CA2207351C - Dental material based on polymerizable waxes - Google Patents
Dental material based on polymerizable waxes Download PDFInfo
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- CA2207351C CA2207351C CA002207351A CA2207351A CA2207351C CA 2207351 C CA2207351 C CA 2207351C CA 002207351 A CA002207351 A CA 002207351A CA 2207351 A CA2207351 A CA 2207351A CA 2207351 C CA2207351 C CA 2207351C
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
- A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
- A61K6/887—Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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Abstract
The invention relates to dental materials based on wax-like polymerizable substances. The dental materials contain (a) 0 to 70 wt.% of at least one polymerizable monomer and/or oligomer;
(b) 0.1 to 5 wt.% of at least one polymerization initiator; (c) 0 to 60 wt.% of one or more fillers, (d) at least 20 wt.% of the wax-like polymerizable substance. They can be kneaded at room temperature and can be modelled in non-polymerized state without additional heating, like conventional waxes. On polymerization, the wax component is covalently incorporated into the polymer.
The dental materials are suitable for producing temporary and permanent dental prostheses.
(b) 0.1 to 5 wt.% of at least one polymerization initiator; (c) 0 to 60 wt.% of one or more fillers, (d) at least 20 wt.% of the wax-like polymerizable substance. They can be kneaded at room temperature and can be modelled in non-polymerized state without additional heating, like conventional waxes. On polymerization, the wax component is covalently incorporated into the polymer.
The dental materials are suitable for producing temporary and permanent dental prostheses.
Description
CA 022073~1 1997-06-09 .' Dental Material Based on Polymerizable Waxes The present invention relates to dental materials based on polymerizable waxes, which are particularly suitable as materials-for temporary and permanent dental prostheses, inlays and crowns.
The term wax is a collective term for a series of natural and synthetic substances. Generally underst-ood by this term are materials which are already easily plastically mouldable below their melting range or softening range, have a translucent to opaque appearance, melt without decomposition above 40~C and already produce liquids of relatively low viscosity slightly above the melting point and which possess a greatly temperature-dependent consistency and solubility. Furthermore, waxes can mostly be polished under light pressure (Ullmann's Enzyklopadie der Technischen Chemie, 4th edition, volume 24, Verlag Chemie, Weinheim 1989).
Waxes are used in the dental field as modelling, casting, occlusion or adhesive waxes. Mixtures of natural waxes and synthetic waxes are used almost exclusively, the physical properties of the waxes being geared to the desired use (K.
Korber, K. Ludwig, Zahnarztliche Werkstoffe und Technologie, G.
Thieme Verlag, Stuttgart, 1982, page 90). For example, a modelling wax suitable for modelling preshaped parts should be easy to mould and have as good a dimensional stability as possible at the temperature of the mouth. Mixtures of paraffin wax, stearin wax, Japan wax and beeswax are suitable for this purpose.
Conventional waxes are generally heated for processing. Curing 3~ takes place by the wax solidifying on subsequent cooling. In this case, relatively large, uncontrollable volume changes generally occur. Furthermore, conventional waxes have the disadvantage that they easily break when being removed from the model and change their shape under even relatively slight mechanical and above all thermal stress.
CA 022073~1 1997-06-09 In order to avoid these disadvantages, mixtures of natural and partially or wholly synthetic waxes with polymerizable monomers or oligomers such as polyfunctional acrylates and methacrylates have recently been used. These mixtures can be specifically cured after treatment and then have a higher mechanical stability than the pure waxes.
For example, mixtures of polyethylene waxes with styrene or acrylate monomers are disclosed in JP-A-92/4748 (C.A. 120 (1993) 136156) and JP-A-91/330047 (C.A. 119 (1993) 282306). Further-more, photopolymerizable waxes for the dental field based on mixtures of natural or synthetic waxes with conventional acrylic compounds and photoinitiators are described in JP-A-90/312256 (C.A. 128 (1992) 27523). The disadvantages of these mixtures are that conventional dental waxes and dental crosslinker monomers do not mix well with one another and that above all the wax is not incorporated into the polymer network on polymerization. The result may therefore be the formation of wax domains, i.e. a multiphase system is formed, the mechanical strength of which is accordingly low.
EP-B-0 110 193 discloses wax-free wax substitutes for producing casting models. These compositions are based on mixtures of di-or polyfunctional meth- or acrylic acid esters, a photoinitiator and optionally a photoactivator and organic fillers. On account of the composition of the materials claimed in EP-B-0 110 193, they do not exhibit any wax-like properties, i.e. the materials cannot be modelled like waxes and consequently the dental technician must replace the usual wax technique with a layer technique which involves a lot of work. Changes or adjustments to the model can then no longer be made, since curing takes place by polymerization after application of the respective layer.
Furthermore, this process has the disadvantage that thin layers can only be produced using slightly filled or unfilled mixtures of di- or polyfunctional (meth)acrylic acid esters, during the CA 022073~1 1997-06-09 .
polymerization of which a considerable volume contraction results.
EP-B-0 380 116 discloses mixtures which, in order to influence the expansion behaviour of the moulding compounds, additionally contain an organic compound having a boiling point and/or a sublimation point in the range above 150~C and which does not react with the organic polymerizable composition. The named compositions are characterized in particular by the fact that they leave no residues upon combustion.
US-A-5 403 188 discloses thermoplastic mouldiny compounds which are suitable for the production of dental impressions. The compounds contain a polymeric thermoplastic material, preferably a polycaprolactone, a polymerizable resin, an initiator and optionally a filler. They are solid at 38 C and practically not mouldable and they are heated for processing. Curing then takes place by cooling. After the impression has been produced, the compounds are additionally cured by a radical polymerization.
The materials have the disadvantage that they only melt down to form highly viscous products. Dental shaping is extremely difficult since the materials are not only viscous in the molten state, but also very sticky.
It is the object of the invention to provide wax-like dental materials which do not have the above-named disadvantages and are also suitable in particular for producing temporary and permanent prostheses.
The object is achieved by dental materials based on polymerizable waxes which contain a) 0 to 70 wt.%, preferably 5 to 70 wt.%, particularly preferably 5 to 60 wt.% and quite particularly preferably 20 to 50 wt.%, of at least one polymerizable monomer and/or oligomer;
CA 022073~1 1997-06-09 i , b) 0.1 to 5 wt.%, preferably 0.2 to 2.0 wt.%, of at least one polymerization initiator;
c) 0 to 60 wt.%, preferably 0 to 50 wt.% and particularly preferably 0 to 30 wt.%, of fillers; and d) at least 20 wt.%, preferably at least 40 wt.%, of a wax-like polymerizable substance.
10 Suitable polymerizable monomers and oligomers are known for example from DE-C-3 941 629 or DE-A-4 029 230. Compounds which have a crosslinking effect such as di-, tri- or tetraethylene glycol di(meth)acrylate, decanediol di(meth)acrylate, bisphenol-A-di(meth)acrylate, trimethylolpropane tri(meth)acrylate, 15 pentaerythritol tetra(meth)acrylate, 2,2-bis(4-methacryloyloxy-2-hydroxypropoxy)-phenylpropane (bis-GMA) and the reaction product of 1 mol of 2,2,4-trimethylhexamethylene diisocyanate with 2 mol of 2-hydroxyethyl (meth)acrylate and mixtures of these monomers are preferred.
Suitable polymerization initiators are known for example from DE-A-4 029 230. Preferred initiators are camphor quinone, 9,10-phenanthrenequinone or diacetyl. Furthermore, the polymerization initiators can be combined with a suitable reducing agent.
