CA1309105C - Dental resin materials - Google Patents
Dental resin materialsInfo
- Publication number
- CA1309105C CA1309105C CA000505596A CA505596A CA1309105C CA 1309105 C CA1309105 C CA 1309105C CA 000505596 A CA000505596 A CA 000505596A CA 505596 A CA505596 A CA 505596A CA 1309105 C CA1309105 C CA 1309105C
- Authority
- CA
- Canada
- Prior art keywords
- weight percent
- dental
- bis
- adhesive according
- polycarbonate
- 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 - Fee Related
Links
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/70—Preparations for dentistry comprising inorganic additives
- A61K6/71—Fillers
- A61K6/77—Glass
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Epidemiology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Oral & Maxillofacial Surgery (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Dental Preparations (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
A dental resin adhesive comprises BIS - GMA and a polycarbonate dimethacrylate of the formula
A dental resin adhesive comprises BIS - GMA and a polycarbonate dimethacrylate of the formula
Description
~ - t 309 1 05 pEI`II 17 .1 CAN~DA
DENTAL llESIN ~!AI~ ;b ¦This invention relates to polymeric condensation products which have been found to be useful in restorative dentistry. More particularly, it relates to polymeric condensation products wtlich can be used as a principal component o~ resinous adhesives, and can be used in dental reRtorative agents. The resLnou~s adhesives of this invention are suitable ~or bonding to virtually all types of dental surfaces, including enamel, dentin, portcelain and metallic sur~aces. They are especially useful in a system for bonding dental restorative materials to exposed dentin.
Filled compositions contalning the resinous adhesives as components are useful, depending on filler content, as crown ¦ and bridge materials, as luting agents or cements, as orthodont c ealants, etc.
In recent years, materials used for dental restoration have comprised principally methacrylate polymers. Typical of these polymeric substances are the acrylic resinous materials disclosed in U.S. Patents No. 3,066,112, No.
3,179,623, No~ 3,194,784, No. 3,751,399 and No. 3,926,906.
Especially noteworthy is the compound which is the condensation product of bisphenol A and glycidyl methacrylate, 2,2'-bis [4-(3-methacryloxy-2-hydroxy propoxy)~phenyl]-propane (hereinafter abbreviated to "BIS-GMA"). Other methacrylate polymers, such as ethylene glyco~
dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate, are also in general use as diluents, polyurethanedimethacrylate is also used as a principle lS polymer in dental restorative materials o~ this type. Since BIS-GMA is highly viscous at room temperature, however, it is generally diluted with a monomer having a lower viscosity such as the aforementioned alkylene glycols or other compatible materialsl including trimethylol propyl trimethacrylate, 1,6-hexanediol dimethacrylate, 1,3-butanediol dimethacrylate, and the like.
~ U ~1 UJ
When these acrylic re inous materials were first developed, they were used unfilled for dental restorative purposes. However, because thcsc acrylic materials exhibit high coefficients of thermal expansion relative to the coefficient of thermal expansion for tooth structure, these unfilled substances soon proved to be less than satis~actory. The disparity in thermal expansion, coupled with high shrinkage upon polymerization, resulted in poor marginal adaptability and ultimately led to secondary decay.
Furthermore, the wear and abrasion characteristics and the overall physical, mechanical and optical properties of these unfilled acrylic resLnous materials were quite poor. Thus, from the o~ltset, composite dental restorative materials containing these methacrylate resins and fillers were developed. The fillers are generally inorganic filler materials based on silica~ silicate glass or ~uartz.
Over the years there have been a number of refinements in the resin matrix component, in the ~iller component, and in the other additives -- notably antioxidants, ultraviolet absorbers, polymerization initiators, polymerization accelerators, etc. -- in dental restorative materials.
There are now available materials which exhibit high diametral tensile strength, excellent optical properties and polishability, and low water absorption wh~le, at the same time, complying with all of the requirements specified in ADA Specification No. 27 for direct filling resins.
Particularly suitable restorative materials are the new compositions having improved inorganic filler materials such 5 as those disclosed in my co-pending application Serial No.
636,970 filed on August 2, 1984, now U.S. Patent No.
4,547,531, disclosing self-curing 2-component compositions, and my application Serial No. 677,595 filed on December 3, 1984, now U.S. Patent No. 4,544,359, disclosing visible light curable compositions.
All of these dental restorative materials are required to adhere permanently to the tooth structure. GeneralIy, the tooth surface is treated with an acid such as 30 - 50 wt. 3 orthophosphoric acid, which etches the enamel tooth sur~ace and exposes enamel rods in honeycomb prismatic structure thereon, ~here adhesion of the cured polymeric material is improved via micromechan`ical interlocking. In addition to this process o etching, the prior art teaches the use of various additives and improved monomeric mixtures which are designed to provide improved adhesion.
Although the acid etching technique by itself or coupled with modification of the resinous material to increase adhesive capability has been beneficial in effectin~ the bonding of dental restorative materials to tooth enamel, there has heretofore been no completely .
.; ' . .
- 1 30q 1 05 satisfactory process for adhering such restorative materials to dentin. Acid etching is not suitable for bonding dental restorative materials to dentin because the tubular structure of dentin provides passageways to the tooth pulp.
The acid would cause great inflammati'on and pain to the patient anfl ulti~atelv lead to ~ul~al necrosis. Furthermore, the hi~h percentage or orqanic (protein) màterial in the dentin results in a lower degree of adhesion as compared with enamel.
There has recently been proposed a method for improving adhesion o~ dental composite materials to dentin surfaces which involves the successive application of (a) an acidic salt such as erric oxalate or ferric citrate, (b) the adcluck of N-(p-tolyl)~glycine and glycidyl methacrylate, the addition reaction product oE N-phenylglycine and glycidyl methacrylate or N-phenylglycine itself, and ta) the addition . reaction product of pyromellitic acid dianhydride and 2-hydroxyethylmethacrylate, the addition reaction product of 3,3',4,4'-benzophenonetetracarboxylic dianhydride and 2-hydroxyethylmethacrylate, or 4-methacry10xyethyltrlmellitic anhydrlde. This multi-step process has, however, not proved satisfactory.
In addition~to much desired improvements in dentin bonding systems, it is also desirable to attain improved bonding to other dental surfaces, sUch as enamel, metallic a1loy~ and particularly pjrrelaln.
S
,~ ., Despite recent advances in the development of filled dental restorative materials which have led to composites having higher resistance to abrasion, better handling characteristics, more satisfactory visual appearance, there also remains considerable room for improvement in these areas, specifically desired are improved filled compositions for use as cro~n and bridge materials, denture-base materials, luting agents or cements and orthodontic a~p~iance sealants.
Accordingly, it is one primary object of this invention to provide a dentin bonding system which employs a non-irritatinc~ pretreatment to yield a proper surface for application of a dental adhesive, It is another primary object o this invention to provide a dental adhesive which is suitablo or bonding to a properly prepared dentin surace. It is a further object of this invention to provide new adhesive materials which are particularly suited for application, with appropriate pretreatmentr to exposed dentin surfaces. Other obiects include the provision of improved adhesive materials for bonding to enamel, metallic alloys and por~elain. Still another object is to provide improved filled compositions for use as luting agents, denture-base material, orthodonticsealants and other dental restorative materials. Other ob]ects of this invention will become apparent from the following specification.
According to the invention, there is provided a dental resin adllesive whicll comprises BIS-G~l~ in an arnount rangir-g Erom about 20 to about 80 weight percent and a polycarbonate dimethacrylate of the formula O O O O
11 ll ll ll C112-C - C - O - A - o - C - (OR)~l-O - C - O - ~ - O - C - C=C112 c,l3 C113 wherein A is Cl- C6 alkylen, R is C2- C5 alkylene having at least 2 carbon atoms in its principal chain and n is an integer from l to 4, said polycarbonate dimetllyacrylate l)eing present in an amount ranging Erom about 20 to about 80 weight percent.
The resinous adhesive compositions disclose~ herein comprise ~S~-G~ and polycarbonate dimethclcrylate condensation products which result from the con(3ellsat1OIl, under eareEully controlled eonditlons, of two parts by welght of c!n hyc3roxyalkylmethaerylate of the formula I
() t'~2 = C - C - O - ~ - Oll C~13 in whieh A 1s Cl - C6 alky1ene, anc3 one part by weight oE a bis(ellloroEormate) oE tlle Eormula II
C1 - C - (~)n - O - C - Cl O O
in whlch R is C2-C5 alkylene having at least two carbon atoms in its principal chain and n ls an lnteger Erom 1 to 4. of particular interest is the novel condensation product of 2-hydroxyethylmethacrylate and trlethylene glycol bis(chloroEormate). rl-ese new adheslve composltions whlch are unfilled, eonstitute the dental adhes1ve materials of this invention. These dental adhesives may be applied to all types of dental surfaces, lncluding enamel, dentin, porcelain and metallic surfaces but are particularly sulted Eor 9pplic9tion 0 pretre t9~ d-~tln 9urf9c99 - . .
, ~ ' ` ~ ' '.. , - '.
, ' .
-- 130'~05 The dental adhesives of this invention include both visible light curable and self-curing compositions. The visible light curable compositions include, in addition to BIS-GMA and the polycarbonate dimethacrylate condensation product, the usual polymerization initiators, polymerization accelerators, ultraviolet absorbers, fluorescent whitening agents, etc. In the self-curing adhesive compositions, the polymerization accelerator can be included in the adhesive composition itself or can be present in a liquid composition which is used for pretreatin~ the exposed dentin.
Methods for bonding dental restorative materials to an exposed dentin surface are also provided. The surface is pretreated by application of 3% ~12O2, 17~ EDTA or 5% NaOCl in non-vital teeth followed by an alcohol solution of an alkali metal salt of benzenesulfinic acid with subsequent evaporation o~ the alcohol from the solution. The treated dentin surface is then coated with a resinous adhesive according to this invention. The adhesive is then cured and an appropriate dental restorative material is applied. Where the adhesive is a sel~-curing composition, the polymerization accelerator can either be included in the adhesive itself or be incorporated into the alcohol pretreatment solution, in which case the accelerator remains on the dentin surface after evaporation of the alcohol.
In addition to the unfilled resinous adhesive compositions, there are also provided filled compositions comprising the new BIS-GMA and pol~carbonate dimethacrylate condensation products as a principal component and varous additives. Such filled compositions are useful for a variety ,~. _ p~ _ of dental treatment and restorative functions including the crown and bridge materials luring agents, or cements, denture-base materials, orthodontic sealants, and dental restorative materials.
According to one aspect of the invention, a dental restorative composition comprises about 20 to about 98 percent by weight resinouscomponent comprising from about 25 to about 35 weight percent o~ BIS-GMA, and from about 65 to about 75 weight percent of a polycarbonate di.methyacrylate o~ the formula O O O O
Il 11 11 ll CH2=C - C - O - A - O C - (~)n - C - O - A - O - C - C=C~12 where A is Cl-C6 alkylene, R is C2-C5 alkylene having at least 2 carbon atoms in its principal chain and n is an integer from 1 to ~, and about 80 to about 2 percent by weight in organlc ~iller.
g .
, , , Tb~ pu.y-~rb~---e ~ILm~ -y a~e n~....ti--- ~ d.ct-usable in this invention are obtained by the condensation reaction o~ an hydroxyalkylmethacrylate of the general formula I
O
CH2 = C - C - O - A - OH
C~13 in which A is Cl - C6 alkylene, and a bi~tchloroformate) of the general formula II
Cl - C - (OR)n - O - C - Cl II
in which R is C2-C5 alkylene having at least two carbon atoms in its principal chain and n is an integer from 1 to 4. By "principal chain" is meant the chain of carbon atoms serving as a bridge hetween the oxygen atoms.
In the hydroxyalkylmethacrylate, the group A can be, for example, methylene, ethylene, propylene, 2,2-dimethylpropylene, butylene, etc. Preferred compounds are those in which A has 2 or 3 carbon atoms, such as 2-hydroxyethylmethacrylate and 2-hydroxypropylmethacrylate, - 1 30~ 1 05 with 2-hydroxyethylmethacrylate particularly preferred. In the bis(chloroformate), examples of the group R include ethyiene, l-methylethylene, 1,2-dimethylethylene, propylene, 2-methylpropylene, 2,2-dimethylpropylene, butylene, etc.
The preEerred groups for R are ethylene, propylene, and with them the preferred values for the integer n are 2 and 3.
