WO2006053154A1

WO2006053154A1 - Wax-like polymerizable dental material

Info

Publication number: WO2006053154A1
Application number: PCT/US2005/040812
Authority: WO
Inventors: Benjamin Jiemin Sun; Andrew Murray Lichkus
Original assignee: Dentsply International Inc.
Priority date: 2004-11-12
Filing date: 2005-11-10
Publication date: 2006-05-18

Abstract

The invention provides polymerizable dental products, which upon polymerization form dental polymeric material.

Description

WAX-LIKE POLYMERIZABLE DENTAL MATERIAL

Related Applications

[0001] This application claims the benefit of U.S. Provisional Application Serial

No. 60/627,198 filed on November 12, 2004.

Technical Field

[0002] The invention relates to wax-like polymerizable materials. This wax- like polymerizable dental material is quickly and easily reshaped. The shaped wax-like polymerizable dental material is cured to form dental products, such as crowns, bridges, dentures, and other restoration devices and appliances.

Background of the Invention

[0003] Volkel et al in US Patent 6,057,383 (and Canadian Patent Application 2207351), assigned to Ivoclar, disclose wax-like polymerizable material for making entire dental products. The prior art does not disclose a wax-like polymerizable material for forming dentures or other high toughness products.

Preferred Embodiment for Carrying Out the Invention [0004] The invention relates to wax-like polymerizable materials. The invention provides wax-like polymerizable dental materials, and methods of forming dental products of high toughness dental polymeric material. This wax- like polymerizable dental material is quickly and easily reshaped. It is reshaped at room temperature by hand or tool, by warming, and shaping while warm and then allowing it to cool to room temperature. The shaped wax-like polymerizable dental material is cured to form dental products. These dental products have superior toughness compared to products formed from prior wax-like polymerizable materials. High toughness dentures are made by positioning artificial teeth in wax-like polymerizable dental material of the invention. The disclosures of US patent application Serial Number 09/670,364 filed September 26, 2000 and US provisional patent application Serial Number 06/237,523 filed October 4, 2000 are incorporated herein by reference in their entirety.

[0005] The invention provides a high toughness dental polymeric material formed from wax-like polymerizable dental material. High toughness dental polymeric dental products include partial dentures and full dentures.

[0006] Working wax-like polymerizable dental material, often includes molding, shaping, and/or carving. When heated, wax-like polymerizable dental material softens. Preferably, wax-like polymerizable dental material is dimensionally stable below 24⁰C and softened at and above 24⁰C. More preferably it is softened at and above 30⁰C. By heating from its dimensionally stable condition, wax-like polymerizable dental material of the invention undergoes a rapid transition to being freely flowable. By cooling from its softened state, wax-like polymerizable dental material of the invention undergoes a rapid transition to being dimensionally stable. Small volumes of wax-like polymerizable dental material may be worked, while being warmed on the dental device. They may be dispensed from a heated syringe-type dispensing device, spatula, electric spatula, disposal dropper or other mechanical or electrical dispenser. To make a denture, wax-like polymerizable dental material is positioned on a stone cast made from an impression of a patient's mouth to make a base plate and wax-like polymerizable dental material is also positioned on a polymeric base plate made from an impression of a patient's mouth. Artificial teeth are positioned in the wax- like polymerizable dental material, which is then shaped by melting and resolidifying. Then the wax-like polymerizable dental material is polymerized to form a denture. Thus the denture is formed without applying inorganic plaster to the artificial teeth and without positioning artificial teeth in a mold as required by conventional lost wax or other similar prior art methods of forming a denture. Compounds, which are readily partially crystallizable and useful in wax-like polymerizable dental material of a preferred embodiment of the invention, include methacrylate (or acrylate) compounds prepared for example by reaction of a urethane pre-oligomer with hydroxylalkymethacrylate. Preferably such compounds have a structure within the scope of one of general formulas I-V below. Preferably the urethane pre-oligomer is linear, comprises isocyanate end groups and has a structure within the scope of general formula I:

wherein Ri and R₂ are either an alkyl having from 1 to 14 carbon atoms or containing at least an aromatic group having from 6 to 14 carbon atoms, m is an integer from 0 to 20, the value of m in the oligomer depends on the molar ratio of diisocyanate to diol used, and the value of m increases as this molar ratio decreases. The diisocyanate portion has the structure OCN-RrNCO and the diol portion has the structure HO-R₂-OH.