25 Suitable for this purpose are in particular 4-dimethylamino-benzoate, N,N'-(2-cyanoethyl)methylaniline, triethanolamine or 2-(dimethylamino)ethyl methacrylate.
The dental materials according to the invention can contain up 30 to 60 wt.% of fillers, but dental materials containing little or no filler are preferred. The fillers are used to increase mechanical strength, to reduce polymerization shrinkage and to control viscosity. Preferred fillers are known for example from DE-C-3 941 629. Particularly preferred are fillers in the form of amorphous spherical materials based on mixed oxides of SiO2, ZrO2 and/or TiO2, microfine fillers such as pyrogenic silicic CA 022073~1 1997-06-09 acid or precipitated silicic acid, and macro or mini fillers such as quartz powder, glass ceramic powder or glass powder.
Preferred as wax-like polymerizable substances are those compounds which represent a longer-chained carboxylic acid, a carboxylic acid derivative, an OH-functionalized compound and/or a derivative of an OH-functionalized compound and which have one or more polymerizable groups. Preferred carboxylic acid derivatives are the esters with polymerizable alcohols, preferred OH-functionalized compounds are alcohols. Preferred as deriva-tives of the OH-functionalized compounds are the esters with polymerizable carboxylic acid derivatives. The wax-like polymerizable substances are preferably used in monomeric form.
Suitable wax-like polymerizable substances are in some cas~s commercially available, such as for example stearyl acrylate (melting point 23 C, Christ Chem.), PEG-1000-dimethacrylate (melting point 20 C) and PEG-4000-diacrylate (melting point 52 C, both from Polysciences, Inc.), or can be produced by chemical modification of suitable carboxylic acids and alcohols.
Preferred for this purpose are carboxylic acids with a melting point of above 60 C, in particular those with a chain length of 16 to 32 carbon atoms. Palmitic acid (melting point: 64 C), stearic acid (melting point: 69~C), eicosanoic acid (C20H40O2;
melting point: 74-76~C), docosanoic acid (C22H44Oz; melting point:
80-82 C), tricosanoic acid (C23H46O2; melting point: 75-83 C), hexacosanoic acid (C26H52O2; melting point: 87-89~C), heptacosanoic acid (C27H54O2; melting point: 88-89 C) or octacosanoic acid (C28H56O2; melting point: 61-63 C) are quite particularly pre-ferred. Mixtures of these carboxylic acids are also suitable.
Mixtures of palmitic or stearic acid with hexacosanoic or heptacosanoic acid are preferred. A particularly suitable starting material for producing the wax-like polymerizable substances according to the invention is Hoechst-Wachs S
CA 022073~1 1997-06-09 (Hoechst, melting point 80 C) which is a mixture of longer-chained aliphatic carboxylic acids (Cl6 to C36).
Longer-chained alcohols with a melting point of above 55 C as starting materials for producing the polymerizable wax-like substances are preferred as alcohols, in particular those with a chain length of 18 to 32 carbon atoms. Quite particularly preferred are 1,2-octadecanediol (Cl8H38O2; melting point: 74-76 C), 1-eicosanol ((C20H4lOH; melting point: 64-66 C), 1-docosanol (C22H45OH; melting point 65-72 C) or 1-hexacosanol (C26H53OH; melting point: 79-81 C), and Hoechst-Wachs KST
(Hoechst, melting point 57-59 C; based on OH-terminated polyethylene oxide).
Starting from the above wax-like carboxylic acids, the introduc-tion of polymerizable groups preferably takes place by reaction with suitable unsaturated compounds, in particular vinyl, (meth)acrylic or allyl compounds, according to known methods of organic chemistry. Polymerizable methacrylate groups can be introduced for example after activation of the COOH groups e.g.
with chloroformate according to the method of the mixed anhydrides in a single-pot reaction by reaction with 2-hydroxy-ethyl methacrylate (HEMA), hydroxypropyl methacrylate or glycerol dimethacrylate (GDMA). Furthermore, introduction of methacrylic groups can also take place by directly reacting the wax-like carboxylic acids with methacrylic acid-2,3-epoxypropyl ester (GMA).
Starting from the above wax-like OH-functionalized compounds, the introduction of polymerizable groups such as e.g. methacrylic groups is possible for example simply by their azeotropic esterification with methacrylic acid or by acylation with methacrylic acid chloride or methacrylic acid anhydride.
Furthermore, the reaction of the OH-functionalized compounds with 2-isocyanatoethyl methacrylate (IEMA) is particularly suitable.
CA 022073~1 1997-06-09 Analogously thereto, the COOH- or OH-functionalized wax-like starting compounds can also be reacted with other suitable unsaturated compounds, so that other polymerizable groups such as acrylic, allyl, vinyl, vinyl ether or styryl groups are S introduced in place of methacrylic radicals. Suitable reagents are e.g. 2-hydroxyethyl acrylate, acrylic acid, acrylic acid chloride, allyl alcohol, 3-buten-1-ol, 2-hydroxyethyl vinyl ether, 4-hydroxymethyl styrene or 4-vinyl benzoic acid.
Methacrylate, acrylate and styryl groups are preferred as polymerizable groups.
In order to produce the dental materials according to the invention, the starting materials are mixed in the stated quantities. The dental materials can contain other materials in addition to the named components, such as for example pigments or dyes. Furthermore, mixtures of different wax-like poly-merizable substances can be used.
The dental materials according to the invention have a wax-like consistency, i.e. they are kneadable to ductile-hard at room or body temperature and can be modelled, plastically moulded or otherwise worked decomposition-free in non-polymerized state without additional heating, like conventional waxes. They exhibit an opaque to partially translucent appearance and can be polished under light pressure. Above ca 40 C they yield slightly viscous, liquid melts which are not prone to cobwebbing.
After modelling, the materials can be cured by polymerization.
The curing preferably takes place by photopolymerization. The wavelength of the light which is necessary to trigger the photopolymerization depends on the photoinitator used, photo-initiators with an excitation wavelength in the wavelength range from 390 to 500 nm being preferred. The photopolymerization can take place in stages at increasing temperatures, i.e. the dental material is initially cured at room temperature by irradiation CA 022073~1 1997-06-09 and then post-polymerized in the temperature range from ca 40 to 80 C, whereby the strength of the materials increases further.
A particular advantage of the wax-like polymerizable substances according to the invention is that they are characterized by a low polymerization shrinkage, which is very advantageous for the dimensional stability of the total material. The pure poly merizable waxes preferably have a polymerization shrinkage of at most 2.2 vol.%, whereas e.g. methyl methacrylate, which is the 10 monomer component of most prosthesis materials, has a volume shrinkage of 20.7 vol.%.
The wax component is covalently incorporated into the formed polymer during polymerization so that a monophase system forms.
15 The cured dental materials therefore have a much greater strength after polymerization than known wax-containing materials. By combining the wax-like polymerizable substances according to the invention with other monomers preferably having a crosslinking effect, dental materials can be produced which after 20 polymerization approach the E modulus of conventional polymethyl methacrylate (PMMA) materials. Thus a preferred dental material consisting of 66.3 wt.% wax monomer, 32.9 wt.% pentaerythritol tetraacetate and 0.8 wt.% of a photoinitiator combination has an E modulus of ca 1.9 GPa after polymerization.
The dental materials according to the invention exhibit a much higher stability in the mouth than conventional materials and are therefore also suitable, unlike known materials, for producing temporary and permanent prostheses.
