JPH0142244B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a denture base lined with a copolymer (A) containing a monomer (I) containing a fluorine-containing oligomer as an ester component, and a method for producing the same. Various methods have been tried in the past to alleviate the occlusal pressure applied to the mucosal surface of the denture base by bonding a lining material to the denture base, but none have been satisfactory. In order to solve this problem, the inventors first
He invented a denture base lined with soft fluorine resin (Japanese Patent Application Laid-Open No. 55-21919). That is, the lining material provided by the present invention has extremely low water absorption, excellent adhesion to the denture base, and can be used stably for a longer period of two years or more than conventional lining materials. However, this invention also had a more complicated surgical procedure than general commercially available products, and some problems remained with respect to flexibility. The present invention provides a means to solve this problem. That is, in order to simplify the lining method of the lining material, it is desirable that the lining material has fluidity during the technical operation and has ideal hardness when the lining operation is completed. The present invention provides a denture base lined with an innovative lining material that perfectly solves this problem, and a method for manufacturing the same. The denture base according to the present invention has the general formula

[Formula] (R ₁ is H or CH ₃ , R ₂ is a fluorine-containing oligomer with a molecular weight of 1500 or less) 100 parts by weight of the monomer (I) component and an alkyl ester of acrylic acid or methacrylic acid (an alkyl group) This is a denture base lined with a copolymer (A) consisting of 3 to 30 parts by weight of a component having 1 to 5 carbon atoms. Further, the method for producing a denture base lined with the above-mentioned copolymer (A) according to the present invention includes adding either 100 parts by weight of the monomer (I) or 3 to 30 parts by weight of an alkyl ester of acrylic acid or methacrylic acid. , dissolve either 0.1 to 2.0 parts by weight of an organic peroxide or 0.05 to 1.0 parts by weight of an aromatic tertiary amine, and mix monomer (I) with an alkyl ester of acrylic acid or methacrylic acid. , which is characterized by being injected and superposed on the lining surface of the denture base. The copolymer (A) according to the present invention has low water absorption and moderate flexibility (Shore hardness 10-85, preferably 10-50).
Therefore, a denture base lined with this copolymer (A) has the effect of relieving occlusal pressure and transmitting it to the oral mucosal surface, and also improves the compatibility and adsorption of the denture and jaw holder. It also has amazing durability with no deterioration even after more than two years have passed since it was applied to the oral cavity. Furthermore, in the present invention, the monomer (I) in which each catalyst is dissolved and the alkyl ester of acrylic acid or methacrylic acid are mixed, and when the mixture becomes slightly viscous, it is injected onto the lining surface of the denture base, and the mixture is poured as it is. By polymerizing, it is possible to line the copolymer (A) with appropriate flexibility.
There is no need to use the conventional method of heating and preforming a lining material sheet and then pressing it onto the lining surface of the denture base, making it extremely easy to obtain a lined denture base. can. Monomer (I), which is a component of copolymer (A), can be produced based on the method described in Japanese Patent Application No. 57-233695 (Japanese Patent Application Laid-open No. 59-117503). That is, for example, the fluorine-containing monomer is replaced with methyl alcohol,
By performing telomerization in alcohol such as ethyl alcohol, the end of the molecular chain is
A fluorine-containing telomer having an OH group is obtained, and monomer (I) is easily obtained by dissolving this fluorine-containing telomer in a solvent such as carbon tetrachloride and causing an ester reaction with acrylic acid chloride or methacrylic acid chloride. be able to. The fluorine-containing monomers used in this case include two or more monomers selected from vinylidene fluoride, vinyl fluoride, trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, and hexafluoropropylene. The fluorine-containing oligomer constituting the ester portion of monomer (I) is preferably a binary or ternary oligomer of the above-mentioned fluorine-containing monomer.
The molecular weight of the oligomer used is 1500 or less;
