JPS6136803B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a soft lining material for denture bases, and the soft lining material in the present invention refers to a mucous membrane conditioning material,
This includes denture stabilizers. 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 addition, there are many products on the market for mucosal conditioning materials used to cure mucosal inflammation caused by incompatibility between the denture base and the oral mucosa, but none of them are sufficient and can only be used for a short period of time. I couldn't help it. These causes are thought to be mainly due to the high absorbency of the material, insufficient adhesion to the denture base, changes in physical properties due to elution of plasticizers, and changes in the material itself over time. In order to solve this problem, the inventors of the present invention have previously invented a denture base lined with a soft fluororesin (Japanese Patent Application Laid-open No. 21919/1983). That is, it has extremely low water absorption, excellent adhesion to the denture base, and can be used more stably for a longer period of two years than conventional lining materials. However, this invention is also not easy to use compared to general commercial products, and some problems remain with respect to flexibility. The present invention overcomes all the above-mentioned drawbacks. The details will be explained below. The present invention is a composition comprising a fluorine-containing copolymer [A] and a fluorine-containing telomer [B],
[A] is a copolymer of two or more fluorinated olefin monomers having 2 to 3 carbon atoms, or a copolymer of one or more of these monomers with ethylene or propylene; [B ] is a telomer consisting of two or more types of fluorinated olefin monomers having 2 to 3 carbon atoms, or a telomer consisting of one or more of these monomers and ethylene or propylene, and [A] and [B] The weight ratio
An object of the present invention is to provide a soft lining material for a denture base, which is characterized by a hardness of 10-70/90-30. Carbon number 2 which is the main raw material of the composition according to the present invention
Many types of fluorinated olefin monomers are known, among which vinylidene fluoride, vinyl fluoride, trifluoroethylene, tetrafluoroethylene, chlorotrifluoroethylene, and hexafluoropropylene are particularly known. Preferably used. Examples of the fluorine-containing copolymer [A] according to the present invention include vinylidene fluoride-chlorotrifluoroethylene copolymer, vinylidene fluoride-chlorotrifluoroethylene-tetrafluoroethylene copolymer, and vinylidene fluoride-chlorotrifluoroethylene copolymer. Two or more types of fluorinated olefin monomers such as hexafluoropropylene-tetrafluoroethylene copolymer, vinylidene fluoride-chlorotrifluoroethylene-hexafluoropropylene copolymer, vinylidene fluoride-vinyl fluoride copolymer, etc. Copolymers of fluorinated olefins and olefins, such as vinyl fluoride-hexafluoropropylene-ethylene copolymers and tetrafluoroethylene-ethylene copolymers, are used. In these copolymers, there is no particular limitation on the proportion of each monomer, but the rigidity is 5 Kg/cm ² to 200
Kg/cm ² soft fluorine resin is preferable. The fluorine-containing telomer [B] according to the present invention may be a mixture of two or more monomers selected from the above-mentioned fluorinated olefin monomers having 2 to 3 carbon atoms or the fluorinated olefin monomer. A taxogen having an average molecular weight of about 200 to 1500, obtained by telomerization using a mixture of one or more of the above and a monomer such as ethylene or propylene as a taxogen, and a telogen such as carbon tetrachloride or methanol. telomer is used. In addition to the above-mentioned carbon tetrachloride and methanol, telogens can be freely selected from commonly known ones such as halogenated methane, halogenated ethane, lower alcohols, and lower ketones, and there are no particular restrictions. , carbon tetrachloride, methanol, ethanol, isopropyl alcohol, and methyl ethyl ketone are preferably used. Telomers are generally synthesized by solution polymerization of a taxogen component in a telogen, but depending on the type of telogen, it can also be carried out by suspension polymerization in water. A general organic peroxide is used as a reaction initiator. The reaction temperature varies depending on the half-life of the organic peroxide used, but for example, it is carried out at 20 to 50°C when dialkyl peroxydicarbonates are used, and 80 to 120°C when ditertiary butyl peroxide is used.
