DE2320038A1 - USE OF UV-LIGHT-CURING RESIN COMPOSITIONS IN DENTAL TECHNOLOGY - Google Patents

Description

Use of UV light curing resin compounds in dental technology

The invention relates to the use of UV light-curing resin compounds as modeling compounds in dental technology, with "Dental technology" should be understood here to mean work on the jaw and / or tooth model. Used in dental technology For a long time there have been numerous hardening compounds for molding and modeling work, e.g. plaster of paris, waxes and auto-polymerizates based on acrylate.

Normally these products fulfill their purpose} but there are also areas of application in which no suitable ones have been found so far Materials could be found or in which the products used were deficient. It was therefore The subject of numerous studies to close such gaps and to improve the modeling materials used in dental technology to provide.

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One of the areas of application in which the materials used always led to unsatisfactory results is that the following:

It is common and desirable when creating dental crowns to create a placeholder layer between the inner surfaces of the crown and the prepared tooth. In the subsequent insertion of the crown, the space originally occupied by the placeholder layer is filled with cement. By interposing this cement layer, not only the fixation of the prosthetic work is achieved, but also In addition, direct heat transfer is avoided, so that the still living tooth stump is not exposed to excessive temperature stimuli is exposed. So far, plaster of paris or cement could be used as materials for such placeholder layers will. However, these materials have the disadvantage that they are difficult to process and very thin in layers easily crumble. Other easily modelable materials, such as waxes, could not be used for this purpose, as the common modeling materials, such as auto-polymerizate, due to the resulting heat of polymerisation Melt the wax spacer layer and do not wax any Ensure sufficient separation from the wax spacer layer. The deep-drawing foils that are otherwise common in dental technology can not used because the necessary plasticizing temperature also melts the placeholder layer made of wax.

Another area of application that does not yet have an in Materials that are satisfactory in every respect are individual ones Impression tray. Here it is important to find a precisely fitting mold from

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to errsugen a jaw model of a patient. For this Up to now, car polymers and deep-drawing polystyrene sheets have been used for this purpose.

It has now been found that UV light-curing resin compositions for use as modeling compounds in dental technology, especially when making models using placeholders and for the production of individual impression trays, suitable,

UV light-curing compositions used for the purposes of the invention are, for example, reaction products from diisocyanates and acrylic or methacrylic acid derivatives with active hydrogen, such as products made from oxalky! esters of acrylic and / or methacrylic acid and hexamethylene diisocyanate, tolylene diisocyanate, 4,4'-diisocyanatodiphenylmethane and / or isophorone diisocyanate, optionally with the use of other hydroxy compounds such as glycols. Further are suitable photopolymerizable reaction products of Bisphenols with epichlorohydrin and acrylic and / or methacrylic acid or of bisphenols with glycidyl acrylates or methacrylates as well as in general also appropriately produced compositions in which polyphenols or phenol-formaldehyde condensates get used. Acrylic and / or methacrylic acid esters with polyols such as glycol can also be used, Diglycol, glycerol, trimethylolpropane, pentaerythritol, sorbitol or similar hydroxy compounds as well as using polyesters made from acrylic or methacrylic acid.

All of these components can either be used alone or in combination with other monomers or thermoplastic additives for the production of the photopolymerizable according to the invention Masses are used.

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Preferred compositions which can be used according to the invention are so-called unsaturated polyester resins and their solutions in copolymerizable monomers.

For example, styrenic solutions of polyesters from unsaturated dicarboxylic acids, such as maleic acid, are particularly suitable Fumaric acid, citraconic acid, itaconic acid, chloromaleic acid, and mono- or polyfunctional hydroxy components, such as Ethylene glycol, propanediol-1,2 and -1,3, butanediol-1,2 and -1,4, glycerine, 1 ^ -Bismethylolcyclohexane. This still counts ether group-containing diols or polyols such as dipropylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol and also to a small extent alkyl- and aryl-substituted diols of the same type.

