JP2568072B2 - Dental resin composition - Google Patents

Description

FIELD OF THE INVENTION This invention relates to polycondensation products found to be useful in restorative dentistry. More specifically, it relates to a polycondensation product that can be used as a major component of resinous adhesives and as a dental restorative. The resinous adhesives of the present invention are suitable for bonding virtually all types of dental surfaces including enamel, dentin, porcelain and metal surfaces. They are particularly useful as a method for bonding dental restorative material to exposed dentin. The filled composition containing a resin adhesive as a component is useful as a crown and bridge material, as a sealant or cement, or as an orthodontic sealant depending on the content of the filler.

PRIOR ART Materials used in recent years for dental restoration mainly consist of methacrylic acid polymer. Typical of these polymeric materials are U.S. Pat.Nos. 3,066,112, 3,179,623, 3,194,784.
Nos. 3,751,399, and 3,926,906. Of particular note is the compound 2,2'-bis [4- (3-methacryloxy-, which is a condensation product of bisphenol A and glycidyl methacrylic acid.
2-hydroxypropoxy) -phenyl] -propane (hereinafter abbreviated as "BIS-GMA"). Other methacrylic acid polymers such as ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate are also commonly used as diluents, but polyurethane dimethacrylate is also a dental agent of this type. The main restorative material is used as a polymer. BI
S-GMA is highly viscous at room temperature, but is generally suitable for other suitable purposes, including the alkylene glycols or trimethylolpropyl trimethacrylates mentioned above, 1,6-hexanediol dimethacrylate, 1,3-butanediol dimethacrylate and the like. It is diluted with a low viscosity monomer such as the material.

Problems to be Solved by the Invention When these acrylic resin materials were first developed, they were used unfilled and for dental purposes. However, acrylic materials have shown a high coefficient of thermal expansion as compared to the coefficient of thermal expansion of the tooth structure, and it has been found that these unfilled substances are not satisfactory. The imbalance in thermal expansion, coupled with a high degree of shrinkage during polymerization, led to poor edge adaptability, leading to secondary collapse. Moreover, these unfilled acrylic resin materials have the property of being worn, and the physical, mechanical and optical properties as a whole are extremely poor. Therefore, composite dental restorative materials containing these methacrylate resins and fillers were developed from the beginning. The filler is generally an inorganic filler based on silica, silicate glass, or quartz.

Over the years, there have been some improvements in resin matrix components, filler components and other additives in dental restorative materials, especially antioxidants, UV absorbers, polymerization initiators, polymerization accelerators etc. . It now exhibits a high degree of diametral tension, excellent optical activity and polishability and low water absorption while at the same time meeting all the requirements detailed in ADA Specification No. 27 for direct filling resins. Materials are available.
A particularly suitable restorative material is co-filed patent application No. 636,970 filed August 2, 1984, which is now a self-curing two-component composition disclosed in US Pat. No. 4,547,531; Patent application No. 677, filed on December 3, 1984,
No. 595, now a new composition containing an improved inorganic filler material such as the visible light curable compositions disclosed in US Pat. No. 4,544,359.

All of these dental restorative materials require permanent bonding to the tooth structure. Generally, the tooth surface is treated with an acid such as orthophosphoric acid at 30 to 50% by weight to corrode the enamel surface of the tooth and expose the rod-shaped enamel above it in the prismatic structure of the honeycomb. However, fine mechanical joining improves the adhesion of the cured resin material. In addition to this method of corrosion, current technology teaches the use of various additives and improved monomer mixtures designed to provide improved adhesion.

Acid corrosion techniques have been beneficial to bond dental restorative materials to the enamel of teeth by themselves or in combination with modification of resin materials to increase adhesive capacity. There has been no completely satisfactory way to bond such restorative materials to dentin. The acid corrosion method is not suitable for bonding dental restorative materials to dentin because the tubular structure of the tooth creates a passage to the pulp. Acid causes great irritation and pain to the patient, leading to medullary necrosis. In addition, since the dentin has a high content of organic substances (proteins), it gives a low degree of adhesion as compared with enamel.

Recently, (a) acid salts such as ferrous oxalate or ferrous citrate, (b) adducts of N- (p-tolyl) -glycine and glycidyl methacrylate, N-phenylglycine and glycidyl metal acrylate. Alternatively, an addition reaction product of N-phenylglycine itself, and (c) an addition reaction product of pyromellitic dianhydride and 2-hydroxyethyl methacrylate, 3,3 ′, 4,4′-benzophenone tetracarboxylic acid dianhydride A method for improving the adhesion of dental composites to dentin surfaces has been proposed, which comprises the sequential application of an addition reaction product with a compound and 2-hydroxyethyl methacrylate or 4-methacryloxyethyl trimellitic anhydride. However, this multi-step method has proved unsatisfactory.

In addition to the many desired improvements in dentin bonding methods, it is also desirable to achieve improved bonding to enamel, metal alloys and other dental surfaces such as porcelain in particular.

Recent developments in the development of filled dental restorative materials have resulted in a high degree of abrasion resistance, more manageable properties,
Despite the resulting composite materials having a more pleasing appearance, there is still considerable room for improvement in this area. Especially desirable are crown and bridge materials,
Improved filled composite materials for use as denture base materials, sealants or cements and orthodontic sealants.