The dental materials according to the invention allow a percep-tible simplification of the production process e.g. of whole prostheses. It has been customary up to now in the production of whole prostheses initially to produce a wax prosthesis which is adapted to the patient in the mouth. As soon as the result is satisfactory, the wax prosthesis is converted by the "lost wax CA 022073~1 1997 - 06 - 09 technique" into a permanent PMMA prosthesis. This additional process step can be avoided using the dental materials according to the invention since the prosthesis can be polymerized and elaborated directly after the adaptation. This means a consider-s able reduction in labour expenditure and therefore in the costsarising in the production of prostheses.
A further area of application of the dental materials according to the invention is in the production of temporary crowns, bridges and inlays. On account of their good mouldability in the patient's mouth, the dental materials according to the invention can be adapted to the tooth stump treated, whereby the material can be shaped by simple scraping and then cured by polymerization. Reinforcements can be inserted into the material prior to polymerization to strengthen bridges in particular.
ExampleExample 1: Synthesis of polymerizable waxes by esterification of Hoechst-Wachs S with HEMA
A mixture of 70 g of Hoechst-Wachs S (186.7 mmol), 22.6 g of collidine (186.7 mmol), 20.3 g of chloroformic acid ethyl ester (186.7 mmol) and 1000 ml of toluene is stirred for 72 hrs at 60 C
with exclusion of moisture. 24.4 g of HEMA (186.7 mmol) and some p-toluenesulphonic acid are added as catalyst and the whole is then stirred for 3 days at 60~C. The reaction preparation is then filtered at 60~C and the filtrate is left to stand in a refrigerator for 12 hrs at 4~C, where~y a white voluminous precipitate is formed which is dried over anhydrous CaCl2 in a desiccator after separation and washing with some acidified water and with ethanol. Ca 60 g (yield 70%) of a wax-like solid are obtained (melting range: 47 - 61 C, determined by differential scanning calorimetry (DSC)).
The viscosity of the wax is ca 0.5 Pa-s above the melting range (measured at 85~C; the viscosity no longer decreases significant-ly with the temperature from ca 61~C).
Evaluation of the H-NMR spectrum shows that 48% of the COOH
groups are esterified with HEMA.
H-NMR (CDCl3): ~ = 5.6 and 6.2 (2s, =CH2), 4.3 (t, CH2O), 2.2 (t, CH2COO), 1.9 (s, CH3) and 1.2 to 1.4 ppm (broad, CH2).
Example 2: Synthesis of a polymeri~able wax by esterification of Hoechst-Wachs S with GDMA
Analogously to Example 1, a mixture of 140 g of Hoechst-Wachs S
(373.4 mmol), 45.2 g of collidine (373.4 mmol), 40.5 g of chloroformic acid ethyl ester (373.4 mmol) and 1000 ml of toluene is reacted with 85.2 g (373.4 mmol) of GDMA. After the treat-ment, 80 g (yield 50%) of a wax-like solid were obtained (melting point 55 - 70~C).
H-NMR (CDCl3): ~ = 5.6 and 6.2 (2s, =CH2), 4.0 to 4.5 (m, CH2O
and CHO), 2.2 (t, CH2COO), 1.9 ts, CH3) and 1.2 to 1.6 ppm (broad, CH2).
25 IR (Film): 3450 (O-H), 2918 (C-H), 1737 (C=O), 1638 (C=C) and 1171 cm~1 (C-O).
Example 3: Synthesis of a polymerizable wax by reaction of Hoechst-Wachs S with GMA
30 A mixture of 40 g (0.11 mol) of Hoechst-Wachs S, 44.6 g (0.31 mol) of GMA, 0.7 g of 1,4-diazabicyclo[2.2.2]octane and 600 ml of toluene is stirred for 5 days at 65 C. After the preparation has been concentrated to ca 200 ml, the mixture is left to stand overnight in a refrigerator. The formed precipitate is filtered off, washed with some acidified water and with ethanol and then CA 022073~1 1997-06-09 dried over anhydrous CaCl2 in a desiccator. Ca 51 g (yield:
almost 100%) of a wax-like solid are obtained (melting point: 40-67 C, by DSC). Evaluation of the H-NMR spectrum shows that 90%
of the COOH groups have reacted with GMA.
H-NMR (CDCl3): ~ = 5.8 and 6.3 (2s, =CH2), 4.3 to 4.7 (m, HOCX-CH2), 2.4 to 2.6 (m, CHz-C=O), 2.2 (s, C_3) and 1.9 to 2.1 ppm (broad, CH3).
IR (Film): 3368 (O-H), 2927 (C-H), 1719 (C=O) and 1638 cm 10 tC=C).
Example 4: Synthesis ~f a polymerizable wax by reaction of octadecanediol-1,2 with IEMA
7.8 g (50.3 mmol) of IEMA are added dropwise to a solution of 7.4 g (25.6 mmol) of octadecanediol-1,2 and 20 mg of Metatin 812 in 80 ml of THF in such a way that the temperature does not exceed 26~C. After stirring for five days, the solvent is distilled off in vacuo, 14.6 g (yield: 97%) of a wax-like solid being obtained (melting point: 42~C).
C32H56N2Oa ( 596.8) Calc.: C 64.42 H 9.53 N 4.65 Found: C 64.38 H 9.41 N 4. 61 25H-NMR (CDCl3): ~ = 5.6 and 6.1 (2s, =CH2), 5.0 (m, >CHO), 4.2 (t, CH2O), 3.5 (t, CH2N), 1.9 (s, CH3) and 1.1 to 1.3 ppm (~road, C~2 ) .
IR (Film): 3365 (N-H), 2835 (C-H), 1720 (C=O) and 1637 cm (C=C) .
CA 022073~1 1997-06-09 Example 5: Synthesis of a polymerizable wax by reaction of Hoechst-Wachs ~ST with IEMA
A solution of 15 g (10 mmol) of Hoechst-Wachs KST, 2.1 g (20 5 mmol) of IEMA and 2 drops of di-n-octyl tin dilaurate as catalyst (Metatin 812, Acima AG) in 225 ml of toluene is stirred for 3 days at 60 C. After the solution has been concentrated to 80 ml in vacuo, the mixture is left to stand overnight in a refriger-ator. The formed precipitate is filtered off, washed with some lO acidified water and with ethanol and then dried in a desiccator over anhydrous CaCl2. 6.7 g (yield: 45%) of a wax-like solid are obtained (melting point: 45 C). Evaluation of the H-NMR
spectrum shows that the OH-groups have been practically quanti-tatively reacted with IEMA.
H-NMR (CDCl3): ~ = 5.7 and 5.0 (2s, =CH2), 5.0 (broad, NH), 4.3 (t, CH2O), 3.6 (broad, C~H2), 3.5 (m, CH2N), 2.0 ppm (s, CH3).
IR (KBr): 2918, 2849 (C-H), 1737 (C=O) and 1637 cm (C=C).
20 Example 6: Substance polymerization of the wax-like monomers 2 g each of wax-like monomer from the above examples are reacted with in each case 10 mg of dibenzoyl peroxide. The polymerization enthalpy resulting on heating from room tempera-ture to 200~C (10~C/min) is then determined by DSC. On the basis 25 of the polymerization enthalpy of lauryl methacrylate as standard, a complete C=C conversion results for the waxes of Examples 1 and 4, whereas a C=C conversion of 78, 69 and 42 mol.%
respectively results for the waxes of Examples 2, 3 and 5. The C=C conversions show that the methacrylate groups of the wax-like monomers can be radically polymerized. Moreover, the volume shrinkage ~-V) occurring during polymerization was determined from the difference between the pycnometrically determined densities of wax monomer and polymer. The ~-V values lie in the - 13 ~
range from a minimum of - 0.7 vol.% (monomer of Example 2) and a maximum of - 2.2 vol.% (monomer of Example 4).