Also saturated di- and monocarboxylic acids such as phthalic acid, Isophthalic acid, terephthalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, norbonene dicarboxylic acid, hexachloronorbonene dicarboxylic acid, Benzoic acid and can be used to a certain extent, whereby it should be noted that that the reactivity then decreases to a noticeable extent. Optionally, mono- or bisfunctional hydroxy compounds, which contain one or more ß, '^ - ethylenically unsaturated ether groups in the molecule, such as trimethylolpropane mono- and / or diallyl ether, glycerol mono- and / or diallyl ether, pentaerythritol mono-, di- or triallyl ether be contained in the polyesters according to the invention. Modification with diisocyanates is also possible and can lead from case to case to products with particularly suitable viscosity properties. Unsaturated polyester resins but are not only suitable for the use according to the invention in a styrenic solution; it is also possible in some

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Cases to completely dispense with copolymerizing monomers or to vary these within wide limits. Suitable monomers are: Acrylates, such as ethyl acrylate, acrylic acid, n-propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl acrylate, Glycidyl acrylate, methyl methacrylate, diethylene glycol diacrylate, Ethylene glycol monomethacrylate, hexamethylene glycol dimethacrylate, 2-hydroxypropyl methacrylate, acrylamide, methacrylamide, N, N-Dimethy! Acrylamide, N-Methylolacrylamide, N-AlIy1-acrylamide, Methylenebisacrylamide, N-methoxymethylacrylamide, N-Allyloxymethylacrylamid, N-Methylolmethacrylamid, N> -Allyloxymethy! Methacrylamid, also divinylbenzene, vinyltoluene, oC-chlorostyrene, allylbenzene, diallylbenzene, diallyl phthalate, Triallyl cyanurate ♦

The above-mentioned photopolymerizable materials contain in order to be usable in the sense of the invention to be, usually a photoinitiator. Photoinitiators are, for example, benzoin derivatives / "DT-OS 1 769 168, 1 769 853, 1 769 854, 1 804 297, 1 807 301, 1 919 678 and DT-AS 1 694 149_7 »but also phenacyl chloride, phenacyl bromide, Desyl chloride and halomethylated benzophenones / "DT-OS 1 949 010_7 as well as anthraquinone derivatives or other aromatic ones Ketones.

To achieve a storable mixture or to increase the shelf life of the photopolymerizable materials, it is in It is usually advisable to use one or more stabilizers. For appropriate additives that usually between 0.001 and 0.2% by weight, hydroquinone, benzoquinone, 3-methylpyrocatechol, hydroquinone methyl ether, Phenothiazine or metal compounds can be used.

Further additives that can be added to the photopolymerizable compositions which can be used according to the invention are pigments,

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Fillers and agents that - the flow behavior of the masses in the Influence the desired senses, for example thixotropic carriers.

As a thixotropic carrier, for example, stearic acid cyclohexylamide may be mentioned, Behenic acid cyclohexylamide, hydrogenated Ricin oil, finely divided silica gel and those in the literature for polyamide resins described for this purpose.

The use of thixotropic carriers in the inventive Compounds is particularly advantageous so that it is when the UV light-curing compounds are applied to the placeholder layer does not come to run off and actually only the surfaces are coated, which afterwards for the creation the crown are necessary.

For example, the invention can be applied to the use of so-called as follows Basic copings are used:

The finished, metal-made crown should only be im The area of the lower third is in contact with the tooth. All other crown areas must be hollow so that a direct one Heat transfer to the still living tooth stump is avoided. In order to save a corresponding gap, is first a placeholder layer was modeled from wax. This placeholder layer ends above the preparation margin in the crown edge area.

Then a suitable insulating layer is applied to the edge area applied, which is then the application of the UV light-curing Mass follows the tooth stump. After the irradiation and the hardening that takes place as a result, the wax placeholder layer becomes removed and the crown is fully modeled using the base coping.

