WO1995034270A1 - Dental composition and method - Google Patents

Abstract

The invention provides dental cement compositions and methods of using them for binding hard tooth material, metal and ceramic. The cement compositions include shelf stable complexes of ethylenically unsaturated monomers reacted with cations. The cements have superior adhesion to tooth without separtely acid etching dentin or enamel. Compositions are useful as dental luting cements, liners, pit and fissure sealants, bases and restoratives.

Description

DENTAL COMPOSITION AND METHOD

This is a continuation-in-part of US patent

application serial number 08/049,221 filed April 19,

1993.

The invention relates to dental compositions and

methods of use thereof to bind hard tooth, metal and

ceramic. The invention provides compositions including

complexes formed by reacting multivalent cation with

acid moieties of ethylenically unsaturated Monomers and

prepolymers. The invention provides compositions with

superior adhesion to dentin, enamel and cementum

without the need for separate steps of acid etching dental enamel to adhere thereto. 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 compositions of the invention show improved mechanical strength, for example, improved bond strength to tooth and are less sensitive to the

effects of moisture.

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 polyal enoic

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 melt-

fabricable 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 melt-

fusible linear polyimide of 2,2-bis(3,4-

dicarboxyphenyl) -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.

Denyer et al in U.S. Patent 4,457,818 discloses

dental compositions from urethane acrylate, diacrylate

monomer, camphorquinone and dimethylaminoethyl

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- (N,N-Dimethylamino)benzoic acid or ester thereof.

Bowen in U.S. Patent 4,588,756 discloses multi-

step 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

polyimides obtained therefrom.

Engelbrecht in U.S. Patent 4,872,936 teaches

dental cement mixtures containing polymerizable

unsaturated monomers and/or oligomers and/or

prepolymers containing acid groups and/or their

reactive acid-derivative 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.

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.

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.

Rheinberger et al in Canadian Patent Application

2,038,695 discloses polymerizable dental materials.

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

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 acid-derivative 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 is to provide new

dental compositions useful as filling materials, cavity

liners and bases, cements, and pit and fissure sealants

other restorative materials which are adhesive to tooth structure.

It is an object of the invention to provide a composition which reduces the steps and time required

to adhere metal or ceramic to tooth structure.

It is an object of the invention to provide an

adhesive composition for adhesion between tooth structure and/or bone and polymeric composites.

It is an object of the invention to provide dental

compositions that are relatively inexpensive and easy to manufacture.

"Monomer" as used herein means monomer or oligomer.

"Set" as used herein means a polymerizable

composition undergoes a change so that it becomes firm, stiff and nonpliable. As used herein "The MAX Lite" means THE MAX™, a

curing unit for light-polymerizable dental materials

sold by Dentsply International Inc. through its L.D.

Caulk Division.

Throughout this disclosure unless otherwise

specified amounts of each component of a composition are in percent by weight.

BRIEF DESCRIPTION OF THE INVENTION

The invention provides dental compositions and

methods of using them for adhering to hard tooth,

structures, metal and ceramic. The compositions

include shelf stable complexes of ethylenically

unsaturated monomers reacted with cations. These

compositions have superior adhesion to tooth without

separately acid etching dentin or enamel. Compositions

of the invention are useful as dental luting cements,

liners, bases and restoratives pit and fissue sealants.

In accordance with a method of polymerization of the invention is provided the sequence of steps of forming a substantially pliable polymerizable composition,

including polymerizable complex coated particles within

the scope of the general formula:

wherein each U independently is a moiety having at

least one acid group and at least one polymerizable

group, each M is a multivalent cation of particle P

which forms a complex by bonding to one or more U, and

t, r and q each independently is a number having an

average value of 1 or more, storing the polymerizable composition for at least 12 hours, and applying the

polymerizable composition to a tooth.

DETAILED DESCRIPTION OF THE INVENTION

Compositions of the invention provide superior

adhesion to dentin, enamel and bone. In a preferred

embodiment 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.