Example 7: Formulations and properties of wax-like dental materials based on wax-like monomers The dental materials listed in Table 1 are produced by means of a 3-roller mill (all quantities are in wt.%).
Testpieces are then moulded from the dental materials and cured by irradiation in a Spectramat (Vivadent, 10 min). The property values obtained using the bending test according to DIN 53452 and 53457 are given in Table 2.
Table 1 Composition of dental materials 15 Component Example 7a Example 7~ Example 7c Wax monomer Example 1: Example 3: Example 2:
72.5 % 72.0 % 66.3 %
SR-295 26.7 % 27.2 % 32.9 %
Camphor 0.3 % 0.3 % 0.3 %
quinone 25 CEMAb) o 5 % 0 5 %
a) Pentaerythritol tetraacrylate b) 2-cyanoethylmethylaniline .
Table 2 Properties of dental materials Example 7a Example 7b Example 7c Bending 5 20 12 strength (MPa) Flexural E- 1010 1320 1940 modulus (MPa) Crowns and inlays were modelled using the material according to Example 7c based on the usual wax method and were then cured in a Spectramat. Solid models were obtained with a very good 15 dimensional stability and a thermal dimensional stability that was excellent compared with conventional wax models.
Example 8: Comparative Example Analogously to Example 7, dental materials were produced using 20 conventional, non-polymerizable waxes (Table 3, all quantities in wt.%).
The production of testpieces was not possible owing to the low strength of the materials; the materials were seriously cracked after irradiation. Mechanical studies could therefore not be carried out.
Table 3 Composition of comparison materials with non-polymerizable waxes Component Example 8a Example 8b Wax monomer Hoechst-Wachs S S-U-Asthetikwachs-O~
66.1 % 66.1 %
SR-295) 33.1 % 33.1 %
Camphor 0.3 % 0.3 %
quinone 15 CEMAb) O.5 % ~-a) Pentaerythritol tetraacrylate b) 2-cyanoethylmethylaniline c) Schuler-Dental Example 9: Comparative E~ample Dental materials with the compositions shown in Table 4 were produced in accordance with US-A-5 403 188 (Example 1, run nos 1, 12, 13, 16 and 17). No wax-like materials were obtained in this case, but thermoplastic materials which display rubber-like viscosity on melting. Furthermore, the melts are highly viscous (polycaprolactone TONE 767: ca 8500 Pa-s above the melting point (65~C)) and non-dripping, whereas the wax melts according to the invention exhibit a low viscosity (Example 1: ca 0.5 Pa-s above the melting range) and are liquid.
CA 022073~1 1997-06-09 , Table 4 Thermoplastic dental materials TONE P-767) Acrylate Viscosity at 65 C
wt.% wt.% (Pa-s) 30b) 1140 30C) 100 45C) 30 a) Polycaprolactone; molecular mass: 40 000 g/mol (Union 20 Carbide) b) Ebercryl 230, aliphatic urethane diacrylate resin (UCB
Chemicals) c) Ebercryl 830, hexafunctional polyester acrylate oligomer (UCB Chemicals)
The term wax is a collective term for a series of natural and synthetic substances. Generally underst-ood by this term are materials which are already easily plastically mouldable below their melting range or softening range, have a translucent to opaque appearance, melt without decomposition above 40~C and already produce liquids of relatively low viscosity slightly above the melting point and which possess a greatly temperature-dependent consistency and solubility. Furthermore, waxes can mostly be polished under light pressure (Ullmann's Enzyklopadie der Technischen Chemie, 4th edition, volume 24, Verlag Chemie, Weinheim 1989).
Waxes are used in the dental field as modelling, casting, occlusion or adhesive waxes. Mixtures of natural waxes and synthetic waxes are used almost exclusively, the physical properties of the waxes being geared to the desired use (K.
Korber, K. Ludwig, Zahnarztliche Werkstoffe und Technologie, G.
Thieme Verlag, Stuttgart, 1982, page 90). For example, a modelling wax suitable for modelling preshaped parts should be easy to mould and have as good a dimensional stability as possible at the temperature of the mouth. Mixtures of paraffin wax, stearin wax, Japan wax and beeswax are suitable for this purpose.
Conventional waxes are generally heated for processing. Curing 3~ takes place by the wax solidifying on subsequent cooling. In this case, relatively large, uncontrollable volume changes generally occur. Furthermore, conventional waxes have the disadvantage that they easily break when being removed from the model and change their shape under even relatively slight mechanical and above all thermal stress.
CA 022073~1 1997-06-09 In order to avoid these disadvantages, mixtures of natural and partially or wholly synthetic waxes with polymerizable monomers or oligomers such as polyfunctional acrylates and methacrylates have recently been used. These mixtures can be specifically cured after treatment and then have a higher mechanical stability than the pure waxes.
For example, mixtures of polyethylene waxes with styrene or acrylate monomers are disclosed in JP-A-92/4748 (C.A. 120 (1993) 136156) and JP-A-91/330047 (C.A. 119 (1993) 282306). Further-more, photopolymerizable waxes for the dental field based on mixtures of natural or synthetic waxes with conventional acrylic compounds and photoinitiators are described in JP-A-90/312256 (C.A. 128 (1992) 27523). The disadvantages of these mixtures are that conventional dental waxes and dental crosslinker monomers do not mix well with one another and that above all the wax is not incorporated into the polymer network on polymerization. The result may therefore be the formation of wax domains, i.e. a multiphase system is formed, the mechanical strength of which is accordingly low.
EP-B-0 110 193 discloses wax-free wax substitutes for producing casting models. These compositions are based on mixtures of di-or polyfunctional meth- or acrylic acid esters, a photoinitiator and optionally a photoactivator and organic fillers. On account of the composition of the materials claimed in EP-B-0 110 193, they do not exhibit any wax-like properties, i.e. the materials cannot be modelled like waxes and consequently the dental technician must replace the usual wax technique with a layer technique which involves a lot of work. Changes or adjustments to the model can then no longer be made, since curing takes place by polymerization after application of the respective layer.
Furthermore, this process has the disadvantage that thin layers can only be produced using slightly filled or unfilled mixtures of di- or polyfunctional (meth)acrylic acid esters, during the CA 022073~1 1997-06-09 .
polymerization of which a considerable volume contraction results.
EP-B-0 380 116 discloses mixtures which, in order to influence the expansion behaviour of the moulding compounds, additionally contain an organic compound having a boiling point and/or a sublimation point in the range above 150~C and which does not react with the organic polymerizable composition. The named compositions are characterized in particular by the fact that they leave no residues upon combustion.
US-A-5 403 188 discloses thermoplastic mouldiny compounds which are suitable for the production of dental impressions. The compounds contain a polymeric thermoplastic material, preferably a polycaprolactone, a polymerizable resin, an initiator and optionally a filler. They are solid at 38 C and practically not mouldable and they are heated for processing. Curing then takes place by cooling. After the impression has been produced, the compounds are additionally cured by a radical polymerization.