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Example 1 ;

From 2352 g of maleic anhydride, 888 g of phthalic anhydride and 2508 g of 1,2-propylene glycol are obtained by conventional means Melt condensation of an unsaturated polyester, which is stabilized with 0.644 g of hydroquinone, 65% dissolved in styrene and 2.5 96 benzoin isopropyl ether is added. Afterward this preparation is applied in a layer thickness of 1 mm to a placeholder layer made of wax and underneath a Philips TL-AK 40 watt fluorescent tube cured in 3 minutes.

Then the base cap obtained is removed, the placeholder layer mechanically removed and the crown can be completely modeled using the base coping.

Example 2 ;

To a solution of 114 g of bisphenol A, 10 g of triethylamine in 200 ml of toluene are added dropwise at 90 ° 142 g of glycidyl methacrylate. The addition is complete after one hour; it is stabilized with 0.256 g phenothiazine and another 2 hours on Heated to reflux. The solvent is then distilled off under reduced pressure. 51.2 g of resinous residue are mixed with 8 g of methyl methacrylate and mixed with 2.5% benzoin isopropyl ether. This preparation is again applied to the placeholder layer and cured under a Philips TL-AK 40 watt fluorescent tube. Otherwise, proceed as in Example 1.

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Example 3 t

2,2-bis- (p-hydroxy-ethoxy-phenyl) -propane-dimethacrylate is produced by transesterification of 2,2-bis- (p-ß-hydroxyethoxy) -phenylpropane and methyl methacrylate analogously to the method of JV Schmitz, J. Amer. Chem. Soc. 22 »(1955). 30 g of the substance is mixed with 4 g of methyl methacrylate, 0.01 % phenothiazine for stabilization and 0.85 g of benzoin isopropyl ether.

The procedure for this preparation is again as in Example 1.

Example 4 ;

An unsaturated polyester made by condensation of 2352 parts by weight. Maleic anhydride, 888 TIn by weight. Phthalic anhydride and 2508 wt. TIn. Propylene glycol-1,2, is 0.12 wt. tin. Hydroquinone added and 65 percent by weight dissolved in styrene. 200 parts by weight. this 80 ° hot polyester molding compound are 0.8 parts by weight. Stearic acid cyclohexylamide mixed in in molten form. After cooling to room temperature, a gel-like mass is obtained. In 100 parts by weight. this mass is 2.5 parts by weight. Benzoin isopropyl ether stirred in.

This preparation is again carried out as described in Example 1.

Example 5 :

A preparation according to Example 1 is produced. To the

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To manufacture an individual tray, a tooth and jaw model is provided with a placeholder layer made of wax. The preparation is then applied in a layer of 3 mm and irradiated with UV light hardened.

Example 6 :

174 parts by weight. 2,4-tolydene diisocyanate, 150 parts by weight. Ethyl acrylate and 0.14 parts by weight. p-Benzoquinone are heated to'65 ° C and in the course of one hour 130 parts by weight. 2-hydroxyethyl methacrylate was added dropwise. This solution is then with 149 wt. TIn. Triethanolamine reacted by keeping the reaction temperature to 65-75 ⁰ C by careful cooling. After stirring for 2 hours, a light yellow, transparent mass is obtained, to which 2.5% benzoin isopropyl ether is added.

The procedure for this preparation is the same as in Example 1.

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Claims (8)

Ίο Claims: ' (1. / Use of UV-light-curing resin compounds in the tooth- ' technology. 2. Use according to claim 1 for the production of models over placeholders. 3. Use according to claim 1 for the production of individual Abforin spoon. 4. Use of unsaturated polyester with polymerizable Monomers mixed with photoinitiators according to Claim 1. 5. Use of diacrylic esters of bifunctional hydroxy compounds in a mixture with photoinitiators according to claim 1. 6. Use of unsaturated polyurethane resins with at least 2 polymerizable double bonds per molecule in a mixture with photoinitiators according to claim 1. 7. Use according to claim 4 with Benzoinäthem primary and secondary alcohols as photoinitiators. 8. Use according to claim 4 with thixotropic carriers for Adjustment of a desired processing viscosity. Le A 14 989 - 10 - 409845/0497