In accordance with the invention is provided a

method of polymerizing polymerizable composition which

includes a polymerizable salt (complex) within the

scope of the general formula (Al) and/or a novel

material within the scope of general formula (Al') :

(U)_r - (M)_q (Al)

wherein each U independently is a moiety having at least one acid group and at least one polymerizable group, each M is a multivalent cation which forms a

complex by bonding to one or more U; P is a particle,

r, t, and q each individually is a number having an

average value of 1 or more. In general formula Al' M

is a cation of particle P. Preferably the particle is

glass or ionomeric polymer. This composition is stable

and adapted to not set in order of increasing

preference for at least 12 hours, 24 hours, or 36

hours, more preferably for at least 7 days and most preferably for at least 1 year in the absence of

polymerization initiation. t is preferably greater than 100, more preferably greater than 1,000 and most

preferably greater than 10,000. A composition in accordance with a preferred embodiment of the invention

includes a substantial portion of polymerizable salt

within the scope of general formula Al in equilibrium

with polymerizable acid(s) and a source of multivalent cation(s) . The polymerizable salt in such compositions

is preferably formed by mixing a polymerizable acid and

a source of multivalent cations in the presence of

water. The polymerizable salt is preferably in equilibrium with the polymerizable acid and a source of

multivalent cations for extended periods of time, for

example, more than one year. These compositions do not

require hermetic sealing to prevent substantial setting

as is required by prior art compositions. Thus, these

compositions advantageously form, for example, one

component compositions which do not substantially set,

and are thus, shelf stable preferably for more than one

year. It is preferred that the salt forms on the outer

surface, perferably as a coating on glass particles

used as multivalent cation sources, and that upon polymerization of the polymerizable group a stronger

material is formed than in prior art compositions which are multicomponent systems and/or do not include water

as a component of the composition applied to a tooth. Preferably these compositions are mixed with Monomers

and/or prepolymers and applied to a tooth. These compositions preferably include at least one Monomer

and/or polymers which does not include an acid moiety.

More specifically the invention provides a

polymerizable composition which includes a

polymerizable salt (complex) within the scope of the general formula (Bl) and/or a novel material within the

scope of the general formula (Bl') :

(Y)₀(B)_s(A)_p (M)₍ (Bl)

(Y)_(B)_s(A) tf- P (Bl')

wherein each Y independently is a polymerizable group,

each A independently is an acid group, each B

independently is a organic moiety, each M independently

is a multivalent cation which forms a complex by

bonding to one or more A; P is a particle and o, p, q,

r, s, and t each independently is a number having an

average value of at least 1. Preferably M is a

multivalent ion of a glass particle. This composition

is adapted to not set for at least 24 hours in the

absence of polymerization initiation.

Preferably polymerizable compositions in

accordance with the invention include at least 1

percent by weight, more preferably at least 3 precent

by weight of polymerizable complexes within the scope

of general formula (Al) . Complexes within the scope of general formulas, Al

and Bl, preferably have molecular weights less than

100,000; more preferably less than 20,000 and most

preferably less than 5,000 and especially preferred are

such complexes having molecular weights less than

1,000.

Particulate material within the scope of general

formulas Al' and Bl' preferably have a particle size

having a longest dimension in order of increasing

preference of: less than 1 mm, less than 0.1 mm, less

than 0.01 mm or less than 0.001 mm.

Dental compositions of the invention include

polymerizable unsaturated substituted aromatic complexes within the scope of the general formula (I) :

(I)

I ⁰I I °I * I_> I ^Rιo ^O I^Ri3 I ° I I °I I °I wherein X is O, S, S, S, N, P, P, P, P, O - P - O, l l l l l

OR,

^R11 ^0R12

C -,

wherein R_x and R₂ each independently is a polymerizable

unsaturated moiety having from 2 to 13 carbon atoms,

R₃, R₄, R₅, and R_e 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, R_X1, 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,

Z and Z₂ each independently is a moiety including an

acid group,

a, m and n each independently is 0 or 1, b, and p independently is an integer from 1 to 10, 1 is

from 1 to 3, and

M is a multivalent cation which reacts with acid

moieties to form a complex.

In accordance with a preferred embodiment of the

invention R_x and R₂ each independently is:

0 0

1 1 1 1

C - ^■ F - O - C C = CH

*8

wherein R₇ a divalent carbon containing radical and

R₈ is hydrogen, halogen or alkyl having from 1 to

10 carbon atoms.

In a preferred embodiment of the invention

compounds are provided withi the scope of general

formula I wherein n and m are zero, X is oxygen,

sulfonyl or ditrifluoromethyl; and R_λ and R₂ are

0

I I ^<?i c - o CH₂- CH₂- 0 - C - C = CH₂

I I Most preferably compounds within the scope of general

formula I are those wherein X is oxygen or

ditrifluoromethyl, and M is barium, calcium, strontium

or aluminium. Preferred polymerizable unsaturated

groups R and R₂ independently are alkenyl, alkenoxy,

cycloalkenyl, arylalkenyl, and alkenaryl moieties; with

vinyl, and styryl moieties being more preferred, and

acryl and methacryl moieties that constitute the

polymerizable groups of many monomers in dental

materials being especially preferred.