The materials have the disadvantage that they only melt down to form highly viscous products. Dental shaping is extremely difficult since the materials are not only viscous in the molten state, but also very sticky.
It is the object of the invention to provide wax-like dental materials which do not have the above-named disadvantages and are also suitable in particular for producing temporary and permanent prostheses.
The object is achieved by dental materials based on polymerizable waxes which contain a) 0 to 70 wt.%, preferably 5 to 70 wt.%, particularly preferably 5 to 60 wt.% and quite particularly preferably 20 to 50 wt.%, of at least one polymerizable monomer and/or oligomer;
CA 022073~1 1997-06-09 i , b) 0.1 to 5 wt.%, preferably 0.2 to 2.0 wt.%, of at least one polymerization initiator;
c) 0 to 60 wt.%, preferably 0 to 50 wt.% and particularly preferably 0 to 30 wt.%, of fillers; and d) at least 20 wt.%, preferably at least 40 wt.%, of a wax-like polymerizable substance.
10 Suitable polymerizable monomers and oligomers are known for example from DE-C-3 941 629 or DE-A-4 029 230. Compounds which have a crosslinking effect such as di-, tri- or tetraethylene glycol di(meth)acrylate, decanediol di(meth)acrylate, bisphenol-A-di(meth)acrylate, trimethylolpropane tri(meth)acrylate, 15 pentaerythritol tetra(meth)acrylate, 2,2-bis(4-methacryloyloxy-2-hydroxypropoxy)-phenylpropane (bis-GMA) and the reaction product of 1 mol of 2,2,4-trimethylhexamethylene diisocyanate with 2 mol of 2-hydroxyethyl (meth)acrylate and mixtures of these monomers are preferred.
Suitable polymerization initiators are known for example from DE-A-4 029 230. Preferred initiators are camphor quinone, 9,10-phenanthrenequinone or diacetyl. Furthermore, the polymerization initiators can be combined with a suitable reducing agent.
25 Suitable for this purpose are in particular 4-dimethylamino-benzoate, N,N'-(2-cyanoethyl)methylaniline, triethanolamine or 2-(dimethylamino)ethyl methacrylate.
The dental materials according to the invention can contain up 30 to 60 wt.% of fillers, but dental materials containing little or no filler are preferred. The fillers are used to increase mechanical strength, to reduce polymerization shrinkage and to control viscosity. Preferred fillers are known for example from DE-C-3 941 629. Particularly preferred are fillers in the form of amorphous spherical materials based on mixed oxides of SiO2, ZrO2 and/or TiO2, microfine fillers such as pyrogenic silicic CA 022073~1 1997-06-09 acid or precipitated silicic acid, and macro or mini fillers such as quartz powder, glass ceramic powder or glass powder.
Preferred as wax-like polymerizable substances are those compounds which represent a longer-chained carboxylic acid, a carboxylic acid derivative, an OH-functionalized compound and/or a derivative of an OH-functionalized compound and which have one or more polymerizable groups. Preferred carboxylic acid derivatives are the esters with polymerizable alcohols, preferred OH-functionalized compounds are alcohols. Preferred as deriva-tives of the OH-functionalized compounds are the esters with polymerizable carboxylic acid derivatives. The wax-like polymerizable substances are preferably used in monomeric form.
Suitable wax-like polymerizable substances are in some cas~s commercially available, such as for example stearyl acrylate (melting point 23 C, Christ Chem.), PEG-1000-dimethacrylate (melting point 20 C) and PEG-4000-diacrylate (melting point 52 C, both from Polysciences, Inc.), or can be produced by chemical modification of suitable carboxylic acids and alcohols.
Preferred for this purpose are carboxylic acids with a melting point of above 60 C, in particular those with a chain length of 16 to 32 carbon atoms. Palmitic acid (melting point: 64 C), stearic acid (melting point: 69~C), eicosanoic acid (C20H40O2;
melting point: 74-76~C), docosanoic acid (C22H44Oz; melting point:
80-82 C), tricosanoic acid (C23H46O2; melting point: 75-83 C), hexacosanoic acid (C26H52O2; melting point: 87-89~C), heptacosanoic acid (C27H54O2; melting point: 88-89 C) or octacosanoic acid (C28H56O2; melting point: 61-63 C) are quite particularly pre-ferred. Mixtures of these carboxylic acids are also suitable.
Mixtures of palmitic or stearic acid with hexacosanoic or heptacosanoic acid are preferred. A particularly suitable starting material for producing the wax-like polymerizable substances according to the invention is Hoechst-Wachs S
CA 022073~1 1997-06-09 (Hoechst, melting point 80 C) which is a mixture of longer-chained aliphatic carboxylic acids (Cl6 to C36).
Longer-chained alcohols with a melting point of above 55 C as starting materials for producing the polymerizable wax-like substances are preferred as alcohols, in particular those with a chain length of 18 to 32 carbon atoms. Quite particularly preferred are 1,2-octadecanediol (Cl8H38O2; melting point: 74-76 C), 1-eicosanol ((C20H4lOH; melting point: 64-66 C), 1-docosanol (C22H45OH; melting point 65-72 C) or 1-hexacosanol (C26H53OH; melting point: 79-81 C), and Hoechst-Wachs KST
(Hoechst, melting point 57-59 C; based on OH-terminated polyethylene oxide).
Starting from the above wax-like carboxylic acids, the introduc-tion of polymerizable groups preferably takes place by reaction with suitable unsaturated compounds, in particular vinyl, (meth)acrylic or allyl compounds, according to known methods of organic chemistry. Polymerizable methacrylate groups can be introduced for example after activation of the COOH groups e.g.
with chloroformate according to the method of the mixed anhydrides in a single-pot reaction by reaction with 2-hydroxy-ethyl methacrylate (HEMA), hydroxypropyl methacrylate or glycerol dimethacrylate (GDMA). Furthermore, introduction of methacrylic groups can also take place by directly reacting the wax-like carboxylic acids with methacrylic acid-2,3-epoxypropyl ester (GMA).
Starting from the above wax-like OH-functionalized compounds, the introduction of polymerizable groups such as e.g. methacrylic groups is possible for example simply by their azeotropic esterification with methacrylic acid or by acylation with methacrylic acid chloride or methacrylic acid anhydride.
Furthermore, the reaction of the OH-functionalized compounds with 2-isocyanatoethyl methacrylate (IEMA) is particularly suitable.
CA 022073~1 1997-06-09 Analogously thereto, the COOH- or OH-functionalized wax-like starting compounds can also be reacted with other suitable unsaturated compounds, so that other polymerizable groups such as acrylic, allyl, vinyl, vinyl ether or styryl groups are S introduced in place of methacrylic radicals. Suitable reagents are e.g. 2-hydroxyethyl acrylate, acrylic acid, acrylic acid chloride, allyl alcohol, 3-buten-1-ol, 2-hydroxyethyl vinyl ether, 4-hydroxymethyl styrene or 4-vinyl benzoic acid.
Methacrylate, acrylate and styryl groups are preferred as polymerizable groups.
In order to produce the dental materials according to the invention, the starting materials are mixed in the stated quantities. The dental materials can contain other materials in addition to the named components, such as for example pigments or dyes. Furthermore, mixtures of different wax-like poly-merizable substances can be used.
The dental materials according to the invention have a wax-like consistency, i.e. they are kneadable to ductile-hard at room or body temperature and can be modelled, plastically moulded or otherwise worked decomposition-free in non-polymerized state without additional heating, like conventional waxes. They exhibit an opaque to partially translucent appearance and can be polished under light pressure. Above ca 40 C they yield slightly viscous, liquid melts which are not prone to cobwebbing.