[0007] Alternatively, urethane pre-oligomer is formed by reaction of at least one diol with excess, at least one diisocyanate to yield a urethane pre-oligomer having a structure within the scope of one or more of general formulas: H-IV

General Formulas:ll-IV

OCN-( Ri-NH-CO-O-R₂-O-OC-NH)_m-(Ri-NH-CO-O-R^I ₂-O-OC-NH)n-Ri-NCO

OCN-( R₁-NH-CO-O-R₂-O-OC-NH)_m-(R"₁-NH-CO-O-R₂-O-OC-NH)n-R^Ii-NCO

III

OCN-(R₁-NH-CO-O-R₂-0-OC-NH)_m-(R"i-NH-CO-0-R^I ₂-0-OC-NH)n-R^li-NCO

IV

wherein Ri _, R'i , R₂ and R'₂ each independently is an alkyl having from 1 to 14 carbon atoms or at least an aromatic group having from 6 to 14 carbon atoms, n and m are each independently integers from 0 to 20, the sum of n and m in the oligomer depends on the molar ratio of diisocyanates to diols used, and the value _. ...w ~w... wi I i αι iu in Ii iureases as tnis molar ratio decreases. The diisocyanates have the structures OCN-RrNCO and OCN-R'rNCO and the diols have the structures HO-R₂-OH and HO-R₂-OH. The more complex structures of urethane pre-oligomer are constructed from at least two different diols and at . least two different diisocyanates.

[0008] Reaction of the urethane pre-oligomer with the ethylenically unsaturated monomer as defined below yields a polymerizable compound having the structure within the scope of the general formula V: CH₂=C(Rs)-CO₂-R₄-CO- NH-(R₁-NH-CO-O-R₂-O-OC-NH)_n-Ri-NH-CO-R₄-O₂C-C(Rs)=CH₂ V wherein R₃ is hydrogen, or an alkyl, such as a methyl group, and R₄ is an alkyl group having from 1 to 14 carbon atoms, and n is an integer from O to 20. The typical ethylenically unsaturated monomer is a hydroxyalkyl (meth) acrylate, e.g. 2- hydroxyethyl methacrylate, hydroxypropyl methacrylate, caprolactone 2- (methacryloyloxy) ethyl ester, etc.

[0009] Preferred mechanical properties of cured resin and the adequate handling properties of compositions, polymerizable compound, are present when the value of n in the compound is not greater than 10; more preferably n is not greater than 5. The preferred value of n in the compound largely depends on the requirements of the specific application. The most preferable value of n in the compound for aromatic ring based diol is between 1 and 3. Therefore, the molar ratio of diisocyanate to diol for aromatic ring based diol is most preferable between 1.33 and 2. The most preferable value of n in the compound for alkyl based diol is between 1 and 4. Therefore, the molar ratio of diisocyanate to diol for alkyl based diol is most preferable between 1.25 and 2.

[0010] Catalysts known in the art may be used to accelerate the formation of the isocyanate-ended pre-oligomer and end-capped ethylenically unsaturated monomer, for examples, tertiary amines and metal salts, e.g. stannous octoate and in particular dibutyl tin dilaurate. Preferred stabilizers used in this invention are butylated hydroxytoluene (BHT) and the methyl ether of hydroquinone (MEHQ).

[0011] Preferably compounds of the invention are difunctional methacrylates including reaction products of bisphenol A propoxylate, 1 ,6-diisocyanatohexane and 2-hydroxyethyl methacrylate, reaction products of bisphenol A propoxylate, trimethyl-1 , 6-diisocyanatohexane and 2-hydroxyethyl methacrylate, a series of reaction products of bisphenol A, trimethyl-1 , 6-diisocyanatohexane and 2- hydroxylethyl methacrylate, a series of reaction products of bisphenol A, 1 ,6- diisocyanatohexane and 2-hydroxylethyl methacrylate, a series of reaction products of trimethyl-1 ,6-diisocyanatohexane, 2,5-dimethyl-2,5-hexanediol and 2- hydroxyethyl methacrylate, a series of reaction products of trimethyl-1 ,6- diisocyanatohexane, 1 ,6-diisocyanatohexane, 2,5-dimethyl-2,5-hexanediol and 2- hydroxyethyl methacrylate, a series of reaction products of trimethyl-1 ,6- diisocyanatohexane, 1 ,6-diisocyanatohexane, bisphenol A propoxylate and 2- hydroxyethyl methacrylate, caprolactone 2-(methacryloyloxy)ethyl ester, and derivatives of above compounds.