Telomer can be obtained with a yield of 90% or more in a reaction time of 20 to 40 hours. After completion of the reaction, it is desirable to completely remove unreacted monomers and excess telogen from the reactants by distillation or other operations. The molecular weight of a telomer is determined primarily by the ratio of taxogen to telogen. The molecular weight preferred for the present invention is 200
To obtain a range of 1500 to 1500, telogen 1 to 100
The polymerization is carried out in the presence of mol, preferably 2 to 50 mol. If the amount of telogen is less than 1 mole per mole of taxogen, the molecular weight will be high and it will not contribute to softening of the fluorine-containing resin with which it is blended. Moreover, if the amount is 100 moles or more, the molecular weight becomes too low and no softening effect can be brought about. The mixing ratio of the fluorine-containing copolymer and the fluorine-containing telomer according to the present invention varies depending on the type of copolymer and telomer, but the weight mixing ratio of copolymer to telomer is preferably in the range of 10 to 70/90 to 30. . The taxogen components of the copolymer and telomer may have the same composition or different compositions, but it is preferable from the viewpoint of compatibility that they have the same composition. Figure 1 shows the penetration resistance (hardness) when the mixing ratio of fluorine-containing copolymer and fluorine-containing telomer is changed.
A diagram showing the relationship between the temperature and the resin temperature is shown. The weight ratios of the copolymer and telomer in FIG. 1 are shown in Table 1. Table 1 No. Fluorine-containing copolymer ^{* **} Fluorine-containing telomer 30 70 25 75 20 80 15 85 10 90 * Vinylidene fluoride/chlorotrifluoroethylene/tetrafluoroethylene 50/30/20 ** Telogen: Carbon tetrachloride Composition is the same as above. From Figure 1, the higher the blending ratio of the copolymer, the harder it becomes, and the lower the blending ratio, the softer it becomes. The higher the blending ratio, the greater the temperature dependence of hardness (Figure 1). ~), and those with a small temperature dependence were found to be small (Fig. 1~). This means that products with a high blending ratio of copolymers are suitable for long-term use as denture base lining materials, while those with a low blending ratio of copolymers are suitable for use as mucous membrane conditioners or denture stabilizers. Indicates that it is suitable for use as a. This is because during the molding process, it is preferable that the denture base lining material be soft (in a heated state) for ease of operation, and at temperatures close to body temperature, it is preferable that it be somewhat hard in order to maintain its shape. be. When used as a mucous membrane conditioning material or denture stabilizing material, the purpose is to cure mucosal inflammation and improve the stability of dentures, so a certain degree of softness is required even at temperatures close to body temperature. The method for measuring the penetration resistance value (hardness) in FIG. 1 is as follows. That is, using a Tensilon tester, 9 g of the sample was placed in a compression cell, the temperature was adjusted to 35°C, and a stainless steel rod with a diameter of 2.3 m/m was inserted into the sample at a speed of 100 mm/min, and the resistance value at that time was measured as g/mm.
This is what is shown. In addition to the above-mentioned properties, the composition of the present invention has a great advantage in that it has extremely low water absorption and its physical properties do not change over a long period of time. Table 2 shows the relationship between the blending ratio of the copolymer and telomer and the water absorption rate. Table 2 Mixing ratio Water absorption copolymer Telomer % (weight) 70 30 0.03 60 40 0.03 50 50 0.03 40 60 0.04 30 70 0.04 20 80 0.03 5 95 0.02 Control Commercial product Viscogale 0.72 〃 Hydrocast 0.61 Shodai The composition of the copolymer and telomer shown in Table 2 is vinylidene fluoride/chlorotrifluoroethylene/tetrafluoroethylene 50/30/20, and the telogen of the telomer was prepared using carbon tetrachloride. In addition, to measure the absorption rate, knead the copolymer and telomer to create a press sheet, and then press this press sheet into a 20 x 20
The graph shows the weight increase in % after cutting into pieces of 1 mm in size and immersing them in pure water at 37°C for 21 days. As is clear from Table 2, the water absorbency was not only superior to commercially available mucous membrane conditioning materials, but there was a marked difference in their superiority. The copolymer and telomer according to the present invention are blended in a predetermined ratio, and after kneading or roll kneading, the thickness is
Press sheet in the range of 0.5 to 1.5m/m, or
Alternatively, it can be used as a block as a mucous membrane conditioner, denture stabilizer, or lining material. For example, when using it as a mucosal conditioning material, the mucosal surface of the denture base is removed to a desired depth, and a milky methyl methacrylate prepolymer is applied to that surface. Cover the entire mucosal surface by pasting a pre-formed press sheet of conditioning material or by stretching the block. The denture covered with this adjustment material is inserted into the oral cavity and the denture is forced into a slightly stronger occlusion. When the denture is removed from the oral cavity, the press sheet is completely adhered to the denture base. Remove the excess adjustment material that protrudes from the lining part and complete the lining operation. The denture base to which this mucous membrane conditioning material was attached was much more stable than that to which conventional mucosa conditioning material was attached, and no adverse effects were observed even after using it for more than 6 months, proving the superiority of the present invention. . Examples will be 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 Methanol in a 6 volume autoclave
5600g, di-n-propyl peroxydicarbonate 10g, vinylidene fluoride 500g, chlorotrifluoroethylene 300g, hexafluoropropylene
I prepared 200g. The taxogen/telogen molar ratio in this experiment was 1:14.96. When the reaction was carried out at 30° C. for 40 hours with stirring, the pressure decreased from 15.6 Kg/cm ² to 4.8 Kg/cm ² . After stopping the reaction and releasing unreacted monomers, the contents were taken out and excess methanol and water were removed by steam distillation and vacuum distillation, resulting in a viscous telomer with an average molecular weight of 1020.