Exemplary R_! and R₂ (meth) crylate moieties include:

O I I

O CH, CH, O C CH = Cr

O CK II I * O - CH - CH - O - C - C = CH ;

CH, O C l ^J II I^d

(- O - CH - CH- -) _n O - C - C = CH₂;

O CH, II I ^d (O - CH₂ - CH ₂-) _n- O - C - C = CH₂;

O CK II I ^J (O - CF - CF -) - O - C - C = CH ; where n preferably is an integer from 1 to 10.

Preferably R_x and R₂ are (meth)acryloyloxyethyl moieties.

Preferred compounds for use in complexes within

the scope of formula I include diesters which are the

adducts of 2,2-bis(3,4-dicarboxylphenyl) hexafluoropropane anhydride, 4,4'-oxydiphthalic

anhydride, 4,4'-sulfonyldiphthalic anhydride, respectively with 2-hydroxyethyl methacrylate. In a

preferred embodiment at least two aromatic rings of a

compound for use in complexes with the scope of formula

I are joined through at least one saturated carbon, oxygen or sulfonyl.

Aromatic dianhydrides preferred for making

compounds for use in complexes 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.

Dental compositions in accordance with a preferred

embodiment of the invention include an acid functional

polymerizable organic ester for use in complexes 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 liquid diluents, and/or filler adjuvants.

Diluent preferably co-polymerizes with the

polymerizable monomer within the scope of general

formula Al. Alternatively the diluent is nonreactive with the polymerizable monomer. Water or low boiling

alcohols such as methanol, ethanol, and isopropanol are

nonreactive diluents. 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 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.

A preferred composition of the invention includes

a monomer compound for use in complexes within the scope of general formula Al, 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

composition in accordance with the invention includes a

compound for use in complexes of general formula Al,

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 for use in complexes within the scope of

general formula Al.

The compounds for use in complexes within the

scope of general formula Al 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 Al are derived acid formed

from the reaction of 4,4' -oxydiphthalic anhydride or

2,2-bis (3,4-dicarboxylphenyl)hexafluorpropane dianhydrides with a polymerizable hydroxyl or

polyhydric compound to form esters and partial esters

thereof.

The new salt 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 have been

reacted with cations, especially those of valence 2 or

greater to form poly-salts. Because the salt 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 carboxyl group itself is most preferred over other acid moieties

or the reactive acid derivative ions. Especially appropriate acid moieties are all those that react with

oxidic, mineral, ceramic, vitreous, or metallic

fillers.

Examples of these other acid moieties include:

o O o 0

1 1 1 1 I I I I

P - OH, - P OR, P - OH. and P OR, I

OH OH OH OH of -phosphorus acids wherein R is alkyl, aryl, or vinyl; the moieties -S0₂H, S0₃H, or -0-S0₃H of sulfuric acids; the moieties:

B - Oh i. - B OR. ^■ OH. and ^■ 0 - B OR,

1 1 1 1 OH OH OH OH

of boron acids wherein R is alkyl, aryl, or vinyl and

cationic acid moieties including -NR₂H+ wherein R is H

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 ion-

exchange, 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 not critically affected by moisture during hardening within

the oral cavity; 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 i 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

unsaturated carboxylic compounds for use in complexes of the present invention the preparation of a preferred series of the compounds 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 to 13 carbon atoms. This yields a

liquid product which is believed to be a mixture of

isomer monomers of general formulas II-IV:

As discussed in detail in Example 3 by reacting

one mole of oxydiphthalic anhydride with two moles of

methacryloyloxyethyl alcohol also known as 2- hydroxyethyl methacrylate .(HEMA) in the presence of

catalyst a liquid product is formed which is believed

to be a mixture of isomer monomers V-VII: (V) ft ft

(VI)

and

(vii)

I I 1 I 0 o

Monomer compounds for use in complexes within the

scope of general formula I are reactive esters which

have at least one unreacted carboxylic acid group and 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.

In accordance with the method of the invention in- vivo polymerization does not harm the patient within whom polymerization of monomer compound (or complexes)

within the scope of general formula I occurs. Preferably 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 used to form 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-

dimethylaminobenzoate (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 "set or cure" of the composition

including the salt monomers, an important

characteristic of the polymers which form is that they

have been prereacted with di- or polyvalent cations.