Accordingly, it is one of the main objects of the present invention to provide a dentin bonding method using a mild pretreatment to obtain a suitable surface for using a dental adhesive. Is. It is another major objective of the present invention to provide a dental adhesive suitable for bonding properly created dentin surfaces.
Yet another object of the present invention is to provide a new adhesive material which is particularly suitable for application to exposed dentin surfaces in combination with a suitable pretreatment. Other purposes include providing improved adhesive materials for bonding to enamel, metal alloys and porcelain. Yet another object is to provide improved filled composites for use as sealants, denture base materials, orthodontic sealants and other dental restorative materials. Other objects of the present invention will be apparent from the following specification.

The present invention provides a resin adhesive composition comprising BIS-GMA and a polycarbonate dimethacrylate condensation product, wherein the resin adhesive composition is 2 parts by weight of Formula I under carefully controlled conditions. Wherein A is a C ₁ -C ₆ alkylene group, and 1 part by weight of formula II (In the formula, R has at least two carbon atoms in the main chain,
A C ₂ -C ₅ alkylene radical, n is an integer of 1 to 4. A) bis (chloroformate). Of particular interest are novel condensation products of 2-hydroxyethyl methacrylate and triethylene glycol bis (chloroformate). These new unfilled adhesive compositions constitute the dental adhesive material of the present invention. These dental adhesives
It can be applied to all kinds of dental surfaces including enamel, dentin, porcelain, but is particularly suitable for use with pretreated dentin surfaces.

The dental adhesive of the present invention includes both visible light curable and self-curing compositions. The visible light curable composition is BIS-GMA
In addition to the polycarbonate dimethacrylate condensation product, a normal polymerization initiator, a polymerization accelerator, an ultraviolet absorber,
Including fluorescent whitening agent. In self-curing adhesive compositions, the polymerization accelerator may be included in the adhesive composition itself or may be present in the liquid composition used to pretreat exposed dentin.

The present invention also provides a method of bonding a dental adhesive material to the exposed dentin surface. Surface coating teeth 3% H ₂ O ₂ without vitality, 17% EDTA, or 5% N _a OCl, then the alcoholic solution of an alkali metal salt of benzene sulfinic acid,
It is then pretreated by evaporating the alcohol from the solution. The treated dentin surface is then coated with the resin adhesive of this invention. The adhesive is then cured and a suitable dental restorative material is applied. When the adhesive is a self-curing composition, the polymerization accelerator can be included in the adhesive itself or added to the alcohol pretreatment solution, and in the latter case, the accelerator is alcohol-evaporated and then dentin. Remains on the surface.

In addition to the unfilled resin adhesive composition, there is also provided a filled composition comprising the new BIS-GMA and polycarbonate dimethacrylate condensation products and various additives as major components. Such filled compositions can be used as a variety of dental and crown and bridge materials, sealants or cements, denture base materials, restorative functions including orthodontic sealants, and dental restorative materials. It is useful.
Polycarbonate dimethacrylate condensation products that can be used in the present invention have the general formula I (Wherein A is a C ₁ -C ₆ alkylene group), hydroxyalkyl methacrylate, and general formula II (In the formula, R has at least two carbon atoms in the main chain,
n is an integer of 1 to 4. ) Is obtained by a condensation reaction with bis (chloroformate). "Main chain" means a chain of carbon atoms that acts as a bridge between oxygen atoms.

In the hydroxyalkyl methacrylate, the A group is, for example, a methylene group, an ethylene group, a propylene group, 2,
It may be a 2-dimethylpropylene group, a butylene group, or the like. Preferred compounds are those such as 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate where A has 2-3 carbon atoms, with 2-hydroxyethyl methacrylate being especially preferred. In bis (chloroformate), examples of the R group include ethylene group, 1-methylethylene group, 1,2-dimethylethylene group, propylene group, 2-methylpropylene group, 2,2-dimethylpropylene group, butylene group. Etc. are included. Preferred R groups are ethylene groups, propylene groups for which the preferred values of the integer n are 2 and 3. A particularly preferred bis (chloroformate) reagent is triethylene glycol bis (chloroformate). Or other diethylene glycol bis (chloroformates), tetraethylene glycol bis (chloroformates), dipropylene glycol bis (chloroformates) and tripropylene glycol bis (chloroformates) are also very suitable. In general, the bis (chloroformates) used in the practice of the present invention are compounds of the above general formula, which are liquid at the temperatures used for condensation reactions.

The hydroxyalkyl methacrylates and various bis (chloroformates) required as starting materials for the polycarbonate dimethacrylate condensation reaction are either commercially available or can be easily prepared by known methods.
For example, the bis (chloroformate) starting material can be prepared by reacting phosgene with the appropriate glycol by methods well known in the art. Triethylene glycol bis (chloroformate) and some other bis (chloroformates) are available from PPG Industries (Chicag
o). It is available from Illinois).

Polycarbonate dimethacrylate condensation product is 2
It can be prepared by reacting moles of hydroxyalkyl methacrylate and 1 mole of bis (chloroformate). The condensation product has the general formula IV (Wherein A, R and n are as defined above).

Preferred polycarbonate dimethacrylate condensation products according to Formula IV have a molecular weight between about 418 and 506. Particularly preferred is the novel polycarbonate dimethacrylate obtained from triethylene glycol bis (chloroformate) and 2-hydroxyethyl methacrylate, of formula V It has a structure of and a molecular weight of 462.

