KR20070031453A - Dental compositions containing oxirane monomers - Google Patents

Abstract

Epoxy Functional Ether Monomers (ie, oxirane monomers) for use in oxirane based dental compositions.

Epoxy functional ether monomers, oxirane monomers, oxirane based dental compositions

Description

Dental composition containing an oxirane monomer {DENTAL COMPOSITIONS CONTAINING OXIRANE MONOMERS}

The present invention relates to a dental composition comprising an oxirane monomer.

Currently all organic based dental restorations, except glass ionomers, are based on methacrylate / acrylate chemicals that exhibit unacceptably high stresses upon curing due to excessively high polymerization shrinkage. Oxirane chemicals have been found to exhibit lower shrinkage and lower polymerization stresses than the best commercial methacrylate based materials.

However, the refractive index of certain oxirane systems currently does not ideally match the refractive index (RI) of the preferred filler (quartz / radiation impermeable molten glass / radiation impermeable sol gel filler). As a result, the translucency (aesthetics) of the composites prepared using this oxirane system is not as high as desired.

In addition, the polymerization stress and Post Gel Shrinkage (strain gauge method) of a particular oxirane restoration system is only about half of the lowest shrinking methacrylate based restorative materials currently available.

Accordingly, there is still a need for novel ingredients with good aesthetics, good mechanical properties and low shrinkage that can be added to oxirane based dental compositions or used alone.

Summary of the Invention

The present invention provides an epoxy functional ether monomer (ie oxirane monomer) for use in a dental composition. Significantly, at least one of the monomers of the present invention, when combined with other oxirane compounds, provides one or more of improved aesthetics, improved mechanical strength and high degree of conversion without adversely affecting contraction or other physical properties of the composite. can do.

Preferably, the epoxy functional ether monomer has the general formula (I).

Wherein A represents a straight or branched chain alkylene, cycloalkylene, arylalkylene or arylcycloalkylene having 1-30 carbon atoms each, wherein one or more carbon and / or hydrogen atoms are optionally one Substituted by any of the above Br, Cl, N or O atoms or a combination thereof, each R independently represents alkyl, aryl or epoxyalkyl, n is 0-4 and a is 2-4.

The monomers may be used alone or in combination with other resin-based reactive components typically used in oxirane based systems such as epoxy compounds comprising aromatic groups, aliphatic groups, cycloaliphatic groups, and combinations thereof in the dental composition. have.

In addition, the compositions typically include an initiator system. The initiator system may comprise one or more initiators. Preferably such initiators can induce cationic ring-opening polymerization reactions.

In certain embodiments, the dental composition also includes a filler system. Other optional ingredients include, for example, colorants, surfactants, flavors, medicaments, stabilizers, viscosity modifiers, diluents, flow regulators, thixotropic agents, antibacterial agents, and polymer thickeners.

Various combinations of each of the components listed herein can be used for the desired effect.

The term "comprises" and variations thereof do not have a limiting meaning when used in the description and claims.

As used herein, the indefinite articles "a," "an," the definite article "the," "at least one" and "at least one" are used interchangeably. Thus, for example, a dental composition comprising "one" oxirane containing monomer may be interpreted to mean a dental composition comprising "one or more" oxirane containing monomers. Similarly, a composition comprising "one" filler may be interpreted to mean that the composition comprises a filler of "one or more" types.

In addition, in this specification, the numerical range representation by the endpoint includes all the numbers included in the range (eg, 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, etc.). .

The above summary of the present invention is not intended to describe each disclosed embodiment or every implementation of the present invention. The following description more particularly exemplifies illustrative embodiments. In several places throughout the application, guidance is provided through a list of examples that can be used in various combinations. In each case, the list mentioned serves only as a representative group and should not be construed as an exclusive list.

Detailed Description of Exemplary Embodiments

The present invention provides an epoxy functional ether monomer for use in a dental composition. These monomers can be used alone or in combination with other resin-based reactive components typically used in oxirane based systems such as epoxy compounds comprising aromatic groups, aliphatic groups, cycloaliphatic groups, and combinations thereof in dental compositions. have.

Epoxy Functional Ether Monomers and Their Preparation

Preferred epoxy functional ether monomers of the present invention have formula (I)

<Formula I>

Wherein A represents a straight or branched chain alkylene, cycloalkylene, arylalkylene or arylcycloalkylene having 1-30 carbon atoms each, wherein one or more carbon and / or hydrogen atoms are optionally one Substituted by at least Br, Cl, N or O atoms or a combination thereof, each R independently represents alkyl, aryl or epoxyalkyl (when n = 0 and R is absent, the open carbon of the aromatic ring is Substituted with H atoms, n is 0-4 and a is 2-4. In the present specification, it will be apparent to those skilled in the art that the R group does not include a halogen.

a is preferably 3, more preferably 2. Preferably, n is 0 (where all open carbon atoms are substituted with H atoms). Preferably, A does not contain halogen. More preferably, A represents alkylene.

According to formula (I), the following compounds are preferred examples of epoxy functional ether derivatives.