The salt compounds and compositions of the invention

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 in a preferred embodiment are 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 of the invention the

cations of the salts are di- and polyvalent cations,

such as Sr, Ca, Al and Ba. 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, oligomers and/or

prepolymers that do not contain any acid groups and/or

salts thereof and/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 readily reactive 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.

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.

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 salt compounds of compositions 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 salt compound within the scope of

general formula I, 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 orthodontic 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 μm to bond

close fitting appliances to prepared teeth. In one

embodiment 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 salt 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.

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 salt 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 oj£ compressjve strength using

international Standard Organization(ISO) 99i7:i99i(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 40 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 5 mm/min. Method of transverse flexural strength using

International Standard Organization(ISO)4049:1988 (F.) 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

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 0.75 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.

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

tooth surface and at right angles to the post until

fracture occurred. The shear bond strength was

calculated. Method of fluoride release - Static Extraction

A 1 mm thick by 20 mm diameter chip of the material was cured for 1 minute on each side with the

Max Lite. A tiny hole was drilled in the chip. The specimen was tied with a nylon thread, suspended in 10

ml deionized water in a plastic jar caped with a lid,

and stored in 37°C oven for one week, or otherwise

indicated. Water in each jar was decanted to a

separate 30 ml plastic beaker. The specimen in the jar

was washed in 1 ml deionized water, and the water rinse

was added to the respective beaker. To the jar, 10 ml

of fresh deionized water was added and put back in the

37°C oven for the next measurement. The solution was diluted with 11 ml Total Ionic Strength Adjustor Buffer

(TISAB) solution and measured with fluoride electrodes.

This method is used to simulate what happens in

the mouth over a long period of time. The water is changed weekly. The values are reported in ppm, in

micrograms of fluoride per gram of sample, and in micrograms of fluoride per centimeter square of sample

surface.

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) hexafluoroisopropylidine-

2,2bis (phthalic acid anhydride) and 12.6 grams (0.097

moles) of HEMA and 0.0006 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: 2500-3500cm^"1, 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

methacrylate the HEMA serves as a solvent for the

esterification reaction.

50 grams (0.155 moles) 3,3 ',4,4 ' -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^"1

broad; 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'-oxybis-

1,3-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 2700-

3550cm^"1 very broad; 1715cm^"1 broad; 1630cm^"1, 1590cm^"1;

1570cm^"1; 1450cm^"1; 1400cm^"1; 1360cm^"1; 1100-1330CIΪI^"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) hydroxypropyl methacrylate 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 SlOO-SSSOcm^"1

very broad; 2900-3000cm^"1; 1715cm^"1; 1630cm^"1; 1590cm^"1;

1570cm^"1; 1445cm^"1; 1400cm^"1; 1100-1330CITI^"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^" , very broad; 1715cm^"1 1635cm^"

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

25 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^"1

broad; 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

Strontium aluminofluorosilicate glass powder used

in Examples 12, 13 and 17 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. It has the following analysis with all

elements except fluorine being calculated as the oxide

of the element:

Composition of strontium

aluminofluorosilicate

Parts by weight

A1₂0₃ 24 . 6

Si0₂ 32 . 1

Na₂0 2 . 9

SrO 28 . 7

F 12 .3

P₂O₅ 4 . 8 The barium aluminofluorosilicate glass particles used

in Examples 8, 10 and 12 through 16 are 7726 glass sold

by Corning. It is preferably formed as disclosed in

Danielson U.S. Patent No. 4,920,082.

EXAMPLE 7

SYNTHESIS OF OEMA/GMA RESIN

31.0 grams (0.1 mole) 4,4- oxydiphthalic anhydride

(ODPA), 11.4 grams of glutaric anhydride (0.1 mole),

39.0 grams of hydroxyethyl methacrylate (HEMA), (0.30

mole), and 0.05 grams of butylated hydroxytoluene are

reacted at room temperature for 30 minutes followed by

stirring at 110°C for 2.0 hours to form a very viscous

mixture of the adduct of ODPA and HEMA (OEMA) and an

adduct of glutaric anhydride and HEMA (GMA) .

EXAMPLE 8

ONE COMPONENT VLC COMPOSITION

30.50 grams of OEMA/GMA resin are formed as

described in Example 7; 2.50 grams of water; 65.10

grams of 2,7,7,9, 15-pentamethyl-4,13-dioxo-3,14-dioxa-

5,12-diaza-hexadecane-l,16-diyl dimethacrylate (UDMA) ; 0.20 grams of camphorquinone; 0.60 grams of EDAB; 1.00

gram of 2-hydroxy-4-methoxybenzophenone (Uvinol M-40

sold by BASF) and 0.50 grams of butylated

hydroxytoluene (BHT) are stirred to form an activated

resin. 5.0 grams of the activated resin is mixed with

15.0 grams of barium aluminofluorosilicate glass powder

(67% silanated and 33% unsilanated) to form a paste

having a shelf stable polymerizable complex which does

not set within 6 months in the absence of

polymerization initiation. The paste is cured by

transmission thereinto of visible light from The Max

lite TM polymerization unit sold by Dentsply

International Inc to form a polymeric material having a

compressive strength of 31533 psi.