Particularly preferred as the bis(chloroformate) reactant i5 triethyleneglycol bis(chloroormate) (~ C(OCH2CH2)30-C-Cl III
but others, ~uch as diethylene glycol bis(chloroformate), tetraethylene glycol bis(chloroformate), dipropylene glycol bis(chloroformate) and tripropylene glycol bis(chloroformate) are also quite suitable. In general, the bis(chloroformates) for use in the practice of this invention include those of the aforementioned generic formula which are liquid at temperatures employed in the condensation reaction.
The hydroxyalkylmethacrylates and the various bis(chloroformates) required as starting materials or the polycarbonate dimethacrylate condensation products are either available commercially or can be easily prepared by known methods. The bis(chloroformate) starting - 1 ~091 05 materials can be prepared, for example, by reaction of phosgene with the appropriate glycol according to methods well known in the art. Triethylene glycol bis(chloroformate) and certain other bis~chloroformates) can be obtained from PPG Industries (Chicago, Illinois).
The polycarbonate dimethacrylate condensation products are prepared by reacting two moles of the hydroxyalkylmethacrylate and one mole of the bi~(chloroformate). Said condensation products have the general formula IV
O O o o 11 , 11 11 ll CH23C`- C - O - A ~ O - C - (OR)n O - C - O - A - o - C - C=CH2 in which A, R and n are defined above. ;.
The preferred polycarbonate dimethacrylate condensation products are those which, based on Formula IV, have a molecular weight between about 418 and 506. Particularly preerred is the novel polycarbonate dimethacrylate obtained with triethylene glycol bis(chloroformatej and 2-hydroxyethylmethacrylate, which has the formula V
O O o o 11 11 : 11 11 2 ~ C o (C~2)~2o-c(oc~2cH2)3o-c-o(cH2)2-o-c-c=c~l2 ¦ CH3 CH3 with a molecular weight oE 462.
The polycarbonate dimethacrylate condensation product is obtained by adding the bis(chloroformate) slowly by drop-wise addition to the hydroxyalkylmethacrylate in a suitable solvent such as pyridine. The solution should be well stirred during the condensation reaction and the temperature should be maintained between about -5C and 10C, preferably between about -2C and 4C. Conveniently, the reaction can be done in an ice bath, thus maintaining a tcmperature of about 3 to ~C. These lo~ temperatures are necessary in order to prevent polymerization. After the condensation reactlon is complete, the product is separated from solvent, unreacted starting materials, by-products, etc., by methods well known in the art, Many of the condensation products included within the scope o~ formula (IV) are known from United States Patent Wo. 3,716,571 issued February 13, 1973, and from Soviet Author's Certiicate No. 732,291 publiahed on May 8, 1980.
They have heretofore found utility as binder compositions in gloss-reinforced plastics, electric insulating compositions, heat resistant compositions, etc., but not as components in dental adhesives or dental restorative compositions. The specific condensation product of triethyleneglycol bis(chloroformate) and 2-hydroxypropylmethacrylate lS a novel substance.
Aromatic polycarbonates derived frcm bisphenol-A by reaction with diphenyl carbonate or phosgene are known `~ 1 30q 1 0~
up to almost any pressure attainable with production apparatus.
Since extremely high pressure apparatus is quite expensive, pressures to about 500 at~ospheres are suggested. Most desirably, the pressure should be in the range of from about 100 to about 400 atmospheres, particularly when employing the aforesaid preferred temperature range. It has been found, however, that the glycol aldehyde selectivity decreases slightly as a result of decreasing the total pressure from about 225 atmospheres to 100 atmospheres. Lowering the total pressure to 500 psig (31 atmospheres) results in a substantial decrease in glycol aldehyde selectivity. ~ reaction pressure of 1,400 to 4,000 psig is preferred.
The reaction pressures represent the total pressure gases aontained in the reactor, i.e., aarbon monoxide and hydrogen, and, if present, any inert diluent gas such as nitrogen. As in any gaseous system, the total pressure is the sum of partlal pressures of component gases~ In the present reactlon, the molar ratio o~ hydrogen to carbon monoxlde can range from about 1~10 to about 10.1, with the preferred ratio, from about l~S to about 5:1, and the reaction pressure can be achieved by adjusting the pressure of these gases in khe reactor. For best results, the molar ratio of carbon monoxide to hydrogen is main~ained at. high values where partial pressures o~ carbon monoxide favour production of glycol aldehyde. Thus, to produce glycol aldehyde, the partial pressure of carbon monoxide is usually adjus~ed to be about 3 to about 10 times that of hydrogen.
- 1 30q 1 05 ¦ products and have been used as denture-base materials; see ¦ Stafford et al, "Polycarbonates: A Preliminary Report on ¦ the Use of Polycarbonates as a Denture Base Material", I Dental Practitioner 17, 217-23 (1967) In contrast to the I .
relatively low molecular weight condensation products usable in this invention, these previously-described polycarbonates have phenylene groups rather than the alkylene groups and have preferred molecular weights in the range o 30,000 to 200,000.
The subject polycarbonate dimethacrylates are suitable for incorporation into dental adhesives, including those which are visible li~ht curable and those which are self-curing. Typically, these polycarbonate dimethacrylates are incorporated into a reslnous composition having from about 20 to about 60 weight percent of BIS-GMA and from about 40 to about 80 weight percent of the polycarbonate dimethacrylate. The preferred ranges for BIS-GMA are 25 to 35 weight percent, particularly about 30 weight percent, and the preferred ranges for the polycarbonate dimethacrylates are from 65 to 75 weight percent, particularly about 70 weight percant. In addition to these monomeric materials, the resinous adhesive compositions of this invention will also typically include polymerization initiators, polymerization accelerators, ultraviolet light absorbers, anti-oxidants, and other additlves well known in the art.
Although a polymerization initiator and a polymerization accelerator are generally used in these resinous adhesive compositions, the presence o a polymerization accelerator - 130~105 ¦ in the self-curing adhesive compositions of this invention ¦ is optional. One of the features of the self-curing dentin ¦ bonding system of this invention is that the polymerization accelerator can be incorporated into the dentin pretreatment composition rather than into the resinous adhesive composition.
.
- 1 30~ 1 05 The polymerization initiators usable in the resinous adhesives o~ this invention are the usual initiators known in the art. For example, visible light curable compositions employ light-sensitive compounds such as benzil, diketones and in particular, dl~camphoroquinone in amounts ranging from about O.OS to 0.5 weight percent. Self-curing compositions will generally contain free radical polymerization initiators such as, for-example, a peroxide in amounts ranging from about 2 to about 6 weight percent.
Particularly suitable free radical initiators are lauroyl peroxide, tributyl hydroperoxide and, more particularly benzoyl peroxide.
The polymerization accelerators usable in the compositions of this invention are the various organic tertiary amines well known in the art. In visible light cured compositions, the tertiary amines are generally acrylate derivatives such as diethylamino ethylacrylate, dimethylamino ethylmethacrylate and, particularly, diethylamino ethylmethacrylate in amounts ranging from about 0.05 to about 0.5 weight percent. In the self~curing compositions, the tertiary amines are generally aromatic tertiary amines, such a~ dimethyl-p-toluidine, dihydroxyethyl-p-toluidine, and the like, in amounts ranging from aboutO.05to about 4.0 weight percent. These can .
optionall be incorporated n a pretreatment ~o1ution rather than in the resinous adhesive, ¦ It is preferred also to employ an ultraviolet absorber in these resinous adhesives in amounts ranging from about 0.05 to about 5.0 weight percent. Such UV absorbers are particularly desirable in the visible light curable compositions in order to avoid discoloration of the resin from any incident ultraviolet light. Suitable UV absorbers are the various benzophenone~, particularly UV-9 and UV-S411 available rom American Cyanamid Company, and benzotriazoles known in the art, particularly 2-(2'-hydroxy-5'-methylphenyl)-benzotriazole, sold under the trademark TINUVIN P by Ciba-Geigy Corporation, Ardsley, New York.
Typical visible light curable dental adhesives according to this invention comprise:
65 - 75 weight percent of the polycarbonate . dimethacrylate condensation product of triethylene glycol bis(chloroformate) and 2-hydroxyethylmethacrylate, 25 - 35 weight percent of BIS-GNA, 0.05 - 0.35 weight percent of dl-camphoroquinone, 0.05 - 0.5 weight percent of diethylamino ethylmethacrylate, and 0.05 - 5 weight percent of TINUVIN P ultraviolet absorber in sp~cieic amoants within these ranges to yield a 100~ by weight polymerization system.
Typical adhesives for use in self-curing systems comprise:
65 - 75 weight percent of the polycarbonate dimethacrylate condensation product of triethylene glycol bis(chloroformate) and 2-hydroxyethylmethacrylate, 25 - 35 wei~ht percent of BIS-GMA, 3.2 - 5.0 weight percent of benzoyl peroxide, and 0.05 -4,5wQight percent of TINUVIN P ultraviolet absorber in specieic amounts within these ranges to yield a 100% by weight polymerization system. In addition, where the polymerization accelerator is incorporated in the resinous adhesive rather than in the dentin pretreatment composition, the adhesive additionally conta~ins from 0.05to 4 weight percent of dihydroxyethyl~p-toluidine.
It is also possib~le to use the polycarbonate dimethacrylate condensation products in adhesives which are both self-curing and visible light curable. In this "combination" system the resinous adhesive composition is ;identical to the visihle lig~ht cura~ble composition described above with the addltion of about 3.2 to about 5.0 weight percent of benzoyl peroxide.~
.
1 30q 1 05 This invention also includes methods for bonding dental restorative material to various surfaces, such as enamel, rr~e,~lî~
porcelain,-~e~ e alloy and particularly to exposed dentin surfaces. For such dentin surafces, the methods include S pretreatment of the dentin surfaces and coatin~ of the treated surfaces with the resinous adhesive compositions of this invention.
When dentin surfaces are exposed as a result of cutting and abrasion which occurs during treatment, there is formed on the dentin surface a "smear layer" composed principally of organic material. This smear layer is believed to cause partial filling of the dentin tubules as well as to obstruct the orifice~ o said tubules. Any pretreatment of the dentin surface must be preceded by removal of the smear lS layer, It has been ound that this gmear layer is readily removed by application, for example, of a 5 percent aqueous ~olution of ~odium hypochlorite, a 17 percent aqueous solution of ethylenediaminetetraacetic acld or a 6 percent citric acid gel. The methods of this invention assume prior removal of the smear layer.
In applying the resinous adhesive compositions of this invention to dentin surfaces, the first step after the usual prophylaxis with, for example, hydrogen peroxide, is a pretreatment of the dentin surface with an alcohol solution containing an alkali metal salt of benzenesulfinic acid, preferably sodium benzenesulfinate salt. If the dental ., .
~ ` ~
restorative composition to be used is a self-curin~
composition, the alcohol pretreatment solution for the dentin can also include an or~anic tertiary amine, ~referably an aromatic amine such as dihydroxyethyl-p-toluidine. Typical alcohol solutions for use in thispretreatment contain from about 3 to about 5 weicJht percent of sodium benzenesulfinate, and from about 1 to about 2-1/2 wei~ht percent of dihydroxyethyl-p-toluidine, the remainder bein~ ethanol.
The alcohol solution is applied to the dentin surface and is then evaporated. Evaporation may be effected by a dry air stream or other methods well known in the art. This pretreatment step fulfills the function of (1) prophylaxis and (2) improvin~ the dentin surface for acceptance of resinous adhesive. The benæenesulfinic acid salt causes a chelatin~ polymerization promotion of the dentin surface with the adhesive and results in partial fillin~ of the tubules o:E the dentin. Thus, the dentin surfaae is made considerably rou~her and this provides for enhanced adhesion. This enhanced susceptibility is obtained without the use of irritatin~ substances such as phosphoric acid.
If the alcohol solution also contains an aromatic tertiary amine, this is deposited on the surface of the dentin and functions as a polymerization acceleratinq a~ent - 130qlO5 when a resinous adhesive, without accelerator, is applied in the third step.
The resinous adhesive compo~sitions of this invention are then coated onto the pretreated dentin surface, according to methods well known in the art. If the resinous adhesive composition is a light curable composition, polymerization is effected by exposure to a visible light source, for example a 150 watt halogen light source or any visible light source which is capable oE generating light within wavelengths ranging Erom about 250 to about 750 nanometers, preferahly from 4S0 to 500 nanometers and more preferably~i~rom 4fi8 to ~92 nanometers, for about 20 to 50 seconds. If the resinou~s adhesive composition is a self-curing composition, a period of about 3 to 6 minutes should be allowed for polymerization.
