CA1076296A - Photo-polymerizable dental restorative and tooth coating composition comprising an oligomeric resin, an acrylate monomer, an organic peroxide and a photosensitizer - Google Patents

Photo-polymerizable dental restorative and tooth coating composition comprising an oligomeric resin, an acrylate monomer, an organic peroxide and a photosensitizer

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Publication number
CA1076296A
CA1076296A CA266,370A CA266370A CA1076296A CA 1076296 A CA1076296 A CA 1076296A CA 266370 A CA266370 A CA 266370A CA 1076296 A CA1076296 A CA 1076296A
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CA
Canada
Prior art keywords
composition
organic peroxide
resin
weight
photosensitizer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
CA266,370A
Other languages
French (fr)
Inventor
Eric T. Reaville
Gudrun M. Streicher
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Monsanto Co
Original Assignee
Monsanto Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Monsanto Co filed Critical Monsanto Co
Application granted granted Critical
Publication of CA1076296A publication Critical patent/CA1076296A/en
Expired legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/026Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from the reaction products of polyepoxides and unsaturated monocarboxylic acids, their anhydrides, halogenides or esters with low molecular weight
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00Preparations for dentistry
    • A61K6/80Preparations for artificial teeth, for filling teeth or for capping teeth
    • A61K6/884Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
    • A61K6/887Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S525/00Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S525/922Polyepoxide polymer having been reacted to yield terminal ethylenic unsaturation
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S528/00Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S528/92Polymers useful for replacing hard animal tissues, e.g. dentures, bones
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31511Of epoxy ether

Abstract

Abstract of the Disclosure A dental restorative composition and tooth coating comprising the combination of an adhesive resin of the oligomeric BIS-GMA type, a low molecular weight reactive extender or diluent acrylate, an organic peroxide catalyst or free radical initiator and, as a photosensitizer, Michler's ketone.

Description

~'7~2~ C~11-21-0255 Background of the Invention This invention relates to a photo-polymerizable composition and, more particularly, to a rapidly photoeurable resin composition useful for dental restorative and tooth coating purposes.
Adhesive compositions that harden when exposed to ultraviolet light have been used for dental restorative purposes for quite some time. In particular, various acrylic resins have been used as binders in tAese compositions. Compounds disclosed in U.S. Patents 3,066,112, 3,179,623 and 3,194,784 are typical lG Of these acrylic resins. Especially noteworthy is a compound having the formula C~3 OH CH 0~l CH
2 C l-O-C~i2C~ICIl2-0~ -C- ~ _o-c~12CHC~2-0-ll~c=cH2 O C~3 . . .
which is glycidyl methacrylate derivative of bisphenol-A, sometimes referred to as bisphenol-A-bis-(~-methacrylato-2-hydroxypropyl) etner or, more conveniently, as ~IS-GMA.
The successful use of BIS-GMA in the adhesive sealing of pits and fissures for caries prevention with use of ultra-violet light has been described by ~uonocore in ~ Amer. ~ent.
Assn. 80 (2)j 324-328 ~1970). 'l'he major components of the adhesive composition were stated to be three parts by weight of the BIS-GM~ and one par* by weight of methyl methacrylate monomer.
The adhesive, to which 2~ benzoyl methyl ether was added just before use, was painted on acid-conditioned enamel surfaces and exposed to ultraviolet light for a few seconds to induce poly-merization hardening.

In the foregoing BIS-GMA dental restorative compositions the low molecular welghtmethyl methacrylate serves essentially as a reactive extender or diluent to reduce the viscosity of the compositions, as noted in U.S. Patents 3,066,122, 3,539~533 and -2- ~
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3,709,8~6, whereby they can be conveniently used in dental a~lications. Tile benzoJl Jnetnyl ether is employed in these compositions as a photosensitizer. This is a substance which absorbs actinic radiation so as to produce free radicals which initiate polymerization and cross-linking reactions.
AnQther substance typically used in the dental res-torative com~ositions is benzoyl peroxide or a similar such compound which ~erves as a free radical initiator or catalyst for the polymerization reaction. -~
While the foregoing dental restorative compositions are useful, a chronic problem which arises in practice is in~
hibition caused by the presence of oxygen. Because of t}liS
inhiblticn by oxygen, tne desired complete hardening of the resin to the surface to which it iS applied is not obtained and, instead, a tacky surface is produced.