EXAMPLE 9

SYNTHESIS OF 6-FDMA/PMA RESIN ADDUCTS WITH HEMA

39.0 grams of HEMA, 0.06 g butylate

hydroxytoluene, and 14.8 grams of phthalic anhydride

are reacted at 100-110°C for 60 minutes. Then 44.4

grams of hexafluoroisopropylidene- 2,2-bis (phthalic

acid anhydride) is added and stirred at between 120°

and 130°C for 4.0 hours to form a clear, slightly yellow resin, mixture of 6FDMA and an adduct of

phthalic anhydride and HEMA (PMA) .

EXAMPLE 10

ONE COMPONENT VLC COMPOSITION

30.10 grams of 6-FDMA/PMA resin formed by

following the procedure of Example 9; 2.50 grams of

water; 65.10 . grams of UDMA; 0.20 grams of

camphorquinone; 0.60 grams of EDAB; 1.00 gram of 2-

hydroxy-4-methoxybenzophenone (Uvinol M-40) ; and 0.50

grams of butylated hydroxytoluene are stirred to form

an activated resin. 2.50 grams of the activated resin

is mixed with 75.0 grams barium aluminofluorosilicate

glass (60% silanted 40% unsilanated) to form a paste

having a shelf stable polymerizable complex. The paste

is cured by transmission thereinto of visible light

from a The Max lite TM polymerization unit sold by

Dentsply International Inc to form polymeric material

having a compressive strength of 29334 psi; a flexural

strength of 72.1 MPA and a flexural modulus of 8939.6

MPA. EXAMPLE 11

SYNTHESIS OF 6-FDMA/GMA RESIN:

39.0 grams (0.30 mole) hydroxyethylmethacrylate,

44.4 grams of hexafluoroisopropylidene - 2,2-bis

(phthalic acid anhydride), 12.0 grams of glutaric

anhydride and 0.06 grams of butylated hydroxytoluene

are reacted at 100°C for 4.0 hours to form a viscous

slightly yellow clean resin, mixture of 6-FDMA and an

adduct of glutaric anhydride and HEMA (GMA) .

EXAMPLE 12

A one component VLC paste composition is formed by

mixing 9.20 grams of 6-FDMA/GMA(formed by following the

procedures of Example 11), 0.80 grams of water; 15.0

grams of urethane dimethacrylate (2,7,7,9,15-

pentamethy-4, 13-dioxo-3,14-dioxa-5,12-diaza-hexadecane-

1,16-diyl dimethacrylate); 0.05 grams of

camphorquinone; 0.30 grams of ethyl-4-

dimethylaminobenzoate (EDAB); 0.0125 grams of butylated

hydroxytoluene; 0.075 grams of Uvinol M-40; 37.5

silanated strontium aluminofluorosilicate glass powder

and 37.5 grams of silanated barium

aluminofluorosilicate glass. The paste is cured by transmission thereinto of visible light from The Max

lite (TM) polymerization unit sold by Dentsply

International Inc to form polymeric material having a

flexural strength of 82 MPa; a flexural modulus of

10948; and compressive strength of 31954 psi.

EXAMPLE 13

10.75 grams of adduct of hexafluoroispropylidene-

2, 2-bis (phthalic anhydride) and 2-hydroxyethyl

methacrylate, 4.61 grams of 2-hydroxyethyl

methacrylate, 7.2 grams of triethylene glycol

dimethacrylate, and 0.98 grams of water are mixed with

0.048 grams of bicyclo (2,2,1) heptane-2, 3-dione

1,7,7-trimethyl, 0.144 grams of 4-ethyl

dimethylaminobenzoate, 0.24 grams of methanone (2-

Hydroxy-methoxyphenyl) phenyl, and 0.024 grams of 2,6-

bis(l, 1-dimethethyl) -4-methyl phenol to form a

polymerizable liquid. 37.24 grams of silanated

strontium aluminofluorosilicate, 38.0 grams of barium

aluminofluorosilicate glass, 0.76 grams of aerosil R-

972 are formed into a power blend which is then mixed

with the polymerizable liquid to form a one-component

light curable dental adhesive paste composition which does not set within 6 months without polymerization

initiation. The paste is cured by transmission

thereinto of visible light from a The Max lite TM

polymerization unit sold by Dentsply International Inc

to form polymeric material having the properties shown

in Tables 1 and 2.

