, specimens were tested on an Instron device for measurement of diametral tensile strength rising a 10 mm/minute crosshead speed.

777

<img file="CA2118959A1_D0021.tif" />

Measurement of Adhesion to dentin: Bond Strength to

Dentin

Extracted human teeth used for the shear bond strength test was treated in 1% sodium hypochlorite for 18 to 24 hours and stored in distilled water in a refrigerator at about 4°C until needed. The teeth were washed with water, mechanically sanded with 120/320/600 grit carborundum paper until a flat dentin surface was exposed.

The teeth were then individually prepared as follows. Each tooth was blown dry with compressed dry air to ensure the dentin surface was free from noticeable moisture. A small plastic straw with 3.7 mm inner diameter and 2 to 3 mm in length was filled with mixed material and seated on the dentin so as to form a post without pressure. The upper open end of the straw was covered with a thin film and cured with The MAX Lite for 40 seconds. The specimens were then stored in distilled water at 37°C for more than 24 hours. The teeth were then vertically mounted in a one inch phenolic ring using self curing polymethyl methacrylate resin to provide a base for testing with the post at right angles thereto. The mounted specimens were loaded in shear in an Instron device for measurement of adhesion of the post to dentin at 5 mm/minute crosshead speed. The load was applied parallel to the prepared

4;

2118939 tooth surface and at right angles to the post until fracture occurred. The shear bond strength was calculated.

Method of measuring fluoride release

Four 1 x 20 mm (diameter) discs of each material were made and conditioned to a constant weight. The initial average weight in grams was recorded. Duplicate setups were used. Each setup consisted of a 500 ml flask which contained 300 ml deionized water, Soxhlet containing two specimens in the thimble, and a water condenser. The specimens were extracted for 24 hours by refluxing water. The water extract was cooled to room temperature and measured for fluoride content. Then, the Soxhlet extraction were repeated with fresh deionized water for six more times.

Using an ion selective electrode, the fluoride concentration in parts per million(ppm) was determined for each extract. The average ppm of the duplicates were recorded.

Having generally described the invention, a more complete understanding can be obtained with reference to certain specific examples, which are included for purposes of illustration only. It should be understood that the invention is not limited to the specific details of the Examples.

EXAMPLE 1

6FDMA is the reaction product of 1 mole of hexafluoroisopropylidine-2,2 bis(phthalic acid anhydride) and 2 moles of 2-hydroxyethyl methacrylate, identified hereafter as HEMA.

13.3 grams (0.03 moles) hexafluoroisopropylidine2,2bis (phthalic acid anhydride) and 12.6 grams (0.097 moles) of HEMA and 0.6 grams of butylated hydroxytoluene are heated in a 100 ml round bottom flask equipped with a thermometer and a water cooled condenser with a drying tube. The mixture is stirred while heating slowly to 100°C. Thereafter the temperature is maintained at 110°C for one hour, then 16 hours overnight at 50°C, then a further 3.5 hours at 110°C. The solution is cooled to room temperature. The solution contains 70% by weight of 6FDMA and 30% by weight of HEMA and has IR absorptions at: 2500-35Q0cmY broad; 1715cm^-1 broad; 1630cm^-1; 1130-1450cm^-1 broad; 1170cm^-1; 950cm^-1; and 800 cm^-1 multiplet.

EXAMPLE 2

SYNTHESIS OF BTDMA

BTDMA is the reaction product of 1 mole of 3,3',4,4'- benzophenone tetracarboxylic acid dianhydride and 2 moles 2-hydroxyethyl methacrylate. When prepared in an excess of 2-hydroxyethyl

<img file="CA2118959A1_D0022.tif" />

<img file="CA2118959A1_D0023.tif" />

methacrylate the HEMA serves as a solvent for the esterification reaction.

grams (0.155 moles) 3,3',4,4¹-benzophenone tetracarboxylic acid dianhydride (Aldrich Chem) is reacted with 82.7 grams HEMA (0.635 moles) (Aldrich Chemical) at 120°C for 1 hour to provide a clear thick liquid containing BTDMA in an excess HEMA, having IR absorptions at 3000 to 3550cm,^-1, very broad; 2950cm^-1broad; 1720cm^-1, broad; 1630cm^-1; 1370-1450cm^-1 multiplets; 1100-1340cm^-1 very broad; 1160cm^-1; 940cm^-1; 810cm^-1; and 650cm^-1. This solution contains 70% by weight of BTDMA and 30% of HEMA.