1985g was obtained. 85 g of this telomer was blended with 15 g of a separately obtained vinylidene fluoride/chlorotrifluoroethylene/hexafluoropropylene and 50/30/20 soft fluorine copolymer (rigidity 67 Kg/cm ² ), and mixed in a kneader at 100°C. After 30 minutes of simmering, a clear rubbery substance was obtained. The penetration degree (hardness) and water absorption rate of this material were as follows. Penetration 34.8g/mm ² (35℃) Water absorption 0.03% (weight) Next, we will show some application examples of this material. The inflammation-inducing part of the complete denture base, where inflammation has occurred in the maxillary oral mucosa due to poor fit, is removed to a depth of 1.5 to 2.0 m.
m Delete. Next, the entire mucosal surface of the maxillary complete denture is cleaned, thoroughly dried, and then the rubber-like material is stretched and pasted onto the entire surface with fingers. Place it back into the patient's mouth, keep it in occlusion for a few minutes, then remove it.
Remove excess rubbery material and reinsert into the oral cavity. Compatibility was significantly improved and mucosal inflammation subsided by the fourth day. Furthermore, since the denture base has good stability, the patient did not notice any deterioration in the fit even after one month had passed when it was used continuously. Furthermore, when a conventional commercially available product was used for similar purposes, it was necessary to replace it with a new one after a week at most, demonstrating the superiority of the present product. Example 2 In an autoclave with a capacity of 6, 6500 g of 1,2-difluoro-1,1,2,2-tetrachloroethane was added as a telogen, 10 g of di-n-propyl peroxydicarbonate as a catalyst, 400 g of vinyl fluoride, and hexafluoro as a taxogen. 400g of propylene and 100g of ethylene were charged. The molar ratio of taxogen to telogen in this composition was 1:2.13. Next, the reaction was carried out for 40 hours with stirring at 40°C, and the pressure decreased from 16.5 Kg/cm ² to 5.1 Kg/cm ² .
After stopping the reaction and releasing unreacted monomers, excess 1,2-difluoro-1,
1,2,2-tetrachloroethane and water were removed to obtain 700 g of viscous telomer (average molecular weight 990). 80 g of this viscous telomer was added to a separately obtained soft fluorine copolymer with a rigidity of 71 kg/cm ² (vinyl fluoride/hexafluoropropylene/ethylene composition ratio).
45/45/10) was blended and mixed in a kneader at 100°C for 30 minutes to obtain a transparent rubbery substance. The penetration degree (hardness) and water absorption rate of this material were as shown below. Penetration 110g/mm ² (35℃) Water absorption 0.03% (weight) Next, we will show some application examples of this material. This material is press-molded at 100℃ into a sheet with a thickness of 1.0m/m. Next, cut a small piece approximately 3 cm wide and 12 cm long from this sheet, soak it in warm water at 70°C for approximately 3 minutes to soften it, and then place it between the partial denture base and the mucous membrane in the lower jaw. quickly pinch the sheet and maintain the occlusal state until the sheet temperature drops to the intraoral temperature. Next, when this is removed, the sheet is molded into the shape of the mucosal surface. Remove excess sheeting along the margins of the denture base. Next, the mucosal surface of the denture base is thoroughly dried and coated with resin milk (a mixture of methyl methacrylate polymer and monomer, which is the raw material for denture bases), the molded sheet is adhered thereto, and it is returned to the oral cavity. After a few minutes of occlusion, a denture base with a well-cushioned lining material is obtained. This lining material becomes thinner day by day due to occlusal pressure, but it is 0.2 to 0.1 m/
Once it reaches around m, it does not get any thinner, so it is still in a condition that can withstand continued use even after one month of use.