Table 1

COMPARISON OF PHYSICAL PROPERTIES

STANDARD STANDARD SELF ADHESIVE

PROPERTY ISO 9917 ISO 4049 COMPOSITE OF EXAMPLE 13

COMPRESSIVE STRENGTH (MPa) >130 234

FLEXURAL STRENGTH (MPa) >50 69 FLEXURAL MODULUS (MPa) 7953

DIAMETRAL STRENGTH (MPa) 43

OPACITY Co . 70 >0 .35 <0 . 90 >0.35,<0.55

RADIOPACITY mm Al >lmm Al 3 mm

COLOR STABILITY SLIGHT CHANGE PASS

SENSITIVE TO AMBIENT LIGHT NO CHANGE PASS IN 1 MINUTE

DEPTH OF CURE (mm) >2 3 4.5

ADHESION TO DENTI (MPa) unetched

ADHESION TO ENAMEL(MPa) unetched

ACID SOLUBLE:

Pb content mg/kg <100 <2 Rs content mg/kg <2 <1

% SALT FORMED BY TITRATION AFTER 2 MONTHS STORAGE AT 70°F TEMPERATURE 20.8

Table 2

STATIC FLUORIDE RELEASE

μg/gram of sample Cum. μg/gram of sample

142.54 142.54

111.83 254.37

95.16 349.54

91.15 440.68

72.30 512.99

73.69 586.67

59.59 646.26

62.68 708.94

Sample used to prepare Table 2 had an average

weight grams of 0.678, an average diameter cm of 2.039,

and average thickness cm of 0.094 and an average

surface area of 7.13.

EXAMPLE 14

A one component VLC composition is formed by

stirring 10.75 grams of 6-FDMA (formed by following the

procedure of Example 1), 4.61 grams of HEMA, 7.2 grams

of TEGDMA, 0.98 grams of distilled water, 0.048 grams

of camphorquinone, 0.144 grams of EDAB, 0.24 grams of

Uvinol M-40 and 0.024 grams of BHT at room temperature

to form a homogeneous activated resin. 2.4 grams of

the activated resin is mixed with 7.6 grams of a powder

blend of 99 grams of barium aluminofluorosilicate

glass, 1 gram of Aerosil R-972 to make a stable paste. The paste is cured to form a polymeric adhesive having

a compressive strength of 225 MPa, a bond strength to

dentin of 1673 psi and a fluoride release shown in

Table 3.

EXAMPLE 15

One component VLC sealant is formed by mixing

25.24 grams of OEMA, (formed by following the procedure

of Example 3) 12.5 grams TEGDMA, 2.0 grams of distilled

water, 0.04 grams of camphorquinone, 0.2 grams EDAB and

0.016 grams BHT to an homogeneous activated resin. 40

grams of barium aluminofluorosilicate glass is added to

the resin to form a stable one component VLC sealant

having which upon exposure to visible light forms a

polymeric material having a compressive strength of

25521 psi, flexural strength 42 MPa, flexural modulus

of 4071 MP and releases fluoride as shown in Table 3.

EXAMPLE 16

One component VLC sealant is formed by stirring

30.93 grams 6-FDMA formed by following the procedure of

Example 1, 1.93 grams distilled water , 14.98 grams

TEGDMA, 0.05 grams of camphorquinone, 0.24 grams EDAB and 0.025 grams BHT to form an activated resin, then

add 51 grams barium aluminofluorosilicate glass and

0.77 grams aerosil R-972. The mixture is mixed to form

a stable one component sealant which upon curing by

exposure to visible light forms a polymeric material

having a compressive strength of 31552 psi, dimetrial

tensile strength of 5085 psi, flexural strength 74

MPa, flexural modulus of 3722 MPa., and a bond strength

to enamel of 1160 psi.

The static fluoride release for samples of

products from Examples 14, 15, and 16 are shown in

Table 3.