The adhesive composition of this invention is also suitable for use on a properly prepared enamel surface and can be simultaneously applied to a pretreated dentin surface and adjacent areas of an enamel surface. Such enamel surfaces can be subjected to etching treatment with, for 3~ 50 I/~to ~0 example,~orthophosphoric acid. Obviously, steps should be taken to shield the exposed dentin from the enamel etching treatment The compositions of this invention are employed in the following manner as a dentin adhesive bonding system where the smear layer has been removed from the dentin surface and adjacent exposed enamel has been acid etched by the use of well-known etching materials such as, for example, orthophosphoric acid gel. Pulp protection is accomplished by use of, for example, a calcium hydroxide composition.
After ~craping any debris from the dentin surface, it is cleaned with an oil-free dental pumice and water. A
3~ hydrogen peroxide solution is then applied as prophylaxis and the dentin sur~ace is washed and dried.
The restoration site is then isolated with a Mylar polyester strip for proper gingival margins, gingival pappilae and adjacent tooth preparation via sliding preshaped/formed contour strip into gingival sulcus. The polyester strip is tightened to seal the gingival margin, thus isolating saliva and gingival cervl~ul~r fluid flow to the restored area. In addition, dental wedges are recommended in order to separate teeth, facilitate interproximal contact and hold the polyester strip in position. Two or three drops of a liquid solution of sodium benzene sulfinate in ethanol are brushed over the dentin surface. If a self-curing adhesive system is used, this alcohol solution can additionally contain dihydroxy-p-toluidine~ The ethanol should be permitted to evaporate, with air drying recommended for this purpose.
~ - 1 3091 05 The resinous adhesive composition is then applied over the etched peripheral enamel beyond cavo-surface margin and over the dry, prepared and conditioned dentin surfaces. An extremely thin layer of resinous adhesive is obtained by removing excess material from enamel and dentin surfaces with a dry brush and jet of oil-fres air. If the adhesive composition is visible light curable, it should be exposed to a visible light source such as, for example, spectra-Lite, Eor about 40 seconds. If a self-curing adhesive composition is used -- with the polymerization accelerator either on the pretreated dent:in surface or in the resinous adhe~sive itself -- a yeriod of about three to five minutes should be allowed Eor yolymerization. Immed;ately-t~lereafter, th dental restorative paste should he placed onl:o the aclhesive.
Alternatively, the restorative paste and the adhesive can be cured simultarleously.
In aclclit~oll to use Eor bondiny restorative materials in . situations where exposed dentin is encountered, the resinous adhesive comyositions oE tlli~s invention are al.so applicable for the bonding oE enarnel, porcelain and metallic alloys, each to each other, or for the bonding of other dental restorative material~s, including all types of acrylic base materials and various crown ancl hridae alloy compositions, -to enamel, porcelain and me-tallic surfaces. They are applied to the surfaces to be adhered bv methods well known in the art.
Typically, the surfaces are prepared by, for example, etching or sand blasting.
* trade mark -or apparatus v,ilable from Jenerlc/Pentron . .. , ~
, The subject adhesive materials are particularly suitable also for promoting the adhesion of various dental restorative materials to porcelain surfaces. Generally, the porcelain surface is etched by, for example, hydrofluoric acid and the resinous adhesive compositions of this invention applied to the etched surfaces. The adhesive is then cured by methods well known in the art such as, for example, heat curing or visible light curing. If visible light curing is desired, the adhesive compositian should also contain the various visible light curing additives dlscussed above. The dental restorative material is then applied to tho cured adhesive. Such restorative materials include virtually all oE the materials currently used in dentistry and can also include the novel filled compositions of this invention.
When using the resinous compositions of this in~ention as a porcelain adhesive, it is preferred that there be a silane coupling agent used between the etched surface of the porcelain and the resinous adhesive composition. The silane coupling agent is brushed onto the etched porcelain surface prior to application of the resinous adhesive.
Useful silane coupling agents may be selected from members of organosilicon monomers such asaminoalkyl(trisalkoxy)silanes which are characterized by the formula R-SiX3, wherein R is an organofunctional group attached to silicon in a hydrolytically stable manner and X designates hydrolyzable groups which are converted to silanol groups upon hydrolysis. Most commonly, R comprises 3-aminopropyl or 3--- 1 30q 1 05 ureidopropyl moiety WtliCtl may be further separated from the silicon group by one or two -Nil(~ll2)-~ moieties wllereill n=l-2. Preferably X is an alkoxy group selected ~rolll tlle group conslsting of methoxy, ethoxy, 2-methoxyetlloxy or is acetoxy speciflcally y - metllacryloxypropyltrillletlloxysilane ~-174*
Union Carbide. Preferred silane coupllng agellts are commerclally available from Unioll Carbide as tile ~110~-~1160*
series which includes 3-aminopropyltri-ethoxysilalle, 3-aminopropyltrimethoxysilane (also available from Dow Corning as 2-6020), N-2 aminoethyl-3-amillopropyl-trillletlloxysilalle, or 3-ureidopropyltriethoxysilane. With such silane-couplillg agentsr the cure system for the resinous adhesive should be a visible llght cure system, rattler than a heat cure system since t~le heat necessary to efect the cure will cause degredatlon of the silane. ~owever, tlle 1asll point of pre~erred sllane ~-17~*i9 275 C well above l~eat curing temperature range.
The filled COlllpO9itiOns oE tl~is inventioll can lnclude all of the inorganic fillers currently used in delltal re9torative materials, tlle amount o sucl~ flllcr belng determined by the specific unctioll of the illcd materials.
Thus, for example, wllere crown and bridge materials are belng prepared, th2 resinous compositolls of this inventio are present lllamounts ranging from about 20 to about ~0 welgllt parcent, and the filler materials are prc~serlt in amounts ranglng from about 60 to about 80 weigllt percent.
Typical compositions ~or crown and bridge materials are about 3~ of the resinous material and about 70~ of the filler. For luting cements, ttle resinous compositions of this invention are present in amouots ranging froln about 43 * tracle mar~s of Union ~arbide to about 55 weiyht percent, the fillers comprising from about 45 to about 57 weight pereent. For orthodontic sealant and orthodontic cement compositons, there will typically be from about 90 to about 98~ of resinous eomponent and about 2 to about 10~ of filler.
The filled compositions of this invention can, in general, inelude any suitable filler material such as a siliea, silieate glass filler or ~uartz ~hich is ea~able of~ein( ?
eovalently bonded to the resin matrix itself or to a eoupling agent whieh is covalently bonded to both.
Particularly suitable as fillers for dental restorative m~terials pre~ared in accordance with tllis invention are those having a particle size ranging from about 0.01 to aboutO.07 microns and prepared by a series of milling steps eomprisin~ wet milling in an aqueous medium, surfaee eteh milllng and silanizing milling in a silane solution. Sueh inor~anie filling materials are disclosed in U.S. Patents No. 4,544,359 and No. 4,547,531. ~s with the unfilled eompositions, the filled and partially filled eompositions can be prepared in both visibLe light eurable formulations and self-curing (paste-paste) formulations. The filled eomposite restorative materials ean be prepared by admixing from about 20 to 30~ by weight, preferably 20-26% by weight, of either the unfilled visible light eurable dental adilesive or tile unfilled self-euring adhesive eompositions with from about 65 to about ~5~ by ., weight, preferably about 75 to 83% by weight of inorganic filler material.
The composite dental restorative material of the present invention preferably comprises an inorganic filler having an average particle size diameter of from about 0.5 to 5 microns homogeneously dispersed in an oryanic polymerizable monomeric matrix comprising a polycarbonate dimethacrylate. In addition, a relatively small amount of fumed silica is also preclispersed within the monomeric matrix.
The inorganic filler primarily comprises an X-ray opaque alkali metal or alkaline ear~h metal silicàte such as lithium silicate, barium silicate and the like. For purposes of illustration, and as the preerred silicate species, barium silicate will hereinafter be employed as being typical of the alkali metal or alkaline earth metal silicates which can be suitably employed in the present ~ r invention. The barium~silicate exhibits substantially the same index of refraction as that of the organic monomeric matrix in which it is dispersed. The filler may additionally contain a relatively small amount of borosilicate glass which imparts greater compressive strength to the resulting composite and enhances the translucency thereof thereby enabling better blending of the restorative material with the adjacent teeth. In addition, the presence of the borosilicate glass helps narrow the gap between the refractive indices of the barium silicate and the organic monomeric matrix.
- 130~105 The ability to provide a composite dental material having improved properties is achieved by the method by which the inorganic filler is prepared. This method involves a sequence of milling operations which includes wet milling to reduce the barium silicate and borosilicate to the requisite particle size and assure a very narrow particle size distribution and to uniformly disperse the borosilicate glass particles throughout the bulk of the barium silicate, Thereafter, the wet milled filler is subject to a further milling operation to etch the surface thereof which has been found to impart a dramatic increase to the diametral tensile strength of the resulting composite. Subsequently, the so treated filler is subjected to a final milling operation during which it is silanized in order to render it compatible with the resin in which it will ultimately be dispersed.
Details of the preparation of the inorganic filler, . which comprises a mixture of from about 5 to about 20% by weight of borosilicate glass and from about 80 to abut 95%
by weight barium silicate, and has an average particle size ~diameter of from about 0.5 to about 5 microns, may be found in the aforementioned ~.SO Patents No. 4,544,539 and No.
DENTAL llESIN ~!AI~ ;b ¦This invention relates to polymeric condensation products which have been found to be useful in restorative dentistry. More particularly, it relates to polymeric condensation products wtlich can be used as a principal component o~ resinous adhesives, and can be used in dental reRtorative agents. The resLnou~s adhesives of this invention are suitable ~or bonding to virtually all types of dental surfaces, including enamel, dentin, portcelain and metallic sur~aces. They are especially useful in a system for bonding dental restorative materials to exposed dentin.
Filled compositions contalning the resinous adhesives as components are useful, depending on filler content, as crown ¦ and bridge materials, as luting agents or cements, as orthodont c ealants, etc.
In recent years, materials used for dental restoration have comprised principally methacrylate polymers. Typical of these polymeric substances are the acrylic resinous materials disclosed in U.S. Patents No. 3,066,112, No.
3,179,623, No~ 3,194,784, No. 3,751,399 and No. 3,926,906.
Especially noteworthy is the compound which is the condensation product of bisphenol A and glycidyl methacrylate, 2,2'-bis [4-(3-methacryloxy-2-hydroxy propoxy)~phenyl]-propane (hereinafter abbreviated to "BIS-GMA"). Other methacrylate polymers, such as ethylene glyco~
dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate, are also in general use as diluents, polyurethanedimethacrylate is also used as a principle lS polymer in dental restorative materials o~ this type. Since BIS-GMA is highly viscous at room temperature, however, it is generally diluted with a monomer having a lower viscosity such as the aforementioned alkylene glycols or other compatible materialsl including trimethylol propyl trimethacrylate, 1,6-hexanediol dimethacrylate, 1,3-butanediol dimethacrylate, and the like.
~ U ~1 UJ
When these acrylic re inous materials were first developed, they were used unfilled for dental restorative purposes. However, because thcsc acrylic materials exhibit high coefficients of thermal expansion relative to the coefficient of thermal expansion for tooth structure, these unfilled substances soon proved to be less than satis~actory. The disparity in thermal expansion, coupled with high shrinkage upon polymerization, resulted in poor marginal adaptability and ultimately led to secondary decay.
Furthermore, the wear and abrasion characteristics and the overall physical, mechanical and optical properties of these unfilled acrylic resLnous materials were quite poor. Thus, from the o~ltset, composite dental restorative materials containing these methacrylate resins and fillers were developed. The fillers are generally inorganic filler materials based on silica~ silicate glass or ~uartz.
Over the years there have been a number of refinements in the resin matrix component, in the ~iller component, and in the other additives -- notably antioxidants, ultraviolet absorbers, polymerization initiators, polymerization accelerators, etc. -- in dental restorative materials.
There are now available materials which exhibit high diametral tensile strength, excellent optical properties and polishability, and low water absorption wh~le, at the same time, complying with all of the requirements specified in ADA Specification No. 27 for direct filling resins.
Particularly suitable restorative materials are the new compositions having improved inorganic filler materials such 5 as those disclosed in my co-pending application Serial No.
636,970 filed on August 2, 1984, now U.S. Patent No.
4,547,531, disclosing self-curing 2-component compositions, and my application Serial No. 677,595 filed on December 3, 1984, now U.S. Patent No. 4,544,359, disclosing visible light curable compositions.