EXAMPLE 3

SYNTHESIS OF OEMA

OEMA is the reaction product of 1 mole 4,4' oxydiphthalic anhydride (chemical name: 5,5’-oxybis1,3-isobenzo furandione) and 2 moles of HEMA.

35,6 grams (0.115 moles) of 4,4'-oxydiphthalic anhydride and 58.0 grams (0.045 moles) of HEMA are reacted at 110°C for 4 hours to provide a clear oily solution of OEMA in an excess of HEMA, having a viscosity of 5250 cps, and IR absorptions at 27003550cm^-'¹ very broad; 1715cm^-1 broad; 1630cm^-1,

1590cm^-1;

1570cm^-1;

50cm^-1 ?

, 1400cm^-1; 1360cm^-1; 1100-1330cm^-1 ;

1165cm^-1; 940cm,-¹; 810cm^-1, and 785cm^-1. This solution contains 70% by weight OEMA and 30% by weight of HEMA.

EXAMPLE 4

SYNTHESIS OF OPMA

OPMA is the reaction product of 1 mole oxydiphthalic anhydride and 2 moles of HPMA.

18.0 grams (0.058 moles) of 4,4’ oxydiphthalic anhydride (Occidental Petroleum) and 32.6 grams (0.226 moles) HPMA (Aldrich) are reacted at 110°C while stirring for 3 hours at 110°C to provide a clear oily solution of OPMA in an excess of HPMA having a viscosity after reaction of 3250 cps at 23°C and the OPMA having IR absorptions at 3100-3550cm^-1 very broad; 2900-3000cm^-1 ; 1715cm^-1; 1630cm^-1; 1590cm^-1; 1570cm^-1;

1445cm^-1; 1400cm^-1; 1100-1330cm^-1 ; 1060cm^-1; 940cm^-1;

810cm^-1. This solution contains 70% by weight OPDMA and 30% by weight of HEMA.

EXAMPLE 5

PREPARATION OF STDMA

STDMA is the reaction product of 1 mole of 4,4' sulfonyldiphthalic dianhydride (STDA) and 2 moles of HEMA. In this example STDMA is prepared in an excess of HEMA.

26.9 grams (0.207 moles) HEMA, 10.4 grams (0.029 moles) STDA and 0.044 grams BHT are placed in a 100ml flask and heated to 90°C. The mixture is held for 1.5 hours at 90°C to 95°C and 1.33 hours at 115°C to 120°C. Then 0.11 grams triphenyl phosphine, 10.2 grams (0.028 moles) STDA, and 4.3 grams (0.033 moles) HEMA are added to the mixture and held at 115°C to 120°C for an additional 1.5 hour to form a solution containing 68.6% by weight of STDMA and 31.4% by weight of HEMA having IR absorptions at 3500cm^-1, very broad; 1715cm^-11635cm^-1; 1300cm^-1 broad, and 1150cm^-1 broad. This solution contains 68.6% by weight of STDMA and 31.4% by weight of HEMA.

EXAMPLE 6

PREPARATION OF OEMA IN TEGMA

OEMA is the reaction product of 1 mole of oxydiphthalic dianhydride (ODPA) and 2 moles of HEMA.

In this example product is prepared in triethylene glycol dimethacrylate (TEGDMA) as a solvent.

19.6 grams (0.063 moles) of ODPA, 30 grams (0.23 moles) HEMA, 0.046 grams of monomethyl hydroquinone and 20 grams of TEGDMA as a solvent are placed in a 250 ml flask. The mixture is heated with stirring to 95°C to 100°C, and 0.06 grams of triphenyl phosphine as catalyst is added and held at 100°C for an additional

<img file="CA2118959A1_D0024.tif" />

minutes. Following this 15.5 grams (0.05 moles) of ODPA and 0.03 grams of triphenyl phosphine are added at 110°C. After stirring at 110°C for 1.5 hours, 0.02 grams of triphenyl phosphine is added and held for one hour at 110°C and then held at 50°C for 7 days. At the end of that time all anhydride is consumed. The reaction forms a solution containing 76.5% by weight OEMA and 23.5 % TEGMA. The OEMA which has IR absorptions at 2500 to 3550 cm^-1 very broad; 1700 cm^-1broad; 1630cm^-1, 1100-1450cm^-1 very broad; 1050cm^-1; 950cm^-1; and 780-900cm^-1. This solution contains 76.5% by weight of OEMA and 23.5% by weight of TEGMA.