Brief Summary of t}le Invention In accordance with the present invention, a rapidly photo~olyrllerizable composition of the oli~omeric BIS-GMA type suitable for dental restorative and tooth coating purpos~s is provided in which cure to a tack-free surface is obtained by the use of a particular ultraviolet sensitizer together with a ~eroxide catalyst. rrhis sensitizer is the compound 4 ,li '-bis (dimethylamino) benzophenone, which also is known as Michler's ketone.
etailed Description of the Invention .: .
In general, the photo-polymerizable composition of the pre~ent invention comprises the combination of an adhesive resin of the oligomeric BIS-GMA type, a low molecular weight reactive extender or diluent acrylate~ a peroxide catalyst or -~
free radical initiator and the aforementioned Michler~s ketone.

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` 1~76~6 C-11-2~-0255 Wnile the speci~ication concludes with claims particularly pointing out and distinctly claiming the subject matter regarded as forming the present invention, it is believed that the invention and its advantages will be better understood from the following description taken in connection with the accompanying drawings in which:
FIG. 1 is a series of curves showing the oxygen pick-up with an exemplary composition of this invention when applied to a test surface and exposed to ultraviolet radiation;
FIG. 2 is a series of curves showing the oxygen pick-up with a stan~ard commercially available dental pit and fissure sealant when applied to a test surface and exposed to ultraviolet radiation.
Although the inventors are not bound by theory, it is believed that Michler's ketone on exposure to actinic radiation produces singlet oxygen which enters into the cross-linking reaction. However, because polymerization also takes place in the absence of oxygen, it is believed that another mechanism i`

also is operative.
Thus, on exposure to actinic radiation, Michler's ket~e absorbs a quantum of energy and becomes an excited state biradLcal. In the presence of oxygen, the energy of some of the excited state moleeules is dissipated by transfe~
to ground state oxygen to produce an excited state species, probably the '~ g species. Other excited state molecules may transfer their energy to the peroxide catalyst, thereby cleaving it and initiating polymerization. In the absence of oxygen, the latter reaction is believed to be predominant.

In the presence of oxygen, singlet oxygen may react with the tertiary nitrogens on Michler's ketone to produce species which enter into the cross-linking reaction. The type of ~4 ~ ~ .

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C~ 21-0255 7 6~ ~ ~

~roducts that singlet oxygen produces by reaàting with tertiary nitrogen is disclosed, for example, by Gollnick and Lindner, Tetrahedron Le~ters 1903-1906 (1973).
Irrespective of its mechanism, it has been found that use of the Michler's ketone produces a rapid cure of the oligomeric ~IS-Gi~A ty~e resin. This rapid cure is obtained fully to the substrate surface. Michler~s ketone is uniquely effective in the pre~ence of oxygen and the composition containing it and can be a~plied in a thin coating, even less than 7 microns tl-ick. ~y way of comparison, many other ketonesg including the closely related benzophenone, 494'-dimetnylbenzophenone, benzil, furil, thionil, xanthone, and antnraquinone are ineffective in the presence of oxygen.
; With certain other photosensitizers, such as thioxanthone and benzoyl ether, it is necessary to apply relatively thick coatings, thereby making it necessary to wipe off or abrade the uncured portion on the surface.
Although Michler's ketone has been disclosed heretofore as a photosensitiæer in~ for example, U.S. patents 3,597,21~, 3,701,721 and 3,772,062, and numerous other patents, the present inventors are not aware of any previously suggested use in a dental restorat.ive composition as defined herein.
It was unexpected to find that Michler's ketone, as dis-tinguished from other ultraviolet photosensitizers, has the aforesaid unique properties in dental restorative compositions.
The amount of Michlerls ketone used in the dental res~
torative composition and tooth coating of this invention need be only a small but effective amount and generally ranges from about ~.25~ to about 2% by weight of the total com-position. For convenient usage, Michler's ketone can be incorporated in the dental restorative composition from admixture with~a suitable solvent such as, for example, chloroform and the like organic solvents.