[0012] Diisocyanates useful for making wax-like polymerizable dental material of the invention include trimethyl-1 ,6-diisocyanatohexane, 1 ,6- diisocyanatohexane, 1 ,8-diisocyanatooctane, isophorone diisocyanate, 4.4"- methylenebis(cyclohexyl isocyanate), cyclohexyl diisocyanate, 3-methylhexane-1 , 6-diisocyanate, 3-ethyl-1 ,6-hexanediisocyanate, 5-methyl-1 ,9- nonanediisocyanate, 5-ethyl-1 ,10-decanediisocyanate, 2,3-dimethyl-1 ,6- hexanediisocyanate, 2,4-dimethyl-1 ,8-octanediisocyanate, 2,4,6-trimethyl-1 J- heptanediisocyanate, 2,3-dimethyl-5-ethyl-1 ,8-octanediisocyanate, 1 ,12- diisocyanatododecane, 2-methyl-4,6,8,10-tetrapropyl-1 ,12-dodecanediisocyanate and the like, and mixtures thereof. Examples of diisocyanates that are also suitable include aromatic diisocyanates, for example, 4,4-methylene bis(phenyl isocyanate), 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1 ,4-phenyl diisocyanate, 1 ,5-naphthalene diisocyanate, 1 ,3-bis (isocyanatomethyl)benzene, 1 ,3-bis(isocyanato-1-methylethyl)benzene, 1 ,3- υis^isocyanatometnyljcyclohexane, 3,3"-bitoluene diisocyanate, 1 ,4-xylylene diisocyanate and the like, and mixtures thereof.

[0013] Examples of diols useful for making compounds for wax-like polymerizable dental material of the invention include 1 ,4-butanediol, 1 ,6- hexanediol, 1 ,10-decanediol, 1 ,9-decanediol, 1 ,12-dodecanediol, 1 ,14- tetradecanediol, 2,5-dimethyl-2, 5-hexanediol, hydrogenated bisphenol A, bisphenol A, propoxylated bisphenol A, ethoxylated bisphenol A, bis(2- hydroxyethyl) terepthalate, hydrogenated polybutadiene diol (GH 000, GI2000, GI3000, etc. from Nippon Soda Co., Ltd. in Japan) and mixtures thereof.

[0014] Examples of methacrylates (or acrylates) useful for making compounds for wax-like polymerizable dental material of the invention include 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 3- hydroxypropyl methacrylate, hydroxypropyl acrylate, glycerol dimethacrylate, glycerolmonomethacrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, 4- hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxycyclohexyl methacrylate, caprolactone 2- (methacryloyloxy)ethyl ester, pentaerythritol triacrylate, 2-hydroxycyclohexyl acrylate and mixture thereof.

[0015] Wax-like polymerizable dental material may include one or more initiating systems to cause them to harden promptly. Light curable wax-like polymerizable dental materials preferably include a light sensitizer, for example camphorquinone, Lucirin TPO, Liquid Lucirin or methyl benzoin which causes polymerization to be initiated upon exposure to activating wavelengths of light; and/or a reducing compound, for example tertiary amine.

[0016] A room temperature or heat activating catalyst system is preferably included in the wax-like polymerizable dental material of the invention. Preferably included is a peroxide capable of producing free radicals when activated by a reducing agent at room temperature or by heating. Preferred peroxides include benzyl peroxide and lauroyl peroxide.

[0017] Wax-like polymerizable dental materials of the invention are believed to rapidly partially recrystallize. This rapid recrystallizability provides a unique combination of free flowability and dimensional stability, depending on its temperature. It is believed that the material rapidly transitions from a freely flowable state by means of rapid crystallization to a dimensionally stable state. The material at solidification temperatures is partially crystalline and the crystallinity present in an amorphous phase results in the effective dimensional stability of the material. "Crystallinity" as used herein refers to regularity and order within a material resulting in a heat of fusion of at least 1.0 J/g at and below 5O⁰C. Heat of Fusion as used herein refers to enthalpy of fusion as determined by ASTM 793-95. Percent crystallinity is determined by measuring the heat of fusion using differential scanning calorimetry according to ASTM test method E 793-95. Toughness used herein is determined by calculation of the area under the curve of flexural test according to ISO 1567 method.