PREPARATION OF POWDERS IN EXAMPLES 7-9 FOR USE IN

EXAMPLES 10-16

Strontium aluminofluorosilicate glass used to make powders in Examples 7-9 is a source of cations in the cement compositions of Examples 10-16, and is made by fusing aluminum oxide, silica, strontium fluoride, aluminum fluoride, aluminum phosphate, and cryolite according to procedures disclosed in U.S. Patent 4,814,362 to form particles which are milled to a mean particle size of 5.5 microns. These particles have the following analysis with all elements except fluorine being calculated as the oxide of the element:

Composition of aluminofluorosilicate glass particles

Parts by weight

A1₂O₃ sio₂

Na₂O

SrO

F

24.6 32.1

28.7

12.3

P2O₅

EXAMPLE 7

Powder is prepared by placing 98.78 grams of strontium aluminofluorosilicate glass powder, 1.0 grams of benzoyl peroxide and 0.2 grams of ascorbyl palmitate and 0.02 grams of cupric acetylacetonate in a bottle and tumbling for an hour, and passing the tumbled mixture through a 3 25 mesh sieve to form a powder product.

EXAMPLE 8

Powder is prepared by placing 79.0 grams of strontium aluminofluorosilicate glass powder, 1.0 grams of benzoyl peroxide, 0.2 grams of ascorbyl palmitate 0.02 grams of cupric acetylacetonate and 19.6 grams of barium aluminum silicate glass powder (Corning Incorporated 7724 glass) having an average particle size of 1 micron in a bottle and tumbling for an hour, and then passing the tumbled mixture through a 325 mesh sieve to form a powder product.

EXAMPLE 9

Powder is prepared by placing 79.2 grams of strontium aluminofluorosilicate glass powder, 20.0 g barium aluminum silicate glass powder, and 0.8 grams of ethyl dimethylamino-benzoate in a bottle and tumbling for an hour, and passing the tumbled mixture through a 325 mesh sieve to form a powder product.

As discussed above the powders of Examples 7-9 are prepared by mixing the components of each composition as in the proportions given in parts by weight shown in Table 1.

TABLE 1

<td></td><td> Composition of the powder of Example 7</td><td> Composition of the powder of Example 8</td><td> Composition of the powder of Example 9</td>

<td> Strontium aluminofluorosilicate glass</td><td> 98.78</td><td> 79.0</td><td> 79.2</td>

<td> Benzoyl peroxide</td><td> 1.0</td><td> 1.0</td><td> —</td>

<td> ascorbyl palmitate</td><td> . 0.2</td><td> 0.2</td><td> --</td>

<td> cupric acetylacetonate</td><td> 0.02</td><td> 0.02</td><td></td>

<td> barium alumina silicate ethyl dimethylamino</td><td></td><td> 19.6</td><td> 20.0 0.8</td>

benzoate

<img file="CA2118959A1_D0025.tif" />

EXAMPLE 10

CEMENT grains of a solution of 70% by weight 6FDMA and 30% by weight HEMA prepared as described in Example 1 is stirred with 5.0 grams of water to form a liquid formulation. 1 gram of this liquid formulation is mixed with 2 grams of powder product prepared as described in Example 7. This mixture reacts with a work time of 3.0 minutes and a set time of 4.0 minutes to form a cement having a bond strength to dentin of 13.8 MPa, a bond strength to enamel of 9.7 MPa.

EXAMPLE 11

CEMENT grams of thick liquid containing BTDMA in an excess of HEMA prepared as described in Example 2 is stirred with 5.0 grams of water to form a liquid formulation. 1 gram of this liquid formulation is mixed with 2 grams of powder product prepared as described in Example 7. This mixture reacts with a work time of 2.3 minutes and a set time of 3.5 minutes to form a cement having a bond strength to dentin of

7.6 MPa, a bond strength to enamel of 10.2 MPa, a diametral tensile strength of 28.6 MPa, and a compressive strength of 116 MPa.