If it exceeds this value, the molding process will be slightly unsatisfactory. Since the ester component of monomer I, which is the main component of copolymer A, is composed of such a fluorine-containing multi-element oligomer, copolymer (A) has appropriate flexibility and excellent durability. The denture base used as the lining material does not undergo any deterioration even after being used for more than two years. As the (meth)acrylic acid alkyl ester which is another component of the copolymer (A), those having an alkyl group of 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms are used. Here, (meth)acrylic acid alkyl ester refers to methacrylic acid alkyl ester or acrylic acid alkyl ester. The polymerization ratio of the monomer (I) component and the (meth)acrylic acid alkyl ester component in the copolymer (A) is 3 to 30 parts by weight of the latter to 100 parts by weight of the former, preferably 5 to 25 parts by weight. used. If the (meth)acrylic acid alkyl ester portion is less than 3 parts by weight, the strength and hardness of the copolymer will be insufficient (too soft);
If it exceeds 30 parts by weight, the strength will be extremely high, but the hardness will also be excessive, making it unsuitable as a soft lining material.
Copolymer (A) can be polymerized by ordinary radical polymerization. The copolymer (A) is made into a sheet as in the conventional method, heated, preformed in a plaster mold, and then placed on the lining surface of a denture base made of acrylic prepolymer molded with plaster in a flask. A denture base lined with the copolymer (A) can also be obtained by applying pressure and crimping with the above-mentioned plaster mold according to a conventional method. but,
The following method according to the invention is preferred because it is extremely simple to obtain a lined denture base. In the present invention, 100 parts by weight of monomer (I) or (meth)
Either 0.1 to 2.0 parts by weight of an organic peroxide or 0.05 to 1.0 parts by weight of an aromatic tertiary amine is dissolved in 3 to 30 parts by weight of an acrylic acid alkyl ester, and the monomer (I ) and (meth)acrylic acid alkyl ester are mixed immediately before use. As the aromatic tertiary amine, dimethyl para-toluidine and di-2-hydroxyethyl para-toluidine are preferably used. The amount used is preferably 0.05 to 1.0 parts by weight. Although many organic peroxides can be used, benzoyl peroxide, ditertiary butyl peroxide, etc., which have a long half-life in the low temperature range, are preferred. The amount used is preferably 0.1 to 2.0 parts by weight. If the amount used is less than the above range, the polymerization rate will be too slow, and if the amount used exceeds the above range, the polymerization rate will be too fast and the polymer may solidify during injection onto the denture base (prepolymer). . Monomer (I) dissolves the aromatic tertiary amine,
The (meth)acrylic acid alkyl ester may dissolve the organic peroxide, or vice versa, the monomer (I) may dissolve the organic peroxide and the (meth)acrylic acid alkyl ester dissolves the aromatic peroxide. A tertiary amine may be dissolved. In any case, the organic peroxide and the aromatic tertiary amine come into contact only by mixing them, and a redox reaction generates radicals even at a low temperature such as room temperature, and a copolymerization reaction occurs. When the two are mixed, copolymerization starts within a few minutes, heat is generated, and the viscosity of the mixed liquid increases. When the mixture becomes viscous to the point where it becomes stringy, pour an appropriate amount onto the lining surface (the surface in contact with the alveolar ridge mucosa) of the acrylic mochi-shaped prepolymer molded in advance in the denture base preparation flask. If pressure is applied using a plaster mold and polymerization is carried out using a conventional method, the mixed solution will form a rubber layer made of copolymer (A) that firmly adheres to the hardened acrylic denture base lining surface, making it a soft material. A lined denture base is obtained. Furthermore, it is also possible to easily regenerate a denture base that has become unsuitable after many years of use. In other words, part or all of the mucosal surface of the denture base that has become unfit is removed to a depth of about 1 inch.
When about 1/4 inch is removed and the mixture becomes stringy, inject an appropriate amount of the mixture onto the removed surface, insert it into the oral cavity, occluse it, and keep it there for a few minutes. It solidifies and produces a rubber layer that firmly adheres to the mucosal surface of the denture base (direct method). Examples will be further described below, but the invention is not limited to these examples as long as they fall within the scope of the claims of the present application. Example 1 A methacrylic prepolymer was filled in a plaster mold in a pre-molded denture base preparation flask using a conventional method, and the mucous membrane surface was lined with a lining material of 1 m/m thick paraffin wax. Secure the volume. next