Preparation of the compound

Epoxy functional ether monomers of the invention are generally commercially available as starting materials (e.g., from Sigma-Aldrich, St. Louis, MO), 2-allylphenol and derivatives thereof, and MCPBA ( m-chloroperbenzoic acid) can be prepared by the following scheme by converting the olefin moiety to an epoxide. This scheme represents the general preparation of a compound as represented by the following formula II (ie, formula I where a = 2).

Examples 1-4 (Compound AD) in the Examples paragraph detail the preparation of Formula II (where n = 0 and A = (CH ₂ ) _x where x = 3, 5, 6 or 10, respectively). .

Epoxy functional ether monomers exhibit dental qualities of up to 2.0% total volume polymerization shrinkage (typically between 1.0% and 2.0% shrinkage), where% is based on the volume of the composition before curing, while maintaining good physical properties. Can be formulated into a complex.

The monomers of the present invention may be used in amounts up to 100% in dental compositions, depending on the use of the composition. Preferably, the total amount of epoxy functional ether monomers in the dental composition is at least 1% by weight, more preferably at least 3% by weight and most preferably at least 5% by weight, based on the total weight of the composition. Preferably, the total amount of epoxy functional ether monomer is 80% by weight or less, more preferably 60% by weight or less and most preferably 40% by weight or less, based on the total weight of the composition.

Oxirane resin

The epoxy functional ether monomers of the present invention can be used alone or as resins in dental compositions, or other resin systems typically used in oxirane based systems such as epoxy compounds comprising aromatic groups, aliphatic groups, cycloaliphatic groups, and combinations thereof. Can be used with reactive components.

Suitable resin-based reactive components (ie photopolymerizable materials and compositions) include epoxy resins (containing cationic active epoxy groups), vinyl ether resins (containing cationic active vinyl ether groups), ethylenically unsaturated compounds (containing free radically active unsaturated groups), and Combinations thereof. Examples of useful ethylenically unsaturated compounds include acrylic esters, methacrylic esters, hydroxy functional acrylic esters, hydroxy functional methacrylic esters and combinations thereof. Also suitable are polymerizable materials which contain both cationic and free radically active functional groups in a single compound. Examples include epoxy functional acrylates, epoxy functional methacrylates, and combinations thereof.

Resin-based reactive components can include compounds having free radically active functional groups, including monomers, oligomers, and polymers having one or more ethylenically unsaturated groups. Suitable compounds contain one or more ethylenically unsaturated bonds and can carry out additive polymerization. Such free radically polymerizable compounds include, for example, (meth) acrylates (ie acrylates and methacrylates) and (meth) acrylamides (ie acrylamides and methacrylamides). Specific examples include mono-, di- or poly-acrylates and methacrylates such as those described in US Pat. No. 6,187,836 to Oxman et al.

The resin-based reactive component may include a compound having a cationic active functional group, for example, a cationic polymerizable epoxy resin. Such polymerizable materials include organic compounds having an oxirane ring polymerizable by ring opening. The materials include monomeric epoxy compounds and epoxides of polymer type and may be aliphatic, cycloaliphatic, aromatic or heterocyclic. In general, the compounds have, on average, at least one polymer per molecule, in some embodiments at least about 1.5, and in other embodiments at least about two polymerizable epoxy groups. Polymeric epoxides are linear polymers having terminal epoxy groups (eg, diglycidyl ethers of polyoxyalkylene glycols), polymers having skeletal oxirane units (eg, polybutadiene polyepoxides), and accessory ( pendant) polymers having epoxy groups (eg, glycidyl methacrylate polymers or copolymers). The epoxide can be a pure compound or a mixture of compounds containing one, two or more epoxy groups per molecule. The “average” number of epoxy groups per molecule is determined by dividing the total number of epoxy groups in the epoxy containing material by the total number of epoxy containing molecules present.

Such epoxy containing materials can be low molecular weight monomer materials to high molecular weight polymers, and the properties of their backbones and substituents can vary widely. Examples of acceptable substituents include halogens, ester groups, ethers, sulfonate groups, siloxane groups, carbosilane groups, nitro groups, phosphate groups and the like. The molecular weight of the epoxy containing material may be about 58 to about 100,000 or more.

Suitable epoxy containing materials useful as resin-based reactive components in the present invention are listed in US Pat. Nos. 6,187,836 (Oxman et al.) And 6,084,004 (Weinmann et al.).

Other suitable epoxy resins useful as resin-based reactive components include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-2-methylcyclohexylmethyl-3,4-epoxy-2 And those containing cyclohexene oxide groups such as epoxycyclohexanecarboxylate exemplified by -methylcyclohexane carboxylate and bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate. For a more detailed list of useful epoxides having this property, see US Pat. Nos. 6,245,828 (Weinmann et al.) And 5,037,861 (Crivello et al.), And US patent application 2003/035899 (Klettke et al.). Other epoxy resins that may be useful in the compositions of the present invention include glycidyl ether monomers. Examples include glycidyl ethers of polyhydric phenols (eg, 2,2-bis- (2,3-epoxy) which can be obtained by reacting polyhydric phenols with excess chlorohydrin, for example epichlorohydrin. Propoxyphenol) diglycidyl ether of propane). Further examples of this type of epoxide are described in US Pat. No. 3,018,262 to Schroeder and in "Handbook of Epoxy Resins" by Lee and Neville, McGraw-Hill Book Co., New York (1967).