<img file="CA2118959A1_D0026.tif" />

21183

EXAMPLE 12

CEMENT grams of oily solution of OEMA in an excess of HEMA prepared as described in Example 3 is stirred with 10.0 grams of water to form a liquid formulation. 1 gram of this liquid formulation is mixed with 2 grams of powder product prepared as described in Example 7. This mixture reacts with a work time of 2.5 minutes and a set time of 3.5 minutes to form a cement having a bond strength to enamel of 9.4 MPa, a diametral tensile strength of 32.3 MPa, a compressive strength of 130 MPa, and a bond strength to amalgam of 17.9 MPa.

EXAMPLE 13

CEMENT grams of oily solution containing OPMA in an excess of HPMA prepared as described in Example 4 is stirred with 5.0 grams of water to form a liquid formulation. 1 gram of this liquid formulation is mixed with 2 grams of powder product prepared as described in Example 7. This mixture reacts with a work time of 2.5 minutes and a set time of 3.5 minutes to form a cement having a bond strength to dentin of 6.3 MPa, a bond strength to enamel of 18.6 MPa, a diametral tensile strength of 27.0 MPa, a compressive strength of 12 0 MPa and a bond strength to amalgam of

20.2 MPa.

EXAMPLE 14

CEMENT

85.9 grams of STDMA prepared in an excess of HEMA as described in Example 5 is stirred with 8.0 grams of water and 6.1 grams of HEMA to form a liquid formulation. 1 gram of this liquid formulation is mixed with 2 grams of powder product prepared as described in Example 7. This mixture reacts with a work time of 2.5 minutes and a set time of 3.0 minutes to form a cement having a bond strength to dentin of 6.5 MPa, a diametral tensile strength of 26.7 MPa, and a compressive strength of 139 MPa.

EXAMPLE 15

CEMENT

91.8 grams of oily solution containing OEMA in an excess of HEMA prepared as described in Example 3 is stirred with 8.0 grams of water and 0.20 grams camphorquinone to form a liquid formulation. 1.0 gram of this liquid formulation is mixed with 1.8 grams of powder product prepared as described in Example 9. This mixture reacts (with a work time of 10 minutes and a set time of 120 minutes if allowed to self-cure), and

<td></td><td></td><td></td><td></td><td> 2118959</td>

<td colspan="2"> is irradiated with</td><td> visible</td><td> light from</td><td> The MAX Lite</td>

<td> having a</td><td colspan="2"> bond strength to</td><td> dentin of</td><td> 11.7 MPa, a</td>

<td> diametral</td><td> tensile</td><td> strength</td><td> of 37.2</td><td> MPa, and a</td>

compressive strength of 154 MPa.

EXAMPLE 15A

SELF-CURING, TWO COMPONENT, POWDER AND LIQUID CEMENT

0.92 grams of the liquid prepared as described in

Example 3 and 0.08 grams of water are dissolved in one another to form a liquid. 1.0 grams of this liquid is added to 2.0 grams of the strontium aluminofluorosilicate containing powder of Example 7. The consistency of the mixture is suitable for use as a luting or crown and bridge or orthodontic cement or as a pit and fissure sealant. Polymerization is induced by the redox polymerization system of benzoyl peroxide, ascorbyl palmitate and copper acetyl acetonate. The liquid contains 8.0% water, and wets the tooth when the cement is applied. The powder and liquid compositions are as follows:

<img file="CA2118959A1_D0027.tif" />

189

PERCENT

POWDER BY _WEIGHT

Strontium fluoroaluminosilicate cement 98.83 (Glass of example 7)

Benzoyl peroxide 1.00 ascorbyl palmitate 0.15 copper acetyl acetonate 0.02

LIQUID___

Product of example 3 92.00

Water 8.00

This cement is adhesive to dentin and enamel without further treatment except cleansing with pumice. The mixture has a work time during which it can be handled and used of 3.0 minutes and a set time of 4.5 minutes. The hardened product has a compressive strength of 149 MPa, a diametral tensile strength of 3 4.2 MPa, a dentin bond strength in 2 4 hours of 10.5 MPa and a bond strength to enamel, in 2 4 hours of 9.0

MPa.