[0018] The wax-like polymerizable dental material of the invention is useful for formation of dental products including full dentures, partial dentures, denture liners, custom trays, artificial teeth, repairs for natural teeth, veneers, denture repairs, denture reline, night guards, splints, retainers, orthodontic components, crowns, bridges, provisional dental devices, inlays, onlays, and tooth restorative fillings, orthodontic appliances, oral orthopedic appliances, temporary dentures, temporary partial dentures; maxillofacial prostheses, obturators, and occular prostheses.

[0019] Compositions in accordance with the invention may further include fillers, pigments, stabilizers, plasticizers and fibers. Preferably, polymerizable dental compositions in accordance with the invention include from about 2 to about 95 percent by weight filler particles. More preferably, these compositions include from about 10 to about 85 percent by weight filler. Nanocomposites and ceramers may be formed from these composites. The fillers preferably include both organic and inorganic particulate fillers to further reduce polymerization shrinkage, improve wear resistance and modify the mechanical and physical properties.

[0020] A preferred embodiment of the invention provides a dental polymeric material formed by light curing wax-like polymerizable dental material shaped into at least a portion of a denture base. Preferably the wax-like polymerizable dental material has a toughness of at least 100 in/in³ and an un-notched impact strength of at least 2 foot-pounds/inch. Preferably the denture comprises denture base, and a tooth comprising an interpenetrating polymer network polymeric matrix and at least 0.1 percent by weight of self-lubricating particles having a particle size less than 500 microns effectively bonded to and distributed in the polymeric matrix. Preferably the bond strength between the tooth and the denture base is at least 4,480 psi.

[0021] "Wax-like" as used herein refers to material which is flowable (fluid) above 4O⁰C, and becomes dimensionally stable (solidifies: i.e. is non-fluid) at least at and below 23⁰C, within 5 minutes. Thus, wax-like material is flowable when it is at and above 4O⁰C, and becomes dimensionally stable when it is at and below 23⁰C. Flowable wax-like material having a temperature from 100⁰C to 40- ⁰C, becomes dimensionally stable within 5 minutes by cooling by exposure to an ambient temperature between 23⁰C and O⁰C. Flowable wax-like material having a temperature from 100⁰C to 4O⁰C, becomes dimensionally stable within (in order of increasing preference) 2, 1 , 0.5 or 0.3 minutes by cooling by exposure to an ambient temperature between 23⁰C and O⁰C.

[0022] "Flexural strength, and flexural modulus" as used herein refers to results of testing according to ASTM D790 (1997). "Notched impact strength" as used herein is also referred to as "notched Izod impact resistance" and refers to results of testing according to ASTM D256 (1997). "Un-notched impact strength" as used herein refers to results of testing according to ASTM D4812 (1993). [0023] In the following examples, unless otherwise indicated, all parts and percentages are by weight; Lucirin TPO refers to 2,4,6- trimethylbenzoyldiphenylphosphine oxide made by BASF, Lucirin TPO-L refers to ethyl-2,4,6-trimethylbenzoylphenylphosphinate and the visible light curing unit used was a TRIAD VLC visible light curing unit modified by adding a fifth light to provide about 30 milliwatts/cm² of from 350 to 450 nm light.

[0024] Rubber modified compounds were used to enhance the toughness of resin cured. Commercial available rubber-modified compounds can be used such as acrylic rubber impact modifier, Paraloid KM334 (sold by Rohm & Hass) and methacrylated butadiene styrene impact modifier, Metablend C223 (sold by ATOCHEM), polybutadiene di(meth)acrylates, Genomer 4246 (sold by ROHN AG), Ebecryl 3604 (sold by UCB chemicals corporation).