All of these dental restorative materials are required to adhere permanently to the tooth structure. GeneralIy, the tooth surface is treated with an acid such as 30 - 50 wt. 3 orthophosphoric acid, which etches the enamel tooth sur~ace and exposes enamel rods in honeycomb prismatic structure thereon, ~here adhesion of the cured polymeric material is improved via micromechan`ical interlocking. In addition to this process o etching, the prior art teaches the use of various additives and improved monomeric mixtures which are designed to provide improved adhesion.
Although the acid etching technique by itself or coupled with modification of the resinous material to increase adhesive capability has been beneficial in effectin~ the bonding of dental restorative materials to tooth enamel, there has heretofore been no completely .
.; ' . .
- 1 30q 1 05 satisfactory process for adhering such restorative materials to dentin. Acid etching is not suitable for bonding dental restorative materials to dentin because the tubular structure of dentin provides passageways to the tooth pulp.
The acid would cause great inflammati'on and pain to the patient anfl ulti~atelv lead to ~ul~al necrosis. Furthermore, the hi~h percentage or orqanic (protein) màterial in the dentin results in a lower degree of adhesion as compared with enamel.
There has recently been proposed a method for improving adhesion o~ dental composite materials to dentin surfaces which involves the successive application of (a) an acidic salt such as erric oxalate or ferric citrate, (b) the adcluck of N-(p-tolyl)~glycine and glycidyl methacrylate, the addition reaction product oE N-phenylglycine and glycidyl methacrylate or N-phenylglycine itself, and ta) the addition . reaction product of pyromellitic acid dianhydride and 2-hydroxyethylmethacrylate, the addition reaction product of 3,3',4,4'-benzophenonetetracarboxylic dianhydride and 2-hydroxyethylmethacrylate, or 4-methacry10xyethyltrlmellitic anhydrlde. This multi-step process has, however, not proved satisfactory.
In addition~to much desired improvements in dentin bonding systems, it is also desirable to attain improved bonding to other dental surfaces, sUch as enamel, metallic a1loy~ and particularly pjrrelaln.
S
,~ ., Despite recent advances in the development of filled dental restorative materials which have led to composites having higher resistance to abrasion, better handling characteristics, more satisfactory visual appearance, there also remains considerable room for improvement in these areas, specifically desired are improved filled compositions for use as cro~n and bridge materials, denture-base materials, luting agents or cements and orthodontic a~p~iance sealants.
Accordingly, it is one primary object of this invention to provide a dentin bonding system which employs a non-irritatinc~ pretreatment to yield a proper surface for application of a dental adhesive, It is another primary object o this invention to provide a dental adhesive which is suitablo or bonding to a properly prepared dentin surace. It is a further object of this invention to provide new adhesive materials which are particularly suited for application, with appropriate pretreatmentr to exposed dentin surfaces. Other obiects include the provision of improved adhesive materials for bonding to enamel, metallic alloys and por~elain. Still another object is to provide improved filled compositions for use as luting agents, denture-base material, orthodonticsealants and other dental restorative materials. Other ob]ects of this invention will become apparent from the following specification.
According to the invention, there is provided a dental resin adllesive whicll comprises BIS-G~l~ in an arnount rangir-g Erom about 20 to about 80 weight percent and a polycarbonate dimethacrylate of the formula O O O O
11 ll ll ll C112-C - C - O - A - o - C - (OR)~l-O - C - O - ~ - O - C - C=C112 c,l3 C113 wherein A is Cl- C6 alkylen, R is C2- C5 alkylene having at least 2 carbon atoms in its principal chain and n is an integer from l to 4, said polycarbonate dimetllyacrylate l)eing present in an amount ranging Erom about 20 to about 80 weight percent.
The resinous adhesive compositions disclose~ herein comprise ~S~-G~ and polycarbonate dimethclcrylate condensation products which result from the con(3ellsat1OIl, under eareEully controlled eonditlons, of two parts by welght of c!n hyc3roxyalkylmethaerylate of the formula I
() t'~2 = C - C - O - ~ - Oll C~13 in whieh A 1s Cl - C6 alky1ene, anc3 one part by weight oE a bis(ellloroEormate) oE tlle Eormula II
C1 - C - (~)n - O - C - Cl O O
in whlch R is C2-C5 alkylene having at least two carbon atoms in its principal chain and n ls an lnteger Erom 1 to 4. of particular interest is the novel condensation product of 2-hydroxyethylmethacrylate and trlethylene glycol bis(chloroEormate). rl-ese new adheslve composltions whlch are unfilled, eonstitute the dental adhes1ve materials of this invention. These dental adhesives may be applied to all types of dental surfaces, lncluding enamel, dentin, porcelain and metallic surfaces but are particularly sulted Eor 9pplic9tion 0 pretre t9~ d-~tln 9urf9c99 - . .
, ~ ' ` ~ ' '.. , - '.
, ' .
-- 130'~05 The dental adhesives of this invention include both visible light curable and self-curing compositions. The visible light curable compositions include, in addition to BIS-GMA and the polycarbonate dimethacrylate condensation product, the usual polymerization initiators, polymerization accelerators, ultraviolet absorbers, fluorescent whitening agents, etc. In the self-curing adhesive compositions, the polymerization accelerator can be included in the adhesive composition itself or can be present in a liquid composition which is used for pretreatin~ the exposed dentin.
Methods for bonding dental restorative materials to an exposed dentin surface are also provided. The surface is pretreated by application of 3% ~12O2, 17~ EDTA or 5% NaOCl in non-vital teeth followed by an alcohol solution of an alkali metal salt of benzenesulfinic acid with subsequent evaporation o~ the alcohol from the solution. The treated dentin surface is then coated with a resinous adhesive according to this invention. The adhesive is then cured and an appropriate dental restorative material is applied. Where the adhesive is a sel~-curing composition, the polymerization accelerator can either be included in the adhesive itself or be incorporated into the alcohol pretreatment solution, in which case the accelerator remains on the dentin surface after evaporation of the alcohol.
In addition to the unfilled resinous adhesive compositions, there are also provided filled compositions comprising the new BIS-GMA and pol~carbonate dimethacrylate condensation products as a principal component and varous additives. Such filled compositions are useful for a variety ,~. _ p~ _ of dental treatment and restorative functions including the crown and bridge materials luring agents, or cements, denture-base materials, orthodontic sealants, and dental restorative materials.
According to one aspect of the invention, a dental restorative composition comprises about 20 to about 98 percent by weight resinouscomponent comprising from about 25 to about 35 weight percent o~ BIS-GMA, and from about 65 to about 75 weight percent of a polycarbonate di.methyacrylate o~ the formula O O O O
Il 11 11 ll CH2=C - C - O - A - O C - (~)n - C - O - A - O - C - C=C~12 where A is Cl-C6 alkylene, R is C2-C5 alkylene having at least 2 carbon atoms in its principal chain and n is an integer from 1 to ~, and about 80 to about 2 percent by weight in organlc ~iller.
g .
, , , Tb~ pu.y-~rb~---e ~ILm~ -y a~e n~....ti--- ~ d.ct-usable in this invention are obtained by the condensation reaction o~ an hydroxyalkylmethacrylate of the general formula I
O
CH2 = C - C - O - A - OH
C~13 in which A is Cl - C6 alkylene, and a bi~tchloroformate) of the general formula II
Cl - C - (OR)n - O - C - Cl II
in which R is C2-C5 alkylene having at least two carbon atoms in its principal chain and n is an integer from 1 to 4. By "principal chain" is meant the chain of carbon atoms serving as a bridge hetween the oxygen atoms.
In the hydroxyalkylmethacrylate, the group A can be, for example, methylene, ethylene, propylene, 2,2-dimethylpropylene, butylene, etc. Preferred compounds are those in which A has 2 or 3 carbon atoms, such as 2-hydroxyethylmethacrylate and 2-hydroxypropylmethacrylate, - 1 30~ 1 05 with 2-hydroxyethylmethacrylate particularly preferred. In the bis(chloroformate), examples of the group R include ethyiene, l-methylethylene, 1,2-dimethylethylene, propylene, 2-methylpropylene, 2,2-dimethylpropylene, butylene, etc.
The preEerred groups for R are ethylene, propylene, and with them the preferred values for the integer n are 2 and 3.
Particularly preferred as the bis(chloroformate) reactant i5 triethyleneglycol bis(chloroormate) (~ C(OCH2CH2)30-C-Cl III
but others, ~uch as diethylene glycol bis(chloroformate), tetraethylene glycol bis(chloroformate), dipropylene glycol bis(chloroformate) and tripropylene glycol bis(chloroformate) are also quite suitable. In general, the bis(chloroformates) for use in the practice of this invention include those of the aforementioned generic formula which are liquid at temperatures employed in the condensation reaction.
The hydroxyalkylmethacrylates and the various bis(chloroformates) required as starting materials or the polycarbonate dimethacrylate condensation products are either available commercially or can be easily prepared by known methods. The bis(chloroformate) starting - 1 ~091 05 materials can be prepared, for example, by reaction of phosgene with the appropriate glycol according to methods well known in the art. Triethylene glycol bis(chloroformate) and certain other bis~chloroformates) can be obtained from PPG Industries (Chicago, Illinois).
The polycarbonate dimethacrylate condensation products are prepared by reacting two moles of the hydroxyalkylmethacrylate and one mole of the bi~(chloroformate). Said condensation products have the general formula IV
O O o o 11 , 11 11 ll CH23C`- C - O - A ~ O - C - (OR)n O - C - O - A - o - C - C=CH2 in which A, R and n are defined above. ;.
The preferred polycarbonate dimethacrylate condensation products are those which, based on Formula IV, have a molecular weight between about 418 and 506. Particularly preerred is the novel polycarbonate dimethacrylate obtained with triethylene glycol bis(chloroformatej and 2-hydroxyethylmethacrylate, which has the formula V
O O o o 11 11 : 11 11 2 ~ C o (C~2)~2o-c(oc~2cH2)3o-c-o(cH2)2-o-c-c=c~l2 ¦ CH3 CH3 with a molecular weight oE 462.
The polycarbonate dimethacrylate condensation product is obtained by adding the bis(chloroformate) slowly by drop-wise addition to the hydroxyalkylmethacrylate in a suitable solvent such as pyridine. The solution should be well stirred during the condensation reaction and the temperature should be maintained between about -5C and 10C, preferably between about -2C and 4C. Conveniently, the reaction can be done in an ice bath, thus maintaining a tcmperature of about 3 to ~C. These lo~ temperatures are necessary in order to prevent polymerization. After the condensation reactlon is complete, the product is separated from solvent, unreacted starting materials, by-products, etc., by methods well known in the art, Many of the condensation products included within the scope o~ formula (IV) are known from United States Patent Wo. 3,716,571 issued February 13, 1973, and from Soviet Author's Certiicate No. 732,291 publiahed on May 8, 1980.
They have heretofore found utility as binder compositions in gloss-reinforced plastics, electric insulating compositions, heat resistant compositions, etc., but not as components in dental adhesives or dental restorative compositions. The specific condensation product of triethyleneglycol bis(chloroformate) and 2-hydroxypropylmethacrylate lS a novel substance.
Aromatic polycarbonates derived frcm bisphenol-A by reaction with diphenyl carbonate or phosgene are known `~ 1 30q 1 0~
up to almost any pressure attainable with production apparatus.
Since extremely high pressure apparatus is quite expensive, pressures to about 500 at~ospheres are suggested. Most desirably, the pressure should be in the range of from about 100 to about 400 atmospheres, particularly when employing the aforesaid preferred temperature range. It has been found, however, that the glycol aldehyde selectivity decreases slightly as a result of decreasing the total pressure from about 225 atmospheres to 100 atmospheres. Lowering the total pressure to 500 psig (31 atmospheres) results in a substantial decrease in glycol aldehyde selectivity. ~ reaction pressure of 1,400 to 4,000 psig is preferred.
The reaction pressures represent the total pressure gases aontained in the reactor, i.e., aarbon monoxide and hydrogen, and, if present, any inert diluent gas such as nitrogen. As in any gaseous system, the total pressure is the sum of partlal pressures of component gases~ In the present reactlon, the molar ratio o~ hydrogen to carbon monoxlde can range from about 1~10 to about 10.1, with the preferred ratio, from about l~S to about 5:1, and the reaction pressure can be achieved by adjusting the pressure of these gases in khe reactor. For best results, the molar ratio of carbon monoxide to hydrogen is main~ained at. high values where partial pressures o~ carbon monoxide favour production of glycol aldehyde. Thus, to produce glycol aldehyde, the partial pressure of carbon monoxide is usually adjus~ed to be about 3 to about 10 times that of hydrogen.
- 1 30q 1 05 ¦ products and have been used as denture-base materials; see ¦ Stafford et al, "Polycarbonates: A Preliminary Report on ¦ the Use of Polycarbonates as a Denture Base Material", I Dental Practitioner 17, 217-23 (1967) In contrast to the I .
relatively low molecular weight condensation products usable in this invention, these previously-described polycarbonates have phenylene groups rather than the alkylene groups and have preferred molecular weights in the range o 30,000 to 200,000.
The subject polycarbonate dimethacrylates are suitable for incorporation into dental adhesives, including those which are visible li~ht curable and those which are self-curing. Typically, these polycarbonate dimethacrylates are incorporated into a reslnous composition having from about 20 to about 60 weight percent of BIS-GMA and from about 40 to about 80 weight percent of the polycarbonate dimethacrylate. The preferred ranges for BIS-GMA are 25 to 35 weight percent, particularly about 30 weight percent, and the preferred ranges for the polycarbonate dimethacrylates are from 65 to 75 weight percent, particularly about 70 weight percant. In addition to these monomeric materials, the resinous adhesive compositions of this invention will also typically include polymerization initiators, polymerization accelerators, ultraviolet light absorbers, anti-oxidants, and other additlves well known in the art.
Although a polymerization initiator and a polymerization accelerator are generally used in these resinous adhesive compositions, the presence o a polymerization accelerator - 130~105 ¦ in the self-curing adhesive compositions of this invention ¦ is optional. One of the features of the self-curing dentin ¦ bonding system of this invention is that the polymerization accelerator can be incorporated into the dentin pretreatment composition rather than into the resinous adhesive composition.
.
- 1 30~ 1 05 The polymerization initiators usable in the resinous adhesives o~ this invention are the usual initiators known in the art. For example, visible light curable compositions employ light-sensitive compounds such as benzil, diketones and in particular, dl~camphoroquinone in amounts ranging from about O.OS to 0.5 weight percent. Self-curing compositions will generally contain free radical polymerization initiators such as, for-example, a peroxide in amounts ranging from about 2 to about 6 weight percent.
Particularly suitable free radical initiators are lauroyl peroxide, tributyl hydroperoxide and, more particularly benzoyl peroxide.
The polymerization accelerators usable in the compositions of this invention are the various organic tertiary amines well known in the art. In visible light cured compositions, the tertiary amines are generally acrylate derivatives such as diethylamino ethylacrylate, dimethylamino ethylmethacrylate and, particularly, diethylamino ethylmethacrylate in amounts ranging from about 0.05 to about 0.5 weight percent. In the self~curing compositions, the tertiary amines are generally aromatic tertiary amines, such a~ dimethyl-p-toluidine, dihydroxyethyl-p-toluidine, and the like, in amounts ranging from aboutO.05to about 4.0 weight percent. These can .
optionall be incorporated n a pretreatment ~o1ution rather than in the resinous adhesive, ¦ It is preferred also to employ an ultraviolet absorber in these resinous adhesives in amounts ranging from about 0.05 to about 5.0 weight percent. Such UV absorbers are particularly desirable in the visible light curable compositions in order to avoid discoloration of the resin from any incident ultraviolet light. Suitable UV absorbers are the various benzophenone~, particularly UV-9 and UV-S411 available rom American Cyanamid Company, and benzotriazoles known in the art, particularly 2-(2'-hydroxy-5'-methylphenyl)-benzotriazole, sold under the trademark TINUVIN P by Ciba-Geigy Corporation, Ardsley, New York.
Typical visible light curable dental adhesives according to this invention comprise:
65 - 75 weight percent of the polycarbonate . dimethacrylate condensation product of triethylene glycol bis(chloroformate) and 2-hydroxyethylmethacrylate, 25 - 35 weight percent of BIS-GNA, 0.05 - 0.35 weight percent of dl-camphoroquinone, 0.05 - 0.5 weight percent of diethylamino ethylmethacrylate, and 0.05 - 5 weight percent of TINUVIN P ultraviolet absorber in sp~cieic amoants within these ranges to yield a 100~ by weight polymerization system.
Typical adhesives for use in self-curing systems comprise:
65 - 75 weight percent of the polycarbonate dimethacrylate condensation product of triethylene glycol bis(chloroformate) and 2-hydroxyethylmethacrylate, 25 - 35 wei~ht percent of BIS-GMA, 3.2 - 5.0 weight percent of benzoyl peroxide, and 0.05 -4,5wQight percent of TINUVIN P ultraviolet absorber in specieic amounts within these ranges to yield a 100% by weight polymerization system. In addition, where the polymerization accelerator is incorporated in the resinous adhesive rather than in the dentin pretreatment composition, the adhesive additionally conta~ins from 0.05to 4 weight percent of dihydroxyethyl~p-toluidine.
It is also possib~le to use the polycarbonate dimethacrylate condensation products in adhesives which are both self-curing and visible light curable. In this "combination" system the resinous adhesive composition is ;identical to the visihle lig~ht cura~ble composition described above with the addltion of about 3.2 to about 5.0 weight percent of benzoyl peroxide.~
.
1 30q 1 05 This invention also includes methods for bonding dental restorative material to various surfaces, such as enamel, rr~e,~lî~
porcelain,-~e~ e alloy and particularly to exposed dentin surfaces. For such dentin surafces, the methods include S pretreatment of the dentin surfaces and coatin~ of the treated surfaces with the resinous adhesive compositions of this invention.
When dentin surfaces are exposed as a result of cutting and abrasion which occurs during treatment, there is formed on the dentin surface a "smear layer" composed principally of organic material. This smear layer is believed to cause partial filling of the dentin tubules as well as to obstruct the orifice~ o said tubules. Any pretreatment of the dentin surface must be preceded by removal of the smear lS layer, It has been ound that this gmear layer is readily removed by application, for example, of a 5 percent aqueous ~olution of ~odium hypochlorite, a 17 percent aqueous solution of ethylenediaminetetraacetic acld or a 6 percent citric acid gel. The methods of this invention assume prior removal of the smear layer.
In applying the resinous adhesive compositions of this invention to dentin surfaces, the first step after the usual prophylaxis with, for example, hydrogen peroxide, is a pretreatment of the dentin surface with an alcohol solution containing an alkali metal salt of benzenesulfinic acid, preferably sodium benzenesulfinate salt. If the dental ., .
~ ` ~
restorative composition to be used is a self-curin~
composition, the alcohol pretreatment solution for the dentin can also include an or~anic tertiary amine, ~referably an aromatic amine such as dihydroxyethyl-p-toluidine. Typical alcohol solutions for use in thispretreatment contain from about 3 to about 5 weicJht percent of sodium benzenesulfinate, and from about 1 to about 2-1/2 wei~ht percent of dihydroxyethyl-p-toluidine, the remainder bein~ ethanol.
The alcohol solution is applied to the dentin surface and is then evaporated. Evaporation may be effected by a dry air stream or other methods well known in the art. This pretreatment step fulfills the function of (1) prophylaxis and (2) improvin~ the dentin surface for acceptance of resinous adhesive. The benæenesulfinic acid salt causes a chelatin~ polymerization promotion of the dentin surface with the adhesive and results in partial fillin~ of the tubules o:E the dentin. Thus, the dentin surfaae is made considerably rou~her and this provides for enhanced adhesion. This enhanced susceptibility is obtained without the use of irritatin~ substances such as phosphoric acid.
If the alcohol solution also contains an aromatic tertiary amine, this is deposited on the surface of the dentin and functions as a polymerization acceleratinq a~ent - 130qlO5 when a resinous adhesive, without accelerator, is applied in the third step.
The resinous adhesive compo~sitions of this invention are then coated onto the pretreated dentin surface, according to methods well known in the art. If the resinous adhesive composition is a light curable composition, polymerization is effected by exposure to a visible light source, for example a 150 watt halogen light source or any visible light source which is capable oE generating light within wavelengths ranging Erom about 250 to about 750 nanometers, preferahly from 4S0 to 500 nanometers and more preferably~i~rom 4fi8 to ~92 nanometers, for about 20 to 50 seconds. If the resinou~s adhesive composition is a self-curing composition, a period of about 3 to 6 minutes should be allowed for polymerization.
The adhesive composition of this invention is also suitable for use on a properly prepared enamel surface and can be simultaneously applied to a pretreated dentin surface and adjacent areas of an enamel surface. Such enamel surfaces can be subjected to etching treatment with, for 3~ 50 I/~to ~0 example,~orthophosphoric acid. Obviously, steps should be taken to shield the exposed dentin from the enamel etching treatment The compositions of this invention are employed in the following manner as a dentin adhesive bonding system where the smear layer has been removed from the dentin surface and adjacent exposed enamel has been acid etched by the use of well-known etching materials such as, for example, orthophosphoric acid gel. Pulp protection is accomplished by use of, for example, a calcium hydroxide composition.
After ~craping any debris from the dentin surface, it is cleaned with an oil-free dental pumice and water. A
3~ hydrogen peroxide solution is then applied as prophylaxis and the dentin sur~ace is washed and dried.
The restoration site is then isolated with a Mylar polyester strip for proper gingival margins, gingival pappilae and adjacent tooth preparation via sliding preshaped/formed contour strip into gingival sulcus. The polyester strip is tightened to seal the gingival margin, thus isolating saliva and gingival cervl~ul~r fluid flow to the restored area. In addition, dental wedges are recommended in order to separate teeth, facilitate interproximal contact and hold the polyester strip in position. Two or three drops of a liquid solution of sodium benzene sulfinate in ethanol are brushed over the dentin surface. If a self-curing adhesive system is used, this alcohol solution can additionally contain dihydroxy-p-toluidine~ The ethanol should be permitted to evaporate, with air drying recommended for this purpose.
~ - 1 3091 05 The resinous adhesive composition is then applied over the etched peripheral enamel beyond cavo-surface margin and over the dry, prepared and conditioned dentin surfaces. An extremely thin layer of resinous adhesive is obtained by removing excess material from enamel and dentin surfaces with a dry brush and jet of oil-fres air. If the adhesive composition is visible light curable, it should be exposed to a visible light source such as, for example, spectra-Lite, Eor about 40 seconds. If a self-curing adhesive composition is used -- with the polymerization accelerator either on the pretreated dent:in surface or in the resinous adhe~sive itself -- a yeriod of about three to five minutes should be allowed Eor yolymerization. Immed;ately-t~lereafter, th dental restorative paste should he placed onl:o the aclhesive.
Alternatively, the restorative paste and the adhesive can be cured simultarleously.
In aclclit~oll to use Eor bondiny restorative materials in . situations where exposed dentin is encountered, the resinous adhesive comyositions oE tlli~s invention are al.so applicable for the bonding oE enarnel, porcelain and metallic alloys, each to each other, or for the bonding of other dental restorative material~s, including all types of acrylic base materials and various crown ancl hridae alloy compositions, -to enamel, porcelain and me-tallic surfaces. They are applied to the surfaces to be adhered bv methods well known in the art.
Typically, the surfaces are prepared by, for example, etching or sand blasting.
* trade mark -or apparatus v,ilable from Jenerlc/Pentron . .. , ~
, The subject adhesive materials are particularly suitable also for promoting the adhesion of various dental restorative materials to porcelain surfaces. Generally, the porcelain surface is etched by, for example, hydrofluoric acid and the resinous adhesive compositions of this invention applied to the etched surfaces. The adhesive is then cured by methods well known in the art such as, for example, heat curing or visible light curing. If visible light curing is desired, the adhesive compositian should also contain the various visible light curing additives dlscussed above. The dental restorative material is then applied to tho cured adhesive. Such restorative materials include virtually all oE the materials currently used in dentistry and can also include the novel filled compositions of this invention.
When using the resinous compositions of this in~ention as a porcelain adhesive, it is preferred that there be a silane coupling agent used between the etched surface of the porcelain and the resinous adhesive composition. The silane coupling agent is brushed onto the etched porcelain surface prior to application of the resinous adhesive.
Useful silane coupling agents may be selected from members of organosilicon monomers such asaminoalkyl(trisalkoxy)silanes which are characterized by the formula R-SiX3, wherein R is an organofunctional group attached to silicon in a hydrolytically stable manner and X designates hydrolyzable groups which are converted to silanol groups upon hydrolysis. Most commonly, R comprises 3-aminopropyl or 3--- 1 30q 1 05 ureidopropyl moiety WtliCtl may be further separated from the silicon group by one or two -Nil(~ll2)-~ moieties wllereill n=l-2. Preferably X is an alkoxy group selected ~rolll tlle group conslsting of methoxy, ethoxy, 2-methoxyetlloxy or is acetoxy speciflcally y - metllacryloxypropyltrillletlloxysilane ~-174*
Union Carbide. Preferred silane coupllng agellts are commerclally available from Unioll Carbide as tile ~110~-~1160*
series which includes 3-aminopropyltri-ethoxysilalle, 3-aminopropyltrimethoxysilane (also available from Dow Corning as 2-6020), N-2 aminoethyl-3-amillopropyl-trillletlloxysilalle, or 3-ureidopropyltriethoxysilane. With such silane-couplillg agentsr the cure system for the resinous adhesive should be a visible llght cure system, rattler than a heat cure system since t~le heat necessary to efect the cure will cause degredatlon of the silane. ~owever, tlle 1asll point of pre~erred sllane ~-17~*i9 275 C well above l~eat curing temperature range.