TABLE 3

STATIC RELEASE OF FLUORIDE IN MICROGRAMS OF

FLUORIDE PER GRAM OF SAMPLE

Polymeric Polymeric Polymeric

Product of Product Of Product of

Week Example 14 Example 15 Example 16

1 857.5 509.6 479.4

2 720.3 296.3 433.0

3 545.3 296.3 376.9

4 458.6 374.2 327.4

6 373.3 283.6 311.9

7 337.4 299.6 279.5

8 282.9 265.4 146.1

9 268.7 261.8 146.1

10 239.7 247.3 146.1

11 232.0 226.8

12 200.8 201.2

Polymerizable Salt Formation:

1.0 grams Ca(OH)₂, and a solution of 0.95 grams

6FDMA, 0.27 grams HEMA and 0.08 grams water are mixed.

The IR spectrum of the mixture is measured immediately

and shows neutralization of the acid and a broad IR

absorption at 1390cm^"1 and 1580cm^" , indicating salt

formation.

1.0 grams of Al₂0₃, a solution of 0.65 grams 6FDMA,

0.27 grams HEMA and 0.08 grams of water are mixed. The IR spectrum of the mixture indicates salt formation by

absorption at 1390cm^"1 and 1580 cm^"1.

EXAMPLE 17

A resin mixture of 6 grams of an adduct of

succinic anhydride and glycerol dimethacrylate (SGMA) ,

1.2 grams of dipentaeryothritol pentaacrylate phosphate

(DPEPAP) , prepared as described in US Patent 4,514,342,

2.4 grams of 2,2-bis [4- (2-hydroxy-3-

methacryloxypropoxy)phenyl] , (Bis-GMA) , 0.573 grams of

water, 0.02 grams of camphorquinone, 0.049 grams of

EDAB and 0.01 grams of butylated hydroxytoluene (BHT)

is mixed in a 50 ml plastic beaker to form a

homogeneous liquid. Then, 31 grams of strontium

aluminofluorosilicate glass powder is added and mixed

to form a uniform paste. The paste is cured by

transmission thereinto of visible light from a The Max

lite TM polymerization unit sold by Dentsply

International Inc to form a polymeric material having

static fluoride release shown in Table 4. TABLE 4

WEEKS ppm μg μg/gram Cum.μg/gram

1 7.5400 82.94 93.37 93.37

2 4.0050 44.06 49.59 142.96

3 3.4850 38.34 43.16 186.12

4 2.7900 30.69 84.44 220.67

5 2.2700 24.97 28.11 248.78

6 2.0800 22.88 25.76 274.54

7 1.9300 21.23 23.90 298.44

8 1.9150 21.07 23.71 322.15

9 1.6450 18.10 20.37 342.52

10 1.1450 12.60 14.18 356.70

11 1.2500 13.75 15.48 372.18

12 1.1480 12.53 14.22 386.39

13 1.0325 11.36 12.79 399.18

14 1.0325 11.36 12.79 411.96

It should be understood that while the present

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.

Claims

What is claimed is:

1. A polymerizable dental composition, comprising: a

polymerizable material within the scope of the general

formula:

wherein each U independently is a moiety having at

least one acid group and at least one polymerizable

group,

each M independently is a multivalent cation of

particle P and forms a complex by bonding to one or more U, and

r, q and t each independently is a number having

an average value of 1 or more, said composition being

adapted to not set for at least 24 hours in the absence of polymerization initiation.

2. A polymerizable composition, comprising: a

polymerizable material within the scope of the general

formula: r TY) - (B) _S (A) _p ^"|_r (M) =K p wherein each Y independently is a polymerizable

group, each A independently is an acid group,

each B independently is a organic moiety, and

each M independently is a multivalent cation of

particle P and forms a complex by bonding to one or

more A,

r, t, o, p, q, and s each independently is a

number having an average value of 1 or more, said

composition being adapted to not set for at least 24

hours in the absence of polymerization initiation.

3. The composition of claim 1 or 2 wherein said M is barium, calcium, strontium or aluminum.

4. The composition of claim 1 or 2 wherein A is a carboxylic moiety and Y is alkylene.

5. The composition of claim 1 or 2 further comprising acrylic monomer, and said acrylic Monomer and said

complex each independently comprises at least 1 percent by weight of said composition.

6. The composition of claim 1 or 2 wherein said

complex comprises at least 3 percent by weight of said composition.

7. The composition of claim 1 or 2 wherein P comprises

glass with a particle size having a longest dimension

less than 0.1 mm and further comprising a polymerization initiator.

8. The composition of claim 1 wherein said complex is

within general formula

0 O i^ R ORj O O O

1 I I I I I I I I I I I I wherein X is O, S, S, S, N, P, P, P, P, P - O,

I I I I

ft

- C

R_x and R₂ each independently is a polymerizable

unsaturated moiety having from 2 to 13 carbon atoms,

R₃, R₄, R₅, and R₆ each independently is hydrogen,

halogen, alkyl of from 1 to 10 carbon atoms or

halogenated alkyl of from 1 to 10 carbon atoms,

R₉, R₁₀, R_1X, 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,

Z_x 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; 1 is a

integer from 1 to 3 and M is multivalent cation.