[0025] Such as the derivatives of poly(acryonitrile-co-butadiene) dicarboxy, diisocyanates and hydroxy! alkyl (meth)acrylate; derivatives of poly(ethylene-co- 1 ,2-butylene) diol, diisocyanates and hydroxyl alkyl (meth)acrylate; derivatives of hydrogenated poly(butadiene) diol, diisocyanates and hydroxyl alkyl (meth)acrylate; derivatives of ethoxylated/propoxylated bisphenol A, diisocyanates and hydroxyl alkyl (meth)acrylate; derivatives of polydiols, alkyl diols or their combinations, diisocyanates and hydroxyl alkyl (meth)acrylate; derivatives of poly(ethylene-co-1 ,2-butylene) diol, diols, diisocyanates and hydroxyl alkyl (meth)acrylate; derivatives of hydrogenated poly(butadiene) diol, diols, diisocyanates and hydroxyl alkyl (meth)acrylate, etc. can be used to enhance the toughness of wax-like polymerizable materials.

EXAMPLE 1

Preparation of Oligomer

[0026] A reactor was charged with 1176 grams of trimethyl-1 ,6- diisocyanatohexane (5.59 mol) and 1064 grams of bisphenol A propoxylate (3.09 mol) under dry nitrogen flow and heated to about 65⁰C. under positive nitrogen pressure. To this reaction mixture, 10 drops of catalyst dibutyltin dilaurate were added. The temperature of the reaction mixture was maintained between 65⁰C and 14O ⁰C for about 70 minutes and followed by additional 10 drops of catalyst dibutyltin dilaurate. A viscous paste-like isocyanate end-capped intermediate product was formed and stirred for 100 minutes. To this intermediate product, 662 grams (5.09 mol) of 2-hydroxyethyI methacrylate and 7.0 grams of BHT as an inhibitor were added over a period of 70 minutes while the reaction temperature was maintained between 68⁰C and 9O⁰C. After about five hours stirring under 7O⁰C, the heat was turned off, and oligomer was collected from the reactor as semi-translucent flexible solid and stored in a dry atmosphere.

EXAMPLE 2 Preparation of Oligomer

[0027] A reactor was charged with 150 grams of 1 ,6-diisocyanatohexane and 200 grams of bisphenol A propoxylate under dry nitrogen flow and heated to about 56⁰C under positive nitrogen pressure. To this reaction mixture, 0.12 gram of catalyst dibutyltin dilaurate was added. The temperature of the reaction mixture was maintained between 65⁰C and 8O⁰C for about 3.5 hours. To this isocyanate end-capped intermediate product, 82.96 grams of 2-hydroxyethyl methacrylate and 2.15 grams of BHT as an inhibitor were added over a period of 50 minutes while the reaction temperature was maintained between 55⁰C and 75⁰C. After about five hours stirring, the heat was turned off, and oligomer was collected from the reactor as semi-translucent flexible solid and stored in a dry atmosphere.

EXAMPLE 3 Preparation of Monomer

[0028] A reaction flask was charged with 700 grams of 1 ,6- diisocyanatohexane and heated to about 7O⁰C under a positive nitrogen pressure. To this reactor were added 1027 grams of 2-hydroxyethyl methacrylate, 0.75 gram of catalyst dibutyltin dilaurate and 4.5 grams of butylated hydroxy toluene (BHT). The addition was slow and under dry nitrogen flow over a period of two hours. The temperature of the reaction mixture was maintained between 7O⁰C and 9O⁰C for another two hours and followed by the addition of 8.5 grams of purified water. One hour later, the reaction product was discharged as clear liquid into plastic containers and cooled to form a white solid and stored in a dry atmosphere.

EXAMPLE 4 Preparation of Monomer

[0029] A reaction flask was charged with 168 grams of 1 ,6- diisocyanatohexane and heated to about 7O⁰C under a positive nitrogen pressure. To this reactor were added 228 grams of 2-hydroxyethyl acrylate, 0.12 gram of catalyst dibutyltin dilaurate and 0.86 grams of butylated hydroxy toluene (BHT). The addition was slow and under dry nitrogen flow over a period of two hours. The temperature of the reaction mixture was maintained between 7O⁰C and 85⁰C for another three hours and followed by the addition of 0.9 grams of purified water. One hour later, the reaction product was discharged as clear liquid into plastic containers and cooled to form a white solid and stored in a dry atmosphere.