Particularly suitable epoxides useful as resin-based reactive components are those containing silicon, useful examples of which are described in international patent publication WO 01/51540 (Klettke et al.).

Further suitable epoxides useful as resin-based reactive components, including many commercially available epoxides, are provided in US Publication 2005-0113477 A1, published May 26, 2005.

Blends of various epoxy containing materials are also contemplated. Examples of such blends include two or more weight average molecular weight distributions of epoxy containing compounds, such as low molecular weight (less than 200), medium molecular weight (about 200 to 10,000) and high molecular weight (greater than about 10,000). Alternatively or additionally, the epoxy resin may contain blends of epoxy containing materials having different chemical properties, for example aliphatic and aromatic, or different functionalities, for example polar and nonpolar.

Other types of useful resin-based reactive components with cationic active functionalities include vinyl ethers, oxetane, spiro-orthocarbonates, spiro-orthoesters, and the like.

If desired, cationic active functional groups and free radical active functional groups may be contained in one molecule. Such molecules can be obtained, for example, by reacting di- or poly-epoxides with one or more equivalents of ethylenically unsaturated carboxylic acid. An example of such a material is the reaction product of UVR-6105 (available from Union Carbide) with one equivalent of methacrylic acid. Commercially available materials having epoxy and free radical active functionality are the cyclomer family, for example cyclomer M-100, M-101, or A-200, available from Daicel Chemical, Japan. And EBECRYL-3605 available from UCB Chemicals Radcure Specialties, Atlanta, GA.

The cationic curable resin-based reactive component may further comprise a hydroxyl containing organic material. Suitable hydroxyl containing materials can be any organic material having at least one, preferably at least two, hydroxyl functionalities. Preferably, the hydroxyl containing material contains at least two primary or secondary aliphatic hydroxyl groups (ie, the hydroxyl groups are bonded directly to the nonaromatic carbon atoms). The hydroxyl group may be located at the end or appended from the polymer or copolymer. The molecular weight of the hydroxyl containing organic material can be very low (eg 32) to very high (eg more than one million). Suitable hydroxyl containing materials may have a low molecular weight, i.e., about 32 to about 200, a medium molecular weight, i.e., about 200 to about 10,000, or a high molecular weight, i.e., greater than about 10,000. All molecular weights used herein are weight average molecular weights.

The hydroxyl containing material may be non-aromatic in nature or contain aromatic functionalities. The hydroxyl containing material may optionally contain heteroatoms such as nitrogen, oxygen, sulfur and the like in the molecular backbone. The hydroxyl containing material can be selected, for example, from naturally occurring or synthetically produced cellulosic materials. The hydroxyl containing material should be substantially free of groups that may be unstable to heat or photolysis. That is, the material should not decompose or release volatile components at temperatures below about 100 ° C. or in the presence of actinic beneficiation that may be encountered during the photopolymerization conditions desired for the polymerizable composition.

Suitable hydroxyl containing materials useful in the present invention are listed in US Pat. No. 6,187,836 to Oxman et al.

The amount of hydroxyl-containing organic material used in the polymerizable composition is determined by the compatibility of the hydroxyl-containing material with the cationic and / or free radically polymerizable component, the equivalent weight and functionality of the hydroxyl-containing material, the desired physical properties in the final composition, It can vary widely depending on factors such as the desired rate of polymerization and the like.

Blends of various hydroxyl containing materials can also be used. Examples of such blends include two or more molecular weight distributions of hydroxyl containing compounds such as low molecular weight (less than about 200), medium molecular weight (about 200 to about 10,000) and high molecular weight (greater than about 10,000). Alternatively or additionally, the hydroxyl containing material may contain blends of hydroxyl containing materials having different chemical properties, for example aliphatic and aromatic, or with different functionalities, for example polar and nonpolar. As a further example, it is possible to use two or more polyfunctional hydroxy materials or a mixture of one or more monofunctional hydroxy materials and a multifunctional hydroxy material.

The resin-based reactive component (s) may also contain hydroxyl groups and free radical active functional groups in a single molecule. Examples of such materials include hydroxyalkyl acrylates and hydroxyalkyl methacrylates such as hydroxyethyl acrylate, hydroxyethyl methacrylate; Glycerol mono- or di- (meth) acrylates; Trimethylolpropane mono- or di- (meth) acrylate, pentaerythritol mono-, di- and tri- (meth) acrylate, sorbitol mono-, di-, tri-, tetra-, or penta- (meth) Acrylates; And 2,2-bis [4- (2-hydroxy-3 methacryloxypropoxy) phenyl] propane.

The resin-based reactive component (s) may also contain hydroxyl groups and cationic active functional groups in a single molecule. Examples include single molecules containing both hydroxyl and epoxy groups.

Initiator system

The composition of the present invention comprises one initiator or a mixture of two or more initiators suitable for curing (e.g., polymerization and / or crosslinking) of an initiator system, ie an oxirane resin system.

Such initiators may be photocured or chemically cured or redox cured. Examples of such initiators are Lewis acids or Bronsted acids, or compounds that release these acids to initiate polymerization, such as BF ₃ or ether adducts thereof (BF ₃ · THF, BF ₃ · Et ₂ O, etc.). , AlCl ₃ , FeCl ₃ , HPF ₆ , HAsF ₆ , HSbF ₆ , or HBF ₄ , or a substance which initiates polymerization after UV or visible light irradiation or by heat and / or pressure, for example (η ⁶ -cumene) (η ⁵ -cyclopentadienyl) iron hexafluorophosphate, (η ⁶ -cumene) (η ⁵ -cyclopentadienyl) iron tetrafluoroborate, (η ⁶ -cumene) (η ⁵ -cyclopentadienyl ) Iron hexafluoroantimonate, substituted diaryliodonium salts and triarylsulfonium salts. Accelerators that can be used include peroxides, diacyl peroxides, peroxydicarbonates and peroxide compounds of the hydroperoxide type. Preferably, hydroperoxide is used. Cumene hydroperoxide is used as a particularly preferred promoter in approximately 70% to 90% solution in cumene. The ratio of photoinitiator to cumene hydroperoxide can vary within a wide range of ratios from 1: 0.001 to 1:10, but preferably a ratio of 1: 0.1 to 1: 6, most preferably 1: 0.5 to 1: 4 is used. do. It is also possible to use complexing agents such as oxalic acid, 8-hydroxyquinoline, ethylenediaminetetraacetic acid and aromatic polyhydroxy compounds.

Suitable photoinitiators for polymerizing cationic photopolymerizable compositions include binary and ternary systems. Typical ternary photoinitiators are EP 0 897 710 (Weinmann et al), US Pat. Iodonium salts, photosensitizers, and electron donating compounds as described in US Publication 2003/0166737 (Dede et al.), And US Publication 2005-0113477 A1 published May 26, 2005.

Suitable iodonium salts include tolyl cumyliodonium tetrakis (pentafluorophenyl) borate, tolyl cumyliodonium tetrakis (3,5-bis (trifluoromethyl) -phenyl) borate, and diaryl iodo Nium salts such as diphenyliodonium chloride, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate and diphenyliodonium tetrafluoroborate. Suitable photosensitizers include monoketones and diketones that partially absorb light in the range of about 450 nanometers (nm) to about 520 nm (preferably between about 450 nm and about 500 nm). More suitable compounds are alpha diketones that partially absorb light in the range from about 450 nm to about 520 nm (more preferably, from about 450 nm to about 500 nm). Preferred compounds are camphorquinone, benzyl, furyl, 3,3,6,6-tetramethylcyclohexanedione, phenanthraquinone and other cyclic alpha diketones. Camphorquinone is most preferred. Suitable electron donating compounds include substituted amines such as ethyl 4- (dimethylamino) benzoate and 2-butoxyethyl 4- (dimethylamino) benzoate, and polycondensed aromatic compounds (eg anthracene) .

The initiator system is present in an amount sufficient to provide the desired rate of cure (eg, polymerization and / or crosslinking). In the case of photoinitiators, this amount depends in part on the light source, the thickness of the layer exposed to radiant energy and the extinction coefficient of the photoinitiator. Preferably, the total amount of initiator system is present at least 0.01% by weight, more preferably at least 0.03% by weight and most preferably at least 0.05% by weight based on the weight of the composition. Preferably, the total amount of initiator system is present at 10 wt% or less, more preferably at most 5 wt%, most preferably at most 2.5 wt%, based on the weight of the composition.

Filler system

The composition of the present invention may optionally comprise a filler system (ie, one or more fillers). Fillers used in filler systems can be selected from a wide variety of conventional fillers incorporated into resin systems. Preferably, the filler system comprises one or more conventional materials suitable for incorporation into compositions used in the medical field, such as fillers currently used in dental restoration compositions. Therefore, the filler system used in the composition of the present invention is incorporated in the resin system.

The filler may be particulate or fibrous in nature. In general, the particulate filler may be defined as having a length to width ratio, or aspect ratio, of 20: 1 or less, more typically 10: 1 or less. Fibers can be defined as having aspect ratios greater than 20: 1, or more typically greater than 100: 1. The shape of the particles may be spherical to elliptical, or may be planar, for example flakes or discs. The macroscopic properties can depend largely on the shape of the filler particles, in particular the uniformity of the shape.

Preferred particulate fillers are finely divided and have an average particle size (preferably diameter) of less than 10 micrometers (ie, microns).

Preferred micrometer-sized particulate fillers have an average particle size of at least 0.2 micrometers and at most 1 micrometer. Nanoparticles have an average primary particle size of less than 200 nm (0.2 micrometers). The filler may have a single or multimodal (eg bimodal) particle size distribution.

Micrometer-sized particles are very effective in improving post-cure wear properties. In contrast, nano fillers are commonly used as viscosity modifiers and thixotropic agents. These materials are known to assemble into agglomerated networks due to their small size, high surface area and associated hydrogen bonds. This type of material (“nano” material) has an average primary particle size (ie, the longest dimension of the non-agglomerated material, eg diameter) of 1000 nanometers (nm) or less. Preferably, the nanoparticulate material has an average primary particle size of at least 2 nanometers (nm), preferably at least 7 nm. Preferably, the nanoparticulate material has an average primary particle size of 50 nm or less, more preferably 20 nm or less. The average surface area of such fillers is preferably at least 20 square meters (m 2 / g) per gram, more preferably at least 50 m 2 / g and most preferably at least 100 m 2 / g.

The filler system may comprise an inorganic material. It may also comprise crosslinked organic materials which are insoluble in the polymerizable resin and optionally filled with an inorganic filler. Preferably, in general, the filler system is non-toxic and suitable for use in the oral cavity.

Suitable fillers may be radiopaque, radiopaque or radiopaque. Typically, fillers used in the dental field are inherently ceramic. Examples of suitable inorganic fillers are glass, colloidal, derived from naturally occurring or synthetic materials such as quartz, nitrides (eg silicon nitride), such as Ce, Sb, Sn, Zr, Sr, Ba or Al. Silica, feldspar, borosilicate glass, kaolin, talc, titania, and zinc glass, zirconia-silica fillers, and low Mohs hardness fillers, such as those described in US Pat. No. 4,695,251 (Randklev). Examples of suitable organic filler particles include filled or unfilled ground polycarbonates, polyepoxides and the like. Preferred filler particles are quartz, submicron silica, and non-glass microparticles of the type described in US Pat. No. 4,503,169 (Randklev). Mixtures of these fillers, as well as combinations of fillers made from organic and inorganic materials, can be used.

Examples of suitable fillers are IOTA-6 fillers (Unimin Corp., Spruce Pine, NC) (milled quartz) with yttrium trifluoride for radiopacity. In addition, descriptions of radiopaque fillers, combinations of radiopaque fillers, and combinations of radiopaque fillers and radiopaque fillers useful in cationic polymerizable compositions are provided in US Pat. No. 6,465,641 (Bretscher et al.). have.

Optionally, the surface of the filler particles may be treated with a surface treatment agent such as a silane-coupling agent to enhance the bond between the filler system and the resin system. The coupling agent may be functionalized with reactive curing groups such as epoxy, (meth) acrylates and the like.

Other suitable fillers are US Pat. Nos. 6,387,981 (Zhang et al.) And 6,572,693 (Wu et al.), As well as international publications WO 01/30305 (Zhang et al.), WO 01/30306 (Windisch et al.), WO 01 /. 30307 (Zhang et al.) And WO 03/063804 (Wu et al.). Filler components described in these documents include nanosize silica particles, nanosize metal oxide particles, and combinations thereof. In addition, the nanofillers are all US Patent Application 10 / 847,782, entitled "Dental Compositions Containing Nanofillers and Related Methods," filed May 17, 2004, and US Patent Application 10 / 847,781, and " US Patent Application 10 / 847,803 entitled "Use of Nanoparticles to Adjust Refractive Index of Dental Compositions".

Preferably, the total amount of filler system is greater than 50 weight percent, more preferably greater than 60 weight percent and most preferably greater than 70 weight percent based on the total weight of the composition. Preferably, the total amount of filler system is 95% by weight or less, more preferably 80% by weight or less, based on the total weight of the composition.

Optional additives

The composition may contain any ingredients such as colorants (eg pigments or dyes commonly used in shading adjustments), surfactants, flavors, medicines, stabilizers (eg BHT), viscosity modifiers, diluents, flow control agents , Thixotropic agents, antibacterial agents, polymer thickeners, and the like. Various combinations of these optional additives can be used as needed. Optionally, such components may include reactive functionality to copolymerize with the resin. Preferably, the total amount of optional components is no greater than 5.0 weight percent, more preferably no greater than about 2.5 weight percent, most preferably no greater than about 1.5 weight percent based on the total weight of the composition.

How to use

The oxirane-containing monomer may be used as a component in the curable dental composition. The dental compositions of the invention can be used, for example, as adhesives for dental restorations or prosthetic devices or orthodontic appliances (eg brackets and bands). Examples of restorations include dental composites, filler materials, sealants, adhesives, and root canal filler materials. Examples of prosthetic devices include crowns (particularly preformed chemical crowns), bridges, veneers, inlays, onlays, posts, pins, and the like. .

Although the objects and advantages of the present invention are further illustrated by the following examples, the specific materials and amounts thereof referred to in these examples, as well as other conditions and details, should not be construed as overly limiting the present invention. Unless stated otherwise, all parts and percentages are by weight, all water is deionized water, and all molecular weights are weight average molecular weights.

Test Methods

Compressive Strength (CS) Test Method

The compressive strength of the test samples was measured according to the American National Standard Institute / American Standards Association (ANSI / ASA) Standard 27 (1993). The sample was filled into a 3.2-mm (inner diameter) Plexiglas tube, the tube was plugged with a silicone rubber plug and axially compressed for 5 minutes with approximately 0.28 mega Pascals (Mpa). The samples were then photocured for 90 seconds by exposing them to two opposingly arranged Visilux Model 2500 blue light guns (3M Co., St. Paul, Minn.). The cured sample was cut with a diamond saw to form a 6-7 mm long cylindrical plug for measuring compressive strength. The plug was stored in distilled water at 37 ° C. for 24 hours before testing. Measurements were performed at a crosshead speed of 1 mm / min using an 10 kilonewton (kN) load cell on an Instron tester (Instron 4505, Instron Corp., Canton, Mass.). . Five cured sample cylinders were prepared, measured and the results were reported in MPa as the average of five measurements.

Post-curing flexural strength (FS) and flexural modulus (FM) test methods

Flexural strength and flexural modulus were measured according to the following test procedure. The paste sample was pressurized at 10,000 pounds per square inch (kpsi) (69 MPa) in a Delrin mold for 5 minutes at room temperature to form a 2 mm × 2 mm × 25 mm test rod. The test rods were immediately cured using two Visilux 2500 dental curing light (threem campani) for a total of 120 seconds at the top three overlapping positions, and a total of two additional 60 seconds at the bottom two overlapping positions. Further curing was performed using a Visillux 2500 dental curing light.

The rod was then lightly sanded with 600-grit sandpaper to remove flash from the molding process. After storage in distilled water at 37 ° C. for 24 hours, an Instron tester (Instron 4505, Canton, MA) in accordance with ANSI / ADA (American National Standard / American Dental Association) Standard 27 (1993) The flexural strength and flexural modulus of the rods were measured at a crosshead speed of 0.75 mm / min. Five cured paste composite rods were prepared and measured and the results were reported in MPa as the average of five measurements.

Gel time test method

The gel time was defined as the shortest time required for the paste sample to convert to a solid so that the sample did not easily be manually piped into a spatula tip. The test procedure was as follows.

Test paste samples (50-70 mg) were placed on white wax paper sheets and rolled into spheres using a mixing stick. The sample was then exposed to a continuous 2 second dose using a timer on Elipar Trilight Dental Cured Light (Three M Company) until the sample gelled. The light was placed as close to the sample as possible without contact. The time that the paste first gelled (easily cured without pie) was recorded as gel time.

Post-gel shrinkage test method

Test paste samples (approximately 20 mg) were made into the shape of a ball by rolling on a duplicate coated paper pad using a spatula or dental applicator. Spherical paste samples are placed in an uncoupled biaxial strain gauge (CEA-06-032WT-120) wired to a Model 2120 signal conditioner (Micro-Measurements Group Inc., Raleigh, North Carolina) I was. The paste was slightly flattened and manipulated so that the paste adhered well to the strain gauge active circuit device. The tip of the XL-2500 optical waveguide (Three M Company) was placed as close to the sample as possible without touching the paste (approximately 1-mm distance). The paste sample was cured for 60 seconds using an XL-2500 waveguide and the microstrain shrinkage registered by the strain gauge was recorded 1 hour after irradiation.

Epoxy Equivalent Weight (EEW g / mole) Test Method

Paste or resin samples were weighed with 0.0001 gram (g) accuracy and placed in a suitable beaker. 0.2 g samples were used for resins with 200-300 EEW and 4.0 g samples were used for fillers or high filling pastes. The weight of the sample was adjusted to distribute 1 to 9 milliliters (ml) volume at the inflection point during titration with 0.1 normal (N) perchloric acid in glacial acetic acid. Acetonitrile (25 ml) was added to a titration beaker using a pipette, which was then covered with Parafilm and sonicated for 2 minutes at room temperature. The sonicator liquid level was the sample solution height. 20% tetrabutylammonium bromide in glacial acetic acid (25 ml) and glacial acetic acid (20 ml) was added sequentially to the beaker using a pipette. The resulting solution was mixed for 2 minutes using a stir bar and then titrated with 0.1N perchloric acid solution in glacial acetic acid using a Mettler DL21 titrator and a METTLER DG 111-SC electrode. The EEW of the sample was calculated as follows: EEW = sample mg / ((total ml-blank ml) × normal concentration of HClO ₄ titrant).

ACTA three-piece wear test method

Accurately describe the ACTA three-piece wear test on test samples compared to the FILTEK Z250 Universal Restorative (Three M Company) .Influence of Shearing Action of Food on Contact Stress and Subsequent Wear of Stress-bearing Composites, P Pallav, et al., Journal of Dental Research, Jan. 1993].

Optical Differential Scanning Calorimeter (DSC) Test Method

Test samples of resin (10 mg) or paste (25 mg) were weighed and placed in a DSC pan and the weight was recorded as ± 0.00001 g. The uncured sample was placed in a sample cell and the same nominal weight of pre-cured sample was placed in the same type of DSC pan on a reference cell of TA Instruments 2920 Light DSC (TA Instruments, New Castle, Germany). The light DSC program was equilibrated for 5 minutes using a slow nitrogen purge at 37 ° C. and the irradiation time was set to use a slow nitrogen purge at 37 ° C. for 1 hour. From the resulting heat flow (Watts / g per gram) versus time curve, the time of maximum reaction rate (peak maximum time), the start time of reaction (induction time) and enthalpy of reaction (curve during 1 hour irradiation) Area below).

Example 1

Synthesis of 1,10-bis [2- (2,3-epoxypropyl) phenoxy) decane (Compound A)

A mixture containing 35 g 2-allylphenol (Sigma-Aldrich), 39 g 1,10-dibromodecane (Sigma-Aldrich) and 36 g potassium carbonate in 150 ml methyl ethyl ketone (MEK) After heating to 80 ° C. for 24 hours, 200 ml of water and 200 ml of hexane were added. The resulting mixture was separated into an organic phase and an aqueous phase. The organic phase was washed with water and then dried over sodium sulfate. The solvent was removed and the remaining liquid was distilled off under vacuum. The boiling material was collected at 210-215 ° C. (0.1 mm Hg, 13 Pascals) to give 26 g of liquid, which was characterized by gas chromatography / mass spectrometry (GC / MS) to characterize 1,10-bis ( 2-allylphenoxy) hexane.

To a solution of 1,10-bis (2-allylphenoxy) hexane (21 g) in 210 ml methylene chloride was added 41.6 g of 77% m-chloroperbenzoic acid (Sigma-Aldrich). After initial cooling by dissolving m-chloroperbenzoic acid, there was some exothermic reaction and the reaction temperature was maintained at 25-26 ° C. by cold water bath. The mixture was stirred for 6 hours. Analysis of the reaction mixture by gas chromatography showed 92% of the desired product. The reaction mixture was poured into a solution containing 40 g of sodium hydroxide in 150 ml of water and 200 ml of hexane. The resulting mixture was stirred and cooled to 10 ° C. using an ice bath. The organic layer was removed, washed with 100 ml of 5% sodium hydrosulfite solution and three times with 100 ml of 10% potassium chloride solution. Solvent was removed and the residue was passed through a silica gel column eluted with 75% hexane 25% ethyl acetate to remove most of the color. The resulting oil was dissolved in 100 ml of 10% ethyl acetate in hexanes and treated with 3 g of basic aluminum oxide while stirring to remove further color. The aluminum oxide was removed by filtration and the solvent was removed to give 13 g of liquid, which was characterized by nuclear magnetic resonance spectroscopy (NMR) to find 1,10-bis [2- (2,3-epoxypropyl) phenoxy C] decane (Compound A).

Example 2

Synthesis of 1,3-bis [2- (2,3-epoxypropyl) phenoxy] propane (Compound B)

Replacing 1,3-bis [2- (2,3-epoxypropyl) phenoxy] propane (Compound B) with 1,10-dibromodecane with 1,3-dibromopropane (Sigma-Aldrich) Synthesis was carried out by the procedure described in Example 1 except that. The overall yield for both steps is 48% and the structure of Compound B was confirmed by NMR.

Example 3

Synthesis of 1,5-bis [2- (2,3-epoxypropyl) phenoxy] pentane (Compound C)

1,3-bis [2- (2,3-epoxypropyl) phenoxy] pentane (Compound C) with 1,10-dibromodecan replaced with 1,5-dibromopentane (Sigma-Aldrich) Synthesis was carried out by the procedure described in Example 1 except that. The overall yield for both steps is 38% and the structure of Compound C was confirmed by NMR.

Example 4

Synthesis of 1,6-bis [2- (2,3-epoxypropyl) phenoxy] hexane (Compound D)

Replacing 1,3-bis [2- (2,3-epoxypropyl) phenoxy] hexane (Compound D) with 1,10-dibromodecan with 1,6-dibromohexane (Sigma-Aldrich) Synthesis was carried out by the procedure described in Example 1 except that. The overall yield for both steps is 25% and the structure of Compound D is confirmed by NMR.

Preparative Compound 1 (Compound E)

The mixture containing 50 g bisphenol A, 42.4 g ethylene carbonate and 24 g triethylamine was heated to 105 ° C. for 24 hours. A water inhaler vacuum was added and the mixture was heated to 110 ° C. to remove most of the triethylamine. The mixture was cooled, dissolved in 300 ml of ethyl acetate and washed with 100 ml of 5% aqueous HCl solution. The organic layer was then washed with 100 ml water, 100 ml 5% potassium carbonate and 100 ml potassium chloride solution. The organic phase was washed with sodium sulphate and the solvent was removed to give an oil which was partially crystallized upon standing. The partially crystallized oil was redissolved in 100 ml of ethyl acetate and hexane was added until cloudy. Upon standing for 2 days, the material crystallises and is filtered to give 25.8 g of 2- (4- {1- [4- (2-hydroxyethoxy) -phenyl] -1-methyl-ethyl} -phenoxy) ethanol Got.

11 g of previously prepared 2- (4- {1- [4- (2-hydroxyethoxy) -phenyl] -1-methyl-ethyl} -phenoxy) ethanol, 11.8 g of 1- (7-oxa A mixture containing -bicyclo [4.1.0] hept-3-yl) -ethanone, (ERL414, Dow Chemical, Midland, Mich.) And 0.3 g sodium acetate was heated to 120 ° C. under nitrogen purge with stirring To assist in the removal of methanol. After 3 hours, the reaction was complete as suggested by thin layer chromatography. The mixture was taken up in ethyl acetate and washed with water. The solvent was removed under vacuum and the residue was extracted for 4 hours using hot hexanes. The residual solvent was removed and the residue was purified by column chromatography on silica gel eluting with 1: 5 ethyl acetate / methylene chloride to give 10.6 g of the product as a clear viscous liquid. The structure of compound E was confirmed by NMR.

Example 5-19 and Comparative Examples 1-4 (C1-C4)

Mixtures of monomers, including oxirane monomers

A series of monomer mixtures were prepared containing the oxirane monomer with other oxirane monomers or with the silicon containing oxirane monomer. The purpose was to form a monomer mixture with a quartz filler (approximately 1.54) and an approximate refractive index (RI) value. The targeted RI value for the monomer mixture was close to 1.535 and was approximately 0.01 increase over the RI expected for polymerization.