EXAMPLE 15B

CEMENT grams of oily solution containing OEMA in an excess of HEMA prepared as described in Example 3 is stirred with 8 grams of water to form a liquid formulation. 1 gram of this liquid formulation is mixed with 2 grams of powder product prepared as described in Example 9. This mixture has a work time of 10.0 minutes and a set time of 12 0 minutes. This mixture reacts to form a cement having a compressive strength of 117 MPa.

EXAMPLE 16

CEMENT grams of oily solution containing OEMA in an excess of HEMA prepared as described in Example 3 is stirred with 10.0 grams of water to form a liquid formulation. 1 gram of this liquid formulation is mixed with 2 grams of powder product prepared as described in Example 8. This mixture reacts to form a cement. This mixture reacts with a work time of 2.5 minutes and a set time of 2.7 minutes to form a cement having a bond strength to dentin of 7.8 MPa, and a compressive strength of 152 MPa.

As described above the powder products of Examples 7 through 9 are mixed with the corresponding liquid in Examples 10 through 16 at a ratio as shown in the following table to provide cement mixtures. The liquids are prepared with stirring and then mixed with the powders prepared as described in Examples 7 through 9. The resulting cements exhibited mechanical and other properties as shown in Table 2.

<img file="CA2118959A1_D0028.tif" />

TABLE 2

SELF CURE CEMENT COMPOSITIONS

<td> Example Number</td><td> 10</td><td> 11</td><td> 12</td><td> 13</td><td> 14</td><td> 15</td><td> 15A</td><td> 1ΞΒ</td><td> 16</td>

<td> LIQUID FORMULATION</td><td colspan="9"></td>

<td> 6FDMA Containing Product of Example 1 (g)</td><td> .95</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td> BTDMA Containing Product of Example 2 (g)</td><td></td><td> .95</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td> STDMA Containing Product of Example 5 (g)</td><td></td><td></td><td></td><td></td><td> .859</td><td></td><td></td><td></td><td></td>

<td> OEMA Containing Product of Example 3 (g)</td><td></td><td></td><td> .90</td><td></td><td></td><td> .918</td><td> .92</td><td> .92</td><td> .90</td>

<td> OPMA Containing Product of Example 4 (g)</td><td></td><td></td><td></td><td> .95</td><td></td><td></td><td></td><td></td><td></td>

<td> HEMA (g)</td><td></td><td></td><td></td><td></td><td> .061</td><td></td><td></td><td></td><td></td>

<td> Water (g)</td><td> .05</td><td> .05</td><td> .01</td><td> .05</td><td> .08</td><td> .080</td><td> .08</td><td> .08</td><td> .10</td>

<td> Camphorqu inone</td><td></td><td></td><td></td><td></td><td></td><td> .002</td><td></td><td></td><td></td>

<td> POWDER FORMULATION</td><td colspan="9"></td>

<td> Powder of Example 7, (g)</td><td> 2.00</td><td> 2.00</td><td> 2.00</td><td> 2.00</td><td> 2.00</td><td></td><td> 2.00</td><td></td><td></td>

<td> Powder of Example 9,(g)</td><td></td><td></td><td></td><td></td><td></td><td> 1.80</td><td></td><td> 2.00</td><td></td>

<td> Powder of Example 8, (g)</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td> 2.0</td>

<td> POLYMERIZED PRODUCT PROPERTIES</td><td colspan="9"></td>

<td> Bond to Dentin, MPa</td><td> 13.8</td><td> 7.6</td><td> 6.6</td><td> 6.3</td><td> 6.5</td><td> 11.7</td><td> 10.5</td><td></td><td> 7.8</td>

<td> Bond to Enamel, MPa</td><td> 9.7</td><td> 10.2</td><td> 9.4</td><td> 18.6</td><td></td><td></td><td> 9.0</td><td></td><td></td>

<td> Bond to Amalgam, MPa</td><td></td><td> —</td><td> 17.9</td><td> 20.2</td><td></td><td></td><td> —</td><td></td><td></td>

<td> Diametral Tensile MPa</td><td></td><td> 28.6</td><td> 32.3</td><td> 27-0</td><td> 26.7</td><td> 37.2</td><td> 34.2</td><td></td><td></td>

<td> Compressive strength MPa</td><td></td><td> 116,</td><td> 130.</td><td> 120.</td><td> 139.</td><td> 154.</td><td> 149</td><td> 117</td><td> 152</td>