9. The composition of Claim 8 in the composition further comprising a diluent comonomer.

10. The composition of Claim 8 in a composition

further comprises glass particles.

11. The composition of Claim 8 wherein n and m are zero.

12. The composition of Claim 8 wherein X is oxygen or

wherein R3 and R4 are fluoπnated methyl moieties. R.

13. The composition of Claim 1 in a composition

further comprising a source of fluoride ion.

14. The composition of claim 1 or 2 wherein said

complex has a molecular weight less than 100,000.

15. The composition of claim 1 or 2 wherein said

complex has a molecular weight less than 20,000.

16. The composition of claim 1 or 2 wherein said

complex has a molecular weight less than 5,000.

17. The polymerizable complex of claim 1 or 2 wherein

said complex has a molecular weight less than 1,000.

18. A method of adhering a dental composition to tooth, comprising:

providing a dental cement, said cement comprising

a polymerizable composition, comprising: a

polymerizable material within the scope of the general

formula:

t

wherein each U independently is a moiety having at

least one acid group and at least one polymerizable group,

each M is a multivalent cation of glass particle P

and forms a complex by bonding to one or more U,

q and r each independently is a number having an

average value of 1 or more, storing said composition for at least 24 hours in

the absence of polymerization initiation, applying said cement to tooth.

19. The method of Claim 18 wherein said applying is

without prior treatment of said tooth material, except

cleaning to increase adhesion of said cement to said

tooth.

20. The method of Claim 18 wherein M is barium,

calcium, aluminum or strontium.

21. The method of Claim 18 further comprising a

diluent comonomer.

22. The method of^' claim 18 wherein said complex is

within general formula:

O O Rg R.

^'10 o o O

I I I I I ^0Rι: I I I I I I wherein X is O, S, S, S, N, P. P, P, O P O,

I I

O

^R11 ^0Ri2 ° "3

- C -, I

R_x and R₂ each independently is a polymerizable

unsaturated moiety having from 2 to 13 carbon atoms,

R₃, R₄, R₅, and R₆ each independently is hydrogen,

halogen, alkyl of from 1 to 10 carbon atoms or

halogenated alkyl of from 1 to 10 carbon atoms,

R₉, R₁₀, R₁₁₇ 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,

Z 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; 1 is an

interger from 1 to 3 and M is multivalent cation.

23. The method of Claim 22 wherein n and m are zero.

R₃ I

24. The method of Claim 22 wherein X is oxygen or C

I wherein R₃ and R₄

R₄ are fluorinated methyl moieties.

25. A dental composition for adhering to a tooth

comprising:

a polymerized dental product formed from a dental

composition comprising: a polymerizable material within

the scope of the general formula:

wherein each U independently is a moiety having at

least one acid group and at least one polymerizable

group,

each M is a multivalent cation of glass particle P

and forms a complex by bonding to one or more U, and q, t and r each independently is a number greater than or equal to 1,

said composition being adapted to not set for at

least 24 hours in the absence of polymerization

initiation.

26. The dental composition of claim 25 wherein said polymerized product is a dental filling material, pit

and fissure sealant, luting cement, base or orthodontic

cement.

27. A method of polymerization, comprising the following sequence of steps:

a) forming a substantially pliable polymerizable

composition, comprising: a polymerizable complex within

the scope of the general formula: (U)_r - (M)_q wherein each U independently is a moiety having at

least one acid group and at least one polymerizable

group,

each M is a multivalent cation which forms a complex by bonding to one or more U, and

r and q each independently is a number having an

average value of 1 or more, b) storing said polymerizable composition for at

least 12 hours, and

c) applying said polymerizable composition to a

tooth.

28. The method of claim 27 further comprising

polymerizing said polymerizable complex in said

polymerizable composition applied to said tooth to form

polymeric material.

29. The method of claim 28 wherein said polymeric

material is a dental luting cement, liner, base or

restorative.

30. The method of claim 27 wherein said polymerizable

complex forms a coating on an outer surface of said

particle.

31. The method of claim 30 wherein said particle

comprises glass with a longest dimension less than 0.1

mm.

32. The method of claim 30 wherein said particle

comprises ionomeric polymer with a longest dimension

less than 0.1 mm.