Polycarbonate dimethacrylate condensation products are obtained by slow dropwise addition of bis (chloroformate) to hydroxyalkyl methacrylate in a suitable solvent such as pyridine. The solution is well stirred during the condensation reaction and the temperature is about -5 ° C to 10 ° C, preferably -2 ° C to 4 ° C
Must be maintained. Conveniently the reaction can be carried out in an ice bath and the temperature maintained between 3 ° C and 4 ° C. These low temperatures are necessary to prevent polymerization. After the condensation reaction is complete, the product can be prepared by methods well known in the art.
Separated from solvents, unreacted starting materials, by-products, etc.

Many condensation products within the scope of formula (IV) are 1973
U.S. Pat. No. 3,716,571 granted Feb. 13, 2013, and 1
Soviet Inventor Certificate No. 732,291 advertised on May 8, 980
No. Until now, they have been used as an adhesive composition such as a resin having enhanced gloss, an electric insulating composition, and a heat-resistant composition, but as a component of a dental adhesive or a dental restorative composition, they have been used. Was not done. A special condensation product of triethylene glycol bis (chloroformate) and 2-hydroxypropyl methacrylate is a new product. Aromatic polycarbonates, obtained from bisphenol A and diphenyl carbonate or phosgene, are known products and are used as materials for denture base materials (Stafford et al., "Polycarbonates": Dentures). Preliminary report on the use of polycarbonate as a substrate material,
Dental Practitione
r) Volume 17, pp. 217-23 (1967). ) In comparison to the relatively low molecular weight condensation materials that can be used in the present invention, these previously described polycarbonates have phenylene groups rather than alkylene groups and have a preferred molecular weight of 30,000 to 200,000.

The subject polycarbonate dimethacrylate is suitable for incorporation into dental adhesives, including those that are visible light curable or self curable. Typically, these polycarbonate dimethacrylates contain from about 20 to about 60 wt% BIS.
-Mixed with a resin composition of GMA and about 40 to about 80 wt% polycarbonate dimethacrylate. The preferred range of BIS-GMA is 25-35% by weight, especially about 30% by weight, and the preferred range of polycarbonate dimethacrylate is 65-35% by weight.
75% by weight, especially 70% by weight. In addition to these monomeric materials, the resin adhesive compositions of the present invention also typically include polymerization initiators, polymerization accelerators, UV absorbers, antioxidants, and well-known in the art. Other additives may be included.

Polymerization initiators and polymerization accelerators are commonly used in these resin adhesive compositions, although the presence of a polymerization accelerator in the self-curing composition of the present invention is optional. One form of the self-hardening dentin bonding method of the present invention is that the polymerization accelerator can be mixed with the dentin pretreatment composition rather than the resin adhesive composition.

The polymerization initiator that can be used in the resin adhesive of the present invention is a conventional initiator known in the art. For example, visible light curable compositions include benzyl diketone and especially
Approximately 0.05% of a light-sensitive compound such as dl-camphoroquinone
~ Use about 0.5% by weight. Self-curing compositions generally
Free radical polymerization initiators, such as peroxides, can be included in about 2 to about 6 weight percent. Particularly suitable free radical initiators are lauroyl peroxide, tributyl hydroperoxide and more suitable benzoyl peroxide.

Polymerization accelerators that can be used in the compositions of the present invention are various organic tertiary amines well known in the art. In visible light curable resins, tertiary amines generally include acrylic acid derivatives, such as diethylaminoethyl acrylate, dimethylaminoethyl methacrylate, and especially diethylaminoethyl methacrylate, from about 0.05 to about
Used in the range of about 0.5% by weight. In self-curing compositions, the tertiary amine generally uses aromatic tertiary amines such as dimethyl-p-toluidine, dihydroxyethyl-p-toluidine, etc. in the range of about 0.05 to about 4.0% by weight. The compound can optionally be mixed into the pretreatment solution rather than the resin adhesive.

Also, in these resin adhesives, the ultraviolet absorber is about 0.
It is preferably used in the range of from 05 to about 5.0% by weight. Such UV absorbers are especially desirable to add to the visible light curable composition to avoid any accidental UV discoloration. Suitable UV absorbers include various benzophenones, especially the American Cyanamide Company (Am
UV-9 and UV-5411, available from the erican Cyanamid Company), and benzotriazoles known in the art, especially Ciba Geigy Corporation.
-Geigy Corporation, Ardsley, New York to TINUVIN
2- (2'-hydroxy-) sold under the trademark P)
5'-methylphenyl) -benzotriazole.

A typical visible light curable dental adhesive of the present invention is 65-75.
Polycarbonate dimethacrylate condensation product of wt% triethylene glycol bis (chloroformate) and 2-hydroxyethyl methacrylate, 25-35 wt% BIS-GMA, 0.05-0.35 wt% dl-dimethylcamphoroquinone, 0.05 Included in the range of .about.0.5% by weight diethylaminoethylmethacrylate, and 0.05 to 5% by weight of Tinuvin Pee UV absorber in individual amounts to give 100% by weight of polymer system.

Typical adhesives used in self-curing systems are 65-75 wt% triethylene glycol bis (chloroformate) and polycarbonate dimethacrylate condensation products of 2-hydroxyethyl methacrylate, 25-35 wt% BIS-GMA. , 3.2 to 5.0% by weight of benzoyl peroxide, and 0.05 to 4.5% by weight of Tinuvin-Pie UV absorber in individual amounts to give 100% by weight of polymer system. Moreover, when the polymerization accelerator is incorporated into the resin adhesive rather than the dentin pretreatment composition, the adhesive further comprises 0.05-4 wt% dihydroxy-p-toluidine.