1~'7~Z~
C~ 21-0255 The oligomeric ~IS-GMA type resin employed in the dental restorative composition of this invention can be con-veniently represented by the following formula:

Ch2-C-C-¦ ~2C~IC1~20<~>-C~ CH2CHc~2-o-c-c-cH2 wherein n ranges from about 1 to 10. Preferably, n = 1 to 5 and mos~ preferably n = 1 to 3. Mixtures of these compounds c~n also be used, for example, a mixture of about equal parts of c~pounds in which n = 1 and n - 3.
The oligomeric BIS-GMA type resin can be prepared by well-known general methods. A preferred method involves first ~orming the polyepoxide and then esterifying the terminal groups. Thus, at least about 2 moles of epihalohydrin can be reacted with about one mole of propylidene diphenol and a sufficient amount of alkali to combine with the halogen of the epihalohydrin to form the polyepoxide whi~h includes structures represented by the following formula:

~CH2CHCH20~-C~-O) CH3 n The chain thus formed may be terminated at one or both ends by an epoxy group II2 C - C - CH2 - ' :.

O

or ~ hydroxyl. Methacrylic acid is then reacted with the poly~
epoxide at the terminal groups to form the desired oligomeric BIS-GMA type resin.

~(17~Z~;
The reac-tive extender or diluent acrylate used in the ~esent inven~ion is a relatively low molecular weight, low viscosity, aliphatic methacrylate monomer such as, for example, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacryla~e, n-butyl methacrylate, iso-butyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, the amyl methacrylates~e~hylene dimethacrylate, butylene dimetnacrylate~ ethylene glycol monomethacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate. These diluents are used in amounts sufficient to lower the viscosity and make the oligomeric BIS GMA resin composition pourable at ordinary room temperatures such as at about ~-25C. Generally, use of from about 3U~ to about 80~ by weight of the oligomeric BIS-GMA
polymer with from about 70% to about 20~ by weight of the diluent acrylate is suitable and use of about equal parts ~y weight of the oligomeric BIS-GMA and the diluent acrylate is preferred.
As the peroxide catalyst or free radical initiator for use in the present invention, any of the known organic peroxides are suitable such as, for example, benzoyl peroxide, phthaloyl peroxide, napthoyl peroxide, alkyl- or alkanoyl-su~tituted pe~oxides such as acetyl, caproyl, lauroyl, tertiary butyl and di-t-~utyl peroxides, alkyl-, alkanoyl- or chloro-substituted benzoyl peroxides such as acetyl benzoyl peroxide, ~ :
dimethyl benæoyl peroxide and 2, 4-dichloro-benzoyl peroxide, hydroperoxides such as di-isopropyl-benzene nydroperoxide,t-butyl .
hydroperoxide, and cumene ~ydroperoxide,and still other peroxides ~ ~:
such as cinnamoyl peroxide, methyl ethyl ketone peroxide and :~
urea peroxide.
.

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:

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~L~76~
Only minor amounts of the peroxide initiators are re~uired and generally from abou-t 0.5`'6 to about 2~ by weight of the total composition is suitable.
It will be ap~reciated that various other substallces can also be employed in the dental resin composition of this invention provided that they do no-t interfere with the basic and novel effects of tne require~ components as defined ilerein.
i'hus, s~slall amounts of pigments such as, for exa~ple, ~he ~`

fluorescent pigments described in U.S. Patent 2,481,844 can be used in the composition, if desired. Inert fillers such as finely ~ivided crystalline quartz, fused silica, aluminum oxide, lithium aluminum silicate and the like inorganic min~rals an~ vitreous particulate fillers such as disclosed in U.S. Patents 3,066,112 and 31503,128 can be incorporated ini ~e dental resin composition to the extent desired.
Application of the a~oresaid composition for dental restorative and tootn coating purposes can be made by con-ventional techniques such as by brushin~, spraying or dipping to ~ve a tnin ~ilrn such as 5 to lU0 microns, on a tooth or dental support which is then exposed to actinic radiation for a few seconds. Thus, exposure to long wave ultraviolet light of flux of about lO5 ergs/cm2/sec for abou-t 15 to 30 seconds is eJninently satisfactory.
In practice, the composition of this invention can be packaged in kit form suitable for distribution to dentists ~ -and dental su~ply houses. For this purpose and in order to pro te shelf stability~ it is desirable to divide the com-ponents into at least two parts in which the organic peroxide free radical initiator is separate from the oligomeric ~IS-GMA
type resin. In this kit form,the diluent acrylate and Michler's ketone can ~e conveniently placed in admixture with the resin in one container and the benzoyl peroxide can be conveniently ~7~;2~
put into admixture with an organic solvent in a second container to thereby reduce the number of cont~iners used.
Prior to use, the dentist or dental technician can readily comDine the contents of the two containers to thereby render the complete composition into an admixture suitable for application to teeth.

An illustrative example of such a kit form of the composition of the present invention comprises a two-package kit of solutions A and B. Solution A can comprise, for example, 48.0 grams of the oligomeric BIS-GMA type resin, 51.3 grams of methyl methacrylate and 0.7 grams of Michler's ketone. Solution can comprise, for exam~le, 16 grams of benzoyl peroxide in 84 grams of chloroform or similar sucn solvent. Prior to use, one part of solution B can be admixed with eight parts of solution A and the mixture then applied to teeth. Other examples of the preparation of the composition in kit form will be apparent to the person skilled in the art.
The following examples will further illustrate the invention although it should be understood that the invention is not limited to these examples. In these examples, the oligomeric BI~ A used waæ Dow*Resin XD 35 86 . 00 . ~ .

A pourable resin mixture is made by t~inning 66.7 parts by weight of oligomeric BIS-GMA with 33,3 parts by weight o~ methyl methacrylate. To this mixture is added 40 parts by weight o~ a 5% by weight solution of benzoyl peroxide in methyl me~hacrylate and 20 parts by weight of a 5% by weight solut.ion :

of 4, 4'-bis-~dimethylamino) benzo~henone dissolved in ehloroform.
The components are thoroughly mixed and then applied by brushing9 spraying and dipping to gi~e a thin film, 5 to 100 microns, on : :

_ * Trademark ~76Z~6 C~ 21-0255 a support which when exposed to long wave ultraviolet light of a flux about 105 ergslcm2/sec becomes tack free in fifteen to thirty seconds.

~XAMPL~ 2 Threel~urable resin mixtures are made ~y thinning 66.7 parts by weight of oligomeric ~IS-GMA with 33.3 parts by weigAt of, respectively, (a) methyl methacrylate, (b~ ethyl methacrylate, and (c) n-propyl methacrylate. Into each mixture is then dissolved one part by weight of 4,4'-bis~(dimethylamino) be.nzophenone. To each mixture is added 40 parts by weight of a 5~ solution of benzoyl peroxide dissolved in methyl methacrylate.
The mixtures are applied by brushing, spraying and dipping to acid-etched, extracted human -teeth in film thickness of S to 100 microns. On exposure to long wave ultraviolet llght of flux of 105 ergs/cm2/sec, the surfaces become tack-free in about fifteen to thirty seconds.
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The Knoop hardneæ of ~he foregoing films is about 22.
'llhe Knoop hardness is measured by the length of an indenture produced by a pyranidyl shaped diamond under a load in accordance with the standard test described in T~ L_~e:9~6~lb National Bureau of Standards 23, 39 (1939) _ By contrast, Nuva Seal (g), a conunercially ~vailable dental pi~ and fissure sealant , did not become tack-free on similar treatment after 10 minutes exposure to ultraviolet light. Excess material had to be removed by rubbing with a wet co-tton ball, which lQft a rough surface of a substantially lower Knoop hardness of abvut 11. EXAM LE 3 In order to demonstrate the excellent oxygen pick-up of the dental restorative composition of this invention, the following tests were carried out in which the aforem~ntioned dental ~it and fissure sealant sold under the trademark Nuva Seal ~ was used as a standard for comparison.
Mixture A
A mixture was made as follows:
Component Percent by Wei~ht Oligomeric BIS-GMA 47.3 Methyl methacrylate 50.6 ~enzoyl peroxide 1.4 Michler's ketone 0.7 100 ~ 096 .
ntains BIS-GMA and methyl methacrylate formulation disclosed in J. Amer. Dent. Assn. 80t2), 324-8 (1970).

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Mixture B
A portion of Mixture A was diluted with 0.2 gram hexa-d~canol per gram of Mixture A to form Mixture B.
Mixture C
A portion of Mixture A was diluted with O.2 gram squalene per gram of Mixture A to form Mixture C.
Mixture D
This mixture consisted of undiluted Nuva Seal ~ dental pit and fissure sealant.
Mixture E
A portion of Mixture D was diluted with 0.4 gram methyl methacrylate and O.2 gram hexadecanol per gr~n of Mixture D to form Mixture E.
Mixture F
A por~ion of Mixtur~ D was diluted with O.4 gram methyl methacrylate and 0.2 gram squalene per gram of Mixture D to form Mixture F.
In the foregoing mixtures, hexadecanol was used as a common solvent to vary the consistency of the compositions being tested and squalene was used as a well-known singlet oxygen acceptorl In Mixtures ~ and F, methyl methacrylate was used as a reactive diluent to provide a viscosity equivalent to that of M.ixtures B and C, respectively.
Samples of the foregoing resin mixtures were each drawn with a wire wound rod on a sheet of release paper~ Transkote ER ~, about 3 inches x 4 inches in size, ~llowed to stand five minutes in air and then inserted in an opening of a Teflon ~ plastic :
gasket. The gasket was about l/B inch thick and had an opening size of about 4 inehes x 5 inches. On the top and bottom sides o the gasket, clear glass pla~es were clamped to effectively seal the sheet from the atmosphere. A connection on the bottom plate led from the opening in the gasket to a fin-e bore capillary 5 ~:~

C~ 21-0255 2~
used as a manometer, which was filled with butyl acetate.
Upon irradiation of the resin mix*ures through the top plate by ultraviolet light, flux of about 4 x 10 3 ergs/cm /sec, the uptake of oxygen was measured by the drop in the manometer fluid.
Figure 1 of the drawings shows the uptake of oxygen with ~ixtures A, B, and C (Curves Mix. ~, B and C) wher~as Figure 2 show~ the oxygen uptake with Mixtures D, E and F
(Curves Mix. D, ~, and F). In the curves shown in these figures the oxygen uptake in centimeters of bu~yl acetate is plotted against time in minutes following the onset of exposure to ultra-violet radiation.
All of Mixtures A through F were drawn with a standard #24 wire wound rod to give a final film thickness of about 22 microns. Figure 1 shows an additional curve G in which Mixture A
was drawn with a #8 wire wound rod to yield a final film thicXness of about 7 microns.
The results demonstrate the excellent rapid oxygen pick-up of the composition of the present invention when compared with the commercially available Nuva Sea ~. The total oxygen pick-up also was substantially better with Mixtures A, B and C as evident by *he amounts shown in the critical early part of the time curve.
In addition, a11 of the films formed by Mixtures A, B and C were tack-free whereas ~he films produced by Mixtures D, E and F were tacky.
Various other exampl~s will be apparent to the person skilled in the art after reading the foregoing description without departing from the spirit and scope of the invention. All such further examples are included within the scope of the claims as appended hereto.

'~:

Claims (7)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:
1. A photo-polymerizable composition suitable for dental restorative and tooth coating purposes comprising from about 30% to about 80% by weight of oligomeric resin having the formula wherein n ranges from about 1 to 10, and mixtures thereof, from about 70% to about 20% by weight low molecular weight low viscosity diluent aliphatic acrylate monomer, from about 0.5% to about 2% by weight organic peroxide free radical initiator and from about 0.25% to about 2% by weight photosensitizer comprising 4,4'-bis(dimethylamino)-benzophenone.
2. The composition of claim 1 in which n ranges from about 1 to 5.
3. The composition of claim 1 in which the diluent acrylate is methyl methacrylate.
4. The composition of claim 1 in which the organic peroxide is benzoyl peroxide.
5. The composition of claim 1 in which n ranges from about 1 to 5, the diluent acrylate is methyl methacrylate and the organic peroxide is benzoyl peroxide.
6. The composition of claim 1 in kit form suitable for use by admixture thereof in which the organic peroxide is packaged in a container separate from the oligomeric resin.
7. In the preparation of a photopolymerizable composition suitable for dental restorative and tooth coating purposes comprising a polymerizable acrylate resin, a low molecular weight low viscosity diluent aliphatic acrylate monomer, an organic peroxide free radical initiator and a photo-sensitizer, the improvement comprising providing as the polymerizable acrylate resin an oligomeric resin having the formula wherein n ranges from about 1 to 10, and mixtures thereof, and providing as the photosensitizer the compound 4,4'-bis(dimethyl-amino)benzophenone, all said components being present in the relative amounts set forth in claim 1.
CA266,370A 1975-11-24 1976-11-23 Photo-polymerizable dental restorative and tooth coating composition comprising an oligomeric resin, an acrylate monomer, an organic peroxide and a photosensitizer Expired CA1076296A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US05/634,554 US4097994A (en) 1975-11-24 1975-11-24 Dental restorative composition containing oligomeric BIS-GMA resin and Michler's ketone

Publications (1)

Publication Number Publication Date
CA1076296A true CA1076296A (en) 1980-04-22

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