In [Formula], R ₂ is 50 parts by weight of vinylidene fluoride, chlorotrifluoroethylene
20 g of fluorine-containing methacrylic acid ester, which is an oligomer with a molecular weight of 1020, consisting of 30 parts by weight, 20 parts by weight of tetrafluoroethylene, and dimethyl p-toluidine.
Place 0.04g in a 100c.c. beaker and use this as liquid (A). Meanwhile, in another beaker, take 4 g of methyl methacrylate and 0.08 g of benzoyl peroxide, and use this as liquid (B). After the benzoyl peroxide is completely dissolved, mix both solutions (A) and (B) and stir until homogeneous. The temperature begins to rise about 6 minutes after mixing, and the viscosity of the mixed liquid increases to the point that it becomes stringy in about 12 minutes. At this time, pour a sufficient amount of the mixed solution onto the prepolymer prepared above (until the grooves of the molded prepolymer are filled), cover it with the other plaster mold, apply pressure as it is, and polymerize using the usual method. In this way, a denture base lined with a rubber-like polymer having appropriate hardness on the mucosal surface can be obtained. This product was removed from the plaster mold, corrected and polished, applied to a 65-year-old man, and used for 24 months without any abnormalities and was still usable. Reference Examples 1 to 9 Various copolymer test pieces were obtained by carrying out polymerization according to Example 1 while changing the component ratio of the fluorine-containing methacrylic acid ester and methyl methacrylate or ethyl methacrylate. Note that the test piece was made from a plaster mold that had been previously cut to the size of the test piece. That is, paraffin wax of the same size as a test piece of a predetermined size is buried in plaster, and when the plaster solidifies, the paraffin wax is washed away, the space is filled with a liquid mixture of a predetermined composition, and the resulting space is heated and polymerized for testing. It was a piece. Table 1 shows the component ratio of the copolymer and the physical properties of the test piece thus obtained. Note that Reference Example 3 is the same copolymer as Example 1 described above. As is clear from Table 1, the copolymer (A) constituting the lining material of the present invention has a moderate hardness of 10 to 50 and 5.0.
It can be seen that it has a tensile strength of more than Kg/cm ² and has a small amount of water absorption. On the other hand, in Reference Examples 1, 5, and 9, in which the component ratio of the copolymer of fluorine-containing methacrylic acid ester and methyl methacrylate or ethyl methacrylate is outside the range of the present application, the hardness is too low (too soft) or too high. It is too hard (too hard) and is not satisfactory as a lining material for denture bases.

[Table] Example 2 A methacrylic prepolymer was filled into a plaster mold in a pre-molded denture making flask using a conventional method, and the mucous membrane surface was lined with 1 m/m thick paraffin wax. Secure enough space to do so. next

In [Formula], R ₂ is 50 parts by weight of vinylidene fluoride, chlorotrifluoroethylene
30 parts by weight of hexafluoropropylene, 20 g of fluorine-containing methacrylic acid ester, which is an oligomer with a molecular weight of 980, and 0.04 g of di-2-hydroxyethyl para-toluidine were placed in a 100 c.c. beaker. (A) Make it into a liquid. Meanwhile, take 3 g of ethyl methacrylate and 0.08 g of ditertiary butyl peroxide into another 100 c.c. beaker,
(B) Make it a liquid. Next, mix both solutions (A) and (B). After about 5 minutes, when the temperature starts to rise and the mixed liquid thickens and becomes stringy, it is poured onto the prepolymer prepared in advance. Cover it with the other plaster mold,
If pressure is applied as it is and polymerization is performed in a conventional manner, a denture base lined with a rubber-like polymer having appropriate hardness on the mucosal surface can be obtained. This product was removed from the plaster mold, corrected and polished, applied to a 70-year-old man, and used for 24 months without any abnormalities and could still be used continuously. A test piece was prepared in the same manner as in the reference example, and its shore hardness was measured and found to be 22.0. Example 3 When relining the mucosal surface of a denture base currently in use with methacrylic resin, the mucosal surface of the denture base was removed to a depth of about 1 m/m in advance to create a clean methacrylic resin surface. That is, a denture prepared according to the normal denture base reverse method is embedded in a flask with plaster, and then a 2 to 3 layer thick layer is placed on the mucous surface of the clean methacrylic resin of the denture base.
Place a mochi-shaped methacrylic resin (prepolymer) to a size of about 1.0 mm and perform trial molding, then secure a volume for lining with 0.7 mm thick paraffin wax. next