<td> Work time, min</td><td> 3.0</td><td> 2.3</td><td> 2.5</td><td> 2.5</td><td> 2.5</td><td> 10.0</td><td> 3.0</td><td> 10.0</td><td> 2.5</td>

<td> Set time, min</td><td> 4.0</td><td> 3.5</td><td> 3.5</td><td> 3.5</td><td> 3.0</td><td> 120.0</td><td> 4.5</td><td> 120.0</td><td> 2.7</td>

2118

ONE COMPONENT LIGHT CURED CEMENT FILLING MATERIAL

COMPOSITIONS

In each of Examples 17 through 21 as shown in the Table 3 liquids are formulated containing an acid functional monomer, diluent comonomers, camphorquinone and catalysts and accelerators for polymerization of the polymerizable material. The strontium aluminofluorosilicate glass is added with stirring to form a one-component precatalyzed mixture adapted to be polymerized by irradiation from The MAX Lite as described previously.

EXAMPLE 17 grams of the oily solution of OEMA in an excess of HEMA prepared as described in Example 3 is stirred with 0.8 grams ethyl dimethylaminobenzoate and 0.2 grams of camphorquinone to form a liquid solution. This liquid solution is stirred with 74.0 grams of strontium aluminumfluorosilicate glass to form a onecomponent precatalyzed product. Upon irradiation of this precatalyzed cement product by visible light from The MAX Lite a polymerized cement product is formed having a bond strength to dentin of 7 MPa, a bond strength to enamel of 12.5 MPa, a diametral tensile strength of 28.6 MPa and a compressive strength of

165.6 MPa.

EXAMPLE 18 grams of the oily solution of OPMA in an excess of HPMA prepared as described in Example 4 is stirred with 0.8 grams ethyl dimethylaminobenzoato and 0.2 grams of camphorquinone to form a liquid solution. This liquid solution is stirred with 74.0 grams of strontium aluminum silicate glass to form a onecomponent precatalyzed product. Upon irradiation of this precatalyzed cement product by visible light from The MAX Lite a polymerized cement product is formed having a bond strength to dentin of 7.5 MPa, a bond strength to enamel of 13.8 MPa, a diametral tensile strength of 2 5.8 MPa and a compressive strength of

167.1 MPa.

EXAMPLE 19 grams of the solution containing 70% by weight of 6FDMA and 30 % by weight HEMA prepared as described in Example 1 is stirred with 0.8 grams 4-ethyl dimethylaminobenzoate and 0.2 grams of camphorquinone to form a liquid solution. This liquid solution is stirred with 74.0 grams of strontium aluminum silicate glass to form a one-component precatalyzed product. Upon irradiation of this precatalyzed cement product by visible light from The MAX Lite a polymerized cement product is formed having a bond strength to dentin of

10.1 MPa a diametral tensile strength of 20.5 MPa and a compressive strength of 157 MPa.

EXAMPLE 20

8.75 grams of the oily solution of OPMA in an excess of HPMA prepared as described in Example 4 is stirred with 12.5 grams of urethanedimethacrylate (prepared as described in Example 1 of U.S. Patent 4,657,941) 3.75 grams of glycerol dimethacrylate (Rohm

Tech. D1108), 0.5 grams of MDEA (methyl diethanolamine) and 0.2 grams of camphorquinone to form a liquid solution. The liquid solution is stirred with 74.0 grams of strontium aluminumfluorosilicate glass to form a one-component precatalyzed product. Upon irradiation of this precatalyzed cement product by visible light from The MAX Lite a polymerized cement product is formed having a bond strength to dentin of 7.9 MPa, a bond strength to enamel of 10.7 MPa, a diametral tensile strength of 27.5 MPa and a compressive strength of 141.5 MPa.

EXAMPLE 21

20.79 grams of the oily solution of OEMA in TEGDMA prepared as described in Example 6 and 2.3 6 grams TEGDMA are stirred with 0.181 grams 4-ethyl dimethylaminobenzoate and 0.046 grams of camphorquinone

<img file="CA2118959A1_D0029.tif" />

<img file="CA2118959A1_D0030.tif" />

211895» to form a liquid solution. This liquid solution is stirred with 76.62 grams of strontium aluminumfluorosilicate glass to form a one-component precatalyzed product. Upon irradiation of this precatalyzed cement product by visible light from The MAX Lite a polymerized cement product is formed having a bond strength to dentin of 4.0 MPa, a bond strength to enamel of 4.7 MPa, a diametral tensile strength of 28.9 MPa and a compressive strength of 182.6 MPa.