The filled COlllpO9itiOns oE tl~is inventioll can lnclude all of the inorganic fillers currently used in delltal re9torative materials, tlle amount o sucl~ flllcr belng determined by the specific unctioll of the illcd materials.
Thus, for example, wllere crown and bridge materials are belng prepared, th2 resinous compositolls of this inventio are present lllamounts ranging from about 20 to about ~0 welgllt parcent, and the filler materials are prc~serlt in amounts ranglng from about 60 to about 80 weigllt percent.
Typical compositions ~or crown and bridge materials are about 3~ of the resinous material and about 70~ of the filler. For luting cements, ttle resinous compositions of this invention are present in amouots ranging froln about 43 * tracle mar~s of Union ~arbide to about 55 weiyht percent, the fillers comprising from about 45 to about 57 weight pereent. For orthodontic sealant and orthodontic cement compositons, there will typically be from about 90 to about 98~ of resinous eomponent and about 2 to about 10~ of filler.
The filled compositions of this invention can, in general, inelude any suitable filler material such as a siliea, silieate glass filler or ~uartz ~hich is ea~able of~ein( ?
eovalently bonded to the resin matrix itself or to a eoupling agent whieh is covalently bonded to both.
Particularly suitable as fillers for dental restorative m~terials pre~ared in accordance with tllis invention are those having a particle size ranging from about 0.01 to aboutO.07 microns and prepared by a series of milling steps eomprisin~ wet milling in an aqueous medium, surfaee eteh milllng and silanizing milling in a silane solution. Sueh inor~anie filling materials are disclosed in U.S. Patents No. 4,544,359 and No. 4,547,531. ~s with the unfilled eompositions, the filled and partially filled eompositions can be prepared in both visibLe light eurable formulations and self-curing (paste-paste) formulations. The filled eomposite restorative materials ean be prepared by admixing from about 20 to 30~ by weight, preferably 20-26% by weight, of either the unfilled visible light eurable dental adilesive or tile unfilled self-euring adhesive eompositions with from about 65 to about ~5~ by ., weight, preferably about 75 to 83% by weight of inorganic filler material.
The composite dental restorative material of the present invention preferably comprises an inorganic filler having an average particle size diameter of from about 0.5 to 5 microns homogeneously dispersed in an oryanic polymerizable monomeric matrix comprising a polycarbonate dimethacrylate. In addition, a relatively small amount of fumed silica is also preclispersed within the monomeric matrix.
The inorganic filler primarily comprises an X-ray opaque alkali metal or alkaline ear~h metal silicàte such as lithium silicate, barium silicate and the like. For purposes of illustration, and as the preerred silicate species, barium silicate will hereinafter be employed as being typical of the alkali metal or alkaline earth metal silicates which can be suitably employed in the present ~ r invention. The barium~silicate exhibits substantially the same index of refraction as that of the organic monomeric matrix in which it is dispersed. The filler may additionally contain a relatively small amount of borosilicate glass which imparts greater compressive strength to the resulting composite and enhances the translucency thereof thereby enabling better blending of the restorative material with the adjacent teeth. In addition, the presence of the borosilicate glass helps narrow the gap between the refractive indices of the barium silicate and the organic monomeric matrix.
- 130~105 The ability to provide a composite dental material having improved properties is achieved by the method by which the inorganic filler is prepared. This method involves a sequence of milling operations which includes wet milling to reduce the barium silicate and borosilicate to the requisite particle size and assure a very narrow particle size distribution and to uniformly disperse the borosilicate glass particles throughout the bulk of the barium silicate, Thereafter, the wet milled filler is subject to a further milling operation to etch the surface thereof which has been found to impart a dramatic increase to the diametral tensile strength of the resulting composite. Subsequently, the so treated filler is subjected to a final milling operation during which it is silanized in order to render it compatible with the resin in which it will ultimately be dispersed.
Details of the preparation of the inorganic filler, . which comprises a mixture of from about 5 to about 20% by weight of borosilicate glass and from about 80 to abut 95%
by weight barium silicate, and has an average particle size ~diameter of from about 0.5 to about 5 microns, may be found in the aforementioned ~.SO Patents No. 4,544,539 and No.
4,547,531-This invention will be better understood by referenceto the following examples which are included here for illustrative purposes only and are not to be construed as limitations, EXAMPLE 1 - Preparation of Condensation Product of 2-Hydroxyethylmethacrylate and Triethylene Glycol bis(Chloroformate).
~ A) The apparatus used was a round-bottom flask containing a magnetic stirring bar and fitted with a unnel and drying tube; said apparatus was fitted on an ice bath and stirring plate. 110 ml of pyridine was poured into the flask and 78.86 grams of 2-hydroxyethylmethacrylate (0.606 moles) was slowly added. To this was added very slowly --over a period of about two hours -- 82.S grams ~0.300 moles) o~ triethylene glycoi bis(chloroformate), A white precipitate began formin~ almost immediately, After the addition was completed, the ice bath was removed and the mixture allowed to stir overnic~ht at room temperature.
(B) The mixture was then slowly added to 77 ml of concentrated hydrochloric acid containing about 120 g of ice.
(C) The mixture from Step (B) was placed in a separatory funnel and oil and aqueous/acid layers were separated, The aqueous/acid layer waæ extracted twice with 150 ml of ethyl acetate (total 450 ml). The oil layer and the ethyl acetate extractants were combined into an organic layer~
(D) The organic layer was washed f iV9 times with 100 ml of 1 molar HCl, once with 100 ml of water, twice with 100 ml of 5% NaOH, once with 100 ml of water, and once with 100 ml of saturated NaCl solution, The product was then dried overnight with MgSO4.
(E) The dried product was decolorized with Carbon Norlte and filtered by gravity filtration. The solvent was removed on a roto-evaporator at a temperature of 40C and the product, a clear water white solution was obtained.
0.03~ of 2,6-di-tert.butyl-4-methylphenol was added as a polymerizatlon inhibitor.
(F) An IR spectrum and size exclusion chromatographic plot shows the molecular weight to be 462.
In like manner, the following additional polycarbonate dimethacrylates are prepared.
EXAMPLE -A- -(OR)n~ Mol. Wt.
NO.
2 CH2 ~OCH2CH2)3 434 3 CH2CH2CH2 (OCH2C~2)3 490 4 CH2CH2 (OCH2C~2)2 418 CH2CH2 (ocH2cH2)4 506 6 CH2 (C~l2cH2cH2)3 504 7 Ci~2 1OCH(CH3)CH2]2 418 8 CH2 (OCH2CH2)4 478 9 CH2 (ocH2cH2cH2c~2)4 446 CH2CH2 ~OCH2CH(CH3)cH2]2 11 CH2 (0CH2CH2CH2cH2c1l2)2 12 CH2-CH2 [OCH2C(CH3)2CH2]2 502 13 CH2-CH2-CH2-cH2 (OCH2CH2)2 474 14 CH2-CH(CH3) 2 2 2 446 CH2-CHtCH3) (OCH2CH2CH2)2 474 `S ~ 30 , :
.
~ 1 309 1 05 EXAM _E 16 - Self-Curing Dentin Adhesive Bondiny System.
A two-component self-curing dentin adhesive bonding system having the followiny constituents was prepared. The first component is a liquid composition having:
~5.60grams of ethanol, 4.00 grams of sodium benzene sulfinate, and o ~o grams of dihydroxy;ethyl-p-toluidin~
The second component is a resin paste composition having:
70.96 grams of a polycarbonate dimethacrylate which is the condensation reaction product of 2-hydroxyethylmethacrylate and triethylene glycol bis(chloroeorlnate), 29.03 grams of BIS-GMA, 0.0373 grams o~ 2,6-ditert.but:yl-4-1nethylphenol (inhibitor), 0.75 grams of TINUVIN P (ultraviolet absorber from . Ciba-Geigy Corporation, Ardsley, New York), 4.00 grams oE benzoyl peroxide (initiator), and 0.0097 grams of UVITEX OB*(fluorescent whitening agent from Ciba-Geigy Corporation, Ardsley, New York).
The liquid composition is used as a pretreatment for exposed dentin surfaces, while the paste composition is an example of a resinous adhesive accordiny to thls invention.
* -trade mark EXAMPLE 17 - Visible Light Cur~ble Dentin Adhesive Bonding System.
A two-component visible light curable dentin adhesive bonding system is prepared, whose first component is identical to the liquid component of Example 16. The second component is identical to the second component of Example 16 except for the absence of the dihydroxyethyl para toluidine and 0.1650g d,l-camphoroquinone and 0.2300g diethylaminoethylmethacrylate to substitute for the benzenyl peroxide.
EXAMPLE 18 - Preparation of Filler Material.
Filler material suitable for use in the dental re~torative compositions of this invention was prepared as follow~.
~oro~ilicate glass rods, available from Corning Glass Work9, Corning, New York, are cut into cylindrical form.
The resulting cylinders are loaded into a 5 gallon glass carboy until the carboy is half filled. The carboy is then filled with water, sealed and tumbled at 175 rpm for 168 hours to condition the glass rods.
The conditioned borosilicate glass rods are recovered and loaded into a 5 gallon polyvinylidene fluoride lined grinding vessel adapted for combined oscillatory and vibratory motion. The grinding vessel is loaded with the glass rods until three-quarters filled. Three kilograms of . ~, .
X-ray opaque barium silicate glass frit ~ESSCHEM T-3000 available from Esschem Corporation, Essington, Pennsylvania) having an average particle size diameter of 10 microns are added to the grinding vessel and then water is added to fill the grinding vessel. The vessel is then sealed and vibrated for 24 hours whereupon the barium silicate frit is ground to an average particle size diameter ranging between about 5and 6 microns and sufficient borosilicate glass is abraded off the rods to provide a barium silicate borosilicate glass mixture comprising about 89% barium silicate and about 11 borosilicate glass.
The resulting aqueous slurry is recovered and strained through a series of 200, 400 and 600 mesh screens. The resulting filtrate is subjected to vacuum filtration and then dried in a convection oven at 120C for 24 hours. The dried, milled filler is recovered and crushed and ground with a mortar and pestle to a fine powder.
Three kilograms of the dried, milled filler are charged to a glass carboy which is filled to one-half it volume with conditioned borosilicate glass rods prepared as described above. The carboy is then filled with six liters of a clear, colorless, aqueous solution of sodium hydroxide exhibiting a pH of 12 which is buffered with NaaHPOy. The loaded carboy is ~ealed and tumbled at 175 rpm for ~ hours. Thereafter, * trade mark . ~ 33 .,, ~ ~
the resulting milled filler is recovered and subjected to vacuum filtration. The filter cake is washed with water until pH indicators in the filtrate indicate neutrality (pH=5.5-7.0) has been essentially obtained. The recovered filter cake is then dried in a convection oven at 120C for 24 hours. The neutralized filter cake is ground to a fine powder with a mortar and pestle.
Silanization of the filler thus obtained is effected by filling a 5 gallon glass carboy to one-half its volume with borosilicate glass rods conditioned in the manner described hereinabove. Six kilograms of a solution of 8~ silane in methanol is charged to the carboy along with 3 kilograms of the milled filler recovered from the aqueous etchant milling step. The carboy is sealed and tumbled for 6 hours at 175 rpm. The silanized slurry is recovered and subjected to vacuum filtration. The resulting filter cake is dried in a vacuum oven for one hour at 120C and then pulverized with mortar and pes~tle giving rise to s;ilanized filler particles having an average particle size of 2.3 microns.
Silanization results in 4.s~ silane being coupled to the filler particles.
` This filler material can be used with resin matrices containing polycarbonate dimethacrylates in either self-curing or visible light curing ccmpositions.
EXAMPLE 19 - Visible Light Curable Filler Dental Restorative Compo~ition.