EXAMPLE 5 Preparation of Monomer

[0030] A reaction flask was charged with 151.25 grams of octadecyl isocyanate and heated to about 7O⁰C under a positive nitrogen pressure. To this reactor were added 125.3 grams of caprolactone 2-(methacryloyloxy)ethyl ester, 0.12 gram of catalyst dibutyltin dilaurate and 0.58 grams of butylated hydroxy toluene (BHT). The addition was slow and under dry nitrogen flow over a period of two hours. The temperature of the reaction mixture was maintained between 7O⁰C and 85⁰C for another 2.5 hours, the reaction product was discharged as clear liquid into plastic containers and cooled to form a semi-opaque solid and stored in a dry atmosphere. EXAMPLE 6 Preparation of Monomer

[0031] A reaction flask was charged with 200 grams of octadecyl isocyanate and heated to about 78⁰C under a positive nitrogen pressure. To this reactor were added 90.6 grams of 2-hydroxyethyi methacrylate, 0.14 gram of catalyst dibutyltin dilaurate and 0.58 grams of butylated hydroxy toluene (BHT). The addition was slow and under dry nitrogen flow over a period of two hours. The temperature of the reaction mixture was maintained between 7O⁰C and 85⁰C for another 3 hours, the reaction product was discharged as clear liquid into plastic containers and cooled to form a white solid and stored in a dry atmosphere.

EXAMPLE 7

Preparation of Rubber-Modified Oligomer

[0032] A reactor was charged with 407.8 grams of GI-1000 (hydrogenated polybutadiene diol), 564 grams of trimethyl-1 ,6-diisocyanatohexane and 77 grams of 1 ,6-diisocyanatohexane under dry nitrogen flow and heated to about 80°C under a positive nitrogen pressure. To this reaction mixture, 0.35 grams of catalyst dibutyltin dilaurate were added. The temperature of the reaction mixture was maintained between 85⁰C and 95⁰C for about 60 minutes and followed by the addition of 355.5 grams of 1 , 10-decanediol under vigorous stirring at 95⁰C. A viscous paste-like isocyanate end-capped intermediate product was formed and stirred for 100 minutes. To this intermediate product, 210 grams of 2- hydroxyethyl methacrylate and 5.0 grams of BHT as an inhibitor were added over a period of 70 minutes while the reaction temperature was maintained between 8O⁰C and 100⁰C. After about four hours stirring around 9O⁰C, the heat was turned off, and oligomer was collected from the reactor as semi-opaque solid and stored in a dry atmosphere. EXAMPLE 8

Preparation of Polymerizable Denture Contour Material

[0033] A wax-like polymerizable dental material was prepared by stirring at

85⁰C a liquid mixture of 21.25 grams of oligomer made the procedure of Example

1 , 46.5 grams of compound of Example 3, 6.5 grams of compound of Example 4,

17.0 grams of rubber-modified oligomer of Example 7, and 8.0 grams of compound of Example 6. 0.35 gram of 2,4,6- trimethylbenzoyldiphenylphosphine oxide, (Lucirin TPO made by BASF), 0.1 gram of red acetate fibers, 0.3 gram of pigment concentrates.

EXAMPLE 9A

Preparation of Polymerizable Denture Base Plate (orReline) Material [0034] A light curable polymerizable material was prepared by stirring at 85⁰C a liquid of 78.0 grams of TBDMA oligomer of Example 1 , 15.0 grams of rubber- modified oligomer of Example 7, 5.0 grams of stearyl acrylate, 0.35 gram of 2,4,6- trimethylbenzoyldiphenylphosphine oxide, (Lucirin TPO made by BASF), 1.5 gram of visible light initiating solution contains 13.3% camphorquinone (CQ), 23.0% methacrylic acid (MAA), 1.3% butylated hydroxytoluene (BHT), 46% N, N- dimethylaminoethylneopentyl acrylate, 16.3% γ- methacryloxypropyltrimethoxysilane and 66.7% 1 ,6-hexanediol dimethacrylate (HDDMA), 0.1 gram of red acetate fibers and 0.05 gram of pigments.

EXAMPLE 9B

Preparation of Polymerizable Denture Base Plate (or Reline) Material [0035] A light curable polymerizable material was prepared by stirring at 85⁰C a liquid of 53.5 grams of TBDMA oligomer of Example 1 , 45.0 grams of rubber- modified oligomer of Example 7, 0.35 gram of ethyl-2,4,6- trimethylbenzoyldiphenylphosphinate, (Lucirin TPO-L made by BASF), 1.0 gram of visible light initiating solution contains 13.3% camphorquinone (CQ), 23.0% methacrylic acid (MAA), 1.3% butylated hydroxytoluene (BHT), 46% N, N- dimethylaminoethylneopentyl acrylate, 16.3% γ- methacryloxypropyltrimethoxysilane and 66.7% 1 ,6-hexanediol dimethacrylate (HDDMA), 0.1 gram of red acetate fibers and 0.05 gram of pigments.