The compositions and physical and mechanical properties of the products described in Examples 17 through 21 are shown in Table 3.

TABLE 3

COMPOSITIONS OP ONE COMPONENT

VLC CEMENTS

Example Number 17 18 19 20 21

LIQUID FORMULATION__

6FDMA Containing Product of — — 25

Example 1 (g)

<td colspan="3"> OEMA Containing Product of</td><td rowspan="2"> 25</td><td rowspan="2"></td><td colspan="2" rowspan="2"> 20.79</td>

<td> Example 6 (g) OEMA Containing</td><td> Product</td><td> of</td>

<td> Example 3 (g) ΟΡΜΑ Containing</td><td> Product</td><td> of</td><td> __</td><td> 25</td><td> 8.75</td><td></td>

Example 4 (g)

UDMA (g) — — — 12.5

GLYCEROL DIMETHACRYLATE* 3.75 (g)

TEGDMA (g)2.35

POWDER FORMULATION

<td> Sr GLASS (g) EDAB (g) CQ (g) MDEA (3) (g)</td><td> 74.0 0.8 0.2</td><td> 74.0 0.8 0.2</td><td> 74.0 0.8 0.2</td><td> 74.0 0.2 0.5</td><td> 7 6.62 0.181 0.046</td>

<td> POLYMERIZED PRODUCT</td><td></td><td></td><td></td><td></td><td></td>

<td> PROPERTIES</td><td></td><td></td><td></td><td></td><td></td>

<td> B.S. TO DENTIN (MPa)</td><td> 7</td><td> 7.5</td><td> 10.1</td><td> 7.9</td><td> 4.0</td>

<td> B.S. TO ENAMEL (MPa)</td><td> 12.5</td><td> 13.8</td><td></td><td> 10.7</td><td> 4.7</td>

<td> D.T.S. (MPa,</td><td> 28.6</td><td> 25.8</td><td> 20.5</td><td> 27.5</td><td> 28.9</td>

<td> C.S. (MPa)</td><td> 165.6</td><td> 167.1</td><td> 157</td><td> 141.5</td><td> 182.6</td>

* ROHM TECH D 1108

I

<img file="CA2118959A1_D0031.tif" />

21i895S

The product of example 2, BTDMA in an excess of HEMA, is strongly orange-yellow colored as prepared. When formulated into a cement according to example 11, and polymerized, the cement has a strong green color which is not practical for use in dental cement compositions, although it exhibits other desirable properties. In contrast, the products of Examples 1, 3, 4 and 5 are light straw colored before polymerization. When formulated into cement compositions, according to Examples 10 and 12 through 20 the products are milky white translucent cements that are suitable for rendering in tooth shades by the addition of pigments.

EXAMPLE 22

CEMENT grams of oily solution containing OEMA in an excess of HEMA prepared as described in Example 3 is stirred with 5 grams of water to form a liquid formulation. 1.0 gram of this liquid formulation is mixed with 3 grams of powder product prepared as described in Example 7. This mixture reacts to form a cement having soxhlet fluoride release over a period of seven days as follows;

SELF ADHESIVE CEMENT

<td> Day</td><td> Daily Fluoride Release pg F~/gram of composite</td><td> Cumulative Fluoride Release pg F^-/gram of composite</td>

<td> 1</td><td> 1817.28</td><td> 1817.28</td>

<td> 2</td><td> 837.69</td><td> 2654.97</td>

<td> 3</td><td> 525.40</td><td> 3180.37</td>

<td> 4</td><td> 548.22</td><td> 3728.59</td>

<td> 5</td><td> 368.63</td><td> 4697.22</td>

<td> 6</td><td> 351.90</td><td> 4449.12</td>

<td> 7</td><td> 305.46</td><td> 4754.58</td>

<td></td><td> It should be understood</td><td> that while the present</td>

invention has been described in considerable detail with respect to certain specific embodiments thereof, it should not be considered limited to such embodiments but may be used in other ways without departure from the spirit of the invention and the scope of the appended claims.

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