It is also possible to use the polycarbonate dimethacrylate condensation product for self-curing and visible light curable adhesives. In this "combination" system, the resin adhesive composition is identical to the visible light curable composition described above with the addition of about 3.2 to about 5.0 weight percent benzoyl peroxide. The present invention also includes methods of bonding dental restorative materials to various surfaces such as enamel, porcelain, metal alloys and especially exposed dentin surfaces. For such a dentin surface, the dentin surface is pretreated and the surface treated with the resin adhesive composition of the present invention is coated.

When the dentin surface is exposed as a result of the cutting and polishing that occurs during the course of treatment, a "contamination layer" is formed on the dentin surface, which is mainly composed of organic material. It is believed that this contaminated layer is formed by partially filling the dentinal tubules as well as filling the mouth of the dentin tubules. The contaminated layer must be removed prior to any pretreatment of the tooth surface. This contaminated layer is, for example, a 5% sodium hypochlorite aqueous solution, a 17% ethylenediaminetetraacetic acid aqueous solution or 6%.
It can be easily removed by applying a% citric acid gel. The method of the present invention presupposes the prior removal of the contaminated layer.

When applying the resin adhesive composition of the present invention to the dentin surface,
The first step after the usual preventative treatment, for example with hydrogen peroxide, is to pretreat the dentin surface with an alcoholic solution of an alkali metal salt of benzenesulfinic acid, preferably sodium salt of benzenesulfinic acid. If the dental restorative composition used is a self-hardening composition, the dentin alcohol pretreatment solution may also comprise an organic tertiary amine, preferably an aromatic amine such as dihydroxyethyl-p-toluidine. . A typical alcohol solution used for this pretreatment contains about 3 to about 5% by weight sodium benzenesulfinate and about 1 to about 21/2% by weight dihydroxyethyl-p-toluidine, the balance being alcohol. is there.

The alcohol solution is applied to the dentin surface and then evaporated. Evaporation is done by a stream of dry air or other methods well known in the art. This pretreatment step serves the functions of (1) prevention and (2) improvement of the adhesiveness of the resin adhesive on the dentin surface. Benzenesulfinate causes accelerated chelation polymerization of the dentin surface with the adhesive, resulting in partial filling of the dentin tubules. Thus, the dentin surface is likely to have a considerable increase in adhesion. This enhanced roughness is achieved without the use of irritants such as phosphoric acid.

If the alcohol solution contains an aromatic tertiary amine, it will be placed on the surface of the dentin and will act as an accelerator when the resin adhesive is applied to the polymerization accelerator in the third step.

The resin adhesive composition of the present invention is then coated onto the pretreated dentin surface by methods well known in the art. When the resin adhesive composition is a photocurable composition, the polymerization is preferably visible light, such as about 250 to about 750 nanometers,
For example, 15 capable of generating light with a wavelength of 450 to 500 nanometers, and more preferably 468 to 492 nanometers.
Achieved by exposure to a 0 watt halogen light source or any visible light source. If the resin adhesive composition is a self-curing composition, it should provide a polymerization time of about 3-6 minutes.

The adhesive composition of the present invention is also suitable for use on properly prepared enamel surfaces and can be applied simultaneously to pretreated dentin surfaces and adjacent enamel surfaces. Such enamel surface can be etched, for example with 30 to 50% by weight orthophosphoric acid. Obviously, measures must be taken to protect the exposed dentin from the enamel etching process.

The composition of the present invention is used as a bonding system to remove contaminating layers from the dentin surface and the adjacent exposed enamel layer by acid etching using well known etching materials such as orthophosphate gel. , Used as a bond system for dentin bonding. Medullary protection is achieved, for example, by using a calcium hydroxide composition.

After scraping all plaque from the dentin surface, clean it with oil-free dental pumice and water. Then, a 3% hydrogen peroxide solution is applied as a preventive measure, and then the dentin surface is washed and dried.

The repair site is then separated from the gingival margin, gingival papilla and adjacent tooth preparation by sliding a prefabricated contoured strip into the gingival sulcus using Mylar polyester strips. A piece of polyester is squeezed to seal the gingival margin and thus the repair site is separated from the flow of saliva and interstitial fluid. Additionally, a dental wedge is recommended to separate the teeth, facilitate contact between adjacent surfaces, and hold the polystel pieces in place. Brush a few drops of sodium benzenesulfinate solution in ethanol onto the dentin surface. If a self-curing adhesive system is used, the alcohol solution can additionally contain dihydroxy-p-toluidine. Evaporation of ethanol or air drying is recommended for this purpose.

The resin adhesive composition is then applied over the cavity edges over the etched enamel and to the dried, conditioned and conditioned dentin surface. An extremely thin layer of resin adhesive is created by removing excess material from the enamel and dentin surfaces with a dry brush and a jet of oil-free air. When the adhesive composition is a visible light cured material, it must be exposed to visible light such as Spectra-Lite for about 40 seconds. When the self-curing adhesive composition is used on a pretreated dentin surface or when used with a polymerization accelerator mixed in the resin adhesive itself,
A time of about 3-5 minutes must be allowed for the polymerization. Immediately thereafter, the dental restorative paste should be placed on top of the adhesive. Alternatively, the restorative paste and adhesive can be cured simultaneously.