After modelling, the materials can be cured by polymerization.
The curing preferably takes place by photopolymerization. The wavelength of the light which is necessary to trigger the photopolymerization depends on the photoinitator used, photo-initiators with an excitation wavelength in the wavelength range from 390 to 500 nm being preferred. The photopolymerization can take place in stages at increasing temperatures, i.e. the dental material is initially cured at room temperature by irradiation CA 022073~1 1997-06-09 and then post-polymerized in the temperature range from ca 40 to 80 C, whereby the strength of the materials increases further.
A particular advantage of the wax-like polymerizable substances according to the invention is that they are characterized by a low polymerization shrinkage, which is very advantageous for the dimensional stability of the total material. The pure poly merizable waxes preferably have a polymerization shrinkage of at most 2.2 vol.%, whereas e.g. methyl methacrylate, which is the 10 monomer component of most prosthesis materials, has a volume shrinkage of 20.7 vol.%.
The wax component is covalently incorporated into the formed polymer during polymerization so that a monophase system forms.
15 The cured dental materials therefore have a much greater strength after polymerization than known wax-containing materials. By combining the wax-like polymerizable substances according to the invention with other monomers preferably having a crosslinking effect, dental materials can be produced which after 20 polymerization approach the E modulus of conventional polymethyl methacrylate (PMMA) materials. Thus a preferred dental material consisting of 66.3 wt.% wax monomer, 32.9 wt.% pentaerythritol tetraacetate and 0.8 wt.% of a photoinitiator combination has an E modulus of ca 1.9 GPa after polymerization.
The dental materials according to the invention exhibit a much higher stability in the mouth than conventional materials and are therefore also suitable, unlike known materials, for producing temporary and permanent prostheses.
The dental materials according to the invention allow a percep-tible simplification of the production process e.g. of whole prostheses. It has been customary up to now in the production of whole prostheses initially to produce a wax prosthesis which is adapted to the patient in the mouth. As soon as the result is satisfactory, the wax prosthesis is converted by the "lost wax CA 022073~1 1997 - 06 - 09 technique" into a permanent PMMA prosthesis. This additional process step can be avoided using the dental materials according to the invention since the prosthesis can be polymerized and elaborated directly after the adaptation. This means a consider-s able reduction in labour expenditure and therefore in the costsarising in the production of prostheses.
A further area of application of the dental materials according to the invention is in the production of temporary crowns, bridges and inlays. On account of their good mouldability in the patient's mouth, the dental materials according to the invention can be adapted to the tooth stump treated, whereby the material can be shaped by simple scraping and then cured by polymerization. Reinforcements can be inserted into the material prior to polymerization to strengthen bridges in particular.
ExampleExample 1: Synthesis of polymerizable waxes by esterification of Hoechst-Wachs S with HEMA
A mixture of 70 g of Hoechst-Wachs S (186.7 mmol), 22.6 g of collidine (186.7 mmol), 20.3 g of chloroformic acid ethyl ester (186.7 mmol) and 1000 ml of toluene is stirred for 72 hrs at 60 C
with exclusion of moisture. 24.4 g of HEMA (186.7 mmol) and some p-toluenesulphonic acid are added as catalyst and the whole is then stirred for 3 days at 60~C. The reaction preparation is then filtered at 60~C and the filtrate is left to stand in a refrigerator for 12 hrs at 4~C, where~y a white voluminous precipitate is formed which is dried over anhydrous CaCl2 in a desiccator after separation and washing with some acidified water and with ethanol. Ca 60 g (yield 70%) of a wax-like solid are obtained (melting range: 47 - 61 C, determined by differential scanning calorimetry (DSC)).
The viscosity of the wax is ca 0.5 Pa-s above the melting range (measured at 85~C; the viscosity no longer decreases significant-ly with the temperature from ca 61~C).
Evaluation of the H-NMR spectrum shows that 48% of the COOH
groups are esterified with HEMA.
H-NMR (CDCl3): ~ = 5.6 and 6.2 (2s, =CH2), 4.3 (t, CH2O), 2.2 (t, CH2COO), 1.9 (s, CH3) and 1.2 to 1.4 ppm (broad, CH2).
Example 2: Synthesis of a polymeri~able wax by esterification of Hoechst-Wachs S with GDMA
Analogously to Example 1, a mixture of 140 g of Hoechst-Wachs S
(373.4 mmol), 45.2 g of collidine (373.4 mmol), 40.5 g of chloroformic acid ethyl ester (373.4 mmol) and 1000 ml of toluene is reacted with 85.2 g (373.4 mmol) of GDMA. After the treat-ment, 80 g (yield 50%) of a wax-like solid were obtained (melting point 55 - 70~C).
H-NMR (CDCl3): ~ = 5.6 and 6.2 (2s, =CH2), 4.0 to 4.5 (m, CH2O
and CHO), 2.2 (t, CH2COO), 1.9 ts, CH3) and 1.2 to 1.6 ppm (broad, CH2).
25 IR (Film): 3450 (O-H), 2918 (C-H), 1737 (C=O), 1638 (C=C) and 1171 cm~1 (C-O).
Example 3: Synthesis of a polymerizable wax by reaction of Hoechst-Wachs S with GMA
30 A mixture of 40 g (0.11 mol) of Hoechst-Wachs S, 44.6 g (0.31 mol) of GMA, 0.7 g of 1,4-diazabicyclo[2.2.2]octane and 600 ml of toluene is stirred for 5 days at 65 C. After the preparation has been concentrated to ca 200 ml, the mixture is left to stand overnight in a refrigerator. The formed precipitate is filtered off, washed with some acidified water and with ethanol and then CA 022073~1 1997-06-09 dried over anhydrous CaCl2 in a desiccator. Ca 51 g (yield:
almost 100%) of a wax-like solid are obtained (melting point: 40-67 C, by DSC). Evaluation of the H-NMR spectrum shows that 90%
of the COOH groups have reacted with GMA.
H-NMR (CDCl3): ~ = 5.8 and 6.3 (2s, =CH2), 4.3 to 4.7 (m, HOCX-CH2), 2.4 to 2.6 (m, CHz-C=O), 2.2 (s, C_3) and 1.9 to 2.1 ppm (broad, CH3).
IR (Film): 3368 (O-H), 2927 (C-H), 1719 (C=O) and 1638 cm 10 tC=C).
Example 4: Synthesis ~f a polymerizable wax by reaction of octadecanediol-1,2 with IEMA
7.8 g (50.3 mmol) of IEMA are added dropwise to a solution of 7.4 g (25.6 mmol) of octadecanediol-1,2 and 20 mg of Metatin 812 in 80 ml of THF in such a way that the temperature does not exceed 26~C. After stirring for five days, the solvent is distilled off in vacuo, 14.6 g (yield: 97%) of a wax-like solid being obtained (melting point: 42~C).
C32H56N2Oa ( 596.8) Calc.: C 64.42 H 9.53 N 4.65 Found: C 64.38 H 9.41 N 4. 61 25H-NMR (CDCl3): ~ = 5.6 and 6.1 (2s, =CH2), 5.0 (m, >CHO), 4.2 (t, CH2O), 3.5 (t, CH2N), 1.9 (s, CH3) and 1.1 to 1.3 ppm (~road, C~2 ) .
IR (Film): 3365 (N-H), 2835 (C-H), 1720 (C=O) and 1637 cm (C=C) .