A monomeric matrix composition is prepared by admixing the following ingredients:
100 grams of the monomeric matrix composition is prepared by admixing the following:
29.00 grams BIS-GMA
70.00 grams PCDMA (condensation product of 2-hydroxymethylmethacrylate and triethyl~ne glycol bis(chloroformate) 0.99 gram TINUVIN P
0.16 grams dl-camphoroquinone 0.23 grams DEA-EMA
0.0097 grams 2,2'-(2,5-thiophenediyl) bis(5-tert-butylbenzoxazole) A filled composite re~toration material of the present invention especially suitable for anterior dental application~ i~ prepared by admixing 30~ by weight of the foregoing monomeric matrix composition with 68% by weight of the inorganic ~iller of Example 18 and 2~ by weight of colloidal fumed silica having an average particle size of about 0.04 micron. The resulting composite is a homogeneous paste comprising the monomeric composition as the matrix with the inorganic filler and the fumed silica uniformly dispersed therein.
~. , ., . , . , ~ .
1 30q 1 05 EXAMPLE 20 - Self-Curing Paste-Paste Dental Restorative Composition.
An initiator resin system is prepared by admixing the following:
29.00 grams BIS-GMA
70.00 grams PCDMA
0.15 grams BHT
4.00 grams LUCIDOL benzoyl peroxide.
0.00097 grams 2,2'-(2,5-thiophenediyl)bis(5-tert-butylbenzoxazole) The initiator paste system is obtained by admixing 21~
by weight o~ the above liquid monomeric compos;tion with 7g%
by weight of the inorganic filler of Example 18 in a planetary mixer under vacuum forming a homogeneous paste.
The paste 1~ passed through a two roll stainless steel mill to ensure homogeneity.
An accelerator resin system is prepared by admixing the ollowing:
29,~0 grams BIS-GMA
70.00 grams PCDMA
0.15 gramq ~HT
loSO grams dihydroxyethyl p toluidene (m.p.:53.5-54~5C) 4,00 grams UV-9 benzophenone The heat cure single paste dental restorative excludes ~. i . `"'.1 i 36 ~1 ~,, , ~ : .
:
any accelerator such as t-amines; dihydroxyethylpara-~oluidine or diethylaminoethylmethacrylate as well as the visible light cure initiator d,l-camphoroquinone with the presence of the heat-cure initiator only specifically benzoyl peroxide.
The accelerator paste system is obtained ~y admixing 30% by weight of the above liquid monomeric composition with 70~ by we~ght of the inorganic filler of Example 18 in a planetary mixer under vacuum forming a homogeneous paste.
The paste is passed through a two roll stainless steel mill to ensure homogeneity.
Essentially equal amounts of the foregoing initiator paste system and accelerator paste system are uniformly admixed for about one minute to form the filled composite restorative material of the present invention.
. ~
~.~1 ~ - 37
~ A) The apparatus used was a round-bottom flask containing a magnetic stirring bar and fitted with a unnel and drying tube; said apparatus was fitted on an ice bath and stirring plate. 110 ml of pyridine was poured into the flask and 78.86 grams of 2-hydroxyethylmethacrylate (0.606 moles) was slowly added. To this was added very slowly --over a period of about two hours -- 82.S grams ~0.300 moles) o~ triethylene glycoi bis(chloroformate), A white precipitate began formin~ almost immediately, After the addition was completed, the ice bath was removed and the mixture allowed to stir overnic~ht at room temperature.
(B) The mixture was then slowly added to 77 ml of concentrated hydrochloric acid containing about 120 g of ice.
(C) The mixture from Step (B) was placed in a separatory funnel and oil and aqueous/acid layers were separated, The aqueous/acid layer waæ extracted twice with 150 ml of ethyl acetate (total 450 ml). The oil layer and the ethyl acetate extractants were combined into an organic layer~
(D) The organic layer was washed f iV9 times with 100 ml of 1 molar HCl, once with 100 ml of water, twice with 100 ml of 5% NaOH, once with 100 ml of water, and once with 100 ml of saturated NaCl solution, The product was then dried overnight with MgSO4.
(E) The dried product was decolorized with Carbon Norlte and filtered by gravity filtration. The solvent was removed on a roto-evaporator at a temperature of 40C and the product, a clear water white solution was obtained.
0.03~ of 2,6-di-tert.butyl-4-methylphenol was added as a polymerizatlon inhibitor.
(F) An IR spectrum and size exclusion chromatographic plot shows the molecular weight to be 462.
In like manner, the following additional polycarbonate dimethacrylates are prepared.
EXAMPLE -A- -(OR)n~ Mol. Wt.
NO.
2 CH2 ~OCH2CH2)3 434 3 CH2CH2CH2 (OCH2C~2)3 490 4 CH2CH2 (OCH2C~2)2 418 CH2CH2 (ocH2cH2)4 506 6 CH2 (C~l2cH2cH2)3 504 7 Ci~2 1OCH(CH3)CH2]2 418 8 CH2 (OCH2CH2)4 478 9 CH2 (ocH2cH2cH2c~2)4 446 CH2CH2 ~OCH2CH(CH3)cH2]2 11 CH2 (0CH2CH2CH2cH2c1l2)2 12 CH2-CH2 [OCH2C(CH3)2CH2]2 502 13 CH2-CH2-CH2-cH2 (OCH2CH2)2 474 14 CH2-CH(CH3) 2 2 2 446 CH2-CHtCH3) (OCH2CH2CH2)2 474 `S ~ 30 , :
.
~ 1 309 1 05 EXAM _E 16 - Self-Curing Dentin Adhesive Bondiny System.
A two-component self-curing dentin adhesive bonding system having the followiny constituents was prepared. The first component is a liquid composition having:
~5.60grams of ethanol, 4.00 grams of sodium benzene sulfinate, and o ~o grams of dihydroxy;ethyl-p-toluidin~
The second component is a resin paste composition having:
70.96 grams of a polycarbonate dimethacrylate which is the condensation reaction product of 2-hydroxyethylmethacrylate and triethylene glycol bis(chloroeorlnate), 29.03 grams of BIS-GMA, 0.0373 grams o~ 2,6-ditert.but:yl-4-1nethylphenol (inhibitor), 0.75 grams of TINUVIN P (ultraviolet absorber from . Ciba-Geigy Corporation, Ardsley, New York), 4.00 grams oE benzoyl peroxide (initiator), and 0.0097 grams of UVITEX OB*(fluorescent whitening agent from Ciba-Geigy Corporation, Ardsley, New York).
The liquid composition is used as a pretreatment for exposed dentin surfaces, while the paste composition is an example of a resinous adhesive accordiny to thls invention.
* -trade mark EXAMPLE 17 - Visible Light Cur~ble Dentin Adhesive Bonding System.
A two-component visible light curable dentin adhesive bonding system is prepared, whose first component is identical to the liquid component of Example 16. The second component is identical to the second component of Example 16 except for the absence of the dihydroxyethyl para toluidine and 0.1650g d,l-camphoroquinone and 0.2300g diethylaminoethylmethacrylate to substitute for the benzenyl peroxide.
EXAMPLE 18 - Preparation of Filler Material.
Filler material suitable for use in the dental re~torative compositions of this invention was prepared as follow~.
~oro~ilicate glass rods, available from Corning Glass Work9, Corning, New York, are cut into cylindrical form.
The resulting cylinders are loaded into a 5 gallon glass carboy until the carboy is half filled. The carboy is then filled with water, sealed and tumbled at 175 rpm for 168 hours to condition the glass rods.
The conditioned borosilicate glass rods are recovered and loaded into a 5 gallon polyvinylidene fluoride lined grinding vessel adapted for combined oscillatory and vibratory motion. The grinding vessel is loaded with the glass rods until three-quarters filled. Three kilograms of . ~, .
X-ray opaque barium silicate glass frit ~ESSCHEM T-3000 available from Esschem Corporation, Essington, Pennsylvania) having an average particle size diameter of 10 microns are added to the grinding vessel and then water is added to fill the grinding vessel. The vessel is then sealed and vibrated for 24 hours whereupon the barium silicate frit is ground to an average particle size diameter ranging between about 5and 6 microns and sufficient borosilicate glass is abraded off the rods to provide a barium silicate borosilicate glass mixture comprising about 89% barium silicate and about 11 borosilicate glass.
The resulting aqueous slurry is recovered and strained through a series of 200, 400 and 600 mesh screens. The resulting filtrate is subjected to vacuum filtration and then dried in a convection oven at 120C for 24 hours. The dried, milled filler is recovered and crushed and ground with a mortar and pestle to a fine powder.
Three kilograms of the dried, milled filler are charged to a glass carboy which is filled to one-half it volume with conditioned borosilicate glass rods prepared as described above. The carboy is then filled with six liters of a clear, colorless, aqueous solution of sodium hydroxide exhibiting a pH of 12 which is buffered with NaaHPOy. The loaded carboy is ~ealed and tumbled at 175 rpm for ~ hours. Thereafter, * trade mark . ~ 33 .,, ~ ~
the resulting milled filler is recovered and subjected to vacuum filtration. The filter cake is washed with water until pH indicators in the filtrate indicate neutrality (pH=5.5-7.0) has been essentially obtained. The recovered filter cake is then dried in a convection oven at 120C for 24 hours. The neutralized filter cake is ground to a fine powder with a mortar and pestle.
Silanization of the filler thus obtained is effected by filling a 5 gallon glass carboy to one-half its volume with borosilicate glass rods conditioned in the manner described hereinabove. Six kilograms of a solution of 8~ silane in methanol is charged to the carboy along with 3 kilograms of the milled filler recovered from the aqueous etchant milling step. The carboy is sealed and tumbled for 6 hours at 175 rpm. The silanized slurry is recovered and subjected to vacuum filtration. The resulting filter cake is dried in a vacuum oven for one hour at 120C and then pulverized with mortar and pes~tle giving rise to s;ilanized filler particles having an average particle size of 2.3 microns.
Silanization results in 4.s~ silane being coupled to the filler particles.
` This filler material can be used with resin matrices containing polycarbonate dimethacrylates in either self-curing or visible light curing ccmpositions.
EXAMPLE 19 - Visible Light Curable Filler Dental Restorative Compo~ition.
A monomeric matrix composition is prepared by admixing the following ingredients:
100 grams of the monomeric matrix composition is prepared by admixing the following:
29.00 grams BIS-GMA
70.00 grams PCDMA (condensation product of 2-hydroxymethylmethacrylate and triethyl~ne glycol bis(chloroformate) 0.99 gram TINUVIN P
0.16 grams dl-camphoroquinone 0.23 grams DEA-EMA
0.0097 grams 2,2'-(2,5-thiophenediyl) bis(5-tert-butylbenzoxazole) A filled composite re~toration material of the present invention especially suitable for anterior dental application~ i~ prepared by admixing 30~ by weight of the foregoing monomeric matrix composition with 68% by weight of the inorganic ~iller of Example 18 and 2~ by weight of colloidal fumed silica having an average particle size of about 0.04 micron. The resulting composite is a homogeneous paste comprising the monomeric composition as the matrix with the inorganic filler and the fumed silica uniformly dispersed therein.
~. , ., . , . , ~ .
1 30q 1 05 EXAMPLE 20 - Self-Curing Paste-Paste Dental Restorative Composition.
An initiator resin system is prepared by admixing the following:
29.00 grams BIS-GMA
70.00 grams PCDMA
0.15 grams BHT
4.00 grams LUCIDOL benzoyl peroxide.
0.00097 grams 2,2'-(2,5-thiophenediyl)bis(5-tert-butylbenzoxazole) The initiator paste system is obtained by admixing 21~
by weight o~ the above liquid monomeric compos;tion with 7g%
by weight of the inorganic filler of Example 18 in a planetary mixer under vacuum forming a homogeneous paste.
The paste 1~ passed through a two roll stainless steel mill to ensure homogeneity.
An accelerator resin system is prepared by admixing the ollowing:
29,~0 grams BIS-GMA
70.00 grams PCDMA
0.15 gramq ~HT
loSO grams dihydroxyethyl p toluidene (m.p.:53.5-54~5C) 4,00 grams UV-9 benzophenone The heat cure single paste dental restorative excludes ~. i . `"'.1 i 36 ~1 ~,, , ~ : .
:
any accelerator such as t-amines; dihydroxyethylpara-~oluidine or diethylaminoethylmethacrylate as well as the visible light cure initiator d,l-camphoroquinone with the presence of the heat-cure initiator only specifically benzoyl peroxide.
The accelerator paste system is obtained ~y admixing 30% by weight of the above liquid monomeric composition with 70~ by we~ght of the inorganic filler of Example 18 in a planetary mixer under vacuum forming a homogeneous paste.
The paste is passed through a two roll stainless steel mill to ensure homogeneity.