EXAMPLE 10

Preparation of Polymerizable Wax-Like Denture Contour Material

[0036] A light curable wax-like polymerizable dental material was prepared by stirring at 85⁰C a liquid mixture of 19.25 grams of oligomer made the procedure of

Example 1 , 49 grams of compound of Example 3, 7.0 grams of compound of

Example 4, 17.0 grams of rubber-modified oligomer of Example 7, and 7.0 grams of compound of Example 5. 0.35 gram of 2,4,6- trimethylbenzoyldiphenylphosphine oxide, (Lucirin TPO made by BASF), 0.1 gram of red acetate fibers, 0.3 gram of pigment concentrates.

EXAMPLE 11

Preparation of Polymerizable Denture Set-up Material

[0037] A light curable polymerizable material was prepared by stirring at 85⁰C a liquid mixture of 39.4 grams of oligomer of Example 1 , 32.0 grams of compound of Example 3, 5.5 grams of compound of Example 4, 14.0 grams of rubber- modified oligomer of Example 7, and 8.5 grams of stearyl acrylate. To this mixture, 0.35 gram of 2,4,6- trimethylbenzoyldiphenylphosphine oxide (Lucirin TPO), 0.2 gram of visible light initiating solution contains 13.3% camphorquinone (CQ), 23.0% methacrylic acid (MAA), 1.3% butylated hydroxytoluene (BHT), 46% N, N-dimethylaminoethylneopentyl acrylate, 16.3% γ- methacryloxypropyltrimethoxysilane and 66.7% 1 ,6-hexanediol dimethacrylate (HDDMA), 0.1 gram of red acetate fibers and 0.05 gram of pigment were added.

EXAMPLE 12

Preparation of a Denture without Forming a Mold Cavity of a Denture Base [0038] A plaster cast of a patient's mouth is coated with a release agent (e.g., Al-Cote and lsolant sold by Dentsply International Inc. or Teflon solution such as Krytox from Dupont). An arch-shaped baseplate resin containing 14 grams of the product of Example 9A is applied and shaped onto the warm cast. The resin is shaped and flowed to fully cover the cast, using finger pressure and trimming to form a baseplate. The baseplate is cured for 10 minutes in the visible light curing unit. A sufficient quantity of the product of Example 11 is formed into a rope. The bottom of rope is melted with electric spatula and the rope is applied to the baseplate. Then the surface of rope is melted and artificial teeth are pressed into the melted surface. Melted product of Example 8 from an about 80⁰C wax pot is applied by using an electric spatula between the teeth and the baseplate to fully embed teeth and to flow into fissures between teeth and to smooth the outer surface of the denture. Hot air from a small nozzle hot air gun may also be applied to let the product of Example 8 flow into fissures between teeth and smooth the outer surface of the denture. The lingual and buccal surfaces of the denture are contoured, trimmed and carved using a spatula. The denture is placed in a patient's mouth for try-in at a dental office and tooth positions are adjusted. The cured baseplate area of denture is poured with thick plaster mix to form a model and the Eclipse or TRIAD Air Barrier Coating is painted on the denture. When cured, the denture is washed with water to remove all traces of Air Barrier Coating. The denture is then finished and polished.

EXAMPLE 13

Preparation of a Partial Denture without Forming a Mold Cavity (investment) of a Denture Base