A photoinitiator was added to each of the prepared monomer mixtures to provide a resin composition comprising the following components in weight percent: EDMAB (0.3%), CPQ (0.5%), Rhodosil 2074 (3.0%), poly-THF (3.0%), Chiracure UVR6105 (2.2%) and oxirane monomer mixture (91.0%). To each of the resulting resin compositions was added an epoxy functional silane treated quartz filler (IOTA-6, 1 micron average particle size, Unimin Corporation, Spruce Pine, North Carolina) to form a paste-like photocurable (polymerizable) composition. It was obtained by the weight ratio of% resin composition and 70% filler. Mixing of the resin and filler components was performed at 3000 revolutions per minute (rpm) using a DAC 150 FVZ Speed Mixer (Flacteck, Landland, South Carolina) to avoid excessive heat generation during mixing. It was performed using a short mixing cycle. The resulting polymerizable paste composition was named Example 5-19 and listed in Table 1 below with Comparative Examples C1-C4 containing only the Reference Compound. It is noted that Examples 16-19 and Comparative Example C1 contained only a single epoxy functional monomer (Compounds A-D and Compound F, respectively) and not the Chiracure UVR6105 used as solvent in the CPQ and EDMAB components of the photoinitiator system. Table 1 below provides the relative amounts of monomers used in the composition and the corresponding RI values of the mixture after addition of the photoinitiator system and before filler addition. (The corresponding resin composition is named Examples 5R-19R and Comparative Examples C1-R to C4-R.)

evaluation

Ames Mutagenicity

Pharmacopeia of the University of Missouri at Kansas City (UMKC), Kansas City, performed Ames mutagenicity assessment of Compound A-D. The results so far have shown that compounds A, C and D are negative in strains TA10 and TA97A. Compound B was negative in strains TA100, TA1535, TA98, TA102, and out of the egg in strain TA97A.

Degree of cure (optical differential scanning calorimeter)

The photo DSC results for Examples 5-19 and Comparative Examples 1-4 are shown in Table 2 (Examples as Filler-Free Resin Compositions) and Table 3 (Examples as Polymerizable Paste Compositions with Fillers). In addition, the following Tables 2 and 3 show the following:

1. measured resin and paste epoxy equivalent weights (EEWs) in g of material per mole of epoxy group, and

2. Calculated resin and paste enthalpy in Joule (J / mole) units per mole of epoxy groups in the material.

EEW = grams per mole of epoxy group (from titration measurement)

J / mole of epoxy group = (J / g) x (g / mole) = J / g × EEW

The J / mole value represents the relative degree of conversion (conversion) achievable at low density radiation (approximately 3 milliwatts per square centimeter (mw / cm2), characteristic of 3M ESPE from St. Paul, TA 2920 light DSC). .

Mechanical properties

Examples 5-19 and Comparative Examples 1-4 (Examples as polymerizable paste compositions with fillers) were evaluated for compressive strength, flexural strength and flexural modulus according to the test methods described herein, and the test results are shown in the following table. 4 is shown.

Gel time, post-gel shrinkage and ACTA triple wear

Examples 5-19 and Comparative Examples 1-4 (Examples as polymerizable paste compositions with fillers) were evaluated for gel time, post-gel shrinkage, and ACTA three wear according to the test methods described herein, and the test results. Is shown in Table 4 below.

The entire disclosures of patents, patent documents, and publications cited herein are each incorporated by reference in their entirety, even if individually cited. Various modifications and variations to the present invention will be apparent to those skilled in the art without departing from the scope and spirit of the invention. It is to be understood that the exemplary embodiments and examples shown herein are not intended to be excessively limiting of the invention, and that these examples and embodiments are present only as examples of the scope of the invention, which are limited only by the claims set out below. do.

Claims (10)

A dental composition comprising an epoxy functional ether monomer having the general formula (I) and an initiator system. <Formula I>

Wherein A represents a straight or branched chain alkylene, cycloalkylene, arylalkylene or arylcycloalkylene having 1-30 carbon atoms each, wherein one or more carbon and / or hydrogen atoms are optionally Substituted by one or more Br, Cl, N or O atoms or a combination thereof, Each R independently represents alkyl, aryl or epoxyalkyl, n is 0-4, a is 2-4) The dental composition of claim 1 wherein a is 3. The dental composition of claim 1 wherein a is 2. The dental composition according to any one of claims 1 to 3, wherein A represents alkylene. The dental composition of claim 4 wherein A represents alkylene having 3-10 carbon atoms. The dental composition according to any one of claims 1 to 5, wherein n is zero. 7. The dental composition of claim 1, further comprising a secondary resin-based reactant selected from the group consisting of epoxy compounds comprising aromatic groups, aliphatic groups, cycloaliphatic groups, and combinations thereof. The dental composition of claim 7 wherein the secondary resin system further comprises a silicon containing reactant. The dental composition of claim 1 further comprising a filler system. 10. The composition according to any one of claims 1 to 9, consisting of colorants, surfactants, flavoring agents, medicaments, stabilizers, viscosity modifiers, diluents, flow regulators, thixotropic agents, antibacterial agents, polymer thickeners and combinations thereof. Dental composition further comprising an additive selected from the group.