In addition to using the restorative material as it is in the presence of exposed dentin, the resin adhesive composition of the present invention also bonds enamel, porcelain and metal surfaces to each other or all acrylic materials. And other dental restorative materials, including various crown and bridge alloy compositions, can also be used to bond enamel, porcelain and metal surfaces. They are applied to the surface for adhesion by methods well known in the art. Typically, the surface is prepared, for example by etching or sandblasting.

The subject adhesive materials are also suitable for promoting the adhesion of various dental restorative materials to porcelain surfaces. Generally, a porcelain surface is etched with, for example, hydrofluoric acid, and the etched surface is coated with the resin adhesive composition of the present invention. The adhesive then comprises various visible light curing additives described above, for example, where heat curing or visible light curing is desired. The dental restorative material is then applied to the cured adhesive. Such restorative materials include virtually all materials now used in dentistry and may also include the novel filled compositions of the present invention.

When the resinous composition of the present invention is used as a porcelain adhesive, it is preferable to have a silane coupling agent used between the etched surface of the porcelain and the resin adhesive composition. The silane coupling agent is brushed onto the etched porcelain surface prior to applying the resin adhesive. Useful silane coupling agents are selected from a group of organosilicon monomers such as aminoalkyl (trisalkoxy) silanes of the formula R-SiX ₃ , where R is attached to the silicon in a hydrolytically stable form. X represents a hydrolyzable group which is converted into a silanol group by hydrolysis. Most commonly, R consists of a 3-aminopropyl group or a 3-ureidopropyl group, which further comprises one or two --NH (CH ₂ )-
It may be separated by n parts (n-1 and 2). Preferable X is an alkoxy group selected from the group consisting of a methoxy group, an ethoxy group, a 2-methoxyethoxy group or an acetoxy group, particularly γ-methacryloxypropyltrimethoxysilane A- of Union Carbide.
It is 174. Preferred silane coupling agents are commercially available from Union Carbide as the A1100-A1160 series, which are 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane (from Dow Corning). Z-6020 is also available), N-2-aminoethyl-3
-Aminopropyl-trimethoxysilane or 3-ureidopropyltriethoxysilane. With regard to such a silane coupling agent, the curability of the resin adhesive is preferably a visible light curing system rather than a thermosetting system, and heat causes decomposition of silane. However, the flash point of the preferred silane, A-174, is 275 ° C, well above the thermoset temperature range.

The filled compositions of the present invention include all inorganic fillers used in modern dental restorative materials, the amount of such fillers being determined by the particular function of the filled material. Thus, for example, when making crown and bridge materials, the resin composition of the present invention is in an amount in the range of about 20 to about 40 wt% and the filling material is in the range of about 60 to about 80 wt%. Exist in the amount. A typical composition of crown and bridge material is about 30% resin material and about 70% filler. As a sealing cement, the resin material of the present invention is about 43 to about 55% by weight, and the filler is about 45 to about 57% by weight. In orthodontic sealants and orthodontic cement compositions, it is typically about 90 to about 98% by weight resinous material and about 2 to about 10% filler.

The filled compositions of the present invention generally include suitable filler materials such as silica, silicate glass fillers or quartz, which are conjugated to a resin matrix or a coupling agent that is conjugated to both. can do. Particularly suitable as a filling material for dental restorative materials produced by the present invention, having a particle size of about 0.01 to about 0.07 microns,
It is obtained by a series of micronization processes consisting of wet micronization in an aqueous medium, surface corrosion micronization and silanization micronization in a silane solution. Such inorganic filler materials are disclosed in US Pat. Nos. 4,544,359 and 4,547,531. Filled or partially filled compositions as well as unfilled compositions can be prepared in visible light curable and self-curing (paste-paste) formulations.
The filled composite restorative material comprises about 20 to about 30% by weight, preferably 20 to 26% by weight of either unfilled visible light curable dental adhesive or unfilled self-curing adhesive composition. , About 65 to about 85% by weight, preferably about 75 to about 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 of about 0.5-5 microns uniformly dispersed in an organic polymerizable monomer matrix comprising polycarbonate dimethacrylate. Moreover, a relatively small amount of pyrogenic silica is predispersed in the monomer matrix. The inorganic filler consists mainly of radiopaque alkali metal or alkaline earth metal silicates such as lithium silicate, barium silicate and the like. For purposes of illustration and as a preferred silicate class, barium silicate is used here as a typical alkali metal and alkaline earth metal silicate suitable for use in the present invention. Barium borosilicate exhibits a refractive index that is substantially the same as that of the organic monomer matrix in which it is dispersed. In addition, the filler can contain a relatively small amount of borosilicate glass, which imparts a large compressive strength to the resulting composite material and also increases the translucency so that the restorative material is better protected by the surrounding teeth. Allows you to blend well. Moreover, the presence of borosilicate glass helps to narrow the refractive index gap between barium silicate and the organic monomer matrix.

The ability to create an improved composite dental material is achieved by the way the inorganic filler is made. This method refines barium silicate and borosilicate to the required particle size to secure a very narrow particle size distribution, and wet pulverization that uniformly disperses borosilicate glass particles in barium silicate powder. Including a step of pulverization operation including. It was then found that the wet milled filler was subjected to further micronization operations to etch its surface, imparting a dramatic increase in tensile strength in diameter of the resulting composition. The filler thus treated is then subjected to a final micronization operation, during which time it is silanized so that it is compatible with the final dispersed resin.