[0039] A removable partial denture framework is fabricated. A separating medium is applied to a gypsum cast of the patient's dentition. A sufficient quantity of the product of Example 9A is applied onto the edentulous areas of the cast and adapted with finger pressure or appropriate instruments. Excess material is trimmed with a hot spatula or knife. A sufficient quantity of the product of Example 9A is adapted into the tissue side finish line of the partial denture framework. The framework is seated on the cast firmly, embedding the uncured material of Example 9A. All rests and tissue stops are varnished as correctly positioned on the cast, indicating that the framework is fully seated. Excess material is removed and these baseplate areas are cured in the visible light curing unit. A rope of the product of Example 11 is adapted onto the precured baseplate/edentulous areas. The rope has a thickness sufficient to cover the ridge lap surfaces of the teeth to provide support for the teeth and to seat the teeth, which are then set up in the rope. A portion the product of Example 10 is applied between the teeth and the baseplate. A small nozzle hot air gun is used to melt the product of Example 10 so that it flows into the fissures between teeth as the outer surface smoothes. The lingual and buccal surfaces of the edentulous areas are contoured, trimmed and carved using an electric hot spatula, sharp tools and hot air gun. The partial denture wax-up is removed from the cast for try-in. The denture is placed in a patient's mouth for try-in at a dental office and tooth positions adjusted if needed. The partial denture is fitted to a modified cast (reduced soft tissue heights of contour). Eclipse or TRAID Air Barrier Coating is painted onto the denture. The denture is then cured in the Eclipse light curing unit for 10 minutes. When cured, the partial denture is washed with water to remove all traces of Air Barrier Coating. The partial denture is then finished and polished.

EXAMPLE 14

Preparation of a Flexible Partial Denture without Forming a Mold Cavity (investment) of a Denture Base

[0040] A separating medium is applied to a gypsum cast of the patients dentition. A sheet of the product of Example 9B is applied onto the cast and adapted with finger pressure, trimmed with scissors or appropriate instruments to form a baseplate with clasps and rests. Excess material is trimmed with scissors, blade, a hot spatula or appropriate instruments to obtain desired metal-free baseplate with clasps and rests correctly positioned on the cast. Excess material is removed and the baseplate is cured in the visible light curing unit. A rope of the product of Example 11 is adapted onto the precured and ground baseplate areas. The rope has a thickness sufficient to cover the ridge lap surfaces of the teeth to provide support for the teeth and to seat the teeth, which are then set up in the rope. A portion the product of Example 10 is applied between the teeth and the baseplate. A small nozzle hot air gun is used to melt the product of Example 10 so that it flows into the fissures between teeth as the outer surface smoothes. The lingual and buccal surfaces of the edentulous areas are contoured, trimmed and carved using an electric hot spatula, sharp tools and hot air gun. The partial denture wax-up is removed from the cast for try-in. The denture is placed in a patient's mouth for try-in at a dental office and tooth positions adjusted if needed. The partial denture is fitted to a modified cast (reduced soft tissue heights of contour). Eclipse or TRAID Air Barrier Coating is painted onto the denture. The denture is then cured in the Eclipse light curing unit for 10 minutes. When cured, the partial denture is washed with water to remove all traces of Air Barrier Coating. The partial denture is then finished and polished.

[0041] It should be understood that while the present invention has been described in considerable detail with respect to certain specific embodiments thereof, it should not be considered limited to such embodiments but may be used in other ways without departure from the spirit of the invention and the scope of the appended claims.

Claims

What is claimed is:

1. A wax-like dental material comprising a polymeriable material that is at least partially crystallizable.

2. A wax-like dental material as in claim 1 , comprising a urethane pre-oligomer.

3. A wax-like dental material as in claim 2, wherein said pre-oligomer is selected from the group consisting of OCN-(R₁-NH-CO-O-R₂-O-OC-NHVR- rNCO; OCN-( Ri-NH-CO-O-R₂-O-OC-NH)_m-(R₁-NH-CO-O-R'₂-O-OC-NH)n- R₁-NCO; OCN-( Ri-NH-CO-O-R₂-O-OC-NH)_m-(R"i-NH-CO-O-R₂-O-OC-NH)- _n-R'_rNCO; and, OCN-CRrNH-CO-O-Rz-O-OC-NHMR'VNH-CO-O-R'z-O- OC-NH)_n-R¹ _I-NCO; wherein R₁ , R'-i , R₂ and R'₂ each independently is an alkyl having from 1 to 14 carbon atoms or at least an aromatic group having from 6 to 14 carbon atoms, and n and m are each independently integers from O to 20.

4. A wax-like dental material formed from the reaction of a pre-oligomer as in claim 3 with an ethylenically unsaturated monomer, said reaction product having the general formula CH₂=C(Ra)-CO₂-R₄-CO-NH-(R₁-NH-CO-O-R₂-O- OC-NH)_n-R₁-NH-CO-R₄-O₂C-C(R₃)=CH₂ wherein R₃ is hydrogen or an alkyl group having from 1 to about 20 carbon atoms, R₄ is an alkyl group having from 1 to 14 carbon atoms, and n is an integer from O to 20.