CA 022073~1 1997-06-09 Example 5: Synthesis of a polymerizable wax by reaction of Hoechst-Wachs ~ST with IEMA
A solution of 15 g (10 mmol) of Hoechst-Wachs KST, 2.1 g (20 5 mmol) of IEMA and 2 drops of di-n-octyl tin dilaurate as catalyst (Metatin 812, Acima AG) in 225 ml of toluene is stirred for 3 days at 60 C. After the solution has been concentrated to 80 ml in vacuo, the mixture is left to stand overnight in a refriger-ator. The formed precipitate is filtered off, washed with some lO acidified water and with ethanol and then dried in a desiccator over anhydrous CaCl2. 6.7 g (yield: 45%) of a wax-like solid are obtained (melting point: 45 C). Evaluation of the H-NMR
spectrum shows that the OH-groups have been practically quanti-tatively reacted with IEMA.
H-NMR (CDCl3): ~ = 5.7 and 5.0 (2s, =CH2), 5.0 (broad, NH), 4.3 (t, CH2O), 3.6 (broad, C~H2), 3.5 (m, CH2N), 2.0 ppm (s, CH3).
IR (KBr): 2918, 2849 (C-H), 1737 (C=O) and 1637 cm (C=C).
20 Example 6: Substance polymerization of the wax-like monomers 2 g each of wax-like monomer from the above examples are reacted with in each case 10 mg of dibenzoyl peroxide. The polymerization enthalpy resulting on heating from room tempera-ture to 200~C (10~C/min) is then determined by DSC. On the basis 25 of the polymerization enthalpy of lauryl methacrylate as standard, a complete C=C conversion results for the waxes of Examples 1 and 4, whereas a C=C conversion of 78, 69 and 42 mol.%
respectively results for the waxes of Examples 2, 3 and 5. The C=C conversions show that the methacrylate groups of the wax-like monomers can be radically polymerized. Moreover, the volume shrinkage ~-V) occurring during polymerization was determined from the difference between the pycnometrically determined densities of wax monomer and polymer. The ~-V values lie in the - 13 ~
range from a minimum of - 0.7 vol.% (monomer of Example 2) and a maximum of - 2.2 vol.% (monomer of Example 4).
Example 7: Formulations and properties of wax-like dental materials based on wax-like monomers The dental materials listed in Table 1 are produced by means of a 3-roller mill (all quantities are in wt.%).
Testpieces are then moulded from the dental materials and cured by irradiation in a Spectramat (Vivadent, 10 min). The property values obtained using the bending test according to DIN 53452 and 53457 are given in Table 2.
Table 1 Composition of dental materials 15 Component Example 7a Example 7~ Example 7c Wax monomer Example 1: Example 3: Example 2:
72.5 % 72.0 % 66.3 %
SR-295 26.7 % 27.2 % 32.9 %
Camphor 0.3 % 0.3 % 0.3 %
quinone 25 CEMAb) o 5 % 0 5 %
a) Pentaerythritol tetraacrylate b) 2-cyanoethylmethylaniline .
Table 2 Properties of dental materials Example 7a Example 7b Example 7c Bending 5 20 12 strength (MPa) Flexural E- 1010 1320 1940 modulus (MPa) Crowns and inlays were modelled using the material according to Example 7c based on the usual wax method and were then cured in a Spectramat. Solid models were obtained with a very good 15 dimensional stability and a thermal dimensional stability that was excellent compared with conventional wax models.
Example 8: Comparative Example Analogously to Example 7, dental materials were produced using 20 conventional, non-polymerizable waxes (Table 3, all quantities in wt.%).
The production of testpieces was not possible owing to the low strength of the materials; the materials were seriously cracked after irradiation. Mechanical studies could therefore not be carried out.
Table 3 Composition of comparison materials with non-polymerizable waxes Component Example 8a Example 8b Wax monomer Hoechst-Wachs S S-U-Asthetikwachs-O~
66.1 % 66.1 %
SR-295) 33.1 % 33.1 %
Camphor 0.3 % 0.3 %
quinone 15 CEMAb) O.5 % ~-a) Pentaerythritol tetraacrylate b) 2-cyanoethylmethylaniline c) Schuler-Dental Example 9: Comparative E~ample Dental materials with the compositions shown in Table 4 were produced in accordance with US-A-5 403 188 (Example 1, run nos 1, 12, 13, 16 and 17). No wax-like materials were obtained in this case, but thermoplastic materials which display rubber-like viscosity on melting. Furthermore, the melts are highly viscous (polycaprolactone TONE 767: ca 8500 Pa-s above the melting point (65~C)) and non-dripping, whereas the wax melts according to the invention exhibit a low viscosity (Example 1: ca 0.5 Pa-s above the melting range) and are liquid.
CA 022073~1 1997-06-09 , Table 4 Thermoplastic dental materials TONE P-767) Acrylate Viscosity at 65 C
wt.% wt.% (Pa-s) 30b) 1140 30C) 100 45C) 30 a) Polycaprolactone; molecular mass: 40 000 g/mol (Union 20 Carbide) b) Ebercryl 230, aliphatic urethane diacrylate resin (UCB
Chemicals) c) Ebercryl 830, hexafunctional polyester acrylate oligomer (UCB Chemicals)
Claims (20)
1. Polymerizable dental material containing (a) 0 to 70 wt.% of at least one polymerizable monomer and oligomer;
(b) 0.1 to 5 wt.% of at least one polymerization initiator;
(c) 0 to 60 wt.% of one or more fillers, (d) at least 20 wt.% of a wax-like polymerizable substance.
(b) 0.1 to 5 wt.% of at least one polymerization initiator;
(c) 0 to 60 wt.% of one or more fillers, (d) at least 20 wt.% of a wax-like polymerizable substance.
2. Polymerizable dental material containing (a) 0 to 70 wt.% of at least one polymerizable monomer or oligomer;
(b) 0.1 to 5 wt.% of at least one polymerization initiator;
(c) 0 to 60 wt.% of one or more fillers, (d) at least 20 wt.% of a wax-like polymerizable substance.
(b) 0.1 to 5 wt.% of at least one polymerization initiator;
(c) 0 to 60 wt.% of one or more fillers, (d) at least 20 wt.% of a wax-like polymerizable substance.
3. Dental material according to claim 1 or 2, wherein the proportion of component (a) is 5 to 70 wt.%.
4. Dental material according to one of claims 1 to 3, wherein the proportion of component (b) is 0.2 to 2.0 wt.%.
5. Dental material according to one of claims 1 to 4, wherein the proportion of component (c) is 0 to 50 wt.%.
6. Dental material according to one of claims 1 to 5, containing at least 40 wt.% of a wax-like polymerizable substance.
7. Dental material according to one of claims 1 to 6 wherein the wax-like polymerizable substance is a longer-chained carboxylic acid, a derivative of such a carboxylic acid, an OH-functionalized compound and a derivative of an OH-functionalized compound and has one or more polymerizable groups.
8. Dental material according to one of claims 1 to 6 wherein the wax-like polymerizable substance is a longer-chained carboxylic acid, a derivative of such a carboxylic acid, an OH-functionalized compound or a derivative of an OH-functionalized compound and has one or more polymerizable groups.
9. Dental material according to claim 7 or 8 wherein the wax-like polymerizable substance is the ester of a carboxylic acid with a polymerizable alcohol.