The details of the preparation of the inorganic filler consist of about 5 to about 20% by weight borosilicate glass and about 80 to about 95% by weight barium silicate and have an average particle size of about 0.5 to about 5 microns in diameter. , These are the aforementioned U.S. Pat.
No. 47,531.

The present invention may be better understood by reference to the following examples, which are set forth herein for purposes of illustration only and are not intended to be limiting. .

Examples Example 1-2 Preparation of condensation product of 2-hydroxyethyl methacrylate and triethylene glycol bis (chloroformate).

(A) The apparatus used was a round bottom flask equipped with a stirrer and equipped with a funnel and a drying tube, which was fixed on an ice bath and a stir plate. 110 ml of pyridine was poured into the flask and 78.86 g of 2-hydroxyethyl methacrylate (0.606 mol) was added slowly. To this was added very slowly-over 8 hours, -82.5 g (0.300 mol) of triethylene glycol bis (chloroformate). Almost immediately after that, a white precipitate started to form. After the addition was complete, the ice bath was removed and the mixture was allowed to reach room temperature with stirring overnight.

(B) The mixture was then added to 77 ml concentrated hydrochloric acid containing about 120 g ice.

(C) The mixture of step (B) was placed in a separatory funnel and the oil and acidic aqueous layer were separated. The acidic aqueous layer was extracted twice with 150 ml of ethyl acetate (450 ml in total). The oil layer and the ethyl acetate extract were combined with the organic layer.

(D) The organic layer is 5 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 10 times.
It was washed once with 0 ml of saturated aqueous NaCl solution. Then the product is M
Dry overnight with gSO ₄ .

(E) The dried product is Carbon Norite.
It was decolorized with Norite) and filtered by gravity filtration. The solvent was removed on a rotary evaporator at a temperature of 40 ° C. to give a clean white aqueous solution. 0.03% of 2,6-di-tert-butyl-4-methylphenol was added as a polymerization inhibitor.

(F) IR spectrum and size exclusion
Chromatographic plot (Size exclusion chr
omatographic plot) showed that the molecular weight was 462.

The following additional polycarbonate dimethacrylates are prepared in a similar manner.

Example 16-Self-curing Dental Adhesive Composition A two-component self-curing dental adhesive composition having the following components was prepared. The first component is a liquid composition containing 95.60 g ethanol, 4.00 g benzenesulfinic acid, and 0.40 g dihydroxy-ethyl-p-toluidine. The second component is polycarbonate dimethacrylate, a condensation reaction product of 70.96 g of 2-hydroxyethyl methacrylate and triethylene glycol bis (chloroformate), 29.03 g of BIS-GMA, 0.0373 g of 2.6-di-tertiary. Butyl-4-butylphenol (inhibitor) 0.75 g of Tinuvin Pee (UV absorber available from Ciba Geigy Corporation, Ardsley, NY), 4.00 g of benzoyl peroxide (initiator), and 0.0097 g of Ubitex.・ Orvie (UVITEX OB)
(A fluorescent whitening agent released from Ciba Geigy Corporation, Ardsley, New York).

The liquid composition is used as a pretreatment agent for the exposed dentin surface, while the paste composition is an example of the resin adhesive of the present invention.

Example 17-Visible Light Curable Dental Adhesive Composition A two component visible light curable dental adhesive composition is prepared with the first component being the same as the liquid component of Example 16. The second component is the same as the second component of Example 16 except that the polymerization accelerator benzoyl peroxide is not present.

Example 18-Preparation of filling material.

Filling materials suitable for use in the dental restorative composition of the present invention were prepared as follows.

Corning Glass Works
rks), Corning, New York (New Y
A borosilicate glass rod, available from Ork), is cut into a cylinder. The resulting cylinder is placed in a 5 gallon glass carboy and half filled. The carboy is then filled with water, sealed and the glass rod conditioned by shaking at 175 rpm for 168 hours.

The conditioned borosilicate glass rod is collected and placed in a milling vessel lined with 5 gallons polyvinylidene fluoride suitable for vibrating action. The grinding tank is filled with glass rods and filled up to three quarters. X-ray opaque barium silicate glass frit with an average particle size of 10 microns (ESSCHEM T-3000, Esschem Corporation, Essington
ton), available from Pennsylvania), and then water is added to fill the grinding tank. The container was then sealed and shaken for 24 hours,
Barium silicate frit is ground to an average particle size of about 5-6 microns and sufficient borosilicate glass is scraped from a glass rod to remove about 89% barium silicate and about 11% borosilicate glass. A barium silicate-borosilicate glass mixture is obtained.

The resulting aqueous slurry is collected and a set of 200, 400 and
Filter through a 600 mesh screen. The resulting filtrate is vacuum filtered and then dried in a convection oven at 120 ° C for 24 hours. The dried and crushed filler is recovered and ground with a mortar in a mortar to a fine powder.

3 kg of the dried, ground filler is added to a glass carboy, which is filled to half its capacity with a conditioned borosilicate glass rod prepared as described above. The carboy is then filled with 6 L of an aqueous solution of clear colorless sodium hydroxide, pH 12, buffered with Na ₂ HPO ₄ . The added carboy is sealed and shaken at 175 rpm for 4 hours. The crushed filler obtained in succession is recovered and vacuum filtered. The filter cake is washed with water until the pH of the filtrate is substantially neutral (pH = 5.5-7.0). The filter cake is then placed in a convection oven at 120 ° C.
And dry for 24 hours. The neutralized filter cake is ground with a mortar in a mortar and pulverized.

Silanization of the filler thus obtained is accomplished by filling it to half volume with a 5 gallon glass carboy conditioned borosilicate glass rod in the manner described above. 6 kg of 8% silane solution in methanol is added to the carboy with 3 kg of ground filler recovered from the aqueous etchant grinding process. Seal the carboy, 6 at 175 rpm
Shake for hours. The silanized slurry is collected and vacuum filtered. The filter cake obtained is placed in a vacuum oven for 120 minutes.
Dry for 1 hour at 0 ° C. and then grind with mortar in a mortar to obtain silanized filler particles with an average particle size of a few microns.

This fill material can use polycarbonate dimethacrylate with a resin matrix in self-curing or visible light curable compositions.

Example 19-Visible Light Curable Filler Dental Restorative Composition A monomer matrix composition is prepared by mixing the following ingredients.

29.00 g BIS-GMA 70.00 g PCDMA (condensation product of 2-hydroxymethyl methacrylate and triethylene glycol bis (chloroformate)) 0.99 g Tinuvin. P 0.16 g dl-camphoroquinone 0.23 g DEA-EMA 0.0097 g 2,2 '-(2,5-thiophenediyl) bis (5-tert-butylbenzoxazole) Especially suitable for anterior dental treatment The composite restorative material containing the filler according to the present invention comprises 30% by weight of the above-mentioned monomer matrix composition,
68 wt% of the inorganic filler of Example 18 and 2 wt% of about 0.04
It is produced by mixing colloidal heat treated silica with an average particle size of microns. The obtained composite material is a uniform paste in which the monomer composition is used as a base material and the inorganic filler and the heat-treated silica are uniformly dispersed therein.

Example 20-Self-Hardening Paste-Paste Dental Restorative Composition An initiator resin composition is prepared by mixing the following ingredients.

29.00 g BIS-GMA 70.00 g PCDMA 0.15 g BHT 4.00 g LUCIDOL benzoyl peroxide 0.0097 g 2,2 '-(2,5-thiophenediyl) bis (5-tert-butylbenzoxazole ) The initiator paste composition was prepared by mixing 21% by weight of the above liquid monomer composition and 79% by weight of the inorganic filler of Example 18 in a planetary mixer under vacuum to form a uniform paste. can get. The paste is passed through a two roll stainless steel mill to ensure uniformity.

The accelerator resin composition is obtained by mixing the following components.

29.00 g BIS-GMA 70.00 g PCDMA 0.15 g BHT 1.50 dihydroxyethyl-p-toluidine (mp: 5
3.5 ° -54.5 ° C.) 4.00 g of UV-9 benzophenone thermoplastic single paste dental restorative is t-amine, dihydroxy-p-toluidine, or diethylaminoethylmethacrylate, or also as a thermoplastic initiator. In particular in the presence of benzoyl peroxide alone any accelerators such as the visible light curing initiator dl-camphoroquinone are excluded.

The accelerator paste composition was obtained by mixing 30% by weight of the above liquid monomer composition and 70% by weight of the inorganic filler of Example 18 in a planetary mixer under vacuum to form a uniform paste. To be The paste is passed through a two roll stainless steel mill to ensure uniformity.

Essentially equivalent amounts in the above-described initiator paste composition and accelerator paste composition are mixed uniformly for about 1 minute to form a composite restorative material having the filler of the present invention added thereto.

EFFECTS OF THE INVENTION The present invention provides a resinous adhesive suitable for bonding to actual dental surfaces including enamel, dentin, porcelain and metal surfaces, and a dental restorative material containing the same as a resin matrix component. Also, in the method of making an exposed dentin surface for bonding the dental restorative material, a method of bonding a dental restorative material having excellent bonding and stability without causing inflammation and pain due to necrosis of the medulla Further, by combining the resin component and the inorganic filler, an improved dental restorative composition was obtained as a crown and bridge material, an orthodontic cement as a sealant, or a sealant.

Claims (31)