The superiority of the present invention has been demonstrated. Example 3 An autoclave with a capacity of 6 was charged with 6000 g of carbon tetrachloride as a telogen, 12 g of di-n-propyl peroxycarbonate as a catalyst, and 600 g of vinylidene fluoride, 360 g of chlorotrifluoroethylene, and 240 g of tetrafluoroethylene as a taxogen. The molar ratio of taxogen to telogen in this composition was 1:2.62. Next, when the reaction is carried out for 40 hours with stirring at 30℃, the pressure increases from 16.0Kg/cm ²
It decreased to 3.0Kg/ ^cm2 . The reaction was stopped here, and excess carbon tetrachloride and water were removed by steam distillation and vacuum distillation, yielding 1260 g of viscous telomer (average molecular weight 1050). Penetration resistance of blends of separately obtained vinylidene fluoride/chlorotrifluoroethylene/tetrafluoroethylene 50/30/20 soft fluororesin copolymer (rigidity 80 Kg/cm ² ) and this telomer in various proportions. The values and water absorption rates are shown in Figures 1 and 2.
It was as shown in the table. In addition, in order to examine the influence of telogen, each telomer was prepared by changing the type of telogen with the same taxogen composition as above, and the water absorption of the composition blended at a weight ratio of 20 copolymer/80 telomer is shown in Table 3. Indicated.

[Table] As is clear from Table 3, the water absorption rate of the present telomer is not affected at all by the type of telogen. Next, an application example of the composition obtained in this example will be shown. A transparent rubber-like substance was obtained by blending 80 g of telomer with 20 g of soft fluororesin and mixing in a kneader at 100°C for 30 minutes. This is press-molded at 100℃ into a sheet with a thickness of 1m/m. Remove the mucosal surface of the denture base that has become unfit to a depth of approximately
Remove 1.0m/m and apply resin milk there. After application, the resin milk applied surface is covered with the sheet according to the present invention, the denture is inserted into the oral cavity, and the denture is occluded slightly forcefully. After removing it from the oral cavity and removing the excess portion, a denture base with a flexible mucosal surface was obtained. This operation improves the fit of the denture and
Comfortable fit was maintained even after one month had passed. On the other hand, the superiority of the present invention was evident from the fact that conventional commercially available products lost compatibility after an average of 7 days.

[Brief explanation of the drawing]

FIG. 1 is a diagram showing the relationship between the penetration resistance value and the resin temperature of compositions in which the proportions of the fluorine-containing copolymer and the fluorine-containing telomer according to the present invention are changed. ～ has a ratio of copolymer and telomer of 30/30/
The compositions are 70, 25/75, 20/80, 15/85, and 10/90.

Claims (1)

[Scope of Claims] 1. In a composition comprising a fluorine-containing copolymer [A] and a fluorine-containing telomer [B], [A]
is a fluorinated olefin monomer having 2 to 3 carbon atoms.
or a copolymer of one or more of these monomers and ethylene or propylene, and [B] is a copolymer of two or more fluorinated olefin monomers having 2 to 3 carbon atoms. or a telomer consisting of one or more of these monomers and ethylene or propylene, where the weight ratio of [A] and [B] is 10 to
A soft lining material for denture bases characterized by a ratio of 70/90 to 30. 2. The fluorinated olefin monomer having 2 to 3 carbon atoms is vinylidene fluoride, vinyl fluoride, trifluoroethylene, tetrafluoroethylene, chlorotrifluoroethylene, or hexafluoropropylene, according to claim 1. Soft lining material for denture bases as described. 3. A telomer consisting of two or more types of fluorinated olefin monomers having 2 to 3 carbon atoms, or a telomer consisting of one or more of these monomers and ethylene or propylene,
The soft lining material for denture bases according to claim 1 or 2, which is a telomer obtained by polymerizing in the presence of 1 to 100 moles of telogen per mole of taxogen. .