In [Formula], R ₂ is 50 parts by weight of vinylidene fluoride, chlorotrifluoroethylene
20 g of fluorine-containing acrylic ester, which is an oligomer with a molecular weight of 1065, consisting of 30 parts by weight, 20 parts by weight of tetrafluoroethylene, and benzoyl peroxide.
Place 0.08g in a 100cc beaker and use this as liquid (A). On the other hand, 3 g of methyl acrylate and 0.04 g of dimethyl para-toluidine are placed in another 100 c.c. beaker and used as liquid (B). After the benzoyl peroxide in solution (A) is completely dissolved, mix both solutions (A) and (B). The temperature begins to rise in about 5 minutes, and the mixture thickens and becomes stringy in about 10 minutes, after which it is poured onto the prepolymer prepared in advance. Cover it with the other plaster mold, apply pressure as it is,
If polymerized by a conventional method, a denture base rebased with a rubber-like polymer having appropriate hardness on the mucosal surface can be obtained. This product was removed from the plaster mold, corrected and polished, applied to a 72-year-old man, and used for 20 months without any abnormalities and was still usable. A test piece was prepared in the same manner as in the reference example, and its shore hardness was measured to be 19. Example 4 The entire mucosal surface of the maxillary complete denture base, which had been worn for 2 years and had become unfitted by a 75-year-old man, was removed to a depth of approximately 1 m/m. next

In [Formula], R ₂ is 50 parts by weight of vinylidene fluoride, chlorotrifluoroethylene
20 g of fluorine-containing methacrylic acid ester, which is an oligomer with a molecular weight of 1020, consisting of 30 parts by weight, 20 parts by weight of tetrafluoroethylene, and dimethyl p-toluidine.
Place 0.04g in a 100cc beaker and use this as liquid (A). Meanwhile, take 4 g of methyl methacrylate and 0.08 g of benzoyl peroxide in another beaker and use this as liquid (B). After the benzoyl peroxide is completely dissolved, mix both solutions (A) and (B) and stir until homogeneous. The temperature begins to rise about 6 minutes after mixing, and the viscosity of the mixture increases to the point that it becomes stringy after about 12 minutes. At this time, a sufficient amount (approximately 10 g) of the mixed solution is injected into the removed mucosal surface of the denture base. Next, it is inserted into the mouth, the upper and lower back teeth are engaged, and the patient is left in this position for 10 minutes. During this time, the mixture rapidly solidifies with heat generation. After 10 minutes, remove it and add more time to complete polymerization.
After standing for 10 minutes, the morphology is corrected and a denture base lined with a rubbery polymer is obtained. This was returned to the 75-year-old man mentioned above, and he used it for one year, but he did not complain of any abnormality and was able to continue using it sufficiently.

Claims (1)

[Claims] 1 100 parts by weight of the monomer (I) component represented by the general formula [Formula] (R ₁ is H or CH ₃ , R ₂ is a fluorine-containing oligomer with a molecular weight of 1500 or less) and acrylic acid or A denture base lined with a copolymer (A) comprising 3 to 30 parts by weight of an alkyl ester of methacrylic acid (alkyl group having 1 to 5 carbon atoms) component. 2 An oligomer in which R ₂ in [Formula] is composed of two or more monomers selected from vinylidene fluoride, vinyl fluoride, trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, and hexafluoropropylene with a molecular weight of 1500 or less. The denture base according to claim 1, characterized in that: 3 100 parts by weight of the monomer (I) represented by the general formula [Formula] (R ₁ is H or CH ₃ , R ₂ is a fluorine-containing oligomer with a molecular weight of 1500 or less) or an alkyl ester of acrylic acid or methacrylic acid (alkyl 0.1 to 2.0 parts by weight of an organic peroxide or 0.05 to 1.0 parts by weight of an aromatic tertiary amine are dissolved in 3 to 30 parts by weight of a component (having a group having 1 to 5 carbon atoms). A method for producing a denture base lined with a copolymer (A), which comprises mixing the monomer (I) and an alkyl ester of acrylic acid or methacrylic acid and injecting and polymerizing the mixture onto the lining surface of the denture base. 4 A patent characterized in that [Formula] is an oligomer consisting of two or more monomers selected from vinylidene fluoride, vinyl fluoride, trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, and hexafluoropropylene. The method according to claim 3.