Essentially equal amounts of the foregoing initiator paste system and accelerator paste system are uniformly admixed for about one minute to form the filled composite restorative material of the present invention.
. ~
~.~1 ~ - 37
Claims (33)
1. A dental resin adhesive which comprises BIS-GMA
in an amount ranging from about 20 to about 80 weight percent and a polycarbonate dimethacrylate of the formula wherein A is C1-C6 alkylene, R is C2-C5 alkylene having at least 2 carbon atoms in its principal chain and n is an integer from 1 to 4, said polycarbonate dimethyacrylate being present in an amount ranging from about 20 to about 80 weight percent.
in an amount ranging from about 20 to about 80 weight percent and a polycarbonate dimethacrylate of the formula wherein A is C1-C6 alkylene, R is C2-C5 alkylene having at least 2 carbon atoms in its principal chain and n is an integer from 1 to 4, said polycarbonate dimethyacrylate being present in an amount ranging from about 20 to about 80 weight percent.
2. A dental resin adhesive according to claim 1 in which, in the polycarbonate dimethacrylate, A is C2 or C3 alkylene, R i? ethylene or propylene, and n is 2 or 3.
3. A dental resin adhesive according to claim 2 in which the polycarbonate dimethacrylate is the condensation product of 2-hydroxyethylmethacrylate and triethylene glycol bis(chloroformate).
4. A dental resin adhesive according to Claim 1 in which the BIS-GMA is present in an amount ranging from 25 to 35 weight percent and the polycarbonate dimethacrylate is present in an amount ranging from about 65 to 75 weight percent.
5. A dental resin adhesive according to Claim 4 in which the BIS-GMA is present in an amount of about 30 weight percent and the polycarbonate dimethacrylate is present in an amount of about 70 weight percent.
6. A dental resin adhesive according to Claim 3 which additionally comprises a polymerization initiator.
7. A dental resin adhesive according to Claim 6 in which the polymerizatin initiator is dl-camphoroquinone.
8. A dental resin adhesive according to Claim 6 in which the polymerization initiator is benzoyl peroxide.
9. A dental resin adhesive according to Claim 3 which additionally contains a polymerization accelerator.
10. A dental resin adhesive according to claim 9 in which the accelerator is dihydroxyethyl-p-toluidine.
11. A dental resin adhesive according to Claim 9 in which the polymerization accelerator is diethylamino ethylmethacrylate.
12. A dental resin adhesive according to Claim 4 which additionally contains an ultraviolet absorber.
13. A dental resin adhesive according to Claim 12 in which the ultraviolet absorber is a benzotriazole.
14. A dental resin adhesive according to Claim 13 in which the ultraviolet absorber is 2-(2'-hydroxy-5'-methylphenyl)-benzotriazole.
15. A visible light curable dental adhesive according to Claim 1 which comprises from about 65 to about 75 weight percent of the polycarbonate dimethacrylate, from about 25 to about 35 weight percent of BIS-GMA, from about 0.05 to about 0.35 weight percent of dl-camphoroquinone as a polymerization initiator, from about 0.05 to about 0.5 weight percent of diethylamino ethylmethacrylate as a polymerization accelerator, and from about 0.05 to about 5 weight percent of 2-(2'hydxoxy-5'-methylphenyl)-benzotriazole or benzophenone as an ultraviolet absorber.
16. A dental adhesive according to Claim 15 in which the polycarbonate dimethacrylate is the condensation product of 2-hydroxyethylmethacrylate and triethylene glycol bis(chloroformate).
17. A dental adhesive according to Claim 1 comprising from about 65 to about 75 weight percent of the polycarbonate dimethacrylate, from about 25 to about 35 weight percent of BIS-GMA, from about 3.2 to about 5.0 weight percent of benzoyl peroxide as a polymerization initiator, and from about 0.05 to about 5 weight percent of 2-(2'-hydroxy-5'-methylphenyl)-benzotriazole as an ultraviolet absorber, said adhesive adapted to be used in conjunction with dihydroxyethyl-p-toluidine as an accelerator.
18. A dental adhesive according to Claim 17 in which the polycarbonate dimethacrylate is the condensation product of 2-hydroxyethylmethacrylate and triethylene glycol bis(chloroformate).
19. A self-curing dental adhesive according to Claim l comprising from about 65 to about 75 weight percent of the polycarbonate dimethacrylate, from about 25 to about 35 weight percent of BIS-GMA, from about 3.2 to about 5.
weight percent of benzoyl peroxide as a polymerization initiator, from about 0.5 to about 4 weight percent of dihydroxyethyl-p-toluidine as a polymerization accelerator, and from about 0.05 to about 5 weight percent of 2-(2'-hydroxy-5'-methylphenyl)-benzotriazole as an ultraviolet absorber.
weight percent of benzoyl peroxide as a polymerization initiator, from about 0.5 to about 4 weight percent of dihydroxyethyl-p-toluidine as a polymerization accelerator, and from about 0.05 to about 5 weight percent of 2-(2'-hydroxy-5'-methylphenyl)-benzotriazole as an ultraviolet absorber.
20. A dental adhesive according to Claim 19 in which the polycarbonate dimethacrylate is the condensation product of 2-hydroxyethylmethacrylate and triethylene glycol bis(chloroformate).
21. The condensation product of 2-hydroxyethylmethacrylate and triethylene glycol bis(chloroformate), said condensation product being represented by the formula
22. A method for bonding a dental restorative material to porcelain which comprises the steps of (1) applying to a prepared or treated surface of said porcelain a curable resinous adhesive comprising from about 25 to about 35 weight percent of BIS-GMA and from about 65 to about 75 weight percent of a polycarbonate dimethacrylate of the formula wherein A is C1-C6 alkylene, R is C2-C5 alkylene having at least 2 carbon atoms in its principal chain and n is an integer from 1 to 4, (2) causing said adhesive to cure, and (3) placing restorative material on the cured adhesive.
23. A method according to Claim 22 in which the polycarbonate dimethacrylate is the condensation product of 2-hydroxyethylmethacrylate and triethylene glycol bis(chloroformate).
24. A method according to Claim 23 in which the porcelain surfce is etched and there is applied to said etched surface a silane coupling agent prior to application of the resinous adhesive.
25. A method according to Claim 23 in which the resinous adhesive is a visible light curable composition.
26. A dental restorative composition which comprises about 20 to about 98 percent by weight resinous component comprising from about 25 to about 35 weight percent of BIS-GMA, and from about 65 to about 75 weight percent of a polycarbonate dimethyacrylate of the formula wherein A is C1-C6 alkylene, R is C2-C5 alkylene having at least 2 carbon atoms in its principal chain and n is an integer from 1 to 4, and about 80 to about 2 percent by weight inorganic filler.
27. A composition according to Claim 26 for use as dental crown and bridge materials comprising from about 20 to about 50 weight percent of the resinous component and from about 50 to about 85 weight percent of inorganic filler.
28. A composition according to Claim 27 in which, in the resinous composition, the polycarbonate dimethacrylate is the condensation product of 2-hydroxyethylmethacrylate and triethylene glycol bis(chloroformate).
29. A composition according to Claim 26 for use as a luring cement which comprises from about 43 to about 55 weight percent of the resinous component and from about 45 to about 57 weight percent of an inorganic filler.
30. A composition according to Claim 29 in which, in the resinous component, the polycarbonate dimethacrylate is the condensation product of 2-hydroxyethylmethacrylate and triethylene glycol bis(chloroformate).
31. A composition according to Claim 26 for use as an orthodontic sealant or orthodontic cement which comprises from about 90 to about 98% of the resinous component and from about 2 to about 10 weight percent of inorganic filler.
32. A composition according to Claim 31 in which, in the resinous component, the polycarbonate dimethacrylate is the condensation product of 2-hydroxyethylmethacrylate and triethylene glycol bis(chloroformate).
33. A dental restorative composition according to Claim 26 in which the inorganic filler has an average particle size diameter ranging from about 0.5 to 5 microns.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US71733285A | 1985-03-29 | 1985-03-29 | |
| US717,332 | 1985-03-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1309105C true CA1309105C (en) | 1992-10-20 |
Family
ID=24881583
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000505596A Expired - Fee Related CA1309105C (en) | 1985-03-29 | 1986-04-01 | Dental resin materials |
Country Status (2)
| Country | Link |
|---|---|
| CA (1) | CA1309105C (en) |
| DE (1) | DE3610808A1 (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3632868C2 (en) * | 1985-03-29 | 1995-09-14 | Pentron Corp | Dental adhesive |
| US5276068A (en) * | 1985-03-29 | 1994-01-04 | Jeneric/Pentron, Inc. | Dental resin materials |
| US4978391A (en) * | 1987-11-13 | 1990-12-18 | Dentsply Management Corp. | Intraoral medicament delivery and procedure |
| PH31064A (en) * | 1990-09-07 | 1998-02-05 | Nycomed As Of Nycoveten | Polymers containing diester units. |
| US5133957A (en) * | 1991-09-18 | 1992-07-28 | Bisco, Inc. | Composition and method for desensitizing dentin |
| DE19646782C2 (en) * | 1996-11-13 | 2000-05-25 | Merck Patent Gmbh | Bioresorbable polymerization products from radiation-curable binder systems |
| DE19749349A1 (en) | 1997-11-07 | 1999-05-12 | Espe Dental Ag | Polymerizable composition and its use as an adhesion promoter |
| DE19806572B4 (en) | 1998-02-17 | 2007-01-25 | 3M Espe Ag | Adhesive attachment of dental filling materials |
| DE19854580A1 (en) * | 1998-11-26 | 2000-05-31 | Up To Dent Ag Balzers | Gel for treatment of dental caries and dental filler based on methacrylate or methacrylate-modified polycarboxylic acid |
| DE102012107535A1 (en) | 2012-08-16 | 2014-02-20 | Bess Pro Gmbh | Bioresorbable adhesives and their use in the medical field |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3200142A (en) * | 1963-02-01 | 1965-08-10 | Rafael L Bowen | Surface-active comonomer and method of preparation |
| DE2531180C2 (en) * | 1975-07-11 | 1982-04-01 | Institut chimičeskoj fiziki Akademii Nauk SSSR, Moskva | Anaerobic mixture |
| JPS5914001B2 (en) * | 1978-08-29 | 1984-04-02 | 株式会社クラレ | dental materials |
| US4479782A (en) * | 1983-04-18 | 1984-10-30 | Scientific Pharmaceuticals, Inc. | Visible light-cured orthodontic adhesive |
-
1986
- 1986-04-01 DE DE19863610808 patent/DE3610808A1/en active Granted
- 1986-04-01 CA CA000505596A patent/CA1309105C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| DE3610808C2 (en) | 1989-10-19 |
| DE3610808A1 (en) | 1986-10-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5276068A (en) | Dental resin materials | |
| EP0643752B1 (en) | Resinous dental composition based on polymerisable polysiloxanes | |
| AU710254B2 (en) | A metal fluoride particle and a dental composition including metal fluoride particles | |
| US5219899A (en) | Pasty dental material which is an organopolysilane filler combined with a polymerizable bonding agent | |
| GB2251861A (en) | Curable composition for dental restoration | |
| EP0983762A1 (en) | Dental restorative composition | |
| CA1309105C (en) | Dental resin materials | |
| US5132337A (en) | Pasty dental material | |
| GB2144754A (en) | Dental filling material | |
| JP3492625B2 (en) | Light-cured tooth cleft filling material composition for caries prevention | |
| JPH0251522B2 (en) | ||
| US5248706A (en) | Process for preparing a pasty dental material which is an organopolysiloxane filler combined with a polymerizable bonding agent | |
| US4880887A (en) | Method for curing dental resins | |
| US5234972A (en) | Dental adhesive comprising an itaconic acid monoester compound | |
| US4923400A (en) | Dental adhesive composition | |
| US4388421A (en) | N-(2-Hydroxy-3-methacryloyloxypropyl)-aminobenzoic acid derivatives and dental adhesive composition containing same | |
| JP2568072B2 (en) | Dental resin composition | |
| JPH11209213A (en) | Dental adhesive composition having sustained release properyy of fluorine | |
| JPS60166603A (en) | Adhesive composition for dental use | |
| JP2732955B2 (en) | Curable composition | |
| JPS5928532B2 (en) | Dental adhesive composition | |
| JP2578212B2 (en) | Maleic acid monoester compounds and adhesives containing them | |
| AU637269B2 (en) | A polymerizable dental material | |
| JP3134045B2 (en) | Diacrylate compound | |
| JP3606325B6 (en) | Resin dental composition based on polymerizable polysiloxanes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKLA | Lapsed |