(57) [Claims] 1. BIS-GMA and formula (In the formula, A is a C _{1 to} C ₆ alkylene group, R is a C _{2 to} C ₅ alkylene group having at least 2 carbon atoms in its main chain, and n is an integer of 1 to 4.) A dental resin composition containing the polycarbonate dimethacrylate according to claim 1. 2. BIS-GMA is present in an amount in the range of about 20-80% by weight and polycarbonate dimethacrylate is about 20-80.
The dental resin composition according to claim 1, which is present in an amount in the range of% by weight. 3. In polycarbonate dimethacrylate, A is a C ₂ or C ₃ alkylene group, R is an ethylene group, or
The dental resin composition according to claim 2, which is a propylene group and n is 2 or 3. 4. Polycarbonate dimethacrylate is 2
Dental resin composition according to claim 3, which is a condensation product of hydroxyethyl methacrylate and triethylene glycol bis (chloroformate). 5. BIS-GMA is present in an amount in the range of about 15-55% by weight and polycarbonate dimethacrylate is about 45-85%.
The dental resin composition according to claim 2, which is present in an amount in the range of% by weight. 6. The dental resin composition according to claim 5, wherein BIS-GMA is present in an amount of about 30% by weight and polycarbonate dimethacrylate is present in an amount of about 70% by weight. 7. The dental resin composition according to claim 4, which further comprises adding a polymerization initiator. 8. The dental resin composition according to claim 7, wherein the polymerization initiator is dl-camphoroquinone. 9. The dental resin composition according to claim 7, wherein the polymerization initiator is benzoyl peroxide. 10. The dental resin composition according to claim 4, which comprises adding a polymerization accelerator. 11. A polymerization accelerator is dihydroxyethyl-p.
-The dental resin composition according to claim 10, which is toluidine. 12. The dental resin composition according to claim 11, wherein the polymerization accelerator is diethylaminoethyl methacrylate. 13. The dental resin composition according to claim 5, which further comprises adding an ultraviolet absorber. 14. The dental resin composition according to claim 13, wherein the ultraviolet absorber is benzotriazole. 15. The dental resin composition according to claim 14, wherein the ultraviolet absorber is 2- (2′-hydroxy-5′-methylphenyl) -benzotriazole. 16. About 65 to about 75 wt% polycarbonate dimethacrylate, about 25 to about 35 wt% BIS-GMA, about 0.05 to about 0.35 wt% dl-camphoroquinone as a weight initiator, a polymerization accelerator. About 0.05 to about 0.5% by weight of diethylaminoethyl methacrylate as an ultraviolet absorber and about 0.05 to about 5% by weight of 2- (2'-hydroxy-5'- as an ultraviolet absorber.
The dental resin composition according to claim 1, which is a visible light curable resin comprising methylphenyl) -benzotriazole or benzophenone. 17. Polycarbonate dimethacrylate is 2
The dental resin composition according to claim 16, which is a condensation product of hydroxyethyl methacrylate and triethylene glycol bis (chloroformate). 18. About 65 to about 75% by weight of polycarbonate dimethacrylate, about 25 to about 35% by weight of BIS-GMA, about 3.2 to about 5.0% of benzoyl peroxide as a polymerization initiator, and about as an ultraviolet absorber. Claims 1. Consisting of 0.05 to about 5% by weight of 2- (2'-hydroxy-5'-methylphenyl) -benzotriazole, suitable for use with dihydroxyethyl-p-toluidine as an accelerator. The dental resin composition according to item. 19. Polycarbonate dimethacrylate is 2
The dental resin composition according to claim 18, which is a condensation product of hydroxyethyl methacrylate and triethylene glycol bis (chloroformate). 20. About 65 to about 75% by weight of polycarbonate dimethacrylate, about 25 to about 35% by weight of BIS-GMA, about 3.2 to about 5.0% by weight of benzoyl peroxide as a polymerization initiator, and about as a polymerization accelerator. 0.5 to about 4% by weight of dihydroxyethyl-p-toluidine, and about 0.05 to about as a UV absorber.
A dental resin composition according to claim 1 which is self-curing and comprises about 5% by weight of 2- (2'-hydroxy-5'methylphenyl) -benzotriazole. 21. Polycarbonate dimethacrylate is 2
The dental resin composition according to claim 20, which is a condensation product of hydroxyethyl methacrylate and triethylene glycol bis (chloroformate). 22. About 25 to about 35% by weight of BIS-GMA and about 65 to
Formula of about 75% by weight (In the formula, A is a C _{1 to} C ₆ alkylene group, R is a C _{2 to} C ₅ alkylene group having at least 2 carbon atoms in its main chain, and n is an integer of 1 to 4.) A dental adhesive composition for dental restoration comprising a curable resin adhesive containing polycarbonate dimethacrylate. 23. Polycarbonate dimethacrylate is 2
The dental adhesive composition according to claim 22, which is a condensation product of hydroxyethyl methacrylate and triethylene glycol bis (chloroformate). 24. About 25 to about 35% by weight of BIS-GMA and about 65 to.
Formula of about 75% by weight (In the formula, A is a C _{1 to} C ₆ alkylene group, R is a C _{2 to} C ₅ alkylene group having at least 2 carbon atoms in its main chain, and n is an integer of 1 to 4.) A dental adhesive composition comprising a resin component composed of polycarbonate dimethacrylate and an inorganic filler. 25. About 15 to about 50% by weight of a resin component and about 50 to
A dental adhesive composition according to claim 24 for use as a dental crown and bridge material consisting of about 85% by weight of inorganic filler. 26. The dental adhesive composition according to claim 25, wherein the polycarbonate dimethacrylate in the resin component is a condensation product of 2-hydroxyethyl methacrylate and triethylene glycol bis (chloroformate). 27. About 43 to about 55 wt% resin component and about 45 to
The dental adhesive composition according to claim 24, which is used as a sealing dental cement comprising about 57% by weight of an inorganic filler. 28. The dental adhesive composition according to claim 27, wherein the polycarbonate dimethacrylate in the resin component is a condensation product of 2-hydroxyethyl methacrylate and triethylene glycol bis (chloroformate). 29. About 90 to about 98% by weight of the resin component and about 2 to 2.
25. An orthodontic sealant or orthodontic cement comprising about 10% by weight inorganic filler.
The dental adhesive composition according to the item. 30. The dental adhesive composition according to claim 29, wherein the polycarbonate dimethacrylate in the resin component is a condensation product of 2-hydroxyethyl methacrylate and triethylene glycol bis (chloroformate). 31. The dental adhesive composition according to claim 24, wherein the inorganic filler has an average particle size in the range of about 0.5 to about 5 microns.