10. Dental material according to claim 9, wherein the carboxylic acid has a melting point of above 60°C.
11. Dental material according to claim 10, wherein the carboxylic acid has a chain length of 16 to 32 carbon atoms.
12. Dental material according to claim 7 or 8, wherein the wax-like polymerizable substance is the ester of an alcohol with a polymerizable carboxylic acid derivative.
13. Dental material according to claim 12, wherein the alcohol has a melting point of above 55°C.
14. Dental material according to claim 13, wherein the alcohol has a chain length of 18 to 32 carbon atoms.
15. Dental material according to one of claims 7 to 14 wherein the polymerizable groups are methacrylic, acrylic, allyl, vinyl, vinyl ether and styryl groups.
16. Dental material according to one of claims 7 to 14 wherein the polymerizable groups are methacrylic, acrylic, allyl, vinyl, vinyl ether or styryl groups.
17. Use of a wax-like polymerizable substance to produce a dental material.
18. Use according to claim 17 wherein the wax-like polymerizable substance is a longer-chained carboxylic acid, a derivative of such a carboxylic acid, an OH-functionalized compound and a derivative of an OH-functionalized compound and has one or more polymerizable groups.
19. Use according to claim 17 wherein the wax-like polymerizable substance is a longer-chained carboxylic acid, a derivative of such a carboxylic acid, an OH-functionalized compound or a derivative of an OH-functionalized compound and has one or more polymerizable groups.
20. Use of a wax-like polymerizable dental material as defined in any one of claims 1 to 16 to produce temporary or permanent dental prostheses, inlays or crowns.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19626356A DE19626356A1 (en) | 1996-06-18 | 1996-06-18 | Dental materials based on polymerizable waxes |
| DE19626356.5 | 1996-06-18 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2207351A1 CA2207351A1 (en) | 1997-12-18 |
| CA2207351C true CA2207351C (en) | 2000-12-26 |
Family
ID=7798559
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002207351A Expired - Fee Related CA2207351C (en) | 1996-06-18 | 1997-06-09 | Dental material based on polymerizable waxes |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0813856A3 (en) |
| JP (2) | JP3151420B2 (en) |
| CA (1) | CA2207351C (en) |
| DE (1) | DE19626356A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3480819B2 (en) * | 1999-06-30 | 2003-12-22 | 日本歯科薬品株式会社 | Dental curable composition |
| US7476347B1 (en) | 1999-11-10 | 2009-01-13 | Dentsply International, Inc. | Process for making denture having integral teeth and denture base |
| US7566412B2 (en) | 1999-11-10 | 2009-07-28 | Dentsply International Inc. | Dental method and device |
| US7175433B2 (en) | 1999-11-10 | 2007-02-13 | Dentsply International Inc. | Dental material and method |
| US6799969B2 (en) | 1999-11-10 | 2004-10-05 | Dentsply Research & Development Corp. | Wax-like polymerizable dental material, method and shaped product |
| US7114951B2 (en) | 1999-11-10 | 2006-10-03 | Dentsply International Inc. | Method and shaped product-formed from low tack and fluorescing polymerizable dental material |
| US6592369B2 (en) * | 2000-09-26 | 2003-07-15 | Dentsply Research & Development Corp. | Wax-like polymerizable dental material, method and shaped product |
| JP5004801B2 (en) * | 2004-11-12 | 2012-08-22 | デンツプライ インターナショナル インコーポレーテッド | Wax-like polymerizable dental material |
| EP2073782B1 (en) * | 2006-09-13 | 2011-07-20 | 3M Innovative Properties Company | Dental compositions including organogelators, products, and methods |
| US20080085493A1 (en) * | 2006-09-29 | 2008-04-10 | Sun Benjamin J | Methods for making provisional and long-term dental crowns and bridges |
| EP2233449B1 (en) * | 2009-03-27 | 2014-12-17 | Ivoclar Vivadent AG | Use of a slip for the production of dental ceramics with hot melt inkjet printing methods |
| JP6865157B2 (en) * | 2014-07-15 | 2021-04-28 | スリーエム イノベイティブ プロパティズ カンパニー | How to use curable dental articles |
| EP3660087B1 (en) | 2018-11-29 | 2024-05-29 | Ivoclar Vivadent AG | Method and material for the production of three-dimensional objects by energy impulse-induced transfer printing |
| EP3660085A1 (en) | 2018-11-29 | 2020-06-03 | Ivoclar Vivadent AG | Support material for energy impulse-induced transfer printing |
| KR102453251B1 (en) | 2022-07-13 | 2022-10-12 | 주식회사 해성특수지 | Primer for paper |
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| JPS533599B2 (en) * | 1973-09-25 | 1978-02-08 | ||
| JPS5935835B2 (en) * | 1980-06-30 | 1984-08-30 | 株式会社小松製作所 | Lift device for three-dimensional transfer feeder |
| US4746685A (en) * | 1984-08-31 | 1988-05-24 | Nippon Oil And Fats Co., Ltd. | Light curable dental composition |
| DE3638359A1 (en) * | 1986-11-10 | 1988-09-29 | Norbert Schipke | Device for vibrational therapy |
| GB8812238D0 (en) * | 1987-06-23 | 1988-06-29 | G C Dental Ind Corp | Light-polymerizable resin compositions for preparation of clasp patterns |
| JPH07107085B2 (en) * | 1987-09-29 | 1995-11-15 | 三井石油化学工業株式会社 | Polymerizable compound and curing agent having acryloyloxyl group and methacryloyloxyl group in one molecule |
| US5037473A (en) * | 1987-11-18 | 1991-08-06 | Antonucci Joseph M | Denture liners |
| DE4108634A1 (en) * | 1991-03-16 | 1992-09-17 | Bayer Ag | DENTAL MATERIALS |
| EP0537774B1 (en) * | 1991-10-18 | 1998-01-07 | Kuraray Co., Ltd. | Antimicrobial polymerizable composition, the polymer and article obtained from the same |
| JP3155316B2 (en) * | 1991-11-11 | 2001-04-09 | 株式会社モルテン | Dental photopolymer resin material |
| CA2124426C (en) * | 1993-06-23 | 2003-04-08 | Louis H. Tateosian | Dental composition, prostheses, and method for making dental prostheses |
| JP3495099B2 (en) * | 1993-08-02 | 2004-02-09 | サンメディカル株式会社 | Curable adhesive composition and adhesive kit |
| US5530038A (en) * | 1993-08-02 | 1996-06-25 | Sun Medical Co., Ltd. | Primer composition and curable composition |
| DE4339009C2 (en) * | 1993-11-10 | 1996-02-22 | Ivoclar Ag | Multi-component dental cement based on calcium hydroxide |
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-
1996
- 1996-06-18 DE DE19626356A patent/DE19626356A1/en not_active Ceased
-
1997
- 1997-06-09 CA CA002207351A patent/CA2207351C/en not_active Expired - Fee Related
- 1997-06-16 EP EP97250185A patent/EP0813856A3/en not_active Withdrawn
- 1997-06-18 JP JP16163297A patent/JP3151420B2/en not_active Expired - Fee Related
-
2000
- 2000-02-16 JP JP2000038888A patent/JP2000186011A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| JPH1059815A (en) | 1998-03-03 |
| JP3151420B2 (en) | 2001-04-03 |
| EP0813856A3 (en) | 2000-05-24 |
| JP2000186011A (en) | 2000-07-04 |
| DE19626356A1 (en) | 1998-01-02 |
| EP0813856A2 (en) | 1997-12-29 |
| CA2207351A1 (en) | 1997-12-18 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed |